JP5628039B2 - レドックス能の高いアルキル芳香族化合物の脱水素触媒およびその製造方法並びにそれを使用した脱水素化方法 - Google Patents
レドックス能の高いアルキル芳香族化合物の脱水素触媒およびその製造方法並びにそれを使用した脱水素化方法 Download PDFInfo
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- JP5628039B2 JP5628039B2 JP2010529569A JP2010529569A JP5628039B2 JP 5628039 B2 JP5628039 B2 JP 5628039B2 JP 2010529569 A JP2010529569 A JP 2010529569A JP 2010529569 A JP2010529569 A JP 2010529569A JP 5628039 B2 JP5628039 B2 JP 5628039B2
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- aromatic compound
- ethylbenzene
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- 239000003054 catalyst Substances 0.000 title claims description 128
- 238000006356 dehydrogenation reaction Methods 0.000 title claims description 43
- -1 alkyl aromatic compounds Chemical class 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 22
- 230000008569 process Effects 0.000 title description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000006479 redox reaction Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 230000001052 transient effect Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 38
- 239000007789 gas Substances 0.000 description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 15
- 229910052700 potassium Inorganic materials 0.000 description 15
- 239000011591 potassium Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 4
- 239000012494 Quartz wool Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- UNDOASFVPXTZNA-UHFFFAOYSA-N potassium iron(2+) oxygen(2-) Chemical compound [O-2].[K+].[Fe+2] UNDOASFVPXTZNA-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 229910018921 CoO 3 Inorganic materials 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 229910002552 Fe K Inorganic materials 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XZEMRTWXURURQM-UHFFFAOYSA-M [OH-].[K+].[O-2].[Fe+2] Chemical compound [OH-].[K+].[O-2].[Fe+2] XZEMRTWXURURQM-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000005194 ethylbenzenes Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 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
- 239000000843 powder Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
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- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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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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Description
2 触媒
3 石英ウール
4 熱電対
5 電気炉
6 エチルベンゼンバブラー
7 H2Oポンプ
8 氷冷トラップ
10 酸化還元過渡応答測定装置
11 触媒
12 石英ウール
13 熱電対
14 エチルベンゼンバブラー
15 H2Oバブラー
16 Heパージガス
17 四重極質量分析計
18 トラップ
La(NO3)3・6H2Oを7.17g、Ba(NO3)2を1.093g、Mn(NO3)3・6H2Oを6.063gそれぞれ電子天秤で計り取り、蒸留水50mLに溶解させた。一方で全金属モル数の3等量に相当するクエン酸一水和物とエチレングリコールを蒸留水に溶解させ、先の金属塩溶解水溶液に溶解させた。この混合溶液を353Kのウォーターバスにて約16時間かけて粘性が出るまで水分を蒸発させた後、ホットスターラー上に移して約573Kに加熱しながら攪拌をしながら完全に乾固した。得られた固体を粉砕し、マッフル炉にて673Kで1時間の仮焼成を行なった後、1123Kで10時間の本焼成を行なった。得られた焼成物を破砕し、フルイを用いて粒径0.50−0.71mmに整粒して、組成がLa0.8Ba0.2MnO3―δの触媒を得た。
図1に示す固定床流通反応装置1を使用して、得られた触媒2のエチルベンゼン脱水素能を測定した。外形10mmの石英管を反応管として使用し、上下に石英ウール3を詰めて1.00gの触媒を固定した。触媒層の中心に外形3mmの石英管の保護管を挿入した熱電対4、石英管の周囲に電気炉5を設置することによって反動温度を制御した。また、エチルベンゼンバブラー6を用いてエチルベンゼンを供給し、H2Oポンプ7を用いて、活性試験は、以下の条件で行なった。
H2O流量/エチルベンゼン流量/N2流量=12mol/1mol/3mol
反応温度=783K、813K、843K、873K、913K
圧力=大気圧
レドックス能を調べる為、図2に示す酸化還元過渡応答測定装置を用いてエチルベンゼンとH2Oをそれぞれ独立で周期的に交互に流通させ、酸化還元反応に利用可能な触媒中の格子酸素原子量の測定を行なった。測定は次の工程により行なった。
0.10gの触媒11を反応管の均熱部に設置して石英ウール12によって上下を固定したのち、He流通下10K・min−1の速度で813Kまで昇温した。続いてエチルベンゼンバブラー14とH2Oバブラー15にHe+Arガスを通じ、エチルベンゼン/H2O/He/Ar=1/12/284/3 ml・min−1の混合ガスを813Kで触媒に接触させ、エチルベンゼン脱水素反応を行なった。転化率が一定になるまで混合ガスを流通させ、その後He+Arガスを停止してHeパージガス16を流通させ、前処理を終了した。
次いで、[数1]に示されるエチルベンゼンによる酸化的脱水素による格子酸素の放出量を調べる為、エチルベンゼンバブラー14にHe+Arガスを通じ、エチルベンゼン/He/Ar=1/296/3 ml・min−1のエチルベンゼン混合ガスを5分間、触媒10に流通させ反応流出物の経時変化を四重極質量分析器17で測定した。エチルベンゼンの酸化的脱水素反応によって生成したH2O量を定量し、触媒の格子酸素放出量(μmol・g−cat)を求めた。
エチルベンゼンと希ガスの混合ガスとの接触が終了した後、Heパージガス16を流してから、[数2]に示されるスチームよる触媒格子の酸素欠陥の再酸化量を調べる為、水蒸気バブラーにHe+Arガスを流し、H2O/He/Ar=12/285/3ml・min―1の混合ガスを5分間供給して生成物質の経時変化を四重極質量分析計17で測定を行なった。水蒸気の接触によって生成したH2量を定量し、触媒の格子酸素欠陥の再生量(μmol・g−cat)を測定した。
Claims (4)
- 水蒸気によって希釈されたアルキル芳香族化合物を接触させ脱水素することによりアルケニル芳香族化合物を生成するためのアルキル芳香族化合物脱水素触媒であって、
該アルキル芳香族化合物脱水素触媒は、LaxBayMnO3−δあるいはLaxBayMnmFenO3−δ(ここで、x+y=1、およびm+n=1)なる構造を有し、
触媒中の格子酸素のうち酸化還元反応に利用可能な酸素量であって酸化還元過渡応答法で測定された酸化還元反応に利用可能な触媒格子酸素量が、触媒中の全格子酸素量に対し2.4%以上であり、かつレドックス能を有する酸化物を含有することを特徴とするアルキル芳香族化合物脱水素触媒。 - アルキル芳香族化合物がエチルベンゼンであり、アルケニル芳香族化合物がスチレンモノマーであることを特徴とする請求項1記載のアルキル芳香族化合物脱水素触媒。
- 請求項1記載のアルキル芳香族化合物脱水素触媒に係る組成物を、押し出し可能混合物を作るのに十分な水と混合することによって押出可能混合物を調製する工程と、押出可能な混合物を成型してペレットを作る工程と、ペレットを乾燥した後、焼成して、完成触媒を作る工程とからなることを特徴とする焼成されたアルキル芳香族化合物脱水素触媒を製造する方法。
- 請求項1記載のアルキル芳香族化合物脱水素触媒の存在下でアルキル芳香族化合物と水蒸気とを接触させることによってアルケニル芳香化合物を生成させるための、アルキル芳香族化合物を脱水素する脱水素化方法。
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