CN115254156B - 负载型Ru单原子合金催化剂和其应用 - Google Patents
负载型Ru单原子合金催化剂和其应用 Download PDFInfo
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- CN115254156B CN115254156B CN202110471979.0A CN202110471979A CN115254156B CN 115254156 B CN115254156 B CN 115254156B CN 202110471979 A CN202110471979 A CN 202110471979A CN 115254156 B CN115254156 B CN 115254156B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 28
- 239000000956 alloy Substances 0.000 title claims abstract description 28
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical class O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 150000003053 piperidines Chemical class 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 22
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 20
- -1 amine compounds Chemical class 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 17
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 11
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 229960001545 hydrotalcite Drugs 0.000 claims description 8
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 8
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 3
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 claims description 3
- 229910020068 MgAl Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- LYUQWQRTDLVQGA-UHFFFAOYSA-N 3-phenylpropylamine Chemical compound NCCCC1=CC=CC=C1 LYUQWQRTDLVQGA-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 235000001258 Cinchona calisaya Nutrition 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 2
- YTFNMBMXTXLGJY-UHFFFAOYSA-N [Ru].ClC=1C(=C(C=CC1)P(C1=CC=CC=C1)C1=CC=CC=C1)Cl Chemical compound [Ru].ClC=1C(=C(C=CC1)P(C1=CC=CC=C1)C1=CC=CC=C1)Cl YTFNMBMXTXLGJY-UHFFFAOYSA-N 0.000 claims description 2
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 claims description 2
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 claims description 2
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- 229940100684 pentylamine Drugs 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
- 229960000948 quinine Drugs 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000006268 reductive amination reaction Methods 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 description 10
- 229910000929 Ru alloy Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229940011182 cobalt acetate Drugs 0.000 description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/033—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to carbocyclic rings
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Abstract
本发明涉及负载型Ru单原子合金催化剂的制备和在糠醛类化合物制哌啶类化合物中的应用，该催化剂是通过负载金属Ru前驱体和3d非贵金属前驱体于羟基磷灰石或镁铝水滑石上，经高温焙烧和还原获得。本发明制备的负载型Ru单原子合金催化剂，对糠醛类化合物还原胺化制哌啶类化合物具有较高的催化活性和目标产物选择性，目标产物收率可达95％。
Description
技术领域
本发明涉及负载型Ru单原子合金催化剂的制备和在糠醛类化合物制哌啶类化合物中的应用，该催化剂是通过负载金属Ru前驱体和3d非贵金属前驱体于羟基磷灰石或镁铝水滑石上，经高温焙烧和还原获得。本发明制备的负载型Ru单原子合金催化剂，对糠醛类化合物还原胺化制哌啶类化合物具有较高的催化活性和目标产物选择性，目标产物收率可达95％。
本发明开辟了一条糠醛类化合物还原胺化制哌啶类化合物的新路径，为生物质合成可再生的高附加值含氮化学品提供了新思路。
背景技术
胺类化合物是一类重要的有机氮化合物，广泛应用于医药，农药，染料和聚合物中。但目前胺类化合物主要来源于不可再生的化石资源，而生物质作为唯一的可再生碳资源，将其转化为高附加值有机氮化合物对于胺类化合物的可持续生产至关重要。从其分子结构来看，选择性地实现生物质平台化合物中含氧官能团向氨基官能团的转化，可为胺类化合物的合成提供一条简单、高效、可再生的新路径。
糠醛作为一种重要的生物质平台化合物，主要来源于半纤维素水解脱水或纤维素己糖转化获得，还原胺化是其合成高附加值糠胺及其衍生物的有效方法。Hara及其合作者发展了Ru/Nb2O5(J.Am.Chem.Soc.,2017,33,11493-11499)和暴露{111}特定晶面的面心立方结构Ru纳米颗粒(Chem.Sci.,2018,9,5949-5956)两种催化剂，可以高效高选择性催化糠醛还原胺化生成糠胺；Kawanam及其合作者发现Rh/Al2O3催化剂在糠醛还原胺化中表现出优异的选择性，糠胺产率可达92％(Green Chem.2016,18,487-496)；另一方面，G.Romanelli及其合作者发展了一种Pt/SiO2-SO3H催化剂，可在室温下实现糠醛与苯甲胺还原胺化(J.Mol.Catal.A:Chem.,2014,392,235-240)。
上述提及的研究报道中，糠醛还原胺化主要产物是糠胺和糠仲胺(式1.1-2)，但对于糠醛还原胺化生成其它高附加值如哌啶及其衍生物的研究尚未报道(式1.3)。
因此，本专利开发了一种负载型Ru单原子合金催化剂，并开辟了一条糠醛类化合物还原胺化制备哌啶类化合物的新路径。该催化剂在糠醛类化合物还原胺化制哌啶类化合物中表现出优异的活性和选择性。
发明内容
本发明的目的是提供一种负载型Ru单原子合金催化剂的制备方法，所制备的催化剂可选择性实现糠醛类化合物还原胺化制哌啶化合物。该方法不仅制备方法简单，且具有优异的催化性能，金属利用率高，具备很好的工业应用前景。
所述负载型Ru单原子合金催化剂的制备方法步骤如下：
1)将Ru前驱体和3d非贵金属前驱体溶解于去离子水中；所述3d非贵金属与Ru的摩尔比为1～1000(优选5-500，更优选10-100)；所述去离子水与Ru的摩尔比为1～10000(优选1000-5000，更优选1500-3000)；
所述3d非贵金属为Fe、Co、Ni、Cu中的一种或两种以上；
2)将羟基磷灰石或镁铝水滑石中的一种或两种置于上述水溶液中，搅拌0.1-12h，60-160℃烘箱干燥5-48h；所述羟基磷灰石或镁铝水滑石中的一种或两种与Ru的质量比为10000～1(优选2000～100，更优选1000～500)；
3)将上述获得的固体研磨，置于马弗炉中，1-20℃/min(优选1-10℃/min，更优选2-5℃/min)升温速率升温至煅烧温度，300-600℃(优选350-500℃，更优选350-450℃)下煅烧0.5-10h(优选1-5h，更优选2-4h)；
4)将上述获得的固体置于管式炉中，通入H2，1-20℃/min(优选1-10℃/min，更优选2-5℃/min)升温速率升温至还原温度，200-600℃(优选300-500℃，更优选350-450℃)下还原0.5-10h(优选1-5h，更优选2-4h)；
5)取出固体粉末，获得负载型Ru单原子合金催化剂。
所所述Ru前驱体为氯化钌、硝酸钌、乙酰丙酮钌、醋酸钌和二氯三三苯基膦钌中的一种或两种以上；所述3d非贵金属前驱体为Fe、Co、Ni、Cu中的一种或两种以上的氯化盐、硝酸盐、磷酸盐、乙酰丙酮盐和醋酸盐中的一种或两种以上。
获得负载型Ru单原子合金催化剂中Ru与3d非贵金属形成合金后，Ru在催化剂中以单原子形式存在；羟基磷灰石的分子组成Ca10(PO4)6(OH)2；镁铝水滑石的分子组成MgAl(OH)3CO3。
所述的催化剂在糠醛类化合物制哌啶类化合物中的应用如下：
在溶剂中，加入所述的负载型Ru单原子合金催化剂，糠醛类化合物，氨气和/或胺类化合物；糠醛类化合物与Ru的摩尔比例为10-8000，氨气和/或胺类化合物与Ru的摩尔比为10-10000，溶剂与Ru的摩尔比为10-100000，于反应器中充入0.1-6MPa H2，反应温度为140-240℃，反应时间为0.5-72h，得到哌啶类化合物。
所述糠醛类化合物为糠醛、糠醇和四氢糠醇中的一种或两种以上；所用溶剂为甲苯，对二甲苯，间二甲苯，邻二甲苯，己烷和环己烷中的一种或两种以上；所述胺类化合物为甲胺，乙胺，丙胺，丁胺，戊胺，己胺，庚胺，辛胺，壬胺，奎胺，环己胺，环戊胺，苯甲胺，苯乙胺，苯丙胺和糠胺中的一种或两种以上；所述糠醛类化合物与Ru的摩尔比例优选为100-2000，氨气和/或胺类化合物与Ru的摩尔优选为100-3000，溶剂与Ru的摩尔比优选为1000-10000，于反应器中优选充入1-2MPa H2，反应温度优选为160-220℃，反应时间优选为20-36h。。
本发明制备的负载型Ru单原子合金催化剂在糠醛类化合物还原胺化制哌啶类化合物中表现优越的催化性能，具体体现在以下几点：
1.催化剂制备简单，Ru以单原子分散，金属利用率高；
2.对糠醛类化合物还原胺化制哌啶类化合物，产率可高达95％以上；
3.单原子Ru催化剂稳定性高，具有较大工业应用价值。
附图说明
图1.Co20Ru1/HAP负载型Ru单原子合金催化剂的X射线吸收精细结构谱图。
图2.Co20Ru1/HAP负载型Ru单原子合金催化剂循环稳定性图。
表1.负载型Ru单原子合金催化剂及单金属Ru、Co催化剂选择性对比表。
具体实施方式
实施例1
称取9.8mg三水氯化钌和209mg醋酸钴溶解于1.5g去离子水中，超声溶解，加入1.0g羟基磷灰石(Ca10(PO4)6(OH)2)，搅拌2h搅拌均匀，置于60℃烘箱中，干燥12h，研磨，将获得的粉末置于马弗炉中，从室温按升温速率5℃/min升至400℃，保持2h，降至室温，取出固体粉末，将获得的粉末置于石英舟中，移入管式炉中，通入60mL/min H2，从室温按升温速率5℃/min升至400℃，保持2h，降至室温，取出固体粉末，获得Co20Ru1/HAP(下标20和1含义为Co与Ru的摩尔比20：1)负载型Ru单原子合金催化剂。附图1为该催化剂的X射线吸收精细结构谱图。
实施例2
称取10.9mg乙酰丙酮钌和209mg醋酸钴溶解于1.5g去离子水中，超声溶解，加入1.0g羟基磷灰石(Ca10(PO4)6(OH)2)，搅拌12h搅拌均匀，置于60℃烘箱中，干燥12h，研磨，将获得的粉末置于马弗炉中，从室温按升温速率5℃/min升至400℃，保持2h，降至室温，取出固体粉末，将获得的粉末置于石英舟中，移入管式炉中，通入60mL/min H2，从室温按升温速率5℃/min升至400℃，保持2h，降至室温，取出固体粉末，获得Ni20Ru1/HAP负载型Ru单原子合金催化剂。
实施例3
称取9.8mg三水氯化钌和209mg醋酸钴溶解于1.5g去离子水中，超声溶解，加入1.0g镁铝水滑石(MgAl(OH)3CO3)，搅拌0.2h搅拌均匀，置于60℃烘箱中，干燥12h，研磨，将获得的粉末置于马弗炉中，从室温按升温速率5℃/min升至400℃，保持2h，降至室温，取出固体粉末，将获得的粉末置于石英舟中，移入管式炉中，通入60mL/min H2，从室温按升温速率5℃/min升至400℃，保持2h，降至室温，取出固体粉末，获得Co20Ru1/MgAl-LDHs负载型Ru单原子合金催化剂。
对比例4
称取9.8mg三水氯化钌溶解于1.5g去离子水中，超声溶解，加入1.0g羟基磷灰石(Ca10(PO4)6(OH)2)，搅拌4h搅拌均匀，置于60℃烘箱中，干燥12h，研磨，将获得的粉末置于马弗炉中，从室温按升温速率5℃/min升至400℃，保持2h，降至室温，取出固体粉末，将获得的粉末置于石英舟中，移入管式炉中，通入60mL/min H2，从室温按升温速率5℃/min升至400℃，保持2h，降至室温，取出固体粉末，获得Ru/HAP负载型催化剂。
对比例5
称取209mg醋酸钴溶解于1.5g去离子水中，超声溶解，加入1.0g羟基磷灰石(Ca10(PO4)6(OH)2)，搅拌8h搅拌均匀，置于60℃烘箱中，干燥12h，研磨，将获得的粉末置于马弗炉中，从室温按升温速率5℃/min升至400℃，保持2h，降至室温，取出固体粉末，将获得的粉末置于石英舟中，移入管式炉中，通入60mL/min H2，从室温按升温速率5℃/min升至400℃，保持2h，降至室温，取出固体粉末，获得Co/HAP负载型催化剂。
实施例6
称取50mg实施例1中Co20Ru1/HAP单原子Ru合金催化剂，1mmol糠醛，3g对二甲苯于50ml反应釜中，并充入0.5MPa NH3(25℃下，根据PV＝nRT公式计算出NH3的摩尔量，P为压力，V为体积50ml，R为常数8.314，T为温度298.13K)和2MPa H2，180℃反应20h。反应结果见表1，循环5次结果见附图2。
实施例7
称取50mg实施例2中Ni20Ru1/HAP催化剂，1mmol糠醛，3g对二甲苯于50ml反应釜中，并充入0.5MPa NH3和2MPa H2(25℃下，根据PV＝nRT公式计算出NH3的摩尔量，P为压力，V为体积50ml，R为常数8.314，T为温度298.13K)，180℃反应20h。反应结果见表1。
实施例8
称取50mg实施例3中Co20Ru1/MgAl-LDHs催化剂，1mmol糠醛，3g对二甲苯于50ml反应釜中，并充入0.5MPa NH3和2MPa H2(25℃下，根据PV＝nRT公式计算出NH3的摩尔量，P为压力，V为体积50ml，R为常数8.314，T为温度298.13K)，180℃反应20h。反应结果见表1。
对比例9
称取50mg对比例4中Ru/HAP催化剂，1mmol糠醛，3g对二甲苯于50ml反应釜中，并充入0.5MPa NH3和2MPa H2(25℃下，根据PV＝nRT公式计算出NH3的摩尔量，P为压力，V为体积50ml，R为常数8.314，T为温度298.13K)，180℃反应20h。反应结果见表1。
对比例10
称取50mg对比例5中Co/HAP催化剂，1mmol糠醛，3g对二甲苯于50ml反应釜中，并充入0.5MPa NH3和2MPa H2(25℃下，根据PV＝nRT公式计算出NH3的摩尔量，P为压力，V为体积50ml，R为常数8.314，T为温度298.13K)，180℃反应20h。反应结果见表1。反应结果见表1。
实施例11
称取50mg实施例1中Co20Ru1/HAP单原子Ru合金催化剂，1mmol糠醛，1mmol丁胺，3g对二甲苯于50ml反应釜中，并充入2MPa H2，200℃反应20h。反应结果见表1。
实施例12
称取50mg实施例1中Co20Ru1/HAP单原子Ru合金催化剂，1mmol糠醛，1mmol苯甲胺，3g对二甲苯于50ml反应釜中，并充入4MPa H2，200℃反应20h。反应结果见表1。
实施例13
称取50mg实施例1中Co20Ru1/HAP单原子Ru合金催化剂，1mmol糠醛，1mmol环己胺，3g对二甲苯于50ml反应釜中，并充入4MPa H2，220℃反应20h。反应结果见表1。
尽管说明书中已对催化剂的制备和糠醛还原胺化制哌啶化合物反应进行了详细、具体的描述，但本发明不限于文中具体的实施方案，凡与本发明精神和范围不相违背的内容也应包含在本申请内。
表1Co20Ru1/HAP负载型Ru单原子合金催化剂及Ru/HAP、Co/HAP催化剂活性对比表
图1给出实施例1中制备得到Co20Ru1/HAP负载型Ru单原子合金催化剂的X射线吸收精细结构谱图。由图1可知，Co20Ru1/HAP催化剂在处出现一个主峰，比/>(Ru-O键)长且比/>(Ru-Ru键)短，由此可推断Co20Ru1/HAP催化剂中Ru与Co成键，无Ru-Ru键，Ru基本以单原子形式存在。
图2给出实施例6中Co20Ru1/HAP负载型Ru单原子合金催化剂循环稳定性图。由图2可知，Co20Ru1/HAP单原子Ru合金催化剂循环使用5次而未出现明显的失活，可知Co20Ru1/HAP单原子Ru合金催化剂具有优异的稳定性和较大的工业应用价值。
表1结合活性数据可以发现Co20Ru1/HAP、Ni20Ru1/HAP和Co20Ru1/MgAl-LDHs催化剂均具备糠醛还原胺化制备哌啶催化活性，而单金属Ru和Co无法完成糠醛到哌啶的转化，产物只停留在四氢糠胺和糠胺；且Co20Ru1/HAP单原子Ru合金催化剂具有优异的底物普适性。
本发明催化剂是通过负载金属Ru前驱体和3d非贵金属前驱体于羟基磷灰石或镁铝水滑石上，经高温焙烧和还原获得。本发明制备的负载型Ru单原子合金催化剂，对糠醛类化合物还原胺化制哌啶类化合物具有较高的催化活性和目标产物选择性，目标产物收率可达95％。
Claims (7)
1.负载型Ru单原子合金催化剂在糠醛类化合物制哌啶类化合物中的应用，其采用如下方法制备获得，包括如下步骤：
1）将Ru前驱体和3d非贵金属前驱体溶解于去离子水中；所述3d非贵金属与Ru的摩尔比为5-500；所述去离子水与Ru的摩尔比为1000-5000；
所述3d非贵金属为Fe、Co、Ni、Cu中的一种或两种以上；
2）将羟基磷灰石或镁铝水滑石中的一种或两种置于上述步骤1）得到的水溶液中，搅拌0.1 - 12 h，60 - 160 ℃烘箱干燥5 - 48 h；所述羟基磷灰石或镁铝水滑石中的一种或两种与Ru前驱体的质量比为2000~100；
3）将上述步骤2）获得的固体研磨，置于马弗炉中，以1 - 20℃ /min升温速率升温至煅烧温度，300 - 600℃下煅烧1 - 5 h；
4）将上述步骤3）获得的固体置于管式炉中，通入H2，以1-20℃/min升温速率升温至还原温度，200-600℃下还原1 - 5 h；
5）取出步骤4）得到的固体粉末，获得负载型Ru单原子合金催化剂。
2.根据权利要求1所述的应用，其特征在于，
所述Ru前驱体为氯化钌、硝酸钌、乙酰丙酮钌、醋酸钌和二氯三三苯基膦钌中的一种或两种以上；
所述3d非贵金属前驱体为Fe、Co、Ni、Cu中的一种或两种以上的氯化盐、硝酸盐、磷酸盐、乙酰丙酮盐和醋酸盐中的一种或两种以上。
3.根据权利要求1或2所述的应用，其特征在于，
获得的所述负载型Ru单原子合金催化剂中Ru与3d非贵金属形成合金后，Ru在催化剂中以单原子形式存在。
4.根据权利要求1所述的应用，其特征在于，
所述羟基磷灰石的分子组成为Ca10(PO4)6(OH)2；所述镁铝水滑石的分子组成为MgAl(OH)3CO3。
5.按照权利要求1所述的应用，其特征在于：在溶剂中，加入所述的负载型Ru单原子合金催化剂，糠醛类化合物，氨气和/或胺类化合物；所述糠醛类化合物与Ru的摩尔比为100 -2000，氨气和/或胺类化合物与Ru的摩尔比为100 - 3000，溶剂与Ru的摩尔比为1000 -10000，于反应器中充入1 - 2MPa H2，反应温度为140 - 240 ℃，反应时间为20 - 36h，得到哌啶类化合物。
6.按照权利要求5所述的应用，其特征在于，
所述糠醛类化合物为糠醛、糠醇和四氢糠醇中的一种或两种以上；
所用溶剂为甲苯，对二甲苯，间二甲苯，邻二甲苯，己烷和环己烷中的一种或两种以上；
所述胺类化合物为甲胺，乙胺，丙胺，丁胺，戊胺，己胺，庚胺，辛胺，壬胺，奎胺，环己胺，环戊胺，苯甲胺，苯乙胺，苯丙胺和糠胺中的一种或两种以上；
所述反应温度为160 - 220 ℃。
7.按照权利要求1所述的应用，其特征在于，
所述步骤3）中以1 - 10℃ /min升温速率升温至煅烧温度，350 - 500℃下煅烧；
所述步骤4）中通入H2，以1 - 10℃ /min升温速率升温至还原温度，300 - 500℃下还原。
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