CN108404977A - Magnetic organic solid base catalyst and preparation method and application thereof - Google Patents
Magnetic organic solid base catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN108404977A CN108404977A CN201810051832.4A CN201810051832A CN108404977A CN 108404977 A CN108404977 A CN 108404977A CN 201810051832 A CN201810051832 A CN 201810051832A CN 108404977 A CN108404977 A CN 108404977A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- organic solid
- catalyst
- solid base
- base catalyst
- Prior art date
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- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 239000007787 solid Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 131
- 239000004005 microsphere Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000007530 organic bases Chemical class 0.000 claims abstract description 12
- 230000032050 esterification Effects 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 162
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 149
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 138
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 137
- 239000003921 oil Substances 0.000 claims description 77
- 235000019198 oils Nutrition 0.000 claims description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 229910052757 nitrogen Inorganic materials 0.000 claims description 69
- 239000002585 base Substances 0.000 claims description 66
- 239000011553 magnetic fluid Substances 0.000 claims description 64
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 52
- 238000002156 mixing Methods 0.000 claims description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 239000003549 soybean oil Substances 0.000 claims description 34
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 31
- 235000012424 soybean oil Nutrition 0.000 claims description 31
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 28
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 27
- 239000000908 ammonium hydroxide Substances 0.000 claims description 27
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 27
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 26
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 26
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 26
- 206010001497 Agitation Diseases 0.000 claims description 26
- 239000005642 Oleic acid Substances 0.000 claims description 26
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000013019 agitation Methods 0.000 claims description 26
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 26
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 26
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 26
- 235000019394 potassium persulphate Nutrition 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 26
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 25
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 25
- 239000012265 solid product Substances 0.000 claims description 25
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 23
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 230000005389 magnetism Effects 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 13
- 150000002148 esters Chemical group 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 10
- 239000006210 lotion Substances 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 7
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 150000001805 chlorine compounds Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- YCSMVPSDJIOXGN-UHFFFAOYSA-N CCCCCCCCCCCC[Na] Chemical compound CCCCCCCCCCCC[Na] YCSMVPSDJIOXGN-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 claims 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- -1 Hydrogen furans Chemical class 0.000 claims 1
- DXRFZHILMCWCNG-UHFFFAOYSA-N N,N-dimethyl-1,8-naphthyridin-2-amine Chemical compound C1=CC=NC2=NC(N(C)C)=CC=C21 DXRFZHILMCWCNG-UHFFFAOYSA-N 0.000 claims 1
- 238000005575 aldol reaction Methods 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 4
- 238000005882 aldol condensation reaction Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 238000010907 mechanical stirring Methods 0.000 description 22
- 238000004108 freeze drying Methods 0.000 description 21
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 21
- 239000000725 suspension Substances 0.000 description 21
- 239000003643 water by type Substances 0.000 description 21
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 19
- 235000003891 ferrous sulphate Nutrition 0.000 description 17
- 239000011790 ferrous sulphate Substances 0.000 description 17
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 17
- 238000009777 vacuum freeze-drying Methods 0.000 description 15
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 description 12
- 238000010298 pulverizing process Methods 0.000 description 12
- 238000002242 deionisation method Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000007710 freezing Methods 0.000 description 8
- 230000008014 freezing Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003225 biodiesel Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 150000002240 furans Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000001484 Pickering emulsion method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000006842 Henry reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 241000183294 Scleropages formosus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0251—Guanidides (R2N-C(=NR)-NR2)
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing 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
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium 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
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
Abstract
The invention provides a magnetic organic solid base catalyst, magnetic nano microspheres with uniform particle size are prepared by miniemulsion polymerization, and then organic base is loaded on the microspheres to obtain a novel magnetic organic solid base catalyst; the method avoids the problem of loss of active points of the traditional supported catalyst, maintains the high efficiency of the catalyst, and effectively prolongs the service life of the catalyst; meanwhile, the separation of the catalyst and a reaction system can be realized under the external magnetic field, so that the separation step of the catalyst is greatly simplified; the magnetic organic solid base catalyst can be applied to ester exchange, esterification or aldol condensation reaction; the preparation method is simple, and the prepared catalyst has the characteristics of high efficiency, energy conservation, no toxicity, easy separation and cyclic utilization.
Description
(1) technical field
The present invention relates to a kind of magnetic organic solid base catalysts and the preparation method and application thereof.
(2) technical background
Base catalyst is common catalyst in Chemical Manufacture and basic research, and it is anti-to be widely used in important chemistry
Ying Zhong, as alkylated reaction, reduction reaction, ammoxidation, Aldol condensation, Knoevenagel condensation, Henry reaction,
Michael additions, ester exchange reaction etc..Traditional homogeneous liquid base catalyst corrosivity is strong, and the separating step after reaction is lengthy and tedious
It is complicated and will produce a large amount of waste liquid, serious destruction is caused to ecological environment, has been unable to meet Green Chemistry and sustainable development
The requirement of exhibition.
Compared with homogeneous catalyst, heterogeneous catalysis reactivity is higher, good reaction selectivity, reaction condition are mild,
Simply it can detach and reuse from reaction solution, improve production efficiency, reduce production cost.So far,
Researcher expands a large amount of research work, including metal oxide-type, hydrotalcite, support type with regard to inoganic solids base catalyst
Solid bases etc..However, solid base catalyst, there is also inevitable disadvantage, active constituent is easy molten in the reaction system
Go out, lead to the bad stability of catalyst, reduces the performance of catalyst, while the group being lost in is divided into the later separation mistake of product
Journey is made troubles.
Contain tertiary phosphine or tertiary amines group in the end group of organic base, base strength is uniform, and active component is not easy to dissolve out, and stablizes
Property it is preferable, can many organic chemical reactions of efficient catalytic, and with that reaction condition is mild, yield is high and selectivity is good etc. is excellent
Point has certain industrial application value.However, organic base is a kind of homogeneous catalyst, need after the completion of reaction cumbersome
Program is removed from product, and cannot be reused.
In recent years, magnetic Nano material has received widespread attention in catalytic field.Fe3O4Magnetic nano-particle preparation side
Method is simple, surface is easily modified, large specific surface area, has many advantages, such as superparamagnetism, often using magnetic nano-particle as heterogeneous catalysis
The carrier of agent.After reaction, catalyst can simplify separation and recovery process under external magnetic field rapidly with product quick separating.
In consideration of it, the present invention prepares a kind of magnetic Nano microsphere of uniform particle diameter by mini-emulsion polymerization, and organic base is carried on micro-
Ball surface prepares a kind of magnetic organic solid base catalyst, and one kind is provided newly for the efficient utilization and recycling of organic alkali catalyst
Thinking.
(3) invention content
For the deficiencies in the prior art, the present invention provides a kind of magnetic organic solid base catalyst and its preparations
Method and application.
Technical scheme is as follows：
A kind of magnetism organic solid base catalyst, is prepared as follows to obtain：
(1) Fe is prepared3O4Magnetic fluid
Ferrous salt, molysite and deionized water are mixed, are stirred at room temperature dissolving, under nitrogen protection, ammonium hydroxide, oleic acid, liter is added dropwise
Temperature collects solid product to 80~90 DEG C of 3~4h of reaction, later Magneto separate, is washed with deionized water to neutrality, obtains Fe3O4Magnetic core,
By gained Fe3O4Magnetic core with etc. the normal octanes of quality mix, removed water through anhydrous sodium sulfate, obtain Fe3O4Magnetic fluid；
The ratio between the amount of substance 1 of the ferrous salt, molysite, oleic acid, deionized water：1~2：0.22~0.3：187.5~
200, particularly preferred 1：2：0.22：187.5；
The concentration of the ammonium hydroxide is in 25~28wt%, the dripping quantity of the ammonium hydroxide：Make the pH of reaction system 9~13；
The ferrous salt is specifically for example：Four water frerrous chlorides, frerrous chloride or ferrous sulfate heptahydrate；
The molysite is specifically for example：Nine water ferric nitrates, iron chloride or Iron trichloride hexahydrate；
(2) nano-magnetic microsphere is prepared
By Fe obtained by step (1)3O4Magnetic fluid, styrene, divinylbenzene, p-chloromethyl styrene, hexadecane mixing,
Ultrasonic disperse uniformly (10min), obtains oil phase；Lauryl sodium sulfate is dissolved in deionized water, obtains water phase；Stirring condition
Under, gained oil phase is added drop-wise in water phase, drips off and continues 2~3h of stirring, be placed in ice-water bath, with 100~300W cells
Pulverizer 10~30min of fine crankshaft, obtains miniemulsion, under nitrogen protection, potassium peroxydisulfate is added in gained miniemulsion, is warming up to
70~80 DEG C of constant temperature polymerizations 17~for 24 hours, reaction solution is post-treated later, obtains nano-magnetic microsphere, gained nano-magnetic microsphere
Surface contain chloromethyl；
The Fe3O4The quality of magnetic fluid, styrene, divinylbenzene, p-chloromethyl styrene, hexadecane, potassium peroxydisulfate
Than being 1：0.46~0.91：0.09~0.1：0.22~0.44：0.038~0.076：0.0075~0.015, particularly preferred 1：
0.91：0.09：0.44：0.038：0.0075；
The ratio between amount of substance of the lauryl sodium sulfate and deionized water is 1：1600~2000, particularly preferred 1：
1600；
Fe in the oil phase3O4Magnetic fluid and the mass ratio of the deionized water in water phase are 1：18~22.5, particularly preferably
1：18；
The method of the post-processing is：After reaction, reaction solution collects solid product, second through methanol demulsification, Magneto separate
Alcohol and deionized water washing, vacuum freezedrying, obtain nano-magnetic microsphere；
(3) magnetic organic solid base catalyst is prepared
Nano-magnetic microsphere, organic base, tetrabutylammonium iodide, 40~60wt% sodium hydroxides obtained by step (2) is water-soluble
Liquid, tetrahydrofuran mix, and 24~48h of back flow reaction under nitrogen protection, reaction solution is post-treated later, obtains magnetic organic solid
Base catalyst；
The chloromethyl on the nano-magnetic microsphere surface, organic base, tetrabutylammonium iodide, sodium hydroxide substance amount it
Than being 1：0.5~5：0.45~0.9：42~50, preferably 1：5：0.45：42；
The chloromethyl content on the nano-magnetic microsphere surface is with the substance of raw material p-chloromethyl styrene in step (2)
Amount calculates；
The volumetric usage of the tetrahydrofuran is calculated as 75~100mL/g with the quality of nano-magnetic microsphere；
The organic base is：1,1,3,3- tetramethylguanidine (TMG), tri- azabicyclics of 1,5,7- [4.4.0] decyl- 5- alkene
(TBD), the 11 carbon -7- alkene (DBU) of 1,8- diazabicyclos [5,4,0], 1,5- diazabicyclos [4,3,0] nonyl- 5- alkene
(DBN), triethylene diamine (DABCO), tetramethylethylenediamine (TEMED), 4-dimethylaminopyridine (DMAP), trimethylamine (TMA),
One kind or two in triethylamine (TEA), tripropyl amine (TPA) (TPA), tri-n-butylamine (TBA), pyridine (Py), dimethylethanolamine (DMEA)
The mixture of kind any of the above ratio；
The method of the post-processing is：After reaction, reaction solution collects solid particle through Magneto separate, with tetrahydrofuran and
Deionized water is washed, and vacuum freezedrying obtains magnetic organic solid base catalyst.
The method of herein described Magneto separate is：Using external magnetic field (such as magnet) by solid product from reaction system point
From.
Herein described room temperature is 20~30 DEG C.
Magnetic organic solid base catalyst made from the application can be applied to the reactions such as transesterification, esterification or aldol condensation
In.
Specifically, the application process is for example：
A, the magnetic organic solid base catalyst strengthens the method for ester exchange reaction, the method under mechanical stirring
For：Soybean oil is warming up to 60 DEG C of preheating 10min, magnetic organic solid base catalyst ultrasonic disperse is formed uniformly in methanol
Dispersion liquid and be added in the soybean oil of preheating, react 12h under 60 DEG C, 300rpm mechanical agitations, be cooled to room temperature later, magnetic
Catalyst is separated and recovered, reaction solution removes solvent under reduced pressure and obtains esterification products；
Gained esterification products detect the conversion ratio of fatty acid methyl ester with gas chromatography；
The mass ratio of the magnetism organic solid base catalyst and soybean oil is 1：20~40；
The ratio between amount of substance of the methanol and soybean oil is 6~18：1, preferably 12~18：1.
B, the magnetic organic solid base catalyst strengthens the method for ester exchange reaction under static Pickering lotions,
The method is：
Magnetic organic solid base catalyst ultrasonic disperse is formed into uniform dispersion liquid in methanol and is added in soybean oil,
Reaction solution is obtained, gained reaction solution emulsification 1min is obtained into Pickering lotions under 10000rpm rotating speeds with homogenizer, is sealed
After be warming up to 60 DEG C of reaction 12h, be cooled to room temperature later, Magneto separate recycles catalyst, and reaction solution removes solvent under reduced pressure and obtain ester
Change product；
Gained esterification products detect the conversion ratio of fatty acid methyl ester with gas chromatography；
The mass ratio of the magnetism organic solid base catalyst and soybean oil is 1: 20~40；
The ratio between amount of substance of the methanol and soybean oil is 9~30: 1, preferably 15~30: 1.
In the method A, B, the amount of the substance of soybean oil is calculated according to its average molecular weight 880.
Compared with prior art, the present invention is prepared for a kind of magnetic Nano microsphere of uniform particle diameter by mini-emulsion polymerization,
Organic base is carried on again and obtains a kind of novel magnetic organic solid base catalyst on microballoon.This method avoid traditional to bear
The problem of supported catalyst active site is lost in, maintains the high efficiency of catalyst, and effectively extends the use longevity of catalyst
Life.Meanwhile the separation of catalyst and reaction system can be realized under externally-applied magnetic field, greatly simplifie the separation step of catalyst
Suddenly.To sum up, the present invention provides a kind of preparation method of simple, efficient magnetic organic solid base catalyst, catalysis obtained
Agent has the characteristics that efficient, energy saving, nontoxic, easily separated, Ke Xunhuanliyong.
(4) specific implementation mode
The present invention is further detailed below by specific embodiment, but protection scope of the present invention is not limited only to
This.
Embodiment 1
It is molten that tetra- water frerrous chlorides of 7.95g, nine water ferric nitrates of 16.16g and 144mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 30mL ammonium hydroxide, 3.4g oleic acid are added dropwise successively, reacts 4h at 80 DEG C.Magneto separate goes out Fe3O4, deionization is used in combination
It is washed to neutrality, obtains Fe3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 6.83g styrene, 0.68g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.285g just
Hexadecane mixing is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 135mL deionized waters and obtain
Oil phase is added dropwise in water phase under mechanical stirring for water phase, and stirring 2h obtains black oil droplet suspension.The cell powder in ice bath
Broken machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
0.056g potassium peroxydisulfates are added with nitrogen displaced air 30min in 300rpm, and 70 DEG C of constant temperature polymerize 17h.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.175g1,1,3,3- tetramethylguanidine, 0.05g tetrabutylammonium iodides, 1mL 50wt% sodium hydroxide solution and
15mL tetrahydrofurans, back flow reaction is for 24 hours under nitrogen protection.Reaction solution uses tetrahydrofuran and deionization to wash successively through Magneto separate
It washs, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-TMG0.24g。
Embodiment 2
It is molten that tetra- water frerrous chlorides of 7.95g, nine water ferric nitrates of 16.16g and 144mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 30mL ammonium hydroxide, 3.4g oleic acid are added dropwise successively, reacts 4h at 80 DEG C.Magneto separate goes out Fe3O4, deionization is used in combination
It is washed to neutrality, obtains Fe3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 135mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 80 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), tri- azabicyclics of 0.21g1,5,7- [4.4.0] decyl- 5- alkene, 0.1g tetrabutylammonium iodides, 1.2mL 50wt%
Sodium hydroxide solution and 15mL tetrahydrofurans, back flow reaction 48h under nitrogen protection.Reaction solution uses tetrahydrochysene furan successively through Magneto separate
It mutters and is washed with deionized water, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-TBD0.25g。
Embodiment 3
5.07g frerrous chlorides, 6.49g iron chloride and 144mL water are added in the reactor, nitrogen is led in mechanical agitation dissolving
30min is added dropwise 30mL ammonium hydroxide, 3.4g oleic acid, reacts 4h at 80 DEG C successively.Magneto separate goes out Fe3O4, and be washed with deionized water into
Property, obtain Fe3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 6.83g styrene, 0.68g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.285g just
Hexadecane mixing is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain
Oil phase is added dropwise in water phase under mechanical stirring for water phase, and stirring 2h obtains black oil droplet suspension.The cell powder in ice bath
Broken machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
0.056g potassium peroxydisulfates are added with nitrogen displaced air 30min in 300rpm, and 80 DEG C of constant temperature polymerize 17h.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), the 11 carbon -7- alkene of 0.23g 1,8- diazabicyclos [5,4,0], 0.1g tetrabutylammonium iodides, 1.2mL50wt%
Sodium hydroxide solution and 15mL tetrahydrofurans, back flow reaction is for 24 hours under nitrogen protection.Reaction solution uses tetrahydrochysene successively through Magneto separate
Furans and deionized water are washed, and magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-DBU0.25g。
Embodiment 4
5.07g frerrous chlorides, 6.49g Iron trichloride hexahydrates and 144mL water are added in the reactor, mechanical agitation dissolving is led to
Nitrogen 30min is added dropwise 30mL ammonium hydroxide, 3.4g oleic acid, reacts 4h at 80 DEG C successively.Magneto separate goes out Fe3O4, and be washed with deionized water
To neutrality, Fe is obtained3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 70 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), the hydrogen-oxygen of 0.19g1,5- diazabicyclos [4,3,0] nonyl- 5- alkene, 0.1g tetrabutylammonium iodides, 1.2mL50wt%
Change sodium solution and 20mL tetrahydrofurans, back flow reaction 48h under nitrogen protection.Reaction solution through Magneto separate, successively use tetrahydrofuran and
Deionized water is washed, and magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-DBN0.24g。
Embodiment 5
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 6.83g styrene, 0.68g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.285g just
Hexadecane mixing is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 135mL deionized waters and obtain
Oil phase is added dropwise in water phase under mechanical stirring for water phase, and stirring 2h obtains black oil droplet suspension.The cell powder in ice bath
Broken machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
0.056g potassium peroxydisulfates are added with nitrogen displaced air 30min in 300rpm, and 70 DEG C of constant temperature polymerize 17h.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.168g triethylene diamines, 0.1g tetrabutylammonium iodides, the sodium hydroxide solution of 1.2mL 50wt% and 15mL tetra-
Hydrogen furans, back flow reaction is for 24 hours under nitrogen protection.Reaction solution is washed with tetrahydrofuran and deionized water successively through Magneto separate, freezing
Magnetic organic solid base catalyst Fe is obtained after vacuum drying3O4@PS-DABCO0.23g。
Embodiment 6
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 135mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 80 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), the sodium hydroxide solution and 15mL of 0.174g tetramethylethylenediamines, 0.1g tetrabutylammonium iodides, 1.2mL 50wt%
Tetrahydrofuran, back flow reaction is for 24 hours under nitrogen protection.Reaction solution is washed with tetrahydrofuran and deionized water successively through Magneto separate, cold
Magnetic organic solid base catalyst Fe is obtained after freezing vacuum drying3O4@PS-TEMED0.23g。
Embodiment 7
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 6.83g styrene, 0.68g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.285g just
Hexadecane mixing is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain
Oil phase is added dropwise in water phase under mechanical stirring for water phase, and stirring 2h obtains black oil droplet suspension.The cell powder in ice bath
Broken machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
0.056g potassium peroxydisulfates are added with nitrogen displaced air 30min in 300rpm, and 80 DEG C of constant temperature polymerize 17h.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.183g4- dimethylamino naphthyridines, 0.1g tetrabutylammonium iodides, 1.2mL 50wt% sodium hydroxide solution and
15mL tetrahydrofurans, back flow reaction is for 24 hours under nitrogen protection.Reaction solution uses tetrahydrofuran and deionization to wash successively through Magneto separate
It washs, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-DMAP0.24g。
Embodiment 8
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 70 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.089g trimethylamines, 0.1g tetrabutylammonium iodides, the sodium hydroxide solution of 1.2mL 50wt% and 15mL tetrahydrochysene furans
It mutters, back flow reaction is for 24 hours under nitrogen protection.Reaction solution is washed with tetrahydrofuran and deionized water successively through Magneto separate, freezing vacuum
Magnetic organic solid base catalyst Fe is obtained after drying3O4@PS-TMA0.21g。
Embodiment 9
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 70 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.152g triethylamines, 0.1g tetrabutylammonium iodides, the sodium hydroxide solution of 1.2mL 50wt% and 15mL tetrahydrochysene furans
It mutters, back flow reaction is for 24 hours under nitrogen protection.Reaction solution is washed with tetrahydrofuran and deionized water successively through Magneto separate, freezing vacuum
Magnetic organic solid base catalyst Fe is obtained after drying3O4@PS-TEA0.23g。
Embodiment 10
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 3.3.3g p-chloromethyl styrenes, 0.57g just
Hexadecane mixing is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain
Oil phase is added dropwise in water phase under mechanical stirring for water phase, and stirring 2h obtains black oil droplet suspension.The cell powder in ice bath
Broken machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 70 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.215g tripropyl amine (TPA)s, 0.1g tetrabutylammonium iodides, the sodium hydroxide solution of 1.2mL 50wt% and 15mL tetrahydrochysene furans
It mutters, back flow reaction is for 24 hours under nitrogen protection.Reaction solution is washed with tetrahydrofuran and deionized water successively through Magneto separate, freezing vacuum
Magnetic organic solid base catalyst Fe is obtained after drying3O4@PS-TPA0.25g。
Embodiment 11
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core is dried over anhydrous sodium sulfate after being mixed with normal octane, obtains Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 70 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.278g tri-n-butylamines, 0.1g tetrabutylammonium iodides, the sodium hydroxide solution of 1.2mL 50wt% and 15mL tetrahydrochysenes
Furans, back flow reaction is for 24 hours under nitrogen protection.Reaction solution is washed with tetrahydrofuran and deionized water successively through Magneto separate, and freezing is true
Magnetic organic solid base catalyst Fe is obtained after sky is dry3O4@PS-TBA0.27g。
Embodiment 12
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core,.With with normal octane extraction mix after magnetic fluid, be dried over anhydrous sodium sulfate, obtain
Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 70 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.119g pyridines, 0.1g tetrabutylammonium iodides, the sodium hydroxide solution of 1.2mL 50wt% and 15mL tetrahydrochysene furans
It mutters, back flow reaction is for 24 hours under nitrogen protection.Reaction solution is washed with tetrahydrofuran and deionized water successively through Magneto separate, freezing vacuum
Magnetic organic solid base catalyst Fe is obtained after drying3O4@PS-Py0.21g。
Embodiment 13
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core,.With with normal octane extraction mix after magnetic fluid, be dried over anhydrous sodium sulfate, obtain
Fe3O4Magnetic fluid.
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 70 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), the sodium hydroxide solution and 15mL of 0.134g dimethylethanolamines, 0.1g tetrabutylammonium iodides, 1.2mL 50wt%
Tetrahydrofuran, back flow reaction is for 24 hours under nitrogen protection.Reaction solution is washed with tetrahydrofuran and deionized water successively through Magneto separate, cold
Magnetic organic solid base catalyst Fe is obtained after freezing vacuum drying3O4@PS-DMEA0.22g。
Embodiment 14
(1) preparation of magnetic fluid
It is molten that 11.12g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 144mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 30mL ammonium hydroxide, 3.4g oleic acid are added dropwise successively, reacts 4h at 80 DEG C.Magneto separate goes out Fe3O4, deionization is used in combination
It is washed to neutrality, obtains Fe3O4Magnetic core passes through after being mixed with normal octane and is dried with anhydrous sodium sulfate, obtains Fe3O4Magnetic fluid.
(2)Fe3O4The preparation of@Chloromethyl PS
Weigh 7.5g magnetic fluids, 6.83g styrene, 0.68g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.285g just
Hexadecane mixing is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 135mL deionized waters and obtain
Oil phase is added dropwise in water phase under mechanical stirring for water phase, and stirring 3h obtains black oil droplet suspension.The cell powder in ice bath
Broken machine fine crankshaft 30min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
0.056g potassium peroxydisulfates are added with nitrogen displaced air 30min in 300rpm, and 70 DEG C of constant temperature polymerize 17h.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
(3)Fe3O4The preparation of@PS-TMG
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.173g1,1,3,3- tetramethylguanidine, 0.05g tetrabutylammonium iodides, 1mL 60wt% sodium hydroxide solution and
15mL tetrahydrofurans, back flow reaction 48h under nitrogen protection.Reaction solution uses tetrahydrofuran and deionization to wash successively through Magneto separate
It washs, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-TMG0.24g。
Embodiment 15
(1) preparation of magnetic fluid
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core passes through after being mixed with normal octane and is dried with anhydrous sodium sulfate, obtains Fe3O4Magnetic fluid.
(2)Fe3O4The preparation of@Chloromethyl PS
Weigh 7.5g magnetic fluids, 6.83g styrene, 0.68g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.285g just
Hexadecane mixing is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 135mL deionized waters and obtain
Oil phase is added dropwise in water phase under mechanical stirring for water phase, and stirring 2h obtains black oil droplet suspension.The cell powder in ice bath
Broken machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
0.056g potassium peroxydisulfates are added with nitrogen displaced air 30min in 300rpm, and 70 DEG C of constant temperature polymerize 17h.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
(3)Fe3O4The preparation of@PS-TMG
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.0346g1,1,3,3- tetramethylguanidine, 0.1g tetrabutylammonium iodides, 1.2mL50wt% sodium hydroxide solution and
20mL tetrahydrofurans, back flow reaction 48h under nitrogen protection.Reaction solution uses tetrahydrofuran and deionization to wash successively through Magneto separate
It washs, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-TMG0.23g。
Embodiment 16
(1) preparation of magnetic fluid
It is molten that 11.12g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 144mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 30mL ammonium hydroxide, 3.4g oleic acid are added dropwise successively, reacts 4h at 80 DEG C.Magneto separate goes out Fe3O4, deionization is used in combination
It is washed to neutrality, obtains Fe3O4Magnetic core passes through after being mixed with normal octane and is dried with anhydrous sodium sulfate, obtains Fe3O4Magnetic fluid.
(2)Fe3O4The preparation of@Chloromethyl PS
Weigh 7.5g magnetic fluids, 6.83g styrene, 0.68g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.285g just
Hexadecane mixing is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 135mL deionized waters and obtain
Oil phase is added dropwise in water phase under mechanical stirring for water phase, and stirring 2h obtains black oil droplet suspension.The cell powder in ice bath
Broken machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
0.056g potassium peroxydisulfates are added with nitrogen displaced air 30min in 300rpm, and 70 DEG C of constant temperature polymerize 17h.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
(3)Fe3O4The preparation of@PS-TMG
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.0173g1,1,3,3- tetramethylguanidine, 0.1g tetrabutylammonium iodides, 1.2mL40wt% sodium hydroxide solution and
15mL tetrahydrofurans, back flow reaction is for 24 hours under nitrogen protection.Reaction solution uses tetrahydrofuran and deionization to wash successively through Magneto separate
It washs, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-TMG0.21g。
Embodiment 17
(1) preparation of magnetic fluid
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core passes through after being mixed with normal octane and is dried with anhydrous sodium sulfate, obtains Fe3O4Magnetic fluid.
(2)Fe3O4The preparation of@Chloromethyl PS
Weigh 7.5g magnetic fluids, 6.83g styrene, 0.68g divinylbenzenes, 3.3g p-chloromethyl styrenes, 0.285g just
Hexadecane mixing is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain
Oil phase is added dropwise in water phase under mechanical stirring for water phase, and stirring 2h obtains black oil droplet suspension.The cell powder in ice bath
Broken machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
0.056g potassium peroxydisulfates are added with nitrogen displaced air 30min in 300rpm, and 80 DEG C of constant temperature polymerize 17h.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
(3)Fe3O4The preparation of@PS-TMG
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.0173g1,1,3,3- tetramethylguanidine, 0.1g tetrabutylammonium iodides, 1.2mL50wt% sodium hydroxide solution and
20mL tetrahydrofurans, back flow reaction 48h under nitrogen protection.Reaction solution uses tetrahydrofuran and deionization to wash successively through Magneto separate
It washs, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-TMG0.21g。
Embodiment 18
(1) preparation of magnetic fluid
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core passes through after being mixed with normal octane and is dried with anhydrous sodium sulfate, obtains Fe3O4Magnetic fluid.
(2)Fe3O4The preparation of@Chloromethyl PS
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 1.65g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 135mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 80 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
(3)Fe3O4The preparation of@PS-TMG
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.0173g1,1,3,3- tetramethylguanidine, 0.05g tetrabutylammonium iodides, 0.5mL40wt% sodium hydroxide solution
With 20mL tetrahydrofurans, back flow reaction is for 24 hours under nitrogen protection.Reaction solution uses tetrahydrofuran and deionized water successively through Magneto separate
It washs, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-TMG0.21g。
Embodiment 19
(1) preparation of magnetic fluid
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core passes through after being mixed with normal octane and is dried with anhydrous sodium sulfate, obtains Fe3O4Magnetic fluid.
(2)Fe3O4The preparation of@Chloromethyl PS
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 1.65g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 70 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
(3)Fe3O4The preparation of@PS-TMG
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.0173g1,1,3,3- tetramethylguanidine, 0.05g tetrabutylammonium iodides, 0.5mL50wt% sodium hydroxide solution
With 20mL tetrahydrofurans, back flow reaction 48h under nitrogen protection.Reaction solution uses tetrahydrofuran and deionized water successively through Magneto separate
It washs, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-TMG0.21g。
Embodiment 20
(1) preparation of magnetic fluid
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core passes through after being mixed with normal octane and is dried with anhydrous sodium sulfate, obtains Fe3O4Magnetic fluid.
(2)Fe3O4The preparation of@Chloromethyl PS
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 1.65g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 135mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 80 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
(3)Fe3O4The preparation of@PS-TMG
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.0346g1,1,3,3- tetramethylguanidine, 0.05g tetrabutylammonium iodides, 0.5mL40wt% sodium hydroxide solution
With 20mL tetrahydrofurans, back flow reaction is for 24 hours under nitrogen protection.Reaction solution uses tetrahydrofuran and deionized water successively through Magneto separate
It washs, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-TMG0.21g。
Embodiment 21
(1) preparation of magnetic fluid
It is molten that 5.56g ferrous sulfate heptahydrates, 10.8g Iron trichloride hexahydrates and 67.5mL water, mechanical agitation are added in the reactor
Solution leads to nitrogen 30min, and 15mL ammonium hydroxide, 1.25g oleic acid are added dropwise successively, reacts 3h at 90 DEG C.Magneto separate goes out Fe3O4, and spend from
Son is washed to neutrality, obtains Fe3O4Magnetic core passes through after being mixed with normal octane and is dried with anhydrous sodium sulfate, obtains Fe3O4Magnetic fluid.
(2)Fe3O4The preparation of@Chloromethyl PS
Weigh 7.5g magnetic fluids, 3.4g styrene, 0.76g divinylbenzenes, 1.65g p-chloromethyl styrenes, 0.57g positive ten
The mixing of six alkane is made into oil phase, ultrasonic disperse 10min.It weighs 1.35g lauryl sodium sulfate and is dissolved in 169mL deionized waters and obtain water
Oil phase is added dropwise in water phase under mechanical stirring for phase, and stirring 2h obtains black oil droplet suspension.The cell pulverization in ice bath
Machine fine crankshaft 10min obtains miniemulsion that is uniform, stablizing.Then acquired miniemulsion is moved into flask, mixing speed
With nitrogen displaced air 30min 0.112g potassium peroxydisulfates are added, 70 DEG C of constant temperature polymerizations are for 24 hours in 300rpm.Most it is demulsified afterwards through methanol,
Magneto separate collects solid product, washes, and freeze-drying obtains nano-magnetic microsphere Fe3O4@Chloromethyl PS。
(3)Fe3O4The preparation of@PS-TMG
0.2gFe is added in the reactor3O4@Chloromethyl PS nano-magnetic microspheres are (through the surface chloromethyl that converts
0.3mmol), 0.0173g1,1,3,3- tetramethylguanidine, 0.05g tetrabutylammonium iodides, 0.5mL50wt% sodium hydroxide solution
With 20mL tetrahydrofurans, back flow reaction 48h under nitrogen protection.Reaction solution uses tetrahydrofuran and deionized water successively through Magneto separate
It washs, magnetic organic solid base catalyst Fe is obtained after vacuum freezedrying3O4@PS-TMG0.21g。
Embodiment 22
Catalyst activity is tested
The soybean oil used in following embodiment is purchased from golden dragonfish and refines level-one soybean oil (5L)
The magnetic organic solid base catalyst Fe prepared using the present invention3O4@PS-TMG, using soybean oil and methanol as raw material
Biodiesel is prepared in batch reactor：Reactor is added in 5g soybean oils and preheats 10min, Fe3O4@PS-TMG ultrasounds point
It dissipates and forms uniform dispersion liquid in 2.72g methanol and reactor is added, reactor is sealed, 300rpm mechanical agitations at 60 DEG C
React 12h.After reaction, it is cooled to room temperature, magnetic recycles catalyst, and decompression, which steams methanol, applies mechanically.Product use
Gas chromatography detects the conversion ratio of fatty acid methyl ester.Table 1 is that catalyst prepared by embodiment 14-21 is applied to soybean oil and first
Conversion ratio when alcohol transesterification reaction.
Table 1
| Catalyst Preparation Example | Catalyst loading | The conversion ratio of fatty acid methyl ester |
| Embodiment 14 | 2.5wt% | 80.1% |
| Embodiment 14 | 5wt% | 99.3% |
| Embodiment 15 | 5wt% | 80.3% |
| Embodiment 16 | 5wt% | 58.4% |
| Embodiment 17 | 5wt% | 75% |
| Embodiment 18 | 5wt% | 49.8% |
| Embodiment 19 | 5wt% | 51.3% |
| Embodiment 20 | 5wt% | 53% |
| Embodiment 21 | 5wt% | 57.4% |
Note：Catalyst loading refers to the mass values of catalyst and soybean oil, similarly hereinafter.
Catalyst activity is tested
The magnetic organic solid base catalyst Fe prepared using embodiment 143O4@PS-TMG are original with soybean oil and methanol
Material prepares biodiesel in batch reactor：Reactor is added in 5g soybean oils and preheats 10min, 5wt%Fe3O4@PS-TMG
Ultrasonic disperse forms uniform dispersion liquid in methanol and reactor is added, and reactor is sealed, and 300rpm machineries stir at 60 DEG C
Mix reaction 12h.After reaction, it is cooled to room temperature, magnetic recycles catalyst, and decompression, which steams methanol, applies mechanically.Product
The conversion ratio of fatty acid methyl ester is detected with gas chromatography.Table 2 is that catalyst prepared by embodiment 14 is applied to different alcohol oil rates
Conversion ratio when (the ratio between amount of substance, similarly hereinafter) ester exchange reaction.
Table 2
| Alcohol oil rate | The conversion ratio of fatty acid methyl ester |
| 6:1 | 74.3% |
| 9:1 | 80.3% |
| 12:1 | 88.1% |
| 15:1 | 99.3% |
| 18:1 | 97.5% |
From table 1 and 2 as can be seen that Fe3O4@PS-TMG catalyst has preferable catalytic effect to ester exchange reaction, wherein
Fe prepared by embodiment 143O4@PS-TMG catalysts soybean oils and the conversion ratio of methanol ester exchange reaction are up to 99.3%.
Embodiment 23
Catalyst activity is tested
The magnetic organic solid base catalyst Fe prepared using embodiment 143O4@PS-TMG are original with soybean oil and methanol
Material prepares biodiesel using static state Pickering emulsion methods：Reactor, Fe is added in 5g soybean oils3O4@PS-TMG ultrasounds point
It dissipates and forms uniform dispersion liquid in 5g methanol and reactor is added, it will under 10000rpm rotating speeds with Portable high speed refiner
Reaction solution emulsification 1min obtains stablizing Pickering lotions, and reactor is sealed, reacts 12h at 60 DEG C.After reaction,
It is cooled to room temperature, magnetic recycles catalyst, and decompression, which steams methanol, applies mechanically.Product with gas chromatography detect aliphatic acid
The conversion ratio of methyl esters.Table 3 is conversion ratio when catalyst prepared by embodiment 14 is applied to ester exchange reaction under different alcohol oil rates.
Table 3
| Catalyst loading | The conversion ratio of fatty acid methyl ester |
| 2.5wt% | 75.1% |
| 5wt% | 99% |
Catalyst activity is tested
The magnetic organic solid base catalyst Fe prepared using embodiment 143O4@PS-TMG are original with soybean oil and methanol
Material prepares biodiesel using static state Pickering emulsion methods：Reactor, 5wt%Fe is added in 5g soybean oils3O4@PS-TMG are super
Sound, which is scattered in a certain amount of methanol, to be formed uniform dispersion liquid and reactor is added, with Portable high speed refiner in 10000rpm
It obtains reaction solution emulsification 1min to stablize Pickering lotions under rotating speed, reactor is sealed, reacts 12h at 60 DEG C.Reaction
After, it is cooled to room temperature, magnetic recycles catalyst, and decompression, which steams methanol, applies mechanically.Product examined with gas chromatography
Survey the conversion ratio of fatty acid methyl ester.When table 4 is that catalyst prepared by embodiment 14 is applied to ester exchange reaction under different alcohol oil rates
Conversion ratio.
Table 4
| Alcohol oil rate | The conversion ratio of fatty acid methyl ester |
| 9:1 | 56.9% |
| 12:1 | 62.7% |
| 15:1 | 88.7% |
| 18:1 | 89.2% |
| 21:1 | 95.3% |
| 24:1 | 98.1% |
| 27:1 | 99% |
| 30:1 | 94.1% |
From table 3 and 4 as can be seen that Fe prepared by embodiment 143O4@PS-TMG catalyst is used for static state Pickering lotions
It is catalyzed the ester exchange reaction of soybean oil and methanol, when alcohol oil rate is 27:Conversion ratio is up to 99.2% when 1, shows and high-speed stirred
The comparable catalytic effect of two phase reaction illustrates that the huge interfacial area of Pickering lotions makees the reinforcing of heterogeneous reaction
With apparent.
Embodiment 24
The recycling of catalyst
Reactor is added in 5g soybean oils, 10min is preheated at 60 DEG C.5wt%Fe3O4@PS-TMG catalyst (embodiments 14
Preparing) ultrasonic disperse forms uniform dispersion liquid in 2.72g methanol and reactor is added.Reaction solution is in 300rpm mechanical agitations
Lower reaction 12h.After reaction, it is cooled to room temperature, magnetic recycles catalyst, and decompression, which steams methanol, applies mechanically.Products therefrom
The conversion ratio of fatty acid methyl ester is detected with gas chromatography.Recycling test result is shown in Table 5.
Table 5
| Cycle-index | The conversion ratio of fatty acid methyl ester |
| 1 | 99% |
| 2 | 98.5% |
| 3 | 98.1% |
| 4 | 97.2% |
| 5 | 96.5% |
Embodiment 25
The recycling of catalyst
Reactor, 5wt%Fe is added in 5g soybean oils3O4@PS-TMG catalyst (preparation of embodiment 14) ultrasonic disperse in
Uniform dispersion liquid is formed in 4.97g methanol and reactor is added, and is emulsified reaction solution under 10000rpm rotating speeds with homogenizer
1min obtains stablizing Pickering lotions, and reactor is sealed, and reacts 12h at 60 DEG C.After reaction, it is cooled to
Room temperature, magnetic recycle catalyst, and decompression, which steams methanol, applies mechanically.Products therefrom detects the conversion of fatty acid methyl ester with gas chromatography
Rate.Recycling test result is shown in Table 6.
Table 6
It can be seen that by table 5,6, Fe prepared by embodiment 143O4@PS-TMG catalyst is after reusing 5 times, fatty acid methyl
The conversion ratio of ester does not reduce substantially, still shows higher catalytic activity.
Comparative example
Using the KOH with TMG equimolar amounts as base catalyst, made in batch reactor using soybean oil and methanol as raw material
Standby biodiesel：Reactor is added in 5g soybean oils and is warming up to 60 DEG C of preheating 10min, 6.8mgKOH ultrasonic disperses are in 2.72g
Methanol forms uniform dispersion liquid and reactor is added, and reactor is sealed, 300rpm mechanic whirl-nett reactions 12h at 60 DEG C.
After reaction, it is cooled to room temperature, detaches, wash, be dried to obtain biodiesel oil product.Products therefrom gas chromatography
Detect the conversion ratio of fatty acid methyl ester.Table 7 is conversion ratio when KOH catalyst is applied to soybean oil and methanol ester exchange reaction.
Table 7
| Catalyst | The conversion ratio of fatty acid methyl ester |
| KOH | 94% |
As seen from Table 7, Fe3O4@PS-TMG catalyst activities are higher than homogeneous KOH catalyst, show higher catalysis
Activity.Also, it cannot be recycled as catalyst using KOH, a large amount of water washing is needed to remove KOH, production in product post-processing
Raw many waste water are big to environmental disruption.And the application catalyst can be by simple Magneto separate, that is, recyclable, and apply mechanically effect
It is same good.
Claims (10)
1. a kind of magnetism organic solid base catalyst, which is characterized in that be prepared as follows to obtain：
(1) Fe is prepared3O4Magnetic fluid
Ferrous salt, molysite and deionized water are mixed, are stirred at room temperature dissolving, under nitrogen protection, dropwise addition ammonium hydroxide, oleic acid are warming up to
80~90 DEG C of 3~4h of reaction, the solid product of Magneto separate collection later, are washed with deionized water to neutrality, obtain Fe3O4Magnetic core, by institute
Obtain Fe3O4Magnetic core with etc. the normal octanes of quality mix, removed water through anhydrous sodium sulfate, obtain Fe3O4Magnetic fluid；
The ratio between the amount of substance 1: 1~2: 0.22~0.3: 187.5~200 of the ferrous salt, molysite, oleic acid, deionized water；
The concentration of the ammonium hydroxide is in 25~28wt%, the dripping quantity of the ammonium hydroxide：Make the pH of reaction system 9~13；
(2) nano-magnetic microsphere is prepared
By Fe obtained by step (1)3O4Magnetic fluid, styrene, divinylbenzene, p-chloromethyl styrene, hexadecane mixing, ultrasound
It is uniformly dispersed, obtains oil phase；Lauryl sodium sulfate is dissolved in deionized water, obtains water phase；Under stirring condition, by gained oil phase
Be added drop-wise in water phase, drip off and continue 2~3h of stirring, be placed in ice-water bath, with 100~300W cell disruptors fine crankshaft 10
~30min, obtains miniemulsion, and under nitrogen protection, potassium peroxydisulfate is added in gained miniemulsion, and it is poly- to be warming up to 70~80 DEG C of constant temperature
Conjunction 17~for 24 hours, reaction solution is post-treated later, obtains nano-magnetic microsphere, and chloromethane is contained on the surface of gained nano-magnetic microsphere
Base；
The Fe3O4Magnetic fluid, styrene, divinylbenzene, p-chloromethyl styrene, hexadecane, potassium peroxydisulfate mass ratio be
1: 0.46~0.91: 0.09~0.1: 0.22~0.44: 0.038~0.076: 0.0075~0.015；
The ratio between amount of substance of the lauryl sodium sulfate and deionized water is 1: 1600~2000；
Fe in the oil phase3O4Magnetic fluid and the mass ratio of the deionized water in water phase are 1: 18~22.5；
(3) magnetic organic solid base catalyst is prepared
By nano-magnetic microsphere, organic base, tetrabutylammonium iodide, 40~60wt% sodium hydrate aqueous solutions, four obtained by step (2)
Hydrogen furans mixes, and 24~48h of back flow reaction under nitrogen protection, reaction solution is post-treated later, obtains magnetic organic solid alkali and urges
Agent；
The chloromethyl on the nano-magnetic microsphere surface, organic base, tetrabutylammonium iodide, sodium hydroxide the ratio between the amount of substance be
1: 0.5~5: 0.45~0.9: 42~50；
The chloromethyl content on the nano-magnetic microsphere surface is with the gauge of the substance of raw material p-chloromethyl styrene in step (2)
It calculates；
The volumetric usage of the tetrahydrofuran is calculated as 75~100mL/g with the quality of nano-magnetic microsphere；
The organic base is：1,1,3,3- tetramethylguanidine, tri- azabicyclics of 1,5,7- [4.4.0] decyl- 5- alkene, 1,8- diazas are double
The 11 carbon -7- alkene of ring [5,4,0], 1,5- diazabicyclos [4,3,0] nonyl- 5- alkene, triethylene diamine, tetramethylethylenediamine, 4-
One or both of dimethylamino naphthyridine, trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, pyridine, dimethylethanolamine with
The mixture of upper arbitrary proportion.
2. magnetism organic solid base catalyst as described in claim 1, which is characterized in that in step (1), the ferrous iron
The ratio between the amount of substance 1: 2: 0.22: 187.5 of salt, molysite, oleic acid, deionized water.
3. magnetism organic solid base catalyst as described in claim 1, which is characterized in that in step (1), the ferrous salt
For：Four water frerrous chlorides, frerrous chloride or ferrous sulfate heptahydrate；The molysite is：Nine water ferric nitrates, iron chloride or six water chlorinations
Iron.
4. magnetism organic solid base catalyst as described in claim 1, which is characterized in that in step (2), the Fe3O4Magnetic
Fluid, styrene, divinylbenzene, p-chloromethyl styrene, hexadecane, potassium peroxydisulfate mass ratio be 1: 0.91: 0.09:
0.44∶0.038∶0.0075。
5. magnetism organic solid base catalyst as described in claim 1, which is characterized in that in step (2), the dodecane
The ratio between amount of substance of base sodium sulphate and deionized water is 1: 1600.
6. magnetism organic solid base catalyst as described in claim 1, which is characterized in that in step (2), in the oil phase
Fe3O4Magnetic fluid and the mass ratio of the deionized water in water phase are 1: 18.
7. magnetism organic solid base catalyst as described in claim 1, which is characterized in that in step (3), the nano magnetic
Property the chloromethyl of microsphere surface, organic base, tetrabutylammonium iodide, sodium hydroxide the ratio between the amount of substance be 1: 5: 0.45: 42.
8. magnetism organic solid base catalyst is in transesterification, esterification or aldol reaction as described in claim 1
Using.
9. application as claimed in claim 8, which is characterized in that the magnetism organic solid base catalyst is applied to mechanical agitation
Lower reinforcing ester exchange reaction, the method for the application are：
Soybean oil is warming up to 60 DEG C of preheating 10min, magnetic organic solid base catalyst ultrasonic disperse is formed in methanol
Even dispersion liquid is simultaneously added in the soybean oil of preheating, reacts 12h under 60 DEG C, 300rpm mechanical agitations, is cooled to room temperature later,
Magneto separate recycles catalyst, and reaction solution removes solvent under reduced pressure and obtains esterification products；
The mass ratio of the magnetism organic solid base catalyst and soybean oil is 1: 20~40；
The ratio between amount of substance of the methanol and soybean oil is 6~18: 1.
10. application as claimed in claim 8, which is characterized in that the magnetism organic solid base catalyst is applied to static state
Strengthen ester exchange reaction under Pickering lotions, the method for the application is：
Magnetic organic solid base catalyst ultrasonic disperse is formed into uniform dispersion liquid in methanol and is added in soybean oil, is obtained
Gained reaction solution emulsification 1min is obtained Pickering lotions under 10000rpm rotating speeds with homogenizer, is risen after sealing by reaction solution
Temperature is cooled to room temperature later to 60 DEG C of reaction 12h, and Magneto separate recycles catalyst, and reaction solution removes solvent under reduced pressure and obtains esterification production
Object；
The mass ratio of the magnetism organic solid base catalyst and soybean oil is 1: 20~40；
The ratio between amount of substance of the methanol and soybean oil is 9~30: 1.
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| CN111672344A (en) * | 2020-06-28 | 2020-09-18 | 浙江工业大学 | Production process for preparing biodiesel by static reaction |
| CN111905738A (en) * | 2020-09-02 | 2020-11-10 | 南京大学 | Preparation method of Fenton-like catalyst for ferroferric oxide coated diamond |
| CN112121862A (en) * | 2020-10-15 | 2020-12-25 | 江西赣江新区有机硅创新研究院有限公司 | Magnetic immobilized platinum catalyst and preparation method and application thereof |
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| CN112705261A (en) * | 2021-02-01 | 2021-04-27 | 福州大学 | Preparation method of Pickering emulsion guanidino ionic liquid catalytic system for ester exchange reaction |
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| CN112121861A (en) * | 2020-10-15 | 2020-12-25 | 江西赣江新区有机硅创新研究院有限公司 | Magnetically-recoverable immobilized platinum catalyst and preparation method and application thereof |
| CN112705261A (en) * | 2021-02-01 | 2021-04-27 | 福州大学 | Preparation method of Pickering emulsion guanidino ionic liquid catalytic system for ester exchange reaction |
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