CN102803130B - 在具有低表面粗糙度的催化剂上氧化氯化氢的方法 - Google Patents
在具有低表面粗糙度的催化剂上氧化氯化氢的方法 Download PDFInfo
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- CN102803130B CN102803130B CN201080024878.9A CN201080024878A CN102803130B CN 102803130 B CN102803130 B CN 102803130B CN 201080024878 A CN201080024878 A CN 201080024878A CN 102803130 B CN102803130 B CN 102803130B
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- catalyst
- ruthenium
- weight
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 36
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 230000003746 surface roughness Effects 0.000 title claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 33
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 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 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- -1 manganese, basic metal Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052706 scandium Inorganic materials 0.000 description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910001055 inconels 600 Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007038 hydrochlorination reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- MAZOHJVAXBNBPX-UHFFFAOYSA-N ruthenium hydrochloride Chemical compound Cl.[Ru] MAZOHJVAXBNBPX-UHFFFAOYSA-N 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J21/04—Alumina
-
- 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
- B01J21/20—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/42—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/54—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids halogen-containing
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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Abstract
本发明涉及一种在流化床方法中在催化剂存在下借助氧气催化氧化氯化氢从而形成氯气的方法，所述催化剂包含处于由平均粒度为10-200μm的α-氧化铝构成的颗粒状载体上的钌，其特征在于该催化剂载体具有低表面粗糙度，且可由已在流化床方法中使用至少500运行小时的废催化剂获得。
Description
本发明涉及一种在催化剂上催化氧化氯化氢的方法，所述催化剂包含处于具有低表面粗糙度的颗粒状载体上的钌。
在由Deacon于1868年开发的氯化氢催化氧化工艺中，在放热平衡反应中借助氧气使氯化氢氧化成氯气。氯化氢至氯气的转化能使氯气的生产与通过氯碱电解生产氢氧化钠的工艺分离。这种分离令人关注，因为世界氯气需求的增长快于氢氧化钠需求增长。此外，氯化氢作为联产品例如从光气化反应，如异氰酸酯的生产中大量获得。
EP-A 0743277公开了一种通过氯化氢催化氧化制备氯气的方法，其中使用含钌负载型催化剂。在该文中，将钌以氯化钌、氯氧化钌、氯钌酸盐配合物、氢氧化钌、钌-胺配合物形式或以其他钌配合物形式施加至载体上。所述催化剂可包含钯、铜、铬、钒、锰、碱金属、碱土金属和稀土金属作为其他金属。
根据GB 1,046,313，将处于氧化铝上的氯化钌(III)作为催化剂用于氯化氢催化氧化工艺中。
DE 10 2005 040286 A1公开了一种用于氯化氢氧化的机械稳定催化剂，其包含处于作为载体的α-氧化铝上的如下组分：
a)0.001-10重量％钌、铜和/或金，
b)0-5重量％一种或多种碱土金属，
c)0-5重量％一种或多种碱金属，
d)0-10重量％一种或多种稀土金属，
e)0-10重量％一种或多种选自钯、铂、锇、铱、银和铼的其他金属。
作为适于掺杂的助催化剂，提及碱金属如锂、钠、钾、铷和铯，优选锂、钠和钾，特别优选钾；碱土金属如镁、钙、锶和钡，优选镁和钙，特别优选镁；稀土金属如钪、钇、镧、铈、镨和钕，优选钪、钇、镧和铈，特别优选镧和铈，或其混合物；以及钛、锰、钼和锡。
在由含镍钢材(例如HC4，Inconel 600等)制成的反应器中运行的流化床催化剂由于该反应器的腐蚀和侵蚀而在Deacon反应过程中生成NiCl2。连续的侵蚀缩短了流化床反应器的寿命。
本发明的目的是克服上述缺点。
该目的通过一种在流化床工艺中在催化剂存在下借助氧气催化氧化氯化氢从而形成氯气的方法实现，所述催化剂包含处于由平均粒度为10-200μm的α-氧化铝构成的颗粒状载体上的钌，其中该催化剂载体具有低表面粗糙度且可由已在流化床工艺使用至少500运行小时的废催化剂获得。
已发现在废流化床催化剂已事先在流化床工艺中使用至少500运行小时的情况下，从该废流化床催化剂中回收的基于α-氧化铝载体颗粒的流化床催化剂导致流化床反应器壁处材料的移除显著降低。优选所用废流化床催化剂已在流化床工艺中使用至少1000运行小时。
优选所述催化剂载体具有优选为30-100，特别优选为40-80的平均直径(d50)。
用于本发明方法中的流化床反应器通常为由含镍材料制成的反应器。镍含量优选为至少10重量％。此外，所述含镍材料可包含一种或多种其他金属作为合金化成分，例如选自铁、钼、铬和钛的金属。含镍材料的实例为HC4(2.4810NiCr15Fe)和Inconel 600(NiMo16Cr16Ti)。
所述流化床在通常3-500倍，优选10-200倍，特别优选30-100倍于流化点时(即流化开始时)的气体速度的气体速度下运行。
本发明所用的粉状催化剂载体优选由包含α-氧化铝作为载体(合适的话呈与其他载体材料的混合物形式)且事先已用于Deacon工艺中的含钌废催化剂获得。通常，所述载体基本上由α-氧化铝构成，但也可包含其他载体材料，例如石墨、二氧化硅、二氧化钛和/或二氧化锆，优选二氧化钛和/或二氧化锆。
本发明所用载体可由包含氧化钌的废催化剂通过如下方式获得：
a)在300-500℃的温度下，在包含氯化氢和合适的话惰性气体的气流中还原所述包含氧化钌的催化剂；
b)在含氧气体存在下，用氢氯酸处理获自步骤a)的还原的催化剂，其中存在于载体上的金属钌以氯化钌形式溶解，并作为氯化钌水溶液分离出去；
或者
a)在150-600℃的温度下，在包含氢气和合适的话惰性气体的气流中还原所述包含氧化钌的催化剂；
b)在含氧气体存在下，用氢氯酸处理获自步骤a)的还原的催化剂，其中存在于载体上的金属钌以氯化钌形式溶解，并作为氯化钌水溶液分离出去。
合适的话，在浓缩后，将所述氯化钌溶液用于制备新鲜催化剂。
本发明所用催化剂通过用所述金属盐水溶液浸渍废0载体材料而获得。所述金属通常以其氯化物、氯氧化物或氧化物的水溶液形式施加至载体上。
在金属盐沉积之前，所述α-氧化铝载体的比表面积通常为0.1-10m2/g。α-氧化铝可通过将γ-氧化铝加热至高于1000℃的温度而制备，并且优选以此方式制备。通常将其煅烧2-24小时。
除钌之外，本发明所用催化剂可包含其他金属作为助催化剂。这些通常以基于所述催化剂重量为至多10重量％的量存在于该催化剂中。
在优选实施方案中，本发明所用催化剂除钌之外，还包含镍。已发现，包含镍掺杂的钌的催化剂具有比不含镍的催化剂更高的活性。据推测该活性的提高可归因于氯化镍的助催化性能和氯化镍所导致的活性组分在催化剂表面上的更好分散。因此，钌以新鲜或再生形式作为微晶尺寸＜7nm的RuO2微晶存在于本发明催化剂上。微晶尺寸以XRD测量中的物质反射峰的半高宽测定。
用于催化氧化氯化氢的含钌催化剂可额外包含一种或多种选自钯、铂、铱和银的其他贵金属的化合物。所述催化剂可进一步包含铼。所述催化剂也可用一种或多种其他金属掺杂。适于作为用于掺杂的助催化剂的金属为碱金属如锂、钠、钾、铷和铯，优选锂、钠和钾，特别优选钾；碱土金属如镁、钙、锶和钡，优选镁；稀土金属如钪、钇、镧、铈、镨和钕，优选钪、钇、镧和铈，特别优选镧和铈；或其混合物，以及钛。
优选用于氯化氢氧化的催化剂包含：
a)0.1-10重量％钌，
b)0-10重量％镍，
c)0-5重量％一种或多种碱土金属，
d)0-5重量％一种或多种碱金属，
e)0-5重量％一种或多种稀土金属，
f)0-5重量％一种或多种选自钯、铂、铱、银和铼的其他金属，在每种情况下基于所述催化剂的总重量。重量百分比基于所述金属的重量，尽管所述金属通常以氧化物或氯化物形式存在于载体上。
除钌之外，所存在的其他金属c)-f)以及合适的话镍的总含量通常不超过5重量％。
本发明所用催化剂以该催化剂重量计，非常特别优选包含0.5-5重量％钌和0.5-5重量％镍。在具体实施方案中，本发明所用催化剂包含处于作为载体的α-氧化铝上的约1-3重量％钌和1-3.5重量％镍，且不含其他活性金属或助催化剂金属，其中钌以RuO2形式存在。
负载的钌催化剂例如可通过用RuCl3和合适的话NiCl2以及用于掺杂的其他助催化剂(优选呈其氯化物形式)的水溶液浸渍载体材料而获得。随后可将粉末干燥，并且合适的话在100-500℃，优选100-300℃的温度下，例如在氮气、氩气或空气气氛下煅烧。所述粉末优选首先在100-150℃下干燥，随后在200-500℃下煅烧。
在催化剂失活后，可回收载体并再次用于制备负载的钌催化剂。
为了实施氯化氢的氧化，将氯化氢料流和含氧料流供入流化床反应器中，并在所述催化剂存在下，使氯化氢部分氧化成氯气，从而得到包含氯气、未反应的氧气、未反应的氯化氢和水蒸汽的产物气流。可源于制备异氰酸酯的工厂的氯化氢料流可包含杂质如光气和一氧化碳。
反应温度通常为150-500℃，反应压力通常为1-25巴，例如4巴。反应温度通常优选＞300℃，特别优选为350-420℃。还有利地是以过当量使用氧气。例如，通常使用过量1.5-4倍的氧气。由于不必担心选择性降低，因此可经济上有利地在较高压力并因此在比在大气压下更长的停留时间下进行。
除所述催化剂之外，流化的催化剂床可包含惰性材料，优选呈额外的非活性载体材料形式。所述非活性惰性材料同样为废催化剂材料，所述废催化剂材料由于在流化床工艺中使用了至少500运行小时而具有低表面粗糙度。惰性材料可以以基于催化剂和惰性材料总和为0-90重量％，优选10-50重量％的量使用。
单程中的氯化氢转化率可限于15-90％，优选40-85％。未反应的氯化氢可在分离出去之后，部分或全部再循环至氯化氢的催化氧化中。反应器入口处的氯化氢与氧气体积比通常为1∶1-20∶1，优选1.5∶1-8∶1，特别优选1.5∶1-5∶1。
然后，可将形成的氯气以常规方式从氯化氢催化氧化中获得的产物气流分离出去。该分离通常包括多个步骤，即从获自氯化氢催化氧化的产物气流中分离未反应的氯化氢，并且合适的话将该氯化氢再循环；干燥所获得的基本上由氯气和氧气组成的剩余气流；以及从干燥的料流中分离氯气。
本发明所用的含钌氯化氢氧化催化剂也可通过将已在氯化氢氧化工艺中使用至少500运行小时的废流化床催化剂再生而获得。这可通过例如如下方式再生：
a)在300-500℃的温度下，在包含氯化氢和合适的话惰性气体的气流中，还原所述催化剂，
b)在200-450℃的温度下，在含氧气流中再次煅烧所述催化剂。
已发现，RuO2可通过氯化氢还原。据推测，发生经由RuCl3至元素钌的还原反应。因此，如果用氯化氢处理部分失活的含氧化钌催化剂，则在足够长的处理时间后，氧化钌可能定量还原成钌。由于该还原反应，RuO2微晶被破坏，且可作为元素钌、作为氯化钌与元素钌的混合物或作为氯化钌存在的钌再分散于该载体上。还原后，钌可借助含氧气体，例如空气再次氧化成催化活性RuO2。已发现，以此方式再次获得的催化剂具有接近于新鲜催化剂的活性。该方法的优点在于，催化剂可在反应器中原位再生，且不需从反应器中取出。
该再生催化剂具有与运行期间有关的低表面粗糙度。
通过以下实施例说明本发明。
实施例实施例1
新鲜催化剂通过用RuCl3水溶液浸渍载体(α-Al2O3粉末，d50＝50μm)，干燥并在300-450℃下煅烧0.5-5.0小时而制备。所述新鲜催化剂具有非常粗糙的表面，因此在流化床工艺中导致反应器的高磨损。
在直径为44mm、高度为990mm且床高为300-350mm的流化床反应器中，使用200标准L·h-1HCl和100标准L·h-1O2，使600g所述催化剂在400℃下运行。所述催化剂以平均直径为50微米(d50)的粉末形式存在。获得61％的氯化氢转化率。所述催化剂在360-380℃下运行。
图1所示的是新鲜催化剂的照片。
图2所示的是运行675小时后的催化剂照片。
图3所示的是运行7175小时后的催化剂照片。
图4所示的是运行9485小时后的催化剂照片。
所述新鲜催化剂表现出粗糙表面，因而使得反应器壁的平均侵蚀速率为0.30mm/年。在675小时后，可以看到催化剂表面稍微变圆，这反映在稍有下降且为0.28mm/年的侵蚀速率中。在7175小时后，所述催化剂变圆至使得侵蚀速率为0.04mm/年的程度。最后，在9485小时后，由于光滑的催化剂表面，侵蚀速率几乎为零。
载体的再循环使得可制备从一开始就几乎不侵蚀反应器壁的新鲜催化剂，并因此大大提高了反应器的寿命。
实施例2
在430℃下，在实施例1所述的流化床反应器中，用100标准L/h气态HCl处理585g失活废流化床催化剂70小时，所述失活废流化床催化剂包含2重量％处于α-Al2O3(平均直径(d50)：50μm)上的RuO2，以及由于含镍反应器的腐蚀和侵蚀而产生的2.5重量％氯化镍。在100℃和剧烈搅拌下，在2500mL玻璃反应器中，将以此方式获得的还原的催化剂用2000mL 20％浓度的HCl溶液处理96小时。在整个处理期间，鼓泡入20标准L/h的空气。通过过滤从固体(载体)中分离含Ru和Ni的上清液，滤饼用500mL水洗涤。合并的水相包含＞98％的钌和镍。将该溶液的一部分蒸发至18mL，获得包含4.2重量％钌和7.0重量％镍的溶液。
实施例3
对200g在实施例1中所述的流化床反应器中运行9485小时后获得的失活流化床催化剂实施实施例2所述的再循环工艺以回收载体。将50g以此方式获得的变圆载体通过喷雾工艺，在旋转玻璃烧瓶中用18mL RuCl3水溶液(Ru含量＝4.2重量％)浸渍，并将所得固体120℃下干燥16小时。将干燥的材料在380℃下在空气中煅烧1小时。以此方式形成的含RuO2催化剂可再用于借助O2的HCl催化氧化。
将2g该催化剂与118g α-Al2O3混合，并在360℃下，在流化床反应器(d＝29mm，流化床高度：20-25cm)中，使9.0标准L/h HCl和4.5标准L/h O2经由玻璃料从下方通过该混合物，并通过将所得气流通入碘化钾溶液中，随后用硫代硫酸钠溶液滴定形成的碘而测定HCl转化率。HCl转化率为37.7％。
实施例4
在400℃下，在直径为108mm、高度为4-4.5m且床高为2.5-3m的流化床反应器中，使用10.5kg·h-1HCl、4.6kg·h-1O2和0.9kg·h-1N2，使21kg获自实施例2的废催化剂(处于α-Al2O3上的RuO2，包含2.5重量％氯化镍)运行。所述催化剂已平均直径(d50)为50微米的粉末形式存在。获得77％的HCl转化率。然后在400℃下关掉氧气20小时，并用10.0kg·h-1HCl代替。20小时后，将催化剂再次煅烧并由此在400℃下，在2.0kg·h-1O2和8.0kg·h-1N2下再活化30分钟。在该处理后，该催化剂在400℃，使用10.5kg·h-1HCl、4.6kg·h-1O2和0.9kg·h-1N2下显示出84％的HCl转化率。
Claims (5)
1.一种在流化床工艺中在催化剂存在下借助氧气催化氧化氯化氢从而形成氯气的方法，所述催化剂包含处于由平均粒度为10-200μm的α-氧化铝构成的颗粒状载体上的钌，其中该催化剂载体具有低表面粗糙度并且由已在流化床工艺使用至少500运行小时的废催化剂获得。
2.根据权利要求1的方法，其中所述颗粒状载体由α-氧化铝构成或者由α-氧化铝和其他载体材料构成。
3.根据权利要求1的方法，其中所述催化剂包含：
a)0.1-10重量％钌，
b)0-10重量％镍，
c)0-5重量％一种或多种碱土金属，
d)0-5重量％一种或多种碱金属，
e)0-5重量％一种或多种稀土金属，
f)0-5重量％一种或多种选自钯、铂、铱、银和铼的其他金属，
在每种情况下基于所述催化剂的总重量。
4.根据权利要求1的方法，其中所述催化剂载体通过如下步骤由包含氧化钌的废催化剂获得：
a)在300-500℃的温度下，在包含氯化氢和任选的惰性气体的气流中还原所述包含氧化钌的催化剂；或者在150-600℃的温度下，在包含氢气和任选的惰性气体的气流中还原所述催化剂；
b)在含氧气体存在下，用氢氯酸处理获自步骤a)的还原的催化剂，其中存在于载体上的金属钌以氯化钌形式溶解，并作为氯化钌水溶液分离出去。
5.根据权利要求1的方法，其中所述催化剂通过用一种或多种包含钌和任选的一种或多种其他助催化剂金属的金属盐溶液浸渍所述载体并干燥和煅烧该浸渍的载体而获得。
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| PCT/EP2010/057814 WO2010142604A1 (de) | 2009-06-10 | 2010-06-04 | Verfahren zur chlorwasserstoffoxidation an einem katalysator mit geringer oberflächenrauhigkeit |
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| KR102287846B1 (ko) * | 2018-12-21 | 2021-08-06 | 한화솔루션 주식회사 | 염소 제조를 위한 염화수소 산화반응용 촉매 및 이의 제조방법 |
| KR102262496B1 (ko) * | 2018-12-21 | 2021-06-07 | 한화솔루션 주식회사 | 염소 제조용 산화루테늄 담지 촉매의 제조방법 및 이에 의해 제조된 촉매 |
| CN115155672A (zh) * | 2022-06-24 | 2022-10-11 | 西安近代化学研究所 | 一种氯化氢氧化催化剂的再生方法 |
| CN116550321A (zh) * | 2023-05-22 | 2023-08-08 | 康纳新型材料(杭州)有限公司 | 一种用于氯化氢氧化制氯气的高分散度钌催化剂及其制备方法 |
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| WO2007125004A1 (de) * | 2006-04-26 | 2007-11-08 | Basf Aktiengesellschaft | Verfahren zur herstellung von katalysatoren für die katalytische chlorwasserstoff-oxidation |
| CN101272852A (zh) * | 2005-08-25 | 2008-09-24 | 巴斯夫欧洲公司 | 基于α-氧化铝的机械稳定催化剂 |
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| US4147660A (en) * | 1976-12-22 | 1979-04-03 | Osaka Gas Company, Ltd. | Method for reactivation of platinum group metal catalyst with aqueous alkaline and/or reducing solutions |
| CA1260229A (en) * | 1986-06-30 | 1989-09-26 | Mitsui Chemicals, Inc. | Production process of chlorine |
| US5707919A (en) * | 1994-11-14 | 1998-01-13 | Mitsui Toatsu Chemicals, Inc. | Catalyst for preparing chlorine from hydrogen chloride |
| CN1182717A (zh) * | 1996-10-31 | 1998-05-27 | 住友化学工业株式会社 | 氯气的生产方法 |
| DE10361519A1 (de) * | 2003-12-23 | 2005-07-28 | Basf Ag | Verfahren zur Herstellung von Chlor durch Gasphasenoxidation von Chlorwasserstoff |
| DE102005061954A1 (de) * | 2005-12-23 | 2007-07-05 | Basf Ag | Verfahren zur Wiedergewinnung von Ruthenium aus gebrauchten Rutheniumoxid-haltigen Katalysatoren |
| JP5169047B2 (ja) * | 2007-07-23 | 2013-03-27 | 住友化学株式会社 | 塩素の製造方法 |
| JP5642706B2 (ja) * | 2008-12-30 | 2014-12-17 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | 塩化水素の酸化用のルテニウム及びニッケル含有触媒 |
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| WO2007125004A1 (de) * | 2006-04-26 | 2007-11-08 | Basf Aktiengesellschaft | Verfahren zur herstellung von katalysatoren für die katalytische chlorwasserstoff-oxidation |
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| JP2012529415A (ja) | 2012-11-22 |
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| WO2010142604A1 (de) | 2010-12-16 |
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