CN109675588A - A kind of sulphur carbon ball supported precious metal catalyst and the preparation method and application thereof - Google Patents
A kind of sulphur carbon ball supported precious metal catalyst and the preparation method and application thereof Download PDFInfo
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- CN109675588A CN109675588A CN201810664887.2A CN201810664887A CN109675588A CN 109675588 A CN109675588 A CN 109675588A CN 201810664887 A CN201810664887 A CN 201810664887A CN 109675588 A CN109675588 A CN 109675588A
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- China
- Prior art keywords
- temperature
- carbon ball
- sulphur
- sulphur carbon
- hydrogen
- Prior art date
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- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000010970 precious metal Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 50
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Substances SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000005864 Sulphur Substances 0.000 claims abstract description 12
- 239000002923 metal particle Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 119
- 239000001257 hydrogen Substances 0.000 claims description 99
- 229910052739 hydrogen Inorganic materials 0.000 claims description 99
- 238000003756 stirring Methods 0.000 claims description 92
- 239000000243 solution Substances 0.000 claims description 90
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 89
- 229920000642 polymer Polymers 0.000 claims description 89
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 77
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- WVYADZUPLLSGPU-UHFFFAOYSA-N carboxyphenyl salicylate Natural products OC(=O)C1=CC=CC=C1OC(=O)C1=CC=CC=C1O WVYADZUPLLSGPU-UHFFFAOYSA-N 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 37
- 238000001291 vacuum drying Methods 0.000 claims description 34
- 239000012298 atmosphere Substances 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 29
- 229960000953 salsalate Drugs 0.000 claims description 28
- 238000013019 agitation Methods 0.000 claims description 27
- 150000002431 hydrogen Chemical class 0.000 claims description 23
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 15
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 15
- 235000018417 cysteine Nutrition 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 238000005360 mashing Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- 238000006073 displacement reaction Methods 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- -1 thio salicyl salicylate Chemical compound 0.000 claims description 6
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims description 5
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 238000010992 reflux Methods 0.000 description 23
- 239000011521 glass Substances 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 239000011148 porous material Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 11
- 238000009833 condensation Methods 0.000 description 11
- 230000005494 condensation Effects 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 208000012839 conversion disease Diseases 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- JFZRMDALLGPEQG-UHFFFAOYSA-N C1=CC=CC=C1.[Pt] Chemical compound C1=CC=CC=C1.[Pt] JFZRMDALLGPEQG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 229910018967 Pt—Rh Inorganic materials 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- UOPIRNHVGHLLDZ-UHFFFAOYSA-L dichlororhodium Chemical compound Cl[Rh]Cl UOPIRNHVGHLLDZ-UHFFFAOYSA-L 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000004376 petroleum reforming Methods 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of sulphur carbon ball supported precious metal catalysts and the preparation method and application thereof.The catalyst is by sulphur carbon ball and is carried on the active component on sulphur carbon ball surface and forms；The element sulphur of the sulphur carbon ball is present on sulphur carbon ball skeleton and surface in the form of C-S key, and wherein the mass ratio of element sulphur and carbon is 0.05~20%；The active component is platinum group metal particle, and partial size is in 4~10nm；The sulphur carbon ball supported precious metal catalyst is spherical in shape, and diameter is between 100~1000nm.The present invention provides application of the catalyst in C=N key selective catalytic hydrogenation reduction reaction.The present invention passes through 4, doping sulphur synthesizes sulphur carbon ball to 4'- thiobis-benzenethiol autohemagglutination in situ, it is present in element sulphur in the form of C-S key on sulphur carbon ball skeleton and surface, metal dispersity and modulation metallic outer-shell electron distribution character can be effectively improved, the characteristics of catalyst is applied in C=N key selective hydrogenation, performance high conversion, high catalytic activity, high stability and high reaction rate.
Description
(1) technical field
The present invention relates to a kind of sulphur carbon ball supported precious metal catalysts and the preparation method and application thereof, and in particular to the catalysis
Application of the agent in C=N key selective hydrogenation.
(2) technical background
Platinum group metal shows excellent catalytic performance in many chemical reactions, such as the carbonyl in homogeneous catalytic reaction
Base addition reaction, acyl chlorides addition reaction, olefin hydrocarbon oxidation reaction, C-C synthetic reaction, heterogeneous catalyst mainly have petroleum reforming Pt-
Re/Al2O3Catalyst, purifying vehicle exhaust Pt-Rh/Al2O3Catalyst, purification of terephthalic acid plus hydrogen Pd/C catalyst, chlorine
For the Pd/C catalyst of Catalytic Hydrogenation of Nitrobenzene.But it needs to be solved in selective hydrogenation reduction reaction there is also Railway Project
Certainly.
1) metal efficiently utilizes.Platinum group metal nature amount is few, expensive, therefore platinum metal catalysts are usual
It is to be loaded on carrier, improves its dispersion degree, reduces surface metal particle size.In selective hydrogenation, carrier
Aluminium oxide, activated carbon, calcium sulfate etc. are generallyd use, wherein recycling is easy, most widely used especially with active carbon acid-fast alkali-proof.In work
Property charcoal supporting platinum-group metals when, surface group influences it very big, has attracted great concern to research in this respect, but tie
By unable to decide which is right.Li Lixiang et al. prepares the active carbon of N doping by heat treating process, and nitrogen-containing functional group significantly improves active carbon
Water dispersible and surface-active, so that platinum grain is mostly distributed in carrier surface [Li Lixiang, Zhang Yan with the uniform particle less than 5nm
Autumn, Sun Pansong wait nitrogen-dopped activated carbon and its platinum catalyst oxygen reduction catalytic activity [J] new carbon, and 2016,31
(3):287-292.]；The activated carbon supported platinum of the standby sulfur doping of Engelhard corporation, the Pt/C catalysis obtained after reduction
The Pt partial size of agent is less than 10nm [Keith C D, Bair D L.Method of preparing a sulfided platinum
on carbon catalyst:,US3275567[P].1966.].But the work of different manufacturers unlike material different batches production
Inevitable the having differences property of property charcoal property, causes the unstability problem of carbon supported noble metal catalyst preparation process.
2) selectivity is to be improved.Platinum group metal activity is high, is often easy to happen excessive hydrogenation.For example, halonitro
Benzene platinum metal catalysts effect under catalytic hydrogenating reduction at halogenated aniline, but have excessive hydrogenation and cause generate dehalogenation pair
Product.In order to improve selectivity, the electronics and architectural characteristic of the usual modulation particles of active components of people, the strategy of use has: 1)
Metal promoter is added, such as Pt/C (Fe) [Xu X, Li X, Gu H, et al.A highly active and
chemoselective assembled Pt/C(Fe)catalyst for hydrogenation of o-
Chloronitrobenzene [J] .Applied Catalysis A:General, 2012,429:17-23.], this kind of catalyst
Have active high and actual production and be applicable in the features such as strong, but its selectivity and stability also need to improve；2) hetero atom modified metal
Or carrier, in heteroatom groups such as carrier surface doping N, S, such as pyridine nitrogen [XiaY, Mokaya R.Synthesis of
ordered mesoporous carbon and nitrogen‐doped carbon materials with graphitic
pore walls via a simple chemical vapor deposition method[J].Advanced
Materials, 2004,16 (17): 1553-1558.], pyrroles's nitrogen [Sevilla M, Valle-Vig ó n P, Fuertes A
B.N‐Doped Polypyrrole‐Based Porous Carbons for CO2 Capture[J].Advanced
Functional Materials, 2011,21 (14): 2781-2787.] and S heterocycle [Luo Hongyuan, Ding Yunjie, Pan Zhendong one kind
Platinum/C catalyst and its application [J] .2005.] etc., groups of these doping can adjust carrier surface for metal active constituent
Anchoring ability, and then modulation metal active particle characteristic electron and size；3) modulation active component particles size.Platinum group metal grain
Son has apparent nanometer size effect, has embodiment in many reactions.The researchs such as Li little Nian find chloro aminobenzen selectivity
There are dimensional effect [Ma L, Chen S, Lu C, et al.Highly selective hydrogenation with palladium nano-cluster
of 3,4-dichloronitrobenzene over Pd/C catalysts without inhibitors[J]
.Catalysis today,2011,173(1):62-67.]。
It is existing the study found that vulcanization supported platinum group metal catalyst be that organic liquid phase hydrogenation reaction can be improved in one kind
The effective catalyst of selectivity, makes the selectivity containing the functional compounds catalytic hydrogenation reaction such as carbonyl, hydroxyl and halogen significantly
It improves, adds in the reaction such as hydrogen in the selection of reduction amination, Halogenated aromatic nitro-group compounds and be all widely used.The surface of carrier is repaired
Decorations, the method for a large amount of basic groups such as doping S is often carrier and sulfur-containing compound such as H2S, simple substance S etc. carries out high temperature roasting
It burns, such methods experiment step is complicated, is not easy to control particular surface sulfur-containing group and is formed；Modification for metallic, it is more
It is that the supported platinum group metals such as Pd/C catalyst and sulfur-containing compound such as diphenyl sulfide etc. are mixed, passes through chemisorption
Power, will be on sulfur-bearing complex adsorption to metal active position.Such methods experiment step is simple, and sulfur-bearing complex and active sites are adsorbed
Power is not strong and causes the effect for adulterating sulphur undesirable, it is often necessary to constantly add into reactor.Therefore, such method is easy to after
Continuous process causes a series of new problems such as separation, pollution.
(3) summary of the invention
The first purpose of this invention is to provide a kind of sulphur carbon ball supported precious metal catalyst, to effectively improve noble metal
Dispersion degree and modulation noble metal electronics distribution character, thus the catalytic performance of regulating catalyst.
A second object of the present invention is to provide a kind of easy to operate, at low cost, expensive suitable for the load of industrialized sulphur carbon ball
The preparation method of metallic catalyst, which can be effectively controlled the morphology and size of carrier, and will can specifically contain in situ
Methylthio group is introduced on the skeleton and surface of carrier, realizes the controllability of doping sulfur-containing group and the high degree of dispersion of metal.
Third object of the present invention is to provide the sulphur carbon ball supported precious metal catalyst alternatively property hydrogenation catalysts
A kind of application of agent, the catalyst are applied in C=N key selective hydrogenation, show high conversion, high catalytic activity, height
The characteristics of stability and high reaction rate.
To achieve the above object, the present invention adopts the following technical scheme:
The present invention provides a kind of sulphur carbon ball supported precious metal catalysts, and the catalyst is by sulphur carbon ball and is carried on
The active component on sulphur carbon ball surface forms；The element sulphur of the sulphur carbon ball be present in the form of C-S key sulphur carbon ball skeleton and
On surface, wherein the mass ratio of element sulphur and carbon is 0.05~20%；The active component is platinum group metal particle,
Partial size is in 4~10nm, and based on the quality of sulphur carbon ball, the activity component load quantity is not higher than 20.0%；The sulphur carbon ball load
Noble metal catalyst is spherical in shape, and diameter is between 100~1000nm, 0.15~1.0ml/g of Kong Rongwei, specific surface area 300
~1000m2/ g, average pore size are 0.5~2nm, and micropore ratio is 60~85%.
Further, the diameter of the catalyst is preferably 200~800nm.
Further, the platinum group metal be preferably can be formed with sulfurous organic compound the platinum of metallo-organic complex, palladium,
The combination of one or more of iridium, ruthenium, rhodium.
Further, platinum group metal can be the one or more such as palladium, platinum, ruthenium.
Further, the load capacity of the active component is preferably 0.2~20%.
The present invention provides a kind of preparation methods of sulphur carbon ball supported precious metal catalyst, include the following steps:
1) cetyl trimethylammonium bromide and cysteine at room temperature, are added in the reaction vessel equipped with deionized water
Solid, stirring are completely dissolved solid；Then the thio salicyl salicylate (salsalate) thiophenol solid of 4,4'- is added, it is complete to solid to continue stirring
Dissolution；The concentrated sulfuric acid is slowly added dropwise again in above-mentioned mixed solution, strict control rate of addition is super to prevent temperature rise caused by heat of solution
Cross 2 DEG C；Continue to stir, rises to 60 DEG C from room temperature with 0.1~1 DEG C/min heating rate, keep 6~12h, then proceed to 0.1
~1 DEG C/min heating rate rises to 90 DEG C, keeps 6~12h, finally continues to rise to boiling with 0.1~1 DEG C/min heating rate,
0.5~2h is kept under condensing reflux state；
After terminating stirring, obtained polymer solution is added in water heating kettle, is arranged 100~200 DEG C of hydrothermal temperature, water
Hot 12~36h of time, then isolated polymer solids, which has chondritic, having a size of 100~1000nm；
Wherein, deionized water, dense H2SO4Solution, cetyl trimethylammonium bromide, cysteine and 4,4'- thiobis water
The feed ratio of poplar acid thiophenol is 100~200ml:2~5ml:0.5~1.5g:1.5~2.5g:5~20g；
2) aqueous solution for the platinum group metal salts that platinum group metal concentration is 0.001~0.03g/mL is prepared；
3) the polymer solids powder for taking step 1) to obtain is sufficiently mixed mashing, is then slowly added dropwise in deionized water
The aqueous solution for the platinum group metal salts that step 2) obtains stirs 3~6h, in whipping process control slurry temperature 30~50 DEG C it
Between, sodium hydroxide solution controls pH between 3.5~6.5；Wherein the aqueous solution of platinum group metal salts and polymer solids powder are thrown
Material is than being 20~100ml:2~30g；After terminating stirring, polymer suspension is filtered, wash, is dried to obtain solid；
4) solid for taking step 3) to obtain is placed in the mixed atmosphere containing hydrogen and vapor and is roasted, and described is mixed
Closing hydrogen volume concentration in atmosphere is 5~30%, vapor volumetric concentration 0.1~5.0%, except hydrogen and water steam in mixed atmosphere
Residual gas outside gas is inert gas or nitrogen, and calcination steps are temperature programming control process: rising to 300~500 from room temperature
DEG C, this step-up temperature rate is 1~3 DEG C/min, and 2~4h is kept under constant temperature；700~900 DEG C are risen to from 300~500 DEG C, this
Step-up temperature rate is 1~3 DEG C/min, and 2~4h is kept under constant temperature, and sulphur carbon ball supported precious metal catalyst can be obtained.Institute
State one of the optional argon gas of inert gas in mixed atmosphere, helium or two kinds.Roasting process, volumetric flow of gas are preferred
Not less than 50ml/min.
In the step (1), preferably following one kind of the separate mode of polymer solids: centrifugation, -10~0 DEG C of cryogenic vacuum
It is dry.Experiment shows that improving centrifugation rate can be improved the yield of polymer solids；And it is dried in vacuo and is also helped at low temperature
In the yield for improving polymer solids.The condition of low-temperature vacuum drying is preferred are as follows: relative degree of vacuum -0.099~-0.05MPa, temperature
Degree is -10~0 DEG C, drying time 10~for 24 hours.
In the step (2), the preparation of the aqueous solution of platinum group metal salts uses the dissolving method of Typical precious metal salt.Platinum family
Metal salt can be palladium chloride, palladium nitrate, chlorine palladium acid, palladium acetate, platinous chloride, platinum tetrachloride, chloroplatinic acid, platinum nitrate, chloroplatinic acid
At least one of sodium, radium chloride, rhodium nitrate, rhodium acetate, iridochloride, iridous chloride, ruthenium trichloride, nitric acid ruthenium.
Invention further provides the sulphur carbon ball supported precious metal catalyst with N- phenyl shown in formula (I) to benzene
Aliphatic ketone shown in diamines and formula (II) is application of the raw material in hydrogen in the reaction of one kettle way prepare compound (III),
Wherein, R, R' are each independently selected from alkyl substituent.
Further, alkyl substituent is preferably C1-C10 alkyl.
Further, alkyl substituent is preferably C1-C4 alkyl, such as methyl, isopropyl, butyl.
The main reaction process of compound (I) and compound (II) is as follows:
The sulphur carbon ball supported precious metal catalyst plays catalysis to second step C=N key selective catalytic hydrogenation reduction reaction
Effect.
Further, the reaction carries out under solvent-free conditions.
Further, the application method of the sulphur carbon ball supported precious metal catalyst are as follows:
It will be shown in 4-aminodiphenylamine shown in dry sulphur carbon ball supported precious metal catalyst, formula (I) and formula (II)
Aliphatic ketone be proportionally added into autoclave, closed reactor is passed through nitrogen displaced air, then with hydrogen displacement nitrogen
Gas, be flushed with hydrogen in gas to kettle to Hydrogen Vapor Pressure be 0.5~3.5MPa (preferably 0.8~2.5MPa), then be arranged reaction temperature be 80~
150 DEG C and temperature program and magnetic agitation starting reaction are opened, hydrogen is added when pressure declines 0.3MPa to designated value, when
Pressure no longer declines in kettle, after continuing constant temperature and pressure stirring certain time (such as 0.5h), stops stirring, is cooled to room temperature, opens kettle
Hydrogenation liquid is taken out, hydrogenation liquid is post-treated to obtain product shown in formula (III).
Again further, 4-aminodiphenylamine shown in formula (I), sulphur carbon ball supported precious metal catalyst and formula (II) institute
The fatty reactive ketone feed ratio shown is 10g:0.1~1.0g:15ml.
Again further, the method for the hydrogenation liquid post-processing are as follows: hydrogenation liquid filters to isolate catalyst, and filtrate is through depressurizing
Up to product after rectifying；In last handling process, the catalyst cake that hydrogenation liquid is obtained by filtration may return to reaction kettle and is catalyzed
Agent is applied.
Compared with prior art, the beneficial effects of the present invention are embodied in:
1) sulphur carbon ball supported precious metal catalyst of the present invention, sulphur carbon ball therein have flourishing microcellular structure.
In addition, element sulphur is present on sulphur carbon ball skeleton and surface in the form of C-S key, hetero atom is on the one hand realized in carrier surface
With uniform, stable, the controllable dispersion in skeleton, on the other hand the particles of active components electronics of energy modulation load thereon is distributed special
Property.These are conducive to modulation precious metal catalyst performance, improve active component dispersion degree and metal utilization.
2) present invention using sulfur-bearing organic carbon source through dehydration, autohemagglutination obtains polymer drops in microcapsules, polymer drops with
Platinum group metal forms complex compound, then is carbonized into sulphur carbon ball supported noble metal material --- and this preparation method both can be effectively controlled load
The morphology and size of body, and stable specific sulfide group can be introduced, so that element sulphur is present in sulphur carbon ball bone in the form of C-S key
Frame and surface realize the controllability of doping sulfur-containing group；And platinum group metal by with the sulfur-containing compound in polymer drops
It forms complex compound to load on carrier, helps to realize the dispersion of its high uniformity.Moreover, the synthetic method letter of sulphur carbon ball of the present invention
Single, cost is relatively low, is conducive to industrial applications.
In the synthetic method, vapor is added in step (4) in mixed atmosphere, is conducive to be formed on carbon ball surface
Hydrophilic radical improves material mass-transfer efficiency convenient for the abundant wetting of carbon ball and hydrogenation liquid, improves reaction rate.
3) catalyst is applied to the coupling of 4-aminodiphenylamine and aliphatic ketone and its follow-up hydrogenation reaction, shows
The excellent catalytic performance of highly selective, high conversion, high stability, high hydrogenation reaction rate, and without adding solvent, it is efficiently green
Colour circle is protected.
(4) Detailed description of the invention
Fig. 1 is the polymer drops SEM figure that embodiment 2 obtains；
Fig. 2 is the TEM figure and Metal Distribution figure for the sulphur carbon ball supported precious metal catalyst that embodiment 2 obtains；
Fig. 3 is the mapping analysis for the sulphur carbon ball supported precious metal catalyst that embodiment 2 obtains；
The sulphur carbon ball graph of pore diameter distribution that Fig. 4 is.
(5) specific embodiment
Below with specific embodiment to further illustrate the technical scheme of the present invention, but protection scope of the present invention is not limited to
This.
Embodiment 1
Take the deionized water of 100ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 0.5g cetyl trimethylammonium bromide and 1.5g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic
Power stirs 1h and is completely dissolved to solid.Then, the 4 of 5g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h extremely
Solid is completely dissolved, and then opens one of glass stopper, and the dense H of 2ml is slowly added dropwise2SO4Solution in above-mentioned mixed solution,
Strict control rate of addition is more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 0.1 DEG C/min liter
Warm rate rises to 60 DEG C, keeps 6h, then proceedes to rise to 90 DEG C with 0.1 DEG C/min heating rate, keeps 6h, finally continue with
0.1 DEG C/min heating rate rises to boiling, keeps 2h under condensing reflux state.After terminating stirring, polymer solution is added to
In water heating kettle, it is arranged 100 DEG C of hydrothermal temperature, then hydro-thermal time 12h obtains the polymer solution low-temperature vacuum drying after hydro-thermal
To polymer solids powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, cryogenic vacuum
Drying condition is relative degree of vacuum -0.099MPa, and temperature is -10 DEG C, drying time 10h.
Obtained 2g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, are then slowly added dropwise 10ml's
The palladium nitrate solution that the palladium content of chlorine palladium acid solution and 10ml that palladium content is 0.001g/mL is 0.001g/mL controls slurries temperature
30 DEG C of degree, sodium hydroxide solution control pH 3.5, magnetic agitation 3h.After terminating stirring, polymer suspension is filtered and spent
Ion water washing 3 times, temperature 60 C is arranged in convection oven, and dry 12h obtains solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and argon gas and is roasted, in the mixed atmosphere
Hydrogen volume concentration is 5%, and vapor volumetric concentration 0.5%, calcination steps are temperature programming control process: being risen to from room temperature
300 DEG C, this step-up temperature rate is 1 DEG C/min, and keeps 2h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature rate
For 1 DEG C/min, and 2h is kept under constant temperature, sulphur carbon ball supported precious metal catalyst can be obtained；Roasting process, volumetric flow of gas
60ml/min.It is characterized through BET, catalyst is spherical in shape, ball size 800~810nm, Kong Rong 0.15ml/g, specific surface area 300m2/
G, average pore size 2nm, micropore ratio is 60%.It is 0.05% through S/C mass ratio in elemental analysis sulphur carbon ball.It characterizes, bears through TEM
It is loaded in the 8~10nm of metallic partial size on sulphur carbon ball surface.Through icp analysis, tenor 2%.
Embodiment 2
Take the deionized water of 100ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 1g cetyl trimethylammonium bromide and 2g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic force and stirs
It mixes 1h and is completely dissolved to solid.Then, the 4 of 8g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h to solid
It is completely dissolved, then opens one of glass stopper, the dense H of 2ml is slowly added dropwise2SO4Solution is in above-mentioned mixed solution, strictly
Rate of addition is controlled, is more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 0.1 DEG C/min heating speed
Rate rises to 60 DEG C, keeps 8h, then proceedes to rise to 90 DEG C with 0.1 DEG C/min heating rate, keeps 8h, finally continue with 0.1 DEG C/
Min heating rate rises to boiling, keeps 2h under condensing reflux state.After terminating stirring, polymer solution is added to water heating kettle
In, it is arranged 100 DEG C of hydrothermal temperature, then the polymer solution low-temperature vacuum drying after hydro-thermal is polymerize by hydro-thermal time 12h
Object solid powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, low-temperature vacuum drying item
Part is relative degree of vacuum -0.099MPa, and temperature is -5 DEG C, drying time 12h.
Obtained 10g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, 25ml is then slowly added dropwise
Palladium content be 0.005g/mL palladium acetate solution and 25ml palladium content be 0.005g/mL dichloride rhodium solution, control slurry
40 DEG C of liquid temperature, sodium hydroxide solution controls pH 6.5, magnetic agitation 3h.After terminating stirring, polymer suspension is filtered simultaneously
It is washed with deionized 3 times, temperature 60 C is arranged in convection oven, and dry 12h obtains solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and nitrogen and is roasted, in the mixed atmosphere
Hydrogen volume concentration is 5%, and vapor volumetric concentration 0.1%, calcination steps are temperature programming control process: being risen to from room temperature
300 DEG C, this step-up temperature rate is 2 DEG C/min, and keeps 2h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature rate
For 2 DEG C/min, and 2h is kept under constant temperature, sulphur carbon ball supported precious metal catalyst can be obtained；Roasting process, volumetric flow of gas
60ml/min.It is characterized through BET, catalyst is spherical in shape, ball size 500~520nm, Kong Rong 1.0ml/g, specific surface area 1000m2/
G, average pore size 2nm, micropore ratio is 75%.It is 0.5% through S/C mass ratio in elemental analysis sulphur carbon ball.It characterizes, bears through TEM
It is loaded in the 6~8nm of metallic partial size on sulphur carbon ball surface.It is characterized through ICP, tenor 6.25%.
Embodiment 3
Take the deionized water of 100ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 1g cetyl trimethylammonium bromide and 2g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic force and stirs
It mixes 1h and is completely dissolved to solid.Then, the 4 of 10g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h to solid
It is completely dissolved, then opens one of glass stopper, the dense H of 2ml is slowly added dropwise2SO4Solution is in above-mentioned mixed solution, strictly
Rate of addition is controlled, is more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 1 DEG C/min heating rate
60 DEG C are risen to, 12h is kept, then proceedes to rise to 90 DEG C with 1 DEG C/min heating rate, keeps 12h, finally continue with 1 DEG C/min
Heating rate rises to boiling, keeps 2h under condensing reflux state.After terminating stirring, polymer solution is added in water heating kettle,
100 DEG C of hydrothermal temperature of setting, the polymer solution low-temperature vacuum drying after hydro-thermal for 24 hours, is then obtained polymer by the hydro-thermal time
Solid powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, low-temperature vacuum drying condition
For relative degree of vacuum -0.01MPa, temperature is -5 DEG C, drying time 14h.
Obtained 10g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, 25ml is then slowly added dropwise
Platinum content be 0.01g/mL platinum acid chloride solution and 25ml platinum content be 0.01g/mL platinous chloride solution, control slurries
Temperature 50 C, sodium hydroxide solution control pH 4.5, magnetic agitation 3h.After terminating stirring, polymer suspension is filtered and is used in combination
Deionized water is washed 3 times, and temperature 60 C is arranged in convection oven, and dry 12h obtains solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and nitrogen and is roasted, in the mixed atmosphere
Hydrogen volume concentration is 5%, and vapor volumetric concentration 5.0%, calcination steps are temperature programming control process: being risen to from room temperature
300 DEG C, this step-up temperature rate is 2 DEG C/min, and keeps 3h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature rate
For 2 DEG C/min, and 3h is kept under constant temperature, sulphur carbon ball supported precious metal catalyst can be obtained；Roasting process, volumetric flow of gas
80ml/min.It is characterized through BET, catalyst is spherical in shape, ball size 800~810nm, Kong Rong 0.8ml/g, specific surface area 1000m2/
G, average pore size 1.9nm, micropore ratio is 74%.It is 5.0% through S/C mass ratio in elemental analysis sulphur carbon ball.It is characterized through TEM,
It is supported on the 8~10nm of metallic partial size on sulphur carbon ball surface.It is characterized through ICP, tenor 12.25%.
Embodiment 4
Take the deionized water of 150ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 1.5g cetyl trimethylammonium bromide and 2g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic force
Stirring 1h is completely dissolved to solid.Then, the 4 of 10g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h to admittedly
Body is completely dissolved, and then opens one of glass stopper, and the dense H of 4ml is slowly added dropwise2SO4Solution is in above-mentioned mixed solution, sternly
Lattice control rate of addition, are more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 1 DEG C/min heating speed
Rate rises to 60 DEG C, keeps 12h, then proceedes to rise to 90 DEG C with 1 DEG C/min heating rate, keeps 12h, finally continue with 1 DEG C/
Min heating rate rises to boiling, keeps 2h under condensing reflux state.After terminating stirring, polymer solution is added to water heating kettle
In, it is arranged 200 DEG C of hydrothermal temperature, then the polymer solution low-temperature vacuum drying after hydro-thermal is polymerize by hydro-thermal time 12h
Object solid powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, low-temperature vacuum drying item
Part is relative degree of vacuum -0.01MPa, and temperature is 0 DEG C, drying time 16h.
Obtained 30g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, 60ml is then slowly added dropwise
0.001g/mL platinic sodium chloride solution, control 30 DEG C of slurry temperature, sodium hydroxide solution controls pH 5.5, magnetic agitation 5h.
After terminating stirring, polymer suspension is filtered and is washed with deionized 3 times, temperature 60 C, dry 12h is arranged in convection oven
Obtain solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and helium and is roasted, in the mixed atmosphere
Hydrogen volume concentration is 10%, and vapor volumetric concentration 4.0%, calcination steps are temperature programming control process: being risen to from room temperature
300 DEG C, this step-up temperature rate is 3 DEG C/min, and keeps 4h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature rate
For 3 DEG C/min, and 4h is kept under constant temperature, sulphur carbon ball supported precious metal catalyst can be obtained；Roasting process, volumetric flow of gas
80ml/min.It is characterized through BET, catalyst is spherical in shape, ball size 400~420nm, Kong Rong 0.45ml/g, specific surface area 850m2/
G, average pore size 1.88nm, micropore ratio is 80%.It is 5.0% through S/C mass ratio in elemental analysis sulphur carbon ball.It is characterized through TEM,
It is supported on the 7~10nm of metallic average grain diameter on sulphur carbon ball surface.It is characterized through ICP, tenor 0.2%.
Embodiment 5
Take the deionized water of 150ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 1.5g cetyl trimethylammonium bromide and 2.5g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic
Power stirs 1h and is completely dissolved to solid.Then, the 4 of 15g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h extremely
Solid is completely dissolved, and then opens one of glass stopper, and the dense H of 4ml is slowly added dropwise2SO4Solution in above-mentioned mixed solution,
Strict control rate of addition is more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 1 DEG C/min heating
Rate rises to 60 DEG C, keeps 12h, then proceedes to rise to 90 DEG C with 1 DEG C/min heating rate, keeps 12h, finally continue with 1 DEG C/
Min heating rate rises to boiling, keeps 2h under condensing reflux state.After terminating stirring, polymer solution is added to water heating kettle
In, it is arranged 200 DEG C of hydrothermal temperature, then the polymer solution low-temperature vacuum drying after hydro-thermal is polymerize by hydro-thermal time 12h
Object solid powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, low-temperature vacuum drying item
Part is relative degree of vacuum -0.05MPa, and temperature is 0 DEG C, and drying time is for 24 hours.
Obtained 16g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, 100ml is then slowly added dropwise
Rhodium content be 0.01g/mL rhodium nitrate solution, control 30 DEG C of slurry temperature, sodium hydroxide solution controls pH 3.5, magnetic force
Stir 6h.After terminating stirring, polymer suspension being filtered and is washed with deionized 3 times, temperature 60 C is arranged in convection oven,
Dry 12h obtains solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and nitrogen and is roasted, in the mixed atmosphere
Hydrogen volume concentration is 30%, and vapor volumetric concentration 3.0%, calcination steps are temperature programming control process: being risen to from room temperature
300 DEG C, this step-up temperature rate is 3 DEG C/min, and keeps 4h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature rate
For 3 DEG C/min, and 4h is kept under constant temperature, sulphur carbon ball supported precious metal catalyst can be obtained；Roasting process, volumetric flow of gas
80ml/min.It is characterized through BET, catalyst is spherical in shape, ball size 400~410nm, Kong Rong 0.25ml/g, specific surface area 650m2/
G, average pore size 1.54nm, micropore ratio is 85%.It is 15.0% through S/C mass ratio in elemental analysis sulphur carbon ball.Through TEM table
Sign, is supported on the 4~5nm of metallic partial size on sulphur carbon ball surface.It is characterized through ICP, tenor 10%.
Embodiment 6
Take the deionized water of 200ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 1.5g cetyl trimethylammonium bromide and 2.5g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic
Power stirs 1h and is completely dissolved to solid.Then, the 4 of 15g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h extremely
Solid is completely dissolved, and then opens one of glass stopper, and the dense H of 5ml is slowly added dropwise2SO4Solution in above-mentioned mixed solution,
Strict control rate of addition is more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 1 DEG C/min heating
Rate rises to 60 DEG C, keeps 6h, then proceedes to rise to 90 DEG C with 0.1 DEG C/min heating rate, keeps 12h, finally continue with 1
DEG C/min heating rate rises to boiling, 2h is kept under condensing reflux state.After terminating stirring, polymer solution is added to hydro-thermal
In kettle, it is arranged 200 DEG C of hydrothermal temperature, the hydro-thermal time for 24 hours, is then gathered the polymer solution low-temperature vacuum drying after hydro-thermal
Close object solid powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, low-temperature vacuum drying
Condition is relative degree of vacuum -0.05MPa, and temperature is -10 DEG C, drying time 20h.
Obtained 30g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, 100ml is then slowly added dropwise
Rhodium content be 0.03g/mL rhodium acetate solution, control 40 DEG C of slurry temperature, sodium hydroxide solution control pH 4, magnetic force stirs
Mix 5h.After terminating stirring, polymer suspension is filtered and is washed with deionized 3 times, temperature 60 C is arranged in convection oven, does
Dry 12h obtains solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and helium and is roasted, in the mixed atmosphere
Hydrogen volume concentration is 20%, and vapor volumetric concentration 2.0%, calcination steps are temperature programming control process: being risen to from room temperature
300 DEG C, this step-up temperature rate is 2 DEG C/min, and keeps 4h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature rate
For 2 DEG C/min, and 4h is kept under constant temperature, sulphur carbon ball supported precious metal catalyst can be obtained；Roasting process, volumetric flow of gas
80ml/min.It is characterized through BET, catalyst is spherical in shape, ball size 200~220nm, Kong Rong 0.2ml/g, specific surface area 600m2/ g,
Average pore size 1.33nm, micropore ratio is 76%.It is 20.0% through S/C mass ratio in elemental analysis sulphur carbon ball.It is characterized through TEM,
It is supported on the 6~8nm of metallic partial size on sulphur carbon ball surface.It is characterized through ICP, tenor 20%.
Embodiment 7
Take the deionized water of 200ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 0.5g cetyl trimethylammonium bromide and 2.5g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic
Power stirs 1h and is completely dissolved to solid.Then, the 4 of 5g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h extremely
Solid is completely dissolved, and then opens one of glass stopper, and the dense H of 5ml is slowly added dropwise2SO4Solution in above-mentioned mixed solution,
Strict control rate of addition is more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 0.5 DEG C/min liter
Warm rate rises to 60 DEG C, keeps 8h, then proceedes to rise to 90 DEG C with 0.5 DEG C/min heating rate, keeps 8h, finally continue with 1
DEG C/min heating rate rises to boiling, 2h is kept under condensing reflux state.After terminating stirring, polymer solution is added to hydro-thermal
In kettle, it is arranged 200 DEG C of hydrothermal temperature, then hydro-thermal time 36h is gathered the polymer solution low-temperature vacuum drying after hydro-thermal
Close object solid powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, low-temperature vacuum drying
Condition is relative degree of vacuum -0.05MPa, and temperature is 0 DEG C, drying time 12h.
Obtained 8g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, are then slowly added dropwise 50ml's
Iridium content is the iridous chloride solution of 0.01g/mL, controls 50 DEG C of slurry temperature, and sodium hydroxide solution controls pH 4.5, magnetic force
Stir 4h.After terminating stirring, polymer suspension being filtered and is washed with deionized 3 times, temperature 60 C is arranged in convection oven,
Dry 12h obtains solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and inert gas and is roasted, the gaseous mixture
Hydrogen volume concentration is 10% in atmosphere, and vapor volumetric concentration 3.0%, calcination steps are temperature programming control process: from room temperature
300 DEG C are risen to, this step-up temperature rate is 1 DEG C/min, and keeps 3h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature
Rate is 1 DEG C/min, and keeps 3h under constant temperature, and sulphur carbon ball supported precious metal catalyst can be obtained；The mixed atmosphere, dehydrogenation
Outside gas, the optional nitrogen of inert gas.Roasting process, volumetric flow of gas 80ml/min.It is characterized through BET, catalyst is spherical in shape, ball
Size 790~800nm, Kong Rong 0.3ml/g, specific surface area 650m2/ g, average pore size 1.85nm, micropore ratio is 75%.Through member
S/C ratio is 1.0% in element analysis sulphur carbon ball.It is characterized through TEM, is supported on the 6~7nm of metallic partial size on sulphur carbon ball surface.Through
ICP characterization, tenor 10%.
Embodiment 8
Take the deionized water of 150ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 1.5g cetyl trimethylammonium bromide and 1.5g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic
Power stirs 1h and is completely dissolved to solid.Then, the 4 of 20g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h extremely
Solid is completely dissolved, and then opens one of glass stopper, and the dense H of 5ml is slowly added dropwise2SO4Solution in above-mentioned mixed solution,
Strict control rate of addition is more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 0.2 DEG C/min liter
Warm rate rises to 60 DEG C, keeps 12h, then proceedes to rise to 90 DEG C with 0.2 DEG C/min heating rate, keeps 12h, finally continue with
1 DEG C/min heating rate rises to boiling, keeps 2h under condensing reflux state.After terminating stirring, polymer solution is added to water
In hot kettle, it is arranged 100 DEG C of hydrothermal temperature, then hydro-thermal time 36h obtains the polymer solution low-temperature vacuum drying after hydro-thermal
Polymer solids powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, and cryogenic vacuum is dry
Dry condition is relative degree of vacuum -0.01MPa, and temperature is -10 DEG C, and drying time is for 24 hours.
Obtained 20g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, 50ml is then slowly added dropwise
Ruthenium content be 0.03g/mL nitric acid ruthenium solution, control 30 DEG C of slurry temperature, sodium hydroxide solution controls pH 3.5, magnetic force
Stir 3h.After terminating stirring, polymer suspension being filtered and is washed with deionized 3 times, temperature 60 C is arranged in convection oven,
Dry 12h obtains solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and nitrogen and is roasted, in the mixed atmosphere
Hydrogen volume concentration is 25%, and vapor volumetric concentration 0.15%, calcination steps are temperature programming control process: being risen to from room temperature
300 DEG C, this step-up temperature rate is 1.5 DEG C/min, and keeps 4h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature speed
Rate is 1.5 DEG C/min, and keeps 4h under constant temperature, and sulphur carbon ball supported precious metal catalyst can be obtained；Roasting process, gas volume
Flow 90ml/min.It is characterized through BET, catalyst is spherical in shape, ball size 390~400nm, Kong Rong 0.35ml/g, specific surface area
750m2/ g, average pore size 1.87nm, micropore ratio is 60%.It is 10.0% through S/C ratio in elemental analysis sulphur carbon ball.Through TEM table
Sign, is supported on the 9~10nm of metallic partial size on sulphur carbon ball surface.It is characterized through ICP, tenor 15%.
Embodiment 9
Take the deionized water of 200ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 1g cetyl trimethylammonium bromide and 2.5g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic force
Stirring 1h is completely dissolved to solid.Then, the 4 of 10g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h to admittedly
Body is completely dissolved, and then opens one of glass stopper, and the dense H of 3ml is slowly added dropwise2SO4Solution is in above-mentioned mixed solution, sternly
Lattice control rate of addition, are more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 0.8 DEG C/min heating
Rate rises to 60 DEG C, keeps 12h, then proceedes to rise to 90 DEG C with 0.8 DEG C/min heating rate, keeps 12h, finally continue with
0.1 DEG C/min heating rate rises to boiling, keeps 2h under condensing reflux state.After terminating stirring, polymer solution is added to
In water heating kettle, it is arranged 100 DEG C of hydrothermal temperature, then hydro-thermal time 36h obtains the polymer solution low-temperature vacuum drying after hydro-thermal
To polymer solids powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, cryogenic vacuum
Drying condition is relative degree of vacuum -0.01MPa, and temperature is -10 DEG C, and drying time is for 24 hours.
Obtained 20g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, 20ml is then slowly added dropwise
Palladium content be 0.01g/mL chlorine palladium acid solution, control 30 DEG C of slurry temperature, sodium hydroxide solution controls pH 3.5, magnetic force
Stir 3h.After terminating stirring, polymer suspension being filtered and is washed with deionized 3 times, temperature 60 C is arranged in convection oven,
Dry 12h obtains solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and nitrogen and is roasted, in the mixed atmosphere
Hydrogen volume concentration is 25%, and vapor volumetric concentration 3.0%, calcination steps are temperature programming control process: being risen to from room temperature
300 DEG C, this step-up temperature rate is 1.5 DEG C/min, and keeps 4h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature speed
Rate is 1.5 DEG C/min, and keeps 4h under constant temperature, and sulphur carbon ball supported precious metal catalyst can be obtained；Roasting process, gas volume
Flow 90ml/min.It is characterized through BET, catalyst is spherical in shape, ball size 590~600nm, Kong Rong 0.25ml/g, specific surface area
550m2/ g, average pore size 1.82nm, micropore ratio is 85%.It is 15.0% through S/C mass ratio in elemental analysis sulphur carbon ball.Through
TEM characterization, is supported on the 4~5nm of metallic average grain diameter on sulphur carbon ball surface.It is characterized through ICP, tenor 2%.
Embodiment 10
Take the deionized water of 200ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 1.5g cetyl trimethylammonium bromide and 2.5g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic
Power stirs 1h and is completely dissolved to solid.Then, the 4 of 20g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h extremely
Solid is completely dissolved, and then opens one of glass stopper, and the dense H of 5ml is slowly added dropwise2SO4Solution in above-mentioned mixed solution,
Strict control rate of addition is more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 1 DEG C/min heating
Rate rises to 60 DEG C, keeps 12h, then proceedes to rise to 90 DEG C with 1 DEG C/min heating rate, keeps 12h, finally continue with 0.1
DEG C/min heating rate rises to boiling, 2h is kept under condensing reflux state.After terminating stirring, polymer solution is added to hydro-thermal
In kettle, it is arranged 200 DEG C of hydrothermal temperature, then hydro-thermal time 36h is gathered the polymer solution low-temperature vacuum drying after hydro-thermal
Close object solid powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, low-temperature vacuum drying
Condition is relative degree of vacuum 0MPa, and temperature is -5 DEG C, drying time 12h.
Obtained 16g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, 100ml is then slowly added dropwise
Palladium content be 0.005g/mL chlorine palladium acid solution, control 40 DEG C of slurry temperature, sodium hydroxide solution controls pH 5.5, magnetic force
Stir 3h.After terminating stirring, polymer suspension being filtered and is washed with deionized 3 times, temperature 60 C is arranged in convection oven,
Dry 12h obtains solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and nitrogen and is roasted, in the mixed atmosphere
Hydrogen volume concentration is 30%, and vapor volumetric concentration 0.2%, calcination steps are temperature programming control process: being risen to from room temperature
300 DEG C, this step-up temperature rate is 3 DEG C/min, and keeps 4h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature rate
For 3 DEG C/min, and 4h is kept under constant temperature, sulphur carbon ball supported precious metal catalyst can be obtained；Roasting process, volumetric flow of gas
100ml/min.It is characterized through BET, catalyst is spherical in shape, ball size 300~310nm, Kong Rong 0.4ml/g, specific surface area 1000m2/
G, average pore size 1.6nm, micropore ratio is 78%.It is 20.0% through S/C mass ratio in elemental analysis sulphur carbon ball.It is characterized through TEM,
It is supported on the 5~7nm of metallic partial size on sulphur carbon ball surface.It is characterized through ICP, tenor 5%.
Embodiment 11
Take the deionized water of 200ml in three-neck flask, load onto condensation reflux unit flatly, in addition two mouthfuls it is close with glass stopper
Envelope；Then 1.5g cetyl trimethylammonium bromide and 2.5g cysteine solid is added, is arranged 30 DEG C of bath temperature, starts magnetic
Power stirs 1h and is completely dissolved to solid.Then, the 4 of 15g, 4 '-thio salicyl salicylate (salsalate) thiophenol solids are added, continue to stir 0.5h extremely
Solid is completely dissolved, and then opens one of glass stopper, and the dense H of 4ml is slowly added dropwise2SO4Solution in above-mentioned mixed solution,
Strict control rate of addition is more than 2 DEG C to prevent temperature rise caused by heat of solution.Continue magnetic agitation, from room temperature with 0.6 DEG C/min liter
Warm rate rises to 60 DEG C, keeps 10h, then proceedes to rise to 90 DEG C with 1 DEG C/min heating rate, keeps 10h, finally continue with
0.1 DEG C/min heating rate rises to boiling, keeps 2h under condensing reflux state.After terminating stirring, polymer solution is added to
In water heating kettle, it is arranged 200 DEG C of hydrothermal temperature, then hydro-thermal time 36h obtains the polymer solution low-temperature vacuum drying after hydro-thermal
To polymer solids powder.Polymer solution obtains in polymer solids powder process by low-temperature vacuum drying, cryogenic vacuum
Drying condition is relative degree of vacuum 0.05MPa, and temperature is 0 DEG C, and drying time is for 24 hours.
Obtained 10g polymer solids powder and 30ml deionized water are sufficiently mixed mashing, 80ml is then slowly added dropwise
Palladium content be 0.005g/mL chlorine palladium acid solution, control 30 DEG C of slurry temperature, sodium hydroxide solution controls pH 3.5, magnetic force
Stir 3h.After terminating stirring, polymer suspension being filtered and is washed with deionized 3 times, temperature 60 C is arranged in convection oven,
Dry 12h obtains solid.
Obtained solid is placed in the mixed atmosphere of hydrogen, vapor and nitrogen and is roasted, in the mixed atmosphere
Hydrogen volume concentration is 30%, and vapor volumetric concentration 4.0%, calcination steps are temperature programming control process: being risen to from room temperature
300 DEG C, this step-up temperature rate is 3 DEG C/min, and keeps 4h under constant temperature；700 DEG C are risen to from 300 DEG C, this step-up temperature rate
For 3 DEG C/min, and 4h is kept under constant temperature, doping sulphur charcoal ball supported precious metal catalyst can be obtained；Roasting process, gas volume
Flow 100ml/min.It is characterized through BET, catalyst is spherical in shape, ball size 290~300nm, Kong Rong 0.38ml/g, specific surface area
850m2/ g, average pore size 1.79nm, micropore ratio is 83%.It is 15.0% through S/C mass ratio in elemental analysis sulphur carbon ball.Through
TEM characterization, is supported on the 8~10nm of metallic partial size on sulphur carbon ball surface.It is characterized through ICP, tenor 6.67%.
Comparative example 1
The carrier active carbon physical parameter: ash 3.0wt%, specific surface area 1500m2/g, micropore specific area
Proportion is not less than 75%, and active carbon particle granularity is D10:2.5 μm, D50:12 μm, D90:30 μm；The material of the active carbon
Matter is coconut husk.
Conventional palladium on carbon hydrogenation catalyst preparation: by 20g coconut husk preparing active carbon in 120 DEG C of vacuum dehydration 3h；Then
In 60 DEG C of processing 6h of hydrochloric acid solution that 100mL concentration is 3mol/mL, it is washed out neutrality and mixes and stir with the water of 50ml later
It mixes；And hydrochloric acid tune pH to 1 is added dropwise, the chlorine palladium acid solution that the 0.05g/ml of 20ml is instilled when after heating to 30 DEG C stirs 5h, then
PH to 8 is adjusted, continues to stir 1h, washing later is to neutrality, dry 6h at 120 DEG C under vacuum later, then hydrogen-argon-mixed
It is gone back at (hydrogen volume concentration is 30% in the mixed atmosphere, volume of gas flow 100ml/min) is 150 DEG C lower
Original restores 3h, obtains 5wt%Pd/C catalyst.Then Na is used2S liquid phase stirs the 5wt%Pd/C of vulcanization preparation sulphuring treatment,
The 5wt%Pd/C catalyst and Na of 1:1 in mass ratio2S.9H2O, which is weighed, to be placed in three-necked flask, and constant temperature stirs 3h at 30 DEG C
It filters, wash afterwards, drying.
Embodiment 12
1 catalyst of 0.1g embodiment, 10gN- diphenyl-para-phenylene diamine and 15ml acetone are added to 50ml autoclave
In, closed reactor is passed through nitrogen, checks whether gas leakage is passed through nitrogen 1.0MPa and replaces sky autoclave if air tight
Gas, so operation are repeated 3 times.After opening hydrogen cylinder main valve, after pressure reducing valve to 1.0MPa Hydrogen Vapor Pressure, kettle upper air is opened
Valve enters hydrogen in reaction kettle.Then again with hydrogen displacement nitrogen 3 times, after be flushed with hydrogen in gas to kettle and be to required pressure
0.8MPa, then it is arranged under conditions of required reaction temperature is 80 DEG C and opens temperature program and magnetic agitation starting reaction, often
Hydrogen is added when pressure declines 0.3MPa to designated value, when pressure no longer declines in kettle, continue after constant temperature and pressure stirs 0.5h,
Stop stirring, be cooled to room temperature, opens kettle and take out hydrogenation liquid, hydrogenation liquid obtains N- isopropyl-N '-phenyl to benzene after separating treatment
Diamines, and filter cake is obtained by filtration.Analyze result are as follows: reaction conversion ratio 100%, N- isopropyl-N '-diphenyl-para-phenylene diamine selectivity
99%, reaction time 8h.
Embodiment 13
1 catalyst of 0.1g embodiment, 10gN- diphenyl-para-phenylene diamine and 15ml acetone are added to 50ml autoclave
In, closed reactor is passed through nitrogen, checks whether gas leakage is passed through nitrogen 1.0MPa and replaces sky autoclave if air tight
Gas, so operation are repeated 3 times.After opening hydrogen cylinder main valve, after pressure reducing valve to 1.0MPa Hydrogen Vapor Pressure, kettle upper air is opened
Valve enters hydrogen in reaction kettle.Then again with hydrogen displacement nitrogen 3 times, after be flushed with hydrogen in gas to kettle and be to required pressure
2.0MPa, then it is arranged under conditions of required reaction temperature is 90 DEG C and opens temperature program and magnetic agitation starting reaction, often
Hydrogen is added when pressure declines 0.3MPa to designated value, when pressure no longer declines in kettle, continue after constant temperature and pressure stirs 0.5h,
Stop stirring, be cooled to room temperature, opens kettle and take out hydrogenation liquid, hydrogenation liquid obtains N- isopropyl-N '-phenyl to benzene after separating treatment
Diamines, and filter cake is obtained by filtration.Analyze result are as follows: reaction conversion ratio 100%, N- isopropyl-N '-diphenyl-para-phenylene diamine selectivity
98%, reaction time 3h.
Embodiment 14
2 catalyst of 0.5g embodiment, 10gN- diphenyl-para-phenylene diamine and 15ml acetone are added to 50ml autoclave
In, closed reactor is passed through nitrogen, checks whether gas leakage is passed through nitrogen 1.0MPa and replaces sky autoclave if air tight
Gas, so operation are repeated 3 times.After opening hydrogen cylinder main valve, after pressure reducing valve to 1.0MPa Hydrogen Vapor Pressure, kettle upper air is opened
Valve enters hydrogen in reaction kettle.Then again with hydrogen displacement nitrogen 3 times, after be flushed with hydrogen in gas to kettle and be to required pressure
1.0MPa, then it is arranged under conditions of required reaction temperature is 90 DEG C and opens temperature program and magnetic agitation starting reaction, often
Hydrogen is added when pressure declines 0.3MPa to designated value, when pressure no longer declines in kettle, continue after constant temperature and pressure stirs 0.5h,
Stop stirring, be cooled to room temperature, opens kettle and take out hydrogenation liquid, hydrogenation liquid obtains N- isopropyl-N '-phenyl to benzene after separating treatment
Diamines, and filter cake is obtained by filtration.Analyze result are as follows: reaction conversion ratio 100%, N- isopropyl-N '-diphenyl-para-phenylene diamine selectivity
98%, reaction time 1h.
Embodiment 15
3 catalyst of 0.1g embodiment, 10gN- diphenyl-para-phenylene diamine and 15ml methyl iso-butyl ketone (MIBK) are added to 50ml high pressure
In reaction kettle, closed reactor is passed through nitrogen, checks whether gas leakage is passed through nitrogen 1.0MPa and sets autoclave if air tight
It ventilates, so operation is repeated 3 times.After opening hydrogen cylinder main valve, after pressure reducing valve to 1.0MPa Hydrogen Vapor Pressure, open on kettle
Intake valve enters hydrogen in reaction kettle.Then again with hydrogen displacement nitrogen 3 times, after be flushed with hydrogen in gas to kettle to required pressure
For 1.5MPa, then it is arranged under conditions of required reaction temperature is 100 DEG C and opens temperature program and magnetic agitation starting reaction,
Hydrogen is added when pressure declines 0.3MPa to designated value, when pressure no longer declines in kettle, continuation constant temperature and pressure stirs 0.5h
Afterwards, stop stirring, be cooled to room temperature, open kettle and take out hydrogenation liquid, hydrogenation liquid obtains N- (1,3- dimethyl butyrate after separating treatment
Base)-N '-diphenyl-para-phenylene diamine, and filter cake is obtained by filtration.Analyze result are as follows: reaction conversion ratio 100%, N- (1,3- dimethyl butyrate
Base)-N '-diphenyl-para-phenylene diamine selectivity 98%, reaction time 1h.
Embodiment 16
4 catalyst of 1.0g embodiment, 10gN- diphenyl-para-phenylene diamine and 15ml methyl iso-butyl ketone (MIBK) are added to 50ml high pressure
In reaction kettle, closed reactor is passed through nitrogen, checks whether gas leakage is passed through nitrogen 1.0MPa and sets autoclave if air tight
It ventilates, so operation is repeated 3 times.After opening hydrogen cylinder main valve, after pressure reducing valve to 1.0MPa Hydrogen Vapor Pressure, open on kettle
Intake valve enters hydrogen in reaction kettle.Then again with hydrogen displacement nitrogen 3 times, after be flushed with hydrogen in gas to kettle to required pressure
For 2.5MPa, then it is arranged under conditions of required reaction temperature is 120 DEG C and opens temperature program and magnetic agitation starting reaction,
Hydrogen is added when pressure declines 0.3MPa to designated value, when pressure no longer declines in kettle, continuation constant temperature and pressure stirs 0.5h
Afterwards, stop stirring, be cooled to room temperature, open kettle and take out hydrogenation liquid, hydrogenation liquid obtains N- (1,3- dimethyl butyrate after separating treatment
Base)-N '-diphenyl-para-phenylene diamine, and filter cake is obtained by filtration.Analyze result are as follows: reaction conversion ratio 99%, N- (1,3- dimethyl butyrate
Base)-N '-diphenyl-para-phenylene diamine selectivity 99%, reaction time 0.5h.
Embodiment 17
5 catalyst of 0.3g embodiment, 10gN- diphenyl-para-phenylene diamine and 15ml acetone are added to 50ml autoclave
In, closed reactor is passed through nitrogen, checks whether gas leakage is passed through nitrogen 1.0MPa and replaces sky autoclave if air tight
Gas, so operation are repeated 3 times.After opening hydrogen cylinder main valve, after pressure reducing valve to 1.0MPa Hydrogen Vapor Pressure, kettle upper air is opened
Valve enters hydrogen in reaction kettle.Then again with hydrogen displacement nitrogen 3 times, after be flushed with hydrogen in gas to kettle and be to required pressure
2.5MPa, then it is arranged under conditions of required reaction temperature is 130 DEG C and opens temperature program and magnetic agitation starting reaction, often
Hydrogen is added when pressure declines 0.3MPa to designated value, when pressure no longer declines in kettle, continue after constant temperature and pressure stirs 0.5h,
Stop stirring, be cooled to room temperature, opens kettle and take out hydrogenation liquid, hydrogenation liquid obtains N- isopropyl-N '-phenyl to benzene after separating treatment
Diamines, and filter cake is obtained by filtration.Analyze result are as follows: reaction conversion ratio 99%, N- isopropyl-N '-diphenyl-para-phenylene diamine selectivity
99.2%, reaction time 4h.
Embodiment 18
6 catalyst of 1.0g embodiment, 10gN- diphenyl-para-phenylene diamine and 15ml acetone are added to 50ml autoclave
In, closed reactor is passed through nitrogen, checks whether gas leakage is passed through nitrogen 1.0MPa and replaces sky autoclave if air tight
Gas, so operation are repeated 3 times.After opening hydrogen cylinder main valve, after pressure reducing valve to 1.0MPa Hydrogen Vapor Pressure, kettle upper air is opened
Valve enters hydrogen in reaction kettle.Then again with hydrogen displacement nitrogen 3 times, after be flushed with hydrogen in gas to kettle and be to required pressure
2.5MPa, then it is arranged under conditions of required reaction temperature is 140 DEG C and opens temperature program and magnetic agitation starting reaction, often
Hydrogen is added when pressure declines 0.3MPa to designated value, when pressure no longer declines in kettle, continue after constant temperature and pressure stirs 0.5h,
Stop stirring, be cooled to room temperature, opens kettle and take out hydrogenation liquid, hydrogenation liquid obtains N- isopropyl-N '-phenyl to benzene after separating treatment
Diamines, and filter cake is obtained by filtration.Analyze result are as follows: reaction conversion ratio 100%, N- isopropyl-N '-diphenyl-para-phenylene diamine selectivity
99%, reaction time 3h.
Embodiment 19
7 catalyst of 0.8g embodiment, 10gN- diphenyl-para-phenylene diamine and 15ml methyl iso-butyl ketone (MIBK) are added to 50ml high pressure
In reaction kettle, closed reactor is passed through nitrogen, checks whether gas leakage is passed through nitrogen 1.0MPa and sets autoclave if air tight
It ventilates, so operation is repeated 3 times.After opening hydrogen cylinder main valve, after pressure reducing valve to 1.0MPa Hydrogen Vapor Pressure, open on kettle
Intake valve enters hydrogen in reaction kettle.Then again with hydrogen displacement nitrogen 3 times, after be flushed with hydrogen in gas to kettle to required pressure
For 2.0MPa, then it is arranged under conditions of required reaction temperature is 150 DEG C and opens temperature program and magnetic agitation starting reaction,
Hydrogen is added when pressure declines 0.3MPa to designated value, when pressure no longer declines in kettle, continuation constant temperature and pressure stirs 0.5h
Afterwards, stop stirring, be cooled to room temperature, open kettle and take out hydrogenation liquid, hydrogenation liquid obtains N- (1,3- dimethyl butyrate after separating treatment
Base)-N '-diphenyl-para-phenylene diamine, and filter cake is obtained by filtration.Analyze result are as follows: reaction conversion ratio 100%, N- (1,3- dimethyl butyrate
Base)-N '-diphenyl-para-phenylene diamine selectivity 99.1%, reaction time 1h.
Embodiment 20
8 catalyst of 0.6g embodiment, 10gN- diphenyl-para-phenylene diamine and 15ml methyl iso-butyl ketone (MIBK) are added to 50ml high pressure
In reaction kettle, closed reactor is passed through nitrogen, checks whether gas leakage is passed through nitrogen 1.0MPa and sets autoclave if air tight
It ventilates, so operation is repeated 3 times.After opening hydrogen cylinder main valve, after pressure reducing valve to 1.0MPa Hydrogen Vapor Pressure, open on kettle
Intake valve enters hydrogen in reaction kettle.Then again with hydrogen displacement nitrogen 3 times, after be flushed with hydrogen in gas to kettle to required pressure
For 2.5MPa, then it is arranged under conditions of required reaction temperature is 150 DEG C and opens temperature program and magnetic agitation starting reaction,
Hydrogen is added when pressure declines 0.3MPa to designated value, when pressure no longer declines in kettle, continuation constant temperature and pressure stirs 0.5h
Afterwards, stop stirring, be cooled to room temperature, open kettle and take out hydrogenation liquid, hydrogenation liquid obtains N- (1,3- dimethyl butyrate after separating treatment
Base)-N '-diphenyl-para-phenylene diamine, and filter cake is obtained by filtration.Analyze result are as follows: reaction conversion ratio 100%, N- (1,3- dimethyl butyrate
Base)-N '-diphenyl-para-phenylene diamine selectivity 99.5%, reaction time 0.5h.
Embodiment 21
9 catalyst of 0.9g embodiment, 10gN- diphenyl-para-phenylene diamine and 15ml acetone are added to 50ml autoclave
In, closed reactor is passed through nitrogen, checks whether gas leakage is passed through nitrogen 1.0MPa and replaces sky autoclave if air tight
Gas, so operation are repeated 3 times.After opening hydrogen cylinder main valve, after pressure reducing valve to 1.0MPa Hydrogen Vapor Pressure, kettle upper air is opened
Valve enters hydrogen in reaction kettle.Then again with hydrogen displacement nitrogen 3 times, after be flushed with hydrogen in gas to kettle and be to required pressure
1.0MPa, then it is arranged under conditions of required reaction temperature is 150 DEG C and opens temperature program and magnetic agitation starting reaction, often
Hydrogen is added when pressure declines 0.3MPa to designated value, when pressure no longer declines in kettle, continue after constant temperature and pressure stirs 0.5h,
Stop stirring, be cooled to room temperature, opens kettle and take out hydrogenation liquid, hydrogenation liquid obtains N- isopropyl-N '-phenyl to benzene after separating treatment
Diamines, and filter cake is obtained by filtration.Analyze result are as follows: reaction conversion ratio 100%, N- isopropyl-N '-diphenyl-para-phenylene diamine selectivity
99.5%, reaction time 5h.
Comparative example 22~30
Using 1 catalyst of comparative example under the corresponding reaction condition of embodiment 12~21, the catalytic hydrogenation reaction of progress
Application as a result, as shown in table 1.
Application result of 1 comparative example of table, 1 catalyst under the corresponding reaction condition of embodiment 12~20
| Embodiment | Reaction condition | Conversion ratio % | Selective % | Reaction time h |
| Embodiment 22 | Embodiment 12 | 93.00 | 98.29 | 10 |
| Embodiment 23 | Embodiment 13 | 94.98 | 98.98 | 5 |
| Embodiment 24 | Embodiment 14 | 92.43 | 98.36 | 3 |
| Embodiment 25 | Embodiment 15 | 91.36 | 97.26 | 4 |
| Embodiment 26 | Embodiment 16 | 93.25 | 97.25 | 1 |
| Embodiment 27 | Embodiment 17 | 90.25 | 97.14 | 7 |
| Embodiment 28 | Embodiment 18 | 91.69 | 96.58 | 2 |
| Embodiment 29 | Embodiment 19 | 91.62 | 95.85 | 3 |
| Embodiment 30 | Embodiment 20 | 90.21 | 94.47 | 2 |
Embodiment 31
The catalyst of embodiment 21 applies experimental result.As shown in table 2.
The catalyst of 2 embodiment 21 of table applies experimental result
Claims (10)
1. a kind of sulphur carbon ball supported precious metal catalyst, the catalyst is by sulphur carbon ball and is carried on the work on sulphur carbon ball surface
Property group is grouped as；The element sulphur of the sulphur carbon ball is present on sulphur carbon ball skeleton and surface in the form of C-S key, wherein sulphur member
The mass ratio of element and carbon is 0.05~20%；The active component is platinum group metal particle, partial size in 4~10nm,
Based on the quality of sulphur carbon ball, the activity component load quantity is not higher than 20.0%；The sulphur carbon ball supported precious metal catalyst is in
Spherical shape, diameter is between 100~1000nm, 0.15~1.0ml/g of Kong Rongwei, and specific surface area is 300~1000m2/ g, it is average
Aperture is 0.5~2nm, and micropore ratio is 60~85%.
2. sulphur carbon ball supported precious metal catalyst as described in claim 1, it is characterised in that: the diameter of the catalyst is
200~800nm.
3. sulphur carbon ball supported precious metal catalyst as described in claim 1, it is characterised in that: the platinum group metal be platinum,
The combination of one or more of palladium, iridium, ruthenium, rhodium.
4. sulphur carbon ball supported precious metal catalyst as described in claim 1, it is characterised in that: the load capacity of the active component
It is 0.2~20%.
5. a kind of preparation method of sulphur carbon ball supported precious metal catalyst as described in claim 1, includes the following steps:
1) cetyl trimethylammonium bromide at room temperature, is added in the reaction vessel equipped with deionized water and cysteine is solid
Body, stirring are completely dissolved solid；Then the thio salicyl salicylate (salsalate) thiophenol solid of 4,4'- is added, it is completely molten to solid to continue stirring
Solution；The concentrated sulfuric acid is slowly added dropwise again in above-mentioned mixed solution, strict control rate of addition is more than 2 to prevent temperature rise caused by heat of solution
℃；Continue to stir, rises to 60 DEG C from room temperature with 0.1~1 DEG C/min heating rate, keep 6~12h, then proceed to 0.1~1
DEG C/min heating rate rises to 90 DEG C, 6~12h is kept, finally continues to rise to 140 DEG C with 0.1~1 DEG C/min heating rate, protect
Hold 0.5~2h；
After terminating stirring, obtained polymer solution is added in water heating kettle, is arranged 100~200 DEG C of hydrothermal temperature, when hydro-thermal
Between 12~36h, then isolated polymer solids, which has chondritic, and size is in 100~1000nm；
Wherein, deionized water, dense H2SO4Solution, cetyl trimethylammonium bromide, cysteine and the thio salicyl salicylate (salsalate) of 4,4'-
The feed ratio of thiophenol is 100~200ml:2~5ml:0.5~1.5g:1.5~2.5g:5~20g；
2) aqueous solution for the platinum group metal salts that platinum group metal concentration is 0.001~0.03g/mL is prepared；
3) the polymer solids powder for taking step 1) to obtain is sufficiently mixed mashing, step is then slowly added dropwise in deionized water
2) aqueous solution of the platinum group metal salts obtained is arranged 30~50 DEG C of bath temperature, starts 3~6h of stirring, wherein platinum group metal salts
Aqueous solution and polymer solids powder feed ratio be 20~100ml:2~30g；After terminating stirring, polymer suspension is taken out
It filters, wash, be dried to obtain solid；
4) solid for taking step 3) to obtain is placed in hydrogen and the mixed atmosphere of inert gas or nitrogen and is roasted, and described is mixed
Closing hydrogen volume concentration in atmosphere is 5~30%, and calcination steps are temperature programming control process: rising to 300~500 from room temperature
DEG C, this step-up temperature rate is 1~3 DEG C/min, and 2~4h is kept under constant temperature；700~900 DEG C are risen to from 300~500 DEG C, this
Step-up temperature rate is 1~3 DEG C/min, and 2~4h is kept under constant temperature, and sulphur carbon ball supported precious metal catalyst can be obtained.
6. preparation method as claimed in claim 5, it is characterised in that: in the step (1), the separate mode of polymer solids
Selected from following one kind: centrifugation, -10~0 DEG C of low-temperature vacuum drying.
7. sulphur carbon ball supported precious metal catalyst as described in claim 1 with 4-aminodiphenylamine shown in formula (I) and
Aliphatic ketone shown in formula (II) is application of the raw material in hydrogen in the reaction of one kettle way prepare compound (III),
Wherein, R, R' are each independently selected from alkyl substituent.
8. the use as claimed in claim 7, it is characterised in that: alkyl substituent is C1-C10 alkyl, preferably C1-C4 alkane
Base.
9. the use as claimed in claim 7, it is characterised in that: the reaction carries out under solvent-free conditions.
10. application as claimed in claim 9, it is characterised in that: the application method of the sulphur carbon ball supported precious metal catalyst
Are as follows:
Aliphatic ketone shown in 4-aminodiphenylamine shown in sulphur carbon ball supported precious metal catalyst, formula (I) and formula (II) is pressed
Ratio is added in autoclave, closed reactor, is passed through nitrogen displaced air, then with hydrogen displacement nitrogen, is flushed with hydrogen gas extremely
It is 0.5~3.5MPa that Hydrogen Vapor Pressure is arrived in kettle, then reaction temperature is arranged and is 80~150 DEG C and opens temperature program and magnetic agitation
Starting reaction, adds hydrogen to designated value when pressure declines 0.3MPa, when pressure no longer declines in kettle, continuation constant temperature and pressure
Stirring after a certain period of time, stops stirring, is cooled to room temperature, opens kettle and takes out hydrogenation liquid, hydrogenation liquid is post-treated to obtain formula (III) institute
The product shown.
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