US20050096216A1 - Process for the production of iron oxide containing catalysts - Google Patents
Process for the production of iron oxide containing catalysts Download PDFInfo
- Publication number
- US20050096216A1 US20050096216A1 US11/002,275 US227504A US2005096216A1 US 20050096216 A1 US20050096216 A1 US 20050096216A1 US 227504 A US227504 A US 227504A US 2005096216 A1 US2005096216 A1 US 2005096216A1
- Authority
- US
- United States
- Prior art keywords
- nitric acid
- nitrate
- solution
- acid
- iron oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 150000001720 carbohydrates Chemical class 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 239000010949 copper Substances 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 150000001413 amino acids Chemical class 0.000 abstract 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- 150000002823 nitrates Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910001960 metal nitrate Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical class [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- QSQUFRGBXGXOHF-UHFFFAOYSA-N cobalt(III) nitrate Inorganic materials [Co].O[N+]([O-])=O.O[N+]([O-])=O.O[N+]([O-])=O QSQUFRGBXGXOHF-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- 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
- B01J23/80—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 zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
- C01B13/185—Preparing mixtures of oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- B01J35/30—
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
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- C01P2002/52—Solid solutions containing elements as dopants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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
- the present invention relates to a process for the production of metal oxide being useful for the preparation of mixed metal oxide catalysts.
- the state of the art methods for preparing mixed metal oxide include use of process by precipitation.
- Metal sulphate is a cheap pure raw material and good catalysts can be obtained by coprecipitation, but with a too high sulphur level.
- metal nitrate is an expensive raw material, and dissolving metals in nitric acid require the expensive nitric acid.
- the general object of this invention is, thus, to provide an improved process for the production of mixed metal oxide containing catalysts by simplified and inexpensive steps. Now an alternative manufacturing route based on metals via nitrates and nitric acid recovery has been invented and developed.
- the advantages of the invention include a high quality catalyst, and furthermore, high product yield through reduced loss of material during the processing.
- the promoters are preferably added in the ratio range on molar base ⁇ PR/Me ⁇ 0.2.
- the final solution will be Me(NO 3 ) 3 solution, optionally containing promoters' PR nitrates.
- the HNO 3 consumption will increase if NO 2 is formed.
- nitric acid due to minor loss of the nitric acid, occasionally small amounts of nitric acid have to be added to the regenerated acid in order to maintain or enhance dissolution of the raw material.
- Decomposition in the above step (d) may be performed by spraying the acidic solution from step (a), (b) or (c) onto the inner surface of one or more rotary kilns, into spray calcination fluid beds, into a steel band conveyor furnace or into a tower falling particles kiln with free supply of air at 250-700° C.
- measures may be taken in order to prevent sticking of the product to the inner surface of the rotary kiln, e.g. by means of one or more sliding chains.
- Adhesion of the prepared material from the decomposed acid solution to the inner side of said furnaces or kilns might also be prevented by other physical or chemical means.
- the metal oxide product is further improved by minor addition of an organic compound capable of reducing nitrates.
- the reaction between the organic compound and the nitrate will then generate a faster decomposition of the nitrates.
- the powder is weakly agglomerated and possible to crush in low energy milling device.
- the method of the invention is suitable for adding different additives (e.g. promoters in the case of catalyst, or other elements for other purposes) before decomposition.
- additives e.g. promoters in the case of catalyst, or other elements for other purposes
- One way to decompose this solution to metal oxide(s) is continuously dripping the stock solution into a rotary kiln.
- the temperature in the rotary kiln may vary between 250-700° C., preferable 350-600° C.
- An essential feature of the invention comprises utilization of additives selected from organic compounds added to the nitrate stock solution. By adjusting additive quantity and/or temperature in the rotary kiln it is possible to control powder characteristics (phase content/crystalline structure, surface area, particle size, microstructure etc).
- additives are selected from carbohydrates (glucose, fructose, lactose, sucrose or other saccharides), glycine and carboxylic acid. Moreover, the powder is agglomerated in hard and large lumps. Low quantity or none of these additives results always in ⁇ -Fe 2 O 3 . High quantity of an organic additive results in ⁇ -F 2 O 3 when the pyrolysis temperature is low.
- Iron was dissolved in nitric acid together with nitrates of the promoters such as Cr, Cu, K and Na in the required proportions and a stock solution was obtained. This solution was dripped at given feed rate into rotary kiln at 350° C. Powder characteristics were measured using XRD analysis and isothermal nitrogen adsorption for specific surface area (according to Brunauer, Emmett and Teller theory). Surface area on synthesised powder (measured by nitrogen adsorption) was 73 m 2 /g.
- the stock solution was prepared similar to Example 1. Then a certain quantity of glucose was dissolved corresponding to the 1 ⁇ 6 of the so-called “stoichiometric ratio” between oxidising (nitrates) and reducing (glucose) reactants. This solution was dripped at given feed rate into a rotary kiln at 400° C.
- the stock solution was prepared similar to Example 1. Then a quantity of glucose was dissolved corresponding to a ratio greater than 1 ⁇ 2 of the so-called “stoichiometric ratio” between oxidising (nitrates) and reducing (glucose) reactants. This solution was dripped at given feed rate into rotary kiln at 350° C.
- Such powders are used in magnetic tape memories.
- the stock solution was prepared similar to Example 1. Then a certain quantity of glucose was dissolved corresponding to the 1 ⁇ 2 of the so-called “stoichiometric ratio” between oxidising (nitrates) and reducing (glucose) reactants. This solution is dripped at given feed rate into rotary kiln at 400° C.
- a mixture of metallic Co and Fe in the molar ratio 1:1 is dissolved in concentrated nitric acid. Aluminium hydroxide is added to an overall molar ratio of Fe:Co:Al of 1:1:2. Finally KNO 3 is added so the molar percentage is 1%.
- This solution is dripped at a constant feed rate into a rotating kiln at 350° C.
- the powder is crushed, sieved, mixed with graphite and pelletised.
- the pellets are calcinated in a conveyor furnace at a temperature of 550° C.
- the pellets are reduced in pure hydrogen and are useful as catalyst for both ammonia synthesis and decomposition.
- a mixture of metallic Cu and Zinc oxide, ZnO, is dissolved in concentrated HNO 3 .
- the molar ratio is 1:1.
- Alumina is added to an overall molar ratio of Cu:Zn:Al of 1:1:1.
- the slurry is decomposed at 350° C.
- the powder is crushed, sieved, mixed with graphite and pelletised.
- the pellets are reduced in dilute hydrogen and are useful as catalyst for methanol synthesis or WGS conversion.
Abstract
A process for the production mixed metal oxide containing catalysts comprising the steps of: dissolution of metals Me=Fe, Ni, Al, Cu, Co, Zn, Cr, in nitric acid providing an acid solution of metal mixed nitrate products, aluminium can be added either as nitrate or hydroxide; addition of a carbonhydrate, an amino acid and/or a carboxylic acid;
-
- decomposition at 250-700° C. with free air supply of the acid solution by spraying onto the inner surface of one or more rotary kilns, into a spray calcination fluid bed, into a tower kiln or into a steel band conveyor furnace to iron oxide and NOx; and optionally
- regeneration of the formed NOx to concentrated nitric acid and recycling of produced nitric acid to the first step.
Description
- The present invention relates to a process for the production of metal oxide being useful for the preparation of mixed metal oxide catalysts.
- The state of the art methods for preparing mixed metal oxide include use of process by precipitation. Metal sulphate is a cheap pure raw material and good catalysts can be obtained by coprecipitation, but with a too high sulphur level. On the other hand, metal nitrate is an expensive raw material, and dissolving metals in nitric acid require the expensive nitric acid.
- The known methods for preparing mixed metal oxide catalysts are costly in terms of purchasing the acid and basic raw materials and after the precipitation, washings and waste-water treatment.
- This is described in U.S. Pat. No. 4,482,645, where Jennings et al. prepare a solution of iron nitrate and chromium nitrate, to which sodium carbonate is added and the formed iron and chromium hydroxides are washed before drying and decomposition to oxides.
- The general object of this invention is, thus, to provide an improved process for the production of mixed metal oxide containing catalysts by simplified and inexpensive steps. Now an alternative manufacturing route based on metals via nitrates and nitric acid recovery has been invented and developed.
- Compared to the known methods, the advantages of the invention include a high quality catalyst, and furthermore, high product yield through reduced loss of material during the processing.
- The process of this invention comprises the following steps involving the metals Me=Co, Zn, Fe, Ni, Cr and/or Cu:
- (a) Dissolution of Me in nitric acid providing an acid solution of (exemplified by a valence 3 metal) Me(NO3)3 by reaction (i):
2Me+8HNO3→2 Me(NO3)3+2 NO+4H2O - (b) Optionally mixing of different metal nitrate solutions, e.g. Fe(NO3)3 solution with Co(NO3)3 solution. Aluminium is added either as nitrate or hydroxide.
- (c) Optionally, addition of promoters. If promoters (PR) as PR=Na, K, Cs, Rb, Mg, Ca, Ba, Sr are desired in the final product, they are added as metal nitrates, carbonates, hydroxides etc to the dissolved Me(III) nitrate. The promoters are preferably added in the ratio range on molar base <PR/Me<0.2.
- The final solution will be Me(NO3)3 solution, optionally containing promoters' PR nitrates.
- The HNO3 consumption will increase if NO2 is formed.
- (d) Thermal decomposition of the combined metal nitrate solution and promoter acid nitrate solution into mixed metal oxide Me2O3 or hydroxyoxide MeOOH optionally containing the promoters as oxides or nitrates depending on the chemical nature of the promoter. NOx gases are also formed during the reaction. The reaction for the pure decomposition of Me(NO3)3 will be as reaction (ii):
2Me(NO3)3→Me2O3+6NO2+1.5O2 - (e) Optionally regeneration of NOx gases from reaction (i) and (ii) in one or in a series of absorption towers to more or less concentrated nitric acid according to reaction (iii):
6NO2+3 H2O+1.5O2→6HNO3
or for NO (iv)
2NO+H2O+1.5O2→2HNO3 - Then the overall reaction for iron alone, i.e. when (i), (ii), (iii) and (iv) are combined, is:
Total: 2Me+1.5O2→Me2O3 - When only the synthesis of the main component Me2O3 is considered, we see that for the total reaction no by-product is formed and the other raw material, oxygen, is taken from the air via the absorption towers.
- The total reaction is somewhat influenced when promoters are included in the mixed metal nitrate solution. The influence is dependent on whether the promoter PR is added as nitrate, hydroxide, oxide etc. If it for example is added as KNO3 with the molar ratio of K/Me=0.01 to total reaction scheme will be:
2Me+1.5O2+0.02KNO3+0.01H2O→Me2O33+0.01K2O+0.02HNO3. - This results in a slight formation of HNO3 that can be used as dissolution.
- NO and NO2 or generally NOx being formed in the above reactions (i) and (ii) is converted into nitric acid again in absorption towers. Reactions (iii) and (iv) result in formation of nitric acid that is recycled and utilised for dissolution of Me, which is the main raw material in the process.
- Though, due to minor loss of the nitric acid, occasionally small amounts of nitric acid have to be added to the regenerated acid in order to maintain or enhance dissolution of the raw material.
- Decomposition in the above step (d) may be performed by spraying the acidic solution from step (a), (b) or (c) onto the inner surface of one or more rotary kilns, into spray calcination fluid beds, into a steel band conveyor furnace or into a tower falling particles kiln with free supply of air at 250-700° C. However, by using these methods, measures may be taken in order to prevent sticking of the product to the inner surface of the rotary kiln, e.g. by means of one or more sliding chains.
- Adhesion of the prepared material from the decomposed acid solution to the inner side of said furnaces or kilns might also be prevented by other physical or chemical means.
- The metal oxide product is further improved by minor addition of an organic compound capable of reducing nitrates. The reaction between the organic compound and the nitrate will then generate a faster decomposition of the nitrates. Furthermore, the powder is weakly agglomerated and possible to crush in low energy milling device.
- The method of the invention is suitable for adding different additives (e.g. promoters in the case of catalyst, or other elements for other purposes) before decomposition. One way to decompose this solution to metal oxide(s) is continuously dripping the stock solution into a rotary kiln. The temperature in the rotary kiln may vary between 250-700° C., preferable 350-600° C. An essential feature of the invention comprises utilization of additives selected from organic compounds added to the nitrate stock solution. By adjusting additive quantity and/or temperature in the rotary kiln it is possible to control powder characteristics (phase content/crystalline structure, surface area, particle size, microstructure etc). Without such organic additives, when adding such an additive, the powder will freely run out from the rotary kiln making a continuous process possible. Preferred additives are selected from carbohydrates (glucose, fructose, lactose, sucrose or other saccharides), glycine and carboxylic acid. Moreover, the powder is agglomerated in hard and large lumps. Low quantity or none of these additives results always in α-Fe2O3. High quantity of an organic additive results in γ-F2O3 when the pyrolysis temperature is low.
- Iron was dissolved in nitric acid together with nitrates of the promoters such as Cr, Cu, K and Na in the required proportions and a stock solution was obtained. This solution was dripped at given feed rate into rotary kiln at 350° C. Powder characteristics were measured using XRD analysis and isothermal nitrogen adsorption for specific surface area (according to Brunauer, Emmett and Teller theory). Surface area on synthesised powder (measured by nitrogen adsorption) was 73 m2/g.
- Disadvantage: The powder was strong adhered to the rotary kiln walls and very hard particles.
- The stock solution was prepared similar to Example 1. Then a certain quantity of glucose was dissolved corresponding to the ⅙ of the so-called “stoichiometric ratio” between oxidising (nitrates) and reducing (glucose) reactants. This solution was dripped at given feed rate into a rotary kiln at 400° C.
- X-ray analysis resulted in α-Fe2O3 with parameters a=5.035 Å, c=13.758 Å and crystallite size D(024)=285 Å.
- Surface area on synthesised powder (measured by nitrogen adsorption) was about 50 m2/g.
- SEM investigation showed a unique microstructure consisting of large porosity with cavities up to 5 μm. Using atomic-resolution TEM, a homogeneous distribution of Fe, Cu, and Cr was found. In the same time very unusual crystal morphology was observed by TEM examination.
- The stock solution was prepared similar to Example 1. Then a quantity of glucose was dissolved corresponding to a ratio greater than ½ of the so-called “stoichiometric ratio” between oxidising (nitrates) and reducing (glucose) reactants. This solution was dripped at given feed rate into rotary kiln at 350° C.
- X-ray analysis resulted in a cubic γ-Fe2O3 with parameter a=8.333 Å, and crystallite size D(440)=97 Å.
- Surface area on synthesised powder (measured by nitrogen adsorption) was 70 m2/g.
- Such powders are used in magnetic tape memories.
- The stock solution was prepared similar to Example 1. Then a certain quantity of glucose was dissolved corresponding to the ½ of the so-called “stoichiometric ratio” between oxidising (nitrates) and reducing (glucose) reactants. This solution is dripped at given feed rate into rotary kiln at 400° C.
- X-ray analysis resulted in α-Fe2O3 and γ-Fe2O3.
- A mixture of metallic Co and Fe in the molar ratio 1:1 is dissolved in concentrated nitric acid. Aluminium hydroxide is added to an overall molar ratio of Fe:Co:Al of 1:1:2. Finally KNO3 is added so the molar percentage is 1%.
- This solution is dripped at a constant feed rate into a rotating kiln at 350° C.
- The powder is crushed, sieved, mixed with graphite and pelletised.
- The pellets are calcinated in a conveyor furnace at a temperature of 550° C.
- The pellets are reduced in pure hydrogen and are useful as catalyst for both ammonia synthesis and decomposition.
- A mixture of metallic Cu and Zinc oxide, ZnO, is dissolved in concentrated HNO3. The molar ratio is 1:1. Alumina is added to an overall molar ratio of Cu:Zn:Al of 1:1:1. The slurry is decomposed at 350° C.
- The powder is crushed, sieved, mixed with graphite and pelletised.
- The pellets are reduced in dilute hydrogen and are useful as catalyst for methanol synthesis or WGS conversion.
Claims (6)
1-6. (canceled)
7. A process for the production of a mixed oxide catalyst with iron oxide and metal oxides selected from one or more of the oxides of Co, Al, Ni, Zn, Cu and Cr, the process comprising the steps of:
(a) providing a nitric acid solution with iron nitrate and a nitrate of one or more metals of Co, Al, Ni, Zn, Cu and Cr;
(b) adding to the nitric acid solution a carbohydrate; and
(c) decomposing the solution obtained in step (b) at a temperature of between 250 and 700° C. with free air supply to obtain the mixed oxide catalyst containing the iron oxide in its alpha and/or gamma form.
8. A process according to claim 7 , wherein the carbohydrate is chosen from glucose, fructose, lactose or sucrose.
9. A process according to claim 8 , wherein the decomposing takes place at 300-450° C.
10. A process according to claim 8 , wherein the amount of glucose being added to the solution of step (b) is between 0.05 to 0.3 mol per iron nitrate mol.
11. A mixed metal oxide containing catalyst produced by a process according to claim 7.
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US11/002,275 US20050096216A1 (en) | 2001-10-15 | 2004-12-03 | Process for the production of iron oxide containing catalysts |
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DKPA200101514 | 2001-10-15 | ||
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US10/265,257 US6875723B2 (en) | 2001-10-15 | 2002-10-07 | Process for the production of iron oxide containing catalysts |
US11/002,275 US20050096216A1 (en) | 2001-10-15 | 2004-12-03 | Process for the production of iron oxide containing catalysts |
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US7309479B2 (en) * | 2005-06-29 | 2007-12-18 | Samsung Engineering Co., Ltd. | Cobalt oxide catalysts |
DE102018126344A1 (en) * | 2018-10-23 | 2020-04-23 | Technische Universität Bergakademie Freiberg | Catalyst for use in converting CO2 to CH4 and process for making a catalyst for use in converting CO2 to CH4 |
CN112615057B (en) * | 2020-12-15 | 2022-08-23 | 广东微电新能源有限公司 | Preparation method of solid-state lithium ion battery and solid-state lithium ion battery |
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- 2002-09-27 EP EP02021613A patent/EP1304164A1/en not_active Withdrawn
- 2002-10-07 US US10/265,257 patent/US6875723B2/en not_active Expired - Fee Related
- 2002-10-14 RU RU2002127434/04A patent/RU2320409C2/en not_active IP Right Cessation
- 2002-10-14 ZA ZA200208264A patent/ZA200208264B/en unknown
- 2002-10-15 CN CNB021475547A patent/CN100369670C/en not_active Expired - Fee Related
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CN100369670C (en) | 2008-02-20 |
ZA200208264B (en) | 2003-07-04 |
EP1304164A1 (en) | 2003-04-23 |
US20030073574A1 (en) | 2003-04-17 |
US6875723B2 (en) | 2005-04-05 |
RU2320409C2 (en) | 2008-03-27 |
CN1411907A (en) | 2003-04-23 |
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