TW201412396A - 丁二烯之製造用觸媒、該觸媒之製造方法及使用該觸媒之丁二烯的製造方法 - Google Patents
丁二烯之製造用觸媒、該觸媒之製造方法及使用該觸媒之丁二烯的製造方法 Download PDFInfo
- Publication number
- TW201412396A TW201412396A TW102114335A TW102114335A TW201412396A TW 201412396 A TW201412396 A TW 201412396A TW 102114335 A TW102114335 A TW 102114335A TW 102114335 A TW102114335 A TW 102114335A TW 201412396 A TW201412396 A TW 201412396A
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- Prior art keywords
- catalyst
- molding
- butadiene
- reaction
- producing
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 171
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000011148 porous material Substances 0.000 claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 14
- 239000011733 molybdenum Substances 0.000 claims abstract description 14
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims description 62
- 239000000843 powder Substances 0.000 claims description 42
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 19
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
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- 239000011575 calcium Substances 0.000 claims description 3
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- 239000011651 chromium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 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 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract 2
- 239000007858 starting material Substances 0.000 abstract 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
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- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
- B01J37/0223—Coating of particles by rotation
-
- 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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
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Abstract
本發明係一種用於製造以正丁烯為原料之丁二烯的觸媒、其製造方法及使用該觸媒之丁二烯之製造方法。具體而言,本發明係一種可自反應初期起穩定地且以高產率製造丁二烯的用於利用正丁烯之氣相接觸氧化脫氫來製造丁二烯的觸媒、其製造方法及丁二烯之製造方法。該觸媒係巨孔(macropore)之細孔容積占整體之細孔容積的80%以上、更佳為占90%以上的含有以鉬作為必需成分之複合金屬氧化物的成型觸媒。
Description
本發明係關於一種於高轉化率、高產率下,自反應初期起由正丁烯穩定地製造丁二烯之觸媒、該觸媒之製造方法及使用該觸媒之丁二烯之製造方法。
丁二烯係用作合成橡膠之原料之重要之化學品,合成橡膠大量使用於汽車之輪胎等。幾乎所有丁二烯係藉由石油之分解步驟而製造。自由異丁烯、正丁烯、丁二烯等構成之C4餾分提取、分離丁二烯而製造。近年來,由於世界性之汽車需求之提高及環境意識之提高,以丁二烯作為製造原料之節能型之汽車輪胎之需求急遽增加。又,由於石腦油裂解器(naphtha cracker)之運行率之降低、源自天然氣體之石油化學原料之利用,而導致持續處於丁二烯之需求量遠遠超出自C4餾分之生產之狀態,因此業界期望開發新的丁二烯製造方法。
周知有由提取丁二烯後所殘留之正丁烯製造丁二烯之方法,例如專利文獻1及專利文獻2中記載有於以鉬、鉍、鐵及鈷為主成分之複合金屬氧化物觸媒之存在下進行氧化脫氫之方法,但是就觸媒活性、丁二烯選擇性、反應運轉之穩定性、觸媒壽命及觸媒製造等觀點而言,先前之觸媒對於工業化而言並不充分,期望對其進行改良。
可認為,該反應之觸媒壽命及反應運轉之不穩定性之原因在於蓄積於觸媒上之碳成分。專利文獻3中記載有,藉由利用惰性之固形物稀釋觸媒,可抑制生成物之逐次反應,從而抑制碳成分之蓄積。然而,該方法中,不僅無法充分地抑制碳成分之蓄積,而且隨著活性成分量之減少而導致產率之減少,活性成分與惰性固形物之混合等使成本增加,因此於工業上較為不利。
專利文獻4中記載有,藉由使公知之觸媒活性成分組成中混合微量之二氧化矽而長時間保持較高之轉化率、選擇率,但該觸媒具有難以穩定地以工業規模製造之缺點。
又,專利文獻5中記載有使觸媒前驅物中混合有細孔形成劑之被覆成型觸媒,亦記載有工業規模之製造。然而,該文獻並未明確地揭示因為混合細孔形成劑製造被覆成型觸媒而產生的對丁烯之轉換率及丁二烯之選擇率之效果。
如此,就觸媒性能或觸媒壽命、於工廠(plant)中之運轉控制之觀點而言,先前之觸媒作為工業用觸媒未必能獲得充分之性能,因而期望進一步之改良。
專利文獻1:日本特公昭49-003498號公報
專利文獻2:日本特開昭58-188823號公報
專利文獻3:日本特開2011-219366號公報
專利文獻4:日本特開2011-178719號公報
專利文獻5:日本特表2011-518659號公報
因此,本發明之目的在於提供一種可自反應初期起由正丁烯穩定地且以高產率製造丁二烯之觸媒、該觸媒之工業製造方法及使用該觸媒製造丁二烯之方法。
本發明人等為達成上述目的而致力研究,結果發現,藉由使用一種巨孔(macropore)之細孔容積占整體之細孔容積的80%以上、較佳為占90%以上的以鉬作為必需成分之複合金屬氧化物的成型觸媒,可自反應初期起由正丁烯穩定地且以高產率製造丁二烯,從而完成本發明。
即,本發明係關於如下者:(1)一種成型觸媒,其係以鉬作為必需成分之複合金屬氧化物的成型觸媒,該成型觸媒之巨孔之細孔容積占整體之細孔容積的80%以上,該成型觸媒用於:將正丁烯於分子狀氧之存在下藉由氣相接觸氧化脫氫反應來製造丁二烯;(2)如(1)之成型觸媒,其中,該成型觸媒之巨孔之細孔容積占整體之細孔容積的90%以上;(3)如(1)或(2)之觸媒,其中,總細孔容積為0.1ml/g以上且0.4ml/g以下;(4)如(1)至(3)中任一項之成型觸媒,其中,上述複合金屬氧化物具有由下述式(1)表示之組成:MoaBibNicCodFefXgYhOx (1)(式(1)中,Mo、Bi、Ni、Co、Fe及O分別表示鉬、鉍、鎳、鈷、鐵及氧,X表示選自由鎢、銻、錫、鋅、鉻、錳、鎂、矽、鋁、鈰、碲、
硼、鍺、鋯及鈦組成之群中的至少一種元素,Y表示選自由鉀、銣、鈣、鋇、鉈及銫組成之群中的至少一種元素,a、b、c、d、f、g、h及x分別表示鉬、鉍、鎳、鈷、鐵、X、Y及氧之原子數,a=12,b=0.1~7,c+d=0.5~20,f=0.5~8,g=0~2,h=0.005~2,x=由各元素之氧化狀態決定的值);(5)如(1)至(4)中任一項之成型觸媒,其係將上述複合金屬氧化物載持於惰性球狀載體而成之球狀的被覆成型觸媒;(6)如(5)之成型觸媒,其係藉由轉動造粒法而載持上述複合金屬氧化物之粉末;(7)一種被覆成型觸媒之製造方法,其係(5)之被覆成型觸媒之製造方法,該方法藉由轉動造粒法而載持上述複合金屬氧化物之粉末;(8)一種丁二烯之製造方法,其使用(1)至(6)中任一項之成型觸媒,將正丁烯於分子狀氧之存在下進行氣相接觸氧化脫氫而製造丁二烯;(9)如(8)之丁二烯之製造方法,其中,反應開始1小時以內之△T與2小時時之△T的變化為20℃以下;(10)如(8)或(9)之丁二烯之製造方法,其中,使用(1)至(6)中任一項之成型觸媒,反應開始1小時以內之△T與2小時時之△T的變化為10℃以下。
根據本發明之觸媒及該觸媒之製造方法,可提供一種自反應初期起由正丁烯穩定地且以高產率製造丁二烯之方法、及較佳地用於該方法之觸媒。
以下,關於本發明之丁二烯之製造用觸媒及該觸媒之製造方法、以及使用本發明之觸媒的丁二烯之製造方法,詳細地說明實施形態。
本發明係一種成型觸媒,其係以可用於固定床多管式反應器之鉬作為必需成分之複合金屬氧化物的成型觸媒,其特徵在於,該成型觸媒所具有之細孔分布中巨孔之細孔容積占整體之細孔容積的80%以上,較佳為占90%以上,該成型觸媒用於:將正丁烯於分子狀氧之存在下進行氣相接觸氧化而製造丁二烯。
本發明中所使用之觸媒係可藉由公知之方法製備且以鉬作為必需成分之複合金屬氧化物之觸媒。較佳之觸媒之構成元素及其構成比可由下述通式(1)表示:MoaBibNicCodFefXgYhOx 式(1)
(式中,Mo、Bi、Ni、Co、Fe及O分別表示鉬、鉍、鎳、鈷、鐵及氧,X表示選自由鎢、銻、錫、鋅、鉻、錳、鎂、矽、鋁、鈰、碲、硼、鍺、鋯及鈦組成之群中的至少一種元素,Y表示選自由鉀、銣、鈣、鋇、鉈及銫組成之群中的至少一種元素,a、b、c、d、f、g、h及x分別表示鉬、鉍、鎳、鈷、鐵、X、Y及氧之原子數,a=12,b=0.1~7、較佳為b=0.5~4,c+d=0.5~20、較佳為c+d=1~12,f=0.5~8、較佳為f=0.5~5,g=0~2、較佳為g=0~1,h=0.005~2、較佳為h=0.01~0.5,x=由各元素之氧化狀態決定的值)。
此處,原料混合液及/或含有作為觸媒活性成分之複合金屬氧化物之混合液係藉由共沈法等公知之方法而製備,此時所使用之原料可使用鉬、鉍、鎳、鈷、鐵、及上述組成式中記載之X及Y等各種金屬元素之硝酸鹽、銨鹽、氫氧化物、氧化物、乙酸鹽等,並無特別限制。亦可藉由改變所供給之金屬鹽之種類及/或量,而獲得含有不同組成之複合金屬氧化物之混合液。
作為混合液之乾燥方法,可使用各種方法,例如可列舉:蒸發乾固法、噴霧乾燥法、滾筒乾燥法、氣流乾燥法、真空乾燥法等。用於乾燥之乾燥機之機種並無特別限定,只要可於80℃~300℃之範圍內進行乾燥,則可藉由在該範圍內適當變更乾燥條件而獲得對應於目的之複合金屬氧化物之乾燥粉末。
將如此獲得之乾燥粉末於300~600℃、較佳為400~500℃下,在空氣或氮氣氣流中進行燒成,可獲得複合金屬氧化物之預燒成粉末(以下稱為預燒成粉末)。以下,將乾燥粉末與預燒成粉末一併表述為觸媒粉末。
所獲得之觸媒粉末可直接用作觸媒,但考慮到工業生產規模之生產效率、作業性,使其成型而形成本發明之觸媒。成型物之形狀並無特別限定,可為球狀、圓柱狀、環狀等。應考慮觸媒之反應效果、觸媒之製造效率、機械強度等而選擇形狀,較佳為球狀。於成型時,可使用乾燥粉末,但較佳為使用單獨之預燒成粉末進行成型。可將分別製備之成分組成不同之觸媒粉末以任意之比率預先混合而進行成型,亦可採用如反覆進行於惰性載體上載持不同種類之觸媒粉末之操作,使觸媒粉末被覆成型為
複數層之方法。再者,於成型時,較佳為混合結晶性纖維素等成型助劑及/或陶瓷晶鬚等強度提高劑。成型助劑及/或強度提高劑之使用量較佳為相對於觸媒粉末分別為30重量%以下。又,成型助劑及/或強度提高劑可於成型前預先與上述觸媒粉末混合,亦可於將觸媒粉末添加於成型機中之同時或前後添加。即,只要最終用於反應之成型觸媒處於本發明之觸媒物性及/或觸媒組成之範圍內,則可採用上述成型形狀或成型方法。
於如上述般進行成型時,成型方法並無特別限制,於成型為圓柱狀、環狀時可使用打錠成型機、擠出成型機等。進而較佳為成型為球狀之情形,可藉由成型機使觸媒粉末成型為球形,較佳為使觸媒粉體(視需要包含成型助劑、強度提高劑)被覆成型於惰性之陶瓷等載體上之方法。此處,作為載持方法,只要有轉動造粒法、使用離心流動塗佈裝置之方法、洗塗(wash coat)等可將觸媒粉末均勻地被覆成型於載體表面之方法,則無特別限定,於考慮觸媒之製造效率等之情形時,較佳為如下方法:於在固定圓筒容器之底部具有平坦之或存在凹凸之圓盤之裝置中使圓盤高速旋轉,由此使加入容器內之載體藉由反覆進行載體自身之自轉運動與公轉運動而劇烈攪拌,並向其中添加觸媒粉末及視需要之成型助劑與強度提高劑,藉此使觸媒粉體被覆成型於載體上。轉動造粒時所施加之相對離心加速度較佳為1G~35G,更佳為1.2G~30G。此處,所謂相對離心加速度,係指於轉動造粒機中投入載體並利用該裝置使其旋轉時,將每單位重量所施加之離心力之大小以與重力加速度之比表示之數值,由下述式(2)表示。其係與距該裝置之旋轉中心之距離之絕對值及旋轉速度之平方成比例地增大。
RCF=1118×r×N2×10-8 (2)
式(2)中,RCF表示相對離心加速度(G),r表示距旋轉中心之距離(cm),N表示旋轉速度(rpm)。
再者,於載持時,較佳為使用黏合劑。作為可使用之黏合劑之具體例,可列舉:水或乙醇、甲醇、丙醇、多元醇、高分子系黏合劑之聚乙烯醇、無機系黏合劑之矽溶膠水溶液等,較佳為乙醇、甲醇、丙醇、多元醇,進而較佳為乙二醇等二醇或甘油等三醇等,特佳為甘油之濃度為5重量%以上之水溶液。藉由適量使用甘油水溶液,可獲得成型性良好、機械強度較高、高活性之被覆成型觸媒。
該等黏合劑之使用量相對於觸媒粉末100重量份,通常為2~60重量份,於甘油水溶液之情形時較佳為10~30重量份。於載持時,黏合劑可與觸媒粉末預先混合,亦可一面將觸媒粉末供給至轉動造粒機一面進行添加。
關於惰性載體之大小,通常使用2~15mm左右之直徑者,於其上載持觸媒粉末,其載持量係考慮觸媒使用條件、例如空間速度、原料烴濃度而決定。
再者,被覆成型觸媒中之觸媒粉末之載持量係由觸媒粉末之重量/(觸媒粉末之重量+載體之重量)×100表示。該式中,分母視情形而包含成型助劑及/或強度提高劑。若載持量過低則活性降低,又,若載持量過高則觸媒層之溫度變高,故而欠佳。較佳之載持量為10~70重量%,進而較佳為30~60重量%。
經成型之觸媒在用於反應前再次進行燒成。再次燒成時之燒成溫度通常為400~700℃,燒成時間通常為3~30小時,較佳為4~15小時,
根據所使用之反應條件而適當設定。再次燒成時之燒成之環境可為空氣環境、氮氣環境等之任一者,工業上較佳為空氣環境。
針對如此獲得之成型觸媒,利用各種分析測定物性值。根據IUPAC,將2nm以下之細孔規定為微孔(micropore),將2nm至50nm之細孔規定為中孔(mesopore),將50nm以上之細孔規定為巨孔。若總細孔中所占之微孔或中孔之比率變多,則於細孔內活性點接近,故而容易進行逐次反應。另一方面,若巨孔之比率較多,則變得難以進行逐次反應,可提高丁二烯之選擇率。本發明之特徵在於:藉由使用巨孔之細孔容積占整體之細孔容積的80%以上、更佳為占90%以上之觸媒,可提高丁二烯之選擇率。又,作為總細孔容積,若較低則無法獲得充分之觸媒活性,又,若過高,則不僅上述副生成物變多,而且作為觸媒之強度亦變得不充分。因此,本發明之特徵在於:作為較佳之總細孔容積,為0.1ml/g以上且0.4ml/g以下。關於本發明之巨孔,係使用汞細孔計(Pore Master 60-GT(Quanta Chrome Co.)),於汞表面張力為480dyn/cm、汞接觸角為140°之基礎上,以汞壓入法測定之值。因此,巨孔之上限為裝置之檢測極限。所謂具有巨孔,係指於由以表示汞相對於試樣1g滲入幾ml之標準容積(Normalized Volume)[ml/g]作為縱軸,以孔徑(Pore diameter)作為橫軸之相關圖表獲得之細孔容積中,具有至少0.01ml/g以上之細孔之情形。
本發明之丁二烯之製造方法係使用上述本發明之觸媒及分子狀氧對正丁烯進行氣相接觸氧化脫氫。
作為成為原料之正丁烯,可單獨使用1-丁烯,或亦可使用包含1-丁烯、反-2-丁烯、順-2-丁烯中之至少2種以上之混合丁烯。
又,作為原料,亦可使用包含來自石腦油分解爐或石油之流動接觸分解設備(FCC設備)之正丁烯之丁烯類。此外,亦可使用以公知之方法製造之正丁烯。又,亦可將反應器出口之未反應原料再次用作反應原料。
作為分子狀氧,通常使用空氣,亦可使用純氧。
上述原料氣體及分子狀氧較理想為藉由惰性氣體加以稀釋而以混合氣體之形式利用。作為稀釋氣體,使用氮氣、氦氣、氬氣、二氧化碳等惰性氣體。亦可使反應氣體中所含之非凝縮性氣體之一部分進行循環而用作稀釋氣體。又,於提高觸媒之活性、選擇性、壽命之方面而言,較佳為稀釋氣體中含有水蒸氣。
作為混合氣體,可列舉相對於該混合氣體100容量%,含有正丁烯1~16容量%、較佳為3~12容量%,含有分子狀氧1~20容量%、較佳為5~16容量%,含有稀釋氣體64~98容量%、較佳為72~92容量%,及含有水蒸氣60容量%以下而成者。
具體而言,本發明之氣相接觸氧化脫氫係藉由如下方式實施:於上述本發明之觸媒之存在下,於250~450℃、較佳為280~400℃之溫度範圍及常壓~10大氣壓(錶壓)之壓力下,以觸媒之每單位體積之空間速度300~5000/hr、較佳為500~3500/hr導入至少包含正丁烯及分子狀氧之混合氣體。
於本發明中,製造丁二烯之反應裝置之形式可為流體床、移動床、固定床中之任一形式,於使用本發明之觸媒之情況下,較佳為固定床。
於固定床中使用本發明之觸媒之情形時,可於反應管中使用
各種物性、活性、載持量及粒徑之觸媒。
反應中之觸媒層之局部之高溫部分(PT)在使工廠穩定地長時間運轉之方面存在問題。作為該指標,可使用自PT減去設定溫度所得之溫度差(△T)來表現,較佳為△T儘可能地小。一般已知,於以Mo作為主成分之複合金屬氧化物中,藉由將觸媒置於高溫下,會使Mo飛散或結晶相變化為MoO3,因此觸媒劣化。即,若於反應時存在△T特別大之部分,則該部分之觸媒失活,觸媒之壽命變短。又,於考慮到穩定之運轉之情形時,亦重要的是自反應開始後1小時以內之△T向經過2小時以上後之△T的變化較少。若該變化較少,則工廠之啟動快速地進行,因此於經濟上較為有利。為了緩和△T及自反應開始後至穩定狀態為止之PT之變化,亦可與惰性物質一併填充,其結果,於反應管之原料氣體流動方向上設置有分割成複數個而形成之觸媒層。作為惰性物質,只要為對反應實質上為惰性者,則無特別限制,可列舉二氧化矽、氧化鋁、氧化鈦或其等之複合體等。於與惰性物質一併填充之情形時,可根據每個經分割之觸媒層設置活性不同之觸媒。
[實施例]
以下,基於實施例更詳細地說明本發明,但本發明並不受該等實施例限定。實施例中之正丁烯轉化率、丁二烯選擇率、丁二烯產率係如下述般進行定義。
正丁烯轉化率=(發生反應之正丁烯之莫耳數)/(所供給之正丁烯之莫耳數)×100
丁二烯選擇率=(所生成之丁二烯之莫耳數)/(發生反應之正丁烯
之莫耳數)×100
丁二烯產率=(正丁烯轉化率/100)×(丁二烯選擇率/100)×100
實施例1
<觸媒>
一面加熱攪拌蒸餾水3000重量份一面溶解鉬酸銨423.8重量份與硝酸鉀1.64重量份而獲得水溶液(A1)。另外,將硝酸鈷302.7重量份、硝酸鎳162.9重量份、硝酸鐵145.4重量份溶解於蒸餾水1000重量份中而製備水溶液(B1),又,於添加濃硝酸42重量份而呈酸性之蒸餾水200重量份中溶解硝酸鉍164.9重量份而製備水溶液(C1)。於上述水溶液(A1)中,一面劇烈攪拌一面依序混合(B1)、(C1),使用噴霧乾燥機對生成之懸濁液進行乾燥,於440℃下燒成6小時,獲得預燒成粉末(D1)。此時之觸媒活性成分之氧除外之組成比以原子比計為Mo=12、Bi=1.7、Ni=2.8、Fe=1.8、Co=5.2、K=0.15。
其後,以向預燒成粉末100重量份中混合有結晶纖維素5重量份之粉末於惰性載體(以氧化鋁、二氧化矽作為主成分之直徑4.5mm之球狀物質)上之載持量成為占50重量%之比率之方式,調整用於成型之載體重量及預燒成粉末重量。使用20重量%甘油水溶液作為黏合劑,使用轉動造粒器載持為直徑5.2mm之球狀,從而獲得被覆成型觸媒(E1)。
於載持成型中,使用直徑23cm之圓柱狀成型機,將底板之轉速設為260rpm。此時之相對離心加速度為8.7G。
將被覆成型觸媒(E1)於空氣環境下以燒成溫度530℃燒成4小時,藉此獲得觸媒(F1)。
<觸媒分析>
上述觸媒(F1)之總細孔容積為0.24ml/g,巨孔之細孔容積所占之比率為99%。
<脫氫反應試驗>
於內徑22.2mm之不鏽鋼製反應管中,將用以測定觸媒層溫度之熱電偶設置於同管軸,自反應管之原料氣體入口側依序填充直徑5.2mm之二氧化矽-氧化鋁球30cm、上述觸媒(F1)8cm,將反應浴溫度設為320℃。於此處,將具有正丁烯:空氣:水=1:10:5之莫耳比之混合氣體以空間速度成為1440h-1之方式設定供給量而導入至反應管內進行脫氫反應。再者,使用1-丁烯為99%之純度之氣體作為正丁烯。利用氣相層析法對反應開始後經過2小時後之出口氣體進行分析。將正丁烯轉化率、丁二烯選擇率、丁二烯產率示於表1。又,將反應剛開始後、經過2小時後之△T示於表1。
自表1可知,於反應開始後經過2小時後,正丁烯轉化率亦成為99.3%之高轉化率,丁二烯產率亦成為89.0%之高產率。反應剛開始後之△T為42.8℃,經過2小時後為39.2℃,未觀察到大幅度之溫度變化,自反應開始初期起即穩定。
根據以上之結果可知,可以高轉化率且高產率長時間由正丁烯獲得丁二烯,且可自反應開始初期起穩定地運轉。
比較例1
<觸媒>
獲得於預燒成粉末(D1)100重量份中混合有結晶纖維素10重量份、Yuken Industry股份有限公司製造之YB-155(擠出成型用成型助劑)10重量份的混合粉末。於該混合粉末中混合100重量份之由日本Aerosil公司製造之Aerosil OX50,以成為環狀之方式進行擠出成型,獲得擠出成型觸媒(E2)。所獲得之成型觸媒(E2)之外徑/內徑/長度(mm)為5.4/3.6/5.0。
於與實施例1同樣之條件下對擠出成型觸媒(E2)進行燒成,藉此獲得觸媒(F2)。
<觸媒分析>
上述觸媒(F2)之總細孔容積為0.42ml/g,巨孔之細孔容積所占之比率為78%。
<脫氫反應試驗>
除使用觸媒(F2)以外,以與實施例1同樣之方式進行脫氫反應試驗。利用氣相層析法對反應開始後經過2小時後之出口氣體進行分析。以與實施例1同樣之方式將反應結果示於表2。
自表2可知,於反應開始初期,△T為97.4℃,與實施例1相比升高50℃以上,產生特別大之發熱。於反應開始後2小時,與實施例1相比,△T亦升高10℃以上。因此,觸媒被置於更高之溫度下,故而於觸媒壽命方面變得不利。反應剛開始後與經過2小時後之△T分別為97.4℃、55.8℃,自剛反應後溫度發生大幅度變化,因此推測工廠之運轉極其困難。
又,可知經過2小時後之丁二烯產率與實施例1相比降低2.5%。其原因為,進行逐次反應,CO或CO2增加,丁二烯選擇率下降。觸媒之活性成分量於比較例1與實施例1中同等,因此推測於本發明中,細孔容積之巨孔與中孔之比率之差較大地影響到逐次反應之多少。若逐次反應增加,則由反應所產生之反應熱變大,其結果為△T變大。
因此,藉由使用本發明之巨孔之細孔容積所占之比率較大之觸媒,可抑制△T且提高丁二烯產率。
比較例2
<觸媒>
獲得於預燒成粉末(D1)100重量份中混合有結晶纖維素5重量份、Yuken Industry股份有限公司製造之YB-155(擠出成型用成型助劑)5重量份的混合粉末。於該混合粉末中混合20重量份之由日本Aerosil公司製造之Aerosil 200,以成為環狀之方式進行擠出成型,獲得擠出成型觸媒(E3)。所獲得之成型觸媒(E3)之外徑/內徑/長度(mm)為5.4/3.6/5.0。
於與實施例1同樣之條件下對擠出成型觸媒(E3)進行燒成,藉此獲得觸媒(F3)。
<觸媒分析>
上述觸媒(F3)之總細孔容積為0.47ml/g,巨孔之細孔容積所占之比
率為79%。
<脫氫反應試驗>
以每單位體積之活性成分量與實施例1或比較例1同等之方式混合觸媒(F3)與惰性物質,以與實施例1及比較例1相同之容量進行填充。作為惰性物質,使用直徑5.2mm之二氧化矽-氧化鋁球。此外,以與實施例1同樣之方式進行脫氫反應試驗。利用氣相層析法對反應開始後經過2小時後之出口氣體進行分析。將反應結果示於表3。
自表3之結果可知,藉由將觸媒以惰性物質加以稀釋,可抑制反應時之發熱,但即便為與實施例1同等之活性成分量,正丁烯轉化率於反應開始後經過2小時後亦下降5.2%。因此,單純將觸媒以惰性物質加以稀釋無法顯示與本發明之觸媒同等之效果。
實施例2
<觸媒>
一面加熱攪拌蒸餾水3000重量份一面溶解鉬酸銨750重量份與硝酸銫13.8重量份而獲得水溶液(A4)。另外,將硝酸鈷695.5重量份、硝酸鎳103重量份、硝酸鐵286重量份溶解於蒸餾水1000重量份中而製備水溶液(B4),又,於添加濃硝酸73重量份而呈酸性之蒸餾水300重量份中溶解硝酸鉍291.8重量份而製備水溶液(C4)。於上述水溶液(A4)中,一面劇烈攪拌
一面依序混合(B4)、(C4),使用噴霧乾燥機對所生成之懸濁液進行乾燥,於460℃下燒成5小時,獲得預燒成粉末(D4)。此時之觸媒活性成分之氧除外之組成比以原子比計為Mo=12、Bi=1.7、Ni=1.0、Fe=2.0、Co=6.8、Cs=0.20。
其後,以向預燒成粉末100重量份中混合有結晶纖維素5重量份之粉末於惰性載體(以氧化鋁、二氧化矽作為主成分之直徑4.0mm之球狀物質)上之載持量成為占50重量%之比率之方式,調整用於成型之載體重量及預燒成粉末重量。使用20重量%甘油水溶液作為黏合劑,載持為直徑4.4mm之球狀,獲得被覆成型觸媒(E4)。
於載持成型中,使用直徑23cm之圓柱狀成型機,將底板之轉速設為260rpm。此時之相對離心加速度為8.7G。
將被覆成型觸媒(E4)於520℃下燒成4小時,獲得觸媒(F4)。
<觸媒分析>
上述觸媒(F4)之總細孔容積為0.25ml/g,巨孔之細孔容積所占之比率為100%。
<脫氫反應試驗>
使用觸媒(F4),將反應溫度設為330℃,除此以外,以與實施例1同樣之方式進行脫氫反應試驗。利用氣相層析法對反應開始後經過2小時後之出口氣體進行分析。以與實施例1同樣之方式將反應結果示於表4。
自表4之結果可知,於與觸媒(F1)不同組成之觸媒(F4)中,亦於反應開始後經過2小時後,正丁烯轉化率成為98.9%之高轉化率,丁二烯產率成為91.0%之高產率。
又,反應初期之△T為26.7℃,可知發熱較少。反應開始經過2小時後之△T成為27.6℃。
因此,與實施例1同樣地未觀察到大幅度之溫度變化,可知自反應開始初期起即穩定。
自以上之結果可知,巨孔之細孔容積所占之比率為80%以上之觸媒可抑制發熱行為,從而穩定地使用,且該觸媒即便△T較小,亦可以較高之正丁烯轉化率使用,可維持較高之丁二烯產率,因此於工業上極其有用。
以上,參照特定之態樣詳細地說明了本發明,但對業者而言清楚明白,可於不脫離本發明之精神及範圍之情況下進行各種變更及修正。
再者,本申請案係基於2012年4月23日提出申請之日本專利申請案(特願2012-098259),其整體藉由引用被援用於此。又,此處引用之所有參照係作為整體而併入。
[產業上之可利用性]
本發明之觸媒可供於自反應初期起由正丁烯穩定地且以高產率製造丁二烯之方法。
Claims (10)
- 一種成型觸媒,其係以鉬作為必需成分之複合金屬氧化物的成型觸媒,該成型觸媒之巨孔(macropore)之細孔容積占整體之細孔容積的80%以上,該成型觸媒用於:將正丁烯於分子狀氧之存在下藉由氣相接觸氧化脫氫反應來製造丁二烯。
- 如申請專利範圍第1項之成型觸媒,其中,該成型觸媒之巨孔之細孔容積占整體之細孔容積的90%以上。
- 如申請專利範圍第1或2項之成型觸媒,其中,總細孔容積為0.1ml/g以上且0.4ml/g以下。
- 如申請專利範圍第1至3項中任一項之成型觸媒,其中,該複合金屬氧化物具有由下述式(1)表示之組成:MoaBibNicCodFefXgYhOx 式(1)(式(1)中,Mo、Bi、Ni、Co、Fe及O分別表示鉬、鉍、鎳、鈷、鐵及氧,X表示選自由鎢、銻、錫、鋅、鉻、錳、鎂、矽、鋁、鈰、碲、硼、鍺、鋯及鈦組成之群中的至少一種元素,Y表示選自由鉀、銣、鈣、鋇、鉈及銫組成之群中的至少一種元素,a、b、c、d、f、g、h及x分別表示鉬、鉍、鎳、鈷、鐵、X、Y及氧之原子數,a=12,b=0.1~7,c+d=0.5~20,f=0.5~8,g=0~2,h=0.005~2,x=由各元素之氧化狀態決定的值)。
- 如申請專利範圍第1至4項中任一項之成型觸媒,其係將該複合金屬氧化物載持於惰性球狀載體而成之球狀的被覆成型觸媒。
- 如申請專利範圍第5項之成型觸媒,其係藉由轉動造粒法而載持該複合 金屬氧化物之粉末。
- 一種被覆成型觸媒之製造方法,其係申請專利範圍第5項之被覆成型觸媒之製造方法,該方法藉由轉動造粒法而載持該複合金屬氧化物之粉末。
- 一種丁二烯之製造方法,其使用申請專利範圍第1至6項中任一項之成型觸媒,將正丁烯於分子狀氧之存在下進行氣相接觸氧化脫氫而製造丁二烯。
- 如申請專利範圍第8項之丁二烯之製造方法,其中,反應開始1小時以內之△T與2小時時之△T的變化為20℃以下。
- 如申請專利範圍第8或9項之丁二烯之製造方法,其中,使用申請專利範圍第1至6項中任一項之成型觸媒,反應開始1小時以內之△T與2小時時之△T的變化為10℃以下。
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US20150126774A1 (en) | 2015-05-07 |
KR20150008864A (ko) | 2015-01-23 |
KR101745555B1 (ko) | 2017-06-09 |
CN104245127B (zh) | 2016-03-30 |
TWI574731B (zh) | 2017-03-21 |
JP5970542B2 (ja) | 2016-08-17 |
CN104245127A (zh) | 2014-12-24 |
SG11201406832UA (en) | 2014-11-27 |
JPWO2013161703A1 (ja) | 2015-12-24 |
EP2842626A4 (en) | 2015-10-28 |
TW201406455A (zh) | 2014-02-16 |
SA113340492B1 (ar) | 2016-03-03 |
EP2842626A1 (en) | 2015-03-04 |
US9573127B2 (en) | 2017-02-21 |
JPWO2013161702A1 (ja) | 2015-12-24 |
TWI569872B (zh) | 2017-02-11 |
JP6034372B2 (ja) | 2016-11-30 |
WO2013161703A1 (ja) | 2013-10-31 |
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