CN1215984C - 具有较高纯度的铁氧化物、制备它们的方法、含有它们的催化剂及其用途 - Google Patents
具有较高纯度的铁氧化物、制备它们的方法、含有它们的催化剂及其用途 Download PDFInfo
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- CN1215984C CN1215984C CN028080793A CN02808079A CN1215984C CN 1215984 C CN1215984 C CN 1215984C CN 028080793 A CN028080793 A CN 028080793A CN 02808079 A CN02808079 A CN 02808079A CN 1215984 C CN1215984 C CN 1215984C
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- catalyzer
- ferriferous oxide
- oxide
- ion content
- ferriferous
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title abstract description 5
- 235000013980 iron oxide Nutrition 0.000 title abstract 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 title abstract 2
- 238000007670 refining Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 21
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 150000003112 potassium compounds Chemical class 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 206010011416 Croup infectious Diseases 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005443 coulometric titration Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- -1 iron oxide compound Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000009996 mechanical pre-treatment Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- 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
-
- B01J35/40—
-
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
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- 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
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- 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
- C01P2006/16—Pore diameter
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- 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
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/01—Waste acid containing iron
Abstract
本发明涉及一种通过在700-1200℃的温度下煅烧铁氧化物而改善该铁氧化物纯度的方法。本发明进一步涉及由本发明方法得到的铁氧化物,以及该铁氧化物作为催化剂或在制备催化剂中的用途,尤其是在制备用于将乙苯脱氢得到苯乙烯的催化剂中的用途。此外,本发明还涉及使用本发明的铁氧化物制备的催化剂。
Description
本发明涉及一种改善铁氧化物纯度的方法,包括在不低于700℃的温度下煅烧铁氧化物。
EP-A-1 027 928描述了一种尤其用于将乙苯脱氢成苯乙烯的催化剂,其使用通过喷雾焙烧铁盐溶液,尤其是盐酸/铁溶液得到的铁氧化物来制备(Ruthner法)。该类铁氧化物的缺点是它们具有高残留氯离子含量。
EP-A-797 481公开了作为尤其用于将乙苯脱氢成苯乙烯的催化剂的原料的铁氧化物,它们通过与其它金属化合物混合并随后煅烧而重构,并且具有非常小的BET表面积。该重构的缺点是铁氧化物被所加入的金属化合物污染。
JP-A-61-72601公开了一种将重质烃裂化成较轻质烃的流化床方法,该方法使用通过将铁氧化物粉末用水淤浆化、喷雾干燥并最后在1200-1600℃的温度下煅烧制备的粉状催化剂。该方法的缺点是成本和不便性很大且煅烧温度高。
EP-A-827 488描述了一种降低铁氧化物中,尤其是通过喷雾焙烧盐酸浸蚀废液产生的铁氧化物中的残留氯离子含量的方法,包括将该铁氧化物与水合金属化合物混合并随后进行煅烧该方法的缺点在于其成本和不便性。
US-A-4,134,858公开了在将铁氧化物用于制备苯乙烯催化剂之前将其在800℃下焙烧。然而,通过该方法不能充分降低该铁氧化物中残留氯离子含量。
US-A-2,414,585公开了将用于制备脱氢催化剂的铁氧化物预煅烧。据说所得铁氧化物具有的BET表面积<8m2/g,优选约4m2/g。该类催化剂仍有待改进。
本发明的目的是克服上述缺点。
我们发现该目的由一种改善铁氧化物纯度的新颖且改进的方法实现,该方法包括在700-1200℃下煅烧铁氧化物。本发明进一步提供了新型铁氧化物及其作为催化剂的用途,以及在制备催化剂中的用途,尤其是在制备将乙苯脱氢成苯乙烯的催化剂中的用途。
本发明方法可以按如下进行。
本发明的纯度改善方法可以用于任何铁氧化物,但优选用于通过加工来自钢浸蚀的盐酸废液产生的铁氧化物,例如尤其是通过喷雾焙烧盐酸浸蚀废液产生的铁氧化物(Ruthner法)。
铁氧化物可以在没有预处理,即例如没有机械预处理的情况下且优选在干燥,即没有用水、酸或碱或某些其它材料预先处理的情况下,在700-1200℃,优选840-1150℃,特别优选850-1100℃,尤其是860-1000℃下间歇或优选连续煅烧通常0.1-24小时,优选0.25-10小时,特别优选0.3-5小时,尤其是0.5-1.5小时。有用的煅烧设备包括所有已知的炉。煅烧可以间歇进行,例如在马弗炉中,或连续进行,例如在旋转管式炉中或在带式煅烧炉中。优选连续方法。煅烧可以仅在一个温度下进行或在不同温度的多段中进行或以连续温度梯度形式进行。当煅烧在旋转管中进行时,该旋转管应装有防止铁氧化物粘于该旋转管壁上并确保铁氧化物连续输送的轻击锤。有利的是,煅烧在没有内部配件的光滑旋转管中进行,且停留时间可以通过旋转速率、进料速率和旋转管的倾斜度来调节。进一步有利的是煅烧在气流如氮气流或空气流下进行,以便可以排出释放的氯化合物并在下游废气涤气中有利地将其除去。氯离子含量有利地可在固定床中降低,即例如在马弗炉中或在带式煅烧炉上的煅烧过程中降低。当煅烧在移动床如旋转管中进行时,与固定床相比,可能需要使用稍高的温度来降低氯离子含量,且这可能导致相比较而言进一步降低的BET表面积。因此,取决于氯离子含量和BET表面积的优选比例,可以有利地选择性地操作固定床或移动床。
然而,可以加入少量水、酸、碱或有机化合物,条件是与纯度改善的干法相比这不会不利地影响纯度已改善的铁氧化物的性能。优选在没有任何预处理的情况下对市购铁氧化物进行煅烧。
可以用于本发明纯度改善方法的铁氧化物包括所有铁氧化物,而与其如何得到无关。天然铁氧化物,优选工业生产的以及市购的铁氧化物是合适的,尤其是通过加工盐酸浸蚀废液产生的铁氧化物。这些铁氧化物可以含有杂质,例如残留氯离子和/或钛、锰、铝、铬、磷、锌、铜、钼、钨、硅、镍、镁、钾、钠、钴、钒、锆、铌、硫、镧、铅、锡和/或钙的化合物。特别合适的是通过喷雾焙烧钢工业中的盐酸浸蚀废液产生的铁氧化物,它们以Fe2O3存在,通常呈赤铁矿晶型,其中残留氯离子含量为0-10000ppm,优选50-5000ppm,特别优选500-2000ppm,BET表面积通常为3-5m2/g。
根据本发明改善纯度的铁氧化物通常具有的残留氯离子含量低于400ppm,优选低于300ppm,特别优选低于250ppm,尤其低于200ppm。由下述激光衍射测定的平均粒度通常大于5μm,即5.1-200μm,优选8-100μm,特别优选10-80μm,非常特别优选12-30μm,且粒度低于1μm的细粒分数通常低于15重量%,优选低于10重量%,特别优选低于5重量%。根据本发明处理的铁氧化物的BET表面积通常为0.4-5m2/g,优选0.4-3.5m2/g,特别优选0.5-3m2/g,尤其为0.6-2.5m2/g,非常特别优选为0.7-2m2/g。根据本发明处理的铁氧化物通常具有赤铁矿结构。它们可以用于所有系列的工业应用,如药物、化妆品、磁带涂料、化学反应、催化剂,或用于制备催化剂,尤其是用于制备乙苯脱氢成苯乙烯用催化剂。
通过乙苯脱氢的苯乙烯工业生产可以通过等温方法或绝热方法进行。等温方法通常在450-700℃,优选520-650℃下在加有水蒸气的气相中于0.1-5巴,优选0.2-2巴,特别优选0.3-1巴,尤其是0.4-0.9巴下操作。绝热方法通常在450-700℃,优选520-650℃下在加有水蒸气的气相中于0.1-2巴,优选0.2-1巴,特别优选0.3-0.9巴,尤其是0.4-0.8巴下操作。用于将乙苯脱氢成苯乙烯的催化剂可以通过水蒸气而再生。
用于将乙苯脱氢成苯乙烯的催化剂通常含有铁氧化物和碱金属化合物如氧化钾。该类催化剂通常还含有许多促进剂。所述促进剂包括例如钙、镁、铈、钼、钨、铬和钛的化合物。这些催化剂可以使用将存在于成品催化剂中的促进剂化合物来制备或使用在生产工艺过程中转化成存在于成品催化剂中的化合物的化合物来制备。所用材料也可以包括改进加工性、机械强度或孔结构的助剂。这类助剂的实例包括马铃薯淀粉、纤维素、硬脂酸、石墨或卜特兰水泥。所用材料可以在混合器、捏合机或优选研磨机中直接混合。它们也可以淤浆化成可喷雾混合物并可喷雾干燥形成粉末。所用材料优选在研磨机或捏合机中在水存在下加工形成可挤出物料。然后将该可挤出物料挤出、干燥并煅烧。优选挤出物具有的直径为2-10mm。挤出物的横截面可以为圆形或某些其它形状。特别优选具有旋转对称横截面,尤其是直径为3mm的横截面的挤出物,以及具有星形横截面或齿轮横截面,尤其是直径为4.5或6mm的横截面的挤出物。可以将挤出物破碎或切割。作为挤出的替代方法,也可以通过压片将催化剂成型。通常而言,与由未根据本发明改善纯度的铁氧化物类似制备的催化剂相比,根据本发明制备的催化剂具有更大的平均孔半径和更小的BET表面积。
使用根据本发明改善纯度的铁氧化物代替常规的现有技术铁氧化物制备的催化剂具有改进的活性和选择性。根据本发明预处理的铁氧化物在该催化剂中所存在的所有铁氧化物中的分数(%)应不低于30重量%,优选不低于60重量%,非常特别优选不低于90重量%。尤其优选根据本发明改善纯度的铁氧化物在全部铁氧化物中的分数(%)为100重量%。已经使用根据本发明改善纯度的铁氧化物制备的乙苯脱氢成苯乙烯用催化剂可以用于所有方法和方法变体中。它们尤其在蒸汽/乙苯(S/EB)比为0.6-2.5kg/kg下有用。它们在蒸汽/乙苯比为0.9-1.5kg/kg下非常特别有用。根据本发明制备的催化剂因低于500ppm,典型的是低于300ppm,尤其是低于200ppm的低氯离子含量和0.3-3μm,典型的是0.5-1.5μm的平均孔径而著称。
实施例
发明实施例1和对比例A使用来自Thyssen-Krupp的HP型(HschPremium)铁氧化物,其根据Ruthner法通过喷雾焙烧盐酸/铁溶液生产。残留氯离子含量在所有情况下通过库仑滴定确定。铁氧化物的粒度使用来自Malvern的Mastersizer S(透镜:300RFmm,测量范围为0.05-880mm)测定。使用MS17型。它为用于在含水介质中分散的样品进料器,该进料器具有内置桨叶搅拌器、整体式超声探针和循环泵。在测量之前,启动整体式超声浴(100%设定值)并在分散5分钟后在持续超声化下进行测量。根据DIN 66133测量BET比表面积并根据DIN 66131测量孔体积和平均孔半径。
发明实施例1
在马弗炉中将2kg来自Thyssen-Krupp的HP型铁氧化物加热到900℃,在该炉中于该温度下放置1小时,然后将该炉冷却。
发明实施例2
在800℃下重复发明实施例1。
发明实施例3
在850℃下重复发明实施例1。
发明实施例4
在950℃下重复发明实施例1。
发明实施例5
在石英玻璃旋转管中在空气流下将20g来自Thyssen-Krupp的HP型铁氧化物加热到900℃,在其中于900℃下保持1小时,然后在其中冷却。
发明实施例6
重复发明实施例5,不同的是将铁氧化物在900℃下保持2小时。
发明实施例7
在空气流下于旋转管中连续煅烧铁氧化物。该旋转管装有三个轻击锤。旋转管的壁温为970℃且铁氧化物的停留时间为约1小时。
按本发明预处理的发明实施例1-7的铁氧化物的物理性能总结于表1中并在该表中与纯度未改善的铁氧化物作比较。
发明实施例8
将通过在4.5升水中悬浮420g碳酸钾(钾碱)、516g水合碳酸铈(40重量%铈含量)、74g七钼酸铵、70g氢氧化钙(水合白垩)、55g菱镁矿和1880g根据发明实施例1改善纯度的铁氧化物所制备的喷雾淤浆喷雾,形成粉末,将该粉末用足量水(约500ml)在淀粉存在下在捏合机中调成糊,形成可挤出物料,将该物料挤出成直径为3mm的线材。然后在120℃下干燥各线材,将其破碎成长约0.8mm,最后在旋转管中于875℃下煅烧1小时。
发明实施例9
在内径为3cm的外部加热的管式反应器中在表3所示条件下测试415ml发明实施例2的催化剂。
对比例A
类似于发明实施例8制备催化剂,不同的是用未改善纯度的铁氧化物(Thyssen-Krupp的HP型)代替发明实施例1的已改善纯度的铁氧化物。
对比例B
在相同反应器中在相同条件下类似于发明实施例3测试415ml对比例A的催化剂。结果总结于表3中。
表1由Ruthner法制备的市购铁氧化物(Thyssen-Krupp的HP型)和发明实施例1-7的通过本发明纯度改善方法由前者制备的铁氧化物的性能
铁氧化物 | 残留氯离子[ppm] | 平均粒度[μm] | 小于1μm的细粒[重量%] | BET表面积[m2/g] |
未处理HP型(Thyssen-Krupp) | 1400 | 11 | 15 | 4.3 |
发明实施例1 | 66 | 19 | 2 | 1.4 |
发明实施例2 | 240 | 15 | 2.5 | 2.1 |
发明实施例3 | 110 | 18 | 1.7 | 1.8 |
发明实施例4 | 19 | 22 | 1 | 1.1 |
发明实施例5 | 230 | - | - | 1.6 |
发明实施例6 | 190 | - | - | 0.7 |
发明实施例7 | 190 | 13 | 1.9 | 0.9 |
表2使用根据本发明改善纯度的铁氧化物制备的发明实施例2的催化剂和根据现有技术制备的对比例A的催化剂的物理性能比较
BET表面积[m2/g] | 孔体积[ml/g] | 平均孔径[μm] | 抗切割性[N] | |
发明实施例8 | 1.3 | 0.27 | 1.28 | 64 |
对比例A | 2.9 | 0.25 | 0.39 | 51 |
表3使用本发明催化剂(发明实施例3)和现有技术催化剂(对比例B)进行的乙苯脱氢成苯乙烯的转化率和选择性比较
LHSV[h-1] | 绝对压力[巴] | 蒸汽/EB比[kg/kg] | 温度[℃] | 发明实施例9EB转化率(苯乙烯选择性) | 对比例BEB转化率(苯乙烯选择性) |
0.85 | 0.5 | 1.4 | 590 | 70.2%(96.2%) | 68.3%(96.1%) |
0.85 | 0.5 | 1.4 | 570 | 54.5%(97.2%) | 53.9%(97.2%) |
0.45 | 0.5 | 1.5 | 550 | 46.7%(97.4%) | 45.7%(97.2%) |
0.45 | 0.4 | 1.1 | 550 | 46.2%(97.9%) | 41.5%(97.9%) |
Claims (16)
1.一种改善铁氧化物纯度的方法,包括通过加工盐酸浸蚀废液来产生所述铁氧化物和直接于840-1150℃下煅烧所述铁氧化物。
2.根据权利要求1的方法,其中所述铁氧化物在850-1000℃下煅烧。
3.根据权利要求1或2的方法,其中使用装有轻击锤的旋转管进行煅烧。
4.根据权利要求1-3中任一项的方法进行纯度改善的铁氧化物,残留氯离子含量低于300ppm。
5.根据权利要求4的铁氧化物,氯离子含量低于200ppm。
6.根据权利要求4或5的铁氧化物,其平均粒度大于5μm且粒度低于1μm的粒度分数低于15重量%。
7.根据权利要求4-6中任一项的铁氧化物作为催化剂或在制备催化剂中的用途。
8.根据权利要求4-6中任一项的铁氧化物在制备用于将乙苯脱氢成苯乙烯的催化剂中的用途。
9.一种使用根据权利要求4-6中任一项的铁氧化物制备的催化剂。
10.根据权利要求9的催化剂,包含20-80重量%铁氧化物和以氧化钾计为5-40重量%的钾化合物。
11.根据权利要求10的催化剂,进一步包含其它的选自钙、镁、铈或钼的化合物的促进剂。
12.根据权利要求9-11中任一项的催化剂,平均孔径大于0.6μm。
13.根据权利要求9-11中任一项的催化剂,BET表面积为0.4-5m2/g。
14.根据权利要求9-11中任一项的催化剂,氯离子含量低于500ppm。
15.根据权利要求9-11中任一项的催化剂,氯离子含量低于200ppm。
16.一种在450-700℃和0.1-5巴的压力下将乙苯脱氢得到苯乙烯的方法,包括使用根据权利要求9-15中任一项的催化剂。
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-
2002
- 2002-04-03 JP JP2002581330A patent/JP4383055B2/ja not_active Expired - Lifetime
- 2002-04-03 KR KR10-2003-7013318A patent/KR20030092062A/ko not_active Application Discontinuation
- 2002-04-03 CN CN028080793A patent/CN1215984C/zh not_active Expired - Fee Related
- 2002-04-03 AT AT02732550T patent/ATE365702T1/de not_active IP Right Cessation
- 2002-04-03 AU AU2002304805A patent/AU2002304805A1/en not_active Abandoned
- 2002-04-03 US US10/473,214 patent/US7186395B2/en not_active Expired - Lifetime
- 2002-04-03 WO PCT/EP2002/003672 patent/WO2002083569A2/de active IP Right Grant
- 2002-04-03 EP EP02732550A patent/EP1379470B9/de not_active Expired - Lifetime
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US7186395B2 (en) | 2007-03-06 |
ATE365702T1 (de) | 2007-07-15 |
JP4383055B2 (ja) | 2009-12-16 |
EP1379470B1 (de) | 2007-06-27 |
AU2002304805A1 (en) | 2002-10-28 |
EP1379470B9 (de) | 2012-05-02 |
EP1379470B2 (de) | 2012-03-14 |
CN1501888A (zh) | 2004-06-02 |
DE50210381D1 (de) | 2007-08-09 |
EP1379470A2 (de) | 2004-01-14 |
US20040097768A1 (en) | 2004-05-20 |
WO2002083569A3 (de) | 2002-12-12 |
DK1379470T3 (da) | 2007-10-08 |
KR20030092062A (ko) | 2003-12-03 |
WO2002083569A2 (de) | 2002-10-24 |
JP2004529843A (ja) | 2004-09-30 |
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