WO2020016555A1 - Catalyst - Google Patents
Catalyst Download PDFInfo
- Publication number
- WO2020016555A1 WO2020016555A1 PCT/GB2019/051942 GB2019051942W WO2020016555A1 WO 2020016555 A1 WO2020016555 A1 WO 2020016555A1 GB 2019051942 W GB2019051942 W GB 2019051942W WO 2020016555 A1 WO2020016555 A1 WO 2020016555A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- equal
- catalyst
- gold
- less
- solvent
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 340
- 239000010931 gold Substances 0.000 claims abstract description 318
- 229910052737 gold Inorganic materials 0.000 claims abstract description 183
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 175
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 159
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 146
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 70
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 69
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 62
- 125000002091 cationic group Chemical group 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims description 150
- 238000000034 method Methods 0.000 claims description 105
- 239000002243 precursor Substances 0.000 claims description 86
- 239000000463 material Substances 0.000 claims description 75
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 70
- 230000003647 oxidation Effects 0.000 claims description 57
- 238000007254 oxidation reaction Methods 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 54
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 41
- 238000002441 X-ray diffraction Methods 0.000 claims description 39
- 238000007038 hydrochlorination reaction Methods 0.000 claims description 31
- 239000002105 nanoparticle Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 238000009835 boiling Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 21
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000539 dimer Substances 0.000 claims description 17
- 239000003446 ligand Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- -1 sulphoxides Chemical class 0.000 claims description 10
- 239000012696 Pd precursors Substances 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical group [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 claims description 6
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical group [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 5
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical group [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 5
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 3
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 150000004685 tetrahydrates Chemical class 0.000 claims description 3
- 150000004684 trihydrates Chemical class 0.000 claims description 3
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 122
- 125000004432 carbon atom Chemical group C* 0.000 description 59
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- 230000000694 effects Effects 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 241000894007 species Species 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000011888 foil Substances 0.000 description 17
- 238000005470 impregnation Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 15
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- 229920006395 saturated elastomer Polymers 0.000 description 13
- 125000004122 cyclic group Chemical group 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 11
- 230000000875 corresponding effect Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 239000003125 aqueous solvent Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 238000011068 loading method Methods 0.000 description 10
- 150000002894 organic compounds Chemical class 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical compound CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 2
- 241001125222 Centurio Species 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000000779 annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229950009390 symclosene Drugs 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- KOODSCBKXPPKHE-UHFFFAOYSA-N propanethioic s-acid Chemical compound CCC(S)=O KOODSCBKXPPKHE-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/462—Ruthenium
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- B01J27/10—Chlorides
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/82—Metals of the platinum group
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
Definitions
- the present invention relates generally to methods of making supported catalysts (e.g. supported gold, ruthenium, palladium, or platinum catalysts), particularly carbon-supported catalysts (e.g. carbon-supported gold, ruthenium, palladium, or platinum catalysts).
- the present invention further relates to the supported catalysts made by said methods and the use of the supported catalysts to make vinyl chloride, for example by acetylene hydrochlorination.
- the present invention relates generally to methods of making supported gold catalysts, particularly carbon-supported gold catalysts, and the catalysts made by said methods.
- the present invention further relates to the use of the supported gold catalysts to make vinyl chloride, for example by acetylene hydrochlorination.
- VCM vinyl chloride monomer
- PVC polyvinyl chloride
- HgCh mercuric chloride
- the mercury catalyst poses significant environmental concerns due to volatile HgCh subliming from the catalyst bed, up to 0.6 kg Hg/tonne VCM production. Due to the environmental impact of this process, the recently ratified Minamata convention dictates that all new VCM plants must use mercury free catalysts and in the near future all existing industrial plants must switch to mercury free alternatives. This has revived the commercial interest in using gold (Au) and other metals as a catalyst for this reaction.
- the conditions used to prepare the gold catalysts are thought to affect the acetylene hydrochlorination reaction profiles.
- acidic and/or strongly oxidising solvents are used to carry out a wet impregnation of a HAuCL precursor in order to obtain active catalysts.
- Concentrated nitric acid, hydrochloric acid and aqua regia a mixture of nitric acid and hydrochloric acid, often in a ratio of 1 :3 v/v nitric acid : hydrochloric acid have been used to produce active catalysts.
- compositions comprising organic compounds (e.g., pyridine, A/,/V-dimethylformamide and imidazole) and thionyl chloride (SOC ) termed“organic aqua regia (OAR)” have been used as alternatives to the acidic and/or strongly oxidising solvents.
- OAR does not provide a real environmentally friendly alternative compared to other approaches.
- active catalysts may be prepared in aqueous media in the presence of sulphur-containing ligands
- the toxicity of sulphur-containing ligands such as thiocyanate makes large scale preparations and utilisation unsuitable.
- Figure 1 shows a) Steady state acetylene conversion of 1% Au/C catalysts prepared by wet impregnation of HAuCU from various alcohol ( ⁇ ), ketone (A), ether ( ⁇ ) and aqueous solvents ( ⁇ ); the dotted line indicates the activity of the conventionally prepared aqua regia catalyst b) X-ray diffraction patterns of fresh 1% Au/C catalysts prepared with these various solvents ( Test Conditions: 90 mg catalyst, 23.5 ml_ min -1 C2H2, 23.7 ml_ min -1 HCI and 2.70 ml_ min 1 Ar, 200 °C);
- Figure 2 shows a) Steady state acetylene conversion of 1% Au/C catalysts prepared by wet impregnation of HAuCU from extra dry acetone with the addition of various amounts of water b) X-ray diffraction patterns of fresh 1% Au/C catalysts prepared with various acetone/water mixtures ( Test Conditions: 90 mg catalyst, 23.5 ml_ min -1 C2H2, 23.7 ml_ min- 1 HCI and 2.70 ml_ min 1 Ar, 200 °C);
- Figure 3 shows Time-online acetylene hydrochlorination activity profile of the Au/C- Acetone (A), Au/C-Aqua regia ( ⁇ ) and AU/C-H2O ( ⁇ ) catalysts ( Test Conditions: 90 mg catalyst, 23.5 ml_ min 1 C2H2, 23.7 ml_ min 1 HCI and 2.7 ml_ min 1 Ar, 200 °C);
- Figure 4 shows a) Representative STEM-HAADF image of the freshly prepared 1 % Au/C-Acetone material b) Au l_3-edge XANES of 1% Au/C-Acetone prior to reaction (- fresh) and after 4 h of reaction (- used), 1% Au/C-aqua regia and Au foil c) Linear combination fitting of the Au L3-edge XANES for 1% Au/C-aqua regia, 1% Au/C-Acetone (fresh) and 1% Au/C-Acetone (used) d) Fourier transform of the k 3 -weighted c EXAFS data of 1% Au/C-Acetone (fresh) and 1% Au/C-Acetone (used), 1 % Au/C-Aqua regia and Au foil;
- Figure 5 shows Two-day time-on-line acetylene hydrochlorination activity profiles of the Au/C-Acetone (A) and Au/C-aqua regia ( ⁇ ) catalysts ( Test Conditions: 90 mg catalyst, 23.5 mL min- 1 C 2 H 2 , 23.7 mL min 1 HCI and 2.7 mL min 1 Ar, 200 °C);
- Figure 6 shows X-ray diffraction patterns of catalysts prepared using various solvents and drying temperatures with nominal metal loading of 1 wt% Au;
- Figure 7 shows X-ray diffraction patterns of fresh Au/C-Acetone catalyst (fresh), Au/C- Acetone after 4h of reaction (used 4 h) and after a further 3 h of reaction (used 7 h);
- Figure 8 shows the acetylene hydrochlorination activity profile of the Au/C-Acetone ( ⁇ ) catalysts ( Test Conditions: 90 mg catalyst, 23.5 mL min 1 C 2 H 2 , 23.7 mL min 1 HCI and
- Figure 9 shows the acetylene hydrochlorination activity profile of the Pt/C-Acetone ( ⁇ ) catalysts ( Test Conditions: 90 mg catalyst, 23.5 mL min 1 C 2 H 2 , 23.7 mL min 1 HCI and
- Figure 10 shows the acetylene hydrochlorination activity profile of the Pd/C-Acetone (A) catalysts ( Test Conditions: 90 mg catalyst, 23.5 mL min 1 C 2 H 2 , 23.7 mL min 1 HCI and
- Figure 11 shows the acetylene hydrochlorination activity profile of the Ru/C-Acetone ( ⁇ ) catalysts ( Test Conditions: 90 mg catalyst, 23.5 mL min 1 C 2 H 2 , 23.7 mL min 1 HCI and
- Figure 12 shows the Fourier transform of the k 3 -weighted c EXAFS data of 1 % Au/C- Acetone (fresh - ⁇ ) and 1% Au/C-Acetone (used - T) and Au foil ( ⁇ );
- Figure 13 shows the Fourier transform of the k 3 -weighted c EXAFS data of 1 % Pt/C- Acetone (fresh - ⁇ ) and 1 % Pt/C-Acetone (used - T) and Pt foil ( ⁇ );
- Figure 14 shows the Fourier transform of the k 2 -weighted c EXAFS data of 1 % Pd/C- Acetone (fresh - ⁇ ) and 1 % Pd/C- Acetone (used - T) and Pd foil ( ⁇ );
- Figure 15 shows the Fourier transform of the k 2 -weighted c EXAFS data of 1 % Ru/C- Acetone (fresh - ⁇ ) and 1 % Ru/C-Acetone (used - T) and Ru foil ( ⁇ );
- Figure 16 shows a representative STEM-HAADF image of the freshly prepared 1 % Au/C- Acetone material
- Figure 17 shows a representative STEM-HAADF image of the used 1 % Au/C-Acetone material
- Figure 18 shows a representative STEM-HAADF image of the freshly prepared 1 % Pt/C- Acetone material
- Figure 19 shows a representative STEM-HAADF image of the used 1 % Pt/C-Acetone material
- Figure 20 shows a representative STEM-HAADF image of the freshly prepared 1 % Pd/C- Acetone material
- Figure 21 shows a representative STEM-HAADF image of the used 1 % Pd/C-Acetone material
- Figure 22 shows a representative STEM-HAADF image of the freshly prepared 1 % Ru/C- Acetone material
- Figure 23 shows a representative STEM-HAADF image of the used 1 % Ru/C-Acetone material
- Figure 24 shows X-ray diffraction patterns of fresh Au/C-Acetone catalyst
- Figure 25 shows X-ray diffraction patterns of fresh Pt/C-Acetone catalyst
- Figure 26 shows X-ray diffraction patterns of fresh Pd/C-Acetone catalyst
- Figure 27 shows X-ray diffraction patterns of fresh Ru/C-Acetone catalyst
- Figure 28 shows Pt l_3-edge XANES of 1 % Pt/C-Acetone prior to reaction compared with Pt foil and Pt(acac)2;
- Figure 29 shows Pd K-edge XANES of 1 % Pd/C-Acetone prior to reaction compared with Pd foil and Pd(acac)2;
- Figure 30 shows Ru K-edge XANES of 1% Ru/C-Acetone prior to reaction compared Ru foil and Ru(acac)3.
- a method for making a catalyst comprising combining a gold, ruthenium, palladium, or platinum precursor, a solvent, and a support material, wherein the solvent comprises an organic solvent and wherein the solvent does not comprise organic aqua regia.
- the precursor is a gold precursor.
- the precursor is a ruthenium precursor.
- the precursor is a palladium precursor.
- the precursor is a platinum precursor.
- a method for making a catalyst comprising combining a gold precursor, a solvent, and a support material, wherein the solvent comprises an organic solvent and wherein the solvent does not comprise organic aqua regia.
- the method comprises forming a solution of the precursor in the solvent, and combining the solution with the support material.
- the method comprises forming a solution of the gold precursor in the solvent, and combining the solution with the support material.
- the method further comprises drying the product of the step of combining the precursor, solvent and support material.
- the method further comprises drying the product of the step of combining the gold precursor, solvent and support material.
- the solvent has an ET(30) polarity equal to or less than about 62.
- the solvent may have an ET(30) polarity equal to or less than about 60 or equal to or less than about 55 or equal to or less than about 50.
- the solvent comprises equal to or less than about 50 vol% water.
- the solvent may comprise equal to or less than about 10 vol% water or equal to or less than about 5 vol% water.
- the solvent has a pH equal to or greater than about 5.
- the solvent may have a pH equal to or greater than about 6 or equal to or greater than about 7.
- the solvent has a boiling point equal to or less than about 120°C.
- the solvent may have a boiling point equal to or less than about 100°C or equal to or less than about 90°C.
- the support material may comprise, consist essentially of or consist of carbon such as activated carbon.
- a catalyst comprising atomically dispersed cationic gold species and a support material, wherein: equal to or greater than about 58% of the gold exists in the Au(l) oxidation state; and/or
- the catalyst provides a steady state acetylene conversion greater than about 18%;
- a catalyst comprising atomically dispersed cationic gold, ruthenium, palladium, or platinum species and a support material.
- the catalyst provides a steady state acetylene conversion greater than about 18 %.
- the fourth aspect of the present invention equal or greater than about 80 % of the gold or ruthenium or palladium or platinum in the catalyst is atomically dispersed.
- the fourth aspect of the present invention equal to or greater than about 60 %, for example equal to or greater than about 70% or equal to or greater than about 80%, of the ruthenium exists in the Ru(lll) oxidation state.
- the fourth aspect of the present invention equal to or greater than about 60%, for example equal to or greater than about 70% or equal to or greater than about 80%, of the palladium exists in the Pd(ll) oxidation state. In certain embodiments of the fourth aspect of the present invention equal to or greater than about 60%, for example equal to or greater than about 70% or equal to or greater than about 80%, of the platinum exists in the Pt(ll) oxidation state.
- a catalyst obtained by and/or obtainable by a method according to any aspect or embodiment of the present invention obtained by and/or obtainable by a method according to any aspect or embodiment of the present invention.
- the catalyst of the fifth aspect of the present invention may be in accordance with the catalyst of the third or fourth aspect of the present invention, including all embodiments thereof in any combination.
- equal to or less than about 10 % of the gold or ruthenium or palladium or platinum in the catalyst exists in the form of nanoparticles.
- equal to or less than about 5 % of the gold or ruthenium or palladium or platinum in the catalyst exists in the form of nanoparticles.
- equal to or less than about 10 % of the gold in the catalyst exists in the form of nanoparticles.
- equal to or less than about 5 % of the gold in the catalyst exists in the form of nanoparticles.
- equal to or greater than about 80 % of the gold or ruthenium or palladium or platinum in the catalyst is atomically dispersed.
- equal to or greater than about 90 % of the gold or ruthenium or palladium or platinum in the catalyst is atomically dispersed.
- equal to or greater than about 80 % of the gold is atomically dispersed.
- equal to or greater than about 90 % of the gold in the catalyst is atomically dispersed.
- equal to or less than about 10 % of the gold or ruthenium or palladium or platinum in the catalyst exists in the form of dimers and sub nanometre clusters. For example, equal to or less than about 5 % of the gold or ruthenium or palladium or platinum in the catalyst exists in the form of dimers and sub nanometre clusters. In certain embodiments of any aspect of the present invention, equal to or less than about 10 % of the gold exists in the form of dimers and sub nanometre clusters. For example, equal to or less than about 5 % of the gold exists in the form of dimers and sub nanometre clusters.
- the catalyst has an X- Ray Diffraction pattern that does not have a 2Q reflection at one or more of 38, 44, 64 and 77°. This may, for example, be particularly applicable to gold catalysts.
- the catalyst has an X- Ray Diffraction pattern that does not have a 2Q reflection at one or both of 42.2 and 44°. This may, for example, be particularly applicable to ruthenium catalysts.
- the catalyst has an X- Ray Diffraction pattern that does not have a 2Q reflection at 40°. This may, for example, be particularly applicable to palladium catalysts.
- the catalyst has an X- Ray Diffraction pattern that does not have a 2Q reflection at one or more of 42.9, 46.4, 67.9, 81.8 and 86.2°. This may, for example, be particularly applicable to platinum catalysts.
- the catalyst in accordance with any aspect or embodiment of the present invention may, for example, provide a steady state acetylene conversion greater than about 3 %.
- the catalyst in accordance with any aspect or embodiment of the present invention may provide a steady state acetylene conversion greater than about 18 %.
- a catalyst in accordance with any aspect or embodiment of the present invention in accordance with any aspect or embodiment of the present invention (including all combinations thereof) in a method of making vinyl chloride, for example in a method of hydrochlorination of acetylene.
- Certain embodiments of any aspect of the present invention may provide one or more of the following advantages: • good (e.g. improved) activity, for example for acetylene hydrochlorination;
- the method comprises combining a gold precursor, ruthenium precursor, palladium precursor, or platinum precursor, a solvent, and a support material.
- precursor is used herein to generally refer to gold precursors, ruthenium precursors, palladium precursors and platinum precursors.
- the method may, for example, comprise combining a gold precursor, a solvent and a support material.
- combining involves contacting the one or more products. This may, for example, comprise mixing or stirring the products together.
- the method may, for example, be referred to as an impregnation or a wet impregnation method, whereby the precursor is impregnated on a catalyst support material, for example whereby the precursor is dissolved in the solvent and then impregnated on a catalyst support material.
- the method may, for example, be referred to as an impregnation or a wet impregnation method, whereby the gold precursor is impregnated on a catalyst support material, for example whereby the gold precursor is dissolved in the solvent and then impregnated on a catalyst support material.
- the method may, for example, be an incipient wetness impregnation method whereby the amount of solution used is calculated to be just enough to fill the pores of the support.
- the method may comprise forming a solution of the precursor in the solvent, and combining the solution with the support material. Therefore, the method may comprise forming a solution of the gold precursor in the solvent, and combining the solution with the support material.
- the method may, for example, comprise dissolving the precursor in the solvent, and combining the solution with the support material.
- the method may, for example, comprise dissolving the gold precursor in the solvent, and combining the solution with the support material.
- the precursor solution may, for example, be combined with the support material in drops, for example with stirring, or by spraying.
- the amount of each of the precursor, solvent and support material may be selected in order to obtain the desired amount of catalyst, for example with a desired gold or ruthenium or palladium or platinum loading level.
- the amount of each of the gold precursor, solvent and support material may be selected in order to obtain the desired amount of catalyst, for example with a desired gold loading level.
- the combining of the precursor, solvent and support material may take place under any suitable conditions.
- the combining of the gold precursor, solvent and support material may take place under any suitable conditions.
- the combining may take place at ambient temperature and/or pressure.
- the combining may take place at a temperature ranging from about 15°C to about 25°C.
- the combining may take place at a pressure ranging from about 95 to about 105 kPa, for example about 101 kPa.
- Stirring may be used to combine the precursor, solvent and support material.
- Stirring may be used to combine the gold precursor, solvent and support material.
- the method may further comprise a drying step.
- the method may further comprise drying the product of the step of combining the precursor, solvent and support material.
- the method may further comprise drying the product of the step of combining the gold precursor, solvent and support material.
- the method may further comprise drying in order to remove the solvent.
- the drying may, for example, occur at a temperature higher than the boiling point of the solvent.
- the drying may occur at a temperature at least about 2°C higher, for example at least about 3°C higher, for example at least about 4°C higher, for example at least about 5°C higher than the boiling point of the solvent.
- the drying may occur at a temperature up to about 15°C higher, for example up to about 12°C, for example up to about 10°C higher than the boiling point of the solvent.
- the drying may occur at a temperature from about 2°C higher to about 15°C higher than the boiling point of the solvent, for example from about 5°C higher to about 10°C higher than the boiling point of the solvent.
- the drying may, for example, occur at a temperature equal to or less than about 120°C.
- the drying may occur at a temperature equal to or less than about 1 10°C, for example equal to or less than about 100°C, for example equal to or less than about 90°C.
- the drying may, for example, occur at a temperature equal to or greater than about 40°C.
- the drying may occur at a temperature equal to or greater than about 50°C or equal to or greater than about 60°C.
- the drying may occur at a temperature ranging from about 40°C to about 120°C, for example from about 50°C to about 100°C, for example from about 60°C to about 90°C.
- the drying may, for example, take place at ambient pressure or higher.
- the drying may take place at a pressure ranging from about 95 to about 105 kPa, for example equal to or greater than about 101 kPa, for example from about 101 kPa to about 105 kPa.
- the drying may, for example, take place until the mass of the product does not change.
- the drying may, for example, take place until all of the solvent is removed.
- the drying may, for example, take place for up to about 24 hours, for example up to about 20 hours, for example up to about 16 hours.
- the drying may, for example, take place under the flow of an inert gas.
- inert gas it is meant a gas that does not react with the catalyst produced by the method.
- the drying may, for example, take place under the flow of nitrogen gas (N2).
- the method for making the catalyst may, for example, be in accordance with the method described in G. Malta et ai, Science, 2017, 355, pages 1399-1403 (the contents of which are incorporated herein by reference), except that a different solvent and optionally a different temperature and/or pressure is used.
- the method for making the catalyst may, for example, exclude the use of any additional reducing agents.
- the method for making the catalyst may, for example, exclude an additional step (i.e. in addition to the steps described herein) intended to reduce the gold, ruthenium, palladium or platinum in the catalyst. This may, for example, be reflected in the atomically dispersed state of the metal species and/or the oxidation state of the metal in the catalyst.
- the catalyst may not comprise or may comprise only a small amount of Au(0) or Ru(0) or Pd(0) or Pt(0).
- the method for making the catalyst may, for example, exclude the use of a linear or branched chain alkene fixing agent.
- the method may, for example, exclude the use of a fixing agent.
- the method for making the catalyst may, for example, exclude a fixing step using a linear or branched chain alkene.
- the method for making the catalyst may, for example, exclude a fixing step.
- the precursor i.e. gold precursor or ruthenium precursor or palladium precursor or platinum precursor
- the precursor may be any compound including gold, ruthenium, palladium, or platinum that is suitable to make a catalyst comprising atomically dispersed cationic gold, atomically dispersed cationic ruthenium, atomically dispersed cationic palladium, or atomically dispersed cationic platinum as described herein.
- the precursor may, for example, dissolve in the solvent used in the method for making a catalyst described herein.
- the precursor may, for example, include one or more acetylacetonate ligands.
- the gold precursor may be any compound including gold that is suitable to make a catalyst comprising atomically dispersed cationic gold as described herein.
- the gold precursor may, for example, dissolve in the solvent used in the method for making a catalyst described herein.
- the gold precursor may, for example, include one or more chloride anions.
- Suitable gold precursors include, for example, elemental gold (Au), chloroauric acid (HAuCU) such as chloroauric trihydrate and/or tetra hydrate), gold (III) chloride (AuCh), gold (I) chloride (AuCI), gold acetate (e.g. gold (III) acetate, Au(0 2 CCH 3 ) 3 ) and combinations of one or more thereof.
- Suitable ruthenium precursors include, for example, ruthenium (III) acetylacetonate (Ru(acac)3), ruthenium (III) chloride (RuCh), and combinations thereof.
- Suitable palladium precursors include, for example, palladium (II) acetylacetonate (Pd(acac)2), palladium (II) acetate (Pd(OAc)2), palladium (II) nitrate dehydrate (Pd(NC>3)2.2H20), and combinations of one or more thereof.
- Suitable platinum precursors include, for example, platinum (II) acetylacetonate (Pt(acac)2), which may also be referred to as platinum (II) 2,4-pentanedionate.
- the solvent may, for example, have an ET(30) polarity equal to or less than about 62.
- the solvent may have an ET(30) polarity equal to or less than about 60, for example equal to or less than about 58, for example equal to or less than about 56, for example equal to or less than about 55, for example equal to or less than about 54, for example equal to or less than about 52, for example equal to or less than about 50, for example equal to or less than about 48, for example equal to or less than about 46, for example equal to or less than about 45, for example equal to or less than about 44, for example equal to or less than about 42, for example equal to or less than about 40.
- the solvent may have an ET(30) polarity equal to or less than about 50.
- the solvent may have an ET(30) polarity ranging from about 20 to about 60, for example from about 25 to about 55, for example from about 30 to about 50, for example from about 35 to about 50.
- the present inventors have provided methods for making a gold or ruthenium or palladium or platinum catalyst that do not require the use of strongly acidic or highly oxidising solvents such as aqua regia and organic aqua regia.
- the present inventors have provided methods for making a gold catalyst that do not require the use of strongly acidic or highly oxidising solvents such as aqua regia and organic aqua regia.
- the presently disclosed methods for making a catalyst also do not require the use of sulphur-containing ligands.
- the solvent comprises an organic solvent.
- the solvent may, for example, consist essentially of or consist of one or more organic solvents.
- the organic solvent may, for example, be selected from the group consisting of alcohols, ketones, esters, ethers, sulphoxides, nitriles and amides.
- the solvent may, for example, comprise, consist essentially of or consist of a mixture of different solvents.
- the solvent may comprise, consist essentially of or consist of a mixture of one or more organic solvents.
- the solvent may, for example, be a non-aqueous solvent.
- the solvent may be a liquid solvent.
- the organic solvent is not organic aqua regia.
- organic aqua regia refers to a solvent comprising (for example consisting essentially of or consisting of) thionyl chloride (SOC ) and one or more organic compounds such as pyridine, N,N- dimethylformamide and imidazole.
- SOC thionyl chloride
- the term“alcohol” may relate to any organic compound in which the hydroxyl functional group (-OH) is bound to a carbon (R-OH).
- R may, for example, be a straight chain or branched chain or cyclic hydrocarbon, which may be saturated or unsaturated.
- R may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the alcohol may, for example be selected from methanol, ethanol, 1-propanol, 2-propanol, n-butanol, sec-butanol, isobutanol and tert-butanol.
- Each R may independently be a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated.
- Each R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the R groups may be linked to form a cyclic molecule, which may be saturated or unsaturated.
- the cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the ketone may, for example, be selected from acetone, butanone, pentanone and hexanone (e.g. cyclohexanone).
- Each R may independently be a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated.
- Each R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the R groups may be linked to form a cyclic molecule, which may be saturated or unsaturated.
- the cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the ester may, for example, be an alkyl acetate such as ethyl acetate.
- ether may relate to any organic compound including an -O- group bound to two carbon atoms (R-O-R).
- R-O-R may independently be a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated.
- Each R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the R groups may be linked to form a cyclic molecule, which may be saturated or unsaturated.
- the cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the ether may, for example, be selected from dialkyl ethers (where each alkyl group may be the same or different) such as diethyl ether and tetrahydrofuran.
- Each R may independently be a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated.
- Each R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the R groups may be linked to form a cyclic molecule, which may be saturated or unsaturated.
- the cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the sulphoxide may, for example, be a dialkyl sulphoxide (where each alkyl group may be the same or different) such as dimethyl sulphoxide (DMSO).
- nitrile may relate to any organic compound including a -CoN group bound to a carbon atom (R-CoN).
- R may be a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated.
- R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- R may form a cyclic molecule, which may be saturated or unsaturated.
- the cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the nitrile may, for example, be selected from alkylnitriles such as acetonitrile.
- Each R may independently be hydrogen or a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated.
- Each R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- one or more R groups may be linked to form a cyclic molecule, which may be saturated or unsaturated.
- the cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms.
- the amide may, for example, be selected from dialkylformamide (where each alkyl group may be the same or different) such as dimethylformamide (DMF).
- DMF dimethylformamide
- hydrocarbons in the alcohols, ketones, esters, ethers, sulphoxides, nitriles and amides may or may not be substituted with one or more other functional groups.
- the solvent may, for example, comprise, consist essentially of or consist of one or more of methanol, ethanol, propanol, butanol, acetone, butanone, ethyl acetate, diethyl ether, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and cyclohexanone.
- the solvent may, for example, comprise, consist essentially of or consist of one or more of methanol, ethanol, propanol, butanol, acetone, butanone, ethyl acetate, diethyl ether and tetrahydrofuran (THF).
- the solvent may comprise, consist essentially of or consist of acetone.
- the solvent may comprise, consist essentially of or consist of one or more of methanol, ethanol, propanol, butanol, acetone, butanone, ethyl acetate, diethyl ether, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and cyclohexanone.
- the solvent may comprise, consist essentially of or consist of one or more of methanol, ethanol, propanol, butanol, acetone, butanone, ethyl acetate, diethyl ether and tetrahydrofuran (THF).
- the solvent may comprise, consist essentially of, or consist of acetone.
- the solvent may, for example, comprise equal to or less than about 50 vol% water.
- the solvent may comprise equal to or less than about 45 vol%, for example equal to or less than about 40 vol%, for example equal to or less than about 35 vol%, for example equal to or less than about 30 vol%, for example equal to or less than about 25 vol%, for example equal to or less than about 20 vol%, for example equal to or less than about 15 vol%, for example equal to or less than about 10 vol%, for example equal to or less than about 5 vol% water.
- the solvent may comprise 0 vol% water.
- the solvent may comprise from 0 vol% to about 50 vol% or from about 0 vol% to about 30 vol% or from about 0% to about 10 vol% water.
- the solvent may, for example, have a boiling point equal to or less than about 120°C.
- the solvent may having a boiling point equal to or less than about 1 15°C or equal to or less than about 1 10°C or equal to or less than about 100°C or equal to or less than about 90°C or equal to or less than about 80°C.
- the solvent may have a boiling point equal to or greater than about 40°C or equal to or greater than about 50°C or equal to or greater than about 60°C.
- the solvent may, for example, have a boiling point ranging from about 40°C to about 120°C or from about 50°C to about 100°C or from about 60°C to about 90°C.
- the solvent may, for example, have a pH equal to or greater than about 5.
- the solvent may have a pH equal to or greater than about 5.5 or equal to or greater than about 6 or equal to or greater than about 6.5 or equal to or greater than about 7 or equal to or greater than about 7.5 or equal to or greater than about 8 or equal to or greater than about 8.5 or equal to or greater than about 9.
- the solvent may, for example, have a pH equal to or less than about 14.
- the solvent may have a pH equal to or less than about 13.5 or equal to or less than about 13 or equal to or less than about 12.5 or equal to or less than about 12.
- the solvent may have a pH ranging from about 5 to about 14 or from about 6 to about 13 or from about 6.5 to about 12.
- the solvent may not comprise, consist essentially of and/or consist of one or more of the following:
- Au e.g. Au(lll)
- Au(lll) complexes other than the gold precursor
- the methods for making a catalyst described in WO 2013/008004 are excluded from the presently disclosed methods for making a catalyst.
- the presently disclosed methods may exclude methods comprising impregnating the catalyst support material with a solution of gold or a compound thereof and a sulphur- containing ligand to form a gold complex and then drying the impregnated support.
- the presently disclosed methods may exclude methods comprising impregnating the catalyst support material with a solution of gold or a compound thereof and a sulphur-containing ligand to form a gold complex.
- a mineral acid refers to any acid derived from one or more inorganic compounds including, for example, sulphuric acid, nitric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, perchloric acid and boric acid.
- a strong acid refers to any acid that completely dissociates in water.
- the catalyst support material may be any support material suitable to make a catalyst comprising atomically dispersed cationic gold or ruthenium or palladium or platinum as described herein.
- the catalyst support material may be any support material suitable to make a catalyst comprising atomically dispersed cationic gold as described herein.
- the catalyst support material may, for example, comprise, consist essentially of or consist of carbon.
- the carbon may, for example, be obtained from natural sources such as peat, wood, coal, graphite or combinations thereof.
- the carbon may, for example, be a synthetic carbon.
- the carbon may, for example, be activated carbon.
- the activated carbon may, for example, have been activated by steam, acid or another chemical.
- Activated carbon refers to a form of carbon that has a high surface area (equal to or greater than about 500 m 2 per gram as determined by N 2 gas adsorption). This is thought to be due to the presence of small, low-volume pores.
- the activated carbon may have a surface area equal to or greater than about 800 m 2 per gram, for example equal to or greater than about 1000 m 2 per gram, for example equal to or greater than about 1500 m 2 per gram, for example equal to or greater than about 2000 m 2 per gram, for example equal to or greater than about 2500 m 2 per gram, for example equal to or greater than about 3000 m 2 per gram.
- the carbon may, for example, be doped carbon.
- the carbon may, for example, be high purity or ultra-high purity carbon.
- the carbon may, for example, be acid washed to remove impurities.
- the catalyst support material may, for example, comprise one or more metal oxides such as zeolites, Ti0 2 , AI 2 C>3, K 2 0, Zr0 2 , Ce0 2 , Si0 2 and combinations of one more thereof.
- the support material e.g. carbon such as activated carbon
- the support material may, for example, be ground to obtain a desired particle size prior to combination with the precursor and solvent.
- the support material e.g. carbon such as activated carbon
- the support material may, for example, be in the form of a powder, granules or particles in various shapes such as spheres, tablets, cylinders, multi-lobed cylinders, rings, monoliths or combinations of one or more thereof.
- the catalyst may, for example, be in the form of a monolith.
- the support material may, for example, have an average particle size ranging from about 10 pm to about 5 cm.
- the support material may have an average particle size ranging from about 20 pm to about 4 cm or from about 30 pm to about 3 cm or from about 40 pm to about 2 cm or from about 50 pm to about 1 cm.
- catalysts which may, for example, be obtained by or obtainable by a method as described herein, including all embodiments thereof.
- the catalyst described herein comprises atomically dispersed cationic gold or ruthenium or palladium or platinum species and a support material.
- the catalyst described herein may, for example, comprise atomically dispersed cationic gold species and a support material.
- the support material may be any support material described herein.
- the atomically dispersed cationic gold or ruthenium or palladium or platinum species may, for example, respectively be in the form of cationic atoms and/or cationic atoms coordinated to one or more ligands such as the ligands from the precursor such as Cl or acetylacetonate.
- the atomically dispersed cationic gold species may, for example, be in the form of cationic gold atoms and/or cationic gold atoms coordinated to one or more ligands such as Cl.
- the catalyst is not a catalyst described in WO 2013/008004.
- the catalyst is not a catalyst comprising a complex of gold with a sulphur-containing ligand on a support and is not a catalyst comprising gold, or a compound thereof, and trichloroisocyanuric acid or a metal dichloroisocyanurate on a support.
- the catalyst is not a catalyst comprising gold or a compound of gold and either a) sulphur, b) a compound of sulphur, or c) trichloroisocyanuric acid or a metal dichloroisocyanurate, on a support.
- Atomic dispersion can be visualized using high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) as described in the examples below. Dimers, sub-nanometre clusters and nanoparticles can also be visualized using HAADF- STEM.
- HAADF-STEM high angle annular dark field-scanning transmission electron microscopy
- the % of gold or ruthenium or palladium or platinum in the catalyst that is atomically dispersed and the % of gold or ruthenium or palladium or platinum that exists in the form of nanoparticles, dimers and sub-nanometre clusters can be calculated by X- Ray absorption data, assuming that Au(l), Au(lll), Ru(lll), Pd(ll), and Pt(ll) are isolated species and Au(0), Ru(0), Pd(0), and Pt(0) are in the form of nanoparticles.
- the % of gold in the catalyst that is atomically dispersed and the % of gold that exists in the form of nanoparticles, dimers and sub-nanometre clusters can be calculated by X-Ray absorption data, assuming that Au(l) and Au(lll) are isolated species and Au(0) is in the form of nanoparticles.
- Equal to or greater than about 80 % of the gold or ruthenium or palladium or platinum in the catalyst may be atomically dispersed.
- equal to or greater than about 82 % or equal to or greater than about 84 % or equal to or greater than about 85 % or equal to or greater than about 86 % or equal to or greater than about 88 % or equal to or greater than about 90 % or equal to or greater than about 92 % or equal to or greater than about 94 % or equal to or greater than about 95 % of the gold or ruthenium or palladium or platinum in the catalyst may be atomically dispersed.
- up to about 100 % or up to about 99 % or up to about 98 % or up to about 97 % or up to about 96 % of the gold or ruthenium or palladium or platinum in the catalyst may be atomically dispersed.
- from about 80 % to about 100 % or from about 85 % to about 100 % or from about 90 % to about 100 % or from about 95 % to about 100 % or from about 95 % to about 98% of the gold or ruthenium or palladium or platinum in the catalyst may be atomically dispersed.
- Equal to or greater than about 80 % of the gold in the catalyst may be atomically dispersed.
- equal to or greater than about 82 % or equal to or greater than about 84 % or equal to or greater than about 85 % or equal to or greater than about 86 % or equal to or greater than about 88 % or equal to or greater than about 90 % or equal to or greater than about 92 % or equal to or greater than about 94 % or equal to or greater than about 95 % of the gold in the catalyst may be atomically dispersed.
- up to about 100 % or up to about 99 % or up to about 98 % or up to about 97 % or up to about 96 % of the gold in the catalyst may be atomically dispersed.
- from about 80 % to about 100 % or from about 85 % to about 100 % or from about 90 % to about 100 % or from about 95 % to about 100 % or from about 95 % to about 98% of the gold in the catalyst may be atomically dispersed.
- Equal to or less than about 10 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of dimers and sub-nanometre particles.
- equal to or less than about 8 % or equal to or less than about 6 % or equal to or less than about 5 % or equal to or less than about 4 % or equal to or less than about 2 % or equal to or less than about 1 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of dimers and sub-nanometre particles.
- 0 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of dimers and sub-nanometre particles.
- the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of dimers and sub-nanometre particles.
- Equal to or less than about 10 % of the gold in the catalyst may exist in the form of dimers and sub-nanometre particles.
- equal to or less than about 8 % or equal to or less than about 6 % or equal to or less than about 5 % or equal to or less than about 4 % or equal to or less than about 2 % or equal to or less than about 1 % of the gold in the catalyst may exist in the form of dimers and sub-nanometre particles.
- 0 % of the gold in the catalyst may exist in the form of dimers and sub-nanometre particles.
- from 0 % to about 10 % or from 0 % to about 5 % or from about 1 % to about 5 % of the gold in the catalyst may exist in the form of dimers and sub-nanometre particles.
- Equal to or less than about 10 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of nanoparticles.
- equal to or less than about 8 % or equal to or less than about 6 % or equal to or less than about 5 % or equal to or less than about 4 % or equal to or less than about 2 % or equal to or less than about 1 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of nanoparticles.
- 0 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of nanoparticles.
- the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of nanoparticles. These values may correspond to the % of gold in the Au(0) or Ru(0) or Pd(0) or Pt(0) oxidation state.
- Equal to or less than about 10 % of the gold in the catalyst may exist in the form of nanoparticles.
- equal to or less than about 8 % or equal to or less than about 6 % or equal to or less than about 5 % or equal to or less than about 4 % or equal to or less than about 2 % or equal to or less than about 1 % of the gold in the catalyst may exist in the form of nanoparticles.
- 0 % of the gold in the catalyst may exist in the form of nanoparticles.
- from 0 % to about 10 % or from 0 % to about 5 % or from about 1 % to about 5 % of the gold in the catalyst may exist in the form of nanoparticles.
- any nanoparticles present in the catalyst may, for example, have an average size ranging from about 1 nm to about 100 nm, for example from about 2 nm to about 50 mn.
- any nanoparticles present in the catalyst may range from about 15 nm to about 30 nm, for example from about 18 nm to about 24 nm. This is measured using the Scherrer equation as described in the examples below.
- the quantity of cationic gold or cationic ruthenium or cationic palladium or cationic platinum species in each oxidation state can be identified by X-Ray Absorption Spectroscopy (XAS) in the X-Ray Absorption Near-Edge Structure (XANES) region as described in the examples below.
- the quantity of cationic gold species in each oxidation state can be identified by X-Ray Absorption Spectroscopy (XAS) in the X-Ray Absorption Near-Edge Structure (XANES) region as described in the examples below.
- the majority of the gold in the catalyst is in the Au(l) oxidation state.
- the majority of the ruthenium in the catalyst is in the Ru(lll) oxidation state.
- the majority of the palladium in the catalyst is in the Pd(ll) oxidation state.
- the majority of the platinum in the catalyst is in the Pt(ll) oxidation state.
- Equal to or greater than about 58 % of the gold in the catalyst described herein may exist in the Au(l) oxidation state.
- equal to or greater than about 60 % or equal to or greater than about 65 % or equal to or greater than about 70 % or equal to or greater than about 75 % of the gold in the catalyst may exist in the Au(l) oxidation state.
- up to about 100 % or up to about 95 % or up to about 90 % or up to about 85 % or up to about 80 % of the gold in the catalyst may exist in the Au(l) oxidation state.
- the gold in the catalyst may exist in the Au(l) oxidation state.
- Equal to or greater than about 60 % of the ruthenium in the catalyst described herein may exist in the Ru(lll) oxidation state.
- equal to or greater than about 65 % or equal to or greater than about 70 % or equal to or greater than about 75 % or equal to or greater than about 80 % of the ruthenium in the catalyst may exist in the Ru(lll) oxidation state.
- up to about 100 % or up to about 95 % or up to about 90 % or up to about 85 % of the ruthenium in the catalyst may exist in the Ru(lll) oxidation state.
- the ruthenium in the catalyst may exist in the Ru(lll) oxidation state.
- Equal to or greater than about 60 % of the palladium in the catalyst described herein may exist in the Pd(ll) oxidation state.
- equal to or greater than about 65 % or equal to or greater than about 70 % or equal to or greater than about 75 % or equal to or greater than about 80 % of the palladium in the catalyst may exist in the Pd(ll) oxidation state.
- up to about 100 % or up to about 95 % or up to about 90 % or up to about 85 % of the palladium in the catalyst may exist in the Pd(ll) oxidation state.
- up to about 60 % to about 100 % or from about 70 % to about 95 % or from about 80 % to about 90 % of the palladium in the catalyst may exist in the Pd(ll) oxidation state.
- Equal to or greater than about 60 % of the platinum in the catalyst described herein may exist in the Pt(ll) oxidation state.
- equal to or greater than about 65 % or equal to or greater than about 70 % or equal to or greater than about 75 % or equal to or greater than about 80 % of the platinum in the catalyst may exist in the Pt(ll) oxidation state.
- up to about 100 % or up to about 95 % or up to about 90 % or up to about 85 % of the platinum in the catalyst may exist in the Pt(ll) oxidation state.
- from about 60 % to about 100 % or from about 70 % to about 95 % or from about 80 % to about 90 % of the platinum in the catalyst may exist in the Pt(ll) oxidation state.
- Equal to or less than about 42 % of the gold in the catalyst described herein may exist in the Au(lll) oxidation state.
- equal to or less than about 40 % or equal to or less than about 35 % or equal to or less than about 30 % or equal to or less than about 25 % of the gold in the catalyst may exist in the Au(lll) oxidation state.
- equal to or greater than about 0 % or equal to or greater than about 1 % or equal to or greater than about 2 % or equal to or greater than about 5 % or equal to or greater than about 10 % or equal to or greater than about 15 % or equal to or greater than about 20 % of gold in the catalyst may exist in the Au(ll l) oxidation state.
- the gold in the catalyst may exist in the Au(lll) oxidation state.
- the ratio of Au(l) : Au(lll) in the catalyst may, for example, be equal to or greater than about 1.
- the ratio of Au(l) : Au(lll) in the catalyst may be equal to or greater than about 1.5 or equal to or greater than about 2 or equal to or greater than about 2.5 or equal to or greater than about 3.
- the ratio of Au(l) : Au(lll) in the catalyst may be up to about 5.
- All of the gold (i.e. 100 %) in the catalyst may, for example, exist in the Au(l) or Au(lll) oxidation state.
- some of the gold in the catalyst may, for example, exist in other oxidation states (such as Au(0)).
- up to about 10 % or up to about 8 % or up to about 6 % or up to about 5 % or up to about 4 % or up to about 2 % of the gold in the catalyst exists in one or more oxidations states different to Au(l) and Au(lll) (for example Au(0) oxidation state).
- Equal to or less than about 10 % or equal to or less than about 8 % or equal to or less than about 6 % or equal to or less than about 5 % or equal to or less than about 4 % or equal to or less than about 2 % of the gold in the catalyst may exist in the Au(0) oxidation state.
- Elemental gold may be identified by the presence of 2Q reflections at 38, 44, 64 and 77° of an X-Ray Diffraction pattern.
- Elemental ruthenium may be identified by the presence of 2Q reflections at 42.2 and 44° of an X-Ray Diffraction pattern.
- Elemental palladium (Pd(0)) may be identified by the presence of the principal 2Q reflection at 40° of an X-Ray Diffraction pattern.
- Elemental platinum may be identified by the presence of 2Q reflections at 42.9, 46.4, 67.9, 81.8 and 86.2° of an X-Ray Diffraction pattern.
- a solvent as described herein improves the dispersion of the gold or ruthenium or palladium or platinum species in the catalyst and therefore respectively reduces the formation of Au or Ru or Pd or Pt nanoparticles present in the catalyst. It is thought that the use of a solvent as described herein improves the dispersion of the gold species in the catalyst and therefore reduces the formation of Au nanoparticles present in the catalyst. Therefore, the diffraction peaks corresponding to metallic Au or metallic Ru or metallic Pd or metallic Pt may be reduced compared to catalysts made with other solvents, particularly aqueous solvents such as water.
- the diffraction peaks corresponding to metallic Au (2Q reflections at 38, 44, 64 and 77° of an X-Ray Diffraction pattern) are reduced compared to catalysts made with other solvents, particularly aqueous solvents such as water. Therefore, the diffraction peaks corresponding to metallic Ru (2Q reflections at 42.2 and 44° of an X-Ray Diffraction pattern) may be reduced compared to catalysts made with other solvents, particularly aqueous solvents such as water. Therefore, the diffraction peaks corresponding to metallic Pd (2Q reflection at 40° of an X-Ray Diffraction pattern) may be reduced compared to catalysts made with other solvents, particularly aqueous solvents such as water.
- the diffraction peaks corresponding to metallic Pt may be reduced compared to catalysts made with other solvents, particularly aqueous solvents such as water. Therefore, in certain embodiments, the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or both of 42.2 and 44°. Therefore, in certain embodiments, the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at 40°.
- the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or more of 42.9, 46.4, 67.9, 81.8 and 86.2°. Therefore, in certain embodiments, the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or more of 38, 44, 64 and 77°. In certain embodiments, the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at at least 64 and 77°.
- the catalysts described herein are thought to have an improved dispersion and consequently an improved activity compared to catalysts made using other solvents, particularly aqueous solvents such as water. Therefore, the catalyst may provide a steady state acetylene conversion equal to or greater than about 3 %. For example, the catalyst may provide a steady state acetylene conversion equal to or greater than about 5 % or equal to or greater than about 10 % or equal to or greater than about 15 % or equal to or greater than about 18 % or equal to or greater than about 20 %. The catalyst may, for example, provide a steady state acetylene conversion up to about 30 % or up to about 25 %.
- the catalyst may, for example, provide a steady state acetylene conversion ranging from about 3 % to about 30 %, for example from about 18 % to about 25 % or from about 19 % to about 25 % or from about 20 % to about 25 %.
- the steady state acetylene conversion refers to the maximum % conversion reached when using the catalyst in a method of acetylene hydrochlorination as described in the examples below.
- the catalysts described herein may, for example, have a gold or ruthenium or palladium or platinum loading level from about 0.01 to about 2 % based on the total weight of the catalyst.
- the catalysts described herein may have a gold or ruthenium or palladium or platinum loading level of from about 0.1 wt% to about 1.5 wt% or from about 0.5 wt% to about 1 wt%.
- the catalysts described herein may, for example, have a gold loading level from about 0.01 to about 2 % based on the total weight of the catalyst.
- the catalysts described herein may have a gold loading level of from about 0.1 wt% to about 1.5 wt% or from about 0.5 wt% to about 1 wt%.
- the catalysts described herein may, for example, be used as catalysts or may be used in a chemical process.
- the catalysts described herein may, for example, be used in methods for making vinyl chloride, particularly in methods for making vinyl chloride by hydrochlorination of acetylene.
- Any suitable conditions for acetylene hydrochlorination could be used and may be selected by persons of ordinary skill in the art using common general knowledge.
- the conditions may, for example, be in accordance with the conditions specified in G. Malta et al., Science, 2017, 355, pages 1399-1403.
- the catalysts described herein may also be used in hydrochlorination of other alkynes or substituted alkynes (for example alkynes having from 2 to 20 carbon atoms, for example from 2 to 10 carbon atoms or from 2 to 8 carbon atoms or from 2 to 6 carbon atoms).
- the catalysts described herein may also be useful in other reactions involving hydrochloric acid and/or chlorine (e.g. CI2).
- a method for making a catalyst comprising combining a gold precursor, a solvent, and a support material, wherein the solvent comprises an organic solvent and wherein the solvent does not comprise organic aqua regia.
- the gold precursor is selected from elemental gold (Au), chloroauric acid (HAuCU) such as chloroauric trihydrate and/or tetrahydrate, gold (III) chloride (AuCh), gold (I) chloride (AICI), gold acetate and combinations of one or more thereof.
- organic solvent is selected from the group consisting of alcohols, ketones, esters, ethers, sulphoxides, nitriles, amides and combinations of one or more thereof.
- the solvent does not comprise a strong mineral acid.
- the solvent comprises equal to or less than about 50 vol% water, for example equal to or less than about 10 vol% water, for example equal to or less than about 5 vol% water.
- the support material comprises carbon such as activated carbon.
- a catalyst comprising atomically dispersed cationic gold species and a support material, wherein:
- the catalyst provides a steady state acetylene conversion greater than about 18%;
- the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or more of 38, 44, 64 and 77°.
- the resulting powder was dried at a boiling point of the solvent used, for 16 h under a flow of N2.
- the catalysts prepared using different solvents were denoted as Au/C-(solvents) and, wherever possible, solvents commercially available as“extra-dry solvents” sealed in nitrogen were used.
- Catalysts were tested for acetylene hydrochlorination in a fixed-bed polyimide (Kapton) microreactor (O.D. 6 , length 20 cm) contained within a heating block powered by two heating cartridges inside the block. The temperature was controlled by a Eurotherm controller with a type K thermocouple positioned in the centre of the heater block. Cakh/Ar (5.01% balanced in Ar, BOC) and HCI/Ar (5.05% balanced in Ar, BOC) gases were dried, using moisture traps, prior to introduction to the reactor. In all cases, the reactor was purged with Ar (99.99% BIP, Air Products) prior to admitting the hydrochlorination reaction mixture.
- Ar 99.99% BIP, Air Products
- the reactor was heated to 200 °C at a ramp rate of 5 °C min -1 and held at this temperature for 30 min, all under a flow of Ar (50 ml min -1 ).
- the reaction gas mixture of Cahh/Ar (23.56 ml min -1 ), HCI/Ar (23.76 ml min -1 ) and additional Ar (2.70 ml min -1 ) was introduced into the heated reactor chamber containing catalyst (90 mg) at a total gas hourly space velocity (GHSV) of -17,600 h 1 , keeping the C2H2: HCI ratio at a constant value of 1 : 1.02.
- GHSV total gas hourly space velocity
- X-ray absorption structure (XAS) spectra for all the Au/C samples were recorded at the Au l_3 absorption edge, in transmission mode, at the B18 beamline of Diamond Light Source, Harwell, UK. The measurements were performed using a QEXAFS set-up with a fast-scanning Si (111) double crystal monochromator. The Demeter software package (Athena and Artemis) was used for XAS data analysis of the Au/C absorption spectra in comparison to standards relative to a Au foil.
- STEM scanning transmission electron microscopy
- JEOL ARM- 200CF scanning transmission electron microscope operating at 200kV.
- This microscope was also equipped with a Centurio silicon drift detector (SDD) system for X-ray energy dispersive spectroscopy (XEDS) analysis.
- SDD Centurio silicon drift detector
- Au/C catalysts were prepared by the method described above without the need for strongly oxidising solvents or the formation of stable complexes with sulfur containing ligands.
- the reason for the high activity of the catalysts prepared with low polarity organic solvents could arise from (i) the hydrophilic/hydrophobic nature of the solvents, providing increased wetting of the carbon support materials which leads to higher dispersions, (ii) the ability to use lower drying temperatures, thus preventing Au agglomeration and (iii) the complete absence of water in the catalyst preparation.
- low polarity solvents with high boiling points such as dimethylformamide (DMF), dimethyl sulphoxide (DMSO) and cyclohexanone. Table 2 reports the polarity, boiling points and drying temperatures used to produce these catalysts along with the acetylene conversion values. Table 2.
- Test Conditions 90 mg catalyst, 23.5 ml_ mirr 1 C2H2, 23.7 ml_ mirr 1 HCI and 2.7 ml_ min 1 Ar, 200 °C.
- the oxidising aqua regia solvent therefore resulted in a catalyst with a lower final conversion to that of the more benign acetone- prepared catalyst and is highly suggestive that the likely different functionality of the carbon supports can play a key role in determining the induction periods of these catalysts through either stronger Au anchoring or facilitating more facile changes in oxidation state.
- EXAFS Extended X-ray absorption fine structure
- Figure 7 shows the XRD pattern of the Au/C-Acetone catalyst after 7 h of reaction, compared with that of the fresh material and the catalyst used for 4 h.
- the characteristic reflections of Au nanoparticles increased slightly in size after 7 h of reaction suggesting the slow sintering of the catalyst at extended reaction times.
- this Au(0) forms during the heat up or initial stages of the reaction before stabilising.
- weak reflections from NaCI could also be observed in the XRD patterns of the catalysts especially when synthesized with ultra-dry solvents. This was attributed to the carbon support materials containing NaCI which could easily recrystallize in the ultra-dry organic solvents, but in aqueous solvents it can be readily dissolved and get well dispersed over the catalyst.
- the gold precursor was HAUCI4.3H2O (Alfa Aesar, 20 mg, assay 49%).
- the ruthenium precursor was Ru (III) acetylacetonate (Aldrich).
- the palladium precursor was Pd (II) acetylacetonate (Aldrich).
- the platinum precursor was Pt (II) 2,4-pentanedionate (Alfa Aesar).
- Catalysts were tested for acetylene hydrochlorination in a fixed-bed polyimide (Kapton) microreactor (O.D. 6 mm, length 20 cm) contained within a heating block powered by two heating cartridges inside the block. The temperature was controlled by a Eurotherm controller with a type K thermocouple positioned in the centre of the heater block. C2H2/Ar (5.01 % balanced in Ar, BOC) and HCI/Ar (5.05% balanced in Ar, BOC) gases were dried, using moisture traps, prior to introduction to the reactor. In all cases, the reactor was purged with Ar (99.99% BIP, Air Products) prior to admitting the hydrochlorination reaction mixture.
- Ar 99.99% BIP, Air Products
- the reactor was heated to 180 °C at a ramp rate of 5 °C min 1 and held at this temperature for 30 min, all under a flow of Ar (50 ml min 1 ).
- the reaction gas mixture of C2H2/Ar (23.56 ml min 1 ), HCI/Ar (23.76 ml min 1 ) and additional Ar (2.70 ml min 1 ) was introduced into the heated reactor chamber containing catalyst (90 mg) at a total gas hourly space velocity (GHSV) of -17,600 h 1 , keeping the C2H2: HCI ratio at a constant value of 1 : 1.02.
- GHSV total gas hourly space velocity
- Powder X-ray diffraction (XRD) spectra were acquired using an X’Pert Pro PAN Analytical powder diffractometer employing a Cu K a radiation source operating at 40 keV and 40 mA. The spectra were analysed using X’Pert High Score Plus software.
- the Au/C, Ru/C, Pt/C and Pd/C catalysts were characterised via X-ray Absorption Spectroscopy (XAS) before reaction (Fresh) and after 240 min of reaction (Used).
- X-ray absorption spectroscopy (XAS) spectra for all the samples were recorded in transmission mode, at the B18 beamline of Diamond Light Source, Harwell, UK. The measurements were performed using a QEXAFS set-up with a fast-scanning Si (111) double crystal monochromator.
- the Demeter software package (Athena and Artemis) was used for XAS data analysis of the absorption spectra.
- X-ray absorption spectroscopy was conducted at the Au L3-edge (11.92 keV), Pt L3-edge, Pd K-edge, or Ru K-edge.
- the X-ray absorption spectra of the fresh catalysts, in addition to the corresponding metal precursors (HAuCL, Pt(acac)2, Pd(acac)2, and Ru(acac)3) and metal foils (Au(0), Pt(0), Pd(0), and Ru(0)) were recorded and analysed in the X-ray absorption near-edge structure (XANES) region and in the Extended X-Ray Absorption Fine Structure (EXAFS) region.
- XANES X-ray absorption near-edge structure
- EXAFS Extended X-Ray Absorption Fine Structure
- the XANES spectra of the catalysts show an overlap with the corresponding metal precursors but not with the metal foil. Since the metal precursors have an oxidation state of Ru(lll), Pd(ll), or Pt(ll) and the metal foils have an oxidation state of (0), the metals in the catalysts have an oxidation state of Ru(lll), Pd(ll), or Pt(ll) (see Figures 24 to 30).
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Abstract
A catalyst comprising atomically dispersed cationic gold or ruthenium or palladium or platinum species and method of making thereof.
Description
CATALYST
TECHNICAL FIELD
The present invention relates generally to methods of making supported catalysts (e.g. supported gold, ruthenium, palladium, or platinum catalysts), particularly carbon- supported catalysts (e.g. carbon-supported gold, ruthenium, palladium, or platinum catalysts). The present invention further relates to the supported catalysts made by said methods and the use of the supported catalysts to make vinyl chloride, for example by acetylene hydrochlorination. In particular, the present invention relates generally to methods of making supported gold catalysts, particularly carbon-supported gold catalysts, and the catalysts made by said methods. The present invention further relates to the use of the supported gold catalysts to make vinyl chloride, for example by acetylene hydrochlorination.
BACKGROUND
The hydrochlorination of acetylene to produce vinyl chloride monomer (VCM) as the precursor to polyvinyl chloride (PVC) is currently a large scale industrial process, particularly in coal rich areas such as China. Over 13 million tonnes of VCM are produced annually through acetylene hydrochlorination with the vast majority utilising mercuric chloride (HgCh) catalysts supported on activated carbon. The mercury catalyst poses significant environmental concerns due to volatile HgCh subliming from the catalyst bed, up to 0.6 kg Hg/tonne VCM production. Due to the environmental impact of this process, the recently ratified Minamata convention dictates that all new VCM plants must use mercury free catalysts and in the near future all existing industrial plants must switch to mercury free alternatives. This has revived the commercial interest in using gold (Au) and other metals as a catalyst for this reaction.
The conditions used to prepare the gold catalysts are thought to affect the acetylene hydrochlorination reaction profiles. Typically, acidic and/or strongly oxidising solvents are used to carry out a wet impregnation of a HAuCL precursor in order to obtain active catalysts. Concentrated nitric acid, hydrochloric acid and aqua regia (a mixture of nitric acid and hydrochloric acid, often in a ratio of 1 :3 v/v nitric acid : hydrochloric acid) have been used to produce active catalysts. Compositions comprising organic compounds (e.g., pyridine, A/,/V-dimethylformamide and imidazole) and thionyl chloride (SOC )
termed“organic aqua regia (OAR)” have been used as alternatives to the acidic and/or strongly oxidising solvents. However, OAR does not provide a real environmentally friendly alternative compared to other approaches. Alternatively, active catalysts may be prepared in aqueous media in the presence of sulphur-containing ligands However, the toxicity of sulphur-containing ligands such as thiocyanate makes large scale preparations and utilisation unsuitable.
It is therefore desirable to provide alternative and/or improved methods for making catalysts suitable to make vinyl chloride by acetylene hydrochlorination. It is therefore desirable to provide alternative and/or improved methods for making gold catalysts suitable to make vinyl chloride by acetylene hydrochlorination.
BRIEF DESCRIPTION OF THE FIGURES
The present invention may be further described with reference to the following Figures in which:
Figure 1 shows a) Steady state acetylene conversion of 1% Au/C catalysts prepared by wet impregnation of HAuCU from various alcohol (·), ketone (A), ether (¨) and aqueous solvents (■); the dotted line indicates the activity of the conventionally prepared aqua regia catalyst b) X-ray diffraction patterns of fresh 1% Au/C catalysts prepared with these various solvents ( Test Conditions: 90 mg catalyst, 23.5 ml_ min-1 C2H2, 23.7 ml_ min-1 HCI and 2.70 ml_ min 1 Ar, 200 °C);
Figure 2 shows a) Steady state acetylene conversion of 1% Au/C catalysts prepared by wet impregnation of HAuCU from extra dry acetone with the addition of various amounts of water b) X-ray diffraction patterns of fresh 1% Au/C catalysts prepared with various acetone/water mixtures ( Test Conditions: 90 mg catalyst, 23.5 ml_ min-1 C2H2, 23.7 ml_ min-1 HCI and 2.70 ml_ min 1 Ar, 200 °C);
Figure 3 shows Time-online acetylene hydrochlorination activity profile of the Au/C- Acetone (A), Au/C-Aqua regia (·) and AU/C-H2O (¨) catalysts ( Test Conditions: 90 mg catalyst, 23.5 ml_ min 1 C2H2, 23.7 ml_ min 1 HCI and 2.7 ml_ min 1 Ar, 200 °C);
Figure 4 shows a) Representative STEM-HAADF image of the freshly prepared 1 % Au/C-Acetone material b) Au l_3-edge XANES of 1% Au/C-Acetone prior to reaction (-
fresh) and after 4 h of reaction (- used), 1% Au/C-aqua regia and Au foil c) Linear combination fitting of the Au L3-edge XANES for 1% Au/C-aqua regia, 1% Au/C-Acetone (fresh) and 1% Au/C-Acetone (used) d) Fourier transform of the k3-weighted c EXAFS data of 1% Au/C-Acetone (fresh) and 1% Au/C-Acetone (used), 1 % Au/C-Aqua regia and Au foil;
Figure 5 shows Two-day time-on-line acetylene hydrochlorination activity profiles of the Au/C-Acetone (A) and Au/C-aqua regia (■) catalysts ( Test Conditions: 90 mg catalyst, 23.5 mL min-1 C2H2, 23.7 mL min 1 HCI and 2.7 mL min 1 Ar, 200 °C);
Figure 6 shows X-ray diffraction patterns of catalysts prepared using various solvents and drying temperatures with nominal metal loading of 1 wt% Au;
Figure 7 shows X-ray diffraction patterns of fresh Au/C-Acetone catalyst (fresh), Au/C- Acetone after 4h of reaction (used 4 h) and after a further 3 h of reaction (used 7 h);
Figure 8 shows the acetylene hydrochlorination activity profile of the Au/C-Acetone (■) catalysts ( Test Conditions: 90 mg catalyst, 23.5 mL min 1 C2H2, 23.7 mL min 1 HCI and
2.7 mL min 1 Ar, 180 °C);
Figure 9 shows the acetylene hydrochlorination activity profile of the Pt/C-Acetone (·) catalysts ( Test Conditions: 90 mg catalyst, 23.5 mL min 1 C2H2, 23.7 mL min 1 HCI and
2.7 mL min-1 Ar, 180 °C);
Figure 10 shows the acetylene hydrochlorination activity profile of the Pd/C-Acetone (A) catalysts ( Test Conditions: 90 mg catalyst, 23.5 mL min 1 C2H2, 23.7 mL min 1 HCI and
2.7 mL min-1 Ar, 180 °C);
Figure 11 shows the acetylene hydrochlorination activity profile of the Ru/C-Acetone (¨) catalysts ( Test Conditions: 90 mg catalyst, 23.5 mL min 1 C2H2, 23.7 mL min 1 HCI and
2.7 mL min-1 Ar, 180 °C);
Figure 12 shows the Fourier transform of the k3-weighted c EXAFS data of 1 % Au/C- Acetone (fresh -■) and 1% Au/C-Acetone (used - T) and Au foil (¨);
Figure 13 shows the Fourier transform of the k3-weighted c EXAFS data of 1 % Pt/C- Acetone (fresh -■) and 1 % Pt/C-Acetone (used - T) and Pt foil (¨);
Figure 14 shows the Fourier transform of the k2-weighted c EXAFS data of 1 % Pd/C- Acetone (fresh -■) and 1 % Pd/C- Acetone (used - T) and Pd foil (¨);
Figure 15 shows the Fourier transform of the k2-weighted c EXAFS data of 1 % Ru/C- Acetone (fresh -■) and 1 % Ru/C-Acetone (used - T) and Ru foil (¨);
Figure 16 shows a representative STEM-HAADF image of the freshly prepared 1 % Au/C- Acetone material;
Figure 17 shows a representative STEM-HAADF image of the used 1 % Au/C-Acetone material;
Figure 18 shows a representative STEM-HAADF image of the freshly prepared 1 % Pt/C- Acetone material;
Figure 19 shows a representative STEM-HAADF image of the used 1 % Pt/C-Acetone material;
Figure 20 shows a representative STEM-HAADF image of the freshly prepared 1 % Pd/C- Acetone material;
Figure 21 shows a representative STEM-HAADF image of the used 1 % Pd/C-Acetone material;
Figure 22 shows a representative STEM-HAADF image of the freshly prepared 1 % Ru/C- Acetone material;
Figure 23 shows a representative STEM-HAADF image of the used 1 % Ru/C-Acetone material;
Figure 24 shows X-ray diffraction patterns of fresh Au/C-Acetone catalyst;
Figure 25 shows X-ray diffraction patterns of fresh Pt/C-Acetone catalyst;
Figure 26 shows X-ray diffraction patterns of fresh Pd/C-Acetone catalyst;
Figure 27 shows X-ray diffraction patterns of fresh Ru/C-Acetone catalyst;
Figure 28 shows Pt l_3-edge XANES of 1 % Pt/C-Acetone prior to reaction compared with Pt foil and Pt(acac)2;
Figure 29 shows Pd K-edge XANES of 1 % Pd/C-Acetone prior to reaction compared with Pd foil and Pd(acac)2;
Figure 30 shows Ru K-edge XANES of 1% Ru/C-Acetone prior to reaction compared Ru foil and Ru(acac)3.
SUM MARY
In accordance with a first aspect of the present invention there is provided a method for making a catalyst, the method comprising combining a gold, ruthenium, palladium, or platinum precursor, a solvent, and a support material, wherein the solvent comprises an organic solvent and wherein the solvent does not comprise organic aqua regia.
In certain embodiments of the first aspect of the present invention the precursor is a gold precursor.
In certain embodiments of the first aspect of the present invention the precursor is a ruthenium precursor.
In certain embodiments of the first aspect of the present invention the precursor is a palladium precursor.
In certain embodiments of the first aspect of the present invention the precursor is a platinum precursor.
In accordance with a second aspect of the present invention there is provided a method for making a catalyst, the method comprising combining a gold precursor, a solvent, and a support material, wherein the solvent comprises an organic solvent and wherein the solvent does not comprise organic aqua regia.
In certain embodiments of the first aspect of the invention, the method comprises forming a solution of the precursor in the solvent, and combining the solution with the support material.
In certain embodiments of the second aspect of the invention, the method comprises forming a solution of the gold precursor in the solvent, and combining the solution with the support material.
In certain embodiments of the first aspect of the invention, the method further comprises drying the product of the step of combining the precursor, solvent and support material.
In certain embodiments of the second aspect of the invention, the method further comprises drying the product of the step of combining the gold precursor, solvent and support material.
In certain embodiments of any aspect of the invention, the solvent has an ET(30) polarity equal to or less than about 62. For example, the solvent may have an ET(30) polarity equal to or less than about 60 or equal to or less than about 55 or equal to or less than about 50.
In certain embodiments of any aspect of the invention, the solvent comprises equal to or less than about 50 vol% water. For example, the solvent may comprise equal to or less than about 10 vol% water or equal to or less than about 5 vol% water.
In certain embodiments of any aspect of the invention, the solvent has a pH equal to or greater than about 5. For example, the solvent may have a pH equal to or greater than about 6 or equal to or greater than about 7.
In certain embodiments of any aspect of the invention, the solvent has a boiling point equal to or less than about 120°C. For example, the solvent may have a boiling point equal to or less than about 100°C or equal to or less than about 90°C.
In certain embodiments of any aspect of the invention, the support material may comprise, consist essentially of or consist of carbon such as activated carbon.
In accordance with a third aspect of the present invention there is provided a catalyst comprising atomically dispersed cationic gold species and a support material, wherein: equal to or greater than about 58% of the gold exists in the Au(l) oxidation state; and/or
equal to or less than about 42% of the gold exists in the Au(lll) oxidation state; and/or
the catalyst provides a steady state acetylene conversion greater than about 18%; and/or
equal to or greater than about 80% of the gold in the catalyst is atomically dispersed.
In accordance with a fourth aspect of the present invention there is provided a catalyst comprising atomically dispersed cationic gold, ruthenium, palladium, or platinum species and a support material.
In certain embodiments of the fourth aspect of the present invention the catalyst provides a steady state acetylene conversion greater than about 18 %.
In certain embodiments of the fourth aspect of the present invention equal or greater than about 80 % of the gold or ruthenium or palladium or platinum in the catalyst is atomically dispersed.
In certain embodiments of the fourth aspect of the present invention equal to or greater than about 58%, for example equal to or greater than about 70%, of the gold exists in the Au(l) oxidation state.
In certain embodiments of the fourth aspect of the present invention equal to or greater than about 60 %, for example equal to or greater than about 70% or equal to or greater than about 80%, of the ruthenium exists in the Ru(lll) oxidation state.
In certain embodiments of the fourth aspect of the present invention equal to or greater than about 60%, for example equal to or greater than about 70% or equal to or greater than about 80%, of the palladium exists in the Pd(ll) oxidation state.
In certain embodiments of the fourth aspect of the present invention equal to or greater than about 60%, for example equal to or greater than about 70% or equal to or greater than about 80%, of the platinum exists in the Pt(ll) oxidation state.
In accordance with a fifth aspect of the present invention there is provided a catalyst obtained by and/or obtainable by a method according to any aspect or embodiment of the present invention. The catalyst of the fifth aspect of the present invention may be in accordance with the catalyst of the third or fourth aspect of the present invention, including all embodiments thereof in any combination.
In certain embodiments of any aspect of the present invention, equal to or less than about 10 % of the gold or ruthenium or palladium or platinum in the catalyst exists in the form of nanoparticles. For example, equal to or less than about 5 % of the gold or ruthenium or palladium or platinum in the catalyst exists in the form of nanoparticles.
In certain embodiments of any aspect of the present invention, equal to or less than about 10 % of the gold in the catalyst exists in the form of nanoparticles. For example, equal to or less than about 5 % of the gold in the catalyst exists in the form of nanoparticles.
In certain embodiments of any aspect of the present invention, equal to or greater than about 80 % of the gold or ruthenium or palladium or platinum in the catalyst is atomically dispersed. For example, equal to or greater than about 90 % of the gold or ruthenium or palladium or platinum in the catalyst is atomically dispersed.
In certain embodiments of any aspect of the present invention, equal to or greater than about 80 % of the gold is atomically dispersed. For example, equal to or greater than about 90 % of the gold in the catalyst is atomically dispersed.
In certain embodiments of any aspect of the present invention, equal to or less than about 10 % of the gold or ruthenium or palladium or platinum in the catalyst exists in the form of dimers and sub nanometre clusters. For example, equal to or less than about 5 % of the gold or ruthenium or palladium or platinum in the catalyst exists in the form of dimers and sub nanometre clusters.
In certain embodiments of any aspect of the present invention, equal to or less than about 10 % of the gold exists in the form of dimers and sub nanometre clusters. For example, equal to or less than about 5 % of the gold exists in the form of dimers and sub nanometre clusters.
In certain embodiments of any aspect of the present invention, the catalyst has an X- Ray Diffraction pattern that does not have a 2Q reflection at one or more of 38, 44, 64 and 77°. This may, for example, be particularly applicable to gold catalysts.
In certain embodiments of any aspect of the present invention, the catalyst has an X- Ray Diffraction pattern that does not have a 2Q reflection at one or both of 42.2 and 44°. This may, for example, be particularly applicable to ruthenium catalysts.
In certain embodiments of any aspect of the present invention, the catalyst has an X- Ray Diffraction pattern that does not have a 2Q reflection at 40°. This may, for example, be particularly applicable to palladium catalysts.
In certain embodiments of any aspect of the present invention, the catalyst has an X- Ray Diffraction pattern that does not have a 2Q reflection at one or more of 42.9, 46.4, 67.9, 81.8 and 86.2°. This may, for example, be particularly applicable to platinum catalysts.
The catalyst in accordance with any aspect or embodiment of the present invention (including all combinations thereof) may, for example, provide a steady state acetylene conversion greater than about 3 %. For example, the catalyst in accordance with any aspect or embodiment of the present invention (including all combinations thereof) may provide a steady state acetylene conversion greater than about 18 %.
In accordance with a sixth aspect of the present invention there is provided a use of a catalyst in accordance with any aspect or embodiment of the present invention (including all combinations thereof) in a method of making vinyl chloride, for example in a method of hydrochlorination of acetylene.
Certain embodiments of any aspect of the present invention may provide one or more of the following advantages:
• good (e.g. improved) activity, for example for acetylene hydrochlorination;
• good (e.g. improved) stability, for example for acetylene hydrochlorination;
• good (e.g. improved) selectivity, for example for vinyl chloride;
• less severe process conditions (e.g. reduced temperature and/or pressure, less acidic reactants, reduced number of reactants);
• environmentally friendly product and/or process.
The details, examples and preferences provided in relation to any particulate one or more of the stated aspects of the present invention will be further described herein and apply equally to all aspects of the present invention. Any combination of the embodiments, examples and preferences described herein in all possible variations thereof is encompassed by the present invention unless otherwise indicated herein, or otherwise clearly contradicted by context. DETAILED DESCRIPTION
Method of Making a Catalyst
There is provided herein a method of making a catalyst. The method comprises combining a gold precursor, ruthenium precursor, palladium precursor, or platinum precursor, a solvent, and a support material. The term“precursor” is used herein to generally refer to gold precursors, ruthenium precursors, palladium precursors and platinum precursors. The method may, for example, comprise combining a gold precursor, a solvent and a support material. As used herein, the term “combining” involves contacting the one or more products. This may, for example, comprise mixing or stirring the products together.
The method may, for example, be referred to as an impregnation or a wet impregnation method, whereby the precursor is impregnated on a catalyst support material, for example whereby the precursor is dissolved in the solvent and then impregnated on a catalyst support material. The method may, for example, be referred to as an impregnation or a wet impregnation method, whereby the gold precursor is impregnated on a catalyst support material, for example whereby the gold precursor is dissolved in the solvent and then impregnated on a catalyst support material. The method may, for example, be an incipient wetness impregnation method whereby the amount of solution used is calculated to be just enough to fill the pores of the support. Therefore, the method
may comprise forming a solution of the precursor in the solvent, and combining the solution with the support material. Therefore, the method may comprise forming a solution of the gold precursor in the solvent, and combining the solution with the support material. The method may, for example, comprise dissolving the precursor in the solvent, and combining the solution with the support material. The method may, for example, comprise dissolving the gold precursor in the solvent, and combining the solution with the support material. The precursor solution may, for example, be combined with the support material in drops, for example with stirring, or by spraying.
The amount of each of the precursor, solvent and support material may be selected in order to obtain the desired amount of catalyst, for example with a desired gold or ruthenium or palladium or platinum loading level. The amount of each of the gold precursor, solvent and support material may be selected in order to obtain the desired amount of catalyst, for example with a desired gold loading level.
The combining of the precursor, solvent and support material may take place under any suitable conditions. For example, the combining of the gold precursor, solvent and support material may take place under any suitable conditions. For example, the combining may take place at ambient temperature and/or pressure. For example, the combining may take place at a temperature ranging from about 15°C to about 25°C. For example, the combining may take place at a pressure ranging from about 95 to about 105 kPa, for example about 101 kPa. Stirring may be used to combine the precursor, solvent and support material. Stirring may be used to combine the gold precursor, solvent and support material.
The method may further comprise a drying step. For example, the method may further comprise drying the product of the step of combining the precursor, solvent and support material. For example, the method may further comprise drying the product of the step of combining the gold precursor, solvent and support material. For example, the method may further comprise drying in order to remove the solvent.
The drying may, for example, occur at a temperature higher than the boiling point of the solvent. For example, the drying may occur at a temperature at least about 2°C higher, for example at least about 3°C higher, for example at least about 4°C higher, for example at least about 5°C higher than the boiling point of the solvent. For example, the drying may occur at a temperature up to about 15°C higher, for example up to about 12°C, for
example up to about 10°C higher than the boiling point of the solvent. For example, the drying may occur at a temperature from about 2°C higher to about 15°C higher than the boiling point of the solvent, for example from about 5°C higher to about 10°C higher than the boiling point of the solvent. The drying may, for example, occur at a temperature equal to or less than about 120°C. For example, the drying may occur at a temperature equal to or less than about 1 10°C, for example equal to or less than about 100°C, for example equal to or less than about 90°C. The drying may, for example, occur at a temperature equal to or greater than about 40°C. For example, the drying may occur at a temperature equal to or greater than about 50°C or equal to or greater than about 60°C. For example, the drying may occur at a temperature ranging from about 40°C to about 120°C, for example from about 50°C to about 100°C, for example from about 60°C to about 90°C.
The drying may, for example, take place at ambient pressure or higher. For example, the drying may take place at a pressure ranging from about 95 to about 105 kPa, for example equal to or greater than about 101 kPa, for example from about 101 kPa to about 105 kPa.
The drying may, for example, take place until the mass of the product does not change. The drying may, for example, take place until all of the solvent is removed. The drying may, for example, take place for up to about 24 hours, for example up to about 20 hours, for example up to about 16 hours.
The drying may, for example, take place under the flow of an inert gas. By inert gas, it is meant a gas that does not react with the catalyst produced by the method. The drying may, for example, take place under the flow of nitrogen gas (N2).
The method for making the catalyst may, for example, be in accordance with the method described in G. Malta et ai, Science, 2017, 355, pages 1399-1403 (the contents of which are incorporated herein by reference), except that a different solvent and optionally a different temperature and/or pressure is used.
The method for making the catalyst may, for example, exclude the use of any additional reducing agents. The method for making the catalyst may, for example, exclude an additional step (i.e. in addition to the steps described herein) intended to reduce the gold,
ruthenium, palladium or platinum in the catalyst. This may, for example, be reflected in the atomically dispersed state of the metal species and/or the oxidation state of the metal in the catalyst. For example, the catalyst may not comprise or may comprise only a small amount of Au(0) or Ru(0) or Pd(0) or Pt(0).
The method for making the catalyst may, for example, exclude the use of a linear or branched chain alkene fixing agent. The method may, for example, exclude the use of a fixing agent. The method for making the catalyst may, for example, exclude a fixing step using a linear or branched chain alkene. The method for making the catalyst may, for example, exclude a fixing step.
The precursor (i.e. gold precursor or ruthenium precursor or palladium precursor or platinum precursor) may be any compound including gold, ruthenium, palladium, or platinum that is suitable to make a catalyst comprising atomically dispersed cationic gold, atomically dispersed cationic ruthenium, atomically dispersed cationic palladium, or atomically dispersed cationic platinum as described herein. The precursor may, for example, dissolve in the solvent used in the method for making a catalyst described herein. The precursor may, for example, include one or more acetylacetonate ligands.
The gold precursor may be any compound including gold that is suitable to make a catalyst comprising atomically dispersed cationic gold as described herein. The gold precursor may, for example, dissolve in the solvent used in the method for making a catalyst described herein. The gold precursor may, for example, include one or more chloride anions.
Suitable gold precursors include, for example, elemental gold (Au), chloroauric acid (HAuCU) such as chloroauric trihydrate and/or tetra hydrate), gold (III) chloride (AuCh), gold (I) chloride (AuCI), gold acetate (e.g. gold (III) acetate, Au(02CCH3)3) and combinations of one or more thereof.
Suitable ruthenium precursors include, for example, ruthenium (III) acetylacetonate (Ru(acac)3), ruthenium (III) chloride (RuCh), and combinations thereof.
Suitable palladium precursors include, for example, palladium (II) acetylacetonate (Pd(acac)2), palladium (II) acetate (Pd(OAc)2), palladium (II) nitrate dehydrate (Pd(NC>3)2.2H20), and combinations of one or more thereof.
Suitable platinum precursors include, for example, platinum (II) acetylacetonate (Pt(acac)2), which may also be referred to as platinum (II) 2,4-pentanedionate. The solvent may, for example, have an ET(30) polarity equal to or less than about 62. For example, the solvent may have an ET(30) polarity equal to or less than about 60, for example equal to or less than about 58, for example equal to or less than about 56, for example equal to or less than about 55, for example equal to or less than about 54, for example equal to or less than about 52, for example equal to or less than about 50, for example equal to or less than about 48, for example equal to or less than about 46, for example equal to or less than about 45, for example equal to or less than about 44, for example equal to or less than about 42, for example equal to or less than about 40. For example, the solvent may have an ET(30) polarity equal to or less than about 50. For example, the solvent may have an ET(30) polarity ranging from about 20 to about 60, for example from about 25 to about 55, for example from about 30 to about 50, for example from about 35 to about 50.
Advantageously, the present inventors have provided methods for making a gold or ruthenium or palladium or platinum catalyst that do not require the use of strongly acidic or highly oxidising solvents such as aqua regia and organic aqua regia. Advantageously, the present inventors have provided methods for making a gold catalyst that do not require the use of strongly acidic or highly oxidising solvents such as aqua regia and organic aqua regia. The presently disclosed methods for making a catalyst also do not require the use of sulphur-containing ligands.
The solvent comprises an organic solvent. The solvent may, for example, consist essentially of or consist of one or more organic solvents. The organic solvent may, for example, be selected from the group consisting of alcohols, ketones, esters, ethers, sulphoxides, nitriles and amides. The solvent may, for example, comprise, consist essentially of or consist of a mixture of different solvents. For example, the solvent may comprise, consist essentially of or consist of a mixture of one or more organic solvents. The solvent may, for example, be a non-aqueous solvent. The solvent may be a liquid solvent. The organic solvent is not organic aqua regia. As used herein, the term“organic aqua regia” refers to a solvent comprising (for example consisting essentially of or consisting
of) thionyl chloride (SOC ) and one or more organic compounds such as pyridine, N,N- dimethylformamide and imidazole.
The term“alcohol” may relate to any organic compound in which the hydroxyl functional group (-OH) is bound to a carbon (R-OH). R may, for example, be a straight chain or branched chain or cyclic hydrocarbon, which may be saturated or unsaturated. R may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. The alcohol may, for example be selected from methanol, ethanol, 1-propanol, 2-propanol, n-butanol, sec-butanol, isobutanol and tert-butanol.
The term“ketone” may relate to any organic compound including a -C=0 group bound to two carbon atoms (R(CO)R). Each R may independently be a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated. Each R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. Alternatively the R groups may be linked to form a cyclic molecule, which may be saturated or unsaturated. The cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. The ketone may, for example, be selected from acetone, butanone, pentanone and hexanone (e.g. cyclohexanone).
The term“ester” may relate to any organic compound including a -C(=0)(OR) group bound to a carbon atom (RC(O)OR). Each R may independently be a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated. Each R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. Alternatively the R groups may be linked to form a cyclic molecule, which may be saturated or unsaturated. The cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. The ester may, for example, be an alkyl acetate such as ethyl acetate.
The term“ether” may relate to any organic compound including an -O- group bound to two carbon atoms (R-O-R). Each R may independently be a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated. Each R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1
to 8 carbon atoms or from 1 to 6 carbon atoms. Alternatively the R groups may be linked to form a cyclic molecule, which may be saturated or unsaturated. The cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. The ether may, for example, be selected from dialkyl ethers (where each alkyl group may be the same or different) such as diethyl ether and tetrahydrofuran.
The term“sulphoxide” may relate to any organic compound including an -S(=0) group, where the S atom is bound to two carbon atoms (R-S(=0)-R). Each R may independently be a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated. Each R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. Alternatively the R groups may be linked to form a cyclic molecule, which may be saturated or unsaturated. The cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. The sulphoxide may, for example, be a dialkyl sulphoxide (where each alkyl group may be the same or different) such as dimethyl sulphoxide (DMSO).
The term“nitrile” may relate to any organic compound including a -CºN group bound to a carbon atom (R-CºN). R may be a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated. R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. Alternatively R may form a cyclic molecule, which may be saturated or unsaturated. The cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. The nitrile may, for example, be selected from alkylnitriles such as acetonitrile.
The term“amide” may relate to any organic compound including a R-C(=0)-NRR group. Each R may independently be hydrogen or a straight chain or branched chain hydrocarbon, which may be saturated or unsaturated. Each R may independently comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. Alternatively one or more R groups may be linked to form a cyclic molecule, which may be saturated or unsaturated. The cyclic molecule may, for example, comprise from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. The amide
may, for example, be selected from dialkylformamide (where each alkyl group may be the same or different) such as dimethylformamide (DMF).
The hydrocarbons in the alcohols, ketones, esters, ethers, sulphoxides, nitriles and amides may or may not be substituted with one or more other functional groups.
The solvent may, for example, comprise, consist essentially of or consist of one or more of methanol, ethanol, propanol, butanol, acetone, butanone, ethyl acetate, diethyl ether, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and cyclohexanone. For example, the solvent may, for example, comprise, consist essentially of or consist of one or more of methanol, ethanol, propanol, butanol, acetone, butanone, ethyl acetate, diethyl ether and tetrahydrofuran (THF). For example, the solvent may comprise, consist essentially of or consist of acetone.
For example, when the precursor is a gold precursor, the solvent may comprise, consist essentially of or consist of one or more of methanol, ethanol, propanol, butanol, acetone, butanone, ethyl acetate, diethyl ether, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and cyclohexanone. For example, when the precursor is a gold precursor, the solvent may comprise, consist essentially of or consist of one or more of methanol, ethanol, propanol, butanol, acetone, butanone, ethyl acetate, diethyl ether and tetrahydrofuran (THF).
For example, when the precursor is a ruthenium precursor, a palladium precursor, or a platinum precursor, the solvent may comprise, consist essentially of, or consist of acetone.
The solvent may, for example, comprise equal to or less than about 50 vol% water. For example, the solvent may comprise equal to or less than about 45 vol%, for example equal to or less than about 40 vol%, for example equal to or less than about 35 vol%, for example equal to or less than about 30 vol%, for example equal to or less than about 25 vol%, for example equal to or less than about 20 vol%, for example equal to or less than about 15 vol%, for example equal to or less than about 10 vol%, for example equal to or less than about 5 vol% water. For example, the solvent may comprise 0 vol% water. For example, the solvent may comprise from 0 vol% to about 50 vol% or from about 0 vol% to about 30 vol% or from about 0% to about 10 vol% water.
The solvent may, for example, have a boiling point equal to or less than about 120°C. For example, the solvent may having a boiling point equal to or less than about 1 15°C or equal to or less than about 1 10°C or equal to or less than about 100°C or equal to or less than about 90°C or equal to or less than about 80°C. For example the solvent may have a boiling point equal to or greater than about 40°C or equal to or greater than about 50°C or equal to or greater than about 60°C. For example, the solvent may, for example, have a boiling point ranging from about 40°C to about 120°C or from about 50°C to about 100°C or from about 60°C to about 90°C.
The solvent may, for example, have a pH equal to or greater than about 5. For example, the solvent may have a pH equal to or greater than about 5.5 or equal to or greater than about 6 or equal to or greater than about 6.5 or equal to or greater than about 7 or equal to or greater than about 7.5 or equal to or greater than about 8 or equal to or greater than about 8.5 or equal to or greater than about 9. The solvent may, for example, have a pH equal to or less than about 14. For example, the solvent may have a pH equal to or less than about 13.5 or equal to or less than about 13 or equal to or less than about 12.5 or equal to or less than about 12. For example, the solvent may have a pH ranging from about 5 to about 14 or from about 6 to about 13 or from about 6.5 to about 12.
One or more of the following may be excluded from use in the presently disclosed methods (e.g. the solvent may not comprise, consist essentially of and/or consist of one or more of the following):
• an aqueous solution of nitric acid;
• an aqueous solution of hydrochloric acid;
• an aqueous solution of a combination of nitric acid and hydrochloric acid (aqua- regia);
• an aqueous solution of hydrogen peroxide;
• thionyl chloride and pyridine;
• thionyl chloride and A/,/\/-dimethylformamide;
• thionyl chloride and imidazole;
• thionyl chloride and one or more organic compounds;
• thionyl chloride;
• pyridine;
• A/,/\/-dimethylformamide;
• imidazole;
• a strong acid;
• a strong mineral acid;
• a sulphur-containing ligand;
· 1 ,10-phenanthroline;
• Au-thiocyanate complexes;
• Schiff-base Au (e.g. Au(lll)) complexes other than the gold precursor;
• Au (e.g. Au(lll)) complexes other than the gold precursor;
• sulphates, sulphonates, thiourea, thionyl chloride, thiopropionic acid, thiomalic acid, thiosulfate and/or thiocyanates.
In certain embodiments, the methods for making a catalyst described in WO 2013/008004 are excluded from the presently disclosed methods for making a catalyst. Thus, the presently disclosed methods may exclude methods comprising impregnating the catalyst support material with a solution of gold or a compound thereof and a sulphur- containing ligand to form a gold complex and then drying the impregnated support. For example, the presently disclosed methods may exclude methods comprising impregnating the catalyst support material with a solution of gold or a compound thereof and a sulphur-containing ligand to form a gold complex.
A mineral acid refers to any acid derived from one or more inorganic compounds including, for example, sulphuric acid, nitric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, perchloric acid and boric acid. A strong acid refers to any acid that completely dissociates in water.
ET(30) polarity is determined by the method disclosed in C. Reichardt, Agnew. Chem. Int. Ed., 1979, 18, pages 98-110, the contents of which are incorporated herein by reference. The catalyst support material may be any support material suitable to make a catalyst comprising atomically dispersed cationic gold or ruthenium or palladium or platinum as described herein. The catalyst support material may be any support material suitable to make a catalyst comprising atomically dispersed cationic gold as described herein. The catalyst support material may, for example, comprise, consist essentially of or consist of carbon. The carbon may, for example, be obtained from natural sources such
as peat, wood, coal, graphite or combinations thereof. The carbon may, for example, be a synthetic carbon. The carbon may, for example, be activated carbon. The activated carbon may, for example, have been activated by steam, acid or another chemical. Activated carbon refers to a form of carbon that has a high surface area (equal to or greater than about 500 m2 per gram as determined by N2 gas adsorption). This is thought to be due to the presence of small, low-volume pores. For example, the activated carbon may have a surface area equal to or greater than about 800 m2 per gram, for example equal to or greater than about 1000 m2 per gram, for example equal to or greater than about 1500 m2 per gram, for example equal to or greater than about 2000 m2 per gram, for example equal to or greater than about 2500 m2 per gram, for example equal to or greater than about 3000 m2 per gram. The carbon may, for example, be doped carbon. The carbon may, for example, be high purity or ultra-high purity carbon. The carbon may, for example, be acid washed to remove impurities.
The catalyst support material may, for example, comprise one or more metal oxides such as zeolites, Ti02, AI2C>3, K20, Zr02, Ce02, Si02 and combinations of one more thereof.
The support material (e.g. carbon such as activated carbon) may, for example, be ground to obtain a desired particle size prior to combination with the precursor and solvent. The support material (e.g. carbon such as activated carbon) may, for example, be ground to obtain a desired particle size prior to combination with the gold precursor and solvent.
The support material may, for example, be in the form of a powder, granules or particles in various shapes such as spheres, tablets, cylinders, multi-lobed cylinders, rings, monoliths or combinations of one or more thereof. The catalyst may, for example, be in the form of a monolith.
The support material may, for example, have an average particle size ranging from about 10 pm to about 5 cm. For example, the support material may have an average particle size ranging from about 20 pm to about 4 cm or from about 30 pm to about 3 cm or from about 40 pm to about 2 cm or from about 50 pm to about 1 cm.
Catalyst
There is also provided herein catalysts which may, for example, be obtained by or obtainable by a method as described herein, including all embodiments thereof.
The catalyst described herein comprises atomically dispersed cationic gold or ruthenium or palladium or platinum species and a support material. The catalyst described herein may, for example, comprise atomically dispersed cationic gold species and a support material. The support material may be any support material described herein. The atomically dispersed cationic gold or ruthenium or palladium or platinum species may, for example, respectively be in the form of cationic atoms and/or cationic atoms coordinated to one or more ligands such as the ligands from the precursor such as Cl or acetylacetonate. The atomically dispersed cationic gold species may, for example, be in the form of cationic gold atoms and/or cationic gold atoms coordinated to one or more ligands such as Cl. In certain embodiments, the catalyst is not a catalyst described in WO 2013/008004. Thus, in certain embodiments, the catalyst is not a catalyst comprising a complex of gold with a sulphur-containing ligand on a support and is not a catalyst comprising gold, or a compound thereof, and trichloroisocyanuric acid or a metal dichloroisocyanurate on a support. In certain embodiments, the catalyst is not a catalyst comprising gold or a compound of gold and either a) sulphur, b) a compound of sulphur, or c) trichloroisocyanuric acid or a metal dichloroisocyanurate, on a support.
Atomic dispersion can be visualized using high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) as described in the examples below. Dimers, sub-nanometre clusters and nanoparticles can also be visualized using HAADF- STEM. The % of gold or ruthenium or palladium or platinum in the catalyst that is atomically dispersed and the % of gold or ruthenium or palladium or platinum that exists in the form of nanoparticles, dimers and sub-nanometre clusters can be calculated by X- Ray absorption data, assuming that Au(l), Au(lll), Ru(lll), Pd(ll), and Pt(ll) are isolated species and Au(0), Ru(0), Pd(0), and Pt(0) are in the form of nanoparticles. The % of gold in the catalyst that is atomically dispersed and the % of gold that exists in the form of nanoparticles, dimers and sub-nanometre clusters can be calculated by X-Ray absorption data, assuming that Au(l) and Au(lll) are isolated species and Au(0) is in the form of nanoparticles.
Equal to or greater than about 80 % of the gold or ruthenium or palladium or platinum in the catalyst may be atomically dispersed. For example, equal to or greater than about 82 % or equal to or greater than about 84 % or equal to or greater than about 85 % or equal to or greater than about 86 % or equal to or greater than about 88 % or equal to or greater than about 90 % or equal to or greater than about 92 % or equal to or greater
than about 94 % or equal to or greater than about 95 % of the gold or ruthenium or palladium or platinum in the catalyst may be atomically dispersed. For example, up to about 100 % or up to about 99 % or up to about 98 % or up to about 97 % or up to about 96 % of the gold or ruthenium or palladium or platinum in the catalyst may be atomically dispersed. For example, from about 80 % to about 100 % or from about 85 % to about 100 % or from about 90 % to about 100 % or from about 95 % to about 100 % or from about 95 % to about 98% of the gold or ruthenium or palladium or platinum in the catalyst may be atomically dispersed.
Equal to or greater than about 80 % of the gold in the catalyst may be atomically dispersed. For example, equal to or greater than about 82 % or equal to or greater than about 84 % or equal to or greater than about 85 % or equal to or greater than about 86 % or equal to or greater than about 88 % or equal to or greater than about 90 % or equal to or greater than about 92 % or equal to or greater than about 94 % or equal to or greater than about 95 % of the gold in the catalyst may be atomically dispersed. For example, up to about 100 % or up to about 99 % or up to about 98 % or up to about 97 % or up to about 96 % of the gold in the catalyst may be atomically dispersed. For example, from about 80 % to about 100 % or from about 85 % to about 100 % or from about 90 % to about 100 % or from about 95 % to about 100 % or from about 95 % to about 98% of the gold in the catalyst may be atomically dispersed.
Equal to or less than about 10 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of dimers and sub-nanometre particles. For example, equal to or less than about 8 % or equal to or less than about 6 % or equal to or less than about 5 % or equal to or less than about 4 % or equal to or less than about 2 % or equal to or less than about 1 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of dimers and sub-nanometre particles. For example 0 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of dimers and sub-nanometre particles. For example from 0 % to about 10 % or from 0 % to about 5 % or from about 1 % to about 5 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of dimers and sub-nanometre particles.
Equal to or less than about 10 % of the gold in the catalyst may exist in the form of dimers and sub-nanometre particles. For example, equal to or less than about 8 % or equal to or less than about 6 % or equal to or less than about 5 % or equal to or less than about 4 % or equal to or less than about 2 % or equal to or less than about 1 % of the gold in the catalyst may exist in the form of dimers and sub-nanometre particles. For example 0
% of the gold in the catalyst may exist in the form of dimers and sub-nanometre particles. For example from 0 % to about 10 % or from 0 % to about 5 % or from about 1 % to about 5 % of the gold in the catalyst may exist in the form of dimers and sub-nanometre particles.
Equal to or less than about 10 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of nanoparticles. For example, equal to or less than about 8 % or equal to or less than about 6 % or equal to or less than about 5 % or equal to or less than about 4 % or equal to or less than about 2 % or equal to or less than about 1 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of nanoparticles. For example 0 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of nanoparticles. For example from 0 % to about 10 % or from 0 % to about 5 % or from about 1 % to about 5 % of the gold or ruthenium or palladium or platinum in the catalyst may exist in the form of nanoparticles. These values may correspond to the % of gold in the Au(0) or Ru(0) or Pd(0) or Pt(0) oxidation state.
Equal to or less than about 10 % of the gold in the catalyst may exist in the form of nanoparticles. For example, equal to or less than about 8 % or equal to or less than about 6 % or equal to or less than about 5 % or equal to or less than about 4 % or equal to or less than about 2 % or equal to or less than about 1 % of the gold in the catalyst may exist in the form of nanoparticles. For example 0 % of the gold in the catalyst may exist in the form of nanoparticles. For example from 0 % to about 10 % or from 0 % to about 5 % or from about 1 % to about 5 % of the gold in the catalyst may exist in the form of nanoparticles. These values may correspond to the % of gold in the Au(0) oxidation state.
Any nanoparticles present in the catalyst may, for example, have an average size ranging from about 1 nm to about 100 nm, for example from about 2 nm to about 50 mn. For example, any nanoparticles present in the catalyst may range from about 15 nm to about 30 nm, for example from about 18 nm to about 24 nm. This is measured using the Scherrer equation as described in the examples below.
The quantity of cationic gold or cationic ruthenium or cationic palladium or cationic platinum species in each oxidation state can be identified by X-Ray Absorption Spectroscopy (XAS) in the X-Ray Absorption Near-Edge Structure (XANES) region as described in the examples below. The quantity of cationic gold species in each oxidation
state can be identified by X-Ray Absorption Spectroscopy (XAS) in the X-Ray Absorption Near-Edge Structure (XANES) region as described in the examples below.
In certain embodiments, the majority of the gold in the catalyst is in the Au(l) oxidation state.
In certain embodiments, the majority of the ruthenium in the catalyst is in the Ru(lll) oxidation state.
In certain embodiments, the majority of the palladium in the catalyst is in the Pd(ll) oxidation state.
In certain embodiments, the majority of the platinum in the catalyst is in the Pt(ll) oxidation state.
Equal to or greater than about 58 % of the gold in the catalyst described herein may exist in the Au(l) oxidation state. For example, equal to or greater than about 60 % or equal to or greater than about 65 % or equal to or greater than about 70 % or equal to or greater than about 75 % of the gold in the catalyst may exist in the Au(l) oxidation state. For example up to about 100 % or up to about 95 % or up to about 90 % or up to about 85 % or up to about 80 % of the gold in the catalyst may exist in the Au(l) oxidation state. For example from about 58 % to about 100 % or from about 60 % to about 95 % or from about 65 % to about 90 % or from about 70 % to about 85 % or from about 70 % to about 80 % or from about 72 % to about 78 % or from about 75 % to about 78 % or from about 75 % to about 80 % of the gold in the catalyst may exist in the Au(l) oxidation state.
Equal to or greater than about 60 % of the ruthenium in the catalyst described herein may exist in the Ru(lll) oxidation state. For example, equal to or greater than about 65 % or equal to or greater than about 70 % or equal to or greater than about 75 % or equal to or greater than about 80 % of the ruthenium in the catalyst may exist in the Ru(lll) oxidation state. For example up to about 100 % or up to about 95 % or up to about 90 % or up to about 85 % of the ruthenium in the catalyst may exist in the Ru(lll) oxidation state. For example from about 60 % to about 100 % or from about 70 % to about 95 % or from about 80 % to about 90 % of the ruthenium in the catalyst may exist in the Ru(lll) oxidation state.
Equal to or greater than about 60 % of the palladium in the catalyst described herein may exist in the Pd(ll) oxidation state. For example, equal to or greater than about 65 % or equal to or greater than about 70 % or equal to or greater than about 75 % or equal to or greater than about 80 % of the palladium in the catalyst may exist in the Pd(ll) oxidation state. For example up to about 100 % or up to about 95 % or up to about 90 % or up to about 85 % of the palladium in the catalyst may exist in the Pd(ll) oxidation state. For example from about 60 % to about 100 % or from about 70 % to about 95 % or from about 80 % to about 90 % of the palladium in the catalyst may exist in the Pd(ll) oxidation state.
Equal to or greater than about 60 % of the platinum in the catalyst described herein may exist in the Pt(ll) oxidation state. For example, equal to or greater than about 65 % or equal to or greater than about 70 % or equal to or greater than about 75 % or equal to or greater than about 80 % of the platinum in the catalyst may exist in the Pt(ll) oxidation state. For example up to about 100 % or up to about 95 % or up to about 90 % or up to about 85 % of the platinum in the catalyst may exist in the Pt(ll) oxidation state. For example from about 60 % to about 100 % or from about 70 % to about 95 % or from about 80 % to about 90 % of the platinum in the catalyst may exist in the Pt(ll) oxidation state.
Equal to or less than about 42 % of the gold in the catalyst described herein may exist in the Au(lll) oxidation state. For example equal to or less than about 40 % or equal to or less than about 35 % or equal to or less than about 30 % or equal to or less than about 25 % of the gold in the catalyst may exist in the Au(lll) oxidation state. For example equal to or greater than about 0 % or equal to or greater than about 1 % or equal to or greater than about 2 % or equal to or greater than about 5 % or equal to or greater than about 10 % or equal to or greater than about 15 % or equal to or greater than about 20 % of gold in the catalyst may exist in the Au(ll l) oxidation state. For example from 0 % to about 42 % or from about 2 % to about 40 % or from about 5 % to about 35 % or from about 10 % to about 30 % or from about 15 % to about 25 % or from about 20 % to about 25 % of the gold in the catalyst may exist in the Au(lll) oxidation state.
The ratio of Au(l) : Au(lll) in the catalyst may, for example, be equal to or greater than about 1. For example, the ratio of Au(l) : Au(lll) in the catalyst may be equal to or greater than about 1.5 or equal to or greater than about 2 or equal to or greater than about 2.5
or equal to or greater than about 3. For example, the ratio of Au(l) : Au(lll) in the catalyst may be up to about 5.
All of the gold (i.e. 100 %) in the catalyst may, for example, exist in the Au(l) or Au(lll) oxidation state. Alternatively, some of the gold in the catalyst may, for example, exist in other oxidation states (such as Au(0)). For example, up to about 10 % or up to about 8 % or up to about 6 % or up to about 5 % or up to about 4 % or up to about 2 % of the gold in the catalyst exists in one or more oxidations states different to Au(l) and Au(lll) (for example Au(0) oxidation state). Equal to or less than about 10 % or equal to or less than about 8 % or equal to or less than about 6 % or equal to or less than about 5 % or equal to or less than about 4 % or equal to or less than about 2 % of the gold in the catalyst may exist in the Au(0) oxidation state.
Any value within the % ranges disclosed herein may be selected, provided the total % when considering all components totals 100 %.
Elemental gold (Au(0)) may be identified by the presence of 2Q reflections at 38, 44, 64 and 77° of an X-Ray Diffraction pattern.
Elemental ruthenium (Ru(0)) may be identified by the presence of 2Q reflections at 42.2 and 44° of an X-Ray Diffraction pattern.
Elemental palladium (Pd(0)) may be identified by the presence of the principal 2Q reflection at 40° of an X-Ray Diffraction pattern.
Elemental platinum (Pt(0)) may be identified by the presence of 2Q reflections at 42.9, 46.4, 67.9, 81.8 and 86.2° of an X-Ray Diffraction pattern.
It is thought that the use of a solvent as described herein improves the dispersion of the gold or ruthenium or palladium or platinum species in the catalyst and therefore respectively reduces the formation of Au or Ru or Pd or Pt nanoparticles present in the catalyst. It is thought that the use of a solvent as described herein improves the dispersion of the gold species in the catalyst and therefore reduces the formation of Au nanoparticles present in the catalyst. Therefore, the diffraction peaks corresponding to metallic Au or metallic Ru or metallic Pd or metallic Pt may be reduced compared to catalysts made with other solvents, particularly aqueous solvents such as water.
Therefore, the diffraction peaks corresponding to metallic Au (2Q reflections at 38, 44, 64 and 77° of an X-Ray Diffraction pattern) are reduced compared to catalysts made with other solvents, particularly aqueous solvents such as water. Therefore, the diffraction peaks corresponding to metallic Ru (2Q reflections at 42.2 and 44° of an X-Ray Diffraction pattern) may be reduced compared to catalysts made with other solvents, particularly aqueous solvents such as water. Therefore, the diffraction peaks corresponding to metallic Pd (2Q reflection at 40° of an X-Ray Diffraction pattern) may be reduced compared to catalysts made with other solvents, particularly aqueous solvents such as water. Therefore, the diffraction peaks corresponding to metallic Pt (2Q reflections at 42.9, 46.4, 67.9, 81.8 and 86.2° of an X-Ray Diffraction pattern) may be reduced compared to catalysts made with other solvents, particularly aqueous solvents such as water. Therefore, in certain embodiments, the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or both of 42.2 and 44°. Therefore, in certain embodiments, the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at 40°. Therefore, in certain embodiments, the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or more of 42.9, 46.4, 67.9, 81.8 and 86.2°. Therefore, in certain embodiments, the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or more of 38, 44, 64 and 77°. In certain embodiments, the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at at least 64 and 77°.
The catalysts described herein are thought to have an improved dispersion and consequently an improved activity compared to catalysts made using other solvents, particularly aqueous solvents such as water. Therefore, the catalyst may provide a steady state acetylene conversion equal to or greater than about 3 %. For example, the catalyst may provide a steady state acetylene conversion equal to or greater than about 5 % or equal to or greater than about 10 % or equal to or greater than about 15 % or equal to or greater than about 18 % or equal to or greater than about 20 %. The catalyst may, for example, provide a steady state acetylene conversion up to about 30 % or up to about 25 %. The catalyst may, for example, provide a steady state acetylene conversion ranging from about 3 % to about 30 %, for example from about 18 % to about 25 % or from about 19 % to about 25 % or from about 20 % to about 25 %.
The steady state acetylene conversion refers to the maximum % conversion reached when using the catalyst in a method of acetylene hydrochlorination as described in the examples below.
The catalysts described herein may, for example, have a gold or ruthenium or palladium or platinum loading level from about 0.01 to about 2 % based on the total weight of the catalyst. For example, the catalysts described herein may have a gold or ruthenium or palladium or platinum loading level of from about 0.1 wt% to about 1.5 wt% or from about 0.5 wt% to about 1 wt%.
The catalysts described herein may, for example, have a gold loading level from about 0.01 to about 2 % based on the total weight of the catalyst. For example, the catalysts described herein may have a gold loading level of from about 0.1 wt% to about 1.5 wt% or from about 0.5 wt% to about 1 wt%.
Use of the Catalyst
The catalysts described herein may, for example, be used as catalysts or may be used in a chemical process. The catalysts described herein may, for example, be used in methods for making vinyl chloride, particularly in methods for making vinyl chloride by hydrochlorination of acetylene.
Any suitable conditions for acetylene hydrochlorination could be used and may be selected by persons of ordinary skill in the art using common general knowledge. The conditions may, for example, be in accordance with the conditions specified in G. Malta et al., Science, 2017, 355, pages 1399-1403.
The catalysts described herein may also be used in hydrochlorination of other alkynes or substituted alkynes (for example alkynes having from 2 to 20 carbon atoms, for example from 2 to 10 carbon atoms or from 2 to 8 carbon atoms or from 2 to 6 carbon atoms). The catalysts described herein may also be useful in other reactions involving hydrochloric acid and/or chlorine (e.g. CI2).
The following numbered paragraphs define particular embodiments of the present invention:
1. A method for making a catalyst, the method comprising combining a gold precursor, a solvent, and a support material, wherein the solvent comprises an organic solvent and wherein the solvent does not comprise organic aqua regia.
2. The method of paragraph 1 , wherein the combining comprises forming a solution of the gold precursor in the solvent, and combining the solution with the support material.
3. The method of paragraph 1 or 2, wherein the method further comprises drying the product of the step of combining the gold precursor, solvent and support material.
4. The method of any preceding paragraph, wherein the gold precursor is selected from elemental gold (Au), chloroauric acid (HAuCU) such as chloroauric trihydrate and/or tetrahydrate, gold (III) chloride (AuCh), gold (I) chloride (AICI), gold acetate and combinations of one or more thereof.
5. The method of any preceding paragraph, wherein the solvent has an ET(30) polarity equal to or less than about 62, for example equal to or less than about 60, for example equal to or less than about 55, for example equal to or less than about 50.
6. The method of any preceding paragraph, wherein the solvent has a boiling point equal to or less than about 120°C.
7. The method of any preceding paragraph, wherein the organic solvent is selected from the group consisting of alcohols, ketones, esters, ethers, sulphoxides, nitriles, amides and combinations of one or more thereof.
8. The method of any preceding paragraph, wherein the solvent does not comprise nitric acid and/or does not comprise hydrochloric acid and/or a combination of nitric acid and hydrochloric acid.
9. The method of any preceding paragraph, wherein the method does not comprise adding a sulphur-containing ligand to the gold precursor, solvent and support material.
10. The method of any preceding paragraph, wherein the solvent does not comprise a strong mineral acid.
11. The method of any preceding paragraph, wherein the solvent comprises equal to or less than about 50 vol% water, for example equal to or less than about 10 vol% water, for example equal to or less than about 5 vol% water.
12. The method of any preceding paragraph, wherein the solvent does not comprise water.
13. The method of any preceding paragraph, wherein the solvent has a pH equal to or greater than about 5 or equal to or greater than about 6.
14. The method of any preceding paragraph, wherein the support material comprises carbon such as activated carbon.
15. The method of paragraph 3, wherein the drying occurs at a temperature above the boiling point of the solvent.
16. The method of paragraph 3 or 15, wherein the drying occurs at a temperature up to about 10°C higher than the boiling point of the solvent.
17. The method of paragraph 3, 15 or 16, wherein the drying occurs at a temperature equal to or less than about 120°C, for example equal to or less than about 110°C, for example equal to or less than about 100°C, for example equal to or less than about 90°C.
18. A catalyst comprising atomically dispersed cationic gold species and a support material, wherein:
equal to or greater than about 58% of the gold exists in the Au(l) oxidation state; and/or
equal to or less than about 42% of the gold exists in the Au(lll) oxidation state; and/or
the catalyst provides a steady state acetylene conversion greater than about 18%; and/or
equal to or greater than about 80 % of the gold exists is atomically dispersed.
19. The catalyst of paragraph 18, wherein:
equal to or less than about 10 % of the gold exists in the form of nanoparticles; and/or
equal to or greater than about 80 % of the gold exists is atomically dispersed; and/or
equal to or less than about 10 % of the gold exists in the form of dimers and sub nanometer clusters; and/or
the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or more of 38, 44, 64 and 77°.
20. The catalyst of paragraph 18 or 19, wherein the catalyst provides a steady state acetylene conversion of greater than about 3%, for example equal to or greater than about 18%.
21. A catalyst obtainable by and/or obtained by the method of any of paragraphs 1 to 17. 22. The catalyst of paragraph 21 , wherein the catalyst has one or more of the features specified in paragraphs 18 to 20.
23. Use of a catalyst of any one of paragraphs 18 to 22 in a method of making vinyl chloride.
24. The use of paragraph 23, wherein the method of making vinyl chloride comprises hydrochlorination of acetylene.
EXAMPLES
Example 1
Methods Catalyst Preparation
All carbon-supported gold catalysts were prepared via a wet impregnation method described in G. Malta et ai, Science, 2017, 355, pages 1399-1403, except that different solvents were used. Activated carbon (Norit® ROX 0.8) was initially ground to obtain a powder (150 - 200 mesh). The gold precursor, HAuCL-3H20 (Alfa Aesar, 20 mg, assay 49%) was dissolved in the required solvent (2.7 ml). The gold precursor solution was added drop-wise, with stirring, to the activated carbon (0.99 g) in order to obtain a catalyst
with a final metal loading of 1 wt.%. The resulting powder was dried at a boiling point of the solvent used, for 16 h under a flow of N2. The catalysts prepared using different solvents were denoted as Au/C-(solvents) and, wherever possible, solvents commercially available as“extra-dry solvents” sealed in nitrogen were used.
The solvents used, their ET(30) polarities, boiling points and related drying temperatures are shown in Table 1 below.
Table 1.
Catalysts were tested for acetylene hydrochlorination in a fixed-bed polyimide (Kapton) microreactor (O.D. 6 , length 20 cm) contained within a heating block powered by two heating cartridges inside the block. The temperature was controlled by a Eurotherm controller with a type K thermocouple positioned in the centre of the heater block. Cakh/Ar (5.01% balanced in Ar, BOC) and HCI/Ar (5.05% balanced in Ar, BOC) gases were dried, using moisture traps, prior to introduction to the reactor. In all cases, the reactor was purged with Ar (99.99% BIP, Air Products) prior to admitting the hydrochlorination reaction mixture. The reactor was heated to 200 °C at a ramp rate of 5 °C min-1 and held at this temperature for 30 min, all under a flow of Ar (50 ml min-1). The reaction gas mixture of Cahh/Ar (23.56 ml min-1), HCI/Ar (23.76 ml min-1) and additional Ar (2.70 ml min-1) was introduced into the heated reactor chamber containing catalyst (90 mg) at a total gas hourly space velocity (GHSV) of -17,600 h 1, keeping the C2H2: HCI ratio at a constant value of 1 : 1.02. Typical time on stream experiments were conducted for 240 min (4 h). The gas phase products were analysed on-line using a Varian 450 GC equipped with a flame ionisation detector (FID). Chromatographic separation and identification of the products was carried out using a Porapak N packed column (6 ft c 1/8" stainless steel). 100 % C2H2 conversion gives a VCM productivity of 35.33 mol kgcat 1 h 1 under the reaction conditions used. The experimental error in acetylene conversion was ±1 % for repeat tests.
Catalyst Characterization Powder X-ray diffraction (XRD) spectra were acquired using an X’Pert Pro PAN Analytical powder diffractometer employing a Cu Ka radiation source operating at 40 keV and 40 mA. The spectra were analysed using X’Pert High Score Plus software. The mean crystallite size of the metallic gold nanoparticles, where possible, were determined using the Scherrer equation assuming a spherical particle shape and a K factor of 0.89 at the reflection arising from the set of (111) Au planes, at 2Q = 38°.
X-ray absorption structure (XAS) spectra for all the Au/C samples were recorded at the Au l_3 absorption edge, in transmission mode, at the B18 beamline of Diamond Light Source, Harwell, UK. The measurements were performed using a QEXAFS set-up with a fast-scanning Si (111) double crystal monochromator. The Demeter software package
(Athena and Artemis) was used for XAS data analysis of the Au/C absorption spectra in comparison to standards relative to a Au foil.
Materials for examination by scanning transmission electron microscopy (STEM) were dry dispersed onto a holey carbon TEM grid. These supported fragments were examined using BF- and HAADF-STEM imaging modes in an aberration corrected JEOL ARM- 200CF scanning transmission electron microscope operating at 200kV. This microscope was also equipped with a Centurio silicon drift detector (SDD) system for X-ray energy dispersive spectroscopy (XEDS) analysis.
Results
It has previously been reported that the preparation of Au/C catalysts via wet impregnation of HAuCL from aqueous solution results in large Au nanoparticles being present in the catalyst. These catalysts have little to no activity towards acetylene hydrochlorination under these dilute reaction conditions (see Liu et al., Catal. Sci. Technol., 2016, 6, pages 5144-5153).
1wt% Au/C catalysts were prepared by the method described above without the need for strongly oxidising solvents or the formation of stable complexes with sulfur containing ligands.
Steady state acetylene hydrochlorination activity was determined at GHSV = 17,600 IT1 and is reported in Figure 1 a for catalysts prepared with a series of solvents such as Ci - C4 alcohols. As the chain length of the alcohol used in the preparation increased, and consequently as the polarity of the solvent decreased, the acetylene hydrochlorination activity of the catalysts increased, from 3 % conversion for catalysts prepared in aqueous solvents to a value of 20 % conversion for samples prepared in C4 alcohols. Ketones such as acetone and 2-butanone, in addition to ethers such as tetrahydrofuran (THF), ethyl acetate and diethyl ether, were also tested to investigate the effect of decreasing the polarity further, resulting in a slight increase in conversion to 23 %. A catalyst prepared by the same method described above but using aqua regia solvent prepared Au/C catalyst gave a steady state conversion of 18 %, meaning that the catalysts prepared by simple wet impregnation of HAuCL from low polarity, easy to handle, solvents such as acetone, 2-butanol and THF performed better than the catalyst
prepared in highly acidic oxidising conditions. All catalysts tested displayed a high selectivity to vinyl chloride monomer (>99 %).
The relative plateau of activity, when decreasing the polarity of the impregnation solvents, occurs at around 20-24 % and is likely to represent a practical limit of the dispersion that can be achieved by the Au-chloride species. X-ray diffraction patterns, reported in Figure 1 b, were recorded for samples prepared with a range of solvent polarities. In the sample prepared by wet impregnation from aqueous solution, clear reflections can be seen at 2Q - 38, 44, 64 and 77° which correspond to the face-centred cubic structure of metallic Au and, using the Schemer equation, corresponds to an average crystallite size of 20 nm. These features are present in the catalyst samples prepared with high polarity solvents, with reflections indicating average nanoparticle sizes ranging from 18-24 nm. These reflections can be seen to gradually decrease in intensity as the polarity of the solvent decreases, indicating a higher dispersion of the Au in the catalysts, corresponding to increased activity. The samples with the highest activities show very weak or un-detectable diffraction peaks corresponding to metallic Au, indicating high dispersions of cationic Au and supporting the premise that Au nanoparticles are not the active species for this reaction.
As the solvents used are not strongly acidic or oxidising, the reason for the high activity of the catalysts prepared with low polarity organic solvents could arise from (i) the hydrophilic/hydrophobic nature of the solvents, providing increased wetting of the carbon support materials which leads to higher dispersions, (ii) the ability to use lower drying temperatures, thus preventing Au agglomeration and (iii) the complete absence of water in the catalyst preparation. To probe this assertion further we investigated the use of low polarity solvents with high boiling points such as dimethylformamide (DMF), dimethyl sulphoxide (DMSO) and cyclohexanone. Table 2 reports the polarity, boiling points and drying temperatures used to produce these catalysts along with the acetylene conversion values.
Table 2.
Test Conditions: 90 mg catalyst, 23.5 ml_ mirr1 C2H2, 23.7 ml_ mirr1 HCI and 2.7 ml_ min 1 Ar, 200 °C.
While all the catalysts prepared with a high boiling point (>120 °C) solvents performed better than the catalyst prepared in aqueous solution, they were not as active as the samples prepared with low boiling point solvents (<120 °C) suggesting that the drying temperature is also a parameter effecting the performance of the catalysts. XRD analysis
(Figure 6) shows that the catalysts prepared at high drying temperatures contained Au nanoparticles, which is consistent with their lower activity. To probe if drying temperature was the only variable determining high activity and dispersion, a catalyst was prepared with acetone and dried at 140 °C for 16 h. As reported in Table 2, this catalyst showed identical activity to the sample prepared with acetone and dried at 40 °C, which demonstrates that effective catalysts can be prepared with low polarity solvents and low drying temperatures, but that these same catalysts can still be stable and just as active even at higher drying temperatures. This suggests that it is the increased wettability of the impregnation solution on the carbon support coupled with mild drying conditions that effectively anchors single highly dispersed Au species, rather than speciation being solely dictated by the drying temperature.
We further investigated the effect of the presence of water on the preparation of catalysts using as purchased extra dry acetone without any further treatment. Adding increasing amounts of water (5-50 vol%) to the acetone resulted in a decrease in activity of the as- prepared catalyst as shown in Figure 2a, until at 50 vol% the activity resembled that of samples prepared in aqueous solution. This measured reduction in activity correlated well with the development of characteristic reflections from metallic Au in the recorded
XRD patterns, Figure 2b. This confirms the negative impact of the presence of water on the preparation of highly dispersed Au catalysts, in the absence of strong oxidising/acidic agents or ligands, to stabilise the supported Au in high oxidation states.
A time-on-line study was performed to compare the activity of the low polarity Au/C- Acetone catalyst with that of the acidic Au/C -aqua regia material and high polarity Au/C- H2O catalyst. Figure 3 shows the high stability of the Au/C-Acetone catalyst under reaction conditions, with a small (3 %) increase in conversion in the first 100 min, indicating a possible minor change in the Au oxidation state and a minimal induction period, followed by a further 140 min of steady conversion. The Au/C -aqua regia catalyst by comparison undergoes a pronounced induction period due to changes in Au oxidation state which have been previously studied by in situ X AS, resulting in a 15 % difference in conversion over the same timeframe. The oxidising aqua regia solvent therefore resulted in a catalyst with a lower final conversion to that of the more benign acetone- prepared catalyst and is highly suggestive that the likely different functionality of the carbon supports can play a key role in determining the induction periods of these catalysts through either stronger Au anchoring or facilitating more facile changes in oxidation state.
Further characterisation of this 1 % Au/C-Acetone catalyst by high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) revealed the Au speciation to be predominatly atomically dispersed Au species as well as some occasional dimeric Au species and sub nano-meter clusters, with no evidence at all of larger Au crystallites. A representative image is shown in Figure 4a.
To further probe the speciation of the Au in the catalyst we conducted X-ray absorption spectroscopy (XAS) at the Au l_3-edge (11.92 keV). The X-ray absorption spectra at the Au l_3-edge of the fresh Au/C-Acetone catalyst and after reaction for 5 h were recorded, in addition to that for the Au/C-aqua regia catalyst, and analysed in the X-ray absorption near-edge structure (XANES) region. Analysis of the normalised white line intesity corresponding to the Au 2p3/2 5d primary transition can be used as a direct probe of the 5d occupancy of the Au species present in the catalyst. Through comparison with standards for Au(lll) (- white line intensity, 1.1) and Au(l) (- white line intensity, 0.6) previously reported in literature (see Chang ei al., RSC Adv. , 2014, 5, pages 6912-6918 and Pantelouris et ai, JACS, 1995, 117, pages 1 1749-11753), it is possible to quantitatively determine the nature of the cationic Au species present in the catalysts.
Analysis of the XANES region of the three Au/C catalysts intially reveals signficantly different post-edge features in comparison to a metallic Au foil, as reported in Figure 4b. This supports the XRD and STEM analysis that there are no extended metallic Au structures present in the fresh catalysts prepared with acetone or aqua regia. The normalised white line height of the fresh samples prepared with acetone and aqua regia suggest that both catalysts are a mixture of Au(l) and Au(lll) species, with the acetone catalyst being slightly more Au(l) rich than the comparable samples prepared using aqua regia, based on a lower normalised white line height intensity ( ca . 0.66 for Au/C-Acetone and ca. 0.78 for Au/C -aqua regia). Three different Au standards were used to perform a linear combination fitting (LCF) analysis of the Au l_3-edge XANES: Au(lll) (KAuCL/[AuCh]_), Au(l) ([AuCL]-), and a Au-foil standard spectra, as is shown in Figure 4c. The LCF confirms the cationic nature of the Au in the acetone derived catalyst with the Au predominantly existing in the Au(l) oxidation state (77%). This is similar in nature to the catalyst prepared using aqua regia albeit with a different distribution of Au(l) - (57%) and Au(lll) - (43%).
After 5 h of use, a small contribution from Au(0) could be detected in the Au/C-Acetone catalyst, indicating some instability of the cationic Au species. The reduction of Au species may be responsible for the deactivation of the catalysts. The stability observed in the acetylene hydrochlorination tests suggests that agglomeration takes place during the heating ramp to reaction temperatures and not actually during the reaction itself. Extended X-ray absorption fine structure (EXAFS) data for the Au/C-Acetone and Au/C- aqua regia catalysts (Figure 4d) indicated a lack of long-range order and no characteristic Au-Au distances, when compared to the Au foil standard, for both of these catalysts, in agreement with the X-ray diffraction and the HAADF-STEM analysis. An increase in intensity of the Fourier transform of the used catalysts at distances corresponding to those of the Au foil was observed in the used catalysts consistent with the LCF analysis.
To determine the stability of the Au/C-Acetone catalyst, a prolonged reaction was performed. After 4 h of reaction, the catalyst was cooled to room temperature under a flow of Ar, left sealed for 16 h, heated under an Ar flow and then tested under reaction conditions for a further 3 h. The same test was performed with the Au/C-aqua regia material for comparison. This test, illustrated in Figure 5, shows the good stability of the Au/C-Acetone catalyst, maintaining a conversion between 19-20 % for over 5 h, indicating that after the first 100 min of reaction the Au oxidation states and dispersion remained relatively stable. Figure 7 shows the XRD pattern of the Au/C-Acetone catalyst
after 7 h of reaction, compared with that of the fresh material and the catalyst used for 4 h. The characteristic reflections of Au nanoparticles increased slightly in size after 7 h of reaction suggesting the slow sintering of the catalyst at extended reaction times. Furthermore, due to the lack of catalyst deactivation it is likely that this Au(0) forms during the heat up or initial stages of the reaction before stabilising. It worth noting that weak reflections from NaCI could also be observed in the XRD patterns of the catalysts especially when synthesized with ultra-dry solvents. This was attributed to the carbon support materials containing NaCI which could easily recrystallize in the ultra-dry organic solvents, but in aqueous solvents it can be readily dissolved and get well dispersed over the catalyst.
In conclusion we show that it is possible to prepare effective Au/C acetylene hydrochlorination catalysts consisting of atomically dispersed cationic Au species by a simple wet impregnation method, using low polarity solvents with low boiling points rather than the aggressive acidic and oxidising solvents typically used. These catalysts perform comparably to catalysts prepared with aqua regia in terms of activity and stability and have been shown to be structurally similar. Furthermore, there was no significant induction period associated with the rapid evolution of Au oxidation state often seen in catalysts prepared with highly oxidising solvents. This preparation method allows the facile preparation of single site Au catalysts with relatively high metal loadings compared to other reported systems and should allow the potential of these materials to be fully exploited by removing the need to deal with highly acidic waste during catalyst preparation.
Example 2
Methods
Catalyst Preparation
All carbon-supported catalysts were prepared via a wet impregnation method described in G. Malta et ai, Science, 2017, 355, pages 1399-1403, except that different solvents were used. Activated carbon (Norit® ROX 0.8) was initially ground to obtain a powder (150 - 200 mesh). The precursor was dissolved in acetone (2.7 ml). The precursor solution was added drop-wise, with stirring, to the activated carbon (0.99 g) in order to obtain a catalyst with a final metal loading of 1 wt.%. The resulting powder was dried at
5-10°C higher than the boiling point of the solvent used (acetone), for 16 h under a flow of N2. Wherever possible, solvents commercially available as“extra-dry solvents” sealed in nitrogen were used.
The gold precursor was HAUCI4.3H2O (Alfa Aesar, 20 mg, assay 49%).
The ruthenium precursor was Ru (III) acetylacetonate (Aldrich).
The palladium precursor was Pd (II) acetylacetonate (Aldrich).
The platinum precursor was Pt (II) 2,4-pentanedionate (Alfa Aesar).
Catalyst Testing
Catalysts were tested for acetylene hydrochlorination in a fixed-bed polyimide (Kapton) microreactor (O.D. 6 mm, length 20 cm) contained within a heating block powered by two heating cartridges inside the block. The temperature was controlled by a Eurotherm controller with a type K thermocouple positioned in the centre of the heater block. C2H2/Ar (5.01 % balanced in Ar, BOC) and HCI/Ar (5.05% balanced in Ar, BOC) gases were dried, using moisture traps, prior to introduction to the reactor. In all cases, the reactor was purged with Ar (99.99% BIP, Air Products) prior to admitting the hydrochlorination reaction mixture. The reactor was heated to 180 °C at a ramp rate of 5 °C min 1 and held at this temperature for 30 min, all under a flow of Ar (50 ml min 1). The reaction gas mixture of C2H2/Ar (23.56 ml min 1), HCI/Ar (23.76 ml min 1) and additional Ar (2.70 ml min 1) was introduced into the heated reactor chamber containing catalyst (90 mg) at a total gas hourly space velocity (GHSV) of -17,600 h 1 , keeping the C2H2: HCI ratio at a constant value of 1 : 1.02. Typical time on stream experiments were conducted for 240 min (4 h). The gas phase products were analysed on-line using a Varian 450 GC equipped with a flame ionisation detector (FID). Chromatographic separation and identification of the products was carried out using a Porapak N packed column (6 ft c 1/8" stainless steel). 100 % C2H2 conversion gives a VCM productivity of 35.33 mol kgcat 1 h 1 under the reaction conditions used. The experimental error in acetylene conversion was ±1 % for repeat tests.
Catalyst Characterisation
Powder X-ray diffraction (XRD) spectra were acquired using an X’Pert Pro PAN Analytical powder diffractometer employing a Cu Ka radiation source operating at 40 keV and 40 mA. The spectra were analysed using X’Pert High Score Plus software.
The Au/C, Ru/C, Pt/C and Pd/C catalysts were characterised via X-ray Absorption Spectroscopy (XAS) before reaction (Fresh) and after 240 min of reaction (Used). X-ray absorption spectroscopy (XAS) spectra for all the samples were recorded in transmission mode, at the B18 beamline of Diamond Light Source, Harwell, UK. The measurements were performed using a QEXAFS set-up with a fast-scanning Si (111) double crystal monochromator. The Demeter software package (Athena and Artemis) was used for XAS data analysis of the absorption spectra.
X-ray absorption spectroscopy (XAS) was conducted at the Au L3-edge (11.92 keV), Pt L3-edge, Pd K-edge, or Ru K-edge. The X-ray absorption spectra of the fresh catalysts, in addition to the corresponding metal precursors (HAuCL, Pt(acac)2, Pd(acac)2, and Ru(acac)3) and metal foils (Au(0), Pt(0), Pd(0), and Ru(0)), were recorded and analysed in the X-ray absorption near-edge structure (XANES) region and in the Extended X-Ray Absorption Fine Structure (EXAFS) region.
Materials for examination by scanning transmission electron microscopy (STEM) were dry dispersed onto a holey carbon TEM grid. These supported fragments were examined using BF- and HAADF-STEM imaging modes in an aberration corrected JEOL ARM- 200CF scanning transmission electron microscope operating at 200kV. This microscope was also equipped with a Centurio silicon drift detector (SDD) system for X-ray energy dispersive spectroscopy (XEDS) analysis. Results
It was found that the Au/C, Ru/C, Pt/C, and Pd/C catalysts were all active for the production of vinyl chloride monomer (see Figures 8 to 11). In all cases, the metal in the catalysts (Au, Ru, Pt and Pd) remained as cations and not in metallic form as predicted (see Figures 24 to 27, which lack 2Q reflections indicating
the presence of Au(0) or Ru(0) or Pt(0) or Pd(0)). For the Ru, Pt and Pd catalysts, a replacement of the ligands surrounding the metal centre, from“acac” to“chlorine”, was observed. Overall, the catalysts are still single metal catalysts (see Figures 12 to 15). This was confirmed by Scanning Electron Transmission Microscopy (STEM). All catalysts comprised atomically dispersed metals (see Figures 16 to 23).
The XANES spectra of the catalysts show an overlap with the corresponding metal precursors but not with the metal foil. Since the metal precursors have an oxidation state of Ru(lll), Pd(ll), or Pt(ll) and the metal foils have an oxidation state of (0), the metals in the catalysts have an oxidation state of Ru(lll), Pd(ll), or Pt(ll) (see Figures 24 to 30).
The foregoing broadly describes certain embodiments of the present invention without limitation. Variations and modifications as will be readily apparent to those skilled in the art are intended to be within the scope of the present invention as defined in and by the appended claims.
Claims
1. A method for making a catalyst, the method comprising combining a gold, ruthenium, palladium, or platinum precursor, a solvent, and a support material, wherein the solvent comprises an organic solvent and wherein the solvent does not comprise organic aqua regia.
2. The method of claim 1 , wherein the combining comprises forming a solution of the precursor in the solvent, and combining the solution with the support material.
3. The method of claim 1 or 2, wherein the method further comprises drying the product of the step of combining the precursor, solvent and support material.
4. The method of any preceding claim, wherein:
(a) the gold precursor is selected from elemental gold (Au), chloroauric acid
(HAuCL) such as chloroauric trihydrate and/or tetrahydrate, gold (III) chloride (AuCh), gold (I) chloride (AICI), gold acetate and combinations of one or more thereof; and/or
(b) the ruthenium precursor is selected from ruthenium (III) acetylacetonate, ruthenium (III) acetylacetonate, and combinations thereof; and/or
(c) the palladium precursor is selected from palladium (II) acetylacetonate,
palladium (II) nitrate dehydrate, palladium (II) acetate, and combinations of one or more thereof; and/or
(d) the platinum precursor is platinum (II) 2,4-pentanedionate.
5. The method of any preceding claim, wherein the solvent:
(a) has an ET(30) polarity equal to or less than about 62, for example equal to or less than about 60, for example equal to or less than about 55, for example equal to or less than about 50; and/or
(b) has a boiling point equal to or less than about 120°C; and/or
(c) comprises equal to or less than about 50 vol% water, for example equal to or less than about 10 vol% water, for example equal to or less than about 5 vol% water; and/or
(d) has a pH equal to or greater than about 5 or equal to or greater than about 6.
6. The method of any preceding claim, wherein the organic solvent is selected from the group consisting of alcohols, ketones, esters, ethers, sulphoxides, nitriles, amides and combinations of one or more thereof.
7. The method of any preceding claim, wherein the solvent does not comprise:
(a) a mineral acid; and/or
(b) nitric acid; and/or
(c) hydrochloric acid; and/or
(d) a combination of nitric acid and hydrochloric acid; and/or
(e) water.
8. The method of any preceding claim, wherein the method does not comprise adding a sulphur-containing ligand to the gold precursor, solvent and support material.
9. The method of any preceding claim, wherein the support material comprises carbon such as activated carbon.
10. The method of claim 3, wherein the drying occurs at a temperature above the boiling point of the solvent, for example up to about 10°C higher than the boiling point of the solvent.
11. The method of claim 3 or 10, wherein the drying occurs at a temperature equal to or less than about 120°C, for example equal to or less than about 110°C, for example equal to or less than about 100°C, for example equal to or less than about 90°C.
12. The method of any preceding claim, wherein the catalyst comprises atomically dispersed and/or cationic gold, ruthenium, palladium, or platinum.
13. A catalyst comprising atomically dispersed cationic gold, ruthenium, palladium, or platinum species and a support material.
14. The catalyst of claim 13, wherein the catalyst provides a steady state acetylene conversion greater than about 3%, for example equal to or greater than about 18%.
15. The catalyst of claim 13 or 14, wherein equal to or greater than about 80% of the gold or ruthenium or palladium or platinum is atomically dispersed.
16. The catalyst of any one of claims 13 to 15, wherein the catalyst comprises atomically dispersed cationic gold species and a support material, and wherein:
equal to or greater than about 58%, for example equal to or greater than about 70%, of the gold exists in the Au(l) oxidation state; and/or
equal to or greater than about 60%, for example equal to or greater than about 70% or equal to or greater than about 80%, of the ruthenium exists in the Ru(lll) oxidation state; and/or
equal to or greater than about 60%, for example equal to or greater than about 70% or equal to or greater than about 80%, of the palladium exists in the Pd(ll) oxidation state; and/or
equal to or greater than about 60%, for example equal to or greater than about 70% or equal to or greater than about 80%, of the platinum exists in the Pt(ll) oxidation state; and/or
equal to or less than about 42% of the gold exists in the Au(lll) oxidation state; and/or
equal to or greater than about 80 % of the gold or ruthenium or palladium or platinum is atomically dispersed;
equal to or less than about 10 % of the gold or ruthenium or palladium or platinum exists in the form of nanoparticles; and/or
equal to or less than about 10 % of the gold or ruthenium or palladium or platinum exists in the form of dimers and sub nanometer clusters; and/or
the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or more of 38, 44, 64 and 77°; and/or
the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or both of 42.2 and 44°; and/or
the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at 40°; and/or
the catalyst has an X-Ray Diffraction pattern that does not have a 2Q reflection at one or more of 42.9, 46.4, 67.9, 81.8 and 86.2°.
17. A catalyst obtainable by and/or obtained by the method of any of claims 1 to 12.
18. The catalyst of claim 17, wherein the catalyst has one or more of the features specified in claims 13 to 17.
19. Use of a catalyst of any one of claims 13 to 18 in a method of making vinyl chloride.
20. The use of claim 19, wherein the method of making vinyl chloride comprises hydrochlorination of acetylene.
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CN112424150A (en) | 2021-02-26 |
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