TW201902827A - Process for carbon dioxide hydrogenation in the presence of a nickel- and magnesium spinel-containing catalyst - Google Patents
Process for carbon dioxide hydrogenation in the presence of a nickel- and magnesium spinel-containing catalyst Download PDFInfo
- Publication number
- TW201902827A TW201902827A TW107118701A TW107118701A TW201902827A TW 201902827 A TW201902827 A TW 201902827A TW 107118701 A TW107118701 A TW 107118701A TW 107118701 A TW107118701 A TW 107118701A TW 201902827 A TW201902827 A TW 201902827A
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- TW
- Taiwan
- Prior art keywords
- catalyst
- range
- nickel
- carbon dioxide
- reactant gas
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 60
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 50
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 43
- 229910052596 spinel Inorganic materials 0.000 title claims description 31
- 239000011029 spinel Substances 0.000 title claims description 30
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 13
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 239000011777 magnesium Substances 0.000 claims abstract description 27
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 26
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 52
- 239000007789 gas Substances 0.000 claims description 38
- 239000000376 reactant Substances 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims description 2
- 229910052566 spinel group Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000523 sample Substances 0.000 description 16
- 238000001354 calcination Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000012018 catalyst precursor Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 230000006798 recombination Effects 0.000 description 10
- 238000005215 recombination Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910020068 MgAl Inorganic materials 0.000 description 2
- 229910003265 NiCr2O4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002459 porosimetry Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910003320 CeOx Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910018565 CuAl Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- TXONVAMTMVNDJZ-UHFFFAOYSA-N [O-2].[Zr+4].[W+4].[O-2].[O-2].[O-2] Chemical compound [O-2].[Zr+4].[W+4].[O-2].[O-2].[O-2] TXONVAMTMVNDJZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/66—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/30—
-
- B01J35/613—
-
- B01J35/647—
-
- B01J35/69—
-
- B01J35/695—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/162—Magnesium aluminates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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Abstract
Description
本發明係關於一種進行二氧化碳氫化之方法，其包含在包括鎳尖晶石及鎂尖晶石之催化劑存在下使二氧化碳與氫反應。The present invention relates to a process for hydrogenating carbon dioxide comprising reacting carbon dioxide with hydrogen in the presence of a catalyst comprising nickel spinel and magnesium spinel.
亦稱為二氧化碳氫化或逆水氣變換反應（reverse water-gas shift reaction，RWGS）之氫及二氧化碳之重組具有極大經濟利益，因為此等方法提供利用二氧化碳作為起始物質製備作為重要基礎化學物質之合成氣之選項。因此，有可能藉由化學途徑結合許多方法中以廢產物得到之二氧化碳。由此可能降低二氧化碳向大氣中之排放。The recombination of hydrogen and carbon dioxide, also known as carbon dioxide hydrogenation or reverse water-gas shift reaction (RWGS), has great economic benefits because these methods provide the synthesis of carbon dioxide as a starting material for the preparation of important basic chemicals. Gas option. Therefore, it is possible to combine the carbon dioxide obtained as a waste product in many methods by a chemical route. This may reduce the emission of carbon dioxide into the atmosphere.
除逆水氣變換反應外，已知以對環境友好的方式使用二氧化碳之其他方法，例如甲烷化及乾式重組，亦即甲烷與二氧化碳之反應。In addition to the reverse water gas shift reaction, other methods of using carbon dioxide in an environmentally friendly manner, such as methanation and dry recombination, that is, the reaction of methane with carbon dioxide, are known.
WO 2015/091310 A1揭示銥催化劑用於烴及二氧化碳之混合物進行乾式重組得到合成氣之用途。WO 2015/091310 A1 discloses the use of a rhodium catalyst for the dry recombination of a mixture of hydrocarbons and carbon dioxide to obtain a syngas.
WO 2015/91310描述用於甲烷及二氧化碳之混合物進行重組之二步方法，其中在第一階段中使反應物氣體與稀有金屬催化劑接觸且在另一階段中與非稀有金屬催化劑接觸。提及鎳及鈷催化劑且經測試為較佳非稀有金屬催化劑。WO 2015/91310之表4概述此等測試結果。發現逆水氣變換反應作為副反應在乾式重組之條件下進行。自甲烷及二氧化碳轉化可見，在七個測試條件中之四者中鈷催化劑催化RWGS反應接近RWGS反應之熱力學上預計的平衡之88%。相比之下，在反應物流中在高甲烷含量存在下，關於RWGS反應，鎳催化劑活性較差，且在七個測試條件中之任一者中均不達到反應之熱力學上預計的平衡。WO 2015/91310 describes a two-step process for the recombination of a mixture of methane and carbon dioxide, wherein the reactant gas is contacted with a rare metal catalyst in a first stage and with a non-rare metal catalyst in another stage. Nickel and cobalt catalysts are mentioned and tested as preferred non-rare metal catalysts. Table 4 of WO 2015/91310 summarizes the results of these tests. It was found that the reverse water gas shift reaction was carried out as a side reaction under the conditions of dry recombination. It can be seen from the conversion of methane and carbon dioxide that the cobalt catalyst catalyzes the RWGS reaction in four of the seven test conditions close to 88% of the thermodynamically predicted equilibrium of the RWGS reaction. In contrast, in the presence of high methane content in the reactant stream, the nickel catalyst was less active with respect to the RWGS reaction and did not reach the thermodynamically predicted equilibrium of the reaction in any of the seven test conditions.
另外，Meshkani Fereshteh等人，「Nickel catalyst supported on mesoporous MgAl2O4 nanopowders synthesized via a homogenous precipitation method for dry reforming reaction」，Research on Chemical Intermediates，第43卷，第1期，第545-559頁(2016-07-18)描述用於甲烷與二氧化碳之乾式重組之鎳催化劑。指明RWGS反應作為副反應發生。鎳催化劑藉助於沈澱反應產生。In addition, Meshkani Fereshteh et al., "Nickel catalyst supported on mesoporous MgAl2O4 nanopowders synthetic via a homogenous precipitation method for dry reforming reaction", Research on Chemical Intermediates, Vol. 43, No. 1, pp. 545-559 (2016-07- 18) Describe a nickel catalyst for dry recombination of methane and carbon dioxide. The RWGS reaction is indicated as a side reaction. The nickel catalyst is produced by means of a precipitation reaction.
出人意料地，並非熟習氫化反應領域之此項技術者已知之所有催化劑展示對於逆水氣變換反應具有良好活性。Surprisingly, all catalysts known to those skilled in the art of hydrogenation reactions exhibit good activity for reverse water gas shift reactions.
合成氣理解為意謂包含氫及一氧化碳且可在多種工業方法中用作基礎化學物質之混合氣體。視其用途而定，合成氣具有不同之氫與一氧化碳之比率。Syngas is understood to mean a mixture of hydrogen and carbon monoxide and which can be used as a base chemical in a variety of industrial processes. Syngas has a different ratio of hydrogen to carbon monoxide depending on its use.
氫又以商業方式經由蒸汽重組方法產生。儘管此等方法具有固有的價格優勢，其反映在氫之成本中，但氫之產生與二氧化碳之高排放有關。Hydrogen is again produced commercially via a steam recombination process. Although these methods have inherent price advantages that are reflected in the cost of hydrogen, the generation of hydrogen is associated with high emissions of carbon dioxide.
德國2010年之CO2排放約9.6億噸CO2當量，其中約5%為化學工業貢獻。自生態及環境觀點而言，在化學工業中，在降低CO2排放上存在極大吸引力，其藉助於改變原料基本成分、低CO2生產技術、使能量需要最佳及利用方法相關之CO2得到大量基礎化學物質實現。適合的基礎化學物質為例如氫及合成氣。後者構成在可用的石化方法中用於生產例如甲醇、二甲醚或費歇爾-托普希產物（Fischer-Tropsch product）之理想界面。對於氫及合成氣的全球需求目前分別為5千萬t/a及2.2億t/a。Germany's CO2 emissions in 2010 were about 960 million tons of CO2 equivalent, of which about 5% contributed to the chemical industry. From an ecological and environmental point of view, in the chemical industry, there is great attraction in reducing CO2 emissions, which is based on a large amount of CO2 related to changing raw material basic components, low CO2 production technology, optimizing energy demand and utilization methods. Chemical substance realization. Suitable base chemicals are, for example, hydrogen and syngas. The latter constitutes an ideal interface for the production of, for example, methanol, dimethyl ether or Fischer-Tropsch products in available petrochemical processes. The global demand for hydrogen and syngas is currently 50 million t/a and 220 million t/a, respectively.
對於藉助於二氧化碳氫化之甲醇產生，Graciani等人提出Cu/CeOx催化劑（J. Graciani、K. Mudiyanselage、F. Xu、A. E. Baber、J. Evans、S. D. Senanayake、D. J. Stacchiola、P. Liu、J. Hrbek、J. Fernandez Sanz、J. A. Rodriguez，Science 345 (2014) 546-550）及Bansode等人提出Cu/ZnO/Al2O3催化劑（A. Bansode、A. Urakawa，J. Catal. 309 (2014) 66-70）。For the production of methanol by means of hydrogenation of carbon dioxide, Graciani et al. proposed Cu/CeOx catalysts (J. Graciani, K. Mudiyanselage, F. Xu, AE Baber, J. Evans, SD Senanayake, DJ Stacchiola, P. Liu, J. Hrbek). , J. Fernandez Sanz, JA Rodriguez, Science 345 (2014) 546-550) and Bansode et al. proposed Cu/ZnO/Al2O3 catalysts (A. Bansode, A. Urakawa, J. Catal. 309 (2014) 66-70) .
除基於Cu之催化劑外，WO2015/135968揭示基於混合Ni、Co、Zn、Fe氧化物之催化劑。In addition to Cu-based catalysts, WO 2015/135968 discloses catalysts based on mixed Ni, Co, Zn, Fe oxides.
此外，用於氫化二氧化碳之含有貴金屬之催化劑描述於US8961829B2中。揭示將鉑沈積於氧化鈰、氧化錳及/或氧化鎂上之催化劑。實施例指定Pt負載量為0.3重量%。Further, a noble metal-containing catalyst for hydrogenating carbon dioxide is described in US8961829B2. A catalyst for depositing platinum on cerium oxide, manganese oxide and/or magnesium oxide is disclosed. The examples specify a Pt loading of 0.3% by weight.
US 2011/0105630揭示用於氫化二氧化碳之基於鉑或基於鈀之催化劑。所描述之可能的載體材料為氧化鋁、氧化鎂、二氧化矽、二氧化鈦、視情況選用之硫酸化二氧化鋯、氧化鎢鋯、三氟化鋁、氟化氧化鋁、膨潤土、沸石、基於碳之載體、分子篩及其組合。較佳指定負載量為10重量%至20重量%。US 2011/0105630 discloses platinum-based or palladium-based catalysts for hydrogenating carbon dioxide. Possible carrier materials described are alumina, magnesia, ceria, titania, optionally sulfated zirconium dioxide, tungsten zirconium oxide, aluminum trifluoride, fluorided alumina, bentonite, zeolite, carbon based Carriers, molecular sieves, and combinations thereof. Preferably, the specified loading is from 10% by weight to 20% by weight.
WO 2013/135710揭示殼管式反應器中之二氧化碳氫化。所揭示之催化劑為具有下式之六鋁酸鹽：LOx(M(y/z)Al(2-y/z)O3)z，其中L = Na、K、Rb、Cs、Mg、Ca、Sr、Ba、Sc、Y、Sn、Pb、Mn、In、Tl、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb及/或Lu且M = Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Zn、Cu、Ag及/或Au。製備此等未負載撐六鋁酸鹽催化劑之模式包含多階段方法，包括沈澱、過濾、洗滌、乾燥、模製及在大於800℃下煅燒之階段。此外，金屬La及Ba昂貴。未揭示二氧化碳氫化之實例。WO 2013/135710 discloses the hydrogenation of carbon dioxide in a shell and tube reactor. The disclosed catalyst is a hexaaluminate having the formula: LOx(M(y/z)Al(2-y/z)O3)z, where L = Na, K, Rb, Cs, Mg, Ca, Sr , Ba, Sc, Y, Sn, Pb, Mn, In, Tl, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and/or Lu and M = Ti Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Zn, Cu, Ag and/or Au. The mode of preparing such unsupported hexaaluminate catalysts comprises a multi-stage process comprising precipitation, filtration, washing, drying, molding, and calcination at greater than 800 °C. In addition, the metals La and Ba are expensive. An example of hydrogenation of carbon dioxide is not disclosed.
WO 2015/135968揭示產生用於高溫二氧化碳氫化及/或重組及/或重組烴化合物及/或二氧化碳之催化劑的方法。所揭示催化劑包含至少一種結晶材料，該結晶材料包含釔及鋁，其為結晶材料之典型特徵，其具有來自以下之群的以下結構中之至少一者：立方石榴石結構、斜方晶鈣鈦礦結構、六角鈣鈦礦結構及/或單斜晶鈣鈦礦結構（亦即Y4AI2O9），其中該催化劑包含Cu、Fe、Co、Zn及/或Ni。含有釔之物質之負載量指定為0.1至10莫耳%。實施例展示在二氧化碳氫化中之良好效能，且亦展示在催化劑上之低碳沈積。實驗在30 000及40 000 h-1之GHSV下進行。製備此等催化劑之模式包含多階段方法，包括沈澱、過濾、洗滌、乾燥、預煅燒、模製及在較佳大於950℃下後煅燒之階段。此外，基於釔之材料昂貴。WO 2015/135968 discloses a process for producing a catalyst for the high temperature carbon dioxide hydrogenation and/or recombination and/or recombination of hydrocarbon compounds and/or carbon dioxide. The disclosed catalyst comprises at least one crystalline material comprising cerium and aluminum, which are typical features of crystalline materials having at least one of the following structures: cubic garnet structure, orthorhombic calcium titanium a mineral structure, a hexagonal perovskite structure and/or a monoclinic perovskite structure (ie, Y4AI2O9), wherein the catalyst comprises Cu, Fe, Co, Zn, and/or Ni. The loading amount of the substance containing cerium is specified to be 0.1 to 10 mol%. The examples demonstrate good performance in hydrogenation of carbon dioxide and also exhibit low carbon deposition on the catalyst. The experiment was carried out at GHSV of 30 000 and 40 000 h-1. The mode of preparing such catalysts comprises a multi-stage process comprising precipitation, filtration, washing, drying, pre-calcination, molding, and post-calcination at preferably greater than 950 °C. In addition, materials based on bismuth are expensive.
根據本發明之目的中之一者為提供一種用於二氧化碳氫化之具有高活性及穩定性，亦即良好耐焦炭堆積性之催化劑。此外，甲烷化趨勢應較小。One of the objects according to the present invention is to provide a catalyst having high activity and stability for hydrogenation of carbon dioxide, that is, good coke-resistant deposition resistance. In addition, the trend of methanation should be small.
另一目的為此催化劑可以低成本生產，意謂可選擇包含最小數量之處理步驟及/或需要較低煅燒溫度之生產模式。Another object is that the catalyst can be produced at low cost, meaning that a production mode comprising a minimum number of processing steps and/or requiring a lower calcination temperature can be selected.
另一目的為此催化劑具有便宜的活性金屬負載。此外，活性金屬負載量應儘可能低，以便效能高且節約資源。Another object is to have a cheap active metal loading for this catalyst. In addition, the active metal loading should be as low as possible for high performance and resource savings.
本發明方法之另一目的亦為適用於在甲烷存在下進行二氧化碳氫化，意謂較佳重組甲烷。Another object of the process of the invention is also to apply to the hydrogenation of carbon dioxide in the presence of methane, meaning that it is preferred to reconstitute methane.
本發明之上下文中之另一目的為鑑別具有特定活性之催化劑，其甚至在高負載（尤其大於10 000 h-1）下仍能夠將反應物氣體混合物轉化成接近熱力學預測的平衡之組成物。具有特定活性之催化劑允許反應器具有較小尺寸且因此使此工廠部分之資金成本保持在較低水準。Another object in the context of the present invention is to identify catalysts having a specific activity which is capable of converting a reactant gas mixture into a composition close to the thermodynamically predicted equilibrium even at high loads (especially greater than 10 000 h-1). Catalysts with specific activities allow the reactor to be of a smaller size and thus keep the capital cost of this plant part at a lower level.
「高溫方法（high-temperature processes）」應理解為意謂在溫度＞ 600℃、尤其＞ 600℃且 ＜ 1400℃下之方法。「催化劑（catalyst）」應理解為意謂呈還原態之催化劑前驅體。"High-temperature processes" are understood to mean methods at temperatures > 600 ° C, especially > 600 ° C and < 1400 ° C. "Catalyst" is understood to mean a catalyst precursor which is in a reduced state.
在下文中提及之所有重量百分比或莫耳百分比均係關於催化劑之總重量。All weight percentages or mole percentages mentioned hereinafter are related to the total weight of the catalyst.
本發明係關於一種進行二氧化碳氫化之方法，其包含在包括含鎳尖晶石及鎂尖晶石之催化劑存在下使二氧化碳與氫反應，其中反應物氣體之二氧化碳之莫耳比例為10%至60%，且氫之莫耳比例為10%至90%，且反應物氣體中之甲烷之莫耳比例在0%與20%之間。The present invention relates to a process for hydrogenating carbon dioxide comprising reacting carbon dioxide with hydrogen in the presence of a catalyst comprising nickel-containing spinel and magnesium spinel, wherein the molar ratio of carbon dioxide of the reactant gas is from 10% to 60% %, and the hydrogen molar ratio is 10% to 90%, and the molar ratio of methane in the reactant gas is between 0% and 20%.
較佳地，在包括含鎳尖晶石之含鎂尖晶石之催化劑存在下使二氧化碳與氫反應得到一氧化碳及水。Preferably, carbon dioxide is reacted with hydrogen in the presence of a catalyst comprising a nickel-containing spinel containing magnesium spinel to provide carbon monoxide and water.
根據本發明使用之催化劑之一有利具體實例為鎳含量在5至30 mol%、較佳10至25 mol%、更佳10至20 mol%範圍內之催化劑。根據本發明使用之催化劑有利具體實例另一有利具體實例為鎂含量在10至40 mol%、較佳15至35 mol%、更佳20至35 mol%範圍內之催化劑。根據本發明使用之催化劑之另一有利具體實例為鋁含量在40至70 mol%、較佳45至65 mol%、更佳50至65 mol%範圍內之催化劑。An advantageous example of one of the catalysts used according to the invention is a catalyst having a nickel content in the range of 5 to 30 mol%, preferably 10 to 25 mol%, more preferably 10 to 20 mol%. Advantageous Examples of Catalysts Used According to the Invention Another advantageous embodiment is a catalyst having a magnesium content in the range of 10 to 40 mol%, preferably 15 to 35 mol%, more preferably 20 to 35 mol%. Another advantageous embodiment of the catalyst used in accordance with the present invention is a catalyst having an aluminum content in the range of 40 to 70 mol%, preferably 45 to 65 mol%, more preferably 50 to 65 mol%.
對於根據本發明使用之催化劑有利的是，鎳以極高度分散形式，亦即精細分佈形式存在於催化劑表面上。根據本發明使用之催化劑宜包括小於200 nm、較佳小於100 nm、較佳不大於70 nm且尤其較佳不大於40 nm之鎳微晶。舉例而言，鎳微晶粒子之尺寸在1至100 nm範圍內，較佳在5至50 nm範圍內。It is advantageous for the catalyst used according to the invention that the nickel is present on the surface of the catalyst in a highly highly dispersed form, i.e. in a finely distributed form. The catalyst used in accordance with the invention preferably comprises nickel crystallites of less than 200 nm, preferably less than 100 nm, preferably not more than 70 nm and especially preferably not more than 40 nm. For example, the size of the nickel microcrystals is in the range of 1 to 100 nm, preferably in the range of 5 to 50 nm.
更佳地，鎳在催化劑中呈均勻形式。更佳地，鎳在載體上或在活性組成物中呈均勻及細粉狀形式。More preferably, the nickel is in a homogeneous form in the catalyst. More preferably, the nickel is in a homogeneous and finely powdered form on the support or in the active composition.
進一步有利的是，載體由極小MgAl2 O4 粒子組成或包含其。根據本發明使用之催化劑宜包括宜小於200 nm、較佳小於100 nm、較佳不大於70 nm且尤其較佳不大於40 nm之鎂尖晶石。舉例而言，鎂尖晶石微晶粒子之尺寸在1至100 nm範圍內，較佳在5至50 nm範圍內。It is further advantageous if the support consists of or comprises very small MgAl 2 O 4 particles. The catalyst used in accordance with the invention preferably comprises magnesium spinel which is preferably less than 200 nm, preferably less than 100 nm, preferably not more than 70 nm and especially preferably not more than 40 nm. For example, the size of the magnesium spinel microcrystals ranges from 1 to 100 nm, preferably from 5 to 50 nm.
根據本發明使用之催化劑前驅體宜具有由鎳及鎂構成之混合氧化物相。此等混合氧化物相宜小於200 nm、較佳小於100 nm、較佳不大於70 nm且尤其較佳不大於40 nm。舉例而言，混合氧化物粒子之尺寸在1至100 nm範圍內，較佳在5至50 nm範圍內。混合氧化物相中鎳及鎂之含量宜為10至30 mol%。The catalyst precursor used in accordance with the invention preferably has a mixed oxide phase comprised of nickel and magnesium. These mixed oxides are preferably less than 200 nm, preferably less than 100 nm, preferably not more than 70 nm and especially preferably not more than 40 nm. For example, the size of the mixed oxide particles is in the range of 1 to 100 nm, preferably in the range of 5 to 50 nm. The content of nickel and magnesium in the mixed oxide phase is preferably from 10 to 30 mol%.
本發明之物質之奈米結構化關於其催化特性具有特定有利的效應。Nanostructured materials of the materials of the invention have a particular advantageous effect with respect to their catalytic properties.
在本發明之一較佳具體實例中，催化劑及/或催化劑前驅體，尤其催化劑前驅體包含鎂尖晶石粒子，其呈與由鎳及鎂構成之混合氧化物相在催化劑及/或催化劑前驅體、尤其催化劑上接觸之形式，包含鎂尖晶石粒子，其呈與金屬鎳及氧化鎂之混合物接觸之形式，以使得宜存在粒子之均勻混合物。In a preferred embodiment of the invention, the catalyst and/or catalyst precursor, particularly the catalyst precursor, comprises magnesium spinel particles in a catalyst and/or catalyst precursor with a mixed oxide phase comprised of nickel and magnesium. The form in contact with the body, particularly the catalyst, comprises magnesium spinel particles in contact with a mixture of metallic nickel and magnesium oxide such that a homogeneous mixture of particles is preferably present.
催化劑前驅體（鎂尖晶石，鎳及鎂之混合氧化物相）及催化劑（金屬鎳及氧化鎂）中之所有粒子宜均勻分佈於催化劑內。The catalyst precursor (magnesium spinel, mixed oxide phase of nickel and magnesium) and all of the catalyst (metal nickel and magnesium oxide) are preferably uniformly distributed in the catalyst.
在本發明之另一較佳具體實例中，根據本發明使用之催化劑前驅體之相組成之典型特徵（由Cu-Kα輻射量測）在於43.15°± 0.15° 2θ（d = 2.09 ± 0.01 Å）下之反射強度不大於44.83 ± 0.20° 2θ（d = 2.02 ± 0.01 Å）下之反射強度；更佳地，43.15°± 0.15° 2θ（d = 2.09 ± 0.01 Å）下之反射強度小於44.83 ± 0.20° 2θ（d = 2.02 ± 0.01 Å）下之反射強度，且甚至更佳地，兩種反射之強度比率I（ 43.15° ） /I（ 44.83° ） 在0.3至1.0、較佳0.5至0.99、甚至更佳0.6至0.97且尤其較佳0.7至0.92範圍內。In another preferred embodiment of the invention, the typical composition of the phase composition of the catalyst precursor used in accordance with the invention (measured by Cu-Kα radiation) is 43.15 ° ± 0.15 ° 2θ (d = 2.09 ± 0.01 Å) The reflection intensity is not greater than the reflection intensity at 44.83 ± 0.20 ° 2θ (d = 2.02 ± 0.01 Å); more preferably, the reflection intensity at 43.15 ° ± 0.15 ° 2θ (d = 2.09 ± 0.01 Å) is less than 44.83 ± 0.20 The intensity of the reflection at ° 2θ (d = 2.02 ± 0.01 Å), and even more preferably, the intensity ratio I ( 43.15 ° ) / I ( 44.83 ° ) of the two reflections is 0.3 to 1.0, preferably 0.5 to 0.99, or even More preferably, it is in the range of 0.6 to 0.97 and particularly preferably in the range of 0.7 to 0.92.
根據本發明使用之催化劑物質或催化劑前驅體物質並非不可亦包含少量，宜小於30重量%、較佳小於20重量%、尤其小於5重量%之鎳尖晶石相及/或氧化鎳。然而，若鎳尖晶石相存在於催化劑前驅體物質中，則必須假定此鎳尖晶石相在本發明方法期間轉化為還原鎳、氧化鎳或混合鎳-氧化鎂。The catalyst material or catalyst precursor material used in accordance with the invention does not have to comprise a minor amount, preferably less than 30% by weight, preferably less than 20% by weight, in particular less than 5% by weight, of the nickel spinel phase and/or nickel oxide. However, if a nickel spinel phase is present in the catalyst precursor material, it must be assumed that this nickel spinel phase is converted to reduced nickel, nickel oxide or mixed nickel-magnesia during the process of the invention.
尤其較佳的一具體實例係關於一種使用催化劑將二氧化碳及氫及視情況存在之甲烷轉化為合成氣之方法，其至少在催化劑前驅體中包含混合鎳-氧化鎂相及鎂尖晶石相及視情況存在之氧化鋁氫氧化物相。各相之典型特徵宜在於混合鎳-氧化鎂之平均微晶尺寸≤ 100 nm、較佳≤ 70 nm、更佳≤ 40 nm，且鎂尖晶石相之平均微晶尺寸≤ 100 nm、較佳≤ 70 nm、更佳≤ 40 nm。A particularly preferred embodiment relates to a method for converting carbon dioxide and hydrogen and, optionally, methane to syngas using a catalyst comprising at least a mixed nickel-magnesia phase and a magnesium spinel phase in a catalyst precursor and Alumina hydroxide phase, as appropriate. The typical characteristics of each phase are preferably that the average crystallite size of the mixed nickel-magnesia is ≤ 100 nm, preferably ≤ 70 nm, more preferably ≤ 40 nm, and the average crystallite size of the magnesium spinel phase is ≤ 100 nm, preferably ≤ 70 nm, more preferably ≤ 40 nm.
在一較佳具體實例中，根據本發明使用之催化劑之典型特徵在於選自藉由XRD得到之相組成、BET表面積、孔隙結構、平均孔徑及/或夯實密度之群的其物理化學特性具有較佳數值：In a preferred embodiment, the catalyst used in accordance with the invention is typically characterized by a physicochemical property selected from the group consisting of phase composition, BET surface area, pore structure, average pore diameter and/or tamping density obtained by XRD. Good value:
催化劑之尤其較佳具體實例之BET表面積值在1至200 m2 /g、較佳5至100 m2 /g、更佳10至70 m2 /g範圍內。特定BET表面積根據DIN 66131測定。Particularly preferred embodiments of the catalyst have a BET surface area value in the range of from 1 to 200 m 2 /g, preferably from 5 to 100 m 2 /g, more preferably from 10 to 70 m 2 /g. The specific BET surface area is determined according to DIN 66131.
進一步較佳的是，當根據本發明使用之催化劑具有至少雙模式孔隙結構，較佳三模式孔隙結構時。催化劑之孔隙結構（剝落分數0.5-1.0 mm）在本文中藉助於根據DIN 66133進行之汞壓孔率測定法， 在此情形下，至少雙模式孔隙結構包含中孔（宜具有1至100 nm範圍內之孔徑）及大孔（宜具有1至300 μm範圍內之孔徑）。大孔之體積宜為0.05至0.5 mL/g、較佳0.075至0.4 mL/g、更佳0.1至0.3 mL/g。中孔之體積宜為0.005至0.4 mL/g、較佳0.01至0.3 mL/g。孔隙之體積及直徑視煅燒溫度而定；溫度愈高，孔隙體積愈低。在催化劑之一較佳組態形式中，平均孔徑（平均孔隙尺寸）大於15 nm、更佳大於18 nm且尤其較佳大於20 nm。平均孔徑宜在15至100 nm、較佳20至100 nm範圍內。It is further preferred that when the catalyst used in accordance with the present invention has at least a dual mode pore structure, preferably a three mode pore structure. The pore structure of the catalyst (exfoliation fraction 0.5-1.0 mm) is herein determined by means of mercury porosimetry according to DIN 66133, in which case at least the bimodal pore structure comprises mesopores (preferably having a range of 1 to 100 nm) Internal pore size) and large pores (preferably have a pore size in the range of 1 to 300 μm). The volume of the macropores is preferably from 0.05 to 0.5 mL/g, preferably from 0.075 to 0.4 mL/g, more preferably from 0.1 to 0.3 mL/g. The volume of the mesopores is preferably from 0.005 to 0.4 mL/g, preferably from 0.01 to 0.3 mL/g. The volume and diameter of the pores depend on the calcination temperature; the higher the temperature, the lower the pore volume. In a preferred configuration of the catalyst, the average pore size (average pore size) is greater than 15 nm, more preferably greater than 18 nm and especially preferably greater than 20 nm. The average pore diameter is preferably in the range of 15 to 100 nm, preferably 20 to 100 nm.
另外，催化劑之一較佳實施例之特徵夯實密度較佳＜ 1500 g/L、更佳＜ 1350 g/L且甚至更佳＜ 1100 g/L。特徵夯實密度宜在600至1100 g/L範圍內。特徵夯實密度藉助於來自JEL之STAV 2003夯實體積計測定。對於量度，使用0.5至1.0 mm催化劑之剝落分數。Additionally, a preferred embodiment of the catalyst has a characteristic tamping density of < 1500 g/L, more preferably < 1350 g/L and even more preferably < 1100 g/L. The characteristic compact density is preferably in the range of 600 to 1100 g/L. The characteristic tamping density was determined by means of a STAV 2003 tamping volume meter from JEL. For the measurement, a peeling fraction of 0.5 to 1.0 mm catalyst was used.
更特定言之，本發明係關於一種進行二氧化碳氫化之方法，其中該方法包含以下步驟： （i）使含CO2 及H2 之反應物氣體與包括含鎳尖晶石及鎂尖晶石之催化劑接觸， （ii）與催化劑接觸之反應物氣體之壓力在1至100巴絕對 範圍內，且與催化劑接觸之反應物氣體之溫度在20至1400℃範圍內， （iii）該方法之GHSV之值在1000至1 000 000 h-1 範圍內， （iv）產生之合成氣之H2 /CO比率在0.1至10範圍內。More particularly, the present invention relates to a process for hydrogenating carbon dioxide, wherein the process comprises the steps of: (i) reacting a reactant gas comprising CO 2 and H 2 with a nickel-containing spinel and a magnesium spinel; Catalyst contact, (ii) the pressure of the reactant gas in contact with the catalyst is in the range of 1 to 100 bar absolute , and the temperature of the reactant gas in contact with the catalyst is in the range of 20 to 1400 ° C, (iii) the GHSV of the method The value is in the range of 1000 to 1 000 000 h -1 , and (iv) the produced syngas has a H 2 /CO ratio in the range of 0.1 to 10.
反應物氣體H2/CO2之莫耳比宜在0.1至20、較佳0.3至10、更佳1至7、尤其2至5範圍內。The molar ratio of the reactant gas H2/CO2 is preferably in the range of 0.1 to 20, preferably 0.3 to 10, more preferably 1 to 7, especially 2 to 5.
反應物氣體宜具有以下組成物：CO2之莫耳比例宜在1%至90%、較佳3%至75%、更佳10%至60%、尤其20%至50%範圍內。H2之莫耳比宜在1%至99%、較佳10%至90%、更佳20%至85%、尤其40%至80%範圍內。CH4之莫耳比例宜在0%至30%、較佳0%至20%、更佳0%至15%、更佳0至10%、尤其0%至5%範圍內。N2之莫耳比例宜在0%至80%、較佳0%至20%、尤其0%至5%範圍內。O2之莫耳比宜在0%至5%、較佳0%至2%、更佳0%至1%、尤其0%至0.5%範圍內。H2O之莫耳比例宜在0%至99%、較佳0%至90%,、更佳0%至40%、更佳0%至20%、更佳0%至15%、更佳0%至10%、尤其0%至5%範圍內。The reactant gas preferably has the following composition: The molar ratio of CO2 is preferably in the range of from 1% to 90%, preferably from 3% to 75%, more preferably from 10% to 60%, especially from 20% to 50%. The molar ratio of H2 is preferably in the range of from 1% to 99%, preferably from 10% to 90%, more preferably from 20% to 85%, especially from 40% to 80%. The molar ratio of CH4 is preferably in the range of 0% to 30%, preferably 0% to 20%, more preferably 0% to 15%, still more preferably 0% to 10%, especially 0% to 5%. The molar ratio of N2 is preferably in the range of from 0% to 80%, preferably from 0% to 20%, especially from 0% to 5%. The molar ratio of O2 is preferably in the range of 0% to 5%, preferably 0% to 2%, more preferably 0% to 1%, especially 0% to 0.5%. The molar ratio of H2O is preferably from 0% to 99%, preferably from 0% to 90%, more preferably from 0% to 40%, more preferably from 0% to 20%, still more preferably from 0% to 15%, even more preferably from 0%. Up to 10%, especially 0% to 5%.
與活性組成物接觸之反應物氣體之壓力宜在3至60巴絕對 、尤其10至30巴絕對 範圍內。The pressure of the reactant gas which is in contact with the active composition is preferably in the range from 3 to 60 bar absolute , especially from 10 to 30 bar absolute .
在高過程壓力、尤其大於5巴、較佳大於10巴、最佳地大於20巴下進行二氧化碳氫化之效能有利，因為合成氣亦在極高壓力下形成。合成氣體可以用於其他方法，其中該合成氣體作為起始物質必須處於高壓力下。藉助於高壓氣體之存在，可用壓縮機設備及壓縮步驟分配。後續方法可為甲醇合成（50巴-100巴）、費歇爾-托普希合成（Fischer-Tropsch synthesis）（40巴-60巴）或其他氣體至液體之合成。The performance of hydrogenation of carbon dioxide at high process pressures, in particular greater than 5 bar, preferably greater than 10 bar, and most preferably greater than 20 bar, is advantageous because the synthesis gas is also formed under very high pressures. The synthesis gas can be used in other processes in which the synthesis gas must be at a high pressure as a starting material. By means of the presence of high pressure gas, it can be distributed by means of compressor equipment and compression steps. Subsequent methods can be methanol synthesis (50 bar to 100 bar), Fischer-Tropsch synthesis (40 bar to 60 bar) or other gas to liquid synthesis.
與活性組成物接觸反應物氣體之溫度宜在600至1300℃、較佳750至1200℃、尤其850至1200℃範圍內。The temperature at which the reactant gas is contacted with the active composition is preferably in the range of from 600 to 1300 ° C, preferably from 750 to 1200 ° C, especially from 850 to 1200 ° C.
該方法之GHSV之值宜處於2000至700 000 h-1 、較佳5000至500 000 h-1 、尤其10 000至300 000 h-1 範圍內。The value of the GHSV of the method is preferably in the range of 2000 to 700 000 h -1 , preferably 5000 to 500 000 h -1 , especially 10 000 to 300 000 h -1 .
較佳地，來自該方法之產物為合成氣，其在體積比率不小於1之氫與一氧化碳之組成範圍內。較佳氫與一氧化碳之比率在1至4範圍內、尤其在1.5至3範圍內。Preferably, the product from the process is a syngas which is within the composition of hydrogen and carbon monoxide in a volume ratio of not less than one. Preferably, the ratio of hydrogen to carbon monoxide is in the range of 1 to 4, especially in the range of 1.5 to 3.
在本發明方法之另一較佳具體實例中，二氧化碳氫化之前為活化製程。活化製程有可能使催化劑以控制方式調節至該製程參數之起點。In another preferred embodiment of the process of the invention, the carbon dioxide is hydrogenated prior to the activation process. The activation process makes it possible to adjust the catalyst in a controlled manner to the starting point of the process parameters.
活化製程包含在300℃至1400℃範圍內之溫度下，在還原氣體氛圍中對催化劑進行熱處理。較佳地，使用控制加熱製程將催化劑加熱至製程溫度。加熱速率較佳在1℃/min至30℃/min範圍內，較佳在5℃/min至15℃/min範圍內The activation process comprises heat treating the catalyst in a reducing gas atmosphere at a temperature in the range of from 300 °C to 1400 °C. Preferably, the controlled heating process is used to heat the catalyst to the process temperature. The heating rate is preferably in the range of 1 ° C / min to 30 ° C / min, preferably in the range of 5 ° C / min to 15 ° C / min
較佳地，活化製程與催化劑之調節相結合；該調節較佳在活化之後進行。調節理解為意謂使催化劑逐步達到標靶反應之製程參數之操作。其原因在於，對於製程之起始點，與持續操作相比，在一些情況下可能需要不同條件。調節步驟有效防止啟動期間催化劑之不受控制之碳化。Preferably, the activation process is combined with the conditioning of the catalyst; the conditioning is preferably carried out after activation. Regulation is understood to mean the operation of the catalyst to gradually progress to the process parameters of the target reaction. The reason for this is that for the starting point of the process, different conditions may be required in some cases compared to continuous operation. The conditioning step effectively prevents uncontrolled carbonization of the catalyst during startup.
催化劑之調節在於例如在二氧化碳、一氧化碳、甲烷、水蒸氣及/或氫存在下將催化劑加熱至製程溫度。催化劑亦可在蒸氣存在下調節。The catalyst is adjusted to heat the catalyst to a process temperature, for example, in the presence of carbon dioxide, carbon monoxide, methane, water vapor, and/or hydrogen. The catalyst can also be adjusted in the presence of steam.
根據本發明使用之催化劑可藉由熟習此項技術者已知之任何合成方法產生，例如如WO 2013/68931中所述。The catalyst used in accordance with the present invention can be produced by any synthetic method known to those skilled in the art, for example as described in WO 2013/68931.
本發明之特徵在於在本發明方法中，使用容易由便宜原料產生之催化劑，有可能展示與先前技術中使用必須以複合方式且使用昂貴原料產生之催化劑相當的效能，亦即在熱力學平衡下轉化。The invention is characterized in that in the process of the invention, the use of a catalyst which is readily produced from inexpensive raw materials, it is possible to demonstrate the performance comparable to that used in the prior art which must be produced in a composite manner and using expensive raw materials, i.e., converted under thermodynamic equilibrium. .
藉助於本發明方法，有可能在惡劣加工條件下、尤其在高溫及高負載下，在催化劑上不沈積大量焦炭下實施該方法。在本發明之上下文中，顯著焦炭沈積視為在催化劑上沈積大於2重量%之焦炭；典型地，藉由壓降顯著升高表明焦炭沈積物高於此值。較佳地，焦炭沈積之碳含量為相對於所用催化劑＜ 2重量%、更佳＜ 1重量%、更佳＜ 0.5重量%、尤其＜ 0.2重量%。由於在壓力為5至40巴之壓力下催化劑之極高熱穩定性及操作穩定性，其可使用幾千小時之長製程運作時間。 A. 產生催化劑 A.1 產生石榴石物質，Y2.68 Ni0.32 Al5 O12 By means of the process according to the invention it is possible to carry out the process without the deposition of large amounts of coke on the catalyst under severe processing conditions, in particular at elevated temperatures and high loads. In the context of the present invention, significant coke deposits are considered to deposit more than 2% by weight of coke on the catalyst; typically, a significant increase in pressure drop indicates that the coke deposit is above this value. Preferably, the carbon content of the coke deposit is < 2% by weight, more preferably < 1% by weight, more preferably < 0.5% by weight, especially < 0.2% by weight, relative to the catalyst used. Due to the extremely high thermal stability and operational stability of the catalyst at a pressure of 5 to 40 bar, it can be used for thousands of hours of process time. A. Producing Catalyst A.1 Producing Garnet Material, Y 2.68 Ni 0.32 Al 5 O 12
催化劑S1根據WO 15/135968 A1中之描述產生。 A.2 產生含鎳之La、Sr或Ba六鋁酸鹽Catalyst S1 was produced as described in WO 15/135968 A1. A.2 Producing nickel-containing La, Sr or Ba hexaaluminate
催化劑S2至S4（參見表II）藉由如下合成方法產生，在本文中例如針對BaNi0.5Al11.5O19-Y ：Catalysts S2 to S4 (see Table II) were produced by the following synthetic methods, for example for BaNi0.5Al11.5O19 -Y :
在攪拌的同時將適當量之Ba(NO3)2及Ni(NO3)2 * 6H2O溶解於500 mL燒杯中之250 mL去離子水中。將Al來源（15.462 g具有42.51 wt%之Al的Disperal）之分散液添加至此溶液中，隨即形成懸浮液。攪拌此懸浮液30分鐘以均質化。懸浮液逐滴急凍於液氮中。冷凍液滴在-10℃及2.56毫巴下冷凍乾燥。Appropriate amounts of Ba(NO3)2 and Ni(NO3)2*6H2O were dissolved in 250 mL of deionized water in a 500 mL beaker while stirring. A dispersion of Al source (15.462 g of Disperal having 42.51 wt% of Al) was added to this solution, followed by formation of a suspension. The suspension was stirred for 30 minutes to homogenize. The suspension was snap frozen in liquid nitrogen. The frozen droplets were freeze dried at -10 ° C and 2.56 mbar.
冷凍乾燥粉末在空氣下煅燒以分解硝酸鹽。加熱速率為1 K/min。將樣品加熱至150℃、250℃及350℃，在達到各溫度時停頓1小時之時間。最終煅燒溫度為450℃且停頓時間又為1小時；此後冷卻至環境溫度。The freeze-dried powder is calcined under air to decompose the nitrate. The heating rate is 1 K/min. The samples were heated to 150 ° C, 250 ° C and 350 ° C and allowed to stand for 1 hour at each temperature. The final calcination temperature was 450 ° C and the dwell time was again 1 hour; thereafter cooled to ambient temperature.
預煅燒樣品經受成形製程。將3重量%之石墨添加至樣品中，劇烈混合。混合物用Korsch XP1粒化機以自動操作粒化。粒化工具之直徑為13 mm且施加用於調節高度2 mm之球粒之力為40 kN。將球粒搗碎且篩分至315-500 μm。The pre-calcined sample is subjected to a forming process. 3 wt% of graphite was added to the sample and mixed vigorously. The mixture was granulated with automatic operation using a Korsch XP1 granulator. The granulation tool has a diameter of 13 mm and the force applied to adjust the pellets with a height of 2 mm is 40 kN. The pellets were chopped and sieved to 315-500 μm.
搗碎且篩分之樣品（315-500 μm）經受最終空氣下煅燒以移除石墨且形成所需六鋁酸鹽相。最終煅燒溫度為1200℃，其中加熱速率為5 K/min且停頓時間為2.5小時。 A.3 產生Pd及Pt催化劑The mashed and sieved sample (315-500 μm) was subjected to final air calcination to remove graphite and form the desired hexaaluminate phase. The final calcination temperature was 1200 ° C with a heating rate of 5 K/min and a standstill of 2.5 hours. A.3 Producing Pd and Pt catalysts
催化劑S5及S6類似於US 2011/0105630之先前技術經由浸漬方法產生：Catalysts S5 and S6 were produced via the impregnation method similar to the prior art of US 2011/0105630:
在直徑10 cm之圓形瓷盤中稱出10 g粒度315至500 μm之Al2O3載體材料。載體層之高度不超過5 mm之值。經由0.5 mL滴管將由1281 μL 0.199莫耳濃度之IrCl3水溶液及1919 μL去離子水構成之浸漬溶液（參見表I）添加至經振盪器（Heidolph Titramax 100樣品振盪器）而保持運動之載體材料中。經浸漬載體亦用刮勺混合且在環境條件下老化，之後乾燥30分鐘。10 g of Al2O3 support material having a particle size of 315 to 500 μm was weighed out in a circular porcelain plate having a diameter of 10 cm. The height of the carrier layer does not exceed a value of 5 mm. An impregnation solution consisting of 1281 μL of a 0.199 molar aqueous solution of IrCl 3 and 1919 μL of deionized water (see Table I) was added via a 0.5 mL dropper to the carrier material that was kept in motion by an oscillator (Heidolph Titramax 100 sample oscillator). . The impregnated support was also mixed with a spatula and aged under ambient conditions, followed by drying for 30 minutes.
乾燥在乾燥烘箱中在80℃下持續16小時實現。乾燥樣品如下在空氣(6 L/min）下在烘箱（Nabertherm TH120/12）中煅燒：加熱速率為1 K/min達至溫度為250℃，停頓時間為1 h，加熱速率為5 K/min達至溫度為400℃，停頓時間為4 h，之後冷卻至環境溫度。 表I：金屬鹽溶液
將適當量之Ni(NO3)2*6H2O（38.759 g（99.2%）及Cr(NO3)3*9H2O（107.58 g（鉻含量12.8 wt%）溶解於250 mL去離子水中且藉助於滴液漏斗引入至含有200 mL Na2CO3溶液之初加料之2 L四頸圓底燒瓶中（0.5 mol/L）。藉助於包含2莫耳濃度之Na2CO3溶液的第二滴液漏斗，使合成步驟期間之pH值保持於9。在pH 9下，在30分鐘內，在攪拌的同時將此金屬硝酸鹽溶液逐滴添加至圓底燒瓶中。在沈澱之後，在攪拌的同時使懸浮液在pH 9下老化60分鐘。此後藉由過濾（圓形紅色帶過濾器）移除固體且藉助於去離子水洗滌，直至其不含硝酸鹽。固體在40℃下乾燥且在800℃下煅燒4小時（加熱速率5 K/min）。Appropriate amounts of Ni(NO3)2*6H2O (38.759 g (99.2%) and Cr(NO3)3*9H2O (107.58 g (chromium content 12.8 wt%) were dissolved in 250 mL of deionized water and introduced by means of a dropping funnel To a 2 L four-necked round bottom flask containing 0.5 mL of Na2CO3 solution (0.5 mol/L). The pH during the synthesis step was maintained by means of a second dropping funnel containing 2 molar concentrations of Na2CO3 solution. 9. At a pH of 9, the metal nitrate solution was added dropwise to the round bottom flask while stirring for 30 minutes. After the precipitation, the suspension was aged at pH 9 for 60 minutes while stirring. The solid is then removed by filtration (circular red band filter) and washed by means of deionized water until it is free of nitrates. The solid is dried at 40 ° C and calcined at 800 ° C for 4 hours (heating rate 5 K) /min).
經煅燒樣品展示痕量鉻酸鈉Na2CrO4，其在去離子水中具有良好溶解度。因此，用125 mL去離子水洗滌樣品三次。在第一洗滌階段中，洗滌水由黃色變為橙色，而其在第三洗滌步驟中保持無色。The calcined sample exhibited traces of sodium chromate Na2CrO4, which has good solubility in deionized water. Therefore, the sample was washed three times with 125 mL of deionized water. In the first wash stage, the wash water changes from yellow to orange while it remains colorless in the third wash step.
在乾燥之後，XRD分析展示NiCr2O4，無痕量之Na2CrO4。量測之BET表面積小於1 m2 /g。After drying, XRD analysis showed NiCr2O4 with no traces of Na2CrO4. The measured BET surface area is less than 1 m 2 /g.
類似地產生催化劑NiAl2 O4 、ZnAl2 O4 及CuAl2 O4 。 A.5 產生六鋁酸鈷催化劑The catalysts NiAl 2 O 4 , ZnAl 2 O 4 and CuAl 2 O 4 were similarly produced. A.5 Production of cobalt hexaaluminate catalyst
催化劑S11根據WO 13/118078 A1中之描述產生。 A.6 來自先前技術之催化劑之綜述Catalyst S11 was produced as described in WO 13/118078 A1. A.6 Summary of catalysts from prior art
表II概述來自先前技術之催化劑。 表II：來自先前技術之催化劑之清單
金屬鹽及水滑石之預混物藉由均勻混合411.4 g粉狀硝酸鎳六水合物（已藉助於研缽及研杵預先濕磨得到細粉狀粉末）及600 g水滑石（Pural MG30，來自Sasol）來製備。將此混合物引入至旋轉爐之管道中。此預混物在旋轉爐中加熱至80℃，且在其中保持在80℃下1小時。管道以2轉/分鐘旋轉，且使150 L/h之空氣流流經管道。冷卻預混物之重量為886 g。The premix of metal salt and hydrotalcite is uniformly mixed with 411.4 g of powdered nickel nitrate hexahydrate (pre-wet milled by means of mortar and pestle to obtain a fine powder) and 600 g of hydrotalcite (Pural MG30 from Sasol) to prepare. This mixture was introduced into a pipe of a rotary furnace. This premix was heated to 80 ° C in a rotary furnace and kept at 80 ° C for 1 hour. The pipe was rotated at 2 revolutions per minute and a 150 L/h air stream was passed through the pipe. The weight of the cooled premix was 886 g.
使400 g預混合中所獲得之樣品經受低溫煅燒。出於此目的，將樣品引入至緊固於旋轉球狀爐中之石英玻璃燒瓶中。將旋轉球狀鍋爐以5℃/min之加熱速率加熱至425℃之標靶溫度，且保持在425℃下一小時。此低溫煅燒在以12轉/分鐘之頻率旋轉之石英燒瓶中進行，同時空氣以1 L/min之流動速率流經燒瓶。The sample obtained in 400 g of the premix was subjected to low temperature calcination. For this purpose, the sample was introduced into a quartz glass flask fastened in a rotating spherical furnace. The rotating spherical boiler was heated to a target temperature of 425 ° C at a heating rate of 5 ° C/min and held at 425 ° C for one hour. This low temperature calcination was carried out in a quartz flask rotating at a frequency of 12 revolutions per minute while air was passed through the flask at a flow rate of 1 L/min.
將低溫煅燒後之獲得樣品與石墨粉末混合且藉助於模壓機壓成錠劑。錠劑之直徑為4.75 mm且厚度為約4至5 mm，且錠劑之側向抗碎強度為60至70 N。The obtained sample obtained after low-temperature calcination was mixed with graphite powder and pressed into a tablet by means of a press. The tablet has a diameter of 4.75 mm and a thickness of about 4 to 5 mm, and the lateral crushing strength of the tablet is 60 to 70 N.
錠劑在篩網研磨機中搗碎且接著推動穿過篩網，以獲得剝落分數＜ 1.6 mm。預壓製物質再次製錠，得到直徑為4.75 mm且厚度為3至4 mm且側向抗碎強度為130至150 N之錠劑。The tablet was chopped in a screen mill and then pushed through the screen to obtain a peel fraction < 1.6 mm. The pre-compacted material was again tableted to obtain a tablet having a diameter of 4.75 mm and a thickness of 3 to 4 mm and a lateral crushing strength of 130 to 150 N.
樣品物質在有空氣穿過之馬弗爐中在850℃下煅燒一小時，且接著冷卻至室溫。樣品物質使用5℃/min之加熱速率再次由室溫加熱至850℃。流經鍋爐（加熱相、煅燒及冷卻相）之空氣之流動速率為6 L/min。經煅燒樣品物質經受化學及物理特性化。在元素分析中可見以下組成：21重量%之NiO、53重量%之Al2 O3 及23重量%之MgO，其中各圖基於氧化物。鎂尖晶石（MgAl2 O4 ）或MgNiO2 在XRD分析中以各相偵測。關於反射，使用謝樂等式（Scherrer equation），詳細測定各相之平均微晶尺寸，結果尖晶石粒子之微晶尺寸為9.0 nm且混合氧化物粒子之微晶尺寸為16.5 nm。The sample material was calcined at 850 ° C for one hour in a muffle furnace with air passing through, and then cooled to room temperature. The sample material was again heated from room temperature to 850 ° C using a heating rate of 5 ° C/min. The flow rate of air flowing through the boiler (heating phase, calcination and cooling phase) was 6 L/min. The calcined sample material is subjected to chemical and physical characterization. The following composition was observed in the elemental analysis: 21% by weight of NiO, 53% by weight of Al 2 O 3 and 23% by weight of MgO, wherein each figure is based on an oxide. Magnesium spinel (MgAl 2 O 4 ) or MgNiO 2 was detected in each phase by XRD analysis. Regarding the reflection, the average crystallite size of each phase was measured in detail using the Scherrer equation. As a result, the crystallite size of the spinel particles was 9.0 nm and the crystallite size of the mixed oxide particles was 16.5 nm.
樣品物質藉助於氮吸附及Hg孔率測定法特性化。樣品物質之BET表面積為67 m2
/g，Hg孔隙體積為0.31 mL/g且孔隙表面積為83 m2
/g，且樣品物質具有單模式孔隙結構。樣品物質之孔隙之平均孔徑為約15 nm。
E1及S1至S4之效能相當。此外，所有相之效能均穩定。V/VI相之來自先前技術之催化劑S5、S6及S8至S10之活性降低或下降。此外，在III至V相中，S9及S10不展示任何甲烷重組（CH4 + H2O → CO + H2）。 表3：在根據表1篩檢之後自催化劑之碳沈積（穩定性之指示）
催化劑S7、S10且尤其S8具有顯著碳沈積。 表4：在750℃至950℃、20巴及GHSV：30000至40000h-1下催化劑S3及E1之催化篩檢之測試方案
根據本發明使用之催化劑E1甚至在高溫及高壓下展示與來自先前技術之S3相當的效能。 表6：在750℃至950℃、20巴及GHSV：40000至80000h-1下催化劑S3及E1之催化篩檢之測試方案
根據本發明使用之催化劑E1甚至在高GHSV下展示與來自先前技術之S3相當的效能。 表8：在750℃、10巴及GHSV：30000至40000h-1下催化劑S11及E1之催化篩檢之測試方案
根據本發明使用之催化劑E1甚至在高GHSV下展示比來自先前技術之催化劑S11較佳的效能。The catalyst E1 used according to the invention exhibits better performance than the catalyst S11 from the prior art even at high GHSV.
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