CN1780789A - Improved catalyst charge design - Google Patents
Improved catalyst charge design Download PDFInfo
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- CN1780789A CN1780789A CNA2004800115048A CN200480011504A CN1780789A CN 1780789 A CN1780789 A CN 1780789A CN A2004800115048 A CNA2004800115048 A CN A2004800115048A CN 200480011504 A CN200480011504 A CN 200480011504A CN 1780789 A CN1780789 A CN 1780789A
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- Prior art keywords
- catalyzer
- ammonia
- subordinate phase
- catalyst
- oxidation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 238000013461 design Methods 0.000 title claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 140
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 71
- 230000003647 oxidation Effects 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 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
- 239000007789 gas Substances 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 107
- 229910052697 platinum Inorganic materials 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 45
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 35
- 239000010948 rhodium Substances 0.000 claims description 31
- 238000005516 engineering process Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- 230000006378 damage Effects 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 231100000614 poison Toxicity 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 230000007096 poisonous effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002574 poison Substances 0.000 claims description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001272 nitrous oxide Substances 0.000 abstract description 5
- 238000006189 Andrussov oxidation reaction Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 30
- 229910052751 metal Inorganic materials 0.000 description 25
- 239000002184 metal Substances 0.000 description 25
- 229910001260 Pt alloy Inorganic materials 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 230000009466 transformation Effects 0.000 description 15
- -1 Co.Yet Chemical class 0.000 description 13
- 230000008859 change Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 150000003818 basic metals Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 238000009940 knitting Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910018921 CoO 3 Inorganic materials 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 238000009954 braiding Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000010285 flame spraying Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001915 proofreading effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018565 CuAl Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 1
- FCWGPGYKWPUQRE-UHFFFAOYSA-N [O-2].[O-2].[O-2].O.[Al+3].[La+3] Chemical compound [O-2].[O-2].[O-2].O.[Al+3].[La+3] FCWGPGYKWPUQRE-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/24—Nitric oxide (NO)
- C01B21/26—Preparation by catalytic or non-catalytic oxidation of ammonia
-
- 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
-
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
-
- B01J35/19—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/24—Nitric oxide (NO)
- C01B21/26—Preparation by catalytic or non-catalytic oxidation of ammonia
- C01B21/265—Preparation by catalytic or non-catalytic oxidation of ammonia characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
- C01C3/0216—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process characterised by the catalyst used
-
- 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
- B01J23/464—Rhodium
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Abstract
A catalyst charge for ammonia oxidation, including the Andrussow process, comprises a first stage ammonia oxidation catalyst capable of oxidising 20 to 99 % of designed ammonia throughput, to produce a first stage product gas comprising unreacted ammonia, oxygen and nitrogen oxides, and a second stage ammonia oxidation catalyst capable of completing the oxidation of unreacted ammonia. In its preferred embodiments, low levels of nitrous oxide are produced and extended campaign lengths may be seen. Improved performance on start-up is another benefit.
Description
The present invention relates to be suitable for the improvement catalyst charge design of the method for oxidation of ammonia.More particularly, the present invention relates to it is believed that technology and economic advantages two sections or multistage catalyst charge can be provided.
The nitric oxide that use atmospheric oxidation ammonia to be formed for nitric acid production, to be used for nitric acid fertilizer or explosive has just been established (Ostwald technology) since 20th century are early stage, and is extensive use of in the whole world.The technology of being established uses platinum or platinum alloy silk screen to serve as catalyzer, uses so that ammonia and airborne oxygen reaction.Produce peace De Luosuofu (Andrussow) technology of prussic acid and use substantially similar technology, and should be regarded as within the scope of the invention.The Pt silk screen provides with " bag " form at several silk screens of installation over each other usually.The successive silk screen can change in filament thickness, alloy composition and others.
In operating process, depend on processing condition, pressure for example, platinum physically or by evaporating from silk screen incurs loss more or less.Although platinum can accumulate in the water cooler parts of equipment, fact proved the recovery difficulty of platinum.Knownly comprise that one or more snugly fit into the palladium in catalyzer silk screen downstream (Pd) base and " capture (catchment) " or " collection " silk screen.A part of Pd itself captures silk screen and assembles the Pt of most of loss, although can replace from capture silk screen simultaneously.The Pd filament can be incorporated into and replace independently Pd capture silk screen in the second or the 3rd silk screen.Advised in the case, continued to use the Pt that is reclaimed to serve as catalyzer.Yet, advantageously show that compare with the Pt silk screen, the Pd silk screen can be with N in the recent period by the research work that the applicant did
2And/or N
2The content of O is mentioned to several times.A kind of mechanism may be:
It is not immediately clear N
2And N
2Whether the generation of O is result or the residual ammonia and the NO of the incomplete oxidation of residual ammonia
xThe result of reaction, but there are indications that residual ammonia is non-required.Because to N
2And N
2The influence of the overall yield of O, for example loss of the NO that causes by above-mentioned reaction, perhaps ammonia or NO
xTo N
2Conversion be non-required equally.
Except the present patent application people to the research and development of the knitting silk screen that replaces the braiding silk screen and introducing, seldom based on the progress that obtains in the past 20 years of the technology of Pt silk screen.
The base metal catalysts that the substantial contribution cost of Pt silk screen has caused being used for ammonia oxidation carries out some exploration.These catalyzer are usually based on oxide compound or the uhligite of cobalt compound such as Co.Yet, compare with Pt base silk screen, although best Co perovskite catalyst is except providing lower fund cost, also can provide some technical superioritys, as if but also having a large amount of shortcomings, mainly is that the murder by poisoning for sulphur compound in the atmosphere has significant susceptibility, therefore, its commercial large-scale application is very limited, just is applied to the public sphere in experimental mode up to now.
Existed in conjunction with platinum gauze and some proposals that contain the Co material.For example, chemical abstracts (Chemical Abstracts) 114:188430 has described the Co in conjunction with 1-2 Pt screen grid and downstream
3O
4Catalyzer.Think that this catalyzer demonstrates the selectivity of the maximum that under 350 ℃ NO is formed, this temperature is more much lower than the service temperature of conventional Pt silk screen catalyzer, and therefore is lower than the normal running temperature of ammonia oxidation equipment.Low temperature is for Co
3O
4Catalyzer is necessary, because known Co
3O
4Catalyzer experiences phase transformation under the temperature more than 850 ℃, form thereby cause in method for ammoxidation NO being had low optionally CoO.In addition, the document is not mentioned the N that is generated
2O content.WO99/64352 has described succeeded by the platinum gauze catalyzer that contains the Co catalyzer, wherein requires to reduce side reaction, for example formation of nitrous oxide.Yet the catalyst system of this combination only demonstrates the N of best 700ppm in lab setup
2O content, this patent application are abandoned and we do not recognize any commerciality of this technology.In fact, platinum or platinum alloy silk screen remain unique a kind of can being purchased and technical acceptable technology now on market.
Silk screen manufacturers be each equipment or for each the burner individual design on the equipment silk screen bag.Because transformation efficiency descends gradually along with going down of platinum gauze effect in use, therefore up-to-date engineering practice is: the design of silk screen bag is intended to the conversion of maximum possible under the operational condition of equipment.At last, when transformation efficiency was reduced to unacceptable level, equipment furnace life termination and catalyzer were replaced.Therefore design and a kind ofly wherein will deliberately be chosen as incomplete catalyst pack or catalyst charge is counterintuitive at the transformation efficiency on the first platinum metal catalysts element.Because incomplete conversion causes the residual ammonia in air-flow, therefore also can increase because of side reaction manufacturing N
2The chance of O.Really, it is extremely important to set up the loss of productive rate in this technology; The slippage of ammonia (slip) can cause producing N
2Side reaction, it must cause the loss of productive rate, and the slippage of ammonia also improves the possibility that can form explosive ammonium nitrate in the catalyzer downstream.
The oxidation furnaces operator and the catalyst charge planner of ammonia still need improved selection, and this is not only the consideration for the fund cost that reduces platinum or platinum alloy silk screen catalyzer, still in order to reduce the loss in the catalyzer of valuable platinum from use.We think, purpose of the present invention (we think in preferred embodiments and when operating under optimum condition, one or more purposes of the present invention can be met) can be expressed as:
The high conversion of ammonia and low N
2O produces;
Provide on one or more in similar pressure drop, productive rate and life-span (" campaign ") or one or more in pressure drop, productive rate and life-span (" campaign ") improvement is provided;
Can reduce the consumption of platinum metals; With
Has improved operation at startup and disengagement phase.
Hereinafter abbreviation " PGM " refers to " platinum metals " sometimes.
Therefore, the invention provides the method for ammoxidation that comprises peace De Luosuofu technology, this method comprises making and contains ammonia source (for example ammonia itself or from the waste gas of urea equipment) and the unstripped gas of oxygen source passes through catalyzer, and under 700-1000 ℃ temperature, operate, it is characterized in that the fs catalyzer (described catalyzer comprise the platinum metal catalysts of high surface area) of unstripped gas by being used for ammonia oxidation, to produce nitrogen-containing oxide, the fs product of oxygen and unreacted ammonia and oxygen source, and described fs product combines use with the subordinate phase catalyzer that is used for ammonia oxidation, with it is characterized in that ammonia oxidation is not to finish in the process of unstripped gas by the fs catalyzer, but in the process of fs product, finish by the subordinate phase catalyzer.Under preferred operational condition, there is slippage from a small amount of ammonia of subordinate phase catalyzer, in the product of subordinate phase, have low N simultaneously
2O produces.
Certainly, be appreciated that the first and second stage catalyst differences.
Can predict, under the ideal condition, method of the present invention can provide the campaign of increase.Other potential advantage of the present invention comprises the running cost of the reduction that causes because of the precious metal cost that reduces and reduces the improved environmental performance that causes because of the total emissions of by product.
In second aspect, the invention provides the method that is designed for the catalyst charge of the ammonia oxidation that comprises peace De Luosuofu technology for the specific feed that contains ammonia source and oxygen source, this method comprises: incorporate first upstream catalyst that is used for ammonia oxidation into, described catalyzer comprises the platinum metal catalysts of abundant amount and the sufficient high surface area of physical arrangement, so that, thereby produce the fs product of the design that contains oxynitride, residual ammonia and oxygen source with the ammonia incomplete amount (from 20% until 99%) the oxidation feed; And incorporate second ammoxidation catalyst that is installed on the first catalyzer downstream into, described subordinate phase catalyzer exists with the excessive amount and the physical arrangement of the residual ammonia in the fs product that is used for the oxidation design.In preferred embodiments, the charging of design catalyzer in use has significant N to guarantee the subordinate phase catalyzer
2O destroys active and the temperature in subordinate phase surpasses 50% N
2O is destroyed, is preferably greater than 80% N
2O is destroyed, the temperature more preferably greater than 90% when destroyed.
The present invention also provides the catalyst charge that is used for ammonia oxidation according to the second aspect present invention design.Further, the invention provides the purposes of catalyst charge in the high yield oxidizing process in prolongation campaign.The furnace life of this productive rate and prolongation is separately for Pt routine, state-of-the-art technology or Pt alloy silk screen catalyst pack.
Catalyst charge of the present invention is desirably the direct conventional silk screen bag of replacing.The size and the processing requirements that depend on burner can be built into the charging of catalyzer single feed unit, and perhaps by a plurality of parts, for example segment, hinged or link segment or analogue make up.Ideal situation is that the charging of catalyzer (no matter single feed unit is still cut apart according to certain mode) all integrally comprises all components.
Should be appreciated that when determining first and second stage catalysts, the present invention includes multiple variant, as comprise and be positioned at before the basic two catalyst layers, insert therebetween or one or more layers other layer afterwards, even other wherein such layer has catalytic effect.
Advantage of the present invention is not need to change conventional operating parameters, as pressure, preheating and turnout (" working load ") to obtain at least some advantages of the present invention.It is desirable to, the order of magnitude of total gas hourly space velocity of first and second stage catalysts (" GHSV ") is 100000hr
-1, be 50000-200000hr suitably
-1
The appropriate designs of fs catalyzer provides the transformation efficiency of 20-99% under normal operating condition, the transformation efficiency of preferred 60-99%, more preferably＞75%, 50-70% especially, but in some embodiments, may wish in the fs, to transform the ammonia of 80-95%.The present invention provides ideally and contains the N less than 1600ppm
2O preferably less than 600ppm, is more preferably less than 500ppm, for example the N in the 100-200ppm scope
2The subordinate phase product of O.The subordinate phase catalyzer is to N therein
2O destroys and especially effectively or wherein has independently downstream N
2O destroys under the situation of catalyzer, and we find that in fact the many gaseous fractions in method for ammoxidation suppress N
2O destroys.Therefore, importantly selecting to carry out representative test before this catalyzer.
Of the present invention aspect all in, the fs catalyzer is the platinum metals ammoxidation catalyst of high surface area, preferred Pt or Pt alloy are as Pt5Rh or Pt10Rh, or other conventional Pt alloy.Selected actual alloy is not crucial for purposes of the invention and it can comprise other alloying component, for example Co or Ir.Pt or Pt alloy can be easily as filament form knitting or the braiding silk screen, for example tensile filament or wire rod perhaps can be the bar belt shapes and/or serve as non-braid.Successive silk screen or layer can comprise the mixture of different-alloy or metal, different-alloy or metal, and/or the filament of different size.This silk screen or layer can be made in a conventional manner.The fs catalyzer can be or comprise " pad " by the knitting silk screen of three-dimensional knit preparation, giving enhanced thickness, and has the filament circle of the degree of depth that extends through pad.
Yet; the present invention includes the catalyzer that can supply alternate high surface area, low pressure drop; wherein catalyst Pt or Pt alloy are carried on basic metal or the ceramic monolith; described ceramic monolith can be the filament shape, be bead or shaped form; be metal or ceramic formula or be monolith forms, as metal or ceramic honeycomb, network, static mixer or its complex compound.Pt or Pt alloy catalyst itself are supported on the oxidation particle, perhaps it can be deposited on the oxide covering on metal or the ceramic monolith.This oxidation particle or carrier are established in catalyst technology well.Compare with the silk screen catalyzer that screen net structure integrity wherein may be had a strong impact on because of the loss from the Pt of filament, the catalyzer of this carrying can provide advantage aspect the campaign.
May receive publicity with Pt or Pt alloy deposition to carrier, for example the approach on pottery or the metal comprises: flame spraying or vacuum or air plasma spraying, it produces the porous settled layer of high surface area.Certainly, also can use on carrier depositing noble metal salt or complex compound and burning or reduction with metallic other routine techniques.Can use this metal spray coating technique, the Pt layer of deposition high surface area on Pt or Pt alloy silk screen; This one deck can further improve the igniting of catalyzer for startup.
The present invention allows to reduce the Pt that is used for Specific Design Work or the total mass of Pt alloy.This " saving " for precious metal may have remarkable economical to device operator and be worth.Especially be under the situation of the granular lanthanum cerium cobaltic trioxide catalyzer bed described in WO98/28073 at the subordinate phase ammoxidation catalyst, we find, in catalyst combination, comprise before the cobaltic trioxide catalyzer, replaceable employed＞20 weight %, preferred＞30 weight %, and the platinum alloy silk screen of weight % and be unlikely to cause the loss of NO efficient most preferably＞40 also can reduce to the content of nitrous oxide comprise below 50% of nitrous oxide content that is obtained before the catalyzer simultaneously.Yet some preliminary study also shows: specific advantage can come from maximum 90% amount of the weight of the catalyst pack that silk screen is only arranged of routine uses Pt or Pt alloy and subordinate phase catalyzer relatively in a small amount.
Can from multiple catalyzer, select the subordinate phase catalyzer.On the one hand, the subordinate phase catalyzer can be the platinum metal catalysts that can be carried, catalyst based as Rh base and/or Ir, perhaps can be (maybe can comprise) basic metal or alkalimetal oxide, especially when basic metal is transition metal or rare earth metal, and can comprise in for example iron, nickel, copper, cobalt, the manganese one or more, perhaps can be platinum, palladium or the ruthenium of (maybe can comprise) silver or carrying.Second catalyzer can be the mixture of one or more basic metal and one or more precious metal.For example, initial test shows and disperses and be carried on the oxidation that Rh catalyzer on the preformed catalyst carrier can effectively be finished residual ammonia, also can reduce non-required side reaction simultaneously.Although this kind Rh catalyzer can comprise other component or promotor, as other platinum metal catalysts, initial sign shows that but this subordinate phase catalyzer does not preferably contain catalysis or promotes component, and is made up of the Rh on its carrier basically.
The suitable catalyzer of being used as the subordinate phase catalyzer comprises and contains cobalt and non-ammoxidation catalyst and these mixture of catalysts that contain cobalt.Be included in PGM catalyzer, La that Au, carrying are arranged in these catalyzer
2O
3, randomly have a micro-Li
2The Co of O
3O
4, some spinel such as CoAl
2O
4, the ABO of some replacement
3Material, some uhligite such as LaCoO
3(it part that comprises wherein that the part of having carried out the A-site with for example Sr or Ce replaces (for example 20mol%) at most or carried out beta-position point with for example Cu replaces the LaCoO of (for example maximum 50mol%)
3), La
2CoO
4, be carried on the Co on aluminum oxide, Thorotrast, cerium dioxide, zinc oxide or the calcium oxide
3O
4, promote and randomly contain the Co of the oxide compound of one or more Mn, Fe, Mg, Cr or Nb by rare earth element or thorium
3O
4Or Bi
2O
3And has the CoO of the Pt on carrier
x
The subordinate phase catalyzer can be the ammoxidation catalyst that contains cobalt, particularly most preferably the blended Co described in WO98/28073 and one or more rare earth oxides.
Under the situation of the catalyzer that carries, can incorporate dipping and combustion step usually into and prepare the catalyzer of carrying in the mode of routine.The catalyzer portability of this carrying is dispersed in whole supported catalyst, perhaps can load on the top layer, in the micropore or around the micropore.Yet, do not think that the deposition method of catalyzer is crucial for purposes of the invention.We wish to mention use flame spraying coating process or use vacuum or air plasma to spray the metallize, thus the possibility of metal refining, particularly platinum metals.This method can the pottery or even metallic catalyst carrier on the deposition high surface area (porous) metal level.Can use similar techniques deposition alkalimetal oxide, especially when in the presence of oxygen or air, spraying.
Can establish the appropriate catalyst load by the experiment under the specified conditions, but for platinum metals (wherein Rh is selected metal), be generally 0.1-10wt%, be more typically 0.3-5wt%, be most suitably 0.5-1.5wt%, with for basic metal, be generally 1-20wt%, be more typically 5-15wt%.Base metal catalysts can comprise the promotor of trace.
Support of the catalyst can provide any refractory metal or the ceramic monolith of competent surface-area and low pressure drop.Suitable metallic carrier comprises heat-stable stainless steel, and it can be incorporated the passivation component into or can improve in the fusible component of catalyzer; Can consider to be called the alloy of " Fecralloy ".Suitable pottery comprises based on those of aluminum oxide, aluminium oxide-silicon oxide, trichroite, zirconium white, zirconium mullite or its analogue.For Rh subordinate phase catalyzer, it seems that aluminum oxide be preferred carrier.Although metallic carrier does not have significant inherent porosity degree usually,, can be coated with (washcoat coating) by wash coat and improve the ability that carrier carries the dispersed catalyst of high surface area unless be the metal foam body form.Suitable wash coat and coating technique be skilled those skilled in the art obtainable and can comprise in aluminum oxide, zirconium white, cerium dioxide, aluminium oxide-silicon oxide, the lanthanum trioxide-aluminum oxide one or more and composition thereof.Known according to automatic emission control catalyst, wash coat can not only help to increase the surface-area (being included in the high temperatures wash coat) of catalyzer, and helps more effectively to use catalyzer.Therefore, wash coat can comprise other component, and these other components are one or more metal oxides or mixed metal oxide normally, particularly from the metal oxide or the mixed metal oxide of transition metal or rare earth metal.
Shaping carrier is the ceramic monolith pellet or the extrudate of moulding easily, as right cylinder or annular, porous cylindrical body or leafy formula carrier, or other low shaping carrier of the pressure drop of high surface area.Shaping carrier can be the single blocks of high surface area, as single flow honeycomb or foams, perhaps even pottery braiding or non-woven fabric.At present preferred carrier is known " Raschig ring ", and it is to have desired size, for example a lot of holes of diameter 5-40mm.Carrier can or be coated with selected catalyst composition dipping.
Can use the subordinate phase catalyzer separately or use with non-catalytic material or with the material mixing of carrying other catalyzer.It can be carried (deposition) on the monolith catalyst carrier, perhaps, then be carried on the metal grill or between metal grill if it is granular.
Can there be the middle layer that places between first and second stage catalysts.It can be an inert, serves as one or both the carrier in the catalyzer, perhaps has function.The function middle layer comprises those that absorb gaseous fraction, perhaps gaseous fraction is changed into inertia or be inertia or harmless relatively product with respect to fs product or subordinate phase product, perhaps change into the product that product NO maybe can change into NO, perhaps change into those layers that can in the subordinate phase reaction, not cause the product of non-required side reaction.For example, the subordinate phase catalyzer is to for example atmospheric constituent, as sulphur or other component (Fe, Se) sensitivity of finding in the gas feed, for example poisons, and then absorption agent or getter can be served as in the middle layer.About this point, we comprise the instruction of we pendent UK Patent Application No.0309747.4 in the present invention.
Optionally, other component can be incorporated in catalyst charge or the bag as the layer before the fs and after the subordinate phase.These layers as the situation in middle layer, can be inertia or have function.Functional layer can be improved the campaign or improve total reaction mass in some respects.Except the physical layer of catalyst charge of the present invention, the present invention also can comprise the additional step that perhaps is far from catalyst charge itself, and this step is improved the others of efficient or performance.For example, sulphur removal can be considered as the oxide-based subordinate phase catalyzer of LaCo favourablely, and the example of suitable sulphur removal protection bed comprises lanthanum trioxide or similar oxide compound.
Although first and second stage catalysts are also inequality, but still can conceive one of them or another is carried on carrier such as the single blocks, wherein the autocatalyst coating technique with state-of-the-art technology is applied on the described single blocks, obtains different catalyst component band applications and is added to " strip " catalyzer on the same single blocks.Certainly, also can use first and second stage catalysts and this structure that are deposited on the single single blocks should be regarded as dropping within the present invention.
The present invention has considered many embodiments of catalyst charge etc., and all these are regarded as according to the present invention, and have hereinafter listed described embodiment with auxiliary reader understanding.Be appreciated that some embodiments may overlap, perhaps may be the subclass of another embodiment and it is also understood that the present invention should not be limited to the listed content of this inventory.
(it can additionally suppress N for embodiment A:Pt or Pt alloy fs catalyzer and subordinate phase ammoxidation catalyst
2O forms or with N
2O is catalytically converted into harmless relatively by product), especially wherein: (i) the fs catalyzer is the Pt or the Pt alloy of carrying, with the subordinate phase catalyzer be that Co is catalyst based, and/or method of the present invention incorporate into by the fs catalyzer through design and specified ammonia slippage, perhaps (ii) in conjunction with additional layer or incorporate N into
2O destroys the non-Co base subordinate phase catalyzer of catalyzer.Embodiment A (i) can comprise ideally through design makes the fs catalyzer of the ammonia react of 90-99% in the unstripped gas with operation, and in conjunction with the subordinate phase catalyzer of oxidized residual ammonia, produces the N of lower aq simultaneously
2O is ideally less than 500ppm, more desirably less than the N of 200ppm
2O.
Embodiment B: non-silk screen PGM fs catalyzer, for example wherein the fs catalyzer be the Pt of carrying or Pt alloy catalyst and wherein the subordinate phase catalyzer to destroying N
2O has high reactivity.
The platinum metals subordinate phase catalyzer of embodiment C:Pt or Pt alloy fs catalyzer and carrying.
Embodiment D:Pt or Pt alloy fs catalyzer, in fs catalyzer downstream part or middle layer in subordinate phase catalyzer upstream portion or extra component; especially wherein middle layer or additional component are served as the protection bed; in conjunction with the subordinate phase catalyzer, to remove or to reduce the effect of sulphur component.The subordinate phase catalyzer may suitably be the Co based perovskite catalysts.
Embodiment E: first and second stage catalysts that randomly have middle layer or bed, it is designed and operates, so that the ammonia slippage from the fs is 20-99wt%, preferred 50-70wt% and particularly the ammonia slippage of initial designs therein can ignore and the subordinate phase product in N
2O content is less than 1600ppm, preferably under the situation less than 500ppm.
Embodiment F:Pt or Pt alloy fs catalyzer and non-Co base subordinate phase catalyzer is combined in subordinate phase catalyzer downstream as bed/layer or incorporate N in the subordinate phase catalyzer into
2O destroys catalyzer.For example, the subordinate phase catalyzer is the platinum metal catalysts and the N of carrying
2It is that Co is catalyst based that O destroys catalyzer.This embodiment is three-tier system basically, provable for high yield system and technology especially favourable.
Embodiment G: first and second stage catalysts, capture component in conjunction with the Pt that for example is installed in subordinate phase catalyzer upstream or downstream, the Pd base captures silk screen suitably.We are surprisingly found out that, can help to make N although Pd captures silk screen
2O, but ammonia from fs catalyzer slippage to the present invention of subordinate phase catalyzer, compare with Pd is captured to place between first and second stage catalysts, the Pd silk screen is placed the below, promptly N can be reduced in the downstream of subordinate phase catalyzer
2The generation of O.It is believed that as if the downstream that the silk screen of any Pd of containing is placed the Pt catalyzer then it will have Pt capture effect.Yet, capture silk screen and preferably contain＞palladium of 10wt%, more preferably＞40wt%.Particularly＞70wt%.The capture of Pd base can comprise trace, and (≤10wt%) a kind of or alloy element is as Ni, Au, Co etc. with also can contain platinum.Typical capture silk screen is 5%Ni: 95%Pd.Preferred preparation Pd captures silk screen to reduce N
2The rhodium of O content and comprising＜5wt%.The preferred silk screen that captures comprises palladium, platinum and rhodium.This silk screen can comprise 8-25wt%, the platinum of preferred 10-20wt%.The example of suitable capture web material comprises＞and the palladium of 92wt%, the rhodium of 2-4wt% and surplus are platinum, and the palladium of perhaps substituting 82-83wt%, the rhodium of 2.5-3.5wt% and surplus are platinum.
Embodiment H: the mixture of catalysts of the subordinate phase catalyzer of fs catalyzer and coating platinum metals or subordinate phase catalyzer and platinum metals carrying.
Embodiment I: fs catalyzer and subordinate phase catalyzer, it has the middle layer, in particular for the protection bed of anti-sulphur, and has specific N
2O destroys the extra bed or the layer in subordinate phase catalyzer downstream of catalyzer.
Embodiment J: have catalyst charge at the protection bed of fs catalyzer upstream.Protection bed can especially be removed poisonous substance, no matter is to the poisonous substance of Pt or to the poisonous substance of subordinate phase catalyzer.Therefore, the protection bed can be removed such as Fe, Si, Cl, Pb, As and materials such as S, P.
Embodiment K: fs catalyzer and non-Co base subordinate phase catalyzer, in conjunction with two downstream bed, especially N
2O destroys catalyzer and captures bed.For example, the fs catalyzer, based on the subordinate phase catalyzer of platinum metals, Co base N
2O destroys catalyzer and the Pd silk screen captures silk screen.
In general, show, obtain high N more than 850 ℃ about for reaching the test that the present invention carries out
2The O transformation efficiency (and use best subordinate phase catalyzer, then this temperature can be lower).This shows active fs catalyzer of preferred selection and design and places catalyzer, is used to destroy N so that produce to be higher than in subordinate phase
2The temperature of O ignition temperature, at least 700 ℃ suitably, preferably at least 850 ℃.Therefore, seem to wish to obtain competent heat release and be used for effectively destroying N in subordinate phase at the fs oxidation ammonia of (volume promptly＞50%) at high proportion
2O.
Now embodiment and the full-scale equipment test embodiment in conjunction with laboratory scale embodiment, interim test scale describes the present invention.
Embodiment 1: the preparation of subordinate phase catalyst sample:
A. use conventional catalyst preparation technology, the Rh of 0.1wt% is impregnated in the Raschig ring (for example available from Saint-Gobain Norpro) of commercial porous gama-alumina, with sample drying and burning, and sample pulverized and sieve into the particle of size range between 250 to 355 microns;
B. the pulverizing sample of Rh of the 0.2wt% on the identical ring among preparation in a similar manner and the sample A;
C. use the washcoat coating technique of standard, be applied to the Rh of the atomizing 0.5wt% on the aluminium oxide catalyst on the ring at the Alpha-alumina of height macropore pottery Raschig, as sample A with sample drying, burning and pulverizing.The final load of Rh is 0.03wt% on coated product.
Use the knitting silk screen of single 95%Pt5%Rh, 10%NH in the catalytic air
3Feedstream, produce and to contain NO
x, N
2O, steam, nitrogen and unreacted NH
3Fs product with oxygen.The fs product directly is passed in second reactor that contains subordinate phase catalyst A, B and C.This equipment makes the temperature on the subordinate phase catalyzer to change in 450 to 800 ℃ scope and can carry out N to the composition in the exhaust jet stream
2O analyzes, and (transformation efficiency is represented N to the results are shown in accompanying drawing 1
2The transformation efficiency of O).A compares with sample, and the sample B of higher load demonstrates higher transformation efficiency, and the transformation efficiency result of sample C is lower, and this shows in order to obtain comparable result need use bigger amount.
Embodiment 2:
In the parallel reactor of high production, test in a large number being carried in various being purchased on the various metals going up and make in a usual manner with patentability oxide carrier (comprising the mixed oxide carrier) or the metal oxide catalyst.To N
2The test that O decomposes draws to draw a conclusion:
1. Cheng Zai alkalimetal oxide catalyzer has low activity, although Ni, preferably at CeO
2On Ni have maximum activity;
2. for the suitable PGM catalyzer of load, Rh＞Pd＞Ir＞＞Ru or Pt;
3. compare with single PGM metal catalyst, mixing the PGM catalyzer provides seldom even negative benefit;
4. add other metal and tend to the performance of deterioration Rh;
5.Rh the absolute activity of catalyzer is decided on carrier, wherein aluminum oxide or cerium dioxide/alumina-zirconia are best; With
6. under " height " load (＞5%), Pt and Ru demonstrate rational activity.
Embodiment 3
Will be from the most highly active N of embodiment 2
2O destroys catalyzer, promptly the 0.5%Rh on the aluminum oxide with comprising NO according to the LaCeCo oxide catalyst of WO98/28073 preparation (be " fresh " and at 1000 ℃ of catalyzer that in air, carry out hydrothermal aging)
x, oxygen and water vapour exemplary gases in, compare at various temperatures.Fresh Rh catalyzer demonstrates best performance from about 500 ℃, is issued to 100% transformation efficiency at about 800 ℃, yet, even aged LaCeCo oxide catalyst also demonstrates the transformation efficiency greater than 90% under 900 ℃.
Embodiment 4
In the laboratory, the catalyzer from the preferred carrying of previous embodiment is carried out the ammonia oxidation test, measure and change into NO
xTransformation efficiency and change into N
2The transformation efficiency of O these two.Following table shows the result:
Result according to following table (ignores N
2The destruction activity of O) separately with regard to ammonia oxidation, the LaCeCo oxide compound of WO98/28073 demonstrates good ammonia oxidation performance and lower N
2O produces, and is better than the platinum metal catalysts of the carrying tested.The activity of platinum metals be used for N
2What O decomposed is active opposite, that is to say: Pt＞Pd＞Rh.Because for NO
xAnd N
2The selectivity of O is identical, so Pd can produce high-load N
2O.
| Catalyzer | Change into NO xTransformation efficiency | Change into N 2The transformation efficiency of O | Amount to |
| The blank Raschig 2Pt1Rh/ of Rh on the Pt aluminium oxide Raschig on Rh/ ceria-zirconia Rh/ ceria-Zirconia-alumina Rh/ zirconia Pt/ ceria-zirconia Pt/ ceria-Zirconia- |
52 24 34 42 44 45 28 79 71 27 38 51 | 10 13 6 22 21 22 25 10 12 22 17 16 | 62 37 41 64 64 67 53 89 83 49 55 67 |
Embodiment 5
Relatively by 6 catalyst charges of forming available from the commercial knitted catalysis agent silk screen of " Prolok " 95%Pt5%Rh of Johnson Matthey of the present invention (as being installed on the fs catalyzer (" the present invention ") that serves as the subordinate phase catalyzer) and identical 6 " Prolok " silk screens (" comparison thing ") bed according to the 50mm bed upstream of the 3mm cylindrical pellets of the LaCeCo oxide compound of WO98/28073.(200 ℃ of preheating temperatures under the condition of the commercial ammonia oxidation equipment of simulation; 4.5bar absolute pressure under air in contain 10.5%NH
3And the feed flow velocity is 7.7m
3/ h), in being the tubular reactor of 40mm, internal diameter carries out test in 30 days.
Use infrared rays and ultraviolet ray-visible light assay method are measured [NO], [NO in the desciccate gas
2] and [N
2O] concentration.Use [the NH in the infra-red spectrometry measurement gaseous feed
3] concentration.Use following formula to calculate the efficient of catalyzer based on nitrogen budgets: to change into NO
XEfficient={ [NO]+[N
2O] }/[NH
3], and the molecular volume of proofreading and correct in the reaction changes.
Can derive following conclusion according to result of study:
Igniting: the present invention is much better than the comparison thing;
Efficient: the present invention equals the comparison thing;
N
2The generation of O: the present invention is frequently than what a order of magnitude of thing;
SO
2Patience: the present invention has same resistance with thing relatively and (added 50ppb SO from the 24th day
2*)
N
2The destruction of O: raw material, added 100ppm from the 21st day, for purposes of the invention, all N
2O is all destroyed; And concerning comparing thing, destruction can be ignored
* typical SO on equipment
2Content is 5ppb, so this test has the effect of acceleration.
Embodiment 6
Except ammonia concentration is 10%+/-0.5%, under the condition identical, carry out a pair of 30 days test in addition, but charging of the present invention only is made up of the identical subordinate phase catalyst bed of 3 Prolok silk screens and 25mm thickness with embodiment 5.
Conclusion is:
Igniting: the present invention is better than the comparison thing;
Efficient: relatively thing is than efficient of the present invention high about 1%;
N
2The generation of O: the present invention is frequently than what a order of magnitude of thing;
N
2The destruction of O: introduced 100ppm N at the 11st day, the 12nd day
2O; It is about 60% that the present invention destroys, and relatively to destroy be 0 to thing;
SO
2Patience: any efficient in two kinds is not all had influence, but a N of the present invention
2O content baseline from 180ppm in 11 days rises to about 800ppm; To comparing the N of thing
2O content is influence not;
SO
2Recovery: the N that is recovered to 700ppm
2O content.
Embodiment 7
On identical device, use identical comparison catalyzer, and use and the 4 slice Prolok silk screens of thickness as the identical subordinate phase catalyzer combination of 50mm, carry out a pair of test in addition.The business machine that the test conditions simulation is different: absolute pressure is 10bar; Flow velocity is 10m
3/ hr; Ammonia concentration be 10% and preheating temperature be 237 ℃.
Conclusion is:
Igniting: the present invention is better than the comparison thing;
Efficient: relatively thing is than efficient of the present invention high about 1.5%;
N
2The generation of O: the present invention is frequently than what a order of magnitude of thing;
N
2The destruction of O: played introducing 100ppm at the 18th day; Relatively thing does not have effect, and the present invention destroys 100%;
SO
2Patience: introduced 50ppb SO at the 19th day
2, efficient there is not influence, but N
2O content slowly increases.
Embodiment 8
Under the condition identical, carry out a pair of 24 days test in addition with embodiment 5, different is that the comparison thing is made up of 1 Prolok silk screen on the alumina granules of 5mm, and embodiments of the invention are made up of 1 Prolok silk screen on the LaCeCo of 50mm oxide particle.These constructive proofs, the remarkable minimizing and the more high-load ammonia of PGM catalyst cupport slide onto in the subordinate phase catalyzer.
Conclusion is:
Efficient: efficiency ratio of the present invention is object height about 12% relatively;
N
2The generation of O: the present invention is frequently than the low order of magnitude of thing;
Do not measure N
2The destruction of O and SO
2Patience.
Embodiment 9
Method according to embodiment 8 is carried out a pair of test in addition, and 2 Pd that wherein will contain the 5wt%Ni-Pd alloy capture the LaCeCoO that is placed on single Prolok sheet material and 50mm
3Between the pellet (layout 1) or be placed on LaCeCoO
3(being the downstream) (layout 2) after the pellet.
Conclusion is:
Efficient: layout 2 is than layout 1 high about 4%;
N
2The generation of O: layout 2＞layout 1, but the two is all frequently than the low order of magnitude of thing;
N
2The destruction of O: do not measure;
SO
2Patience: layout 2＞layout 1.
Make ammonia and air in internal diameter is the tubulose laboratory reaction device of 28mm, oxidation take place.Reaction conditions is as follows:
Flow velocity: 3.3 ± 0.1m
3The air of/hr-ammonia mixture
Form: 10.5 ± 0.3%NH
3
Preheating temperature: 203 ℃
Pressure and exhaust temperature change and provide in following table.
Use spectrometer analysis NO, NO in product gas
2And N
2The composition of O, and Ar is as the inertia internal standard substance.Use [the NH of infrared light assay method measurement in gaseous feed
3] concentration.Use Ar as internal standard substance, use following formula: change into NO
xTransformation efficiency={ [NO]+[NO
2]/[NH
3], and the molecular volume of proofreading and correct in reaction changes the efficient of calculating catalyzer.
Be placed on that catalyzer layout in the reactor comprises or:
A) at the La of 50mm
0.8Ce
0.2CoO
3Thickness on the pellet (3mm) is 76 microns individual layer platinum-rhodium wire net (NitroLok 95: 5 is available from Johnson Matthey plc), perhaps
B) repetition of the embodiment 10a of the two-layer platinum-rhodium wire net of use, perhaps
C) be that thickness on the 0.5wt%Rh on the aluminium oxide catalyst of 25mm is 76 microns individual layer platinum-rhodium wire net at thickness, perhaps according to the preparation of the method for embodiment 1
D) repetition of embodiment 10c, wherein with Pd: Ni is that 95: 5 two-layer capture silk screen is placed on Pt and Rh/Al
2O
3Between the oxide catalyst.
Tested 15-21 hour.In following table, listed the gained result in 3-5 hour under steady state conditions:
| Embodiment | Pressure (bar) | Exhaust temperature (℃) | NO xEfficient (%) | N 2The generation of O |
| 10a | 5.2 | 838 | 85 | 153 |
| 10b | 5.3 | 831 | 84 | 232 |
| 10c | 5.3 | 896 | 65 | 1209 |
| 10d | 5.7 | 865 | 85 | 1151 |
As a comparison, similarly using identical equipment under the condition, 4 layers of platinum-rhodium wire net can make the N of 2345ppm
2O (under 90.0% efficient).In addition, be placed on individual layer platinum-rhodium wire 50mm particulate state CuAl off the net
2O
4The efficient that (nitrous oxide decomposition catalyst) provides only is 58%, and N
2O is produced as 278ppm.Therefore, catalyst combination of the present invention can have high-level efficiency and lower N simultaneously concurrently
2The generation of O, wherein the quantity of platinum significantly descends, thereby causes the slippage of ammonia between first and second stage catalysts.
Embodiment 11
Use and contain gross weight (it is 92: 8 silk screen (can be used as Nitrolok 800 and Nitrolok 760 is available commercially from JohnsonMatthey PLC) by 6 Pt: Rh as the fs catalyzer of 24.25kg, 4 Pt: Rh are that silk screen (can be used as Prolok 750 and be available commercially from Johnson Matthey PLC) and 1 Pt: Rh: Pd of 95: 5 is that 90: 5: 5 (can be used as Nitrolok820 and be available commercially from Johnson Matthey PLC) formed) and weight be that (it is the particulate state La of 100mm by the thickness according to 4 cellular type pellet form of WO98/28073 preparation for the subordinate phase catalyzer of 480kg
1-xCe
xCoO
3The bed composition) catalyst combination is carried out the test of full-scale equipment.
The operating parameters of equipment is as described below:
| Operational condition | Numerical value | Unit |
| The equipment capacity air flow quantity, the ratio preheating temperature working pressure catalyst temperature burner diameter of (adding before the catalyzer) ammonia, (when having catalyzer) | 750 132321 10.5 237 10.0 920 1.94 | Metric ton/day 100%HNO 3 Nm 3/h mol％((NH 3)/(NH 3+ air)) ℃ Bar ℃ rice |
The result is as described below:
Initial efficient is 94%, its single phase that can use with the typical case only the technology of Pt silk screen compare favourably.
Stopping efficient is 90% (is 90 days meters according to designing the campaign): average efficiency is 92% (in the time of 90 days).
With the single phase average N in the waste gas in the technology of Pt silk screen only
2O is that 463ppm compares, according to the present invention, and the average N in the waste gas
2O is 154ppm.Therefore, the present invention has made N
2The generation of O descends＞50%.Single phase only the processing requirement of Pt silk screen use the heavy platinum catalyst of extra 15kg, this shows that the present invention can greatly save the platinum in the catalyst combination.Compare with 90 days PRACTICE OF DESIGN, actual duration of test runs is 112 days (average efficiency in the time of 112 days is 91%).Therefore, the present invention can make the campaign increase＞20%.After this test, check silk screen show ammonia from fs catalyzer slippage to cobalt catalyst.Weight loss by platinum catalyst is calculated, and determines that whole ammonia oxidations of 29.3% occur in La
1-xCe
xCoO
3On the catalyzer.
Claims (14)
1. one kind comprises the method for ammoxidation of pacifying De Luosuofu technology, this method comprises makes the unstripped gas that contains ammonia source and oxygen source mixture pass through catalyzer, and under 700-1000 ℃ temperature, operate, it is characterized in that unstripped gas is by being used for the fs catalyzer of ammonia oxidation, described catalyzer comprises the platinum metal catalysts of high surface area, to produce nitrogen-containing oxide, the fs product of oxygen and unreacted ammonia and oxygen source, and described fs product combines use with the subordinate phase catalyzer that is used for ammonia oxidation, with it is characterized in that ammonia oxidation is not to finish in the process of unstripped gas by the fs catalyzer, but in the process of fs product by the subordinate phase catalyzer, finish, comprise the subordinate phase product of the negligible unreacted ammonia of quantity with generation.
2. the process of claim 1 wherein that the described method of operation contains less than 1600ppm with generation, preferably less than 500ppm N
2The subordinate phase product of O.
3. claim 1 or 2 method are wherein operated described method and be not less than 700 ℃ temperature to set up in subordinate phase.
4. any one method of claim 1-3, wherein operate described method so that in the feed ammonia slippage of 1-80% volume by the fs catalyzer, to finish the oxidation on the subordinate phase catalyzer.
5. the method for claim 4, wherein the slippage of ammonia is greater than 25% volume.
6. the method for aforementioned any one claim, this method comprise using and be selected from following one or more additional stage: absorbing catalyst poisonous substance or convert it into harmless form absorbs or collects the platinum that shifts from the fs catalyzer; Be present in the subordinate phase or the N in the subordinate phase product with catalysis destruction
2O.
7. be designed for the method for the catalyst charge of the ammonia oxidation that comprises peace De Luosuofu technology for the specific feed that contains ammonia source and oxygen source, this method comprises: incorporate first upstream catalyst that is used for ammonia oxidation into, described catalyzer comprises the platinum metal catalysts of abundant amount and the sufficient high surface area of physical arrangement, so that with incomplete amount, ammonia in the as many as 99% oxidation feed, thus the fs product of the design that contains oxynitride, ammonia and oxygen source produced; And incorporate second ammoxidation catalyst that is installed on the first catalyzer downstream into, described subordinate phase catalyzer exists with the excessive amount and the physical arrangement of the residual ammonia in the fs product that is used for the oxidation design.
8. the method for claim 7, wherein the subordinate phase catalyzer is as N
2It also is effective that O destroys catalyzer.
9. claim 7 or 8 method, wherein the subordinate phase catalyzer effectively destroys greater than 80% under the subordinate phase temperature of design, is preferably greater than 90% N
2O.
10. claim 7,8 or 9 method, this method comprises incorporating into and is selected from following one or more additional stage: absorption agent/getter/capture silk screen is provided, so that from feed or from the fs product, remove catalyzer poison, the perhaps Pt that shifts from the fs catalyzer and be provided for catalysis and destroy N
2The catalyzer of O.
11. the method for claim 10, the capture silk screen that wherein contains palladium places between first and second stage catalysts.
12. the method for claim 10 or 11 wherein captures silk screen and comprises＜rhodium of 5wt%.
13. be used for the catalyst charge of ammonia oxidation, it designs and makes up according to any one method of claim 7-12.
14. the purposes of the catalyst charge of claim 13 in the method for ammoxidation of high conversion, campaign prolongation.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0309747.4 | 2003-04-29 | ||
| GB0309747 | 2003-04-29 | ||
| GB0315643.7 | 2003-07-04 |
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|---|---|
| CN1780789A true CN1780789A (en) | 2006-05-31 |
| CN100363252C CN100363252C (en) | 2008-01-23 |
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ID=27741488
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800115048A Expired - Fee Related CN100363252C (en) | 2003-04-29 | 2004-04-27 | Improved catalyst charge design |
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| Country | Link |
|---|---|
| EP (1) | EP1633677A2 (en) |
| JP (1) | JP2006525216A (en) |
| KR (1) | KR20060017503A (en) |
| CN (1) | CN100363252C (en) |
| BR (1) | BRPI0409944A (en) |
| CO (1) | CO5660283A2 (en) |
| GB (1) | GB0315643D0 (en) |
| IL (1) | IL171472A (en) |
| NO (1) | NO20054967L (en) |
| TW (2) | TW200502162A (en) |
| WO (1) | WO2004096703A2 (en) |
| ZA (2) | ZA200508788B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102753264A (en) * | 2010-02-12 | 2012-10-24 | 约翰森·马瑟公开有限公司 | Catalyst structures |
| CN107206356A (en) * | 2014-12-19 | 2017-09-26 | 庄信万丰股份有限公司 | Catalyst manufacture method |
| CN107278172A (en) * | 2014-12-31 | 2017-10-20 | 芬兰国家技术研究中心股份公司 | Method for forming catalytic nanometer coating |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0416982D0 (en) * | 2004-07-30 | 2004-09-01 | Johnson Matthey Plc | Oxidation process |
| RU2397810C2 (en) * | 2006-03-10 | 2010-08-27 | Умикоре Аг Унд Ко. Кг | Catalyst and method of decomposing dinitrogen monoxide and method and device for producing nitric acid |
| PL2145663T3 (en) * | 2008-07-16 | 2011-04-29 | Umicore Ag & Co Kg | Catalyst for converting nitrous oxide and its application in industrial nitric acid production |
| GB0819094D0 (en) * | 2008-10-20 | 2008-11-26 | Johnson Matthey Plc | Catalyst containment unit |
| US8524185B2 (en) | 2008-11-03 | 2013-09-03 | Basf Corporation | Integrated SCR and AMOx catalyst systems |
| IT1401698B1 (en) * | 2010-09-13 | 2013-08-02 | Sued Chemie Catalysts Italia | CATALYST FOR THE DECOMPOSITION OF DANGEROUS PROSTOSIS. |
| DE102012106732A1 (en) | 2012-07-24 | 2014-01-30 | Heraeus Materials Technology Gmbh & Co. Kg | catalyst |
| NO20130145A1 (en) * | 2013-01-28 | 2014-07-29 | Yara Int Asa | An ammonia oxidation catalyst for the preparation of nitric acid based on metal dipped yttrium |
| NO335207B1 (en) * | 2013-01-28 | 2014-10-20 | Yara Int Asa | Catalytically active component of catalyst, catalyst and use thereof. |
| EP3056267A1 (en) * | 2015-02-12 | 2016-08-17 | Umicore AG & Co. KG | Catalyst gauze and installation for the catalytic oxidation of ammunia |
| CZ307189B6 (en) * | 2017-01-30 | 2018-03-07 | Ústav fyzikální chemie J. Heyrovského AV ČR, v. v. i. | A method of production of catalysts of a perovskite structure, catalysts perovskite structure and their use for high temperature decomposition of N2O |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8516333D0 (en) * | 1985-06-28 | 1985-07-31 | Johnson Matthey Plc | Nitric oxide |
| GB9302531D0 (en) * | 1993-02-09 | 1993-03-24 | Johnson Matthey Plc | Improvements in pt recovery |
| US5478549A (en) * | 1994-12-15 | 1995-12-26 | E. I. Du Pont De Nemours And Company | Production of nitric oxide |
| GB9626516D0 (en) * | 1996-12-20 | 1997-02-05 | Ici Plc | Ammonia oxidation |
| ATE265391T1 (en) * | 1997-08-12 | 2004-05-15 | Basf Ag | METHOD FOR PRODUCING NITRIC ACID AND DEVICE FOR CARRYING OUT THE METHOD |
| DE19819882A1 (en) * | 1998-04-27 | 1999-10-28 | Basf Ag | Reactor for catalytically oxidizing ammonia to nitrogen oxides |
| GB9812276D0 (en) * | 1998-06-09 | 1998-08-05 | Ici Plc | Catalytic process |
| DE19841740A1 (en) * | 1998-09-09 | 2000-03-16 | Porzellanwerk Kloster Veilsdor | Ceramic catalyst for the selective decomposition of N2O and process for its production |
| AU6761100A (en) * | 1999-08-10 | 2001-03-05 | Engelhard Corporation | Recovery of precious metal |
| RU2145935C1 (en) * | 1999-08-11 | 2000-02-27 | Институт катализа им.Г.К.Борескова СО РАН | Method of ammonia conversion |
| DE10001540B4 (en) * | 2000-01-14 | 2005-06-23 | Uhde Gmbh | Elimination of nitrous oxide in nitric acid production |
| ES2234844T3 (en) * | 2000-05-15 | 2005-07-01 | W.C. Heraeus Gmbh | PROCEDURE AND DEVICE FOR RECYCLING NITROGEN PROTOXIDE. |
| GB0118322D0 (en) * | 2001-07-27 | 2001-09-19 | Ici Plc | Catalyst or sorbent beds |
-
2003
- 2003-07-04 GB GBGB0315643.7A patent/GB0315643D0/en not_active Ceased
-
2004
- 2004-04-27 BR BRPI0409944-3A patent/BRPI0409944A/en not_active IP Right Cessation
- 2004-04-27 KR KR1020057020493A patent/KR20060017503A/en not_active Application Discontinuation
- 2004-04-27 CN CNB2004800115048A patent/CN100363252C/en not_active Expired - Fee Related
- 2004-04-27 JP JP2006506185A patent/JP2006525216A/en not_active Withdrawn
- 2004-04-27 EP EP04729673A patent/EP1633677A2/en not_active Withdrawn
- 2004-04-27 WO PCT/GB2004/001785 patent/WO2004096703A2/en active Application Filing
- 2004-04-29 TW TW093112054A patent/TW200502162A/en unknown
- 2004-04-29 TW TW093112091A patent/TWI346087B/en not_active IP Right Cessation
-
2005
- 2005-10-19 IL IL171472A patent/IL171472A/en not_active IP Right Cessation
- 2005-10-26 NO NO20054967A patent/NO20054967L/en not_active Application Discontinuation
- 2005-10-28 ZA ZA200508788A patent/ZA200508788B/en unknown
- 2005-10-28 ZA ZA200508783A patent/ZA200508783B/en unknown
- 2005-11-22 CO CO05118375A patent/CO5660283A2/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102753264A (en) * | 2010-02-12 | 2012-10-24 | 约翰森·马瑟公开有限公司 | Catalyst structures |
| CN102753264B (en) * | 2010-02-12 | 2015-08-12 | 约翰森·马瑟公开有限公司 | Catalyst structure |
| CN107206356A (en) * | 2014-12-19 | 2017-09-26 | 庄信万丰股份有限公司 | Catalyst manufacture method |
| CN107278172A (en) * | 2014-12-31 | 2017-10-20 | 芬兰国家技术研究中心股份公司 | Method for forming catalytic nanometer coating |
Also Published As
| Publication number | Publication date |
|---|---|
| IL171472A (en) | 2011-01-31 |
| WO2004096703A3 (en) | 2005-01-20 |
| ZA200508788B (en) | 2006-08-30 |
| TWI346087B (en) | 2011-08-01 |
| TW200502162A (en) | 2005-01-16 |
| JP2006525216A (en) | 2006-11-09 |
| CO5660283A2 (en) | 2006-07-31 |
| EP1633677A2 (en) | 2006-03-15 |
| WO2004096703A2 (en) | 2004-11-11 |
| ZA200508783B (en) | 2006-07-26 |
| TW200513435A (en) | 2005-04-16 |
| BRPI0409944A (en) | 2006-04-25 |
| KR20060017503A (en) | 2006-02-23 |
| WO2004096703A8 (en) | 2005-03-17 |
| NO20054967L (en) | 2005-11-23 |
| GB0315643D0 (en) | 2003-08-13 |
| CN100363252C (en) | 2008-01-23 |
| NO20054967D0 (en) | 2005-10-26 |
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