CN102164668B - 连续生产催化剂的方法 - Google Patents
连续生产催化剂的方法 Download PDFInfo
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- CN102164668B CN102164668B CN200980137555.8A CN200980137555A CN102164668B CN 102164668 B CN102164668 B CN 102164668B CN 200980137555 A CN200980137555 A CN 200980137555A CN 102164668 B CN102164668 B CN 102164668B
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- alloy
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 87
- 239000002184 metal Substances 0.000 claims abstract description 87
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 31
- 238000005275 alloying Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000004696 coordination complex Chemical class 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000002161 passivation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000002902 organometallic compounds Chemical group 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- DTIGTFJLLYWKTF-UHFFFAOYSA-N 2-methylnona-2,4-diene Chemical group CCCCC=CC=C(C)C DTIGTFJLLYWKTF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 229910000521 B alloy Inorganic materials 0.000 claims 1
- -1 platinum group metals Chemical class 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229910002844 PtNi Inorganic materials 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910002848 Pt–Ru Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000218213 Morus <angiosperm> Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000005414 inactive ingredient Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B01J35/393—
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及一种连续生产催化剂的方法，该催化剂包含铂族金属与至少一种选自铂族金属或过渡金属的第二金属作为成合金金属的合金，其中将包含铂族金属的催化剂与至少一种各自包含成合金金属的配合物混合形成合金前体，且其中将合金前体在连续运转炉中加热以生产合金。
Description
本发明涉及一种连续生产催化剂的方法，该催化剂包含铂族金属与选自铂族金属和过渡金属的第二金属的合金。
包含铂族金属与第二金属的合金的催化剂例如用于燃料电池。催化剂通常以催化活性层的形式施用于离子导电膜。该催化剂层通常施用于膜的两面。提供有催化剂层的膜位于两个多孔气体扩散层之间。反应气体各自通过气体扩散层接近膜。同时，气体扩散层用于提供和导走由反应物吸收或释放的电子。实际的还原或氧化反应在位于膜和气体扩散层之间的催化剂层中进行。膜又确保燃料电池中的离子电荷传输。膜的另一任务是在两个电极之间形成不透气屏障。
该催化剂例如适合用作燃料电池中的阴极催化剂。这允许在称为低温燃料电池如质子交换膜电池(PEMFC)和高温燃料电池如磷酸燃料电池(PAFC)中的应用。为了用于直接甲醇燃料电池(DMFC)，阴极催化剂除了用于氧气还原的高电流密度之外必须具有对甲醇的高耐受性。
例如由J.Applied Electrochemistry(1998)，第673-682页中已知热处理过的卟啉-过渡金属配合物或例如由J.Electrochem.Soc.，145(10)，1998，第3463-3471页中已知的过渡金属硫化物如ReRuS或MoRuS体系例如具有用于还原氧气的高电流密度并表现出对甲醇的良好耐受性。然而，这些催化剂不能达到Pt基催化剂的活性并且在燃料电池的酸性介质中在较长时间范围内也不足够稳定以确保令人满意的电流密度。
由US-A 2004/0161641中已知与过渡金属成合金的铂催化剂具有对甲醇的良好耐受性并确保用于还原氧气的足够高的电流密度。因此，由US-A2004/0161641中已知，例如活性耐甲醇阴极催化剂应该具有对氧气非常高的结合能同时对氢气的低结合能。对氧气的高结合能确保用于还原氧气的高电流密度，而对氢气的低结合能抑制甲醇电解氧化脱氢成一氧化碳并因此增强甲醇耐受性。根据US-A 2004/0161641，这些性能由元素Fe、Co、Ni、Rh、Pd、Pt、Cu、Ag、Au、Zn和Cd的合金所拥有。然而，适合作为耐甲醇阴极催化剂的合金组合物的具体实例并没有给出。
作为对使用耐甲醇催化剂的选择，可以选择更合适的膜以减少甲醇渗透例如在Platinum Metals Rev.2002，46，(4)中提及。例如，较厚的Nafion膜可以用于该目的。然而，减少甲醇渗透的同时导致膜电阻增加，其最终导致燃料电池性能下降。
生产包含铂和钌的催化剂例如描述在A.J.Dickinson等人，“Preparation of a Pt-Ru/C Catalyst from carbonyl complexes for fuel cellapplications”，Elektrochimica Acta 47(2002)，第3733-3739页中。为此，将[Ru3(CO)12]、[Pt(CO)2]x和活性碳与邻二甲苯混合。将该混合物在143℃下加热回流伴随恒定机械搅拌24小时。混合物随后冷却并将邻二甲苯通过蒸馏除去。加热回流在空气气氛中进行。所述方法导致催化剂富含钌。
生产用于直接甲醇燃料电池的Pt-Ru催化剂的制备技术的概述由H.Liu等人，“A review of anode catalysis in the direct methanol fuel cell”，Journal of Power Sources，155(2006)，第95-110页中给出。所述合适的生产方法为首先用包含金属的前体浸渍碳载体，将胶态金属合金颗粒施用于载体上并在微乳液中合成金属微粒。将胶态金属合金颗粒施用于载体上和在微乳液中合成金属微粒要求使用非常贵的原料，例如表面活性剂。为此，碳载体的浸渍最经常用于生产催化剂。然而，浸渍的缺点在于通常难以控制纳米颗粒的大小和其分布。另外，使用高沸点溶剂，如通常在浸渍的情况下，尤其是在生产工业相应量的催化剂中是有问题的。
在另一已知方法中，铂催化剂首先在第一步骤中生产。将其过滤、洗涤和干燥并且然后再分散于通常为水的液态反应介质中。待合金化的元素以合适的可溶性盐形式加入分散体中并借助合适的沉淀剂优选碳酸钠沉淀。将所得分散体过滤，将已分离出的固体洗涤、干燥并随后在还原气氛下经受高温处理。然而，该方法的缺点为已经过滤、洗涤和干燥过一次的产物不得不经历第二次该顺序的工艺步骤。
因此，本发明的目的是提供一种不具有现有技术已知方法缺点的生产催化剂的方法。具体而言，本发明的目的是提供一种方法，借助于该方法具有可再现的纳米颗粒尺寸和分布的催化剂可以连续生产。
该目的通过一种生产催化剂的方法实现，该催化剂包含铂族金属与至少一种选自铂族金属和过渡金属的第二金属作为成合金金属的合金，该方法包括如下步骤：
(a)将包含铂族金属的催化剂与至少一种各自包含成合金金属的热分解性化合物混合得到合金前体，
(b)在连续运转炉中加热合金前体生产合金。
本发明生产的催化剂对酸稳定且具有用于还原氧气的高电流密度，如燃料电池中阴极催化剂所需要的。另外本发明生产的催化剂对甲醇污染也非常耐受。
在步骤(a)中包含铂族金属的催化剂与至少一种包含成合金金属的配合物混合优选得到干燥或潮湿的粉末。这样，避免了不得不使包含铂族金属的洗涤和干燥过的催化剂重新过滤、洗涤和干燥的需要。仅在步骤(b)中加热以获得下述合金。
作为用于形成合金的连续运转炉，优选使用旋转管式炉或带式煅烧炉。尤其是使用旋转管式炉时，在生产合金过程中通过配合物分解形成的气态化合物可以除去，因此也可以生产相对大量的催化剂。
包含铂族金属的催化剂例如为金属粉末的形式。
为实现足够良好的催化剂活性，催化剂必须具有大的比表面积。这优选通过包含载体且铂族金属与第二金属的合金施用于载体上的催化剂实现。为实现大表面积，载体优选多孔的。
将催化剂施用于载体上时，催化剂材料的个体颗粒通常包含于载体表面上。催化剂通常不作为在载体表面上的邻接层存在。
为生产包含载体的催化剂，优选包含铂族金属的催化剂预先包含载体。
在此载体通常为施加催化活性材料或包含催化活性材料的催化非活性材料。可用作载体的合适的催化非活性材料例如为碳或陶瓷。其它合适的载体材料例如为氧化锡，优选半导体氧化锡、可以碳涂覆的γ-氧化铝、二氧化钛、二氧化锆或二氧化硅，且优选后者以初级粒径为50-200nm的微粒形式存在。氧化钨和氧化钼也是合适的且其也可以作为青铜即作为亚化学计量氧化物存在。其它合适的载体为元素周期表IV-VII族过渡金属优选钨和钼的碳化物或氮化物。
然而，特别优选碳作为载体材料。碳作为载体材料的优点在于它是导电的。当催化剂用作燃料电池中的电催化剂如作为燃料电池的阴极时，其必须为导电的以确保燃料电池的功能。用作载体的碳可以作为例如活性碳、碳黑、石墨或纳米结构碳存在。合适的碳黑例如为Vulcan XC72或Ketjenblack EC300。若碳作为纳米结构碳存在，则优选使用碳纳米管。为生产催化剂，将铂族金属施用于载体材料上。
当包含铂族金属的催化剂进一步包含载体时，铂族金属通常首先沉积于载体上。这通常在溶液中进行。为此，金属化合物例如可以在溶剂中的溶液存在。金属可以共价、离子或配位形式存在。另外，金属也可以作为前体或通过借助于碱沉淀相应氢氧化物还原沉积。沉积铂族金属的其它可能方法为用包含金属的溶液浸渍(初湿含浸法)、化学气相沉积(CVD)或物理气相沉积(PVD)法以及其它所有借助于其金属可以沉积的本领域技术人员已知的方法。优选首先沉淀铂族金属的盐。该沉淀随后干燥并热处理以生产包含铂族金属的催化剂。
这种包含铂族金属的载体或非载体催化剂的生产是已知的且相应催化剂可以商购得到。
对本发明而言，铂族金属为铑、铱、镍、钯、铂、铜、银和金。然而，在本发明的优选实施方案中，铂族金属为铂或钯，非常特别优选铂。
当用于步骤(a)的包含铂族金属的催化剂为非载体形式时，铂族金属优选作为粒度为1-200μm的粉末存在。在这种情况下，铂族金属的初级粒度为2-20nm。然而，铂族金属粉末也可以另外包含催化非活性组分。其用作例如隔离剂。为此合适的材料例如为所有也可用作催化剂载体的材料。
所述至少一种包含于热分解性化合物，优选配合物，尤其是金属-有机配合物中且选自铂族金属和过渡金属的成合金金属优选选自钌、钴、镍和钯。
所述至少一种成合金金属优选作为金属-有机配合物存在。优选形成金属-有机配合物的配体为烯烃，优选二甲基辛二烯，芳族化合物，优选吡啶，2，4-戊二酮。还优选所述至少一种成合金金属以混合的环戊二烯基-羰基配合物或作为纯的或混合的羰基、膦、氰基或异氰基配合物存在。
优选所述至少一种成合金金属作为具有乙酰丙酮化物或2，4-戊二酮作为配体的金属-有机配合物存在。所述至少一种成合金金属优选以离子形式存在。
为将至少一种选自铂族金属和过渡金属的成合金金属与包含铂族金属的催化剂混合，优选包含成合金金属的热分解性化合物以干燥形式存在。然而，作为选择，热分解性化合物也可以作为在溶剂中的溶液存在。在这种情况下，优选溶剂选自乙醇、己烷、环己烷、甲苯和醚化合物。优选醚化合物为开链醚，例如二乙醚、二正丙醚或2-甲氧基丙烷，以及环醚如四氢呋喃或1，4-二烷。
若包含至少一种成合金金属的热分解性化合物以在溶剂中的溶液存在，则包含铂族金属的催化剂与至少一种金属-有机化合物或至少一种金属配合物的混合物在步骤(b)中的热处理之前干燥。干燥可以在室温下或在高温下进行。若干燥在高温下进行，则优选温度高于溶剂的沸点。选择干燥时间以使干燥后包含铂族金属的催化剂与至少一种配合物的混合物中溶剂的比例小于5重量％，优选小于2重量％。
包含铂族金属的催化剂与至少一种包含成合金金属的配合物的混合通过任何本领域技术人员已知的用于混合固体的方法进行。合适的固体混合器通常包含待混合材料在其中移动的容器。合适的固体混合器例如为桨式混合机、螺杆式混合机、斗式混合机或气动混合机。
当热分解性化合物以在溶剂中的溶液存在时，包含铂族金属的催化剂与至少一种溶解的配合物的混合物优选通过本领域技术人员已知的常规分散方法生产。这使用例如其中包含快速旋转刀片或叶片的容器进行。该装置的实例为
然而，特别优选包含铂族金属的催化剂还为自由流动的。这通常为当催化剂的残留水分含量至多为50重量％水时的情况。若催化剂不必完全干燥使用，则包含铂族金属的催化剂的残余水分含量优选为20-30重量％水。由于低含水量，包含铂族金属的催化剂与至少一种包含成合金金属的配合物的混合物维持自由流动。这尤其是对用作连续运转炉的旋转管式炉令人满意的操作而言是基本先决条件。包含铂族金属的催化剂的残余水分含量例如通过在生产过程中在空气中干燥获得。然而，其也可以使用完全干燥的催化剂。
为生产铂族金属与至少一种选自铂族金属和过渡金属的成合金金属的合金，将在步骤(a)中通过将包含铂族金属的催化剂与至少一种包含成合金金属的热分解性化合物混合而生产的粉末加热。为此，将步骤(a)中生产的混合物在连续运转炉中升温至90-900℃，优选350-900℃，更优选400-850℃，尤其是400-650℃。由于加热，所述至少一种配合物分解且结合于此的金属释放。金属与铂族金属结合。这形成其中无序金属晶粒并排存在的合金。个体金属晶粒的大小通常为2-7nm。
在一个优选实施方案中，加热在两个温度段中进行，且第一温度段的温度低于第二温度段的温度。加热也可以在多于两个温度段中进行。在此，优选后续温度段的温度在每种情况下高于之前温度段的温度。然而，优选加热在两个温度段中进行。
当步骤(b)中加热合金前体在两个温度段中进行时，优选第一温度段的温度为300-500℃，优选350-480℃，尤其是370-460℃，且第二温度段的温度为500-700℃，更优选550-680℃，尤其是570-660℃。第二温度段的温度比第一温度段的温度高优选至少100℃，更优选至少150℃。
步骤(b)中在连续运转炉中的停留时间优选为30分钟至10小时，更优选45分钟至5小时，尤其是1小时至2小时。
步骤(b)中加热合金前体优选在还原气氛下进行。还原气氛优选包含氢气。氢气的比例取决于待生产的催化剂的组成。在还原气氛中氢气的比例可以高达100体积％。优选使用其中氢气浓度通常小于30体积％，一般小于20体积％的H2/N2气体气氛。还原气氛中的氢气比例特别优选小于10体积％，尤其是约5体积％。尤其是在Pt-Ni催化剂或Pt-Co催化剂的生产中，还原气氛中氢气的比例优选为4-10体积％，尤其是约5体积％。
除了氢气，优选还原气氛包含至少一种惰性气体。优选还原气氛包含氮气。然而，作为选择，其也可以使用例如氩气代替氮气。其也可以使用氮气和氩气的混合物。然而，优选氮气。
特别优选还原气氛不包含任何除了氢气和惰性气体之外的其它成分。然而，例如由于气体生产方法而存在痕量的其它气体应该例外。
在步骤(b)中加热形成合金之后，优选进行钝化。为此，例如将生产的合金在惰性气氛下冷却至室温。惰性气氛优选为氮气气氛或氩气气氛。其也可以使用氮气和氩气的混合物。步骤(b)中生产的合金也可以例如在离开连续运转炉后引入水流中进行钝化。
由本发明方法生产的催化剂适合用作例如燃料电池的电极材料。其中可使用该催化剂的典型燃料电池例如为质子交换膜燃料电池(PEMFC)、直接甲醇燃料电池(DMFC)、直接乙醇燃料电池(DEFC)和磷酸燃料电池(PAFC)。由本发明方法生产的催化剂特别适合作为阴极催化剂，即用于还原氧气的催化剂。其它合适的应用为甚至在燃料电池外电解氧化甲醇或氢气、电解还原氧气、氯碱电解和电解水。由本发明方法生产的催化剂也可以例如作为3效催化剂或柴油氧化催化剂例如用于汽车尾气催化，或用于化学工业中催化加氢或脱氢。该加氢/脱氢包括例如不饱和脂族、芳族和杂环化合物的加氢，羰基、腈基、硝基和羧酸及其酯的脱氢，氨化加氢，矿物油和一氧化碳加氢。脱氢的实例为石蜡、萘、烷基芳烃和醇的脱氢。加氢或脱氢可以在气相或液相中进行。
实施例
比较例1
为生产碳载体铂催化剂，将100g商购碳黑载体(CABOT XC72)借助于分散装置分散于4L水中。将溶于250ml水中的57.14gPt(NO3)2加入悬浮液中。然后将4250ml乙醇加入混合物中并将混合物加热至沸腾。将悬浮液回流沸腾5小时，冷却至60℃，通过Büchner漏斗上的滤纸过滤且将固体用10L冷水洗涤以使其不含NO3。
将洗涤过的潮湿滤饼形式的所得碳载体铂催化剂随后用3L水重新打浆。悬浮液的pH借助于约20滴65％浓度HNO3设成2.1。将溶于400ml H2O中的48.86g Ni(NO3)·6H2O加入悬浮液中。将混合物随后充分混合10分钟且pH借助于约290ml 10％浓度Na2CO3溶液增加至8.5。将悬浮液另外在75℃和pH8.5下搅拌1小时。将由18ml 35％浓度甲醛溶液稀释至100ml制得的6.3％浓度甲醛溶液随后加入且混合物在75℃下再搅拌1小时。
反应完全后，将悬浮液冷却至约60℃且催化剂抽吸滤过Büchner漏斗上的滤纸并用15L冷水洗涤固体以使其不含NO3。催化剂随后在氮气气氛下在旋转管式炉中于80℃的炉温下干燥48小时。
为形成PtNi合金，将获得的产物在包含15体积％氢气的氢气/氩气气氛中以5℃/min的速度加热至500℃，保持该温度30分钟并且随后再次以5℃/min的速度加热至850℃，保持该温度另外30分钟，随后冷却至室温并在氮气中钝化，其中将空气逐步加入直到出现空气气氛。
在该方法中生产的催化剂的铂含量为23.2重量％，镍含量为6.8重量％且水含量小于0.5重量％。PtNi晶粒大小为9.0nm且晶格常数为
比较例2
为生产载体铂催化剂，将75.8g商购碳黑载体(CABOT XC72)借助于分散装置分散于3L水中。将1L 4％浓度硝酸铂溶液加入溶液中。随后将4.25L乙醇加入且混合物回流5小时。所得催化剂分散体在吸滤器中过滤且使所得滤饼在空气中干燥直到其残余水分含量为22重量％。随后将干燥的滤饼连续经过0.4mm的筛。
将以这种方法制得的11.5g碳载体铂催化剂与4.47g乙酰丙酮镍混合并引入可以分批操作的旋转管式炉中。随后将混合物在氮气流下于100℃干燥两小时。气流随后转变成0.8L/h氢气和15L/h氮气的气流且将混合物逐步加热至600℃。随后将以这种方法制得的催化剂冷却并借助于空气/氮气在室温下钝化。
制得的催化剂的铂含量为21.6重量％，镍含量为8.7重量％，水含量为0.5重量％。PtNi晶粒的晶粒大小为2.4nm且PtNi合金的晶格常数为
实施例
碳载体铂催化剂如比较例2中所述生产。
将以这种方法制得的28.8g碳载体铂催化剂与11.2g乙酰丙酮镍混合并引入可以连续操作的旋转管式炉的储蓄器中。旋转管式炉具有三个加热区，且第一加热区调节为400℃，第二和第三加热区各自调节为600℃。旋转管式炉中的气体气氛为5体积％氢气在95体积％氮气中的混合物。设置旋转管式炉的输送速度以使50g/h催化剂经过旋转管式炉传递。在旋转管式炉加热区中的产物的停留时间为1小时。
离开旋转管式炉后，将所得产物在接收器中收集并随后在旋转管式炉外的空气/氮气气流中钝化。
以这种方法制得的催化剂的铂含量为17.8重量％，镍含量为7.9重量％，水含量为0.6重量％。PtNi晶粒的晶粒大小为2.4nm且PtNi合金的晶格常数为
Claims (16)
1.一种连续生产催化剂的方法，所述催化剂包含铂族金属与至少一种选自铂族金属和过渡金属的第二金属作为合金金属的合金，所述方法包括如下步骤：
(a)将包含铂族金属的催化剂与至少一种各自包含合金金属的热分解性化合物混合得到合金前体，
(b)将合金前体在连续运转炉中加热生产合金，
其中加热在两个温度段中进行，且第一温度段的温度低于第二温度段的温度，第一温度段的温度为350-480℃，第二温度段的温度为550-680℃，其中步骤(b)中的加热在还原气氛下进行，所述还原气氛包含氢气，且其中还原气氛中氢气的比例小于20体积％。
2.根据权利要求1的方法，其中所述连续运转炉为旋转管式炉或带式煅烧炉。
3.根据权利要求1的方法，其中第二温度段的温度比第一温度段的温度高至少100℃。
4.根据权利要求1的方法，其中在连续运转炉中的停留时间为30分钟至10小时。
5.根据权利要求1的方法，其中包含铂族金属的催化剂作为金属粉末存在或进一步包含载体。
6.根据权利要求5的方法，其中所述载体为碳载体。
7.根据权利要求1的方法，其中包含铂族金属的催化剂的残留水分含量至多为50重量％水。
8.根据权利要求1的方法，其中所述铂族金属为铂。
9.根据权利要求1的方法，其中所述合金金属选自钌、钴、镍和钯。
10.根据权利要求1的方法，其中所述至少一种各自包含合金金属的热分解性化合物为金属-有机化合物或金属配合物。
11.根据权利要求10的方法，其中所述金属配合物为具有烯烃，芳族化合物，2,4-戊二酮作为配体的金属配合物，混合的环戊二烯基-羰基配合物，或纯的或混合的羰基、膦、氰基或异氰基配合物。
12.根据权利要求11的方法，其中所述烯烃为二甲基辛二烯。
13.根据权利要求11的方法，其中所述芳族化合物为吡啶。
14.根据权利要求10的方法，其中所述金属配合物为具有乙酰丙酮化物或2,4-戊二酮作为配体的金属配合物。
15.根据权利要求10的方法，其中所述至少一种金属-有机化合物或所述至少一种包含至少一种合金金属的金属配合物作为粉末或作为在溶剂中的溶液存在。
16.根据权利要求1的方法，其中在步骤(b)中加热形成合金之后进行钝化。
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