CN118022834A - Magnetic heteropolyacid salt polymer composite catalyst, preparation method and application thereof - Google Patents
Magnetic heteropolyacid salt polymer composite catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN118022834A CN118022834A CN202410444500.8A CN202410444500A CN118022834A CN 118022834 A CN118022834 A CN 118022834A CN 202410444500 A CN202410444500 A CN 202410444500A CN 118022834 A CN118022834 A CN 118022834A
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- China
- Prior art keywords
- magnetic
- polymer
- quaternary ammonium
- composite catalyst
- paa
- Prior art date
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- Granted
Links
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 87
- 229920000642 polymer Polymers 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 150000003839 salts Chemical class 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 229920000083 poly(allylamine) Polymers 0.000 claims abstract description 21
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 26
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 claims description 17
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- -1 aliphatic quaternary ammonium salt Chemical class 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- PGQAXGHQYGXVDC-UHFFFAOYSA-N dodecyl(dimethyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(C)C PGQAXGHQYGXVDC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- URXQDXAVUYKSCK-UHFFFAOYSA-N hexadecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[NH+](C)C URXQDXAVUYKSCK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000007885 magnetic separation Methods 0.000 abstract description 10
- 125000003277 amino group Chemical group 0.000 abstract description 7
- 239000006249 magnetic particle Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006053 organic reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- 238000003756 stirring Methods 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000001035 drying Methods 0.000 description 23
- 239000002245 particle Substances 0.000 description 21
- 238000005406 washing Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002122 magnetic nanoparticle Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- WTPYRCJDOZVZON-UHFFFAOYSA-N 3,5,5-Trimethylhexanal Chemical compound O=CCC(C)CC(C)(C)C WTPYRCJDOZVZON-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940032296 ferric chloride Drugs 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920001688 coating polymer Polymers 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- KTOXGWMDJYFBKK-UHFFFAOYSA-L manganese(2+);diacetate;dihydrate Chemical compound O.O.[Mn+2].CC([O-])=O.CC([O-])=O KTOXGWMDJYFBKK-UHFFFAOYSA-L 0.000 description 2
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000013460 polyoxometalate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002468 redox effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical class CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- QAXZWHGWYSJAEI-UHFFFAOYSA-N n,n-dimethylformamide;ethanol Chemical compound CCO.CN(C)C=O QAXZWHGWYSJAEI-UHFFFAOYSA-N 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004383 yellowing Methods 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
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Abstract
The invention belongs to the field of materials, and particularly discloses a magnetic heteropolyacid salt polymer composite catalyst, a preparation method and application thereof. The magnetic heteropolyacid salt polymer composite catalyst comprises heteropolyacid salt and a carrier, wherein the carrier comprises a core and a polymer coated outside the core; the inner core comprises Fe 3O4 nano particles; the polymer comprises polyallylamine; and carrying out quaternary ammonium group modification treatment on the surface of the polymer-coated carrier. The preparation method provided by the invention utilizes the polymer with high content of amino groups to wrap the magnetic particles, then reacts with the quaternary ammonium group reagent, grafts a large amount of quaternary ammonium groups on the surface of the magnetic particles, realizes high solid-supported synthesis of heteropoly acid, effectively solves the problems of low load of active components of the heteropoly acid and easy loss in liquid phase organic reaction, and the prepared catalyst has excellent reusability, high catalytic efficiency and low cost, and is convenient for magnetic separation.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a catalyst, in particular to a magnetic heteropolyacid salt polymer composite catalyst, a preparation method and application thereof.
Background
3, 5-Trimethylhexanoic acid, commonly known as isononanoic acid, is an important fine organic chemical basic raw material. The modified polyurethane has excellent wettability, permeability and emulsifying property, and is widely used for preparing industrial products such as high-grade lubricants, medical intermediates, coatings, metal soaps, metal processing fluids and the like. The metal salts of isooctanoic acid are excellent paint driers, polymer stabilizers and preservatives, and esters thereof are also useful in the cosmetic field. In addition, when the modified alkyd resin is used for alkyd resin modification, the yellowing resistance and the impact resistance of the resin can be improved. With the rapid increase of the demand of highly branched fatty acids, the development and production of isononanoic acid have great market prospects.
The currently reported methods for producing isononanoic acid include a direct oxidation method of isononanol, a diisobutylene hydrogen esterification method, a hydroformylation method and an aldehyde oxidation method. The method is characterized in that isononanal is prepared by hydroformylation of diisobutylene, hydrogen and carbon monoxide, isononanal is further oxidized to obtain isononanoic acid, and the technology is a main production technology at present due to wide raw material sources, easiness in large-scale production and higher product yield.
Wherein, the oxidation step of isononanal has higher dependence on the catalyst, and is a key link for preparing isononanoic acid. This step generally uses a metal salt as a homogeneous catalyst, and a system and a catalyst for preparing isononanoic acid by oxidation of isononanal are reported in patent CN202310170549.4, and the system comprises an oxidation reaction system, a main catalyst recovery system, a cocatalyst recovery system, and a product separation system, and uses a transition metal salt of acetic acid and naphthenic acid as a catalyst. In addition, hydroxylamine hydrochloride has better effect for oxidizing fatty aldehyde into corresponding fatty acid. However, the homogeneous catalysis system is difficult to separate from the reaction system, and the subsequent separation and purification process is affected. Therefore, the development of heterogeneous catalysts is an effective way to solve the problems, as reported in patent CN201711396736.5, for preparing isononanoic acid metal-organic framework catalysts, which have higher selectivity and yield, but have the problems of poor stability and high production cost. Patent CN202110084627.X discloses a sulfonated mesoporous silicon-carbon composite catalyst, hydrogen peroxide is adopted as an oxidant to prepare isononanoic acid, reaction conditions are mild, byproducts are few, but the catalyst cost is high, strong bases such as sodium hydroxide and the like are used, the requirement on equipment is high, and the product yield is not ideal. Therefore, the development of highly efficient heterogeneous catalysts remains an important research focus for this type of reaction.
The heteropolyacid is a polyoxometalate with acidity and redox property, has excellent selective oxidation performance due to containing a plurality of valence-variable metal elements, and is widely used in various oxidation reactions of hydrocarbons, aldehydes, alcohols and the like, but the high polarity makes the polyoxometalate difficult to separate from a reaction system in a liquid phase reaction system. Although the solid-supporting of the heteropoly acid can simplify the separation problem of the liquid-solid system, the simple impregnation method is difficult to avoid the problems that the heteropoly acid is dissolved in the liquid phase, and finer particles can accumulate in a reaction pipeline to cause pipeline blockage and the like. The magnetic separation is an effective solution, and patent CN101229517A discloses a preparation method of nano magnetic-supported heteropoly acid, firstly, silicon dioxide is used for coating magnetic ferroferric oxide particles, then hexadecyl trimethyl ammonium bromide is used for modifying the surface of the magnetic ferroferric oxide particles, a sol-gel technology is used for forming secondary coating, and heteropoly acid is added at the same time, so that the magnetic ferroferric oxide particles are embedded between two layers of silicon dioxide. However, the hydrophilic end of cetyltrimethylammonium bromide in this method is easily adsorbed to the silica inner layer, and thus it is not effective to support the heteropolyacid. Patent CN201410160201.8 reports a method for grafting magnetic nano particles of extractant to be combined with heteropoly acid to adsorb heteropoly acid in vanadium-containing solution, and the method also uses silicon dioxide to coat magnetic ferroferric oxide particles, and then uses silane coupling agent to graft amine extractant, but the grafting amount is lower, and the preparation requirement of heteropoly acid with high solid content can not be satisfied.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a magnetic heteropoly acid salt polymer composite catalyst, a preparation method and application thereof. Compared with the traditional method for preparing the heteropoly acid catalyst, the preparation method provided by the invention has the advantages that the polymer with high content of amino groups is used for wrapping the magnetic particles, then the magnetic particles are reacted with the quaternary ammonium group reagent, a large number of quaternary ammonium groups are grafted on the surface of the magnetic particles, so that the high-solid-supported synthesis of the heteropoly acid is realized, the problems of low loading amount of the active components of the heteropoly acid and easy loss in liquid-phase organic reaction are effectively solved, and the prepared catalyst has excellent reusability, high catalytic efficiency and low cost and is convenient for magnetic separation.
The specific technical scheme is as follows:
The invention aims at providing a magnetic heteropolyacid salt polymer composite catalyst, which comprises heteropolyacid salt and a carrier, wherein the carrier comprises an inner core and a polymer coated outside the inner core;
The inner core comprises Fe 3O4 nano particles;
the polymer comprises polyallylamine;
Carrying out quaternary ammonium group modification treatment on the surface of a carrier coated with the polymer;
the heteropolyacid salt is fixedly supported on a carrier;
Specifically, the magnetic heteropolyacid salt polymer composite catalyst has the following chemical expression ：PAxByMo12- nVnO40/Fe3O4-PAA-N(R12R2)+;
Wherein: a is at least one of Cu, zn and K; b is at least one of Ni, fe, co, mn, sb, sn elements; PAA is polyallylamine; r1 is a methyl functional group; r2 is an alkyl functional group with 10-20 carbon atoms;
Wherein: x and y are molar coefficients, x is more than or equal to 0.1 and less than or equal to 3, y is more than or equal to 0.1 and less than or equal to 3, and n is more than or equal to 1 and less than or equal to 3.
Further, in the formula: r2 is preferably a dodecyl function or a hexadecyl function.
Wherein, quaternary ammonium group modification treatment is carried out by using a quaternizing agent, and the quaternizing agent is preferably epoxypropyl dimethyl dodecyl ammonium chloride or/and epoxypropyl dimethyl hexadecyl ammonium chloride.
More specifically, the magnetic heteropolyacid salt polymer composite catalyst is preferably at least one of the following chemical formulas:
PCu1.5Fe1.5Mo10V2O40/Fe3O4-PAA-N(R12R2)+;
PK2.8Co0.5Mo10V2O40/Fe3O4-PAA-N(R12R2)+;
PZn0.1Ni0.3Mo10V2O40/Fe3O4-PAA-N(R12R2)+;
PCuSn0.1Mo10V2O40/Fe3O4-PAA-N(R12R2)+；
PK1.5MnMo11VO40/Fe3O4-PAA-N(R12R2)+；
PZn0.2Mn2.8Mo9V3O40/Fe3O4-PAA-N(R12R2)+.
the second object of the present invention is to provide a preparation method of the magnetic heteropolyacid salt polymer composite catalyst, which comprises the following steps:
(1) Fe 3O4 is obtained, and the Fe 3O4 is specifically Fe 3O4 nano particles;
(2) Polymer coating: coating Fe 3O4 by using polyallylamine to obtain a magnetic polymer;
(3) Quaternary ammonium group modification: carrying out surface modification on the polymer-coated Fe 3O4 by using a quaternizing reagent to obtain a quaternary ammonium group modified magnetic polymer;
(4) Heteropolyacid impregnation: preparing an impregnating solution comprising heteropoly acid, a compound containing an element A and a compound containing an element B, and mixing the quaternary ammonium group modified magnetic polymer with the impregnating solution to prepare the magnetic heteropoly acid salt polymer composite catalyst.
Polyallylamine is coated on Fe 3O4 nano particles to form a high molecular coating polymer of Fe 3O4 nano particles, the polyallylamine contains a large number of amino groups, the amino groups are uniformly distributed in the polymer, and an added epoxypropyl long-chain fatty quaternary ammonium group reagent takes the amino groups as reaction sites to carry out ring opening reaction so as to enable the epoxypropyl long-chain fatty quaternary ammonium group reagent to be grafted on the surface of a magnetic polymer carrier; after secondary surface treatment, the grafted quaternary ammonium salt has strong electropositivity, can react with the negatively charged heteropolyacid to form heteropolyacid ammonium salt, firmly anchors the heteropolyacid active component on the surface of the magnetic polymer carrier, improves the bonding strength of the heteropolyacid and the carrier, ensures that the heteropolyacid has strong stability, and avoids the problem of dissolution loss in a solvent; meanwhile, as a large amount of quaternary ammonium salt can be grafted, the load of the heteropoly acid can be greatly improved, and the preparation of the high-load heteropoly acid salt is realized.
Further, in step (1), the Fe 3O4 nanoparticles are preferably synthesized using a hydrothermal method.
Specifically, the method for synthesizing the Fe 3O4 nano-particles by the hydrothermal method preferably comprises the following steps: adding ferric chloride and sodium acetate into ethylene glycol, stirring for 10-30 min at 20-50 ℃ to obtain a colorless transparent solution, transferring the solution into an autoclave, and crystallizing for 8-48 h at 150-200 ℃; and after crystallization, separating to obtain Fe 3O4 nano particles.
In the step (1), the mass ratio of the ferric chloride to the sodium acetate is 1 (2-5).
In the step (1), the dosage ratio of ferric chloride to ethylene glycol is 1g (40-100 mL).
Wherein in step (1), the separation is magnetic separation.
Wherein, in the step (1), after separation, washing and drying are performed. The washing conditions are preferably washing with ethanol and deionized water several times each; the drying condition is preferably 60-80 ℃ for 10-24 hours.
Further, in the step (2), before the coating of Fe 3O4 with polyallylamine, the Fe 3O4 nanoparticles are preferably dispersed. Oleic acid is preferably used as a dispersant, and Fe 3O4 is mixed with oleic acid before coating Fe 3O4 with polyallylamine. Polyallylamine is adsorbed and aggregated on the surface of the polyallylamine to form the polyallylamine-coated Fe 3O4 magnetic polymer.
The oleic acid with strong affinity is easy to adsorb on the surface of Fe 3O4 nano particles to form an adsorption film, so that aggregation of Fe 3O4 nano particles is avoided, and the dispersibility of Fe 3O4 nano particles in a solution is improved; polyallylamine is further aggregated on the surfaces of the dispersed particles to form a high polymer coating polymer of Fe 3O4 nano particles.
Specifically, in step (2), the polymer coating method preferably includes: and (3) placing the Fe 3O4 nano particles into an organic solvent, adding oleic acid, stirring at room temperature for 30 min-1 h, adding polyallylamine, stirring at room temperature for 15-30 min, heating to 50-90 ℃ and stirring for 2-6 h, cooling to room temperature, continuing stirring for 12-48 h, and separating to obtain the Fe 3O4 -PAA magnetic polymer.
Wherein in the step (2), the organic solvent is preferably N, N-dimethylformamide.
In the step (2), the dosage ratio of the Fe 3O4 nano-particles to the oleic acid is preferably 1g (4-18) mL.
In the step (2), the mass ratio of the Fe 3O4 nano-particles to the polyallylamine is preferably 1 (4-12).
In the step (2), the dosage ratio of the Fe 3O4 nano-particles to the organic solvent is preferably 1g (50-300) mL.
Wherein in step (2), the separation is magnetic separation.
Wherein, in the step (2), after separation, washing and drying are performed. The washing conditions are preferably washing with ethanol N, N-dimethylformamide and deionized water several times each; the drying condition is preferably 120-150 ℃ for 10-24 hours.
Further, in the step (3), the quaternizing agent is preferably an aliphatic quaternary ammonium salt having not less than 10 carbon atoms, more preferably epoxypropyl dimethyl dodecyl ammonium chloride or/and epoxypropyl dimethyl hexadecyl ammonium chloride.
Specifically, in step (3), the method for modifying the quaternary ammonium group preferably includes: dispersing the magnetic polymer obtained in the step (2) in alkali or/and alkali salt solution, carrying out ultrasonic treatment for 20 min-2 h, then adding a quaternizing agent into the solution, and stirring the solution for 4-10 h at 50-80 ℃.
In the step (3), the alkali or/and the alkali salt solution is preferably sodium hydroxide solution, and the mass concentration of the sodium hydroxide solution is preferably 0.5-2 wt%.
In the step (3), the dosage ratio of the magnetic polymer to the sodium hydroxide solution is preferably 1g (8-15) mL.
In the step (3), the mass ratio of the magnetic polymer to the quaternizing agent is 1 (5-15).
Wherein, in the step (3), after the quaternization reaction is finished, washing and drying are performed. The washing conditions are preferably washing with deionized water and ethanol several times; the drying condition is preferably 80-100 ℃ for 10-24 hours.
Wherein, in the step (3), the quaternizing agent is preferably prepared by: under stirring, adding an equimolar amount of epichlorohydrin to dodecyl dimethylamine (or hexadecyl dimethylamine) by using a dropping funnel, and then heating the mixture to 60-90 ℃ and stirring for 1-4 h. After the reaction is finished, the crude product is preferably washed by diethyl ether, and is dried in vacuum for 8-24 hours at 80-100 ℃ to obtain the quaternizing agent.
Further, in the step (4), the compound containing the element a and the compound containing the element B are preferably at least one of nitrate, carbonate, sulfate, acetate, oxalate, chloride, hydroxide and oxide of the corresponding elements.
Further, in the step (4), the heteropolyacid is preferably phosphomolybdic vanadium heteropolyacid.
In the step (4), the mass ratio of the heteropoly acid to the quaternary ammonium group modified magnetic polymer is (0.5-4): 1.
Specifically, the heteropolyacid impregnation of step (4) preferably includes: dissolving heteropoly acid in deionized water to obtain a heteropoly acid solution; then dripping the mixture of the compound containing the element A and the compound containing the element B into the heteropoly acid solution, heating and stirring for 20 min-1 h at 50-80 ℃ to obtain an impregnating solution; and (3) adding the quaternary ammonium group modified magnetic polymer obtained in the step (3) into the impregnating solution to form suspension, heating and stirring for 4-48 hours at 50-80 ℃, and separating to obtain the magnetic heteropoly acid salt polymer composite catalyst.
Wherein in step (4), the separation is magnetic separation.
Wherein, in the step (4), after separation, washing and drying are performed. Deionized water and ethanol are preferably used as washing solutions; the drying condition is preferably 60-120 ℃ for 12-24 hours.
The invention further aims to provide an application of the magnetic heteropoly acid salt polymer composite catalyst in catalyzing isononanal oxidation to isononanoic acid.
Test results prove that the magnetic heteropolyacid salt polymer composite catalyst can improve the conversion rate and the selectivity of the reaction.
The beneficial effects of the invention are as follows:
(1) According to the preparation method, the polymer containing amino groups is selected to coat the magnetic particles, then the polymer is subjected to quaternization treatment, a large amount of quaternary ammonium salt can be grafted by utilizing amino groups which are uniformly distributed and rich on the polymer, and the heteropolyacid is stably anchored on the surface of the magnetic polymer carrier by combining the extremely strong positive electricity of the quaternary ammonium salt and the heteropolyacid with negative electricity.
(2) The hydrophobic long-chain aliphatic quaternary ammonium salt is used as a grafting material of the magnetic polymer, and after being combined with the heteropoly acid, the hydrophobic isononyl aldehyde is easy to adsorb on the surface of the long-chain aliphatic quaternary ammonium heteropoly acid salt when the magnetic polymer is used for chemical reaction, so that the diffusion rate of reactants is improved, and the improvement of the reaction conversion rate can be promoted.
(3) The A element and the B element introduced in the heteropoly acid can play roles in regulating the acid-base property of the catalyst and enhancing the redox property. Under the synergistic effect of the elements, the catalyst prepared by the invention has good catalytic effect, the conversion rate can reach more than 96 percent, and the selectivity can reach more than 90 percent.
(4) The magnetic heteropolyacid salt polymer composite catalyst prepared by the invention can be separated from a reaction system through magnetic separation, and has stable recycling performance.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a magnetic heteropolyacid salt polymer composite catalyst of the present invention;
FIG. 2 is a scanning electron microscope image of a sample of the magnetic heteropolyacid salt polymer composite catalyst PCu1.5Fe1.5Mo10V2O40/Fe3O4-PAA-N(R12R2)+ in example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern (XRD) of a sample of the magnetic heteropolyacid salt polymer composite catalyst PCu1.5Fe1.5Mo10V2O40/Fe3O4-PAA-N(R12R2)+ of example 1 of the present invention;
FIG. 4 is an infrared spectrum of a sample of the magnetic heteropolyacid salt polymer composite catalyst PCu1.5Fe1.5Mo10V2O40/Fe3O4-PAA-N(R12R2)+ in example 1 of the present invention.
Detailed Description
The principles and features of the present invention are described below in connection with examples, which are set forth only to illustrate the present invention and not to limit the scope of the invention. The experimental methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
In the specific embodiment, the method comprises the following steps: the polyallylamine used was purchased from Shanghai Jizhui Biotechnology Co., ltd, and had an average molecular weight of Mw=15000 and a purity of 95%.
In the specific embodiment, the method comprises the following steps: the epoxypropyl dimethyl dodecyl ammonium chloride is prepared by the following method: an equimolar amount of epichlorohydrin was slowly added to dodecyldimethylamine with stirring, and the mixture was then heated to 80 ℃ and stirred for 2h. After the reaction is finished, washing the crude product by diethyl ether, and vacuum drying at 100 ℃ for 12 hours to obtain the quaternizing agent epoxypropyl dimethyl dodecyl ammonium chloride.
The preparation method of epoxypropyl dimethyl hexadecyl ammonium chloride is referred to above, except that the equivalent molar amount of dodecyl dimethylamine is replaced by hexadecyl dimethylamine.
Example 1
The preparation method of the magnetic heteropolyacid salt polymer composite catalyst comprises the following steps:
(1) Preparation of Fe 3O4 nanoparticles: adding 2g of ferric chloride hexahydrate and 4g of anhydrous sodium acetate into 100mL of ethylene glycol, stirring at 40 ℃ for 15min to obtain a colorless transparent solution, transferring the solution into an autoclave with a polytetrafluoroethylene substrate, and crystallizing at 180 ℃ for 24h; after crystallization, magnetically separating, washing with ethanol and deionized water for 3 times, and drying at 80deg.C for 18 hr to obtain Fe 3O4 nanometer particles.
(2) Polymer coating: 2g of Fe 3O4 nano particles are put into 200mL of N, N-dimethylformamide, 10mL of oleic acid is added, stirring is carried out for 30min at room temperature, 10g of polyallylamine is added, stirring is carried out for 30min, heating is carried out to 80 ℃ and stirring is carried out for 4h, cooling is carried out for 24h after cooling to room temperature, magnetic separation is carried out, then each of the nano particles is washed 3 times by N, N-dimethylformamide and deionized water, and drying is carried out for 10h at 100 ℃ to obtain the magnetic polymer particles.
(3) Quaternary ammonium group modification: dispersing 2g of the dried magnetic polymer particles obtained in the step (2) in 20mL of 1wt% sodium hydroxide solution, and carrying out ultrasonic treatment for 30min; then 20g of epoxypropyl dimethyl dodecyl ammonium chloride was added thereto and stirred at 80 ℃ for 4 h; washing with deionized water and ethanol for 3 times, and drying at 80 ℃ for 12 hours to obtain the quaternary ammonium group modified magnetic polymer particles.
(4) Heteropolyacid impregnation: 1.92g of phosphomolybdic vanadium heteropoly acid (H 5PMo10V2O40·10H2 O) is dissolved in 30mL of deionized water to obtain a heteropoly acid solution; then, dropwise adding 25mL of water mixture of 0.3g of copper acetate monohydrate and 0.61g of ferric nitrate nonahydrate into the phosphomolybdic vanadium heteropolyacid solution, and stirring for 30min at 60 ℃ to obtain an impregnating solution; adding 2g of the quaternary ammonium group modified magnetic polymer particles obtained in the step (3) into the impregnating solution to form a suspension, stirring at 80 ℃ for 24 hours, magnetically separating, washing 3 times by using deionized water and ethanol, drying at 80 ℃ for 12 hours, and drying to obtain the magnetic heteropoly acid salt polymer composite catalyst.
The composition of the obtained catalyst is PCu1.5Fe1.5Mo10V2O40/Fe3O4-PAA-N(R1 2R2)+,, the synthesis principle of the catalyst is shown in figure 1, a scanning electron microscope is shown in figure 2, an XRD (X-ray diffraction) is shown in figure 3, and an infrared spectrogram is shown in figure 4.
Example 2
Referring to example 1, the difference from example 1 is that in step (4): a "25 mL water mixture of 0.3g copper acetate monohydrate and 0.61g ferric nitrate nonahydrate" was replaced with a "25 mL water mixture of 0.21g potassium chloride and 0.15g cobalt nitrate hexahydrate".
Other technical features are the same as those of embodiment 1.
The composition of the catalyst obtained is PK2.8Co0.5Mo10V2O40/Fe3O4-PAA-N(R12R2)+.
Example 3
Referring to example 1, the difference from example 1 is that in step (4): a "25 mL water mixture of 0.3g copper acetate monohydrate and 0.61g ferric nitrate nonahydrate" was replaced with a "25 mL water mixture of 0.03g zinc nitrate hexahydrate and 0.087g nickel nitrate hexahydrate".
Other technical features are the same as those of embodiment 1.
The composition of the catalyst obtained is PZn0.1Ni0.3Mo10V2O40/Fe3O4-PAA-N(R12R2)+.
Example 4
Referring to example 1, the difference from example 1 is that,
The step (1) is as follows: adding 5g of ferric chloride hexahydrate and 10g of anhydrous sodium acetate into 200mL of ethylene glycol, stirring at 25 ℃ for 15min to obtain a colorless transparent solution, transferring the solution into an autoclave with a polytetrafluoroethylene substrate, and crystallizing at 160 ℃ for 48h; after crystallization, magnetically separating, washing with ethanol and deionized water for 3 times, and drying at 80deg.C for 18 hr to obtain Fe 3O4 nanometer particles.
In the step (4): a "25 mL water mixture of 0.3g copper acetate monohydrate and 0.61g ferric nitrate nonahydrate" was replaced with a "25 mL water mixture of 0.2g copper acetate monohydrate and 0.026g tin tetrachloride".
Other technical features are the same as those of embodiment 1.
The composition of the resulting catalyst was PCuSn 0.1Mo10V2O40/Fe3O4-PAA-N(R12R2)+.
Example 5
Referring to example 1, the difference from example 1 is that,
The step (2) is as follows: 2g of magnetic Fe 3O4 nano particles are put into 200mL of N, N-dimethylformamide, 30mL of oleic acid is added, stirring is carried out for 30min at room temperature, 20g of polyallylamine is added, stirring is carried out for 30min, heating is carried out to 50 ℃ and stirring is carried out for 6h, cooling is carried out to room temperature, stirring is continued for 48h, magnetic separation is carried out, then each of the nano particles is washed 3 times by the N, N-dimethylformamide and deionized water, and drying is carried out for 10h at 100 ℃ to obtain the magnetic polymer particles.
The step (4) is as follows: 3g of phosphomolybdic vanadium heteropoly acid (H 4PMo11VO40·10H2 O) is dissolved in 50mL of deionized water to obtain heteropoly acid solution; then, 0.17 g potassium chloride and 0.41g 25 mL water of manganese acetate dihydrate are added into the solution of the phosphomolybdic vanadium heteropolyacid in a dropwise manner, and the solution is stirred for 30min at 50 ℃ to obtain an impregnating solution; adding 1g of the quaternary ammonium group modified magnetic polymer particles obtained in the step (3) into the impregnating solution to form a suspension, stirring at 60 ℃ for 12 hours, magnetically separating, washing 3 times by using deionized water and ethanol, drying at 80 ℃ for 12 hours, and drying to obtain the magnetic heteropoly acid salt polymer composite catalyst.
Other technical features are the same as those of embodiment 1.
The composition of the resulting catalyst was PK 1.5MnMo11VO40/Fe3O4-PAA-N(R12R2)+.
Example 6
Referring to example 1, the difference from example 1 is that,
The step (3) is as follows: dispersing dried 2g of magnetic polymer particles in 30mL of 1wt% sodium hydroxide solution, sonicating for 1h, then adding 10g of epoxypropyl dimethyl hexadecyl ammonium chloride thereto, and stirring at 50 ℃ for 10 h; washing with deionized water and ethanol for 3 times, and drying at 80 ℃ for 12 hours to obtain the quaternary ammonium group modified magnetic polymer particles.
The step (4) is as follows: 1.87g of phosphomolybdic vanadium heteropoly acid (H 6PMo9V3O40·10H2 O) is dissolved in 30mL of deionized water to obtain a heteropoly acid solution; then, dropwise adding 25mL of water mixture of 0.06 g zinc nitrate hexahydrate and 0.75g manganese acetate dihydrate into the phosphomolybdic vanadium heteropolyacid solution, and stirring for 30 min at 60 ℃ to obtain an impregnating solution; and (3) adding 0.95g of the quaternary ammonium group modified magnetic polymer particles obtained in the step (3) into the impregnating solution to form a suspension, stirring at 60 ℃ for 24 hours, performing magnetic separation, washing 3 times by using deionized water and ethanol, drying at 80 ℃ for 12 hours, and drying to obtain the magnetic heteropoly acid salt polymer composite catalyst.
Other technical features are the same as those of embodiment 1.
The composition of the catalyst obtained is PZn0.2Mn2.8Mo9V3O40/Fe3O4-PAA-N(R12R2)+.
Comparative example 1
Referring to example 1, the difference from example 1 is that: and (3) step (4) is not included.
The other technical features are the same as those of example 1.
Comparative example 2
Referring to example 1, the difference from example 1 is that: does not contain step (3); namely: the heteropolyacid impregnation is directly carried out without quaternary ammonium group modification.
The other technical features are the same as those of example 1.
Comparative example 3
Referring to example 1, the difference from example 1 is that:
In the step (2): instead of coating the magnetic nanoparticles with a polymer, the magnetic nanoparticles are coated with SiO 2. The specific method comprises the following steps: mixing water, ethanol and ethyl orthosilicate according to a molar ratio of 2:8:1, stirring at room temperature for 15min, magnetically stirring at 40 ℃ for 2h, dropwise adding aqueous solution of nitric acid to enable the pH value to be 3, and continuously stirring for 30min to obtain silica sol; and (3) putting 2g of magnetic nano particles into 30mL of silica sol, magnetically stirring for 2 hours at 50 ℃ to obtain gel, and drying and grinding to obtain the SiO 2 coated magnetic nano particles.
The step (3) is as follows: the magnetic nanoparticles coated with SiO 2 were aminated using gamma-chloropropyl trimethoxysilane under toluene reflux. The specific method comprises the following steps: dispersing 2g of SiO 2 coated magnetic nano particles in 50mL of toluene, adding 20mL of gamma-chloropropyl trimethoxysilane, carrying out reflux stirring reaction for 24h at 80 ℃, filtering, washing 3 times by using absolute ethyl alcohol, and drying for 12h at 100 ℃ to obtain the amination modified magnetic SiO 2 coated nano particles.
The other technical features are the same as those of example 1.
Test 1
The catalysts obtained in examples 1 to 6 and comparative examples 1 to 3 were evaluated for activity by using a glass reaction vessel with magnetic stirring. 10mL isononyl aldehyde, 20mL acetonitrile and 0.5g catalyst are added into a 100mL three-neck flask, after the temperature is raised to 60 ℃, 12.5mL 30wt% hydrogen peroxide is dropwise added, the reaction temperature is kept, after 2 hours of reaction, the catalyst is magnetically separated, the residual solution is quantitatively analyzed by a gas chromatography through an internal standard method, and the reaction result is shown in Table 1.
TABLE 1 evaluation results of catalyst reactivity
| Experiment number | Isononanal conversion/% | Isononanal selectivity/% |
| Example 1 | 98.6 | 91.6 |
| Example 2 | 97.6 | 90.8 |
| Example 3 | 96.1 | 91.3 |
| Example 4 | 97.7 | 91.4 |
| Example 5 | 97.8 | 92.1 |
| Example 6 | 96.5 | 90.4 |
| Comparative example 1 | 40.5 | 63.2 |
| Comparative example 2 | 86.4 | 77.6 |
| Comparative example 3 | 88.5 | 87.7 |
As can be seen from table 1, compared with comparative example 1, the addition of the heteropoly acid in example 1 significantly improved both isononaldehyde conversion and isononanoic acid selectivity of the resulting catalyst; compared with comparative example 2, the magnetic polymer in example 1 is subjected to quaternary ammonium surface treatment, and the isononanal conversion rate and isononanoic acid selectivity of the obtained catalyst are both obviously improved. The isononanal conversion and isononanoic acid selectivity of the resulting catalyst were better than comparative example 3, example 1, which used amino-containing polymer-coated magnetic nanoparticles.
Test 2
The heteropolyacid composite oxide catalyst obtained in example 1 was tested for its reusability, and the specific operating steps were:
(1) Isononanoic acid was prepared in accordance with the method of test 1 using the magnetic heteropolyacid salt polymer composite catalyst of example 1;
(2) After the reaction is finished, magnetically separating the catalyst particles, washing the catalyst particles three times by using deionized water and acetone respectively, drying the catalyst particles at 100 ℃, and continuously using the catalyst particles as a catalyst for isononyl aldehyde oxidation reaction, wherein the reaction method is the same as that of test 1;
(3) The reaction liquid phase product was subjected to gas chromatography detection analysis, and the conversion of isononanal and the selectivity of isononanoic acid were calculated, and the results are shown in table 2.
TABLE 2 reusability of Isononic acid prepared by Isononic aldehyde Oxidation catalyzed by magnetic Heteropoly acid salt Polymer Complex catalyst
| Number of times of use | Isononanal conversion/% | Isononanoic acid selectivity/% |
| 1 | 98.6 | 91.6 |
| 2 | 97.8 | 90.3 |
| 3 | 96.8 | 90.7 |
| 4 | 96.2 | 89.9 |
| 5 | 96.4 | 90.3 |
As can be seen from Table 2, the catalyst of the present invention has good reusability when used for catalyzing the oxidation of isononanal to isononanoic acid.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A magnetic heteropolyacid salt polymer composite catalyst comprises heteropolyacid salt and a carrier, and is characterized in that the carrier comprises an inner core and a polymer coated outside the inner core;
The inner core comprises Fe 3O4 nano particles;
the polymer comprises polyallylamine;
Carrying out quaternary ammonium group modification treatment on the surface of a carrier coated with the polymer;
The magnetic heteropolyacid salt polymer composite catalyst has the following chemical expression ：PAxByMo12-nVnO40/Fe3O4-PAA-N(R12R2)+;
Wherein: a is at least one of Cu, zn and K; b is at least one of Ni, fe, co, mn, sb, sn elements; PAA is polyallylamine; r1 is a methyl functional group; r2 is an alkyl functional group with 10-20 carbon atoms;
Wherein: x and y are molar coefficients, x is more than or equal to 0.1 and less than or equal to 3, y is more than or equal to 0.1 and less than or equal to 3, and n is more than or equal to 1 and less than or equal to 3.
2. The magnetic heteropolyacid salt polymer composite catalyst according to claim 1, which is at least one of the following chemical formulas:
PCu1.5Fe1.5Mo10V2O40/Fe3O4-PAA-N(R12R2)+;
PK2.8Co0.5Mo10V2O40/Fe3O4-PAA-N(R12R2)+;
PZn0.1Ni0.3Mo10V2O40/Fe3O4-PAA-N(R12R2)+;
PCuSn0.1Mo10V2O40/Fe3O4-PAA-N(R12R2)+；
PK1.5MnMo11VO40/Fe3O4-PAA-N(R12R2)+；
PZn0.2Mn2.8Mo9V3O40/Fe3O4-PAA-N(R12R2)+.
3. a method for preparing the magnetic heteropolyacid salt polymer composite catalyst according to claim 1 or 2, comprising the steps of:
(1) Obtaining Fe 3O4;
(2) Polymer coating: coating Fe 3O4 by using polyallylamine to obtain a magnetic polymer;
(3) Quaternary ammonium group modification: carrying out surface modification on the polymer-coated Fe 3O4 by using a quaternizing reagent to obtain a quaternary ammonium group modified magnetic polymer;
(4) Heteropolyacid impregnation: preparing an impregnating solution comprising heteropoly acid, a compound containing an element A and a compound containing an element B, and mixing the quaternary ammonium group modified magnetic polymer with the impregnating solution to prepare the magnetic heteropoly acid salt polymer composite catalyst.
4. A method according to claim 3, wherein in step (2): fe 3O4 was mixed with oleic acid before coating Fe 3O4 with polyallylamine.
5. A method according to claim 3, wherein in step (3): the quaternizing agent is aliphatic quaternary ammonium salt with carbon atom number not less than 10.
6. The method according to claim 5, wherein the quaternizing agent is epoxypropyl dimethyl dodecyl ammonium chloride or/and epoxypropyl dimethyl hexadecyl ammonium chloride.
7. A method according to claim 3, wherein in step (4): the compound containing the element A and the compound containing the element B are at least one of nitrate, carbonate, sulfate, acetate, oxalate, chloride, hydroxide and oxide of corresponding elements.
8. A method according to claim 3, wherein in step (4): the heteropolyacid is phosphomolybdic vanadium heteropolyacid.
9. Use of a magnetic heteropoly acid salt polymer composite catalyst according to claim 1 or 2 for catalyzing the oxidation of isononanal to isononanoic acid.
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| WO2015161659A1 (en) * | 2014-04-21 | 2015-10-29 | 中国科学院过程工程研究所 | Method for simultaneously preparing high-purity vanadium and heteropolyacid catalyst |
| CN107029723A (en) * | 2017-06-02 | 2017-08-11 | 扬州大学 | A kind of preparation method of magnetic heteropolyacid salt catalyst |
| CN107175131A (en) * | 2017-06-02 | 2017-09-19 | 扬州大学 | The method that cation modified method prepares magnetic heteropolyacid salt catalyst |
| CN112657510A (en) * | 2020-12-31 | 2021-04-16 | 华南理工大学 | Catalyst for preparing isononanoic acid by catalytic oxidation of isononanol and preparation method and application thereof |
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| WO2015161659A1 (en) * | 2014-04-21 | 2015-10-29 | 中国科学院过程工程研究所 | Method for simultaneously preparing high-purity vanadium and heteropolyacid catalyst |
| CN107029723A (en) * | 2017-06-02 | 2017-08-11 | 扬州大学 | A kind of preparation method of magnetic heteropolyacid salt catalyst |
| CN107175131A (en) * | 2017-06-02 | 2017-09-19 | 扬州大学 | The method that cation modified method prepares magnetic heteropolyacid salt catalyst |
| CN112657510A (en) * | 2020-12-31 | 2021-04-16 | 华南理工大学 | Catalyst for preparing isononanoic acid by catalytic oxidation of isononanol and preparation method and application thereof |
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