TW200911364A - A catalyst, its preparation and use - Google Patents
A catalyst, its preparation and use Download PDFInfo
- Publication number
- TW200911364A TW200911364A TW097116346A TW97116346A TW200911364A TW 200911364 A TW200911364 A TW 200911364A TW 097116346 A TW097116346 A TW 097116346A TW 97116346 A TW97116346 A TW 97116346A TW 200911364 A TW200911364 A TW 200911364A
- Authority
- TW
- Taiwan
- Prior art keywords
- catalyst
- compound
- indium
- iron oxide
- hydrocarbon
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 123
- 238000000034 method Methods 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 229910052738 indium Inorganic materials 0.000 claims abstract description 41
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 38
- 150000002430 hydrocarbons Chemical class 0.000 claims description 38
- 239000004215 Carbon black (E152) Substances 0.000 claims description 32
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 14
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 229910003437 indium oxide Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
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- 239000010959 steel Substances 0.000 claims description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229910021618 Indium dichloride Inorganic materials 0.000 claims description 4
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
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- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- RDQSSKKUSGYZQB-UHFFFAOYSA-N bismuthanylidyneiron Chemical compound [Fe].[Bi] RDQSSKKUSGYZQB-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001751 lycopene Substances 0.000 description 1
- OAIJSZIZWZSQBC-GYZMGTAESA-N lycopene Chemical compound CC(C)=CCC\C(C)=C\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C=C(/C)CCC=C(C)C OAIJSZIZWZSQBC-GYZMGTAESA-N 0.000 description 1
- 229960004999 lycopene Drugs 0.000 description 1
- 235000012661 lycopene Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 229940071575 silver citrate Drugs 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- IKHZKATVXPFKTI-UHFFFAOYSA-N tellanylideneiron Chemical compound [Fe].[Te] IKHZKATVXPFKTI-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- ZCIHMQAPACOQHT-ZGMPDRQDSA-N trans-isorenieratene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/c1c(C)ccc(C)c1C)C=CC=C(/C)C=Cc2c(C)ccc(C)c2C ZCIHMQAPACOQHT-ZGMPDRQDSA-N 0.000 description 1
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
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- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/28—Molybdenum
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- 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
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- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
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Landscapes
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
200911364 九、發明說明: 【發明所屬之技術領域】 本發明係關於觸媒、製備該觸媒之方法及使可脫氮之煙 脫氫之方法。 【先前技術】 脫氫觸媒及該等觸媒之製法已為吾人所習知。以氧化鐵 為主之觸媒常用於可脫氫之煙之脫氣以產生(除其他化合 物外)對應之經脫氫的烴。在該可脫氣之煙催化脫氯為經 脫氫的烴領域中,吾人-直致力於研發展示改良性能之脫 氫觸媒。 歐洲專利第1G27928號揭示以氧化鐵為主之脫氫觸媒, 其藉由喷霧培燒鐵鹽溶液並添加選自由下列組成之群之其 他觸媒組份製得:Be、Mg、Ca、&、Ba、Se、Ti、z卜
Hf、V、Ta、M。、W、Mn、Tc、Re、Ru、〇s c。、灿、
Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、恥、a卜以、 Ο
In、T卜 Na ' Cs、La、Li、Ge、Sn、扑、出、以、&、
Nd、Pm、Sm ' Eu、Gd、Tb、Dy、h〇、&、Tm、竹及
Lu。該等觸媒通常具有一或多種鉀化合物。 【發明内容】 本發明提供包含氧化鐵、驗金屬或其化合物、及鋼或其 化合物之脫氫觸媒。 、 在較佳實施例中,本發明提供包含氧化鐵、驗金屬或其 化合物、及銦或其化合物之脫氯觸媒,其中該姻或其化合 物係以每莫耳以⑽計算之氧化鐵至少約以毫莫耳銦: 130977.doc 200911364 量存在。 本發明進一步提供製備脫氩觸媒之方法,其包含製備氧 化鐵、驗金屬或其化合物、及銦或其化合物之混合物並锻 燒該混合物,其中該銦係以每莫耳以FhO3計算之氧化鐵 至少約0.5毫莫耳銦的量存在。 本發明亦提供製備脫氫觸媒之方法,其包含製備氧化 鐵、驗金屬或其化合物、及選自由氧化銦、氣氧化鋼、硝 酸銦、氣化銦、二氯化銦及三氣化銦組成之群之銦化合物 C>ι 之混合物並锻燒該混合物。 本發明進一步提供使可脫氫之烴脫氫之方法,其包含使 包含可脫氫之烴之進料與包含氧化鐵、鹼金屬或其化合 物、及銦或其化合物之觸媒接觸。 本發明還進一步提供使用經脫氫之烴製造聚合物或共聚 物之方法,其包含使該經脫氫之烴聚合以形成包含衍生自 該經脫氫之烴之單體單元的聚合物或共聚物,其中該經脫 、 氫之烴係在如上所述使可脫氫之烴脫氫之方法中製備。 u 【實施方式】 本發明提供滿足經改良之脫氫觸媒需要之觸媒。該觸媒 包含氧化鐵、鹼金屬或其化合物、及銦或其化合物。包含 銦之觸媒較不含有銦之類似觸媒更具選擇性。另外,包含 銦及銀之觸媒可能較不含有銦及銀之類似觸媒更具活性。 該脫氫觸媒係以氧化鐵為主之觸媒。此外,鐵可以鉀鐵 氧體形式或以與任何其他觸媒組份(包括銦)之複合物形式 存在。該觸媒包含10重量%至9〇重量%之以Fe2〇3計算之氧 130977.doc 200911364 化鐵。該觸媒較佳包含40重量%至85重量%之氧化鐵,且 更佳包含60重量%至8〇重量%之氧化鐵。 氧化鐵可藉由彼等熟習此項技術者所習知之任何方法形 成或處理。另夕卜,該觸媒可包含一或多種氧化鐵類型。氧 化鐵可如美國專利中請公開案第2003/0i44566號中所述藉 由對-化鐵實施熱分解形成氧化鐵來形成,其在下文中稱 為回熱爐氧化鐵。可視情況對回熱爐氧化鐵實施處理以將
氧化鐵中之殘㈣化物含量降低至至多2_ ppm或較佳至 多1500 ppm。氧化鐵可藉由在第6族金屬或可水解之金屬 氯化物存在下喷—氯化鐵形成。另—選擇為,氧化鐵 可藉由沉澱方法形成。 在該氧化鐵用於該觸媒中之前可藉由美國專利第 5,668,075號及美國專利第5,962,757號中所述方法實施重 構。如美國專利第5,4〇1,485號中所述,在該氧化鐵用於該 觸媒中之前可對其實施處理、洗滌或熱調節。 該氧化鐵可為紅氧化鐵、黃氧化鐵或黑氧化鐵。黃氧化 鐵為水合氧化鐵,—般描述AFe2(VH2Q或__。合 添加黃氧化鐵時,至少5重量%、或較佳至少1〇重量%之觸 媒中之總乳化鐵(以Μ〗計算)可為黃氧化鐵,且至多㈣ Μ之總氧化鐵可為黃氧化鐵。紅氧化鐵之實例可藉由锻 燒精由—Η方法製得之黃氧化鐵製得。可存在於該觸 媒中之提供氧化鐵之化合物包括針鐵礦、赤鐵礦、磁鐵 礦、磁赤鐵礦及纖鐵礦。 該觸媒中之驗金屬係選自包括鐘、鈉、卸、飯、錄及妨 130977.doc 200911364 之驗金麟,且較佳係鉀。可使用—或多種該等金屬。驗 金屬可以驗金屬化合物形式存在於該觸媒中。驗金屬通常 以母莫耳以Fe2〇3計算之氧化鐵至少G 2莫耳、較佳至少 〇广莫耳、更佳至少0.45莫耳、且最佳至少〇 55莫耳的總 量存在。鹼金屬通常以每莫耳氧化鐵至多5莫耳、或較佳 至夕1莫耳的里存在1金屬化合物可包括氫氧化物;碳 酸鹽’碳酸氫鹽;m酸鹽,例如甲酸鹽、乙酸鹽、草酸豳
及擰檬酸鹽;確酸鹽;及氧化物。較佳之驗金屬化合物: 碳酸鉀。 Μ 銦可則壬油化合物形式存在,且較佳為氧化銦。鋼可 以㈣銦化合物、銅顆粒或銦奈米顆粒形式添加。鋼較佳 以氧化銦、氫氧化銦或硝酸銦添加。銦通常以每莫耳以 以2〇3計算之氧化鐵至少〇5毫莫耳、較佳至少5毫莫耳且更 佳至少10毫莫耳、且最佳至少4〇毫莫耳的總量存在。銦通 常以每莫耳氧化鐵至多丨莫耳、且較佳至多Q5莫耳的總量 存在。 该觸媒可進一步包含鑭系元素。鑭系元素係選自原子數 介於57至66範圍内(包括57及66)之鑭系元素之群。鑭系元 素較佳為鈽。鑭系元素可以鑭系元素化合物形式存在。鑭 系元素通常以每莫耳以FoO3計算之氧化鐵至少〇 〇2莫耳、 較佳至少0.05莫耳、更佳至少0.06莫耳的總量存在。鑭系 元素通常以每莫耳氧化鐵至多〇2莫耳、較佳至多〇15莫 耳、更佳至多0.丨4莫耳的總量存在。鑭系元素化合物可包 括氫氧化物,·碳酸鹽;碳酸氫鹽;羧酸鹽,例如甲酸鹽、 130977.doc 200911364 乙酸鹽、草醆鹽及檸檬酸鹽;硝酸睡 鑭系元素化合物係碳酸鈽。 -’ ^化物。較佳之 可進—步包含驗土金屬或其化合 為約或•,且其較佳為 ⑯土金屬可 以%〇3計算之氧化㈣丨 ㉟化合物每莫耳 异炙虱化鐵至少〇.〇1莫耳、 的量存在。鹼土全屬彳卜人 、 >'〇.〇2莫耳 '、且較佳至多叫耳的量存在。減鐵至多1莫 可=1:進::==金第屬6或其化合物。第6族金屬 %〇3計曾之氣/ 屬通常以每莫耳以 六士 莫耳、較佳至少0.02莫耳的番 子在。第6族金屬通常以每莫耳氧化鐵至 至多0.1莫耳的量存在。 旲耳較佳 該觸媒可進一步包含銀或其化合物。銀可以銀'氧化鈒 =乳“式存在。銀較佳以氧化銀、路酸銀、銀鐵氧 確酸銀、或碳酸銀形式添加至觸媒混合物中。 可與氧化鐵組合之其他觸媒組份包括選自由下列組成之 群之金屬及其化合物:Sc、Υ、Ti、Zr、Hf、V、Nb、 h、心、施、Tc、Re、Ru、0s、Co、Rh、lr、Ni、pd、
Pt、CU、AU、Zn、Cd、Hg、A卜 Ga、T卜 Si、Ge、Sn、
Pb、p、Aq、qu . , Bl、s、Se&Te。可藉由彼等熟習此項技 ,者所習知之任何方法添加該等組份。該等其他觸媒組份 可包括氫氧化物;碳酸氫鹽;碳酸鹽;m酸鹽,例如甲酸 鹽、乙酸鹽、草酸鹽及檸檬酸;确,酸鹽;及氧化物。鈀、 鉑、釕、铑、銥、銅、及鉻係較佳之其他觸媒組份。 130977.doc -10· 200911364 觸媒可藉由彼等熟習此項技術者所習知之任何方法製 備。例如,可形成包含氧化鐵、驗金屬或其化合物、銦或 其,合物及任何其他觸媒組份之膏糊。可研磨及/或捏製
等觸媒、’且伤之混合物或可使任何該等組份之均質或異質 各液次潰於氡化鐵上。每一組份之足量可根據擬製備觸媒 之、成來°十算。適用方法之實例可參見美國專利第 5’668’075號;美目# μ第5,962,757號;美_專利第 5’689’023號;美_專利第5,171,914號;美_專利第 5’190’906娩、美國專利第6,191,〇65號、及歐洲專利 1027928號,該等專利皆以引用方式併入本文中。 在觸媒形成中,可使包含氧化鐵、鹼金屬或其化合物、 $或其化合物及任何其他觸媒組份之混合物成形為任何適 宜形式之顆粒,例如,銳劑、球狀物、丸劑、輕狀物、三 葉體、扭曲三葉體、四葉體、環狀物、星狀物、空心及實 心圓柱體、及如美國專利申請公開案第2〇〇5_〇232853號令 所述之不對稱葉形顆粒。添加適量水(例如以混合物重量 計最多30重量%、一般2至2〇重量%)可有助於成形為: 粒。若添加水,則在锻燒前其可至少部分地被去除。適宜 成形方法係造粒、擠出、及壓製。混合物可經噴霧或噴霧 乾燥而非藉由造粒、擠出或壓製來形成觸媒。若需要,、噴 霧乾燥可擴展至包括造粒及锻燒。 、 其他化合物可與用於幫助使觸媒成形及/或掩出之製程 的混合物組合,例如飽和或不飽和脂肪酸(例如棕搁酸、 硬脂酸、或油酸)或其鹽、多醣衍生醆或其鹽、或石墨、 130977.doc 200911364 澱粉、或纖維素。可施用脂肪酸或多醣衍生酸之任何鹽, 例如銨鹽或本文上述任何金屬之鹽。就其分子結構而言, 月曰肪酸可包含6個至30個碳原子(包括6個及3〇個),較佳1〇 個至25個碳原子(包括10個及25個)。當使用脂肪酸或多醣 衍生酸時,其可與製備觸媒中所用之金屬鹽組合以形成脂 肪酸或多醣衍生酸之鹽。相對於混合物重量,其他化合物 之適宜量為(例如)至多】重量%、尤其為〇 〇〇1至〇 5重量 %。 在形成後,可對該觸媒混合物實施乾燥及缎燒。乾燥通 常包含在約30 C至約500〇C、較佳約1 〇〇〇c至約3〇〇。(:下加 熱該觸媒。乾燥時間通常係約2分鐘至5小時,較佳為約5 分鐘至約1小時。煅燒通常包含一般在惰性氣氛(例如氮氣 或氦氣)或氧化性氣氛(例如含氧氣體、空氣、富氧空氣或 氧氣/惰性氣體混合物)中加熱該觸媒。锻燒溫度一般為至 少約600°C、或較佳至少約7〇0〇c、更佳至少825°c。煅燒 溫度一般為至多約1 600。(:、或較佳至多約丨3〇〇°c。一般而 a,锻燒之持續時間係自5分鐘至1 2小時,更一般而言為 自10分鐘至6小時。 根據本發明所形成之觸媒可展示眾多種物理特性。觸媒 表面結構(通常關於孔隙體積 '中值孔徑及表面積)可在寬 範圍内選擇。觸媒表面結構可受選擇之煅燒溫度及時間、 及擠出輔助物之應用影響。 適且的’觸媒孔隙體積為至少〇.〇 1 ml/g,更適宜地至少 〇.〇5 ml/g。適宜地,觸媒孔隙體積為至多〇 5 ml/g,較佳 130977.doc -12- 200911364 至多〇·4 ml/g,更佳至多0.3 ml/g,且最佳至多0.2 ml/g。 適宜地,觸媒中值孔徑為至少50〇 A,尤其至少1〇〇〇 A。 適宜地,觸媒中值孔徑為至多20000 A,尤其至多15000 A。在較佳實施例中,中值孔徑介於2000至10000人範圍 内。本文所用之孔隙體積及中值孔徑係根據ASTM D4282-92使用Micromeretics Autopore 9420模型藉由壓汞法來量 測’絕對壓力為6000 psia (4.2x107 Pa);(接觸角為130。, 水銀表面張力為0.473 N/m)。本文所用之中值孔徑定義為 在達到50%壓汞體積時的孔徑。 觸媒表面積較佳介於0.(^-20 m2/g之間,更佳介於〇丨_1〇 m2/g之間。 觸媒之抗壓強度適宜為至少1 〇 N/mm,且其更適宜介於 20至l〇〇N/mm之間’例如約55或60N/mm。 在另一態樣中’本發明提供使可脫氫之烴脫氫之方法, 其藉由使可脫氫之烴及蒸汽與根據本發明製得之以氧化鐵 為主之觸媒接觸產生對應之經脫氫之烴來實施。 藉由該脫氫方法所形成之經脫氫之烴係具有以下通式之 化合物: r1r2c=ch2 其中R1及R2獨立代核基、縣或笨基或氯原子 該可脫氫之烴係具有以下通式之化合物: κ XV πκη3 其中R1及R2獨立代表烧基、烯基或苯基或氫原子。 適宜苯基可具有一或多個甲基作為取代基。適宜烷基通 130977.doc 13 - 200911364 常具有2個至20個碳原子/分子,且較佳為3個至8個碳原 子,例如正丁烷及2-甲基丁烷之情形。適宜烷基取代基係 丙基(-CH2_CH2_CH3)、2·丙基(即,i•甲基乙基,_CH(_CH3)2)、 丁基(-CH2-CH2-CH2-CH3)、2-甲基-丙基(_CH2_CH(_CH3)2)、及 己基(-CH2-CH2-CH2-CH2-CH2-CH3) ’ 尤其係乙基(_Ch2_Ch3)。 適宜烯基通常具有約4個至約20個碳原子/分子,且較佳為 4個至8個碳原子/分子。 忒可脫氫之烴可為經烷基取代之苯,但亦可應用其他芳 香族化合物,例如經烷基取代之萘、蒽、或吡啶。適宜之 可脫氫之烴的實例係丁基苯、己基苯、(2_甲基丙基)苯、 (1-曱基乙基)苯(即,異丙苯)、i•乙基·2_曱基-笨、丨,4-二 乙基苯、乙基苯、i-丁烯、2_甲基丁烷及3_甲基小丁烯。 亦可利用本方法將正T烧經由i•丁 _化成^丁二稀且 將2-甲基丁烷經由第三戊烯轉化成異戊二烯。 可藉由该方法產生之較佳經脫氫之烴的實例係丁二烯、 α-曱基苯乙烯、二乙烯基苯、異戊二烯及苯乙烯。 該脫氫方法通常為氣相方法;其中使包含反應物之氣體 進料與固體觸媒接觸。觸媒可以觸媒粒子流化床形式或以 填充床形式存在。該方法可以分批製程或連續製程來實 施。氫可為該脫氳方法之另一產物,且所討論之脫氫可為 非氧化性脫氫。實施該脫氫方法之適用方法之實例可參見 美國專利第5,689,023號;美國專利第5,171,914號;美國專 利第5,190,906號;美國專利第6,191,〇65號,及歐洲專利第 1027928號,該等專利皆以引用方式併入本文中。 130977.doc -14· 200911364 較佳使用水’水可呈蒸汽形式作為進料之額外組份。水 的存在將使脫氫方法期間焦炭沈積於觸媒上之速率減小。 一般而言,進料中水與可脫氫之烴之莫耳比介於i至π之 間’更一般而言為3至30,例如5至1 〇。 脫氫方法一般在50(TC至70(TC、更一般在55〇。(:至65〇它 (例如600°C、或63〇t )範圍之溫度下實施。在—個實施例 中,該脫氫方法係在等溫下實施。在其他實施例中,該脫 氫方法係以絕熱方式實施,在此情形下,所提及溫度為反 應器入口溫度,且隨著脫氫進行,通常溫度最多可降低 15〇°C,更通常降低1〇至120。(:。絕對壓力通常在1〇至3〇〇 kPa、更通常在20至200 kPa範圍内,例如50 kPa、或12〇 kPa。 若需要,可使用一個、兩個、或更多個反應器,例如三 個或四個。該等反應器可串聯或平行作業。其可彼此獨立 或不彼此獨立地作業,且各反應器可在相同或不同條件下 作業。 當使用填充床反應器以氣相方法實施該脫氫方法時, LHSV可較佳地在0.01·10 h-i範圍内,更佳在〇丨_2 h_,範圍 内。本文所用之術語「LHSV」意指液體小時空間流速 (Liquid Hourly Space Velocity),其定義為在正常條件 (即’ 〇°C與1巴絕對壓力)下量測的烴類進料之液體體積流 速除以觸媒床體積,或若有兩個或更多個觸媒床,則除以 該等觸媒床之總體積。 該脫氫方法之條件可經選擇以使可脫氫之烴之轉化率在 130977.doc 15 200911364 或更佳35-75莫耳%範圍 2〇·100莫耳%、較佳30-80莫耳% 内。 觸媒活性(丁7〇)定義為在仏 , μ. 々任、·,°疋作業條件下在脫氫方法中 J脱虱之煙之轉化裘主7λ (轉化羊為7以耳%時的溫度。因此,更 性之觸媒比較不具活性夕艇丄甘 八 觸媒具有較低之Τ70。對應之選 擇性(S70)定義為在轉化率 、 為70莫耳%之溫度下對期望產物 <選擇性。
/藉由任何習知手段自脫氫方法之產物回收經脫氫之 經。舉,而言’脫氫方法可包括分㈣反應性蒸館。若需 ^脫氫方法可包括氯化步驟,其中使至少部分產物經受 氫化’藉由氫化使至少部分在脫氫期間所形成之任何副產 物轉化成經脫氫之烴。經受氫化之該部分產物可為富含副 產物之*分產物。該氫化已為業内所習知。舉例而言,自 美國專利第5,5()4,268號;纟國專利第5,156,816;及美國專 利第4,822,936號所獲知之方法可方便地應用於本發明中, 該等專利以引用方式併入本文中。 脫氫方法之一個較佳實施例係使乙基苯非氧化性脫氫形 成苯乙稀。該實施例通常包含在約500〇C至約700。(:之溫度 下向含有觸媒之反應區供應包含乙基苯及蒸汽之進料。蒸 >飞通常以介於約7至約15之間之蒸汽與烴的莫耳比存在於 進料中。另一選擇為,該方法可在較低之蒸汽與烴之莫耳 比下實施’該莫耳比介於約1至約7之間、較佳介於約2至 約6之間。 脫氮方法之另—較佳實施例係使乙基苯氧化性脫氫形成 130977.doc 16 200911364 苯乙稀。該實施例通常包含在約5〇〇。〇至約800〇C之溫度下 向含有觸媒之反應區供應乙基苯及諸如氧、碘化物、硫、 二氧化硫或二氧化碳等氧化劑。該氧化性脫氫反應係放熱 反應’因此該反應可在較低溫度下及/或較低蒸汽與油比 率下實施。 脫氯方法之另一較佳實施例係使異戊烯脫氫形成異戊二 烯。該實施例通常包含在約525t:至約675它之溫度下向含 有觸媒之反應區供應包含2_甲基_ι_ 丁烯、2_甲基_2_ 丁烯、 及3-甲基-1 -丁烯之混合異戊烯進料。該方法通常在大氣壓
力下實施。蒸汽通常以介於約135至約3丨之間之蒸汽與烴 之莫耳比添加至進料中D 脫氫方法之另一較佳實施例係使丁烯脫氫形成丁二烯。 該實施例通常包含在約5〇〇t至約7〇〇。〇之溫度下向含有觸 媒之反應區供應包含丨_ 丁烯及2_ 丁烯(順式及/或反式同分 異構體)之混合丁烯進料。 由於大多數該等脫氫方法之吸熱性質,額外之熱輸入通 常是需要的以維持戶斤需要之溫度以維持轉化率纟選擇性。 熱可在反應區之前、反應區之間(當存在兩個或更多個反 應區時)添加或直接添加至反應區中。 適宜加熱方法之較佳實施例係使用習用熱交換器。製程 流可在進人第-或任何隨後反應器之前加熱。較佳之熱來 源包括蒸汽及其他經加熱之製程流。 適宜加熱方法之另一較佳實施例係使用如美國專利第 7,025,940號中所述之無焰分佈式燃燒加熱器系統,該專利 130977.doc -17- 200911364 以引用方式併入本文中。 適宜加熱方法之另一較佳實施例係催化或非催化氧化性 再加熱。該類型加熱方法之實施例闡述於美國專利第 4,914,249號;美國專利第4,812,597號;及美國專利第 4,717,779中;該等專利皆以引用方式併入本文中。 藉由該脫氫方法所產生之經脫氫之烴可在聚合方法及共 聚合方法中用作單體。舉例而言’所獲得之苯乙稀可用於 產生聚苯乙稀及苯乙稀/二烯橡膠。藉由使用較低成本之 f) 觸媒之本發明所達成之改良的觸媒性能可導致用於產生經 脫氫之烴之更有吸引力的方法,且因此導致更有吸引力之 方法,其包含產生經脫氫之烴及隨後在包含該經脫氫之烴 單體單元之聚合物及共聚物之製造中使用該經脫氫之烴。 對於適用聚合觸媒、聚合方法、聚合物處理方法及所得聚 合物之用途’可參閱H.F. Marks等人(編輯), 「Encyclopedia of Polymer Science and Engineering」,第 2 版,紐約,第16卷,第1-246頁及其中所引用之參考文 〇 獻。 提供以下實例以闡釋本發明’但不應將其理解為限制本 -· 發明之犯圍。只例 1_ 15 係與 hte Aktiengesellschaft, 、 Heidelberg ’德國合作實施。其他實例係使用標準等溫測 試條件實施。 實例1(比較) 觸媒係藉由將以下組合製備:13.5 g藉由熱分解氣化鐵 製得之氧化鐵(Fe203)、1.5 g黃氧化鐵(Fe〇〇H)、3.97 g碳 130977.doc -18· 200911364 酸斜、2.07 g碳酸鈽(呈含有52重量%之以之水合(^2((:〇3)3 形式)、0.24 g三氧化鉬及〇 24 g碳酸鈣。向該混合物中添 加水並將該混合物研磨丨5分鐘。擠出該混合物以形成直徑 為3 mm且長約3 mm之顆粒。使顆粒在空氣中於17〇〇c下乾 燥15分鐘且隨後在空氣中於9〇〇<>c下煅燒j小時。將顆粒用 研缽及研杵粉碎並用合適網篩篩分以使粒徑介於315_5〇〇 μηι之間。 將1.1 ml觸媒樣品裝載至多孔反應器(内徑5 mm)之等溫 區並用於自乙基苯製備苯乙烯。在觸媒床上面及下面裝載 惰性物質。測試條件如下:出口分壓為76 kpa,蒸汽與乙 基苯之莫耳比為10,且1^8¥為〇 65 ^。在該測試中,將 溫度最初保持在5901達約18天時間段。隨後將該觸媒在 二個不同溫度之每一溫度下測試Μ小時:約59(rc、約593 C及約596 C。在三個溫度下所量測之乙基苯之轉化率 (「c」)及對苯乙烯之選擇性(「s」)顯示於表1中。一式兩 份對該觸媒進行測試且所顯示之數據係平均結果。 實例2-5 觸媒係根據本發明製備。使W例1巾所述之成份。實 例2-5之4等觸媒含有如表i中所示之以不同形式及量(每莫 耳以Fe2〇3計算之氧化鐵之毫莫耳數)添加之銦。該等觸媒 係在與貝例1觸媒相同之條件下測試,且觸媒性能顯示於 表中 式兩伤對實例2之觸媒進行測試且所顯示之數據 係平均結果。 130977.doc -19- 200911364 f
S% 95.8 96.7 96.3 96.4 97.5 pM 00 cn 〇 OO 'Ί U ON r—^ 卜 ON V〇 r-H Ρ ON ν〇 OS v〇 On 00 ON Η in in in >〇 in m vd ON Os v〇 <^ 〇\ % O) rn OO Ί U a\ 5 On v〇 5 Os 城: P m Os m Q\ in OS Η in in in yn 寸 ^—4 卜 卜 00 vb 〇\ ON On vd ON 0| o v〇 vq CN 1 U V〇" v〇 00 v〇 l〇 v〇 00 »r> Ρ 〇\ On 冢 g CN Os Η κη in l〇 τ〇Η 〇 沄 環 荽 < m X f**l K ^rn o o έ 5 <N m 寸 S -20- 130977.doc 200911364 自實例1-5可以看出’含有銦之觸媒較沒有銦之觸媒更 具選擇性。 實例6(比較)及7-12 實例6-12展示當以氯化銦添加銦時對觸媒性能之影響。 實例6之觸媒係按照實例1之方法製備及測試,且實例7_12
<觸嫘係按照實例1之方法製備,除如表2中所示以不同形 式及量(每莫耳以以2〇3計算之氧化鐵銦之毫莫耳數)添加氣 化銦外。冑該等觸媒最初保持在。隨後將該 等觸媒在三個不同溫度之每—溫度下測試叫、時:約^ C、約595。(:及約60(TC。在:個、、田疮丁私曰, 皿度下所量測之乙基苯之 率(C」)及對苯乙烯之選 u 一 ^伴r玍(ί>」)顯不於表2中。 式兩伤對實例6之觸媒進 έ士果。 刃忒且所顯不之數據係平均 自實例6 -1 2可 不具有銦之觸媒 、 3有以乳化鋼添加之銦之觸媒較 更具選擇性。
130977.doc 200911364
第三溫度 S% 95.8 96.4 98.1 96.4 98.2 95.9 98.2 C% 72.7 70.9 56.5 70.5 42.2 73.4 56.5 P Η 600 600 600 599 600 o § ON in 第二溫度 S% 96.2 96.9 98.3 96.9 99.1 96.3 98.3 C% 69.7 66.7 51.6 66.6 37.9 70.4 51.4 Ρ Η in On ΟΝ 595 595 ON 594 第一溫度 s% 96.7 97.3 98.4 97.3 99.1 96.7 99.1 c% 66.2 62.3 47.0 62.5 34.2 66.8 46.0 Ρ Η 590 590 590 589 590 590 〇\ OO IT) 塌 Ο in 化合物 Ν/Α InCl InCl InCl2 InCl2 InCl3 InCl3 實例 6(組合物) 卜 00 〇 <N -22- 130977.doc 200911364 實例13(比較)及14-is 實例13-15展示當以氧化銦添加銦時對觸媒性能之影 響。實例13之觸媒係按照實例丨之方法製備及測試,且實 例14-15之觸媒係按照實例丨之方法製備,除如表3中所示 以不同i (母莫耳以FhO3計算之氧化鐵銦之毫莫耳數)添加 氧化銦外。將該等觸媒最初保持在59〇<t達2〇天。隨後將 該等觸媒在四個不同溫度之每一溫度下測試24小時:約 590°C、約593t、約596。(:及約599t。在四個溫度下所量 測之乙基苯之轉化率(「C」)及對苯乙烯之選擇性(「s」) 顯示於表3中。一式兩份對實例丨3之觸媒進行測試且所顯 示之數據係平均結果。 自實例1 3 -1 5可以看出,含有以氧化銦添加之銦之觸媒 較不具有銦之觸媒更具選擇性。 130977.doc 23- 200911364 育四溫度 \ S% 95.3 95.8 96.2 C% 74.0 73.4 71.9 Ρ Η Os ON iri 598 598 育三溫度 S% 95.6 96.1 96.4 C% 72.3 71.5 70.1 Ρ Η 596 in ON iT) 594 育二溫度 s% 95.8 96.2 96.4 c% 70.7 70.5 69.3 Ρ Η m in 592 客一溫度 s% 96.1 96.4 96.6 c% 68.7 68.8 67.9 ο。 Η 590 589 00 00 ITi 環 ♦1 〇 化合物 N/A ΙΠ2〇3 ΙΠ2〇3 寸 -寸M_ 〇〇-卜卜60- 130977.doc • 24- 200911364 實例16-17(比較)及18_19 實例16-17之觸媒係藉由將900 g含有0.08重量%之〇1且具 有3.3 m/g表面積之氧化鐵(Fe2〇3)(藉由熱分解氯化鐵製 得)及100 g黃氧化鐵(Fe〇〇H)與足量碳酸鉀、碳酸鈽(呈含 有52重量/〇之Ce之7]c合Ce2(C03)3形式)、三氧化!目及碳酸 鈣加以組合來製備以得到具有如表4中所示組成之觸媒。 添加水(相對於無水混合物之重量約為1〇重量%)以形成膏
糊,並擠出該膏糊以形成直徑3麵之圓柱體,隨後將其切 割成6 mm長度。將該等顆粒在17〇()(:下乾燥15分鐘。將實 例16之觸媒在空氣中於825t下煅燒丨小時,且將實例I?之 觸媒在空1中於下锻燒i小時。锻燒後每種觸媒之组 成以毫莫耳/莫耳以Fe2〇3計算之氧化鐵顯示於表彳中。實例 心9之觸媒係按照實例16.17之方法製備,除添加氧化鋼 以得到如表4中所示之組合物外。將實㈣之觸媒在空氣 中於8抓下炮燒1小時,且將實㈣之觸媒在空氣中於 900°C下煅燒1小時。 使用該觸媒之_ ^樣品在等溫㈣條件下於經設計 用於連續作業之反應器中自乙基苯製備苯乙烤。條件如 下:絕對塵力為76心,蒸汽與乙基苯之莫耳比為10,且 LHSV為0.65 在該測試中,將溫度最初保持在_達 約10天時間段。稍後調節該溫 ^十 及以這到乙基苯之70莫耳〇/〇 轉化率CT70)。量測在選定溫度下對 (S70)。 ,〜、伴I王 130977.doc •25- 200911364 表4 實例 組成,毫莫耳/莫耳氧化鐵 T70 S70 Iri2〇3 Mo Ce Ca K °C % 16(組合物) 0 18 80 25 620 588.8 95.1 17(組合物) 0 18 80 25 620 593.5 95.6 18 15 18 80 25 620 589.1 95.5 19 50 18 80 25 620 590.7 96.2 自實例1 6-1 9可以看出,含有銦之觸媒較在相同溫度下 煅燒之不含有銦之類似觸媒更具選擇性。 熟習此項技術者可改變上文所示的許多變量及其他變量 以獲得對於具體應用最有效之脫氫觸媒。亦可添加其他觸 媒組份以改變觸媒之特性及性能。可在諸如乾燥時間及溫 度、煅燒時間及溫度、及處理速度等變量方面改變觸媒製 造方法以改變觸媒之特性及性能。
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Claims (1)
- 200911364 十、申請專利範圍:-種脫氫觸媒’其包含氧化鐵、鹼金屬或其化合物、及 銦或其化合物,其中該銦或其化合物係以每莫耳以ho〗 十算之氧化鐵至少約〇 5毫莫耳銦的量存在。 如請求項1之觸媒,其中該銦或其化合物係以每莫耳以 Fe2〇3計算之氧化鐵約5至約500毫莫耳銦的量存在。 士叫求項1或2之觸媒,其中該銦或其化合物係以每莫耳 x Fe2〇3 §十算之氧化鐵約1〇至約3〇〇毫莫耳銦的量存在。 如:求項1至3中任一項之觸媒,其中該鋼或其化合物係 以母莫耳以Fe2〇3計算之氧化鐵約15至約1 50毫莫耳銦的 量存在。 5.如叫求項丨至4中任一項之觸媒,其中該鹼金屬或其化合 物包含鉀。 σ 如吻求項1至5中任一項之觸媒,其中該觸媒進一步包人 鋼系元素或其化合物0 S 7.如明求項6之觸媒,其中該鑭系元素或其化合物 鈽。 ^ 3 女口月求項1至7中任一項之觸媒,其進一纟包含鹼土 或其化合物。 求項8之觸媒,其中該驗土金屬或其化合物八 金5。 。3 1 〇 ·如請求項]5 ^2 、至9中任一項之觸媒,其進一步包含第6 屬或其化合物。 金 /項10之觸媒’其中該第6族金屬或其化合物包含 130977.doc 200911364 紹〇 ’其中該觸媒進—步包 12.如請求項1至u中任一項之觸媒 含銀或其化合物。 13. 其中該觸媒進—步包 、鈦及銅組成之群之 如請求項1至!2中任一項之觸媒, 含選自由&、鉑、釕、锇、铑、銥 金屬。 14. 如明求項u13中任一項之觸媒,其中該氧化鐵包含 由熱分解齒化鐵所形成之回熱爐氧化鐵。U 15. :凊求項m中任一項之觸媒’其中該氧化鐵係藉由 在重構劑存在下實施熱處理來重構。 16. -種製備脫氫觸媒之方法,其包含製備氧化鐵、驗金屬 或其化合物、及銅或其化合物之混合物並锻燒該混合 物’其中該銦係以每莫耳以Fe2〇3計算之氧化鐵至少約 0.5毫莫耳銦的量存在。 17·如請求項16之方法,其中該錮化合物係選自由氫氧化 銦硝馱銦、氣化銦、二氣化銦及三氣化銦組成之群。 18.如請求項16或17之方法’其進一步包含向該混合物中添 加鹼土金屬或其化合物。 19·如請求項16或17之方法,其進一步包含向該混合物中添 加第6族金屬或其化合物。 2〇,如請求項16至19中任一項之方法,其中該煅燒係在約 600 C至約1300°C之溫度下實施。 2 1 ·如凊求項1 6至2〇中任一項之方法,其中該煅燒係在約 750 C至約1200。(:之溫度下實施。 130977.doc 200911364 22. 如請求項16至21中任一項之方本,甘士 4 項之方法,其中該煅燒係在高於 800°C之溫度下實施。 23. -種使可脫氫之烴脫氫之方法,其包含使包含可脫氯之 烴之進料與包含氧化鐵、驗金屬或其化合物、及铜或其 化合物之觸媒接觸,其中該銦或其化合物係以每莫耳以 FhCh計算之氧化鐵至少約〇 5毫莫耳銦的量存在。 24. 如請求項23之方法,其中該銦化合物係選自由氯氧化 銦、硝酸麵、氯化銦、二氯化銦及三氯化銦組成之群。 25. 如請求項23或24之方法,其中該可脫氫之烴包含乙基 苯。 26.如請求項23至25中任-項之方法,其中該進料進—步包 含蒸汽。 27·如請求項26之方法’其中該蒸汽係以每莫耳可脫氫之烴 0.5至12莫耳蒸 之莫耳比存在於該進料中。28·如„月求項26之方法,其中該蒸汽係以每莫耳可脫氫之烴 1至6莫耳蒸 >飞之莫耳比存在於該進料中。 29. -種使用經脫氫之烴來製造聚合物或共聚物之方法,其 包3使β玄經脫氫之烴聚合以形成包含衍生自該經脫氫之 烴之單體單元的聚合物或共聚物,其中該經脫氫之烴係 以如”月求項23至28中任-項之使可脫氫之烴脫氫之方法 來製備。 130977.doc 200911364 七、指定代表圖: (一) 本案指定代表圖為:(無) (二) 本代表圖之元件符號簡單說明: 八、本案若有化學式時,請揭示最能顯示發明特徵的化學式: (無)130977.doc
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TW097116346A TW200911364A (en) | 2007-05-03 | 2008-05-02 | A catalyst, its preparation and use |
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EP (1) | EP2158174A2 (zh) |
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KR (1) | KR20100017488A (zh) |
CN (1) | CN101679144A (zh) |
AR (1) | AR066416A1 (zh) |
BR (1) | BRPI0810782A2 (zh) |
CA (1) | CA2685679A1 (zh) |
RU (1) | RU2009144771A (zh) |
TW (1) | TW200911364A (zh) |
WO (1) | WO2008137572A2 (zh) |
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US20110105818A1 (en) * | 2009-10-31 | 2011-05-05 | Fina Technology, Inc. | Dehydrogenation Catalyst with a Water Gas Shift Co-Catalyst |
PL3140039T3 (pl) * | 2014-05-09 | 2021-01-25 | Basf Se | Ulepszony katalizator do odwodorniania węglowodorów |
CN106582689B (zh) * | 2015-10-16 | 2019-07-09 | 中国石油化工股份有限公司 | 用于制备苯乙烯的脱氢催化剂 |
CN109569636B (zh) * | 2017-09-29 | 2020-06-09 | 中国石油化工股份有限公司 | 高活性低水比乙苯脱氢催化剂及其制备方法 |
WO2019212218A1 (ko) * | 2018-05-02 | 2019-11-07 | 한양대학교 산학협력단 | 광소결 나노잉크, 광소결 방법 그리고 전도성 나노 구조체 |
CN115487833B (zh) * | 2021-06-18 | 2024-03-26 | 中国石油化工股份有限公司 | 低水比环境下脱氢的催化剂及其制备方法和应用和乙苯脱氢方法 |
Family Cites Families (14)
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US3872027A (en) * | 1970-02-13 | 1975-03-18 | Petro Tex Chem Corp | Oxidative dehydrogenation catalysts and their method of preparation |
US4162234A (en) * | 1974-07-22 | 1979-07-24 | The Standard Oil Company | Oxidation catalysts |
GB1523772A (en) * | 1974-07-22 | 1978-09-06 | Standard Oil Co | Oxidation catalysts |
US4429171A (en) * | 1980-11-28 | 1984-01-31 | Asahi-Dow Limited | Method for manufacture of orthomethylated phenol compounds |
US4404123A (en) * | 1982-12-15 | 1983-09-13 | Mobil Oil Corporation | Catalysts for para-ethyltoluene dehydrogenation |
JPS6092224A (ja) * | 1983-10-26 | 1985-05-23 | Nippon Zeon Co Ltd | 共役ジオレフインの製造法 |
US6287432B1 (en) * | 1987-03-13 | 2001-09-11 | The Standard Oil Company | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions |
JPH04277030A (ja) * | 1991-03-05 | 1992-10-02 | Nissan Gaadoraa Shokubai Kk | エチルベンゼン脱水素触媒 |
AU707906B2 (en) * | 1994-12-14 | 1999-07-22 | Shell Internationale Research Maatschappij B.V. | Restructured iron oxide |
DE19843242A1 (de) * | 1998-09-11 | 2000-03-23 | Inst Angewandte Chemie Berlin | Verfahren zur Herstellung aktiver und/oder selektiver Feststoff-Katalysatoren aus anorganischen oder metallorganischen Feststoffen oder Gemischen davon |
DE50012271D1 (de) * | 1999-02-10 | 2006-04-27 | Basf Ag | Katalysator zur Dehydrierung von Ethylbenzol zu Styrol |
US20040133054A1 (en) * | 2002-12-06 | 2004-07-08 | Pelati Joseph E. | Dehydrogenation catalyst and process for preparing the same |
US20050075243A1 (en) * | 2003-10-07 | 2005-04-07 | Sud-Chemie, Inc. | Catalyst for dehydrogenation of hydrocarbons |
AU2005307751A1 (en) * | 2004-11-18 | 2006-05-26 | Shell Internationale Research Maatschappij B.V. | An improved process for the manufacture of an alkenyl aromatic compound under low steam-to-oil process conditions |
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- 2008-05-01 US US12/113,871 patent/US20090281256A1/en not_active Abandoned
- 2008-05-01 WO PCT/US2008/062260 patent/WO2008137572A2/en active Application Filing
- 2008-05-01 RU RU2009144771/04A patent/RU2009144771A/ru not_active Application Discontinuation
- 2008-05-01 KR KR1020097024925A patent/KR20100017488A/ko not_active Application Discontinuation
- 2008-05-01 CA CA002685679A patent/CA2685679A1/en not_active Abandoned
- 2008-05-01 CN CN200880018406A patent/CN101679144A/zh active Pending
- 2008-05-01 EP EP08747378A patent/EP2158174A2/en not_active Withdrawn
- 2008-05-01 JP JP2010506643A patent/JP5266312B2/ja not_active Expired - Fee Related
- 2008-05-02 TW TW097116346A patent/TW200911364A/zh unknown
- 2008-05-02 AR ARP080101859A patent/AR066416A1/es unknown
Also Published As
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RU2009144771A (ru) | 2011-06-10 |
JP5266312B2 (ja) | 2013-08-21 |
EP2158174A2 (en) | 2010-03-03 |
KR20100017488A (ko) | 2010-02-16 |
CN101679144A (zh) | 2010-03-24 |
BRPI0810782A2 (pt) | 2014-10-29 |
JP2010525940A (ja) | 2010-07-29 |
CA2685679A1 (en) | 2008-11-13 |
AR066416A1 (es) | 2009-08-19 |
US20090281256A1 (en) | 2009-11-12 |
WO2008137572A2 (en) | 2008-11-13 |
WO2008137572A3 (en) | 2009-01-22 |
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