NL2005700C2 - Catalyst for hydrogen production, such as in separation enhanced reforming. - Google Patents
Catalyst for hydrogen production, such as in separation enhanced reforming. Download PDFInfo
- Publication number
- NL2005700C2 NL2005700C2 NL2005700A NL2005700A NL2005700C2 NL 2005700 C2 NL2005700 C2 NL 2005700C2 NL 2005700 A NL2005700 A NL 2005700A NL 2005700 A NL2005700 A NL 2005700A NL 2005700 C2 NL2005700 C2 NL 2005700C2
- Authority
- NL
- Netherlands
- Prior art keywords
- catalyst
- boron
- porous
- compound
- nickel
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 171
- 239000001257 hydrogen Substances 0.000 title claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000002407 reforming Methods 0.000 title description 14
- 238000000926 separation method Methods 0.000 title description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 180
- 239000011148 porous material Substances 0.000 claims description 80
- 229910052759 nickel Inorganic materials 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 70
- 230000008569 process Effects 0.000 claims description 60
- 229910052796 boron Inorganic materials 0.000 claims description 51
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 239000007789 gas Substances 0.000 claims description 42
- 229930195733 hydrocarbon Natural products 0.000 claims description 41
- 150000002430 hydrocarbons Chemical class 0.000 claims description 41
- 239000004215 Carbon black (E152) Substances 0.000 claims description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 25
- 238000006057 reforming reaction Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 24
- 150000001639 boron compounds Chemical class 0.000 claims description 22
- 239000000395 magnesium oxide Substances 0.000 claims description 18
- -1 aluminum compound Chemical class 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 17
- 150000002681 magnesium compounds Chemical class 0.000 claims description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 12
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 150000002816 nickel compounds Chemical class 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910015900 BF3 Inorganic materials 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 6
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 229910021540 colemanite Inorganic materials 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- YNLFEVAOQLXINF-UHFFFAOYSA-N methylsulfanylmethane;tribromoborane Chemical compound CSC.BrB(Br)Br YNLFEVAOQLXINF-UHFFFAOYSA-N 0.000 claims description 3
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- 229910021539 ulexite Inorganic materials 0.000 claims description 3
- 229910015845 BBr3 Inorganic materials 0.000 claims description 2
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 claims description 2
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 claims 2
- AQKGPRGFKXWCTO-UHFFFAOYSA-N B(F)(F)F.[Na] Chemical compound B(F)(F)F.[Na] AQKGPRGFKXWCTO-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229910020068 MgAl Inorganic materials 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 description 33
- 239000000243 solution Substances 0.000 description 28
- 239000002245 particle Substances 0.000 description 25
- 239000011777 magnesium Substances 0.000 description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 238000005470 impregnation Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 229910052596 spinel Inorganic materials 0.000 description 14
- 229910000836 magnesium aluminium oxide Inorganic materials 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 230000009849 deactivation Effects 0.000 description 10
- 238000005245 sintering Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000011651 chromium Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000000629 steam reforming Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000001399 aluminium compounds Chemical class 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 238000012430 stability testing Methods 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 229920001983 poloxamer Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 239000002594 sorbent Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910011255 B2O3 Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910020889 NaBH3 Inorganic materials 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- DUVVGYBLYHSFMV-YGEZULPYSA-N 4-methyl-n-[[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]carbamoyl]benzamide Chemical compound C1=CC(C)=CC=C1C(=O)NC(=O)N[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 DUVVGYBLYHSFMV-YGEZULPYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical compound [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910003111 Mg(Al)O Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910018505 Ni—Mg Inorganic materials 0.000 description 1
- 229920002023 Pluronic® F 87 Polymers 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001993 poloxamer 188 Polymers 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
-
- 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
- B01J21/005—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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/643—
-
- B01J35/647—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
Catalyst for hydrogen production, such as in separation enhanced reforming Field of the invention
The invention relates to a catalytic process for the production of hydrogen, 5 especially a separation enhanced reforming process, a porous catalyst that can be used in such process, as well as a process for the production of such porous catalyst per se.
Background of the invention
The use of nickel catalysts in steam reforming of hydrocarbons is known in the 10 art. US6416731, for instance, describes a process for catalytic steam reforming of a carbonaceous feedstock with improved resistance to sulphur poisoning and sintering characterized by contacting the feedstock with a nickel catalyst supported on magnesium aluminium spinel, MgO.xAkC^, wherein the spinel support has a specific surface area Asp[m2/g] higher than 400*exp(-Tc/400 °C) obtained by calcination at a 15 temperature Tc [°C], W02008049266 describes a process for the conversion of hydrocarbons to hydrogen and one or more oxides of carbon, comprising contacting the hydrocarbon with steam and/or oxygen in the presence of a spinel-phase crystalline catalyst comprising a catalytically active metal. There is also described a method for making a 20 catalyst suitable for the conversion of hydrocarbons to hydrogen and one or more oxides of carbon comprising adding a precipitant to a solution or suspension of a refractory oxide or precursor thereof and a catalyst metal-containing compound to form a precipitate which is calcined in an oxygen-containing atmosphere to produce a crystalline phase with a high dispersion of catalyst metal. There is further described a 25 crystalline catalyst comprising the elements nickel, magnesium, aluminium and a lanthanide element, in which the crystalline phase is a spinel phase.
Summary of the invention
The catalytic conditions for (oxidative) steam reforming in combination with a 30 membrane and/or a sorbent separator may substantially deviate of usual conditions in industrial hydrogen and/or syngas production (without such separator). When applying separation enhanced processes, wherein the endothermal reaction may be promoted by separation of an endothermal reaction product, the general working temperature is 2 lower than the usual conditions in industrial hydrogen and/or syngas production. This generates a desire to provide alternative catalysts that may be thermally activated at lower temperatures. Often, the stability of the catalyst in hydrogen lean and hydrocarbon rich conditions may favour the formation of carbon-rich deposits (e.g.
5 graphite, graphene, soot and the likes) that may act as catalyst poison. Also this generates a desire to provide alternative catalysts that may be more stable under such conditions.
In general, the catalyst for steam reforming of hydrocarbons to provide on an industrial scale hydrogen and/or syngas is preferably nickel (Ni) based. Nickel, 10 however, appeared in some of the present applications to be unstable and/or not reactive enough. Alternatively, noble metals may be applied, but those are more expensive, which is also not desired.
Hence, it is an aspect of the invention to provide an alternative catalyst for hydrogen formation (including in an embodiment syngas formation) via steam 15 reforming, which preferably further at least partly obviates one or more of above-described drawbacks. It is especially an aspect to provide such catalyst that is especially suitable for application in separation enhanced steam reforming. However, it is also an aspect to provide such alternative catalyst for a hydrogen production process, wherein no separation is applied during the reaction, for instance state of the art 20 industrial reforming.
It is further an aspect of the invention to provide an alternative hydrogen formation (including in an embodiment syngas formation) process, especially a separation enhanced process. It is yet a further aspect of the invention, to provide a catalyst with high catalytic activity and stability, even at separation enhanced 25 separation conditions, which may especially be used in the process of the invention.
To this end, the invention provides a catalyst comprising Ni, B, and Mg for the hydrogen (¾) (and syngas) production in especially a catalytic (oxidative) steam reforming of a hydrocarbon comprising gas (such as methane, natural gas, etc.), especially applied in combination with a separator selective for a predetermined 30 reaction product, such as CO2, for instance by means of a membrane selective for CO2. In an embodiment, alternatively, the optional separator is selective for a predetermined reaction product, such as H2, for instance by means of a membrane selective for H2.
3
Especially, the catalyst is a porous catalyst, especially having pores have pore sizes in the range of 0.1-50 nm, especially 0.1-20 nm, even more especially 5-15 nm
In a first aspect, the invention provides a process for the production of hydrogen (H2) comprising subjecting a hydrocarbon comprising gas in a reaction chamber to a 5 reforming reaction in the presence of a catalyst, and optionally in the presence of separator selective for a predetermined reaction product of the reforming reaction, such as a membrane selective for a predetermined reaction product of the reforming reaction, to produce a hydrogen containing gas, wherein the catalyst comprises a, preferably porous, catalyst based on at least magnesium oxide and aluminium oxide, wherein the, 10 preferably porous, catalyst further comprises boron and nickel, and wherein the catalyst preferably comprises pores having a pore size in the range of 0.1-50 nm, especially 0.1-20 nm, even more especially 5-15 nm.
In a specific embodiment, wherein the separator is applied, the process further comprises selectively removing at least part of the predetermined reaction product from 15 the reaction chamber via the separator. Hence, in a specific embodiment, the invention provides a process for the production of hydrogen comprising subjecting a hydrocarbon comprising gas in a reaction chamber to a reforming reaction in the presence of a catalyst and a membrane (“separator”), selective for a predetermined reaction product of the reforming reaction, to produce a hydrogen containing gas and selectively 20 removing at least part of the predetermined reaction product from the reaction chamber via the membrane, wherein the catalyst comprises a, preferably porous, catalyst based on at least magnesium oxide and aluminium oxide, wherein the, preferably porous, catalyst further comprises boron and nickel, and wherein the catalyst preferably comprises pores having a pore size in the range of 0.1-50 nm, especially 0.1-20 nm. 25 Instead of a membrane, also a sorbent may be applied as separator.
An advantage of this process, concomitant with the use of this catalyst, is that the reaction temperature can be lower, such as about 400-750 °C, like 500-700 °C, whereas the catalyst of the invention may be as efficient as state of the art catalysts which may have working temperatures at about 850-1000 °C. It surprisingly appears that the 30 catalyst both reduces carbon formation (on Ni) and maintains the desire catalyst (particle) size. Further, the presence of Mg may have a positive effect on catalyst performance and stability, and may prevent formation of undesired spinel crystals.
4
In the absence of the separator, such as a selective membrane, the process conditions may include a temperature of over 700 °C, such as about 850-1000 °C, especially about 900-1000 °C. Also under these conditions the catalyst of the invention may show its advantages with respect to stability. Hence, the invention may also 5 include subjecting a hydrocarbon comprising gas in a reaction chamber to a reforming reaction in the presence of a catalyst at a temperature in the range of 700-1000 °C, especially 850-1000 °C (in the absence of a separator, such as a selective membrane).
Herein, the term “hydrocarbon comprising gas” refers to a gas that comprises one or more types of hydrocarbons. For instance, the hydrocarbon comprising gas may 10 comprise or consist of natural gas. However, the hydrocarbon comprising gas may also comprise one or more higher hydrocarbons, such as ethane or propane. The hydrocarbon comprising gas may also comprise one or more unsaturated hydrocarbons. Especially, the hydrocarbon comprising gas comprises CH4.
The hydrocarbon comprising gas is subjected to a reforming reaction. This 15 implies that the hydrocarbon comprising gas is mixed with water vapour (steam). In another embodiment, wherein CO2 reforming is applied, this may imply that the hydrocarbon comprising gas is mixed with a CO2 comprising gas.
Under reforming conditions, and in the presence of a catalyst, at least part of the hydrocarbon of the hydrocarbon comprising gas is converted into H2 and other 20 components, especially CO and/or CO2. The reforming reaction is an endothermic reaction. Hence, it is advantageous when a separator is used which selectively separates a component from the reaction product(s) of the reforming reaction, i.e. a separation enhanced steam reforming. As indicated above, the components formed may for instance be H2, or CO or CO2. Optionally, the separator may be selective for H2 and 25 CO, and not for CO2, or for CO and CO2, and not for H2. In the former case, syngas is removed via the separator (especially a membrane), which may be used for the further production of desired hydrocarbons. In the latter case, a gas may be obtained that is relatively pure in H2. As will be clear to the person skilled in the art, the separator may also be selective for H2. Dependent upon the desired reaction product, the specific type 30 of separator may be applied. The separator may be a sorbent, especially configured to absorb or adsorb one or more of the reaction products. In another embodiment, the separator may be a membrane, selective for one or more of the reaction products.
5
The hydrocarbon comprising gas and the steam (or CO2 comprising gas) are introduced in a reaction chamber of a reactor. Such reaction chamber may be a single chamber or a plurality of chambers. If a plurality of chambers is applied, those may be arranged parallel or sequential.
5 In an embodiment, the reaction chamber also includes the separator. Such constructions are known in the art, and are for instance described in W02004021495 or W02006034086, etc. An example of a suitable technology for CO2 separation is for instance sorption and membrane enhanced water gas shift and sorption and membrane enhanced reforming.
10 The hydrocarbon comprising gas may be subjected to a reforming reaction at a temperature in the range of 400-750 °C, especially 500-700 °C. Due to the presence of the catalyst of the invention and also due to the presence of the separator, the temperature can be in these relative low temperature regions, while still providing a relative efficient conversion of the hydrocarbon to H2.
15 In the absence of the separator, the temperature may for instance be in the range of 400-1000 °C, such as 700-1000 °C, like 750-950 °C. Hence, in an embodiment, the hydrocarbon comprising gas may be subjected to a reforming reaction at a temperature in the range of 700-1000 °C, especially 750-950 °C, especially in the absence of such separator, as it may be the case in industrial stream reforming processes.
20 Therefore, in general, the hydrocarbon comprising gas may be subjected to a reforming reaction at a temperature in the range of 400-1000 °C, wherein with separator, the temperature may especially be in the range of 400-900 °C, even more especially 400-800°C, yet even more especially 400-750 °C, and wherein without separator, the temperature may especially be in the range of 700-1000 °C.
25 Herein, the term “reforming” may in an embodiment also refer to prereforming.
Hence, in a further aspect, the invention also provides the use of a catalyst as described herein to let at least part of a hydrocarbon comprising gas react in a reforming reaction to a hydrogen containing gas, especially at a reaction temperature in the range of 400-1000 °C. In this way, the hydrocarbon in the hydrcarbon containing 30 gas may be converted into H2 (and CO and/or C02). In an embodiment, this may be a reforming reaction, in another embodiment, this may be a prereforming reaction. In yet a further embodiment, this may be a sorption enhanced reforming, such as with a 6 sorbent or a membrane (selective for a predetermined reaction product of the reforming reaction).
The catalyst used in the preferred embodiment comprises a porous support material. As indicated herein, the catalyst may essentially consist of such catalyst.
5 Herein, the term porous especially refers to pore of size 0.1-50 nm, especially 0.1-20 nm. Especially, the porous catalyst comprises pores having a pore size in the range of 1-20 nm, such as at least 2 nm, more preferably a pore size in the range of 5-15 nm, especially 8-13 nm. Further, preferably at least 20 % of the Ni, more preferably at least 50 % of the Ni (as reduced Ni) is present in such pores. Here, the percentage relates to 10 the total amount of Ni comprised by the porous catalyst (i.e. wt.%). In a specific embodiment, the catalyst has high surface area (most often between 100 and 300 m2/g), large pore widths (8-13 nm), relatively large pore volume (0.3-1.4 cm3/g).
In an embodiment, the porous catalyst comprises (porous) magnesium aluminium mixed oxide material, such as MgA^CE, AI2O3, MgO, MgO-AkCh, Ni-MgO-AhCh, 15 etc.. Especially, the porous catalyst comprises porous MgAbCE and Mg0-Al203 mixed oxide but as indicated above, also other type of material may be applied. In the remainder of the text the mixed oxide is referred to as Mg(Al)0.
The porous catalyst may not only (further) comprise Ni and B, but may also comprise other materials, (i.e. other than magnesium, aluminium, nickel and boron. For 20 instance, in an embodiment, the porous catalyst further comprises one or more of T (titanium), Ca (calcium), Cr (chromium), Fe (Iron), Zr (Zirconium), Mn (manganese), such as one or more of Ca and Ti. Especially such materials may further increase stability of the catalyst and/or improve catalyst performance. In an embodiment, the porous catalyst does not comprise further activators than Ni.
25 The phrase “based on at least magnesium oxide and aluminium oxide” indicates that those materials are basis of the framework of the porous catalyst. Especially, the porous catalyst is a magnesium aluminium oxide material, as indicated above, i.e. a mixed oxide. Ti, Ca, Cr, Fe, Zr and Mn may also be used as framework material, but may also be non-framework material, and may be present in the pores. Especially, Ni is 30 no framework material, and is substantially present in the pores. B may be framework material or may be in the pores (as non-framework material). The phrase “wherein the porous catalyst further comprises boron and nickel” indicates that those materials are present (at least) in the pores of the porous catalyst. They may be present as compound, 7 such as boron oxide or boric acid, and for instance nickel oxide. Nickel and/or boron materials may be impregnated to the magnesium oxide and aluminium oxide based porous catalyst, for instance with a nickel salt and/or boric acid.
Boron may in an embodiment also be provided to the catalyst by physical-5 mixing, e.g. by using boron powder or any of the other boron compounds mentioned herein.
The weight of nickel relative to the total weight of the porous catalyst is preferably selected from the range of 4-70 wt.%, preferably 15-25 wt.%. The total weight of the porous catalyst thus refers to the porous catalyst, including boron, nickel 10 and optionally other activators (than Ni). Here, the weight of nickel relates to the element nickel, and not to nickel oxide (whereas, as indicated herein, in general under non-reaction conditions, nickel will be present as nickel oxide, and under reaction conditions as metallic nickel). Further, the weight of boron (B) relative to the total weight of the porous catalyst is preferably selected from the range of 0.1-20 wt.%, 15 preferably 0.5-5 wt.%. The total weight of the porous catalyst thus refers to the porous catalyst, including boron, nickel and optionally other activators (than Ni). Here, the weight of boron relates to the element boron, and not to boric acid.
It especially appears that such catalyst provides the desired catalytic properties. With larger pores, nickel still have ample space in pores and sinter too much and soot 20 formation may be too large. With smaller pores, very small nickel particles with very high activity are formed in such pores but a large fraction of the nickel will locate at the external surface of the support, making them prone to sintering. With lower Ni content, the activity may be too low, and with higher Ni content soot formation may be again too high. Especially good results may be obtained with pores having sizes in the 25 range of 5-15 nm.
As indicated above, the nickel may be present as nickel oxide. However, under reaction conditions, preferably nickel is present as metallic nickel. Within the pores, metallic nickel particles may form, having dimensions that are imposed by the pore size. Hence, in a specific embodiment, prior to subjecting a hydrocarbon comprising 30 gas in a reaction chamber to a reforming reaction, the catalyst is subjected to reducing conditions. And, also for this reason the pore size is preferably in the range of 5-15 nm, even more especially 8-13 nm, because then relative good results may be obtained in view of stability, soot formation, and yield. Likewise, the amount of nickel relative to 8 the total weight of the porous catalyst is preferably selected from the range of 15-25 wt.%, relative to the total weight of the porous catalyst, preferably equal to or lower than 22.5 wt.%.
In a further aspect, the invention is also directed to the porous catalyst per se.
5 Hence, in an embodiment, the invention provides a porous catalyst based on at least magnesium oxide and aluminium oxide, wherein the porous catalyst further comprises boron and nickel, and wherein the porous catalyst comprises pores having a pore size in the range of 0.1-50 nm, especially 0.1-20 nm, such as 1-20 nm, preferably 5-15 nm, like 8-13 nm. Especially, the porous catalyst comprises a magnesium aluminium oxide 10 material (denoted Mg(Al)O), such as porous MgO-AkCh mixed oxide and MgAhOzt. The porous catalyst may further comprise one or more of Ti, Ca, Cr, Fe, Zr, Mn, such as one or more of Ca and Ti. Further embodiments are described above (and below).
In yet a further aspect, the invention also provides a process for the production of a porous catalyst comprising providing a magnesium compound, an aluminium 15 compound, a nickel compound, a boron compound, and a pore former, forming in a formation process a porous material by combining the magnesium compound, the aluminium compound and the pore former and subjecting these compounds to crystallisation conditions to provide a porous material, and calcining the thus formed porous material, wherein the boron compound is present during the formation process 20 and/or wherein the boron compound is applied to the porous material obtained by the formation process, and wherein the magnesium compound is present during the formation process and/or wherein the magnesium compound is applied to the porous material obtained by the formation process. In this way, the porous catalyst is formed.
This may especially be a sol-gel process. The hydrolysis of aluminium alkoxide 25 with preferably an alcohol like ethanol takes place in the presence of an organic structure directing agent which is capable of forming meso-sized micelles that are bounded by the hydrolyzing aluminium alkoxide source. Appropriate time of the sol-gel synthesis process is from 1.5 to 12 days and temperature of the synthesis from room temperature or higher, depending on type copolymer. In an embodiment, the 30 magnesium compound comprises soluble magnesium salt, such as Mg(N03)2.
In a further embodiment, the aluminium compound comprises a organo-aluminium compound, such as aluminium- isopropoxide sec-butoxide, acetylacetonate and the likes.
9
In yet a further embodiment, the nickel compound comprises a soluble nickel salt, such as Ni(N03)2. Examples of suitable nickel compounds are for instance nickel nitrate, nickel acetate, nickel chloride, and nickel bromide, etc.
The boron compound preferably comprise one or more compounds selected from 5 the group consisting of (1) boric acid, (2) a water soluble boron containing compound such as selected from the group consisting of borax (Na2B405(C>H)4»8(H20)), colemanite (CaB304(0H)3»(H20)), ulexite (NaCaB506(0H)6*5(H20)) and kemite (Na2B406(0H)3»3(H20)), (3) a boron halide, such a selected from the group consisting of boron trifluoride (BF3), boron trichloride (BCI3), and an alkali metal borohalide, 10 such as e.g. sodium borofluoride (NaBF4), (4) boron tribromide dimethyl sulphide complex solution in methylene chloride (CH^kS^BBr?, (5) sodium tetra borate deca hydrate, (6), an alkali metal borohydride, such as e.g. a KBH4 solution, (6) boric oxide, (7) an alkyl borate, (8) sodium cyano boro hydride NaBH3(CN), and (9) boron powder.
As indicated above, nickel is preferably present in the pores. This may for 15 instance be achieved by applying a (aqueous) solution, or optionally an aqueous slurry, of a nickel salt to the porous material. This may also be achieved by producing the porous material in the presence of the nickel compound. After production of the catalyst, including calcination and reduction, the nickel may especially be present as metallic nickel.
20 As indicated above, boron may be present in the pores. This may for instance be achieved by applying the boron compound, an (aqueous) liquid composition with the boron compound, or optionally an aqueous slurry, with the boron compound to the porous material. This may also be achieved by producing the porous material in the presence of the boron compound. After production of the catalyst, including calcination 25 and reduction, boron may especially be present as nickel boride although low amounts of elementary boron and boron oxide may be present too. Hence, boron may be present in the pores, but may alternatively or additionally also be present at the surface of the porous material. Boron may in an embodiment also be provided to the catalyst by physically mixing the boron compound, e.g. by using boron powder or any of the other 30 boron compounds mentioned herein, with the porous material.
In yet a further embodiment, the boron compound comprises boric acid. In yet a further embodiment, wherein the pore former comprises a triblock copolymer having a molecular weight in the range of 3000-18000 Da, such as pluronic 123 10 (HO(CH2CH20)2o(CH2CH(CH3)0)7o(CH2CH20)2oH, which corresponds to a molecular weight of around 5800 Da weight) or pluronic F127 (molecular weight of around 12600 Da weight). Other options are pluronic F87, F68 and F108. Synthesis may also concern a mixture of various copolymers. Calcination, preferably above 500 °C, is especially 5 advantageous to remove organic residual material from the pores.
The term “substantially” herein, such as in “substantially consists”, will be understood by the person skilled in the art. The term “substantially” may also include embodiments with “entirely”, “completely”, “all”, etc. Hence, in embodiments the adjective substantially may also be removed. Where applicable, the term 10 “substantially” may also relate to 90% or higher, such as 95% or higher, especially 99% or higher, even more especially 99.5% or higher, including 100%. The term “comprise” includes also embodiments wherein the term “comprises” means “consists of’.
It should be noted that the above-mentioned embodiments illustrate rather than 15 limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. Use of the verb "to comprise" and its conjugations does not exclude the presence of elements or steps other than those stated in a claim. The article "a" or 20 "an" preceding an element does not exclude the presence of a plurality of such elements. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
25 Examples EXAMPLE 1 Nickel particle size
Nickel was impregnated on MgAl204 support (30 nm particles, 60 m2/g) using a stock solution prepared by dissolving Ni(N()3)2.6H20 in 100 ml demiwater (100gr/100ml). For impregnation, the solution was added to the support drop wisely as 30 to achieve 19.8 % and 40 wt% Ni for two independent impregnations. After impregnation the sample was again calcined, with 0.5°C/min-600°C-4hr.
Alternatively, smaller nickel particles were prepared with homogeneous deposition precipitation (HDP). For HDP first 1 or 2 g of MgAl204 was mixed in a 11 large amount of water (150 mL). Nickel salt was then added in an amount equal to obtain 5,15 and 20 wt% ofNickel (pH ~ 7- 9). The pH was brought to 2 with a HNO3 1M solution. The suspension was stirred and heated at 90°C. An aqueous solution of urea (20 mL) was added to start precipitation. The pH was monitored during 5 precipitation and typically after 16 to 24 hour the precipitation was finished, the mixture subsequently cooled down and filtrated. The oven-dried sample was then calcined, with 0.5°C/min-600°C-4hr.
STABILITY TESTING:
Stability testing of catalysts under 2 conditions at 600°C, 1 atm.: Condition with 10 H/C=10 (RC1: 7.5%CH4, 22.5%H20) was periodically changed to H/C=2.9 (RC3: 1.3%CH4,0.14%CO,11.6%CO2, 16%H20); the latter condition represents a (low H/C) membrane condition. Catalysts were diluted with inert alumina in order measure true catalyst activity, i.e. far from equilibrium conversion.
Ni particle size in relation to methane conversion activity and deactivation 15 expressed by -kd (h'1), the latter represents the slope of the decay toward lower conversion. Xinitial is the methane conversion activity in percent converted methane after 10 minutes on stream.
|Ni (wt%) lirm |-I<Cd*10(fr') RC1 |-Kd*10(h‘‘) RC3 |X initial (%) NÏHDP8 ~~l 11.13 - 30 NÏHDP5 Ϊ4ΑΊ3 ~\ 234 73
NiHDP 20.1 ÏÖ5 094 ÖÖÏ 81
Niimp Ï9TK4 ft89 L60 75
Niimp 40.4 19J L47 2^67 73 20 There are 2 deactivation paths active: carbon deactivation, more carbon with bigger particle size and sintering gains importance at smaller particle sizes as indicated from TPR and EXAFS analysis. So an optimum particle size to prevent extensive deactivation exists: larger particles produce carbon, smaller particles sintering/re-structure. Oxidation of the reduced Ni metallic active site by reaction was concluded to 25 not contribute by XAS and TPR/TPO studies. From this study the 10-13 nm particles (on average) obtained with impregnation of nickel nitrate with an amount equalling 19-20 wt% Ni appears to be especially a good choice for high conversion activity and 12 improved stability. The stability is however still to be improved significantly, which will be accomplished by anchoring the Ni particles in an porous Mg(Al)0 structure to reduce their susceptibility toward migration and sintering. In order to further suppress the carbon formation activity of the Ni-Mg(Al)0 catalyst the effect of so-called 5 promoters was attempted, see Example 2.
EXAMPLE 2: Synthesis of MgAl204 support with Nickel and second metals (Sn, Pt, Cu, Pd, La, Ce, Pr, Gd, Boron impregnated).
Nickel was impregnated on MgAl204 support using a stock solution prepared by 10 dissolving Ni(N03)2.6H20 in 100ml demiwater(100gr/ 100ml). For impregnation, the solution was added to the support drop wisely as to achieve 20 or 40 wt% Ni. After impregnation the sample was again calcined, with 0.5°C/min-600°C-4hr.
The second metallic component was impregnated onto the Nickel containing MgAl2C>4 using a metal salt solution. After impregnation the sample was again 15 calcined, with 0.5°C/min-600oC-4hr.
STABILITY TESTING:
Stability testing of catalysts under 2 conditions at 600°C, 1 atm.: Condition with H/C=10 is denoted ‘’Reference conditions RC” using 7.5%CH4, 22.5%H20, bal. N2, 20 and was periodically changed to H/C=2.9 (1.3%CH4,0.14%CO,11.6%CO2, 16%H20, bal. N2); the latter condition represents a (low H/C) simulated membrane condition. RC1 and RC3 denote respectively the first and third period the catalyst is exposed to the reference condition (RC3: at the time of RC3 the catalyst has been exposed to two previous periods of reference condition and 2 periods of simulated membrane 25 conditions).
Catalysts were diluted with inert alumina (1:27) in order measure true catalyst activity, i.e. far from equilibrium conversion. Space velocity (SV) = 1290,000 h'1.
M |Ni (wt%) |M (wt%) |X ini (873K) |-Kd* 1()(1/1) RC1 ||-Kd* 10(¾1) RC3 edx Ëf8 Ö 75 Ö89 1.60 SÏï Ëf8 Ö5 12 0/72 073 13 M |Ni (wt%) |M (wt%) |X ini (873K) |-Kd*10(h') RC1 |-Kd*10(h‘‘) RC3 edx
Pt 1975 0.5 31 1.2 0.9
Pd 195 0.5 40 1.4 0.96 Π7 195 2 70 359 357
La 195 T~9 40 251 ÖÖÖ
Ce 195 2Λ 73 L3 L72
Cc 195 85 71 L22 258
Fr 195 2 71 L23 L67
Gd Ϊ9Γ9 2 71 257 554
Gd 405 2 71 250 450 CÜ 205 2A 45 025 ËÖ B 4ΪΤΪ 25" 78 ÖÖÏ ÖÖ2 B 195 L4 86 057 027 B 195 25 90 Ö45 ÖÖÏ
Only Lanthanum and Boron stabilize the Ni-catalyst against deactivation after repeated exposure to simulated membrane conditions and extended operation times. When using Boron, with the MgAl204 support the higher amount of nickel for the 5 catalyst is beneficial. The 40 wt% Ni system suffers from deactivation by carbon only and the effect of boron here is mainly to block carbon deposition onto the catalyst and therefore the carbon route toward deactivation (note that the sintering contribution of the 40 wt% Ni system is insignificant due to the larger particle size).
However the deactivation of the lower loaded Ni catalyst is predominated by Ni 10 particle sintering and the effect of Boron is only obvious at extended times on stream when the Ni particle size is increased during RC1 (high -Kd) and the predominating deactivation transits from sintering toward carbon, which in turn is effectively blocked by B, see the low -Kd during RC3. As was known from literature Lanthanum shows very good carbon gasification behaviour and therefore high stability but the problem is 15 the conversion: the initial conversion drops substantially after loading the Ni catalyst with La.
EXAMPLE 3: Synthesis of Nickel containing porous Mg(Al)0 catalyst 14
Solution 1) prepared at room temperature: Pluronic 123 was dissolved in 10 to 20 ml Ethanol, under vigorous stirring.
Solution 2) prepared at room temperature: The components magnesium nitrate (1 gram), aluminium isopropoxyide (3.2 grams) and nickel nitrate (2 gram) were 5 combined in a beaker in the fume hood and first ethanol (10 ml) was added, subsequently (2.6 ml) nitric acid (65%). The salts were dissolved by rigorous stirring.
Solution 2 was added to solution 1, sealed with PE-film and stirred during 5 hours at room temperature. After 5 hours, the solution was placed in an oil bad and heated up to 60°C. Crystallization was initiated under evaporation during 48 hours 10 under a small air flow. After 48 hours the sample was calcined in the tube oven, with l°C/min to 650°C - 700 °C with an air flow of 50 ml/min and kept there for 4hr.
EXAMPLE 4: Synthesis of Nickel containing porous Mg(Al)0 catalyst subsequently impregnated by Boron 15 The Nickel containing porous Mg0-Al203 mixed oxide catalyst prepared in
Example 3 was impregnated with Boron. The Boron was impregnated onto the Nickel containing porous magnesium aluminate using 2 to 3 ml of Boric acid (approx. 0.6 M). After impregnation the sample was again calcined, with 0.5°C/min-600°C-4hr.
20 EXAMPLE 5: Synthesis of porous Mg(Al)0 support with Nickel impregnated
Solution 1) prepared at room temperature: Pluronic 123 was dissolved in 10 to 20 ml Ethanol, under vigorous stirring.
Solution 2) prepared at room temperature: The components magnesium nitrate (1 gram) and aluminium isopropoxyide (3.2 grams) were combined in a beaker in the 25 fume hood and first ethanol (10 ml) was added, subsequently (2.6 ml) nitric acid (65%). The salts were dissolved by rigorous stirring.
Solution 2 was added to solution 1, sealed with PE-film and stirred during 5 hours at room temperature. After 5 hours, the solution was placed in an oil bad and heated up to 60°C. Crystallization was initiated under evaporation during 48 hours 30 under a small air flow. After 48 hours the sample was calcined in the tube oven, with l°C/min to 650°C - 700 °C with an air flow of 50 ml/min and kept there for 4hr.
15
Typical hysteresis loops in nitrogen adsorption isotherms gives information on porosity of the materials. The formation of ordered hexagonal p6mm symmetry porous structures can also be obtained from X-ray diffraction patterns.
The nickel was impregnated on calcined support using a stock solution prepared 5 by dissolving Νϊ(Νθ3)2.6Η2θ in 100ml demi water(100gr/100ml). For impregnation, the solution was added to the support drop wisely as to achieve 19 wt% Ni. After impregnation the sample was again calcined, with 0.5°C/min-600°C-4hr.
EXAMPLE 6: Synthesis of porous MgO-AhCL support with Nickel impregnated and sequentially impregnated with Boron 10 The Nickel impregnated porous MgO-AECL catalyst prepared in Example 5 was impregnated with Boron. The Boron was impregnated onto the Nickel containing porous magnesium aluminate using 2 to 3 ml of Boric acid (approx. 0.6 M). After impregnation the sample was again calcined, with 0.5°C/min-600°C-4hr.
15 EXAMPLE 7: Synthesis of Nickel and Boron containing porous MgO-AbCL catalyst
Solution 1) prepared at room temperature: Pluronic 123 was dissolved in 10 to 20 ml Ethanol, under vigorous stirring.
Solution 2) prepared at room temperature: The components magnesium nitrate (1 gram), aluminium isopropoxyide (3.2 grams), nickel nitrate (2 gram) and 2 to 3 ml of 20 Boric acid (approx. 0.6 M) were combined in a beaker in the fume hood and first ethanol (10 ml) was added, subsequently (2.6 ml) nitric acid (65%). The salts were dissolved by rigorous stirring.
Solution 2 was added to solution 1, sealed with PE-film and stirred during 5 hours at room temperature. After 5 hours, the solution was placed in an oil bad and 25 heated up to 60°C. Crystallization was initiated under evaporation during 48 hours under a small air flow. After 48 hours the sample was calcined in the tube oven, with l°C/min to 650°C - 700 °C with an air flow of 50 ml/min and kept there for 4hr.
EXAMPLE 8: Synthesis of AI2O3 supported Nickel catalyst 30 Alumina, A1-4172P (gamma alumina -328 m2/g, BASF/Engelhard) was used as the support material. The nickel was impregnated on calcined support using a stock solution prepared by dissolving Νϊ(Νθ3)2·6Η2θ in 100ml demi water (100gr/100ml). For impregnation, the solution was added to the support drop wisely as to achieve 19 16 wt% Ni. After impregnation the sample was again calcined, with 0.5°C/min-600°C-4hr. Part of the Nickel impregnated AI2O3 catalyst was impregnated with Boron.
The Boron was impregnated onto the Nickel containing AI2O3 using 2.19 ml H3BO3 solution (1.885 g H3BO3 in 50 ml) for 0.496 g nickel impregnated A1203. After 5 impregnation the sample was again calcined, with 0.5°C/min-600°C-4hr.
EXAMPLE 9: Synthesis of MgO supported Nickel catalyst
Magnesium oxide (MgO, 99% sigma Aldrich, SA 100 m2/g) was used as the 10 support material. The nickel was impregnated on calcined support using a stock solution prepared by dissolving Ni(N03)2-6H20 in 100ml demi water (lOOgr/lOOml). For impregnation, the solution was added to the support drop wisely as to achieve 19 wt% Ni. After impregnation the sample was again calcined, with 0.5°C/min-600°C-4hr.
15 EXAMPLE 10: Stability tests with porous Mg(Al)0 catalysts
Stability testing of catalysts under 2 conditions at 600°C, 1 atm.: Condition with H/C=10 is denoted ‘’Reference conditions RC” using 7.5%CH4, 22.5%H20, bal. N2, and was periodically changed to H/C=2.9 (1.3%CH4,0.14%CO,11.6%CO2, 16%H20, bal. N2); the latter condition represents a (low H/C) simulated membrane condition. 20 RC1 and RC3 denote respectively the first and third period the catalyst is exposed to the reference condition (RC3: at the time of RC3 the catalyst has been exposed to two previous periods of reference condition and 2 periods of simulated membrane conditions). Catalysts were diluted with inert alumina (1:27) in order measure true catalyst activity, i.e. far from equilibrium conversion. SV = 1190,000 h"1, Treduction 650 25 °C
M Ni (wt%) B (wt%) X ini (873K) -Kd* 10(h-1) -Kd* 10(h-1) edx RC1 RC3
Example 3 Ni/Mg/Al-one 19.8 0 86 0.74 0.25 pot porous
Example 4 Ni/Mg/Al one 19.8 2.8 90 0.71 0.01 pot -porous -B impregnated
Example 7 Ni/B/Mg/Al 19^ Ï8 90 Ë21 002 17 M Ni (wt%) B (wt%) X ini (873K) -Kd* 10(h-1) -Kd* 10(h-1) eek RC1 RC3 one pot porous
Example 5 Mg/Al porous 19.8 0 78 1.75 0.22 -Ni impregnated
Example 6 Mg/Al porous 19.2 2.8 91 0.1 0.01 -Ni impregnated - B impregnated
Example 8 N1-AI2O3 19 0 30 1.63 25.98 N1-B-AI2O3 19 ÏI 25 Ë56 3.04
Example 9 Ni-MgO 41 0 2 n.d. n.d
All porous Mg(Al)0 supported Ni and Ni-Boron catalysts show very high conversion activity and very good stability. The presence of boron also clearly 5 improves the stability compared to the Ni only systems. Compared to the MgAhC^ Ni-B (Example 2) the Mg(Al)0 support of porous character excels in the stabilization of small Ni particle obtained at low Ni loadings (19wt%).
The combination of the Ni metallic active site and the magnesium-aluminium support lattice gives rise to some conversion activity enhancing synergy. For Ni-B 10 Mg(Al)0 the Boron, provided the amount of Boron exceeds 2.5 wt%, eases the reduction of NiO to metallic Ni (the active sites for the rate determining methane activation step) contrary to the M-B-AI2O3, described in the state-of-the -art literature on Ni-B catalyst, for which Ni-aluminate is formed and B has no effect on the reduction degree of Ni. The enhanced reduction of the nickel accomplishes a higher 15 amount of metallic nickel sites after reduction at 650 °C and somewhat increased conversion activity for the Ni-B combination catalysts.
Also, boron might adsorb on the γ -AI2O3 support to form aluminium borate (9AI2O3-2B2O3). The MgO supported reference catalyst did not show any conversion activity under the conditions. Note that both the reference MgO and reference AI2O3 20 had an higher surface area and available nickel surface area compared to the MgAl204.
18
The nickel supported by MgAl2C>4 is therefore surprisingly much more active than the analogue alumina and MgO supported catalysts under the specific conditions.
EXAMPLE 11: Nickel particle agglomeration at elevated temperatures 5 Tramp up and Tramp down : 300 - 750 - 300 °C
T calcination 650 °C; T reduction 650 °C: SV = 955,000 h"1 7.5%CH4, 22.5%H20, bal. N2.
19 wt%Ni Ni-porous MgO-AfCf Ni-porous MgO- Ni-MgAl204 Ni-MgAl204 A1203 T (°C) Conversion Tup Conversion Tdown Conversion Tup Conversion Tdown 458 31 30 25 7 509 58 57 54 38 557 78 78 78 71 611 93 93 93 93 708 93 93 93 93 10 A temperature hysteresis is found in case of the MgAl204 material: the high reaction temperature of 700 - 750 °C causes nickel particles located on the external surface to grow in size which is reflected in a loss of methane conversion activity when going to lower temperature operation again. In case of the pore supported nickel particles the nickel particles are stabilized against sintering/particle growth inside the 15 pores and no such loss in conversion activity is noticed after high temperature operation. The stabilization of the Ni particles is also beneficial for the regulation of carbon: larger Nickel particles are also more actively forming carbon and would require more Boron to prevent carbon-induced deactivation. The high temperature tolerance of the pore Mg(Al)0 based Ni catalysts also shows promise for use under (high 20 temperature) conditions of industrial reforming and reforming catalysis in fuel processors.
Further specific embodiment: 19 1. A process embodiment for the production of hydrogen comprising (1) subjecting a hydrocarbon comprising gas in a reaction chamber to a reforming reaction in the presence of a catalyst and a membrane selective for a predetermined reaction product of the reforming reaction to produce a hydrogen containing gas and (2) 5 selectively removing at least part of the predetermined reaction product from the reaction chamber via the membrane, wherein the catalyst comprises a porous catalyst based on at least magnesium oxide and aluminium oxide, wherein the porous catalyst further comprises boron and nickel, and wherein the porous catalyst comprises pores having a pore size in the range of 0.1-20 nm.
10 2. The process embodiment according to process embodiment 1, wherein prior to subjecting a hydrocarbon comprising gas in the reaction chamber to the reforming reaction, the porous catalyst is subjected to reducing conditions.
3. The process embodiment according to any one of the preceding process embodiments, wherein the hydrocarbon comprising gas is subjected to the reforming 15 reaction at a temperature in the range of 400-750 °C, especially 500-700 °C.
4. The process embodiment according to any one of the preceding process embodiments, wherein the hydrocarbon comprising gas comprises CH4.
5. The process embodiment according to any one of the preceding process embodiments, wherein the porous catalyst comprises pores having a pore size in the 20 range of 5-15 nm.
6. The process embodiment according to any one of the preceding process embodiments, wherein the porous catalyst comprises a magnesium aluminium oxide material.
7. The process embodiment according to any one of the preceding process
25 embodiments, wherein the porous catalyst comprises porous MgAfeCV
8. The process embodiment according to any one of the preceding process embodiments, wherein the porous catalyst further comprises one or more of Ti, Ca, Cr, Fe, Zr, Mn, such as one or more of Ca and Ti.
9. The process embodiment according to any one of the preceding process 30 embodiments, wherein the weight of nickel relative to the total weight of the porous catalyst is selected from the range of 4-70 wt.%, preferably 15-45 wt.%.
10. The process embodiment according to any one of the preceding process embodiments, wherein the weight of boron relative to the total weight of the porous 20 catalyst is selected from the range of 0.1-20 wt.%, preferably 0.5-5 wt.%, relative to the total weight of the porous catalyst.
11. A porous catalyst based on at least magnesium oxide and aluminium oxide, wherein the porous catalyst further comprises boron and nickel, and wherein the porous 5 catalyst comprises pores having a pore size in the range of 0.1-20 nm.
12. The catalyst according to porous catalyst embodiment 11, wherein the porous catalyst comprises a magnesium aluminium oxide material.
13. The catalyst according to any one of porous catalyst embodiments 11-12, wherein the porous catalyst comprises porous MgAl204.
10 14. The catalyst according to any one of porous catalyst embodiments 11-13, wherein the porous catalyst comprises pores having a pore size in the range of 8-13 nm.
15. The catalyst according to any one of porous catalyst embodiments 11-14, wherein the porous catalyst further comprises one or more of Ti, Ca, Cr, Fe, Zr, Mn, such as one or more of Ca and Ti.
15 16. A process embodiment for the production of a porous catalyst comprising: a. providing a magnesium compound, an aluminium compound, a nickel compound, a boron compound, and a pore former; b. forming in a formation process a porous material by combining the magnesium compound, the aluminium compound and the pore former and subjecting 20 these compounds to crystallisation conditions to provide a porous material; and c. calcining the thus formed porous material, wherein the boron compound is present during the formation process and/or wherein the boron compound is applied to the porous material obtained by the formation process, and wherein the magnesium compound is present during the 25 formation process and/or wherein the magnesium compound is applied to the porous material obtained by the formation process.
17. The process embodiment according to process embodiment 16, wherein the magnesium compound comprises a soluble magnesium salt, wherein the aluminium compound comprises a organo-aluminium compound, wherein the nickel compound 30 comprises a soluble nickel salt, wherein the boron compound especially comprises boric acid and wherein the pore former comprises a triblock copolymer having a molecular weight in the range of 3000-18000 Da.
21 18. The process embodiment according to any one of the process embodiments 16-17, wherein the boron compound comprise one or more compounds selected from the group consisting of (1) boric acid, (2) a water soluble boron containing such as selected from the group consisting of borax (Na2B405(0F[)4*8(F[20)), colemanite 5 (CaB304(0H)3»(H20)), ulexite (NaCaB506(0H)6»5(H20)) and kemite (Na2B406(0H)3»3(H20)), (3) a boron halide, such a selected from the group consisting of boron trifluoride (BF3), boron trichloride (BCI3), and an alkali metal borohalide, such as e.g. sodium borofluoride (NaBF4), (4) boron tribromide dimethyl sulphide complex solution in methylene chloride (CH3)2S*BBr3, (5) sodium tetra borate deca 10 hydrate, (6), an alkali metal borohydride, such as e.g. a KBH4 solution, (6) boric oxide, (7) an alkyl borate, (8) sodium cyano borohydride NaBH3(CN), and (9) boron powder.
19. Use of a catalyst according to any one of the porous catalyst embodiments 11-16 to let at least part of a hydrocarbon comprising gas react in a reforming reaction to a hydrogen containing gas.
15 Combinations of one or more embodiments is possible.
Claims (19)
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PCT/NL2011/050780 WO2012067505A2 (en) | 2010-11-16 | 2011-11-15 | Catalyst for hydrogen production |
CA2817490A CA2817490C (en) | 2010-11-16 | 2011-11-15 | Catalyst for hydrogen production |
US13/885,636 US9168511B2 (en) | 2010-11-16 | 2011-11-15 | Catalyst for hydrogen production |
EP11785156.8A EP2640509B1 (en) | 2010-11-16 | 2011-11-15 | Catalyst for hydrogen production |
RU2013127252/04A RU2585610C2 (en) | 2010-11-16 | 2011-11-15 | Catalyst for producing hydrogen |
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WO2004000456A2 (en) * | 2002-06-21 | 2003-12-31 | Isis Innovation Limited | Catalyst |
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GB1283780A (en) * | 1969-10-04 | 1972-08-02 | Boris Petrovich Kornilov | A catalyst for the conversion of hydrocarbons and a method for effecting same |
US5399537A (en) * | 1992-12-21 | 1995-03-21 | Amoco Corporation | Method for preparing synthesis gas using nickel catalysts |
US6416731B1 (en) * | 1998-12-22 | 2002-07-09 | Haldor Topsoe A/S | Process for catalytical steam reforming of a hydrocarbon feedstock |
WO2004000456A2 (en) * | 2002-06-21 | 2003-12-31 | Isis Innovation Limited | Catalyst |
WO2006114682A2 (en) * | 2005-04-26 | 2006-11-02 | Element Six (Production) (Pty) Ltd | Cubic boron nitride compacts |
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