US20150175634A1 - Preparation of Phenol- or Thiophenyl-Sulfonic Acid Functionalized Solid Acids - Google Patents
Preparation of Phenol- or Thiophenyl-Sulfonic Acid Functionalized Solid Acids Download PDFInfo
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- US20150175634A1 US20150175634A1 US14/139,961 US201314139961A US2015175634A1 US 20150175634 A1 US20150175634 A1 US 20150175634A1 US 201314139961 A US201314139961 A US 201314139961A US 2015175634 A1 US2015175634 A1 US 2015175634A1
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- Prior art keywords
- sba
- acid
- functionalized
- solid
- aryl
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Links
- 239000011973 solid acid Substances 0.000 title description 12
- 238000002360 preparation method Methods 0.000 title description 11
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 44
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 64
- 239000011148 porous material Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 30
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 17
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 17
- 239000000741 silica gel Substances 0.000 claims description 16
- 229910002027 silica gel Inorganic materials 0.000 claims description 16
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 alkyl phenol Chemical compound 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- 239000011343 solid material Substances 0.000 claims description 9
- 229930192474 thiophene Natural products 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 150000001491 aromatic compounds Chemical class 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 claims description 8
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910006024 SO2Cl2 Inorganic materials 0.000 claims description 4
- 229910006251 ZrOCl2.8H2O Inorganic materials 0.000 claims description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 claims description 3
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 3
- 229910006504 ZrSO4 Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- BAKVCODNMVLWCZ-UHFFFAOYSA-L zirconium(4+);acetate;hydroxide Chemical compound [OH-].[Zr+4].CC([O-])=O BAKVCODNMVLWCZ-UHFFFAOYSA-L 0.000 claims description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 230000032050 esterification Effects 0.000 abstract description 23
- 238000005886 esterification reaction Methods 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 98
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 87
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 58
- 235000021314 Palmitic acid Nutrition 0.000 description 49
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 23
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 16
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 12
- 229910052906 cristobalite Inorganic materials 0.000 description 12
- 229910052682 stishovite Inorganic materials 0.000 description 12
- 229910052905 tridymite Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 238000003795 desorption Methods 0.000 description 8
- 238000006277 sulfonation reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229960004592 isopropanol Drugs 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical group CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 4
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 4
- 229920002415 Pluronic P-123 Polymers 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 4
- 229940075495 isopropyl palmitate Drugs 0.000 description 4
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 4
- 238000001757 thermogravimetry curve Methods 0.000 description 4
- OUFLYDYJVULAOW-UHFFFAOYSA-N 4-methyl-2-(3-trimethoxysilylpropyl)phenol Chemical compound OC1=C(C=C(C=C1)C)CCC[Si](OC)(OC)OC OUFLYDYJVULAOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 230000005465 channeling Effects 0.000 description 3
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- AQOQOFGGZQEQRW-UHFFFAOYSA-N dimethoxy-propyl-(thiophen-3-ylmethoxy)silane Chemical compound S1C=C(C=C1)CO[Si](OC)(OC)CCC AQOQOFGGZQEQRW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 235000019737 Animal fat Nutrition 0.000 description 2
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- YJSUVDUQHJOSEO-UHFFFAOYSA-N C.C.C.C1=CSC=C1.CO[Si](CCCC1=CC=CS1)(OC)OC.CO[Si](CCCCl)(OC)OC Chemical compound C.C.C.C1=CSC=C1.CO[Si](CCCC1=CC=CS1)(OC)OC.CO[Si](CCCCl)(OC)OC YJSUVDUQHJOSEO-UHFFFAOYSA-N 0.000 description 1
- LUYZHWHFYCKVAN-UHFFFAOYSA-N CC1=CC=C(O)C=C1.CO[Si](CCCC1=C(O)C=CC(C)=C1)(OC)OC.CO[Si](CCCCl)(OC)OC Chemical compound CC1=CC=C(O)C=C1.CO[Si](CCCC1=C(O)C=CC(C)=C1)(OC)OC.CO[Si](CCCCl)(OC)OC LUYZHWHFYCKVAN-UHFFFAOYSA-N 0.000 description 1
- GIMDTBJMMJNSMT-UHFFFAOYSA-N CO[Si](CCCCl)(OC)OC.CO[Si](CCC[Ar])(OC)OC.C[Si](C)(C)CCC[Ar].C[Si](C)(C)CCC[Ar]S(=O)(=O)O.[H][Ar] Chemical compound CO[Si](CCCCl)(OC)OC.CO[Si](CCC[Ar])(OC)OC.C[Si](C)(C)CCC[Ar].C[Si](C)(C)CCC[Ar]S(=O)(=O)O.[H][Ar] GIMDTBJMMJNSMT-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910006077 SO2O2 Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002481 ethanol extraction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FUBACIUATZGHAC-UHFFFAOYSA-N oxozirconium;octahydrate;dihydrochloride Chemical compound O.O.O.O.O.O.O.O.Cl.Cl.[Zr]=O FUBACIUATZGHAC-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
Definitions
- the disclosure relates to preparation of solid acids.
- Solid acids are widely used in industry. There are two important types of solid acids, one is acid aluminosilicate zeolite, and the other one is acid resin (such as amberlyst-15 having a polystyrene backbone).
- acid resin such as amberlyst-15 having a polystyrene backbone.
- the pore size of the acid aluminosilicate zeolite is too small to accommodate large medical molecules, and the reaction temperature needed by the acid aluminosilicate zeolite is usually 200-300° C. to present enough acidity.
- the acid resin the acid resin will be swelled by solvents to affect the effective acid amount, and the thermal stability of the acid resin is kind of poor. Therefore, the acid resin is usually deteriorated after reaction and difficult to be regenerated.
- the present disclosure provides a method of preparing an aryl sulfonic acid-functionalized solid to be a solid acid.
- the method comprises the following steps. First, a 3-arylpropyl trimethoxysilane is formed by reacting 3-chloropropyl trimethoxysilane with an aromatic compound. Then, an aryl-functionalized solid is formed by grafting the 3-arylpropyl trimethoxysilane onto an inorganic solid material in an organic solvent under a reflux condition. Next, an aryl sulfonic acid-functionalized solid is formed by sulfonating the aryl-functionalized solid by a sulfonating agent.
- the aromatic compound is phenol, alkyl phenol, thiophene, or alkyl thiophene.
- the inorganic solid material is silica gel or Zr(OH) 4 powders.
- the organic solvent is toluene, xylene, ethylbenzene, or octane.
- the aryl-functionalized solid is sulfonated at 80° C. for 24 hours.
- the sulfonating agent is concentrated sulfuric acid, a mixture of oleum and concentrated sulfuric acid, or SO 2 Cl 2 .
- the present disclosure provides a method of preparing an aryl sulfonic acid-functionalized solid to be a solid acid.
- the method comprises the following steps. First, a 3-arylpropyl trimethoxysilane is formed by reacting 3-chloropropyl trimethoxysilane with an aromatic compound. Then, an aryl-functionalized solid is formed by co-condensing the 3-arylpropyl trimethoxysilane and a precursor of an inorganic solid by a hydrothermal reaction. Next, an aryl sulfonic acid-functionalized solid is formed by sulfonating the aryl-functionalized solid in concentrated sulfuric acid.
- the precursor of the inorganic solid is tetramethyl orthosilicate, tetraethyl orthosilicate, or sodium silicate.
- the inorganic solid comprises a porous silica material.
- the porous silica material is SBA-15 or MCM41.
- a reactant composition of the hydrothermal reaction comprises a pore directing agent, the precursor of the inorganic solid, acid, and water in a molar ratio of 0.02:1:0.05-0.3:7-9:179-230.
- the pore directing agent is EO 20 PO 70 EO 20 , EO 40 PO 60 EO 40 , EO 100 PO 65 EO 100 , or cetyl trimethylammonium bromide.
- the acid is HCl, HNO 3 , H 2 SO 4 , or HClO 4 .
- the reactant composition of the hydrothermal reaction further comprises Zr(IV) ions, and atomic ratio of Zr(IV):Si is in 0-0.1.
- a source of the Zr(IV) ions is ZrOCl 2 , ZrSO 4 , ZrO(NO 3 ) 2 , or zirconium(IV) acetate hydroxide.
- a reactant composition of the hydrothermal reaction comprises 0.017 EO 20 PO 70 EO 20 :1 tetraethyl orthosilicate:0.05-0.43 3-arylpropyl trimethoxysilane:0.05 ZrOCl 2 .8H 2 O:7.9 HCl:220 H 2 O in molar ratio.
- the aryl-functionalized solid is sulfonated at 80° C. for 24 hours.
- the sulfonating agent is concentrated sulfuric acid, a mixture of oleum and concentrated sulfuric acid, or SO 2 O 2 .
- FIG. 1 is the TGA profile of PholSO 3 H—SiO 2 .
- FIG. 2 shows the TGA profiles of the ZrO 2 materials before and after functionalized with H 2 SO 4 , phenol and phenolsulfonic acid groups.
- FIGS. 3A and 3B are the small-angle XRD patterns of ethanol extracted xPhol-SBA-15-p materials prepared with various PholTMS/(TEOS+PholTMS) molar percentages and those after sulfonation, respectively.
- FIGS. 4A and 4B are the nitrogen adsorption-desorption isotherms of ethanol extracted xPhol-SBA-15-p materials prepared with various PholTMS/(TEOS+PholTMS) molar percentages and those after sulfonation, respectively.
- FIG. 5 shows XRD patterns of SBA-15-p, 15Thio-SBA-15-p and 15ThioSO3H-SBA-15.
- FIG. 6 shows the nitrogen adsorption-desorption isotherms of SBA-15-p, ethanol extracted 15Thio-SBA-15-p and dried 15ThioSO 3 H-SBA-15 samples.
- FIGS. 7A and FIG. 7B show the conversions of palmitic acid in the esterification of palmitic acid with MeOH and iPrOH, respectively.
- PA palmitic acid
- MeOH methanol
- iPrOH iso-propanol
- FIG. 9 shows the conversion of palmitic acid as a function of reaction period over 15ThioSO 3 H-SBA-15-p, in comparison to that over commercially available Amberlyst-15 resin.
- FIG. 10 demonstrates the recyclability of the 15ThioSO3H-SBA-15-p catalyst.
- FIG. 11 shows the esterification of palmitic acid with methanol over ZrO 2 , SO 3 H—ZrO 2 , and PholSO 3 H—ZrO 2 .
- FIGS. 12A and 12B show the conversions of palmitic acid over different solid acid catalysts in the esterification of palmitic acid with MeOH and iPrOH, respectively.
- 3-chloropropyl trimethoxysilane was used as a starting material to perform a Friedel-Crafts reaction with an aromatic compound, such as phenol, alkyl phenol, thiophene, or alkyl thiophene, to obtain 3-arylpropyl trimethoxysilane.
- the 3-arylpropyl trimethoxysilane can be used to functionalize an inorganic solid material, such as a silica material, a zirconia material, a titania material, or other metal oxide materials, to obtain an aryl-functionalized solid.
- the silica material above can be silica gel or a porous silica material. This step can be performed by a grafting method or a co-condensation method.
- an inorganic solid material having free —OH functional groups on its surface is needed.
- the 3-arylpropyl trimethoxysilane above is used to react with the —OH group of the inorganic solid material in an organic solvent under a reflux condition for 1-48 hours, such as atleast 24 hours.
- the solid material can be silica gel or Zr(OH) 4 powder.
- the Zr(OH) 4 powder is a precursor of zirconia powder.
- the organic solvent can be an anhydrous organic solvent with boiling points higher than 80° C., such as toluene, xylene, ethylbenzene, or octane, for example.
- 3-arylpropyl trimethoxysilane and a precursor of an inorganic solid is co-condensed in an aqueous solution containing a pore-directing agent to form an aryl-functionalized solid by hydrothermal reaction.
- the inorganic solid can be a porous silica material, such as SBA-15 or MCM41, for example.
- a pore directing agent, a silica source, acid, and water are needed for the hydrothermal reaction.
- the molar ratio of the pore directing agent, the silica source, the 3-arylpropyl trimethoxysilane, the acid, and water can be 0.02:1:0.05-0.45:7-9:179-230, for example.
- the pore directing agent can be EO 20 PO 70 EO 20 , EO 40 PO 60 EO 40 , EO 100 PO 65 EO 100 , or cetyl trimethylammonium bromide, for example.
- the silica source can be tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), or sodium silicate, for example.
- the acid can be HCl, HNO 3 , H 2 SO 4 , or HClO 4 , for example.
- the hydrothermal reaction is usually performed at a temperature of 90-100° C. under static condition for 6-72 hours, such as at least 24 hours.
- a neutral pore directing agent and Zr(IV) ions are used.
- the neutral pore directing agent can be EO 20 PO 70 EO 20 .
- the source of the Zr(IV) ions can be ZrOCl 2 , ZrSO 4 , ZrO(NO 3 ) 2 , or zirconium(IV) acetate hydroxide.
- the atomic ratio of Zr(IV):Si is in 0-0.1, such as 0.05.
- the aromatic ring of the aryl-functionalized solid is sulfonated by a sulfonating agent to obtain an aryl sulfonic acid-functionalized solid as a solid acid.
- the sulfonating agent can be concentrated sulfuric acid, a mixture of oleum and concentrated sulfuric acid, or SO 2 Cl 2 .
- the sulfonation can be performed at 60-90° C. for 6-36 hours.
- PholTMS was grafted onto silica gel to form phenol-functionalized silica gel, which is denoted by Phol-SiO 2 .
- phenol-functionalized silica gel was sulfonated by concentrated H 2 SO 4 to form phenolsulfonic acid-functionalized silica gel, which is denoted by PholSO 3 H—SiO 2 .
- a phenol-functionalized silica gel was prepared first.
- 2.0 mL of PholTMS synthesized above was reacted with 4 g of silica gel (Sigma Aldrich) in 10 mL of toluene under reflux for 24 hours.
- the obtained solid product Phol-SiO 2 was filtered and dried at 100° C.
- a phenolsulfonic acid-functionalized silica gel was prepared.
- 4 g of Phol-SiO 2 powder in 40 mL of concentrated H 2 SO 4 was heated at 80° C. for 24 hours. After cooling and diluting the mixture with 150 mL of water, the solid product PholSO 3 H—SiO 2 was collected by filtration and dried at 100° C.
- physicochemical properties of pristine silica gel and PholSO 3 H—SiO 2 were analyzed.
- the analyzed physicochemical properties included sulfur content, acid capacity, specific surface area (S BET ), pore volume (V Total ), pore diameter ( ⁇ P ), and thermogravimetric analysis (TGA).
- Nitrogen physisorption isotherms were used to analyze specific surface area (S BET ), pore volume (V Total ), pore diameter ( ⁇ P ) of the samples.
- the Nitrogen physisorption isotherms were taken at liquid nitrogen temperature (77 K) by using a Micrometerics TriStar 3000 system. Prior to the experiments, the samples were outgassed at 120° C. for 6-8 h under vacuum (10 ⁇ 3 Torr).
- the acid capacities of the samples were determined by acid-base titration using NaCl solution as an ion-exchange agent.
- a 50 mg sample in powder form was ion-exchanged with 20 mL 2M NaCl solution at ambient temperature for at least 24 h, followed by filtration and washing with 3 mL of deionized water. The filtrates were then titrated with a 0.01 M NaOH solution.
- FIG. 1 is the TGA profile of PholSO 3 H—SiO 2 . Before 100° C., about 15% weight loss of adsorbed moisture was desorbed. This result shows that the PholSO 3 H—SiO 2 was hygroscopic. Above 340° C., the weight loss was attributed to the decomposition of phenol and sulfonic acid groups.
- PholTMS was co-condensed with a zirconia source, such as Zr(OH) 4 , to form phenol-functionalized zirconia, which is denoted by Phol-ZrO 2 .
- phenol-functionalized zirconia was sulfonated by concentrated H 2 SO 4 to form phenolsulfonic acid-functionalized zirconia, which is denoted by PholSO 3 —ZrO 2 .
- phenol-functionalized zirconia was prepared first.
- the preparation of phenol-functionalized zirconia was performed by grafting PholTMS onto the surface of Zr(OH) 4 powder, which is a precursor of zirconia.
- PholTMS was reacted with 1 g of Zr(OH) 4 powder in 20 mL toluene solvent under reflux for 24 h.
- the solid product Phol-ZrO 2 was collected by filtration and drying at 100° C.
- phenolsulfonic acid-functionalized zirconia was prepared. 1 g of Phol-ZrO 2 powders with a mixture of 5 mL oleum (i.e. fuming sulfuric acid) and 20 mL concentrated H 2 SO 4 were heated at 80° C. for 24 h. After cooling and diluting the mixture with 1 L of deionized water, the solid product PholSO 3 H—ZrO 2 was filtered and dried at 100° C.
- oleum i.e. fuming sulfuric acid
- H 2 SO 4 concentrated H 2 SO 4
- sulfonic acid-functionalized zirconia (denoted by SO 3 H—ZrO 2 ) was also prepared. 1 g of Zr(OH) 4 was reacted directly with a mixture of 5 mL oleum and 20 mL concentrated H 2 SO 4 at 80° C. for 10 hours. After cooling and diluting the mixture with 1 L of deionized water, the solid product was filtered, dried at 200° C. for 10 h.
- FIG. 2 shows the TGA profiles of the ZrO 2 materials before and after functionalized with H 2 SO 4 , phenol and phenosulfonic acid groups, respectively.
- the materials functionalized with phenol (Phol-ZrO 2 ) and phenosulfonic acid groups (PholSO 3 H—ZrO 2 ) are more hygroscopic because they adsorb larger amounts of moisture, which was desorbed below 100° C.
- these two samples of Phol-ZrO 2 and PholSO 3 H—ZrO 2 have additional weight losses at ca. 350° C. It should correspond to the decomposition of phenol groups.
- SBA-15 is a mesoporous silica material.
- PholTMS was co-condensed with a silica source to form phenol-functionalized platelet SBA-15, which is denoted by Phol-SBA-15-p.
- phenol-functionalized platelet SBA-15 was sulfonated by concentrated H 2 SO 4 to form phenolsulfonic acid-functionalized platelet SBA-15, which is denoted by PholSO 3 H-SBA-15-p.
- phenol-functionalized SBA-15 was prepared first.
- the preparation of phenol-functionalized SBA-15 was performed by co-condensing a silica source, such as tetraethyl orthosilicate (TEOS), and PholTMS in the presence of Zr(IV) ions.
- a silica source such as tetraethyl orthosilicate (TEOS)
- PholTMS tetraethyl orthosilicate
- TEOS prehydrolysis in the acidic synthesis solution containing Zr(IV) ions before the introduction of PholTMS was necessary in order to obtain a well-ordered pore structure and platelet morphology.
- the reactant compositions were 0.017 P123:1 TEOS:0.05-0.45 PholTMS:0.05 ZrOCl 2 .8H 2 O:7.9 HCl:220 H 2 O, in molar ratio.
- the synthesized gel sealed in a polypropylene bottle was stirred at 35° C. for 24 h and hydrothermally heated under static conditions at 90° C. for another 24 h.
- a solid precipitate collected by filtration was washed thoroughly with deionized water, followed by drying at 50° C. overnight.
- P123 was removed from the solid materials by ethanol extraction at 78° C. for 1 day.
- the resulting phenol-functionalized SBA-15 are designated as xPhol-SBA-15-p, where “x” represents the PholTMS/(TEOS+PholTMS) molar percentage in the synthesis gels and “p” indicates the platelet morphology.
- phenolsulfonic acid-functionalized platelet SBA-15 was prepared. 4 g of xPhol-SBA-15-p powder in 40 mL concentrated H 2 SO 4 was heated at 80° C. for 24 hours. After cooling and diluting the mixture with 150 mL of water, the solid product was filtered and dried at 100° C.
- the resultant products, phenolsulfonic acid-functionalized platelet SBA-15 are termed as xPholSO 3 H-SBA-15, where x is 15, 20, 25, or 30.
- FIGS. 3A and 3B are the small-angle XRD patterns of ethanol extracted xPhol-SBA-15-p materials prepared with various PholTMS/(TEOS+PholTMS) molar percentages and those after sulfonation, respectively.
- FIG. 3A three well-resolved diffraction peaks corresponding to the (100), (110) and (200) planes of 2D-hexagonal p6 mm pore structure are observed on xPhol-SBA-15-p materials, especially those of low PholTMS contents.
- FIG. 3B these diffraction peaks are almost disappeared after suflonation reaction. This phenomenon suggested that the ordered pore structure is no longer present after treating the porous materials in sulfonic acid of such a high concentration.
- FIGS. 4A and 4B are the nitrogen adsorption-desorption isotherms of ethanol extracted xPhol-SBA-15-p materials prepared with various PholTMS/(TEOS+PholTMS) molar percentages and those after sulfonation, respectively.
- the characteristic type IV isotherm with H1 hysteresis loop was seen at P/P 0 of 0.5-0.7. This indicated that large mesopores with narrow pore size distributions were present, and the 15Phol-SBA-15-p material is similar to the pure SBA-15-p material.
- the hysteresis loops shift toward low P/P 0 region as the PholTMS/(TEOS+PholTMS) molar percentage is further increased. This implied that the pore diameter decreases as more organic moieties are incorporated on the pore walls.
- the xPholSO 3 H-SBA-15-p sulfonated materials have similar type IV isotherms with N 2 hysteresis loops corresponding to the cage-like pore structures. It indicates that the channeling pores are partially obstructed.
- ThioTMS was co-condensed with a silica source to form thienyl-functionalized platelet SBA-15, which is denoted by Thio-SBA-15-p. Then, thienyl-functionalized platelet SBA-15 was sulfonated by concentrated H 2 SO 4 to form thienylsulfonic acid-functionalized platelet SBA-15, which is denoted by ThioSO3H-SBA-15-p.
- the preparation conditions are similar to those of phenolsulfonic acid-functionalized platelet SBA-15, except that the PholTMS was replaced by ThioTMS. Therefore, the preparation details of ThioSO 3 H-SBA-15-p are omitted here.
- thienyl-functionalized platelet SBA-15 are abbreviated as xThio-SBA-15-p, where “x” represents the ThioTMS/(TEOS+ThioTMS) molar percentage in the synthesis gels and “p” indicates the platelet morphology.
- the corresponding thienylsulfonic acid-functionalized platelet SBA-15 materials are abbreviated as xThioSO 3 H-SBA-15-p.
- FIG. 5 shows XRD patterns of SBA-15-p, 15Thio-SBA-15-p and 15ThioSO 3 H-SBA-15.
- FIG. 5 Three well-resolved diffraction peaks corresponding to the (100), (110) and (200) planes of 2D-hexagonal p6 mm pore structure are observed for 15Thio-SBA-15-p, but the (110) and (200) peaks are hardly seen for 15ThioSO 3 H-SBA-15.
- FIG. 6 shows the nitrogen adsorption-desorption isotherms of SBA-15-p, ethanol extracted 15Thio-SBA-15-p and dried 15ThioSO 3 H-SBA-15 samples.
- the hysteresis loops of functional materials shifted toward lower P/P 0 region. This implied that the pore diameter decreased as organic moieties were incorporated on the pore walls.
- the sulfonated material has a very small hysteresis loop, indicating that the channeling pores are partially obstructed.
- Biodiesel refers to a vegetable oil- or animal fat-based diesel fuel consisting of long-chain alkyl (methyl, ethyl, or propyl) esters, and is typically made by chemically reacting lipids (e.g., vegetable oil, animal fat) with a short-chain alcohol producing fatty acid esters.
- lipids e.g., vegetable oil, animal fat
- recycled frying oil is used as the source of oil to react with cheap methanol or isopropanol to produce biodiesel.
- large amount of free fatty acids in the recycled frying oil often poison the base catalyst used. Therefore, an acid catalyst has to be used first to pre-treat the recycled frying oil to lower the amount of the free fatty acid in the recycled frying oil. Industry even hope that a strong acid can be use to catalyze the transesterification reaction to simplify the preparation process.
- the aryl sulfonic acid-functionalized solid prepared above are used to catalyze the esterification of palmitic acid (PA) with methanol (MeOH) or iso-propanol (iPrOH) to test the catalytic activity of the aryl sulfonic acid-functionalized solid prepared above.
- PA palmitic acid
- MeOH methanol
- iPrOH iso-propanol
- the phenolsulfonic acid-functionalized SBA-15 (15PholSO 3 H-SBA-15-p) was used as the solid acid catalyst in the liquid phase esterification of palmitic acid (PA) with methanol (MeOH) and iso-propanol (iPrOH) to form methylpalmitate and iso-propylpalmitate as the products, respectively.
- PA palmitic acid
- MeOH methanol
- iPrOH iso-propanol
- the reactions were carried out at the reflux temperatures of the alcohols.
- the esters were found to be the only products in the present reaction condition based on the GC and GC-MS analyses.
- FIG. 7A and FIG. 7B show the conversions of palmitic acid in the esterification of palmitic acid with MeOH and iPrOH, respectively.
- the conversions of palmitic acid are shown as a function of reaction period over 15PholSO3H-SBA-15-p and commercially available Amberlyst-15 resin. It is clearly shown that the conversions of palmitic acid over 15PholSO 3 H-SBA-15-p increase much faster than those over Amberlyst-15 resin. After 12 hours reaction, significantly larger amounts of esters are obtained over 15PholSO 3 H-SBA-15-p than Amberlyst-15 resin.
- Table 5 demonstrates the recyclability of the 15PholSO3H-SBA-15-p catalyst.
- the used catalyst was regenerated by simple filtration and drying at 100° C.
- the catalytic activities of 15PholSO 3 H-SBA-15-p were well retained in comparison to that of the fresh catalyst after recycling for two times.
- PA palmitic acid
- MeOH methanol
- iPrOH iso-propanol
- FIGS. 8A and 8B show that the conversions of PA over xPholSO 3 H-SBA-15-p at 3 h increase slightly with the increase of the phenolsulfonic acid loadings, and reach equilibrium after 12 h.
- the conversions of PA in esterification with iPrOH in FIG. 8B are higher than those with MeOH in FIG. 8A due to higher reflux temperature of iPrOH than MeOH. Nevertheless, the conversions of PA are much lower over Amberlyst-15 resin than over the functionalized SBA-15. After 12 h reaction, significantly larger amounts of esters are obtained over xPholSO 3 H-SBA-15-p than Amberlyst-15 resin.
- the thienylsulfonic acid-functionalized SBA-15 (15ThioSO 3 H-SBA-15-p) was used as the solid acid catalyst in the liquid phase esterification of palmitic acid (PA) with methanol (MeOH) to form methylpalmitate.
- the reaction was carried out at the reflux temperature of MeOH.
- FIG. 9 shows the conversion of palmitic acid as a functional of reaction period over 15ThioSO 3 H-SBA-15-p, in comparison to that over commercially available Amberlyst-15 resin. It is clearly shown that the conversion of palmitic acid over 15ThioSO 3 H-SBA-15-p increases much faster than that over Amberlyst-15 resin. After 9 hours reaction, significantly larger amounts of esters are obtained over 15ThioSO 3 H-SBA-15-p than Amberlyst-15 resin.
- FIG. 10 demonstrates the recyclability of the 15ThioSO 3 H-SBA-15-p catalyst.
- Liquid phase esterification of palmitic acid (PA) with methanol (MeOH) was carried out for 24 hours before the catalyst was separated by filtration and drying at 100° C.
- the recycled catalyst was introduced to a new batch of reactants and the reaction proceeded at the same condition as that of the fresh catalyst.
- the conversions at 12th hour were recorded and shown in FIG. 10 . There are negligible losses of catalytic activities after five times of recycles.
- the ZrO 2 materials functionalized with H 2 SO 4 and phenosulfonic acid groups were used as the solid acid catalysts in the liquid phase esterifications of palmitic acid (PA) with MeOH.
- the reactions were carried out at the reflux temperature of MeOH.
- Methyl palmitate was obtained as the only product in the present reaction condition based on the GC and GC-MS analyses.
- the esterification of palmitic acid (PA) with MeOH was carried out at 60° C. in order to totally dissolve PA in the reaction mixture.
- FIG. 11 shows the esterifications of palmitic acid with methanol over ZrO 2 , SO 3 H—ZrO 2 , and PholSO 3 H—ZrO 2 . It is clearly shown that the esterification rates of palmitic acid with methanol over PholSO 3 H—ZrO 2 are faster than those over ZrO 2 and SO 3 H—ZrO 2 .
- the phenolsulfonic acid-functionalized on different solid supports were used as the catalysts in the liquid phase esterification of palmitic acid (PA) with MeOH and iPrOH to form methylpalmitate and iso-propylpalmitate as the products, respectively.
- the reactions were carried out at the reflux temperature of MeOH.
- FIG. 12A and FIG. 12B show the conversions of palmitic acid in the esterification of palmitic acid with MeOH and iPrOH, respectively.
- the conversions of palmitic acid are shown as a function of reaction period over different phenolsulfonic acid-functionalized solids, in comparison to that over commercially available Amberlyst-15 resin. It is clearly shown that the conversions of palmitic acid over phenolsulfonic acid-functionalized solids increase much faster than those over Amberlyst-15 resin. After 12 hours reaction, significantly larger amounts of esters are obtained over phenolsulfonic acid-functionalized solids than those over Amberlyst-15 resin.
- 15PholSO 3 H-SBA-15-p prepared by co-condensation gives slightly higher conversions than phenolsulfonic acid-functionalized silica gel and zirconia, both are prepared by grafting methods. Nevertheless, the conversions of palmitic acid after 12 hours are very similar for these three phenolsulfonic acid-functionalized solids.
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Abstract
Description
- 1. Technical Field
- The disclosure relates to preparation of solid acids.
- 2. Description of Related Art
- Solid acids are widely used in industry. There are two important types of solid acids, one is acid aluminosilicate zeolite, and the other one is acid resin (such as amberlyst-15 having a polystyrene backbone). However, the pore size of the acid aluminosilicate zeolite is too small to accommodate large medical molecules, and the reaction temperature needed by the acid aluminosilicate zeolite is usually 200-300° C. to present enough acidity. As for the acid resin, the acid resin will be swelled by solvents to affect the effective acid amount, and the thermal stability of the acid resin is kind of poor. Therefore, the acid resin is usually deteriorated after reaction and difficult to be regenerated.
- In one aspect, the present disclosure provides a method of preparing an aryl sulfonic acid-functionalized solid to be a solid acid. The method comprises the following steps. First, a 3-arylpropyl trimethoxysilane is formed by reacting 3-chloropropyl trimethoxysilane with an aromatic compound. Then, an aryl-functionalized solid is formed by grafting the 3-arylpropyl trimethoxysilane onto an inorganic solid material in an organic solvent under a reflux condition. Next, an aryl sulfonic acid-functionalized solid is formed by sulfonating the aryl-functionalized solid by a sulfonating agent.
- According to an embodiment, the aromatic compound is phenol, alkyl phenol, thiophene, or alkyl thiophene.
- According to another embodiment, the inorganic solid material is silica gel or Zr(OH)4 powders.
- According to yet another embodiment, the organic solvent is toluene, xylene, ethylbenzene, or octane.
- According to yet another embodiment, the aryl-functionalized solid is sulfonated at 80° C. for 24 hours.
- According to yet another embodiment, the sulfonating agent is concentrated sulfuric acid, a mixture of oleum and concentrated sulfuric acid, or SO2Cl2.
- In another aspect, the present disclosure provides a method of preparing an aryl sulfonic acid-functionalized solid to be a solid acid. The method comprises the following steps. First, a 3-arylpropyl trimethoxysilane is formed by reacting 3-chloropropyl trimethoxysilane with an aromatic compound. Then, an aryl-functionalized solid is formed by co-condensing the 3-arylpropyl trimethoxysilane and a precursor of an inorganic solid by a hydrothermal reaction. Next, an aryl sulfonic acid-functionalized solid is formed by sulfonating the aryl-functionalized solid in concentrated sulfuric acid.
- According to an embodiment, the precursor of the inorganic solid is tetramethyl orthosilicate, tetraethyl orthosilicate, or sodium silicate.
- According to another embodiment, the inorganic solid comprises a porous silica material.
- According to yet another embodiment, the porous silica material is SBA-15 or MCM41.
- According to yet another embodiment, a reactant composition of the hydrothermal reaction comprises a pore directing agent, the precursor of the inorganic solid, acid, and water in a molar ratio of 0.02:1:0.05-0.3:7-9:179-230.
- According to yet another embodiment, the pore directing agent is EO20PO70EO20, EO40PO60EO40, EO100PO65EO100, or cetyl trimethylammonium bromide.
- According to yet another embodiment, the acid is HCl, HNO3, H2SO4, or HClO4.
- According to yet another embodiment, the reactant composition of the hydrothermal reaction further comprises Zr(IV) ions, and atomic ratio of Zr(IV):Si is in 0-0.1.
- According to yet another embodiment, a source of the Zr(IV) ions is ZrOCl2, ZrSO4, ZrO(NO3)2, or zirconium(IV) acetate hydroxide.
- According to yet another embodiment, a reactant composition of the hydrothermal reaction comprises 0.017 EO20PO70EO20:1 tetraethyl orthosilicate:0.05-0.43 3-arylpropyl trimethoxysilane:0.05 ZrOCl2.8H2O:7.9 HCl:220 H2O in molar ratio.
- According to yet another embodiment, the aryl-functionalized solid is sulfonated at 80° C. for 24 hours.
- According to yet another embodiment, the sulfonating agent is concentrated sulfuric acid, a mixture of oleum and concentrated sulfuric acid, or SO2O2.
- The foregoing presents a simplified summary of the disclosure in order to provide a basic understanding to the reader. This summary is not an extensive overview of the disclosure and it does not identify key/critical elements of the present disclosure or delineate the scope of the present disclosure. Its sole purpose is to present some concepts disclosed herein in a simplified form as a prelude to the more detailed description that is presented later. Many of the attendant features will be more readily appreciated as the same becomes better understood by reference to the following detailed description considered in connection with the accompanying drawings.
-
FIG. 1 is the TGA profile of PholSO3H—SiO2. -
FIG. 2 shows the TGA profiles of the ZrO2 materials before and after functionalized with H2SO4, phenol and phenolsulfonic acid groups. -
FIGS. 3A and 3B are the small-angle XRD patterns of ethanol extracted xPhol-SBA-15-p materials prepared with various PholTMS/(TEOS+PholTMS) molar percentages and those after sulfonation, respectively. -
FIGS. 4A and 4B are the nitrogen adsorption-desorption isotherms of ethanol extracted xPhol-SBA-15-p materials prepared with various PholTMS/(TEOS+PholTMS) molar percentages and those after sulfonation, respectively. -
FIG. 5 shows XRD patterns of SBA-15-p, 15Thio-SBA-15-p and 15ThioSO3H-SBA-15. -
FIG. 6 shows the nitrogen adsorption-desorption isotherms of SBA-15-p, ethanol extracted 15Thio-SBA-15-p and dried 15ThioSO3H-SBA-15 samples. -
FIGS. 7A andFIG. 7B show the conversions of palmitic acid in the esterification of palmitic acid with MeOH and iPrOH, respectively. -
FIGS. 8A and 8B show the catalytic activities of SBA-15 functionalized with various amounts of phenolsulfonic acid (xPholSO3H-SBA-15-p, x=15, 20, 25, 30) in the liquid phase esterification of palmitic acid (PA) with methanol (MeOH) and iso-propanol (iPrOH) to form methylpalmitate and iso-propylpalmitate as the products, respectively. -
FIG. 9 shows the conversion of palmitic acid as a function of reaction period over 15ThioSO3H-SBA-15-p, in comparison to that over commercially available Amberlyst-15 resin. -
FIG. 10 demonstrates the recyclability of the 15ThioSO3H-SBA-15-p catalyst. -
FIG. 11 shows the esterification of palmitic acid with methanol over ZrO2, SO3H—ZrO2, and PholSO3H—ZrO2. -
FIGS. 12A and 12B show the conversions of palmitic acid over different solid acid catalysts in the esterification of palmitic acid with MeOH and iPrOH, respectively. - In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. It will be apparent, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are schematically shown in order to simplify the drawing.
- In scheme 1, 3-chloropropyl trimethoxysilane was used as a starting material to perform a Friedel-Crafts reaction with an aromatic compound, such as phenol, alkyl phenol, thiophene, or alkyl thiophene, to obtain 3-arylpropyl trimethoxysilane.
- Next, the 3-arylpropyl trimethoxysilane can be used to functionalize an inorganic solid material, such as a silica material, a zirconia material, a titania material, or other metal oxide materials, to obtain an aryl-functionalized solid. The silica material above can be silica gel or a porous silica material. This step can be performed by a grafting method or a co-condensation method.
- In the grafting method, an inorganic solid material having free —OH functional groups on its surface is needed. The 3-arylpropyl trimethoxysilane above is used to react with the —OH group of the inorganic solid material in an organic solvent under a reflux condition for 1-48 hours, such as atleast 24 hours. The solid material can be silica gel or Zr(OH)4 powder. The Zr(OH)4 powder is a precursor of zirconia powder. The organic solvent can be an anhydrous organic solvent with boiling points higher than 80° C., such as toluene, xylene, ethylbenzene, or octane, for example.
- In the co-condensation method, 3-arylpropyl trimethoxysilane and a precursor of an inorganic solid is co-condensed in an aqueous solution containing a pore-directing agent to form an aryl-functionalized solid by hydrothermal reaction. The inorganic solid can be a porous silica material, such as SBA-15 or MCM41, for example.
- In a typical method of preparing an aryl-functionalized porous silica material, a pore directing agent, a silica source, acid, and water are needed for the hydrothermal reaction. The molar ratio of the pore directing agent, the silica source, the 3-arylpropyl trimethoxysilane, the acid, and water can be 0.02:1:0.05-0.45:7-9:179-230, for example. The pore directing agent can be EO20PO70EO20, EO40PO60EO40, EO100PO65EO100, or cetyl trimethylammonium bromide, for example. The silica source can be tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), or sodium silicate, for example. The acid can be HCl, HNO3, H2SO4, or HClO4, for example. The hydrothermal reaction is usually performed at a temperature of 90-100° C. under static condition for 6-72 hours, such as at least 24 hours.
- For synthesizing above-mentioned SBA-15 with short channeling pores, a neutral pore directing agent and Zr(IV) ions are used. The neutral pore directing agent can be EO20PO70EO20. The source of the Zr(IV) ions can be ZrOCl2, ZrSO4, ZrO(NO3)2, or zirconium(IV) acetate hydroxide. The atomic ratio of Zr(IV):Si is in 0-0.1, such as 0.05.
- Finally, the aromatic ring of the aryl-functionalized solid is sulfonated by a sulfonating agent to obtain an aryl sulfonic acid-functionalized solid as a solid acid. The sulfonating agent can be concentrated sulfuric acid, a mixture of oleum and concentrated sulfuric acid, or SO2Cl2. The sulfonation can be performed at 60-90° C. for 6-36 hours.
- Some working examples are described below.
- First, two 3-arylpropyl trimethoxysilanes were synthesized as examples. One was 3-(2-hydroxy-5-methylphenyl)-propyltrimethoxysilane, and the other was 3-thienyl-propyltrimethoxysilane.
-
- As shown in
Scheme 2, a new 3-arylpropyl trimethoxysilane compound, 3-(2-hydroxy-5-methylphenyl)-propyltrimethoxysilane (abbreviated PholTMS) was synthesized. 60 g of p-cresol and 100 g of 3-chloropropyltrimethoxysilane were mixed under reflux for 24 hours. The product was confirmed by NMR spectrum, and the yield was more than 99%. 1H NMR of PholTMS (400 MHz, CD3OD): δ 0.65 (t, 2H), 1.56 (p, 2H), 2.34 (s, 3H), 2.63 (t, 2H), 3.58 (s, 9H), 6.5-7 (m, 3H). -
- As shown in
Scheme 3, a new 3-arylpropyl trimethoxysilane compound, 3-thienyl-propyltrimethoxysilane (abbreviated ThioTMS) was synthesized. 60 g of thiophene, 100 g of 3-chloropropyltrimethoxysilane and 0.1 g of anhydrous AlCl3 were mixed under reflux for 24 hours. The product was confirmed by NMR spectrum, and the yield was more than 99%. 1H NMR of ThioTMS (400 MHz, CD3OD): δ 0.65 (t, 2H), 1.56 (p, 2H), 2.66 (t, 2H), 3.58 (s, 9H), 6.5-7 (m, 2H), 7.35 (d, 1H). - In this embodiment, PholTMS was grafted onto silica gel to form phenol-functionalized silica gel, which is denoted by Phol-SiO2. Then, phenol-functionalized silica gel was sulfonated by concentrated H2SO4 to form phenolsulfonic acid-functionalized silica gel, which is denoted by PholSO3H—SiO2.
- Accordingly, a phenol-functionalized silica gel was prepared first. In this step, 2.0 mL of PholTMS synthesized above was reacted with 4 g of silica gel (Sigma Aldrich) in 10 mL of toluene under reflux for 24 hours. Then, the obtained solid product Phol-SiO2 was filtered and dried at 100° C.
- Next, a phenolsulfonic acid-functionalized silica gel was prepared. In this step, 4 g of Phol-SiO2 powder in 40 mL of concentrated H2SO4 was heated at 80° C. for 24 hours. After cooling and diluting the mixture with 150 mL of water, the solid product PholSO3H—SiO2 was collected by filtration and dried at 100° C.
- Some physicochemical properties of pristine silica gel and PholSO3H—SiO2 were analyzed. The analyzed physicochemical properties included sulfur content, acid capacity, specific surface area (SBET), pore volume (VTotal), pore diameter (φP), and thermogravimetric analysis (TGA).
- Nitrogen physisorption isotherms were used to analyze specific surface area (SBET), pore volume (VTotal), pore diameter (φP) of the samples. The Nitrogen physisorption isotherms were taken at liquid nitrogen temperature (77 K) by using a Micrometerics TriStar 3000 system. Prior to the experiments, the samples were outgassed at 120° C. for 6-8 h under vacuum (10−3 Torr).
- The acid capacities of the samples were determined by acid-base titration using NaCl solution as an ion-exchange agent. A 50 mg sample in powder form was ion-exchanged with 20 mL 2M NaCl solution at ambient temperature for at least 24 h, followed by filtration and washing with 3 mL of deionized water. The filtrates were then titrated with a 0.01 M NaOH solution.
- The obtained data are shown in Table 1 and
FIG. 1 . In Table 1, the acid capacity of PholSO3H—SiO2 was close to the sulfur content, and both are around 1 mmol/g.FIG. 1 is the TGA profile of PholSO3H—SiO2. Before 100° C., about 15% weight loss of adsorbed moisture was desorbed. This result shows that the PholSO3H—SiO2 was hygroscopic. Above 340° C., the weight loss was attributed to the decomposition of phenol and sulfonic acid groups. -
TABLE 1 Some physicochemical properties of pristine silica gel and PholSO3H—SiO2 Acid S Content[a] Capacity[b] SBET [c] VTotal [d] ΦP [e] Sample (mmol/g) (mmol H+/g) (m2/g) (cm3/g) (nm) Silica gel 0 — 600 — — PholSO3H—SiO2 0.995 0.965 157 0.15 18.5 [a]Determined by HCS elemental analysis using a Heraeus VarioEL analyzer [b]Determined by acid-base titration [c] Calculated by Brunauer-Emmett-Teller (BET) method in the P/P0 range around 0.05-0.25 [d] Determined by Barrett-Joyner-Halenda (BJH) method using the N2 desorption isotherms [e]Determined by Barrett-Joyner-Halenda (BJH) method using the N2 desorption isotherms - In this embodiment, PholTMS was co-condensed with a zirconia source, such as Zr(OH)4, to form phenol-functionalized zirconia, which is denoted by Phol-ZrO2. Then, phenol-functionalized zirconia was sulfonated by concentrated H2SO4 to form phenolsulfonic acid-functionalized zirconia, which is denoted by PholSO3—ZrO2.
- Accordingly, phenol-functionalized zirconia was prepared first. The preparation of phenol-functionalized zirconia was performed by grafting PholTMS onto the surface of Zr(OH)4 powder, which is a precursor of zirconia. In the preparation of phenol-functionalized zirconia, 1 g of PholTMS was reacted with 1 g of Zr(OH)4 powder in 20 mL toluene solvent under reflux for 24 h. The solid product Phol-ZrO2 was collected by filtration and drying at 100° C.
- Next, phenolsulfonic acid-functionalized zirconia was prepared. 1 g of Phol-ZrO2 powders with a mixture of 5 mL oleum (i.e. fuming sulfuric acid) and 20 mL concentrated H2SO4 were heated at 80° C. for 24 h. After cooling and diluting the mixture with 1 L of deionized water, the solid product PholSO3H—ZrO2 was filtered and dried at 100° C.
- For comparison, sulfonic acid-functionalized zirconia (denoted by SO3H—ZrO2) was also prepared. 1 g of Zr(OH)4 was reacted directly with a mixture of 5 mL oleum and 20 mL concentrated H2SO4 at 80° C. for 10 hours. After cooling and diluting the mixture with 1 L of deionized water, the solid product was filtered, dried at 200° C. for 10 h.
-
FIG. 2 shows the TGA profiles of the ZrO2 materials before and after functionalized with H2SO4, phenol and phenosulfonic acid groups, respectively. The materials functionalized with phenol (Phol-ZrO2) and phenosulfonic acid groups (PholSO3H—ZrO2) are more hygroscopic because they adsorb larger amounts of moisture, which was desorbed below 100° C. Moreover, these two samples of Phol-ZrO2 and PholSO3H—ZrO2 have additional weight losses at ca. 350° C. It should correspond to the decomposition of phenol groups. - SBA-15 is a mesoporous silica material. In this embodiment, PholTMS was co-condensed with a silica source to form phenol-functionalized platelet SBA-15, which is denoted by Phol-SBA-15-p. Then, phenol-functionalized platelet SBA-15 was sulfonated by concentrated H2SO4 to form phenolsulfonic acid-functionalized platelet SBA-15, which is denoted by PholSO3H-SBA-15-p.
- Accordingly, phenol-functionalized SBA-15 was prepared first. The preparation of phenol-functionalized SBA-15 was performed by co-condensing a silica source, such as tetraethyl orthosilicate (TEOS), and PholTMS in the presence of Zr(IV) ions.
- In a typical synthesis procedure of phenol-functionalized SBA-15, 2.0 g of pore-directing agent such as EO20PO70EO20 (Aldrich, Pluronic P123, Mn=5800) and 0.33 g of zirconyl chloride octahydrate (ZrOCl2.8H2O, Acros) were dissolved in 80 g of 2.0 M HCl (Acros) aqueous solution at 35° C. To this solution, 4.2 g of TEOS (Acros) was added and hydrolyzed for 2 hours before the addition of various amounts of PholTMS. It should be noticed that TEOS prehydrolysis in the acidic synthesis solution containing Zr(IV) ions before the introduction of PholTMS was necessary in order to obtain a well-ordered pore structure and platelet morphology. The reactant compositions were 0.017 P123:1 TEOS:0.05-0.45 PholTMS:0.05 ZrOCl2.8H2O:7.9 HCl:220 H2O, in molar ratio.
- The synthesized gel sealed in a polypropylene bottle was stirred at 35° C. for 24 h and hydrothermally heated under static conditions at 90° C. for another 24 h. A solid precipitate collected by filtration was washed thoroughly with deionized water, followed by drying at 50° C. overnight. P123 was removed from the solid materials by ethanol extraction at 78° C. for 1 day. The resulting phenol-functionalized SBA-15 are designated as xPhol-SBA-15-p, where “x” represents the PholTMS/(TEOS+PholTMS) molar percentage in the synthesis gels and “p” indicates the platelet morphology.
- Some physicochemical properties of the resulting xPhol-SBA-15-p solids are shown in Table 2. In Table 2, the BET surface area (SBET), pore volume (VTotal) and pore diameter (φP) values decreased with the increase of PholTMS concentration in the synthesis solution. This result indicated that the self-assemble process of pore directing agent P123 and silica precursor was interfered by PholTMS. The maximal amount of phenol groups incorporated in platelet SBA-15 by this co-condensation method is about 1.4 mmol/g.
-
TABLE 2 Some physicochemical properties of xPhol-SBA-15-p F.G. content [a] (mmol/g) SBET [d] VTotal [e] ΦP [f] Sample gel[b] solid[c] (m2/g) (cm3/g) (nm) SBA-15- p 0 — 823 0.98 7.0 15Phol-SBA-15-p 1.05 1.012 504 0.67 5.2 20Phol-SBA-15-p 1.40 1.355 475 0.46 3.6/4.1[g] 25Phol-SBA-15-p 1.75 1.421 416 0.41 3.6/4.0[g] 30Phol-SBA-15-p 2.10 1.433 377 0.40 3.5/4.0[g] [a]Functional group content [b]Functional group content in the synthesis gel. [c]Determined by HC elemental analysis [d]Calculated by Brunauer-Emmett-Teller (BET) method in the P/P0 range around 0.05-0.25 [e]Determined by Barrett-Joyner-Halenda (BJH) method using the N2 desorption isotherms [f]Determined by Barrett-Joyner-Halenda (BJH) method using the N2 desorption isotherms [g]Peak maxima at the pore size distribution profiles - Next, phenolsulfonic acid-functionalized platelet SBA-15 was prepared. 4 g of xPhol-SBA-15-p powder in 40 mL concentrated H2SO4 was heated at 80° C. for 24 hours. After cooling and diluting the mixture with 150 mL of water, the solid product was filtered and dried at 100° C. The resultant products, phenolsulfonic acid-functionalized platelet SBA-15, are termed as xPholSO3H-SBA-15, where x is 15, 20, 25, or 30.
- Some physicochemical properties of the resulting phenolsulfonic acid-functionalized SBA-15 are shown in Table 3. The sulfur contents of xPholSO3H-SBA-15-p materials determined by elemental analysis are close to the phenol content, implying that each phenol group undergoes sulfonation. On the other hand, the BET surface areas of all the sulfonated materials decrease to ca. 330-380 m2/g, VTotal values to ca. 0.3 cm3/g and φp values to ca. 3.5 nm. The values are little influenced by the acid loadings.
-
TABLE 3 Some physicochemical properties of the resulting phenolsulfonic acid-functionalized SBA-15 F.G. content (mmol/g) [a] Phe- S Con- SBET [d] VTotal [e] ΦP [f] Sample nol[b] tent[c] (m2/g) (cm3/g) (nm) 15PholSO3H-SBA-15-p 1.012 1.067 387 0.32 3.5 20PholSO3H-SBA-15-p 1.355 1.380 331 0.29 3.6 25PholSO3H-SBA-15-p 1.421 1.437 340 0.32 3.6 30PholSO3H-SBA-15-p 1.433 1.444 330 0.33 3.5 [a] Functional group content [b]Determined by HC elemental analysis [c]Determined by HCS elemental analysis [d]Calculated by Brunauer-Emmett-Teller (BET) method in the P/P0 range around 0.05-0.25 [e]Determined by Barrett-Joyner-Halenda (BJH) method using the N2 desorption isotherms [f]Determined by Barrett-Joyner-Halenda (BJH) method using the N2 desorption isotherms -
FIGS. 3A and 3B are the small-angle XRD patterns of ethanol extracted xPhol-SBA-15-p materials prepared with various PholTMS/(TEOS+PholTMS) molar percentages and those after sulfonation, respectively. InFIG. 3A , three well-resolved diffraction peaks corresponding to the (100), (110) and (200) planes of 2D-hexagonal p6 mm pore structure are observed on xPhol-SBA-15-p materials, especially those of low PholTMS contents. However, inFIG. 3B , these diffraction peaks are almost disappeared after suflonation reaction. This phenomenon suggested that the ordered pore structure is no longer present after treating the porous materials in sulfonic acid of such a high concentration. -
FIGS. 4A and 4B are the nitrogen adsorption-desorption isotherms of ethanol extracted xPhol-SBA-15-p materials prepared with various PholTMS/(TEOS+PholTMS) molar percentages and those after sulfonation, respectively. InFIG. 4A , for the 15Phol-SBA-15-p material prepared with PholTMS/(TEOS+PholTMS) molar percentage of 15%, the characteristic type IV isotherm with H1 hysteresis loop was seen at P/P0 of 0.5-0.7. This indicated that large mesopores with narrow pore size distributions were present, and the 15Phol-SBA-15-p material is similar to the pure SBA-15-p material. The hysteresis loops shift toward low P/P0 region as the PholTMS/(TEOS+PholTMS) molar percentage is further increased. This implied that the pore diameter decreases as more organic moieties are incorporated on the pore walls. InFIG. 4B , the xPholSO3H-SBA-15-p sulfonated materials have similar type IV isotherms with N2 hysteresis loops corresponding to the cage-like pore structures. It indicates that the channeling pores are partially obstructed. - In this embodiment, ThioTMS was co-condensed with a silica source to form thienyl-functionalized platelet SBA-15, which is denoted by Thio-SBA-15-p. Then, thienyl-functionalized platelet SBA-15 was sulfonated by concentrated H2SO4 to form thienylsulfonic acid-functionalized platelet SBA-15, which is denoted by ThioSO3H-SBA-15-p.
- The preparation conditions are similar to those of phenolsulfonic acid-functionalized platelet SBA-15, except that the PholTMS was replaced by ThioTMS. Therefore, the preparation details of ThioSO3H-SBA-15-p are omitted here. In addition, thienyl-functionalized platelet SBA-15 are abbreviated as xThio-SBA-15-p, where “x” represents the ThioTMS/(TEOS+ThioTMS) molar percentage in the synthesis gels and “p” indicates the platelet morphology. The corresponding thienylsulfonic acid-functionalized platelet SBA-15 materials are abbreviated as xThioSO3H-SBA-15-p.
- Some physical properties of 15Thio-SBA-15-p and 15ThioSO3H-SBA-15-p are shown in Table 4. The S content of 15ThioSO3H-SBA-15-p is almost doubled after sulfonation. This implied that each thienyl group undergoes substitution of one sulfonyl acid group. On the other hand, the BET surface area, total pore volume and pore diameter decrease after the incorporation of thienyl moieties, and they were further decreased after sulfonation reaction.
-
TABLE 4 Some physical properties of SBA-15-p, 15Thio-SBA-15-p and 15ThioSO3H-SBA-15-p S/Si (molar ratio) SBET [c] VTotal [d] ΦP [e] Sample gel[a] solid[b] (m2/g) (cm3/g) (nm) SBA-15- p 0 — 823 0.98 7.0 15Thio-SBA-15-p 0.15 0.10 513 0.65 5.2 15ThioSO3H-SBA-15-p — 0.22 362 0.32 3.2 [a]S content in the synthesis gel [b]Determined by CHS elemental analysis [c]Calculated by Brunauer-Emmett-Teller (BET) method in the P/P0 range around 0.05-0.25 [d]Determined by Barrett-Joyner-Halenda (BJH) method using the N2 desorption isotherms [e]Determined by Barrett-Joyner-Halenda (BJH) method using the N2 desorption isotherms -
FIG. 5 shows XRD patterns of SBA-15-p, 15Thio-SBA-15-p and 15ThioSO3H-SBA-15. InFIG. 5 . Three well-resolved diffraction peaks corresponding to the (100), (110) and (200) planes of 2D-hexagonal p6 mm pore structure are observed for 15Thio-SBA-15-p, but the (110) and (200) peaks are hardly seen for 15ThioSO3H-SBA-15. -
FIG. 6 shows the nitrogen adsorption-desorption isotherms of SBA-15-p, ethanol extracted 15Thio-SBA-15-p and dried 15ThioSO3H-SBA-15 samples. In comparison to that of siliceous SBA-15-p, the hysteresis loops of functional materials shifted toward lower P/P0 region. This implied that the pore diameter decreased as organic moieties were incorporated on the pore walls. On the other hand, the sulfonated material has a very small hysteresis loop, indicating that the channeling pores are partially obstructed. - Biodiesel refers to a vegetable oil- or animal fat-based diesel fuel consisting of long-chain alkyl (methyl, ethyl, or propyl) esters, and is typically made by chemically reacting lipids (e.g., vegetable oil, animal fat) with a short-chain alcohol producing fatty acid esters. At present, recycled frying oil is used as the source of oil to react with cheap methanol or isopropanol to produce biodiesel. However, large amount of free fatty acids in the recycled frying oil often poison the base catalyst used. Therefore, an acid catalyst has to be used first to pre-treat the recycled frying oil to lower the amount of the free fatty acid in the recycled frying oil. Industry even hope that a strong acid can be use to catalyze the transesterification reaction to simplify the preparation process.
- Accordingly, the aryl sulfonic acid-functionalized solid prepared above are used to catalyze the esterification of palmitic acid (PA) with methanol (MeOH) or iso-propanol (iPrOH) to test the catalytic activity of the aryl sulfonic acid-functionalized solid prepared above.
- The phenolsulfonic acid-functionalized SBA-15 (15PholSO3H-SBA-15-p) was used as the solid acid catalyst in the liquid phase esterification of palmitic acid (PA) with methanol (MeOH) and iso-propanol (iPrOH) to form methylpalmitate and iso-propylpalmitate as the products, respectively. The reactions were carried out at the reflux temperatures of the alcohols. The esters were found to be the only products in the present reaction condition based on the GC and GC-MS analyses.
-
FIG. 7A andFIG. 7B show the conversions of palmitic acid in the esterification of palmitic acid with MeOH and iPrOH, respectively. InFIGS. 7A and 7B , the conversions of palmitic acid are shown as a function of reaction period over 15PholSO3H-SBA-15-p and commercially available Amberlyst-15 resin. It is clearly shown that the conversions of palmitic acid over 15PholSO3H-SBA-15-p increase much faster than those over Amberlyst-15 resin. After 12 hours reaction, significantly larger amounts of esters are obtained over 15PholSO3H-SBA-15-p than Amberlyst-15 resin. - Table 5 demonstrates the recyclability of the 15PholSO3H-SBA-15-p catalyst. The used catalyst was regenerated by simple filtration and drying at 100° C. The catalytic activities of 15PholSO3H-SBA-15-p were well retained in comparison to that of the fresh catalyst after recycling for two times.
-
TABLE 5 Recyclability of the 15PholSO3H-SBA-15-p catalyst Number Conversion of palmitic acid (PA) at 3 h (%) of recycling[a] with methanol with iso-propanol Fresh 74.7 82.2 1st 73.3 81.0 2nd 73.1 81.3 [a]Recycling the catalyst after 24 h catalytic reaction -
FIGS. 8A and 8B show the catalytic activities of SBA-15 functionalized with various amounts of phenolsulfonic acid (xPholSO3H-SBA-15-p, x=15, 20, 25, 30) in the liquid phase esterification of palmitic acid (PA) with methanol (MeOH) and iso-propanol (iPrOH) to form methylpalmitate and iso-propylpalmitate as the products, respectively. The conversions of PA at 3 h and 12 h reaction period over PholSO3H-SBA-15-p are compared with that over commercially available Amberlyst-15 resin. -
FIGS. 8A and 8B show that the conversions of PA over xPholSO3H-SBA-15-p at 3 h increase slightly with the increase of the phenolsulfonic acid loadings, and reach equilibrium after 12 h. The conversions of PA in esterification with iPrOH inFIG. 8B are higher than those with MeOH inFIG. 8A due to higher reflux temperature of iPrOH than MeOH. Nevertheless, the conversions of PA are much lower over Amberlyst-15 resin than over the functionalized SBA-15. After 12 h reaction, significantly larger amounts of esters are obtained over xPholSO3H-SBA-15-p than Amberlyst-15 resin. - The thienylsulfonic acid-functionalized SBA-15 (15ThioSO3H-SBA-15-p) was used as the solid acid catalyst in the liquid phase esterification of palmitic acid (PA) with methanol (MeOH) to form methylpalmitate. The reaction was carried out at the reflux temperature of MeOH.
-
FIG. 9 shows the conversion of palmitic acid as a functional of reaction period over 15ThioSO3H-SBA-15-p, in comparison to that over commercially available Amberlyst-15 resin. It is clearly shown that the conversion of palmitic acid over 15ThioSO3H-SBA-15-p increases much faster than that over Amberlyst-15 resin. After 9 hours reaction, significantly larger amounts of esters are obtained over 15ThioSO3H-SBA-15-p than Amberlyst-15 resin. -
FIG. 10 demonstrates the recyclability of the 15ThioSO3H-SBA-15-p catalyst. Liquid phase esterification of palmitic acid (PA) with methanol (MeOH) was carried out for 24 hours before the catalyst was separated by filtration and drying at 100° C. The recycled catalyst was introduced to a new batch of reactants and the reaction proceeded at the same condition as that of the fresh catalyst. The conversions at 12th hour were recorded and shown inFIG. 10 . There are negligible losses of catalytic activities after five times of recycles. - The ZrO2 materials functionalized with H2SO4 and phenosulfonic acid groups were used as the solid acid catalysts in the liquid phase esterifications of palmitic acid (PA) with MeOH. The reactions were carried out at the reflux temperature of MeOH. Methyl palmitate was obtained as the only product in the present reaction condition based on the GC and GC-MS analyses. The esterification of palmitic acid (PA) with MeOH was carried out at 60° C. in order to totally dissolve PA in the reaction mixture.
-
FIG. 11 shows the esterifications of palmitic acid with methanol over ZrO2, SO3H—ZrO2, and PholSO3H—ZrO2. It is clearly shown that the esterification rates of palmitic acid with methanol over PholSO3H—ZrO2 are faster than those over ZrO2 and SO3H—ZrO2. - The phenolsulfonic acid-functionalized on different solid supports were used as the catalysts in the liquid phase esterification of palmitic acid (PA) with MeOH and iPrOH to form methylpalmitate and iso-propylpalmitate as the products, respectively. The reactions were carried out at the reflux temperature of MeOH.
-
FIG. 12A andFIG. 12B show the conversions of palmitic acid in the esterification of palmitic acid with MeOH and iPrOH, respectively. InFIGS. 12A and 12B , the conversions of palmitic acid are shown as a function of reaction period over different phenolsulfonic acid-functionalized solids, in comparison to that over commercially available Amberlyst-15 resin. It is clearly shown that the conversions of palmitic acid over phenolsulfonic acid-functionalized solids increase much faster than those over Amberlyst-15 resin. After 12 hours reaction, significantly larger amounts of esters are obtained over phenolsulfonic acid-functionalized solids than those over Amberlyst-15 resin. - Among the three phenolsulfonic acid-functionalized solids, 15PholSO3H-SBA-15-p prepared by co-condensation gives slightly higher conversions than phenolsulfonic acid-functionalized silica gel and zirconia, both are prepared by grafting methods. Nevertheless, the conversions of palmitic acid after 12 hours are very similar for these three phenolsulfonic acid-functionalized solids.
- Accordingly, various aryl sulfonic acid-functionalized solids were prepared above. The catalytic activity of the prepared aryl sulfonic acid-functionalized solids was also test, and it showed that the catalytic activity was better than commercialize Amberlyst-15 resin. This result shows that the prepared aryl sulfonic acid-functionalized solids are suitable to be used as a strong solid acid.
- All the features disclosed in this specification (including any accompanying claims, abstract, and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, each feature disclosed is one example only of a generic series of equivalent or similar features.
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US7815883B2 (en) * | 2008-12-23 | 2010-10-19 | National Taiwan University | Preparation of organic-functionalized mesoporous silica with platelet morphology and short mesochannels |
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US8624035B2 (en) * | 2008-10-22 | 2014-01-07 | Universita' Degli Studi Di Torino | Functionalized cyanine having a silane linker arm, a method of preparing thereof and uses thereof |
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