CN113831238B - Method for preparing methyl lactate by catalytic conversion of carbohydrate - Google Patents
Method for preparing methyl lactate by catalytic conversion of carbohydrate Download PDFInfo
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- CN113831238B CN113831238B CN202010587401.7A CN202010587401A CN113831238B CN 113831238 B CN113831238 B CN 113831238B CN 202010587401 A CN202010587401 A CN 202010587401A CN 113831238 B CN113831238 B CN 113831238B
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- molecular sieve
- scm
- methyl lactate
- carbohydrate
- reaction
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 59
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 title claims abstract description 54
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 title claims abstract description 54
- 229940057867 methyl lactate Drugs 0.000 title claims abstract description 54
- 150000001720 carbohydrates Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title claims description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 137
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 137
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 56
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 50
- 239000008103 glucose Substances 0.000 claims description 50
- 239000002253 acid Substances 0.000 claims description 38
- 235000014633 carbohydrates Nutrition 0.000 claims description 20
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 8
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 7
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 7
- 229930091371 Fructose Natural products 0.000 claims description 6
- 239000005715 Fructose Substances 0.000 claims description 6
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229920001202 Inulin Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 2
- 229940029339 inulin Drugs 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 42
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 26
- 238000003756 stirring Methods 0.000 description 25
- 101000804764 Homo sapiens Lymphotactin Proteins 0.000 description 22
- 102100035304 Lymphotactin Human genes 0.000 description 22
- 239000002243 precursor Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 19
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 238000003795 desorption Methods 0.000 description 14
- 238000009835 boiling Methods 0.000 description 13
- 239000007810 chemical reaction solvent Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- 238000009616 inductively coupled plasma Methods 0.000 description 10
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910007928 ZrCl2 Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- PEGCFRJASNUIPX-UHFFFAOYSA-L ditert-butyltin(2+);dichloride Chemical compound CC(C)(C)[Sn](Cl)(Cl)C(C)(C)C PEGCFRJASNUIPX-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 238000002119 pyrolysis Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing methyl lactate by catalytically converting carbohydrate. The method adopts an A-SCM-1 molecular sieve as a catalyst, and obtains methyl lactate through one-step catalytic reaction after mixing a substrate carbohydrate with methanol. The method can realize high-efficiency conversion of the carbohydrate under mild reaction conditions, and the product methyl lactate has high selectivity, and the catalyst has outstanding circulation stability and good industrial application prospect.
Description
Technical Field
The invention relates to a method for preparing methyl lactate by catalytically converting carbohydrate.
Background
In recent years, in order to alleviate the energy crisis problem caused by shortage of fossil resources, a series of platform compounds are prepared from primary biomass, and then conversion strategies of preparing fine chemicals and biofuels through upgrading means are attracting attention of scientists. Methyl lactate is used as an important platform compound, is widely applied to other fields such as perfume, additive, plasticizer, medicine, energy and the like, and has very wide industrial application value. How to prepare methyl lactate with high selectivity from biomass is a hot spot of research today.
The traditional synthesis method of methyl lactate is to esterify lactic acid and methanol by using sulfuric acid as a catalyst. Wherein sulfuric acid is easy to cause equipment corrosion, can bring about environmental pollution, and has high separation cost; lactic acid is also prone to side reactions such as intramolecular and intermolecular dehydration, polymerization carbonization, etc., and generates a large amount of three wastes. In another method, methyl lactate is prepared from carbohydrate in supercritical methanol solution through catalytic conversion, and glucose is taken as an example, and the reaction mechanism is as follows:
the metal chloride can be used as Lewis acid (L acid) catalyst for glucose isomerization and fructose reverse aldol condensation reaction. Zhou et al (Journal of Molecular CATALYSIS A: chemical,2014, 388-389, 74-80) first examined the reactivity of transition metal chlorides such as SnCl 4、AlCl3 and CrCl 3, catalyzing glucose. The SnCl 4 catalyst was found to show the best activity after 2.5h at 160 ℃, glucose conversion was complete and methyl lactate yield was 28%. Although the metal chloride shows good catalytic activity, it causes corrosion of equipment to some extent, and causes problems of environmental pollution and excessive separation cost. Thus, researchers have increasingly used readily-separable solid acid catalysts to catalyze the production of methyl lactate from glucose.
Taarning (Science, 2010,328,602-605) research on preparing Sn-Beta catalyst for converting monosaccharide or disaccharide into methyl lactate. Glucose is used as a substrate, and the yield of methyl lactate reaches 43% under the reaction condition of 160 ℃ and 16 hours. Carlos et al (Journal of Chemical Technology and Biotechnology,2014,89,1344-1350) have studied the catalytic performance of Sn-MCM-41 molecular sieves in the conversion of glucose to methyl lactate. Under the reaction condition of 160 ℃ and 20 hours, the Sn-MCM-41 (Si/Sn=55) catalyst shows the optimal catalytic performance, and the yield of the methyl lactate reaches 43.6 percent. But the selectivity of methyl lactate is still low by adopting Sn-Beta and Sn-MCM-41 molecular sieves.
Melero et al (Catalysis today.2018, 304, 80-88) realized one-step preparation of propyl lactate from xylose by using Zr-USY molecular sieve as catalyst and isopropanol as solvent. However, the yield of the target product methyl lactate is relatively low, the maximum yield is only about 9%, and the catalyst has serious carbon deposition and quick deactivation. The Yang et al (Journal of catalysis.2016, 333, 207-216) designed and prepared mesoporous Zr-SBA-15 catalyst, and realized that methyl lactate was prepared from xylose with high stability, and the catalytic activity was basically maintained after 5 cycles. However, the yield of methyl lactate is only 35.9% at maximum, and the catalytic performance is required to be improved. Subsequently, verma et al (Green chemistry.2017,19, 1969-1982) designed to prepare nano Ga-Zn/HNZY molecular sieves, and realized one-step high selectivity catalysis of carbohydrates to methyl lactate. The highest yield of the methyl lactate reaches 55%, but after the catalyst is recycled for the second time, the carbon deposition of the catalyst is serious, and the yield of the methyl lactate is rapidly reduced. The inherent micropore characteristic of the molecular sieve is unfavorable for the diffusion of biomass macromolecules, and the catalyst is quickly deactivated due to carbon deposition in the pore channels of the molecular sieve.
In summary, the prior art mainly has the problems of low product selectivity or poor catalyst circulation stability, and the like, which brings great problems to industrial practical application.
Disclosure of Invention
The invention aims to solve the technical problems of low product selectivity or poor catalyst circulation stability and the like in the prior art, and provides a method for preparing methyl lactate by catalytic conversion of carbohydrate.
The invention provides a method for preparing methyl lactate by catalytically converting carbohydrate, which comprises the steps of taking an A-SCM-1 molecular sieve as a catalyst, mixing a substrate carbohydrate with methanol, and carrying out one-step catalytic reaction to obtain methyl lactate; wherein A in the A-SCM-1 molecular sieve is selected from at least one of Sn and Zr.
Further, the A-SCM-1 molecular sieve has an MWW topological framework structure, and the A component is positioned in the framework of the molecular sieve.
Further, the a-SCM-1 molecular sieve has a schematic chemical composition as shown in the formula "mSiO 2·nAl2O3·pAO2", wherein: m/n is more than or equal to 10 and less than or equal to 500, m/p is more than or equal to 10 and less than or equal to 500; preferably, the m/n is more than or equal to 20 and less than or equal to 60, and the m/p is more than or equal to 20 and less than or equal to 70; the total acid amount of the A-SCM-1 molecular sieve is 80-650 mu mol g -1, preferably 150-450 mu mol g -1,The acid/Lewis acid (B acid/L acid) ratio is 0.04 to 1.20, preferably 0.10 to 0.80.
Further, 80% or more of the A-SCM-1 molecular sieve crystals are flaky crystals with the thickness of less than 10 nm.
Further, the content of the components in the A-SCM-1 molecular sieve is not less than 2.5wt%, preferably 2.5wt% to 6wt%.
Further, the A-SCM-1 molecular sieve is preferably a Zr-SCM-1 molecular sieve or a Sn-SCM-1 molecular sieve.
Further, the carbohydrate raw material is at least one of glucose, fructose, xylose, sucrose, inulin, cellulose, starch and the like.
Further, the reaction temperature of the reaction is 140-240 ℃, preferably 160-220 ℃; the reaction time is 1 to 24 hours, preferably 4 to 16 hours.
Further, the carbohydrate to catalyst mass ratio is 0.5-10:1, preferably 1-4:1; the mass ratio of the methanol to the carbohydrate is 10-80:1, preferably 20-60:1.
The invention also provides a Sn-SCM-1 molecular sieve, which has a schematic chemical composition shown as a formula 'mSiO 2·nAl2O3·pSnO2', wherein: m/n is more than or equal to 10 and less than or equal to 500, m/p is more than or equal to 10 and less than or equal to 500; preferably, the m/n is more than or equal to 20 and less than or equal to 60, and the m/p is more than or equal to 20 and less than or equal to 70; the Sn-SCM-1 molecular sieve has a total acid content of 80-650 mu mol g -1, preferably 150-450 mu mol g -1, and a B acid/L acid ratio of 0.04-1.20, preferably 0.10-0.80.
The preparation method of the A-SCM-1 molecular sieve comprises the following steps:
Selecting an SCM-1 molecular sieve for ion exchange and roasting to obtain an H-SCM-1 molecular sieve as a parent, mixing with an acid solution, pretreating at a certain temperature, washing, drying and roasting the product to obtain a molecular sieve with partial dealumination; and mixing the dealuminated molecular sieve with a precursor containing the component A, and drying and roasting the obtained product to obtain the A-SCM-1 molecular sieve.
Further, the SCM-1 molecular sieve and its preparation method are further described in chinese patent application CN104511271B, which is incorporated herein by reference in its entirety.
Further, in the preparation method of the A-SCM-1 molecular sieve, the acid solution is at least one selected from solutions prepared from organic acid and inorganic acid, preferably at least one selected from oxalic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid and benzoic acid.
Further, the concentration of the acid solution in the preparation method of the A-SCM-1 molecular sieve is 0.001 to 10mol/L, preferably 0.01 to 8mol/L, more preferably 0.1 to 6mol/L.
Further, the pretreatment conditions in the preparation method of the A-SCM-1 molecular sieve are 30-100 ℃ for 0.25-24 hours, preferably 35-90 ℃ for 0.5-18 hours, and more preferably 40-80 ℃ for 0.75-12 hours.
Further, the precursor containing A in the preparation method of the A-SCM-1 molecular sieve is selected from at least one of an A-containing organic metal complex, an A metal salt and an A metal hydroxide; for example, when A is tin, it may be at least one of tin-containing organometallic complex, tin salt, and tin hydroxide; examples of the tin-containing organometallic complex include tributyltin chloride (C 12H27 ClSn), dimethyltin dichloride (C 2H6Cl2 Sn), di-t-butyltin dichloride [ (CH 3)3C]2SnCl2), stannous oxalate (SnC 2O4), and dibutyltin maleate (C 12H20O4 Sn), but are not limited thereto.
Further, the roasting conditions in the preparation method of the A-SCM-1 molecular sieve are as follows: roasting for 1-12 hours at 300-650 ℃, wherein the roasting atmosphere is oxygen or air.
The present invention provides a high purity a-SCM-1 molecular sieve product having a MWW structure, the molecular sieve having a schematic chemical composition as shown in the formula "mSiO 2·nAl2O3·pAO2", which chemical composition has not been previously obtained in the art. The Sn state is determined by XPS (X-ray photoelectron spectroscopy) test or ultraviolet raman. Therefore, sn in the Sn-SCM-1 molecular sieve provided by the invention effectively enters the framework of the molecular sieve, and the proper ratio of B acid to L acid is obtained through pyridine desorption infrared diagram.
According to the invention, by adopting the A-SCM-1 molecular sieve, especially the Zr-SCM-1 molecular sieve or the Sn-SCM-1 molecular sieve as a catalyst, the high-efficiency conversion of carbohydrate is realized under the mild reaction condition, and the selectivity of the product methyl lactate is high; the Zr-SCM-1 molecular sieve or Sn-SCM-1 molecular sieve provided by the invention belongs to a two-dimensional layer stripping material, and can effectively promote the diffusion of biomass macromolecules, even oligomers, thereby being beneficial to the adsorption of substrates and the desorption of products, increasing the selectivity of target products and inhibiting the deactivation of catalysts. The invention adopts the A-SCM-1 molecular sieve as the catalyst, has outstanding circulation stability, and can be recycled for five times without deactivation of the catalyst.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of an SCM-1 molecular sieve precursor of example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the Sn-SCM-1 molecular sieve obtained in example 1;
FIG. 3 is an X-ray photoelectron spectrum (XPS) of the Sn-SCM-1 molecular sieve obtained in example 1;
FIG. 4 is a pyridine desorption infrared ray (Py-FTIR) of the Sn-SCM-1 molecular sieve obtained in example 1;
FIG. 5 is an XRD pattern of the Sn-SCM-1 molecular sieve obtained in example 1.
Detailed Description
The reaction product methyl lactate was analyzed qualitatively and quantitatively by gas chromatography-mass spectrometry (GC-MS) and the conversion of the soluble carbohydrates of the product was analyzed by High Performance Liquid Chromatography (HPLC). The gas chromatograph is Agilent 7890A of Agilent corporation, U.S., the chromatographic column is HP-5 nonpolar capillary column (30 m,0.53 mm), the gas chromatograph is Agilent 7890B, the detector is hydrogen Flame Ionization Detector (FID), the chromatographic column is SE-54 capillary column (30 m,0.53 mm). The high performance liquid chromatography adopts Agilent 1200 type analysis, and the chromatographic column is SHODEX SC1011 sugar column (8×300 mm).
The amount of acid and the type of acid in the catalyst were measured by a pyridine adsorption infrared method (Nicolet Model 710 spectrometer). The specific operation steps are as follows: a. sample pretreatment. The sample (about 30 mg) was pressed into a thin disk 13mm in diameter and loaded into an infrared sample cell. Thereafter, the samples were pretreated under vacuum cell conditions at 400℃for 1h. After the sample cell cooled to room temperature, the sample extra-fuchsin data was scanned as background. b. Pyridine adsorption. Pyridine vapor was introduced in situ at room temperature and under vacuum until adsorption reached equilibrium for 1h. c. And (3) pyridine desorption. After the adsorption is finished, vacuumizing is carried out at 100 ℃ until the internal pressure is not changed, the desorption time is 40min, and the infrared absorption spectra are respectively scanned and recorded. The difference spectrum before and after pyridine adsorption is the obtained pyridine adsorption-infrared absorption spectrum. Semi-quantitative calculation of acid amount of the sample was performed according to the spectrum:
Where r and w are the diameter (cm) and mass (g) of the catalyst thin disk, and A is the integrated value of absorbance at a specified wavenumber peak according to the scanning pyridine adsorption-infrared absorption spectrum. IMEC is an integrated molar extinction coefficient, IMEC L is 2.22, and IMEC B is 1.67.
The XRD measurement method of the molecular sieve product comprises the following steps: analysis of the phase of the sample by means of an X-ray powder diffractometer of the type IV Rigaku Ultima, japan, cuK alpha radiation sourceThe nickel filter has 2-50 DEG of 2 theta scanning range, 35KV of operating voltage, 25mA of current and 10 DEG/min of scanning speed.
The determination of the binding energy of the surface elements of the catalyst was carried out on an X-ray photoelectron spectrometer ESCA LAB-250) from Thermo company, and the measured element signals were corrected using C1s=284.6eV as an internal standard.
An inductively coupled plasma atomic emission spectrometer (ICP) model is Varian 725-ES, and an analysis sample is dissolved by hydrofluoric acid to obtain the element content.
The carbohydrate conversion formula takes glucose as a substrate as an example:
Percent conversion of glucose = (molar amount of glucose reacted)/(molar amount of glucose as substrate reacted) ×100%.
The yield of the product methyl lactate is calculated by taking glucose as a substrate as an example:
Yield% of product methyl lactate = (molar amount of methyl lactate produced by reaction)/(molar amount of glucose as substrate 2 x 100%).
The selectivity% of product methyl lactate = (molar amount of methyl lactate produced by reaction)/(molar amount of glucose reacted 2x 100%.
For the convenience of understanding the present invention, examples are set forth below, but are merely to aid in understanding the present invention and are not to be construed as limiting the invention in any way.
Example 1
The preparation method of the embodiment 1 described in the patent CN 104511271B is used for synthesizing the SCM-1 molecular sieve, the molecular sieve is exchanged for 4 times by using an ammonium nitrate solution with the concentration of 1mol/L, the molecular sieve is filtered and dried, and then the molecular sieve is roasted for 5 hours at 550 ℃ to obtain the H-SCM-1 molecular sieve, the silicon-aluminum ratio (atomic ratio) of the molecular sieve is 14.6, an SEM (scanning electron microscope) image of the molecular sieve is shown as a figure 1, and the size of the crystal is thinner, the shape of a sheet and the thickness is less than 10nm.
The H-SCM-1 molecular sieve is selected as a treatment object to prepare the Sn-SCM-1 molecular sieve, and the preparation method comprises the following specific steps: adding the roasted H-SCM-1 molecular sieve into H 2C2O4 solution with the concentration of 3mol/L, wherein the solid-liquid ratio (mass) is 1:20, and pretreating the mixture for 1 hour under the condition of water bath stirring at 60 ℃. The product was washed centrifugally to a solution ph=7, dried overnight at 110 ℃, and then calcined in a muffle furnace at 550 ℃ for 5 hours. Then adding an organic metal precursor containing Sn (CH 3)2SnCl2, wherein the mass ratio of Sn (the theoretical amount of Sn in the organic metal precursor) to the SCM-1 molecular sieve is 1:25, and fully grinding the mixture in a mortar to obtain a uniformly dispersed mixture.
Drying the product in a110 ℃ oven, and roasting at 550 ℃ for 5 hours to obtain a Sn-SCM-1 molecular sieve, wherein an SEM (scanning electron microscope) image of a sample is shown in FIG. 2 and is similar to the appearance of the SCM-1 in FIG. 1; the XPS spectrum of the sample is shown in figure 3, which shows that Sn successfully enters the framework of the SCM-1 molecular sieve; the pyridine desorption infrared diagram of the sample is shown in fig. 4. The Si/al=26.1 (atomic ratio), si/sn=49.7 (atomic ratio) of the sample was measured using inductively coupled plasma atomic emission spectroscopy (ICP). The total acid amount was 284. Mu. Mol. G -1 calculated from the pyridine desorption infrared chart, and the B/L acid ratio was 0.53, in which the tin content was 3.8wt%.
Example 2
The H-SCM-1 molecular sieve in the example 1 is selected as a treatment object to prepare the Sn-SCM-1 molecular sieve, and the specific preparation steps are as follows: adding the roasted H-SCM-1 molecular sieve into H 2C2O4 solution with the concentration of 2mol/L, wherein the solid-liquid ratio (mass) is 1:15, and pretreating the mixture for 1.5 hours under the condition of water bath stirring at 50 ℃. The product was washed centrifugally to a solution ph=7, dried overnight at 110 ℃, and then calcined in a muffle furnace at 550 ℃ for 4 hours. Then adding an organic metal precursor containing Sn (CH 3)2SnCl2, wherein the mass ratio of Sn (the theoretical amount of Sn in the organic metal precursor) to the SCM-1 molecular sieve is 1:30, and fully grinding the mixture in a mortar to obtain a uniformly dispersed mixture.
The product was dried in an oven at 110℃and then calcined at 550℃for 5 hours to give a Sn-SCM-1 molecular sieve, and the XPS spectrum of the sample was similar to that of FIG. 3, with Sn entering the framework of the SCM-1 molecular sieve. Si/al=25.2 (atomic ratio), si/sn=59.6 (atomic ratio) of the sample was measured using inductively coupled plasma atomic emission spectroscopy (ICP). The total acid amount was 248. Mu. Mol. G -1 calculated from the pyridine desorption IR chart, and the B/L acid ratio was 0.72, wherein the tin content was 3.2wt%.
Example 3
The H-SCM-1 molecular sieve in the example 1 is selected as a treatment object to prepare the Sn-SCM-1 molecular sieve, and the specific preparation steps are as follows: adding the roasted H-SCM-1 molecular sieve into H 2C2O4 solution with the concentration of 1mol/L, wherein the solid-liquid ratio (mass) is 1:25, and pretreating the mixture for 2 hours under the condition of water bath stirring at 55 ℃. The product was washed centrifugally to a solution ph=7, dried overnight at 110 ℃, and then calcined in a muffle furnace at 550 ℃ for 5 hours. Then adding an organic metal precursor containing Sn (CH 3)2SnCl2, wherein the mass ratio of Sn (the theoretical amount of Sn in the organic metal precursor) to the SCM-1 molecular sieve is 1:20, and fully grinding the mixture in a mortar to obtain a uniformly dispersed mixture.
Drying the product in a 110 ℃ oven, and roasting at 550 ℃ for 5 hours to obtain the Sn-SCM-1 molecular sieve; the XPS spectrum of the sample is similar to that of FIG. 3, with Sn entering the framework of the SCM-1 molecular sieve. Si/al=24.4 (atomic ratio), si/sn=40.7 (atomic ratio) of the sample was measured using inductively coupled plasma atomic emission spectroscopy (ICP). The total acid amount calculated from the pyridine desorption infrared chart was 379. Mu. Mol. G -1, and the B/L acid ratio was 0.42, wherein the tin content was 4.7wt%.
Example 4
The H-SCM-1 molecular sieve in the example 1 is selected as a treatment object to prepare the Sn-SCM-1 molecular sieve, and the specific preparation steps are as follows: adding the roasted H-SCM-1 molecular sieve into H 2C2O4 solution with the concentration of 4mol/L, wherein the solid-liquid ratio (mass) is 1:30, and pretreating the mixture for 0.75 hours under the condition of water bath stirring at the temperature of 75 ℃. The product was washed centrifugally to a solution ph=7, dried overnight at 110 ℃, and then calcined in a muffle furnace at 550 ℃ for 5 hours. Then adding an organic metal precursor containing Sn (CH 3)2SnCl2, wherein the mass ratio of Sn (the theoretical amount of Sn in the organic metal precursor) to the SCM-1 molecular sieve is 1:25, and fully grinding the mixture in a mortar to obtain a uniformly dispersed mixture.
The product was dried in an oven at 110℃and then calcined at 550℃for 5 hours to give a Sn-SCM-1 molecular sieve, and the XPS spectrum of the sample was similar to that of FIG. 3, with Sn entering the framework of the SCM-1 molecular sieve. The Si/al=27.2 (atomic ratio), si/sn=49.5 (atomic ratio) of the sample was measured using inductively coupled plasma atomic emission spectroscopy (ICP). The total acid amount was 272. Mu. Mol. G -1, the B/L acid ratio was 0.52, and the tin content was 3.8wt% as calculated from the pyridine desorption infrared chart.
Example 5
The H-SCM-1 molecular sieve in the example 1 is selected as a treatment object to prepare the Sn-SCM-1 molecular sieve, and the specific preparation steps are as follows: adding the roasted H-SCM-1 molecular sieve into HNO 3 solution with the concentration of 1mol/L, wherein the solid-liquid ratio (mass) is 1:20, and pretreating the mixture for 2.5 hours under the condition of water bath stirring at 60 ℃. The product was washed centrifugally to a solution ph=7, dried overnight at 110 ℃, and then calcined in a muffle furnace at 550 ℃ for 5 hours. Then adding an organic metal precursor containing Sn (CH 3)2SnCl2, wherein the mass ratio of Sn (the theoretical amount of Zr in the organic metal precursor) to the SCM-1 molecular sieve is 1:30, and fully grinding the mixture in a mortar to obtain a uniformly dispersed mixture.
The product was dried in an oven at 110℃and then calcined at 550℃for 5 hours to give a Sn-SCM-1 molecular sieve, and the XPS spectrum of the sample was similar to that of FIG. 3, with Sn entering the framework of the SCM-1 molecular sieve. The Si/al=27.8 (atomic ratio), si/sn=60.2 (atomic ratio) of the sample was measured using inductively coupled plasma atomic emission spectroscopy (ICP). The total acid amount was 207. Mu. Mol. G -1 calculated from the pyridine desorption IR chart, and the B/L acid ratio was 0.71, wherein the tin content was 3.2wt%.
Example 6
The H-SCM-1 molecular sieve in the example 1 is selected as a treatment object to prepare the Zr-SCM-1 molecular sieve, and the specific preparation steps are as follows: adding the roasted H-SCM-1 molecular sieve into H 2C2O4 solution with the concentration of 1.3mol/L, wherein the solid-to-liquid ratio (mass) is 1:25, and pretreating the mixture for 1.25 hours under the condition of water bath stirring at 60 ℃. The product was washed centrifugally to a solution ph=7, dried overnight at 110 ℃, and then calcined in a muffle furnace at 550 ℃ for 6 hours. Then adding organic metal precursor Cp 2ZrCl2 containing Zr, wherein the mass ratio of Zr (theoretical amount of Zr in the organic metal precursor) to SCM-1 molecular sieve is 1:35, and fully grinding the mixture in a mortar to obtain a uniformly dispersed mixture.
Drying the product in a 110 ℃ oven, and roasting at 550 ℃ for 5 hours to obtain a Zr-SCM-1 molecular sieve; the XPS spectrum of the sample is similar to that of FIG. 3, with Zr entering the framework of the SCM-1 molecular sieve. Si/al=27.1 (atomic ratio), si/zr=46.9 (atomic ratio) of the sample was measured using inductively coupled plasma atomic emission spectroscopy (ICP). The total acid amount was 247. Mu. Mol. G -1 calculated from the pyridine desorption infrared chart, and the B/L acid ratio was 0.74, in which the zirconium content was 2.8% by weight.
Example 7
The H-SCM-1 molecular sieve in the example 1 is selected as a treatment object to prepare the Zr-SCM-1 molecular sieve, and the specific preparation steps are as follows: adding the roasted H-SCM-1 molecular sieve into H 2C2O4 solution with the concentration of 1mol/L, wherein the solid-liquid ratio (mass) is 1:25, and pretreating the mixture for 2 hours under the condition of water bath stirring at 55 ℃. The product was washed centrifugally to a solution ph=7, dried overnight at 110 ℃, and then calcined in a muffle furnace at 550 ℃ for 5 hours. Then adding organic metal precursor Cp 2ZrCl2 containing Zr, wherein the mass ratio of Zr (theoretical amount of Zr in the organic metal precursor) to SCM-1 molecular sieve is 1:25, and fully grinding the mixture in a mortar to obtain a uniformly dispersed mixture.
Drying the product in a 110 ℃ oven, and roasting at 550 ℃ for 5 hours to obtain a Zr-SCM-1 molecular sieve; the XPS spectrum of the sample is similar to that of FIG. 3, with Zr entering the framework of the SCM-1 molecular sieve. Si/al=24.8 (atomic ratio), si/zr=40.2 (atomic ratio) of the sample was measured using inductively coupled plasma atomic emission spectroscopy (ICP). The total acid amount was 328. Mu. Mol. G -1, the B/L acid ratio was 0.46, and the zirconium content was 3.8% by weight, calculated from the pyridine desorption infrared chart.
Examples 8 to 14
With glucose as a substrate and methanol as a reaction solvent, 0.2g of the A-SCM-1 molecular sieve in examples 1 to 7, 0.4g of glucose and 16g of methanol were added to a stirred autoclave, respectively. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction was carried out at 180℃for 6 hours, and the reaction solution was analyzed to obtain the glucose conversion and the selectivity of the target product methyl lactate, as shown in Table 1.
TABLE 1 evaluation results of catalysts of examples 8-14
Example 15
In this example, 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.4g of fructose and 16g of methanol were added to a stirred autoclave using fructose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 6 hours at 180 ℃, the conversion rate of fructose is more than 99% by analyzing the reaction liquid, and the selectivity of the target product methyl lactate is 62.7%.
Example 16
In this example, 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.4g of xylose and 16g of methanol were added to a stirred autoclave using xylose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 6 hours at 180 ℃, the xylose conversion rate is more than 99% by analyzing the reaction liquid, and the selectivity of the target product methyl lactate is 60.7%.
Example 17
In this example, sucrose was used as a substrate and methanol was used as a reaction solvent, and 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.4g of sucrose and 16g of methanol were charged into a stirred autoclave. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 6 hours at 180 ℃, the sucrose conversion rate is more than 99% and the selectivity of the target product methyl lactate is 57.1%.
Example 18
In this example, 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.4g of glucose and 16g of methanol were charged into a stirred autoclave using glucose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 6 hours at 160 ℃, the glucose conversion rate is more than 99% by analyzing the reaction liquid, and the selectivity of the target product methyl lactate is 48.4%.
Example 19
In this example, 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.4g of glucose and 16g of methanol were charged into a stirred autoclave using glucose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 6 hours at 200 ℃, the glucose conversion rate is more than 99% by analyzing the reaction liquid, and the selectivity of the target product methyl lactate is 54.1%.
Example 20
In this example, 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.4g of glucose and 16g of methanol were charged into a stirred autoclave using glucose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 4 hours at 180 ℃, the glucose conversion rate is 87% by analyzing the reaction liquid, and the selectivity of the target product methyl lactate is 52.6%.
Example 21
In this example, 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.1g of glucose and 4g of methanol were charged into a stirred autoclave using glucose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 6 hours at 180 ℃, the glucose conversion rate is more than 99% by analyzing the reaction liquid, and the selectivity of the target product methyl lactate is 44.5%.
Example 22
In this example, 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.8g of glucose and 32g of methanol were charged into a stirred autoclave using glucose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 6 hours at 180 ℃, the glucose conversion rate is more than 99% by analyzing the reaction liquid, and the selectivity of the target product methyl lactate is 51.7%.
Example 23
In this example, 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.4g of glucose and 8g of methanol were charged into a stirred autoclave using glucose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 6 hours at 180 ℃, the glucose conversion rate is more than 99% by analyzing the reaction liquid, and the selectivity of the target product methyl lactate is 54.6%.
Example 24
In this example, 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.4g of glucose and 24g of methanol were charged into a stirred autoclave using glucose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 6 hours at 180 ℃, the glucose conversion rate is more than 99% by analyzing the reaction liquid, and the selectivity of the target product methyl lactate is 52.2%.
For a more visual description of the reaction conditions and results of the above examples, the results for each parameter level are listed in Table 1.
Table 2 results of catalyst performance for examples 15-24
Example 25
The catalyst prepared in example 1 was washed and dried, and then put into the next reaction, and the reaction was carried out for 5 times in a total cycle, and the results are shown in Table 3. 0.2g of the Sn-SCM-1 molecular sieve prepared in example 1, 0.4g of glucose and 16g of methanol were charged into a stirred autoclave with glucose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. Reacting for 6 hours at 180 ℃, and analyzing the reaction liquid to obtain the glucose conversion rate and the methyl lactate selectivity.
TABLE 3 glucose conversion and methyl lactate selectivity under conditions of recycle of Sn-SCM-1 molecular sieves
| Number of times of application | Glucose conversion/% | Methyl lactate selectivity/% |
| 1 | >99 | 58.6 |
| 2 | >99 | 57.3 |
| 3 | >99 | 57.5 |
| 4 | >99 | 56.8 |
| 5 | >99 | 55.7 |
Comparative example 1
The H-SCM-1 molecular sieve in the example 1 is selected as a treatment object to prepare the Sn-SCM-1 molecular sieve, and the specific preparation steps are as follows: adding the roasted H-SCM-1 molecular sieve into H 2C2O4 solution with the concentration of 0.5mol/L, wherein the solid-to-liquid ratio (mass) is 1:35, and pretreating the mixture for 1.25 hours under the condition of water bath stirring at 70 ℃. The product was washed centrifugally to a solution ph=7, dried overnight at 110 ℃, and then calcined in a muffle furnace at 550 ℃ for 5 hours. Then adding an organic metal precursor containing Sn (CH 3)2SnCl2, wherein the mass ratio of Sn (the theoretical amount of Sn in the organic metal precursor) to the SCM-1 molecular sieve is 1:40, and fully grinding the mixture in a mortar to obtain a uniformly dispersed mixture.
Drying the product in a 110 ℃ oven, and roasting at 550 ℃ for 5 hours to obtain the Sn-SCM-1 molecular sieve; the XPS spectrum of the sample is similar to that of FIG. 3, with Sn entering the framework of the SCM-1 molecular sieve. The Si/al=23.9 (atomic ratio), si/sn=79.3 (atomic ratio) of the sample was measured using inductively coupled plasma atomic emission spectroscopy (ICP). The total acid amount was 213. Mu. Mol. G -1 calculated from the pyridine desorption IR chart, and the B/L acid ratio was 1.3, wherein the tin content was 2.4wt%.
Methyl lactate was prepared in the same manner as in example 1 using the above-mentioned Sn-SCM-1 molecular sieve as a catalyst. 0.2g of the Sn-SCM-1 molecular sieve of comparative example 1, 0.4g of glucose and 16g of methanol were charged into a stirred autoclave with glucose as a substrate and methanol as a reaction solvent. And 0.5MPa nitrogen is filled to prevent the organic solvent from boiling. And (3) heating the mixture to a preset temperature by adopting a temperature programming heating sleeve, and stirring the mixture by adopting magnetic force. The reaction is carried out for 6 hours at 180 ℃, the reaction liquid is analyzed to obtain the glucose conversion rate of more than 99, and the selectivity of the target product methyl lactate is 32.1%.
Comparative example 2
The Sn-MCM-41 molecular sieve is synthesized according to the preparation method described in Journal of catalysis.2003, 219, 242-246, and the specific preparation steps are as follows: 6.5g cetyltrimethylammonium bromide (CTAB) was weighed out and dissolved in a beaker containing 20mL of water and stirred, heated in a water bath and maintained at 40 ℃. An organometallic precursor (Bu) 3 SnCl containing Sn was dissolved in 1.2mL deionized water, and the mass ratio of Sn (the theoretical amount of Sn in the organometallic precursor) to SCM-1 molecular sieve was 1:25, and was added dropwise to the CTAB solution while stirring. Stirring for 10min, and then dripping 4.2mL of tetraethoxysilane, and stirring for 0.5h. The pH of the solution was adjusted to about 11 by dropwise addition of 25% tetramethylammonium hydroxide, at which time a large amount of white precipitate was formed. After stirring for 4h, the white gel was transferred to a stainless steel crystallization kettle with polytetrafluoroethylene liner and treated at 140℃for 14h. Naturally cooling, filtering, washing with deionized water, drying at 50 ℃ overnight, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the Sn-MCM-41 molecular sieve.
Methyl lactate was prepared and tested for recycling performance in the same manner as in example 25 using the above-described Sn-MCM-41 molecular sieve as a catalyst, and the results are shown in table 4. The results show that the catalytic cycle stability of the Sn-MCM-41 molecular sieve is obviously lower than that of the Sn-SCM-1 molecular sieve.
TABLE 4 glucose conversion and methyl lactate selectivity under recycle conditions
| Number of times of application | Glucose conversion/% | Methyl lactate selectivity/% |
| 1 | >99 | 44.6 |
| 2 | >99 | 40.3 |
| 3 | >99 | 32.1 |
| 4 | >99 | 26.4 |
| 5 | >99 | 25.8 |
Claims (11)
1. A method for preparing methyl lactate by catalytic conversion of carbohydrate comprises the steps of taking an A-SCM-1 molecular sieve as a catalyst, mixing a substrate carbohydrate with methanol, and carrying out one-step catalytic reaction to obtain methyl lactate; wherein A in the A-SCM-1 molecular sieve is selected from at least one of Sn and Zr;
The A-SCM-1 molecular sieve has a schematic chemical composition as shown in the formula "mSiO 2·nAl2O3·pAO2", wherein: m/n is more than or equal to 10 and less than or equal to 60, m/p is more than or equal to 20 and less than or equal to 70; the total acid amount of the A-SCM-1 molecular sieve is 150-450 mu mol.g -1, and the ratio of B acid to L acid is 0.10-0.80.
2. The method of claim 1, wherein the a-SCM-1 molecular sieve has a MWW topology framework structure, and the a component is located in the framework of the molecular sieve.
3. The method of claim 1, wherein 80% or more of the a-SCM-1 molecular sieve crystals are platelet crystals having a thickness of less than 10 nm.
4. The method of claim 1, wherein the a-SCM-1 molecular sieve has an a component content of 2.5wt% to 6wt%.
5. The method of claim 1, wherein the a-SCM-1 molecular sieve is a Zr-SCM-1 molecular sieve or a Sn-SCM-1 molecular sieve.
6. The method of claim 1, wherein the carbohydrate source is at least one of glucose, fructose, xylose, sucrose, inulin, cellulose, starch.
7. The method according to claim 1, wherein the reaction temperature of the reaction is 140-240 ℃; the reaction time is 1-24h.
8. The method according to claim 1, wherein the reaction temperature of the reaction is 160-220 ℃; the reaction time is 4-16h.
9. The method of claim 6, wherein the carbohydrate to catalyst mass ratio is 0.5-10:1; the mass ratio of the methanol to the carbohydrate is 10-80:1.
10. The method of claim 6, wherein the carbohydrate to catalyst mass ratio is 1-4:1; the mass ratio of the methanol to the carbohydrate is 20-60:1.
11. A Sn-SCM-1 molecular sieve having a schematic chemical composition as shown in formula "mSiO 2·nAl2O3·pSnO2", wherein: m/n is more than or equal to 10 and less than or equal to 60, m/p is more than or equal to 20 and less than or equal to 70; the total acid amount of the Sn-SCM-1 molecular sieve is 150-450 mu mol.g -1, and the ratio of B acid to L acid is 0.10-0.80.
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