CN108698844B - 用于改造氨装置的方法 - Google Patents
用于改造氨装置的方法 Download PDFInfo
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- CN108698844B CN108698844B CN201780013118.XA CN201780013118A CN108698844B CN 108698844 B CN108698844 B CN 108698844B CN 201780013118 A CN201780013118 A CN 201780013118A CN 108698844 B CN108698844 B CN 108698844B
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- steam
- iron
- catalyst
- high temperature
- pressure drop
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 105
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052742 iron Inorganic materials 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000009420 retrofitting Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 23
- 239000008188 pellet Substances 0.000 claims description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 235000013980 iron oxide Nutrition 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- -1 zinc aluminate Chemical class 0.000 claims description 3
- 239000005749 Copper compound Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 3
- 239000007789 gas Substances 0.000 description 66
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 239000001569 carbon dioxide Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 239000003570 air Substances 0.000 description 14
- 238000000629 steam reforming Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000002407 reforming Methods 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 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 2
- 239000005751 Copper oxide Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- QEFDIAQGSDRHQW-UHFFFAOYSA-N [O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[Cr+3].[Fe+2] QEFDIAQGSDRHQW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Classifications
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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
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
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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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
- C01B2203/0445—Selective methanation
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/068—Ammonia synthesis
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/02—Thermal reforming
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
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Abstract
描述了一种用于改造氨生产设施的方法,所述氨生产设施具有前端,所述前端包括以烃原料进料速率用烃原料进料的一个或多个重整器以及用得自所述一个或多个重整器的重整气进料且包含含铁水煤气变换催化剂的固定床的高温变换反应器,所述前端以第一蒸汽与碳比率和第一压降运行,所述方法包括以下步骤:(i)用低蒸汽水煤气变换催化剂替换所述含铁水煤气变换催化剂以形成经改进的前端,(ii)以第二蒸汽与碳比率和第二压降运行所述经改进的前端,其中所述第二蒸汽与碳比率比所述第一蒸汽与碳比率低至少0.2且所述第二压降小于所述第一压降,以及(iii)提高所述一个或多个重整器的烃原料进料速率。
Description
本发明涉及一种用于改造高温变换工艺的方法。更具体而言,本发明涉及一种用于改造氨装置中的高温变换工艺的方法。
常规地,通过使氢气和氮气在高压下反应的哈伯-博施(Haber-Bosch)工艺来生产氨。该反应的总化学计量是:
通常地,通过在被称为初级重整的工艺中对诸如天然气的烃原料蒸汽重整,以产生包含未反应烃、氢气、二氧化碳和一氧化碳的料流来获得氢气。氮气可由多种来源提供,但往往通过用空气对初级重整的产物进行次级重整以产生粗合成气来提供。然后使用催化水煤气变换转化,通常在包括在含铁催化剂的床上的高温变换阶段的两个阶段中,以将一氧化碳的至少一些转化至二氧化碳并形成另外的氢气。然后例如通过吸收来去除二氧化碳。剩余料流往往经受催化甲烷化,以将残留量的一氧化碳和二氧化碳转化至甲烷。来自甲烷转化器的料流将主要由氢气和氮气组成且具有痕量的甲烷,然后被压缩并传递至氨反应器,其中氢气与氮气反应形成氨。
将包括以下的多种因素考虑在内来决定氨装置中的最小蒸汽与碳比率:化学转化效率,跨过初级重整器的碳形成,和特别是防止高温变换催化剂过度还原的需要,所述过度还原可导致合成气中不需要的烃形成。多个装置还是压降限制的,使得经过装置的压降限制了总生产率。这意指固有压降的减小可使得装置通过量增加。降低蒸汽与碳比率使经过装置的流量减少并因此减小压降。
EP2590893(A1)公开了一种由含烃原料生产氨合成气的方法,利用以下的步骤:初级重整,用氧化剂料流次级重整,并且对合成气进一步处理,包括变换、去除二氧化碳和甲烷化,其中由次级重整输送的合成气在200与350℃之间的温度在铜/氧化锌/氧化铝催化剂上经受中温变换(MTS),并且通过安装上游预重整器、利用低于2的蒸汽与碳比率来运行初级重整。公开了用于改造氨装置的对应方法,其中现有的高温变换(HTS)反应器经改进在中温下运行,或用新的MTS反应器替换,并且将预重整器安装在初级重整器的上游,以使得初级重整器中蒸汽与碳比率可降低至1.5至2范围内的值。
我们已意识到可采用替代方法来降低蒸汽与碳比率且提高产量而不需安装预重整器和MTS反应器。
因此,本发明提供一种用于改造并运行氨生产设施的方法,所述氨生产设施具有前端,所述前端包括用烃原料进料的一个或多个重整器以及用得自所述一个或多个重整器的重整气进料且包含含铁水煤气变换催化剂的固定床的高温变换反应器,所述前端以第一蒸汽与碳比率和第一压降运行,所述方法包括以下步骤:(i)用低蒸汽水煤气变换催化剂替换含铁水煤气变换催化剂以形成经改进的前端,(ii)以第二蒸汽与碳比率和第二压降运行经改进的前端,其中第二蒸汽与碳比率比第一蒸汽与碳比率低至少0.2且第二压降小于第一压降,并且然后(iii)提高所述一个或多个重整器的烃原料进料速率。
由替换水煤气变换反应器中的催化剂和调整蒸汽与碳比率引起的前端压降减小允许氨工艺的操作员增加至一个或多个重整器的烃原料流量并且进而制造更多的氨。因此,本申请中的术语“改造”意指增加现有氨生产设施的氨产量的方法。
合成气生成阶段可基于对诸如天然气、石脑油或炼油厂废气的烃原料蒸汽重整。这可通过以下来实现:在燃烧或气体加热式蒸汽重整器中的外部加热式催化剂填充管中用蒸汽对烃原料初级重整,并且任选地在次级重整器中,通过用含氧气体使初级重整的气体混合物经受部分燃烧并且然后使部分燃烧的气体混合物经过蒸汽重整催化剂的床来对初级重整的气体混合物次级重整。含氧气体可为空气、氧气或富氧空气。初级重整催化剂通常包含负载在诸如α氧化铝或者铝酸镁或铝酸钙的成形耐火氧化物上、1-30重量%范围内含量的镍。替代地,可使用结构化催化剂,其中镍或贵金属催化剂被提供为已形成的金属或陶瓷结构上的涂布表面层,或者催化剂可被提供于设置在管内的多个容器中。蒸汽重整反应在高于350℃的温度在蒸汽重整催化剂上于管中进行,并且通常离开管的工艺流体处于650-950℃范围内的温度。围绕管外部流动的热交换介质可具有900-1300℃范围内的温度。压力可在10-80巴绝压范围内。在次级重整器中,使可含有烃原料的另一部分的初级重整气体在通常安装于接近重整器顶部的燃烧器设备中部分燃烧。然后使部分燃烧的重整气体绝热地经过设置在燃烧器设备下方的蒸汽重整催化剂的床,以使气体组成趋向平衡。用于吸热蒸汽重整反应的热量由热的部分燃烧的重整气体供应。随着部分燃烧的重整气体接触蒸汽重整催化剂,其通过吸热蒸汽重整反应冷却至900-1100℃范围内的温度。次级重整器中蒸汽重整催化剂的床通常包含负载在成形耐火氧化物上、1-30重量%范围内含量的镍,但可使用层状床,其中最上面的催化剂层包含在氧化锆载体上的诸如铂或铑的贵金属。这类蒸汽重整设备和催化剂可商购获得。
替代地,可通过以下来实现蒸汽重整:使烃和蒸汽的混合物经过包含蒸汽重整催化剂的床的绝热预重整器,并且然后使预重整的气体混合物经过以与次级重整器相同的方式运行的自热重整器,以产生含有氢气、碳氧化物和蒸汽的气流。在用空气或富氧空气对自热重整器进料的情况下,氮气也将存在于气流中。在绝热预重整中,将烃和蒸汽的混合物在300-620℃范围内的入口温度传递至粒状含镍预重整催化剂的固定床。这类催化剂通常包含≥40重量%的镍(表示为NiO),并且可通过用氧化铝以及诸如氧化硅和氧化镁的促进剂化合物共沉淀含镍材料来制备。再次,压力可在10-80巴绝压范围内。
在优选方法中,氨生产设施前端包括燃烧式蒸汽重整器和任选的次级重整器。因此,合成气生成阶段优选包括在燃烧式蒸汽重整器中用蒸汽对烃原料、特别是天然气初级重整,以产生包含氢气、一氧化碳、二氧化碳和蒸汽的气流,以及任选的次级重整阶段,其中在次级重整器中使用空气、富集空气或氧气对任选地具有烃的另一部分的初级重整气体进一步重整。优选空气。
氨生产设施前端进一步包括高温变换反应器,所述反应器包含含铁水煤气变换催化剂的固定床。通过在升高的温度和压力下使气体混合物在水煤气变换催化剂上经过,来使通常包含氢气、一氧化碳、二氧化碳和蒸汽且潜在地还包含甲烷和氮气的重整气流任选地在温度调整之后经受一个或多个催化水煤气变换阶段。如果存在不足的蒸汽,则在气流经受水煤气变换转化之前可将蒸汽添加至气流。水煤气变换反应可描绘如下:
该反应可在一个或多个阶段中进行,包括在包含高温变换催化剂的高温变换反应器中进行的高温变换步骤。对于高温变换催化剂而言,变换反应器的入口温度优选在280-500℃范围内,更优选300-450℃,且最优选310-380℃,以使得在延长时段内催化剂的性能最大化。变换过程优选绝热地运行而不需冷却催化剂床,尽管需要时可应用一些冷却,例如通过在压力下使冷却水经过设置在催化剂床内的管。变换反应器的出口温度优选≤600℃,更优选≤550℃,以使催化剂的寿命和性能最大化。任选地,可使来自高温变换反应器的变换气流冷却并经受选自中温变换和/或低温变换的水煤气变换的一个或多个另外的阶段。中温变换和低温变换催化剂通常是铜-氧化锌-氧化铝组合物。对于中温变换催化剂而言,入口温度可在190-300℃范围内,且对于低温变换催化剂而言,入口温度可为185-270℃。含有蒸汽的合成气的流动速率可使得经过反应器中水煤气变换催化剂的一个或多个床的气体时空速度(GHSV)为≥6000小时-1。变换阶段可在1-100巴绝压、更优选15-50巴绝压范围内的压力下运行。
在本发明中,用低蒸汽高温水煤气变换催化剂替换高温变换反应器中的含铁高温水煤气变换催化剂,并且经过前端的蒸汽与碳比率由较高的第一蒸汽与碳比率调整至较低的第二蒸汽与碳比率。第二蒸汽与碳比率比第一蒸汽与碳比率低至少0.2,并且可比第一蒸汽与碳比率低至少0.3或0.4。可通过降低至一个或多个蒸汽重整器之前工艺的蒸汽流动速率来进行调整。第一蒸汽与碳比率可为≥1.5,但更通常为≥2,例如2.5至3.5。通过调整蒸汽与碳比率,在高温变换反应器入口处蒸汽与干气体比率可有用地降至≤0.45:1,优选≤0.42:1。
另外,通过降低蒸汽比率来减小经过前端的压降。前端压降可被认为是添加蒸汽的点与在水煤气变换的下游使变换气体冷却以冷凝未反应蒸汽作为水之间的压降。经过前端的第一压降可为≥5巴表压,例如5至20巴表压范围内,通常10-20巴表压。第二压降小于第一压降,优选比第一压降小至少1巴表压。
本发明的方法包括在通过替换高温变换催化剂和降低蒸汽与碳比率来减小前端压降之后,提高所述一个或多个重整器的烃原料进料速率。提高烃原料进料速率使前端压降朝向工艺前端的第一压降回增。在提高烃流动速率之后前端压降可在第一前端压降的90-100%范围内。
被替换的含铁水煤气变换催化剂可为常规的氧化铬(chromia)促进的磁铁矿催化剂。这类催化剂通常呈圆柱形粒料的形式。
低蒸汽水煤气变换催化剂可为增强的含铁高温变换催化剂或无铁高温变换催化剂。
增强的含铁水煤气变换催化剂具有使其能够以比被替换的催化剂更低的蒸汽与碳比率运行的性质。因此,增强的含铁高温变换催化剂可具有高几何表面积(GSA)和/或可含有一种或多种变换促进剂。可通过添加合适的碱性反应物如氢氧化钠或碳酸钠,从铁和金属盐的溶液中沉淀铁和其他金属化合物(在加热时分解成氧化物)来制造增强的含铁高温变换催化剂。然后将所得沉淀物洗涤、干燥并优选煅烧。如由氮物理吸附测定的BET表面积优选在20-40m2/g范围内,优选20-34m2/g,最优选20-30m2/g。干燥或煅烧的催化剂前体通常具有60至95重量%的铁氧化物含量(表示为Fe2O3)。如果存在氧化铬,则前体中的铁与铬原子比可在6至20范围内,特别是8至12。干燥或煅烧的材料可被压片以形成催化剂前体粒料。粒料可为圆柱形,具有3-10mm范围内的长度,和5-15mm范围内、优选5mm-10mm的直径。
低蒸汽水煤气变换催化剂粒料的几何表面积优选大于被替换的催化剂。不应使用比被替换的催化剂更小的粒料直径或长度来增加几何表面积,因为此举增加了经过水煤气变换反应器的压降,这是不期望的。相反,优选通过围绕粒料外周用两个、三个或更多个凸起或凹槽对催化剂成形来增加几何表面积。特别优选的形状是具有长度C和直径D的圆柱形粒料,其中圆柱形粒料的表面具有沿着其长度延伸的两个或更多个凹槽,所述圆柱具有长度为A和B的半球形端,使得(A+B+C)/D在0.25至1.25范围内,且(A+B)/C在0.03至0.3范围内。优选(A+B+C)/D在0.50至1.00范围内,更优选0.55至0.70,最优选0.55至0.66。优选(A+B)/C在0.05至0.25范围内,更优选0.1至0.25。粒料可具有3至12、优选3至7、更优选3至5个半圆、椭圆或U形凹槽,所述凹槽围绕粒料的周长均匀间隔且沿着其长度轴向延伸。当存在5个凹槽时,凹槽可具有0.1D至0.4D、优选0.1D至0.25D范围内的宽度d",当存在4个凹槽时d"优选为0.2-0.30D,且当存在3个凹槽时d"优选为0.25-0.4D,并且期望地,总凹槽宽度为≤粒料周长的35%。优选的形状是圆柱形粒料,具有4至5mm的长度、8至9mm的直径,且具有沿着粒料的长度轴向延伸的三、四或尤其是五个均匀间隔的***凹槽。低蒸汽高温变换催化剂的粒料表面积优选≥235mm2。低蒸汽高温变换催化剂的表面积表示为m2/立方米的催化剂粒料,优选≥520m2/m3,更优选≥530m2/m3,最优选≥535m2/m3。
在还原之前,含铁高温变换催化剂期望地含有氧化铜或氧化锰作为变换促进剂。铁与铜或锰原子比优选在10:1至100:1范围内。优选增强的含铁高温变换催化剂包含用氧化铬和/或氧化铝稳定的一种或多种铁氧化物,且可任选地含有氧化锌和一种或多种铜化合物。在用于变换反应前,使粒料经受还原条件,其中氧化铁还原至磁铁矿(Fe3O4),且存在的任何三氧化铬还原至倍半氧化铬,即三氧化二铬(Cr2O3)。这种还原往往在其中待实现变换反应的反应器中进行。可通过掺合具有至少2的长径比和至少5000埃(500nm)且优选小于15000埃(1500nm)的最大尺寸的催化剂前体颗粒至催化剂前体粒料中来显著提高增强的含铁高温变换催化剂的活性。优选增强的含铁高温变换催化剂包含针状氧化铁颗粒。含有铁和铬氧化物的这类催化剂组合物描述于US5656566中。替代地,可期望用氧化铝或另一种稳定化氧化物来至少部分替换铁基催化剂中的氧化铬。期望地,还可存在氧化锌和铜。这类催化剂描述于例如EP2237882中。
替代地,低蒸汽高温变换催化剂可为无铁水煤气变换催化剂。这种类型的合适的催化剂包括包含铝酸锌尖晶石的那些。因此低蒸汽水煤气变换催化剂可包含锌氧化铝尖晶石和氧化锌的混合物,组合有选自Na、K、Rb、Cs和它们的混合物的碱金属。这类催化剂描述于例如EP2141118和EP2300359中。替代地,低蒸汽高温变换催化剂可包含掺杂金属的氧化锌/氧化铝组合物。例如,合适的催化剂含有锌和铝的氧化物,连同选自Na、K、Rb、Cs、Cu、Ti、Zr、稀土元素和它们的混合物的一种或多种促进剂。这类催化剂描述于例如EP2924002中。无铁催化剂可为圆柱形粒料或如上文所述被成形。
在氨的生产中,从前端回收的变换气体混合物可经受二氧化碳去除阶段、甲烷化以去除痕量的碳氧化物,任选地调整H2:N2摩尔比,并且然后是氨合成。
可使用任何合适的二氧化碳去除单元。二氧化碳去除单元可通过以下方式起作用:反应性吸收,诸如被称为aMDEATM或BenfieldTM单元的那些,其是基于使用可再生胺或碳酸钾洗剂;或物理吸收,基于在低温下使用甲醇、二醇或另一种液体,诸如RectisolTM、SelexolTM单元。二氧化碳去除还可使用合适的固体吸附材料通过变压吸附(PSA)来进行。二氧化碳去除单元还可主要通过由于低运行温度所致的冷凝起作用来同时去除残留蒸汽。这类二氧化碳去除设备和溶剂可商购获得。
在甲烷化阶段中,氢气流中的残留一氧化碳和二氧化碳可在甲烷转化器中经甲烷化催化剂转化至甲烷。可对甲烷转化器使用任何合适的布置。因此甲烷转化器可绝热或等温地运行。可使用一个或多个甲烷转化器。可使用镍基甲烷化催化剂。例如,在单一甲烷化阶段中,来自二氧化碳去除阶段的气体可在200-400℃范围内的入口温度进料至粒状含镍甲烷化催化剂的固定床。这类催化剂通常是粒状组合物,包含20-40重量%的镍。这类甲烷化设备和催化剂可商购获得。甲烷化的压力可在10-80巴绝压范围内。
所得含有氢气和氮气的合成气体(合成气)在第一和一个或多个另外的压缩阶段中压缩至氨合成压力并传递至氨生产单元。如果在合成气生成步骤中使用空气或富氧空气,则充足的氮气可能已存在于氢气流中,但如果并非如此,则可将例如来自空气分离单元或硝酸装置排出气的另外的氮气添加至合成气。
氨生产单元包括包含氨合成催化剂的氨转化器。合成气中的氮气和氢气在催化剂上一起反应形成氨产物。氨合成催化剂通常是铁基的,但可使用其他氨合成催化剂。反应器可绝热地运行或可等温地运行。催化剂床可为轴向和/或径向流动,并且一个或多个床可提供于单个转化器容器内。在催化剂上的转化通常不完全,并且因此通常将合成气传递至含有从氨转化器回收的部分反应的气体混合物的回路,并将所得混合物进料至催化剂。进料至回路的合成气混合物可具有2.2-3.2的氢气与氮气比率。在氨生产单元中,氢气/氮气混合物可在例如80-350巴绝压、对于大规模装置而言优选150-350巴绝压范围内的高压和300-540℃、优选350-520℃范围内的温度在氨合成催化剂上经过。
氨生产单元中所产生的氨可被销售和/或一部分转化成硝酸、硝酸铵或尿素。可使用任何合适的用于生产硝酸、硝酸铵或尿素的工艺。
减小的前端压降还可以这样的方式部署以便:a)降低空气压缩机排出压力,进而允许另外的瓶颈工艺空气压缩机的速率提高;b)降低所需烃供应压力,进而允许另外的瓶颈烃压缩机或压力限制的天然气供应的速率提高;和c)提高合成气压缩机吸入压力,以允许另外的瓶颈合成气压缩机的速率提高。
现将参考以下实施例来描述本发明。
实施例1
使用Aspen HYSYS对大规模氨工艺建模以确定改变蒸汽比率的效果。工艺的单元运行如下:纯化,初级和次级蒸汽重整,高温和低温变换,CO2去除,甲烷化,压缩和氨合成。利用常规铁基高温变换催化剂运行的工艺在高温变换(HTS)单元的入口处以0.48的蒸汽与干气体摩尔比运行。用低蒸汽水煤气变换催化剂KATALCOTM 71-6替换常规铁基高温变换催化剂,使蒸汽与干气体比率能够降至0.40。相应地,初级重整器的入口处蒸汽与碳比率从2.9降至2.5。
该实施例中使用的增强的含铁高温变换催化剂KatalcoTM 71-6是一种具有20-30m2/g范围内BET表面积的共沉淀铁氧化铬高温变换催化剂。被替换的常规铁基催化剂和KATALCOTM 71-6催化剂均为圆柱形粒料,具有4.8-4.9mm范围内的长度和8.3至8.5mm范围内的直径。
蒸汽比率的降低使得能够在装置的前端上对于等同的压降而言通过量增加6%,其中蒸汽/水和工艺空气与工艺气体流量同步增加。这种增加的装置通过量对应于至合成气压缩的摩尔流量的4.6%增加和在氨产量方面3.4%的增加。
当通过量被合成气压缩机限制时,蒸汽与干气体比率的降低提高了对压缩机入口的供应压力,降低了压力比率并因此使得流动速率提高。对于以100%速度接近其最优效率运行的典型压缩机而言,压缩机性能曲线的梯度使得压力比率的降低将在这种情况下(对应于压力比率中1%的下降)能够使通过量增加4%。这种增加的装置通过量对应于至合成气压缩的摩尔流量的2.8%增加和在氨产量方面2%的增加。
Claims (9)
1.一种用于改造氨生产设施的方法,所述氨生产设施具有前端,所述前端包括以烃原料进料速率用烃原料进料的一个或多个重整器以及用得自所述一个或多个重整器的重整气进料且包含含铁水煤气变换催化剂的固定床的高温变换反应器,所述高温变换反应器在280-500℃范围内的入口温度运行,和所述前端以第一蒸汽与碳比率和第一压降运行,所述方法包括以下步骤:(i)用低蒸汽水煤气变换催化剂替换所述含铁水煤气变换催化剂以形成经改进的前端,所述低蒸汽水煤气变换催化剂选自增强的含铁高温变换催化剂和无铁高温变换催化剂,(ii)以第二蒸汽与碳比率和第二压降运行所述经改进的前端,其中所述第二蒸汽与碳比率比所述第一蒸汽与碳比率低至少0.2且所述第二压降小于所述第一压降,以及(iii)提高所述一个或多个重整器的烃原料进料速率,
其中所述无铁高温变换催化剂包含铝酸锌尖晶石;或包含锌和铝的氧化物,连同选自Na、K、Rb、Cs、Cu、Ti、Zr、稀土元素和它们的混合物的一种或多种促进剂;和
其中所述增强的含铁高温变换催化剂是沉淀的含铁催化剂,具有60至95重量%的表示为Fe2O3的铁氧化物含量,具有20-34m2/g范围内的BET表面积;或是沉淀的含铁催化剂,具有60至95重量%的表示为Fe2O3的铁氧化物含量,呈具有长度C和直径D的圆柱形粒料的形式,其中所述圆柱形粒料的表面具有沿着其长度延伸的两个或更多个凹槽,所述圆柱具有长度为A和B的半球形端,使得(A+B+C)/D在0.25至1.25范围内,且(A+B)/C在0.03至0.3范围内;或是沉淀的含铁催化剂,具有60至95重量%的表示为Fe2O3的铁氧化物含量,包含用氧化铬和/或氧化铝稳定的一种或多种铁氧化物以及针状氧化铁颗粒,并且任选地含有氧化锌和一种或多种铜化合物。
2.根据权利要求1所述的方法,其中所述氨生产设施前端包括燃烧式蒸汽重整器和任选的次级重整器。
3.根据权利要求1或权利要求2所述的方法,其中所述第二蒸汽与碳比率比所述第一蒸汽与碳比率低至少0.3。
4.根据权利要求1或权利要求2所述的方法,其中所述第二蒸汽与碳比率比所述第一蒸汽与碳比率低至少0.4。
5.根据权利要求1或权利要求2所述的方法,其中在所述含铁水煤气变换催化剂的替换之后,使所述高温变换反应器的入口处的蒸汽与干气体比率降低至≤0.45:1。
6.根据权利要求1或权利要求2所述的方法,其中在所述含铁水煤气变换催化剂的替换之后,使所述高温变换反应器的入口处的蒸汽与干气体比率降低至≤0.42:1。
7.根据权利要求1或权利要求2所述的方法,其中经过所述前端的第二压降比经过所述前端的第一压降小至少1巴表压。
8.根据权利要求1所述的方法,其中所述无铁高温变换催化剂包含锌氧化铝尖晶石和氧化锌的混合物,组合有选自Na、K、Rb、Cs和它们的混合物的碱金属。
9.根据权利要求1或权利要求2所述的方法,其中通过在步骤(iii)中提高烃原料进料速率,将所述第二压降增加至所述第一压降的90-100%。
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