WO2008030140A2 - Catalyseur de conversion de monoxyde de carbone par la vapeur, procédé de sa fabrication et procédé de son utilisation - Google Patents
Catalyseur de conversion de monoxyde de carbone par la vapeur, procédé de sa fabrication et procédé de son utilisation Download PDFInfo
- Publication number
- WO2008030140A2 WO2008030140A2 PCT/RU2007/000470 RU2007000470W WO2008030140A2 WO 2008030140 A2 WO2008030140 A2 WO 2008030140A2 RU 2007000470 W RU2007000470 W RU 2007000470W WO 2008030140 A2 WO2008030140 A2 WO 2008030140A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- iron
- chromium
- carbon monoxide
- aqueous solution
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011651 chromium Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 11
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229910052598 goethite Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 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 claims abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910001018 Cast iron Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 229910001208 Crucible steel Inorganic materials 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- -1 iron-chromium hydroxyl compound Chemical class 0.000 abstract description 5
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002823 nitrates Chemical class 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 14
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- 229910052595 hematite Inorganic materials 0.000 description 9
- 239000011019 hematite Substances 0.000 description 9
- 238000000629 steam reforming Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 235000013980 iron oxide Nutrition 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910002588 FeOOH Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910001060 Gray iron Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- WHTMVEKFWMRAJC-UHFFFAOYSA-N [Cu].[Cr].[Fe] Chemical class [Cu].[Cr].[Fe] WHTMVEKFWMRAJC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical class [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical class [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001157043 Syngonium Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NHCAIXHAILVQNQ-UHFFFAOYSA-N [C]=O.[Cr].[Fe] Chemical compound [C]=O.[Cr].[Fe] NHCAIXHAILVQNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical class [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000049 iron hydride Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003923 scrap metal Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- 229910006299 γ-FeOOH Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- 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
- B01J37/12—Oxidising
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- Carbon monoxide vapor conversion catalyst method for preparing it and method for using it
- the invention relates to a method for producing hydrogen by steam reforming of carbon monoxide and to catalysts for this process and may find application in various industries.
- the steam reforming reaction of carbon monoxide is a step in the process of producing hydrogen from natural gas.
- the steam reforming reaction of CO is exothermic, the conversion depth is determined by thermodynamic equilibrium, which is uniquely related to the temperature of the gas mixture at the outlet of the catalyst layer.
- steam conversion of carbon monoxide is carried out in two stages: in the temperature range (1) 350-500 0 C on the iron-chromium catalyst and (2) 190-300 0 C on the copper-zinc-aluminum catalyst [Catalysts used in the nitrogen industry. Under the total. Edited by A.M. Alekseev. Cherkasy. NIITEhim. 1979].
- the most promising catalysts at the 1st stage of the process are currently catalysts based on iron-chromium and iron-chromium-copper compounds.
- the main requirements for them are: (1) sulfur content not more than 0.03 wt.%, (2) chromium content 6+ not more than 0.05 wt.%, (3) catalyst activity, which ensures the process at temperatures at the beginning of the layer less than 350 0 C , for example at 320-330 0 C, (4) environmental safety of cooking technology.
- the sulfur content in the catalyst is limited due to the fact that under the reaction medium conditions, sulfur compounds present in the known catalysts in the form of sulfates are converted to gaseous H 2 S and CS 2 and poison the copper-containing catalyst for low-temperature steam reforming of CO.
- the best way to reduce the sulfur content is to use raw materials that do not contain sulfur or contain a small amount of sulfur, which decreases during the preparation of the catalyst (deposition, washing of the catalyst mass).
- Environmental safety of cooking technology means the minimum formation of NO and NO 2 and their sanitary absorption, the absence of chromium 6+ and copper 2+ in the effluent, or their content within the accepted sanitary standards.
- a known method of producing a catalyst for steam conversion of carbon monoxide (SU 651838, B01J37 / 04, 03/15/79), containing 7.2 wt.% Cr 2 O 3 , mixing iron oxide Fe 2 O 3 with chromic acid, followed by molding, drying and annealing.
- a known method of producing a catalyst (SU 1790064, BOlJ 37/04,
- 07/20/01 obtained by mixing iron oxide with an aqueous solution of chromic acid and a manganese salt, followed by molding of granules, drying and calcining them. Before calcination, additionally administered compounds of Mg, or Ca, Nd or Pr.
- the disadvantages include the high cost of the resulting catalyst.
- an iron-chromium catalyst (RU 2275963, B01J37 / 03, 05/10/06) by mixing chromic anhydride with iron compounds prepared by precipitating the iron hydroxide compound with a solution of ammonia or sodium carbonate from iron sulfate solutions, followed by washing, molding and calcining at 280- 420 0 C.
- the use of iron sulfate as a raw material requires a large amount of water and a long time to remove sulfur.
- the disadvantages include the high chromium content 6+ and the relatively low activity of the catalyst in the entire temperature range, especially at temperatures below 35O 0 C (see the prototype described in example 6).
- Variants of this invention involve the mixing of chromic anhydride with hydroxyl compounds of iron and calcining the resulting mixture at 50-200 ° C before molding the catalyst, which does not allow to avoid the above-mentioned disadvantages, but additionally leads to severe shrinkage of the catalyst during its use.
- iron-chromium carbon monoxide conversion catalyst for water vapor [RO 100112, B01J23 / 08, 08/14/1990], obtained by heating in air at 25O 0 C the precursor, which is obtained using solutions of iron (III) nitrates, chromium (III) and a suitable alkaline agent (ammonia solution, sodium hydroxide).
- the disadvantages of the catalyst include its low activity and high chromium content 6+. The increased content of Cr +6 is a consequence of calcination in air.
- the use of nitrate salts as a raw material leads to a high cost of the catalyst.
- the catalyst is obtained by mixing with a solution of ammonia, purged with CO 2 , solutions of iron (III) nitrates, chromium (III) and copper nitrate, followed by drying and calcination in air at 350-450 0 C.
- Iron nitrates (III) and Cr (III) are obtained by dissolution in 23 wt.% nitric acid of metallic scrap and chromium hydrochloric anhydride with a purge of air at 40-60 0 C.
- the disadvantages of the known catalyst are:
- the narrow temperature range of the catalyst is 300-360 0 C.
- the invention solves the problem of developing a catalyst with high activity in the steam reforming reaction in the temperature range of 250—35O 0 C.
- the present invention proposes to solve the problem a steam conversion catalyst of carbon monoxide, containing in its composition the phase of the hydroxy compound of iron 3+ and chromium 3+ with the structure of goethite (FeOOH, Pbpm (2 / m 2 / m 2 / m), ICSD 28247, 6.1. 1.2) and / or hydrohematite FeO (1 5- Q Sx) (OH) x [E. Wolska, Zeitschh. f ⁇ g Kristallogg. V154, Nl / 2, 1981, p. 69-71].
- the atomic ratio of iron to chromium in it is more than 1.
- the catalyst may additionally contain more than 1.0 wt.% Copper.
- the catalyst containing one of the above hydroxide phases has activity in the steam reforming reaction in the temperature range of 250-350 0 C, significantly exceeding the known analogues, containing mainly the phase with the structure of hematite Ot-Fe 2 O 3 or magnetite Fe 3 O 4 , as this is illustrated by the examples below.
- the present invention also provides a method for producing a catalyst using metallic iron or a composition containing metallic iron as a raw material, a chromium 6+ compound or its aqueous solution, a copper 2+ compound or its aqueous solution and an aqueous solution of nitric acid.
- the proposed method for the preparation of a carbon monoxide conversion catalyst containing iron and chromium includes a sequence of actions: mixing metallic iron or a composition containing metallic iron with a chromium 6+ compound or its aqueous solution and an aqueous solution of nitric acid with an initial concentration of 6.0-46 wt .% at temperatures below 4O 0 C; bubbling the resulting mixture with air at a temperature of 40-60 0 C, mixing the resulting solution and an aqueous solution of carbonate and / or ammonium hydroxide and / or potassium and / or sodium, washing the precipitate from the mother liquor with water, filtering the precipitate and drying it.
- the method allows to obtain hydroxo compounds with the above structures
- composition containing metallic iron As a composition containing metallic iron, cast iron or steel is used.
- the specific structure of the resulting compounds is determined by the preparation parameters, such as the temperature of mixing of the raw materials, the pH of the mother liquor solution and others.
- a composition of metallic iron products of metallurgical industries, as well as scrap metal or waste from engineering industries, can be used, however, the use of gray cast iron is preferable.
- Gray cast iron has a low content of 5 sulfur (it is actually possible to achieve a content of 0.02 wt.%) And phosphorus.
- Carbon and silicon contained in cast iron do not impair the performance of the catalyst, but can improve its formability.
- Manganese contained in cast iron can have a positive effect on the catalytic properties (as the use of manganese as a promoting additive is proposed
- the present invention also provides a method for carrying out a CO steam reforming process using the above catalysts at temperatures above 25 0 0 C.
- the advantages of the proposed catalyst are: a wide range of operating temperatures with high activity in the range of 250-350 0 C, sulfur content of not more than 0.03 wt.%; the content of chromium (VI) is not more than 0.05 wt.%
- the advantages of the proposed method for the preparation of the catalyst are: the absence of emission of NO and NO 2 ; lack of chromium (VI) in the effluent; fast 0 washing, good filterability of sediment.
- the advantage of the method for implementing the process of steam conversion of carbon monoxide is the ability to carry out the process in a wide temperature range. Including at a temperature in the initial catalyst layer is lower than for a conventional catalyst.
- Example 1 The catalyst composition Fe 0 9 Cr 0 1 with the structure of goethite.
- pH (8.0-8.5) and temperature (68-70 0 C) are kept constant.
- the precipitate is washed by decantation.
- the catalyst mass is dried at 9O 0 C and calcined in a stream of a mixture of nitrogen and steam for 1 h at 25O 0 C.
- the diffractogram of the obtained catalyst is shown in FIG. 1.
- the diffractogram is obtained on a D-500 diffractometer (Siemeps company) in Cu-K 0 radiation with a graphite monochromator on the reflected beam at a voltage of 35 kV and a current strength of 35 mA.
- the IR spectrum of the obtained catalyst is shown in FIG. 2.
- the IR spectrum is obtained in the range of 250-4000 cm ′′ on a VoetMM-102 Fourier spectrometer. The samples are prepared by pressing in a KBr matrix.
- Figure 1 also shows the data of the ⁇ - model diffraction pattern
- FeOOH (goethite) calculated according to ICSD 28247.
- the observed diffractogram and IR spectrum indicate that the obtained catalyst is a Fe 3+ O (OH) compound with goethite structure - orthorhombic syngony, space group Pb ⁇ m (2 / m 2 / m 2 / m), given a class. 6.1.1.2.].
- Example 2 The catalyst composition Fe 0 9 Cr 0 l with the structure of hydrohematite.
- the catalyst is prepared analogously to example 1, however, the mixture of cast iron, chromic anhydride and an aqueous solution of nitric acid is carried out at 15 ° C for 2 hours, the mixture is bubbled with air at 55 ° C, and precipitation is carried out at pH (7.5-8.0) . Calcination of the dry catalyst mass is carried out at 35 O 0 C. 1 mass% of graphite is added to the resulting mass and tabletted into 5 mm x 5 mm cylindrical tablets. The diffraction pattern of the obtained catalyst before the introduction of graphite into it is shown in FIG. 3. The IR spectrum of the obtained catalyst is shown in FIG. four.
- the diffractogram of the catalyst contains two broad reflections at d of about 2.7 A and 2.5 A, characterizing the compound as a strongly disordered phase with a cubic structure.
- the IR spectrum of the obtained catalyst in the region of natural vibrations is close to hydrohematite (E. Wolska, Zeitskhg. Fur Kgistallogr. V.154, N. 1/2, 1981, p. 69-71).
- the IR spectrum contains an absorption band in the region of 920 cm "1 , which is distinctive for hydrohematites from OFe 2 O 3 oxide, hematite.
- the IR spectrum contains absorption bands in the region of water vibrations (3400 cm “ 1 and 1630 cm “ 1 ) and impurity anions CO 3 and NO 3 in the region of 1340-1540 cm “1 .
- the phase transition of a catalyst with a hydrohematite structure to a hematite structure occurs exothermically only in the temperature range 560-590 0 C.
- the catalyst calcined at 600 0 C in a stream of nitrogen has the structure of well crystallized hematite.
- Example 3 The catalyst composition Feo .89 Cro.o 9 Cuo . o 2 with goethite structure
- the catalyst is prepared analogously to example 1, however, 0.35 g of CuO and 2 g of a 15 wt.% nitric acid solution are additionally added to the mixture of iron, chromium and nitric acid compounds.
- the diffractogram of the obtained catalyst is shown in FIG. 5.
- Figure 5 also shows the data of the model diffraction pattern of FeOOH (goethite) calculated according to ICSD 28247.
- the observed diffraction pattern indicates that the obtained catalyst is a compound Fe 3+ O (OH) with the structure of goethite - orthorhombic syngonium, space group ⁇ b ⁇ m (2 / m 2 / m 2 / m), Dana class. 6.1.1.2.].
- Characteristic data on the catalytic properties of the obtained catalyst are presented in the table.
- Example 4 The catalyst composition Fe O 89 Cr 0 O gCu 0 O2 with the structure of hydrohematite.
- the catalyst is prepared analogously to example 2, however, as a composition containing metallic iron, 8.8 g of steel filings are used, and 0.35 g of CuO and 2 g of 15 wt.% Nitric are additionally added to a mixture of iron, chromium and nitric acid compounds acids.
- the diffraction pattern of the obtained catalyst before the introduction of graphite into it is shown in FIG. 6.
- the IR spectrum of the obtained catalyst is shown in FIG. 7.
- the IR spectrum of the obtained Fe — Cr — Cu catalyst in the region of natural vibrations closely matches the spectrum of hydrohematite (E. Wolska, Zeitschr. Fur Ktistallogr. V. 154, N. 1/2, 1981, pp. 69-71).
- the band in the region of 920 cm '1 which is observed in the spectra of hydrohematites and distinguishes them from hematite, is well pronounced.
- the IR spectrum contains absorption bands in the region of water vibrations (3400 cm “1 and 1630 cm “ 1 ) and impurity anions CO 3 and NO 3 in the region 1340-1540 cm “1 .
- Example 5 The catalyst composition Fe 0 73 Cr 007 C u 02 with the structure of hydrohematite.
- the catalyst is prepared analogously to example 2, however, a mixture of compounds of iron, chromium and nitric acid is additionally introduced 4.2 g of CuO and 24 g of 15 wt.% Nitric acid.
- the IR spectrum of the obtained catalyst is shown in FIG. 8.
- the IR spectrum of the obtained Fe-Cr-Cu catalyst in the region of natural vibrations closely matches the spectrum of hydrohematite (E. Wolska, Zeitschr. Fur Kristallogr. V. 154, N. 1/2, 1981, p. 69-71).
- the band in the region of 920 cm “1 which is observed in the spectra of hydrohematites and distinguishes them from hematite, is well defined.
- the IR spectrum contains absorption bands in the region of water vibrations (3400 cm “ 1 and 1630 cm “ ) and CO 3 impurity anions and NO 3 in the region of 1340-1540 cm “1 . Characteristic data on the catalytic properties of the obtained catalyst are presented in the table.
- the catalyst composition Fe 09 Cr 0 1 with the structure of hematite is prepared according to the patent RU 2275963, by sequentially performing (1) precipitation of the iron (II) compound from a solution of iron (II) sulfate with a mixture of carbonate and sodium hydroxide solutions, (2) washing the precipitate by decantation, (3) calcining at 25O 0 C, (4) sequential washing with a calcined mass by decantation and on a filter; (5) mixing the washed mass with chromic anhydride, (6) molding into extrudates with a diameter of 3 mm, (7) heat treatment at a temperature of 35O 0 C.
- a diffractogram of the obtained catalyst is shown in FIG. 9.
- the IR spectrum of the obtained catalyst is shown in FIG. 10.
- FIG. Figure 9 also shows the data of the model diffraction pattern of Qj-Fe 2 O 3 (hematite) calculated according to ICSD 64599.
- the catalyst composition Fe O 89 Cr O o 9 Cu 0 O2 with a hematite structure Fe O 89 Cr O o 9 Cu 0 O2 with a hematite structure.
- the catalyst is prepared according to patent RU 2275963, analogously to example 6, however, the deposition is carried out from a mixture of solutions of iron (II) sulfate and copper (II) sulfate in proportions corresponding to the composition of the catalyst; graphite is added to the catalyst to facilitate molding.
- the diffractogram of the obtained catalyst is shown in FIG. 11.
- the data presented in FIG. 11 indicate that the resulting catalyst has the structure of ⁇ -Fe 2 O 3 (hematite).
- the reaction rate constants of the steam reforming of CO on the catalyst fraction 0.25-0.5 mm
- the ratio of pap: gaz 0.8.
- the activation of the catalysts was carried out in two stages: (1) raising the temperature to 200 0 C in a stream of nitrogen; (2) raising the temperature to 300- 32O 0 C in a stream of wet reaction mixture.
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP07834984A EP2077152A2 (en) | 2006-09-06 | 2007-08-23 | Catalyst for vapour conversion of carbon monoxide methods for the production and for the use thereof |
EA200900346A EA013871B1 (ru) | 2006-09-06 | 2007-08-23 | Катализатор паровой конверсии монооксида углерода, способ его приготовления и способ его использования |
US12/439,871 US20100196260A1 (en) | 2006-09-06 | 2007-08-23 | Catalyst for vapour conversion of carbon monoxide methods for the production and for the use thereof |
EEP200900023A EE200900023A (et) | 2006-09-06 | 2007-08-23 | Süsinikmonooksiidi aurkonversiooni katalüsaator, meetod selle valmistamiseks ja kasutamiseks |
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RU2006132151 | 2006-09-06 | ||
RU2006132151/04A RU2314870C1 (ru) | 2006-09-06 | 2006-09-06 | Катализатор паровой конверсии моноксида углерода, способ его приготовления и способ его использования |
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WO2008030140A2 true WO2008030140A2 (fr) | 2008-03-13 |
WO2008030140A3 WO2008030140A3 (fr) | 2008-04-24 |
WO2008030140A9 WO2008030140A9 (fr) | 2009-05-22 |
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PCT/RU2007/000470 WO2008030140A2 (fr) | 2006-09-06 | 2007-08-23 | Catalyseur de conversion de monoxyde de carbone par la vapeur, procédé de sa fabrication et procédé de son utilisation |
Country Status (8)
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US (1) | US20100196260A1 (ru) |
EP (1) | EP2077152A2 (ru) |
EA (1) | EA013871B1 (ru) |
EE (1) | EE200900023A (ru) |
LT (1) | LT5649B (ru) |
RU (1) | RU2314870C1 (ru) |
UA (1) | UA92263C2 (ru) |
WO (1) | WO2008030140A2 (ru) |
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RU2445160C1 (ru) * | 2011-04-05 | 2012-03-20 | Государственное образовательное учреждение высшего профессионального образования "Ивановский государственный химико-технологический университет" | Способ приготовления катализатора среднетемпературной конверсии оксида углерода водяным паром |
RU2677650C1 (ru) * | 2017-12-27 | 2019-01-18 | Акционерное общество "Ангарский завод катализаторов и органического синтеза" (АО "АЗКиОС") | Железохромовый катализатор для паровой конверсии оксида углерода |
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SU651838A1 (ru) | 1977-07-14 | 1979-03-15 | Предприятие П/Я В-2609 | Способ приготовлени катализатора дл конверсии окиси углерода |
RO100112A2 (ro) | 1987-12-03 | 1990-08-14 | Combinatul Chimic Craiova Jude | Procedeu de obtinere a unui catalizator pentru conversia oxidului de carbon |
SU1790064A1 (ru) | 1990-11-11 | 1996-05-20 | Кемеровское производственное объединение "Азот" | Способ получения катализатора для конверсии монооксида углерода |
BG62040B1 (bg) | 1995-05-05 | 1999-01-29 | Атанас Андреев | метод за получаване на желязо-хром-мед оксиден катализатор за конверсия на въглероден оксид с водна пара |
RU2170615C1 (ru) | 2000-08-24 | 2001-07-20 | Довганюк Владимир Федорович | Способ приготовления катализатора паровой конверсии оксида углерода и катализатор паровой конверсии оксида углерода |
RU2275963C2 (ru) | 2004-04-13 | 2006-05-10 | Общество с ограниченной ответственностью "Алвиго-М" | Способ приготовления железохромового катализатора (варианты) |
Family Cites Families (8)
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DE3318131A1 (de) * | 1983-05-18 | 1984-11-22 | Süd-Chemie AG, 8000 München | Eisenoxid-chromoxid-katalysator fuer die hochtemperatur-co-konvertierung |
EP0466338B1 (en) * | 1990-06-26 | 1995-12-20 | Toda Kogyo Corp. | Spindle-shaped magnetic iron based alloy particles and process for producing the same |
US5830425A (en) * | 1993-02-09 | 1998-11-03 | Sud-Chemie Ag | Chromium-free catalyst based on iron oxide for conversion of carbon monoxide |
RU2059430C1 (ru) * | 1993-04-30 | 1996-05-10 | Государственный научно-исследовательский и проектный институт азотной промышленности и продуктов органического синтеза | Катализатор для паровой конверсии оксида углерода |
GB9407512D0 (en) * | 1994-04-15 | 1994-06-08 | Ici Plc | Catalysts |
JPH10510524A (ja) * | 1994-12-14 | 1998-10-13 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | 大粒子の脱水素化触媒および方法 |
US7939463B1 (en) * | 2002-05-15 | 2011-05-10 | Sud-Chemie Inc. | Preparation of iron oxides |
US7037876B2 (en) * | 2002-05-15 | 2006-05-02 | Sud-Chemie Inc. | High temperature shift catalyst prepared with a purity iron precursor |
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2006
- 2006-09-06 RU RU2006132151/04A patent/RU2314870C1/ru not_active IP Right Cessation
-
2007
- 2007-08-23 WO PCT/RU2007/000470 patent/WO2008030140A2/ru active Application Filing
- 2007-08-23 UA UAA200903311A patent/UA92263C2/ru unknown
- 2007-08-23 EA EA200900346A patent/EA013871B1/ru not_active IP Right Cessation
- 2007-08-23 EE EEP200900023A patent/EE200900023A/xx unknown
- 2007-08-23 EP EP07834984A patent/EP2077152A2/en not_active Withdrawn
- 2007-08-23 US US12/439,871 patent/US20100196260A1/en not_active Abandoned
-
2009
- 2009-03-05 LT LT2009016A patent/LT5649B/lt not_active IP Right Cessation
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RU2170615C1 (ru) | 2000-08-24 | 2001-07-20 | Довганюк Владимир Федорович | Способ приготовления катализатора паровой конверсии оксида углерода и катализатор паровой конверсии оксида углерода |
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EE200900023A (et) | 2009-06-15 |
LT2009016A (en) | 2009-12-28 |
WO2008030140A9 (fr) | 2009-05-22 |
US20100196260A1 (en) | 2010-08-05 |
EP2077152A2 (en) | 2009-07-08 |
LT5649B (lt) | 2010-04-26 |
EA013871B1 (ru) | 2010-08-30 |
WO2008030140A3 (fr) | 2008-04-24 |
RU2314870C1 (ru) | 2008-01-20 |
EA200900346A1 (ru) | 2009-06-30 |
UA92263C2 (ru) | 2010-10-11 |
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