CN114870837B - 一种碱金属修饰的负载型金属催化剂及其制备方法和应用 - Google Patents
一种碱金属修饰的负载型金属催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 31
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims abstract description 44
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 30
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 60
- 239000000395 magnesium oxide Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000011068 loading method Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 24
- 239000010949 copper Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- NSQYDLCQAQCMGE-UHFFFAOYSA-N 2-butyl-4-hydroxy-5-methylfuran-3-one Chemical compound CCCCC1OC(C)=C(O)C1=O NSQYDLCQAQCMGE-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910014155 Na—Pt Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- -1 methyl furfural Chemical compound 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical group Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明公开了一种碱金属修饰的负载型金属催化剂及其制备方法和应用，属于金属催化剂技术领域。通过将金属前驱体与碱金属前驱体溶于水中，负载到载体上，干燥后，在空气气氛中焙烧后得到碱金属修饰的负载型金属催化剂，将所得的催化剂用于催化5‑羟甲基糠醛加氢制备2,5‑呋喃二甲醇，2,5‑呋喃二甲醇的选择性可达到99％，本发明的催化剂成本低、无需还原处理、催化反应条件温和，具有商业化推广应用价值。
Description
技术领域
本发明属于金属催化剂技术领域，具体涉及一种碱金属修饰的负载型金属催化剂、制备方法及该催化剂在催化5-羟甲基糠醛加氢制备2,5-呋喃二甲醇中的应用。
背景技术
5-羟甲基糠醛(HMF)是一种重要的平台化合物，可以由源于生物质的葡萄糖和果糖经脱水过程大量产生，其化学性质活泼，可通过加氢、氧化、酯化、开环反应合成一系列具有高附加值的化学品。
2,5-呋喃二甲醇具有二元醇的性质，可用于合成医药和香料药物中间体，可以作为单体合成聚酯、聚氨酯等聚合材料(CN107442177A)。通过催化5-羟甲基糠醛选择性加氢可以制备2,5-呋喃二甲醇(BHMF)。
目前，用于催化HMF选择性加氢制备BHMF的催化剂主要为负载型金属催化剂(CN110204519A)。比如：Pt/Al2O3催化剂应用于催化HMF加氢反应，BHMF的收率是85％(GreenChem.2012,14,1626-1634)。类似地，Au/Al2O3催化剂应用于催化HMF加氢反应，BHMF的收率是96％(RSC Adv.,2013,3,1033-1036)。目前存在的主要问题是选择性偏低，另外，如制备过程复杂、成本高、选择性低，限制了其进一步的工业应用。然而，将碱金属修饰的负载型金属催化剂用于催化HMF选择性加氢制备BHMF的相关研究还未见报道。
发明内容
本发明为解决现有技术的不足，本发明的目的在于提供一种碱金属修饰的负载型金属催化剂、制备方法及该催化剂在催化5-羟甲基糠醛加氢制备2,5-呋喃二甲醇中的应用，本发明的碱金属修饰的负载型金属催化剂，能够提高催化剂的活性、选择性和稳定性，该催化剂的合成路径简单、容易操作、成本低、2,5-呋喃二甲醇选择高，具有商业化推广应用价值。
为了实现上述目的，本发明采用如下技术方案：
本发明提供一种碱金属修饰的负载型金属催化剂的制备方法，主要包括以下步骤：将金属前驱体与碱金属前驱体溶于水中，负载到载体上，于40～120℃条件下干燥，在空气气氛中200～700℃焙烧1～10h，得到碱金属修饰的负载型金属催化剂；所述的金属为贵金属或非贵金属中的一种或两种以上；所述的贵金属为Pt、Pd、Rh、Ir、Ru、Au、Ag中的一种，所述的非贵金属为Cu、Co、Ni中的一种，所述碱金属为Na、K、Rb、Cs的一种或两种以上；所述载体为碱金属元素中一种或两种以上的碱性金属氧化物。
基于以上技术方案，优选的，焙烧温度为300～400℃，焙烧时间为2～4h。
基于以上技术方案，优选的，所述的载体包括氧化锌、氧化铝、氧化镁、氧化铝镁、氧化钙、氧化钡、氧化镧中的一种或两种以上。
基于以上技术方案，优选的，所述碱金属前驱体中的碱金属的负载量为0.1～1wt％；所述金属前驱体中的金属的负载量为0.1～20wt％。
基于以上技术方案，优选的，贵金属负载量为0.1wt％～1wt％，非贵金属负载量为1wt％～20wt％。
基于以上技术方案，优选的，所述的金属前驱体为相应金属的硫酸盐、硝酸盐、磷酸盐、醋酸盐、氯化物。
基于以上技术方案，优选的，所述的碱金属前驱体为相应金属的氯化盐、碳酸盐、硝酸盐、氢氧化物。
本发明另一方面提供上述制备方法制备的碱金属修饰的负载型金属催化剂。
本发明还提供一种催化5-羟甲基糠醛加氢制备2,5-呋喃二甲醇的方法，采用上述的碱金属修饰的负载型金属催化剂，以5-羟甲基糠醛、氢气为反应原料，低碳醇为反应溶剂，使用间歇式反应釜，通过催化加氢反应合成2,5-呋喃二甲醇。
基于以上技术方案，优选的，贵金属与5-羟甲基糠醛的摩尔质量比为1:500～1:5000，非贵金属与5-羟甲基糠醛的摩尔质量比为1:100～1:500，反应温度为60～180℃，氢气压力为0.5～5MPa，所述低碳醇为甲醇、乙醇、正丙醇、正丁醇、异丙醇中的一种。
本发明相对于现有技术具有如下优点和有益效果：
(1)本发明的碱金属修饰的负载型金属催化剂能够提高催化剂的活性、选择性和稳定性，该催化剂的合成路径简单、容易操作、成本低、无需还原处理、催化反应条件温和，对提高BHMF选择性有重要意义，具有商业化推广应用价值。
(2)在催化5-羟甲基糠醛加氢制备2,5-呋喃二甲醇反应中，5-羟甲基糠醛容易聚合，吸附在催化剂表面，降低催化剂的活性和选择性。本发明的负载型金属催化剂经过碱金属的修饰，可以极大地降低5-羟甲基糠醛的聚合，提高催化剂的活性与2,5-呋喃二甲醇选择性，载体表面的碱性位点可以吸附5-羟甲基糠醛上的醛基基团，金属活化氢气，二者协同催化实现较高的选择性。
具体实施方式
下面结合实施例对本发明进行详细的说明，但本发明的实施方式不限于此，显而易见地，下面描述中的实施例仅是本发明的部分实施例，对于本领域技术人员来讲，在不付出创造性劳动性的前提下，获得其他的类似的实施例均落入本发明的保护范围。
对比例1
Pt/TiO2催化剂的制备：使用超纯水配制氯铂酸水溶液，Pt的浓度为3.8mg/mL，取0.26mL氯铂酸水溶液与1g TiO2搅拌混合均匀，获得Pt/TiO2前驱体，在烘箱80℃干燥10小时，空气中350℃焙烧3小时，得Pt/TiO2催化剂；铂的载量为0.1wt％。
实施例1
操作同对比例1，区别仅在于将TiO2替换为MgO，得Pt/MgO催化剂。
实施例2
操作同对比例1，区别仅在于将TiO2替换为γ-Al2O3，得Pt/Al2O3催化剂。
实施例3
操作同对比例1，区别仅在于将TiO2替换为MgO，焙烧温度改为250℃，得Pt/MgO-250催化剂。
实施例4
操作同对比例1，区别仅在于将TiO2替换为MgO，焙烧温度改为500℃，得Pt/MgO-500催化剂。
实施例5
操作同对比例1，区别仅在于将TiO2替换为ZnO，得Pt/ZnO催化剂。
实施例6
操作同对比例1，区别仅在于将TiO2替换为碱性复合氧化物MgAlOx，得Pt/MgAlOx催化剂；复合氧化物MgAlOx由铝镁水滑石(CasNo:11097-59-9，购买于麦克林公司)在500℃空气中焙烧3小时获得。
实施例7
操作同实施例1，区别仅在于将氯铂酸替换为氯金酸，得Au/MgO催化剂。金的载量为0.1wt％。
实施例8
操作同实施例1，区别仅在于将氯铂酸替换为氯化铱，得Ir/MgO催化剂。铱的载量为0.1wt％。
实施例9
操作同实施例1，区别仅在于将氯铂酸替换为氯化钌，得Ru/MgO催化剂。钌的载量为0.1wt％。
实施例10
Cu/MgO催化剂的制备：使用超纯水配制硝酸铜水溶液，Cu的浓度为25mg/mL；取2mL硝酸铜水溶液与1g MgO搅拌混合均匀，获得Cu/MgO前驱体，在烘箱80℃干燥10小时，空气中350℃焙烧3小时，得Cu/MgO催化剂。铜的载量为5wt％。
实施例11
Na-Pt/MgO催化剂的制备：使用超纯水配制氯铂酸水溶液，Pt的浓度为3.8mg/mL，取0.26mL氯铂酸水溶液，并加入2.3mg碳酸钠，搅拌至完全溶解，所得溶液与1g MgO搅拌混合均匀，获得Na-Pt/MgO前驱体，在烘箱80℃干燥10小时，空气中350℃焙烧3小时，得Na-Pt/MgO催化剂。铂的载量为0.1wt％，钠的含量为0.1wt％。
实施例12
操作同实施例11，区别仅在于将碳酸钠换为1.5mg硝酸铯，得Cs-Pt/MgO催化剂。铯的含量为0.1wt％。
实施例13
Na-Cu/MgO催化剂的制备：使用超纯水配制硝酸铜水溶液，Cu的浓度为25mg/mL，取2mL硝酸铜水溶液，并加入2.3mg碳酸钠，搅拌至完全溶解，所得溶液与1g MgO搅拌混合均匀，获得Na-Cu/MgO前驱体，在烘箱80℃干燥10小时，空气中350℃焙烧3小时，得Na-Cu/MgO催化剂。铜的载量为5wt％，钠的含量为0.1wt％。
实施例14
操作同实施例12，区别仅在于将焙烧温度改为500℃，得Na-Cu/MgO-500催化剂。
实施例15
采用反应釜测试对比例1和实施例1-13制备的催化剂催化5-羟甲基糠醛加氢制备2,5-呋喃二甲醇反应的性能，具体步骤为：
(1)取催化剂100mg、HMF 63mg、异丙醇10mL放入25mL的反应釜中，将反应釜密闭并检查气密性，用氢气冲洗反应釜3次，之后冲入2MPa氢气，加热到120℃开始计时，反应1小时；
(2)反应结束后，收集液相产物，用气相色谱进行分析，色谱分析条件为：采用DB-35MS色谱柱，采用氢火焰检测器(FID)，氢气作为载气，内标法，十二烷为内标物。
(3)产物分析
(a)HMF转化率：
C-HMF＝(反应起始时HMF的量－反应结束时HMF的量)/反应起始时HMF的量×100％
(b)BHMF选择性：
S-BHMF＝反应结束时BHMF的量/(反应起始时HMF的量－反应结束时HMF的量)×100％。
对比例1和实施例1-13制备的催化剂催化5-羟甲基糠醛加氢制备2,5-呋喃二甲醇反应的性能如表1所示。
表1.不同催化剂催化5-羟甲基糠醛加氢制备2,5-呋喃二甲醇的实验结果
| 催化剂编号 | 催化剂组成 | C-HMF(％) | S-BHMF(％) |
| 对比例1 | Pt/TiO2 | 28 | 10 |
| 实施例1 | Pt/MgO | 84 | 90 |
| 实施例2 | Pt/Al2O3 | 46 | 93 |
| 实施例3 | Pt/MgO-250 | 34 | 90 |
| 实施例4 | Pt/MgO-500 | 35 | 90 |
| 实施例5 | Pt/ZnO | 25 | 93 |
| 实施例6 | Pt/MgAlOx | 33 | 94 |
| 实施例7 | Au/MgO | 44 | 93 |
| 实施例8 | Ir/MgO | 64 | 92 |
| 实施例9 | Ru/MgO | 25 | 92 |
| 实施例10 | Cu/MgO | 52 | 93 |
| 实施例11 | Na-Pt/MgO | 84 | 98 |
| 实施例12 | Cs-Pt/MgO | 78 | 99 |
| 实施例13 | Na-Cu/MgO | 99 | 99 |
| 实施例14 | Na-Cu/MgO-500 | 69 | 99 |
从表1数据可见，酸性载体TiO2负载的金属催化剂在催化5-羟甲基糠醛加氢制备2,5-呋喃二甲醇反应中的转化率和选择性均较低；碱性载体负载的金属催化剂具有90～93％的2,5-呋喃二甲醇选择性；催化剂制备过程焙烧温度主要影响反应的活性，对选择性影响不大，副产物主要是1～3％的5-甲基糠醛，在催化剂中引入碱金属之后，2,5-呋喃二甲醇选择性可以提高到99％。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (5)
1.一种碱金属修饰的负载型金属催化剂在催化5-羟甲基糠醛加氢制备2,5-呋喃二甲醇中的应用，其特征在于，所述的碱金属修饰的负载型金属催化剂的制备方法，包括以下步骤：将金属前驱体与碱金属前驱体溶于水中，负载到载体上，于40～120℃条件下干燥，在空气气氛中350℃焙烧3h，得到碱金属修饰的负载型金属催化剂；所述的金属为Pt或Cu，所述碱金属为Na；
所述的载体为氧化镁；
所述碱金属前驱体中的碱金属的负载量为0.1wt%；当金属为Pt时，金属负载量为0.1wt%；当金属为Cu时，金属负载量为5wt%。
2.根据权利要求1所述的应用，其特征在于，所述的金属前驱体为相应金属的硫酸盐、硝酸盐、磷酸盐、醋酸盐、氯化物。
3.根据权利要求1所述的应用，其特征在于，所述的碱金属前驱体为相应碱金属的氯化盐、碳酸盐、硝酸盐、氢氧化物。
4.根据权利要求1所述的应用，其特征在于，采用所述的碱金属修饰的负载型金属催化剂，以5-羟甲基糠醛、氢气为反应原料，低碳醇为反应溶剂，通过催化加氢反应合成2,5-呋喃二甲醇。
5.根据权利要求4所述的应用，其特征在于，反应温度为60～180℃，氢气压力为0.5～5MPa，所述低碳醇为甲醇、乙醇、正丙醇、正丁醇、异丙醇中的一种。
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