JP2015511209A - 炭化水素改質方法、ヘキサアルミネート含有触媒、ヘキサアルミネート含有触媒の製造方法 - Google Patents
炭化水素改質方法、ヘキサアルミネート含有触媒、ヘキサアルミネート含有触媒の製造方法 Download PDFInfo
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- JP2015511209A JP2015511209A JP2014556177A JP2014556177A JP2015511209A JP 2015511209 A JP2015511209 A JP 2015511209A JP 2014556177 A JP2014556177 A JP 2014556177A JP 2014556177 A JP2014556177 A JP 2014556177A JP 2015511209 A JP2015511209 A JP 2015511209A
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- catalyst
- hexaaluminate
- mol
- range
- aluminum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 205
- 238000000034 method Methods 0.000 title claims abstract description 113
- 238000002407 reforming Methods 0.000 title claims abstract description 31
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 230000008569 process Effects 0.000 claims abstract description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 61
- 239000010941 cobalt Substances 0.000 claims abstract description 61
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
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- 229910052788 barium Inorganic materials 0.000 claims abstract description 37
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 35
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 22
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 46
- 230000015572 biosynthetic process Effects 0.000 claims description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 42
- 239000013078 crystal Substances 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 26
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- 150000001768 cations Chemical class 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
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- 238000001035 drying Methods 0.000 claims description 13
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- 238000002156 mixing Methods 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
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- 238000007493 shaping process Methods 0.000 claims description 3
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- 238000006555 catalytic reaction Methods 0.000 description 7
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- FZKDURCLMTYEER-UHFFFAOYSA-N cobalt lanthanum Chemical compound [Co].[Co].[Co].[La] FZKDURCLMTYEER-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
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- -1 transition metal cations Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
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- 229910052737 gold Inorganic materials 0.000 description 1
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- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 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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- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
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- 230000000670 limiting effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- 238000011002 quantification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
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- 238000011105 stabilization Methods 0.000 description 1
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- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000000357 thermal conductivity detection Methods 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
Description
アルミネート若しくはペロブスカイト(即ちSrAl2O4、LaAlO3等)をもたらす各場合で、Ba、Sr、Laからなる群からのカチオン種とアルミニウム含有種とから生じ、または、当業者に公知のLa、Sr、Ba、Al元素の他の相が主に第2相として形成される。そこから、遊離酸化アルミニウムの割合と、付随するルイス酸点の数が最小化可能となる。しかし、上記の説明は、本発明をいかなる方法でも限定する意図ではない。
(i)アルミニウム源、好ましくは微細化した酸化及び/又は水酸化変性アルミニウムを製造する工程、
(ii)微細化したアルミニウム源を、可融性(fusible)又は溶解性(soluble)のコバルト含有化合物と少なくとも1種の更なる溶解性又は可融性金属塩と接触させる工程、
(iii)前記アルミニウム源と溶解した又は溶融した金属塩を混和する工程、
(iv)混合物を乾燥させる工程、
(v)混合物を低温焼成する工程、
(vi)造形又は成形する工程、及び
(vii)混合物を高温焼成する工程。
ヘキサアルミネート含有触媒/ヘキサアルミネート相
本発明の開示のために、用語「ヘキサアルミネート含有触媒」は、ヘキサアルミネート相が高割合で含有された材料を含むものである。これは、ヘキサアルミネート含有触媒が、ある実施形態では、第2相を一定の割合で含有することも可能なことを意味する。用語ヘキサアルミネート相は、マグネトプランバイト(magnetoplumbite)構造及び/又はベータ‐アルミネート構造(ベータ’、ベータ’’アルミネート構造等)の型と同様又は類似のシート構造を持つ相を含む。触媒が第2相を含む場合は、第2相の割合は、0〜50質量%の範囲、好ましくは3〜40質量%の範囲、より好ましくは5〜30質量%の範囲である。
アルミニウム源としては、原則、全てのアルミニウム含有出発材料を使用可能であり、好ましいアルミニウム源は、シュードベーマイト、ベーマイト、ギブサイト、バイヤライト、ガンマ‐酸化アルミニウム、シータ‐酸化アルミニウム、ハイドロタルサイト(マグネシウムハイドロタルサイト等)、コロイド状塩基性酸化アルミニウム、並びに当業者に公知の他のコロイド状アルミニウム源、及びそれらの混合物からなる群より選択される。それらに含まれるものとして、特に下記製品、特に、Sasol(サソール)社の、Disperalと全てのDisperalタイプ、Dispal、Pural、Puralox、Catalox、Catapal及び全てのPural MGタイプがある。
このような金属塩の例は、特に、硝酸塩、亜硝酸塩、ハロゲン化合物、塩素酸塩、臭素酸(塩)、ヨウ素酸塩、硫酸塩、亜硫酸塩である。特に、硝酸塩、亜硝酸塩、又は硝酸及び亜硝酸を持つ塩溶融物(salt melts)である。
本発明は、炭化水素の改質方法も提供し、炭化水素は好ましくはメタンであって、二酸化炭素の存在下で改質が行われる。特に、当該方法は下記工程を含む。
(a.2)改質ガスと接触させている間、反応装置又はその内部に存在する触媒を、700℃を超え、好ましくは800℃を超え、より好ましくは900℃を超える温度で加熱する工程と、
(a.3)反応を起こす間、反応装置を、5barを超え、好ましくは10barを超え、より好ましくは15barを超える処理圧力で、動作させる工程と、
(a.4)500hr−1以上20000hr−1以下の範囲、好ましくは1500hr−1以上10000hr−1以下の範囲、より好ましくは2000hr−1以上5000hr−1以下の範囲のGHSVで触媒上に改質ガス流を通過させる工程。
触媒E3を製造するため、ガラスビーカー中にある硝酸コバルトと硝酸ランタンを、先ず、250mlの蒸留水と混合し、完全に溶解させた。硝酸コバルトは83.1gのCo(NO3)3x6H2Oであり、硝酸ランタンは284.9gのLa(NO3)3x6H2Oである。金属塩溶液は、250gのベーマイトと混合し、それにより懸濁液を形成する。使用するベーマイトは、SASOL社のDisperalである。
本発明の方法を説明するため、6つの異なるヘキサアルミネート含有触媒サンプル(B1〜B3、E1〜E3)を、6つの反応装置が平行に配置された実験触媒装置で、改質ガスの変換用の処理条件下で試験した。触媒サンプルB1〜B3は、硝酸ニッケルと硝酸ランタン塩から製造したヘキサアルミネート含有サンプルである。サンプルE1〜E3は、硝酸コバルトと硝酸ランタン塩から製造したものである。触媒サンプルB1〜B3は、硝酸コバルト塩の代わりに硝酸ニッケルを使用する、上記Iで説明した本発明の触媒E1〜E3と同じ製造プロセスで得たものである。試験した触媒の組成の概要を表1に示す。
プロセス条件の概要と、改質試験で得た触媒データを表2に示す。
実験例2からの触媒サンプルの一部を、変更した試験条件で更なる触媒試験に供した。供給材料の組成と試験工程2を表3に示す。試験では、サンプルE2は、表2で示した試験と比較すると、非常に低蒸気分圧を持つ供給材料を供給した。試験工程2は、第1の試験工程から、水素を供給ガスに少数の工程でのみ添加した点を変更した。水素を供給ガスに導入したそれらのプロセス段階では、水素ガスの含有量は低く、5体積%又は10体積%であった。第1のプロセス段階(S01からS04)では、熱力学的平衡状態にはならず、それに近い状態にもならなかった。熱力学的平衡状態の周辺にある状態とならなかった考えられる説明は、高蒸気分圧では、触媒が先ず不完全にのみ還元したことであろう。
更なる試みで、実施例E1、E2及びE4で記載したように製造した本発明の触媒の例と、実施例B2で記載したように製造した比較サンプルとを、水素を含有しない供給ガスを使用した触媒的改質に用いた。これらの研究の結果と、供給ガス組成と温度に関する実験条件を表5に示す。サンプルE1とE2は、ヘキサアルミネート相がコバルトとランタンを含有するヘキサアルミネート含有触媒であり、サンプルE4はヘキサアルミネート相がコバルトとストロンチウムを含むヘキサアルミネート含有触媒であり、そして、サンプルB2は、ヘキサアルミネート相がニッケルとランタンを含むヘキサアルミネート含有触媒である。
Claims (15)
- 炭化水素、好ましくはメタンをCO2存在下で改質する方法であって、
(a.1)70体積%を超える炭化水素、好ましくはメタンと、CO2とを含む改質ガスを、ヘキサアルミネート含有触媒と接触させる工程と、
(a.2)前記改質ガスと接触する際に、700℃を超える温度、好ましくは800℃を超える温度、より好ましくは900℃を超える温度で触媒を加熱する工程と、
(a.3)反応を行う間、5barを超える圧力、好ましくは10barを超える圧力、より好ましくは15barを超える圧力で反応装置を動作させる工程と、
(a.4)前記触媒に接触する前記改質ガスを、GHSVが500hr−1以上20000hr−1以下、好ましくはGHSVが1500hr−1以上10000hr−1以下、より好ましくはGHSVが2000hr−1以上5000hr−1以下にする工程と、を含み、
前記ヘキサアルミネート含有触媒が、コバルトと、Ba、Sr、Laからなる群より選択される少なくとも1種の更なる金属とを含む炭化水素の方法。 - 前記ヘキサアルミネート含有触媒は、Co含有量が2〜15mol%の範囲、好ましくは3〜10mol%、より好ましくは4〜8mol%の範囲であり、Ba、Sr、Laからなる群より選択される更なる金属の含有量が2〜25mol%、好ましくは3〜15mol%、より好ましくは4〜10mol%の範囲であり、Alの含有量が70〜90mol%の範囲であり、
前記触媒は、好ましくは、シータ‐酸化アルミニウム、アルファ‐酸化アルミニウム、LaAlO3、BaAl2O4、SrAl2O4、CoAl2O4、La‐安定化酸化アルミニウム、La‐安定化酸化水酸化アルミニウムからなる群より選択される、酸化物第2相を、0〜50質量%、好ましくは3〜40質量%、より好ましくは5〜30質量%の範囲で含む請求項1記載の炭化水素の改質方法。 - 前記ヘキサアルミネート含有触媒は、コバルト対アルミニウムのモル比が0.05以上0.09以下、好ましくは0.06以上0.08以下の範囲であり、
Ba、Sr、Laからなる群より選択される少なくとも1種の元素(MBaSrLa)対アルミニウムのモル比が、0.09以上0.25以下、好ましくは0.092以上0.20以下の範囲であり、かつ、
コバルト対前記Ba、Sr、Laからなる群より選択される少なくとも1種の元素(MBaSrLa)のモル比が1.0以上0.3以下、好ましくは0.85以上0.40以下の範囲にある請求項1又は請求項2に記載の炭化水素の改質方法。 - 前記ヘキサアルミネート含有触媒は、BET表面積が2m2/gより大きく、好ましくは4m2/gより大きく、より好ましくは8m2/gより大きく、特に15m2/gより大きい請求項1〜3のいずれか1項に記載の炭化水素の改質方法。
- 工程(a.1)で供給される前記改質ガスは、H2O含有量が最大30体積%である請求項1〜4のいずれか1項に記載の炭化水素の改質方法。
- 改質プロセスの前に、活性化プロセス及び/又は調整プロセスを行う請求項1〜5のいずれか1項に記載の炭化水素の改質方法。
- 供給流体は、蒸気を含み、かつ、CH4/CO2/H2O成分が、ガス量の比で、35/35/30から48/48/4まで、好ましくは43/43/14から45/45/10までの範囲で存在する組成を持つ請求項1〜6のいずれか1項に記載の炭化水素の改質方法。
- 前記方法により製造される合成ガスは、H2/CO比が0.8以上1.2以下の範囲であり、前記合成ガスのH2/CO比は、好ましくは0.9以上1.1以下の範囲である請求項1〜7のいずれか1項に記載の炭化水素の改質方法。
- 前記触媒が、Pt、Rh、Pd、Irからなる群より選択される少なくとも1種の貴金属含有プロモータを含み、前記貴金属含有プロモータの含有量は、0.1〜3mol%であり、及び/又は、前記触媒が更にカチオンを含み、当該カチオンは、好ましくはMg、Ca、Ga、Be、Ni、Fe、Cr、Mnからなる群より選択され、より好ましくはMgである請求項1〜8のいずれか1項に記載の炭化水素の改質方法。
- ヘキサアルミネート含有触媒であって、
ヘキサアルミネート含有相が、コバルトと、Ba、Sr及びLaからなる群より選択される少なくとも1種の更なる金属とを含み、
Co含有量が、2〜15mol%の範囲、好ましくは3〜10mol%、より好ましくは4〜8mol%の範囲であり、
Ba、Sr及びLaからなる群より選択される少なくとも1種の更なる金属の含有量が、2〜25mol%、好ましくは3〜15mol%、より好ましくは4〜10mol%であり、
アルミニウムの含有量が、70〜90mol%の範囲であり、
前記触媒が酸化物第2相を、0〜50質量%、好ましくは3〜40質量%、より好ましくは5〜30質量%の範囲で含み、
当該酸化物第2相は、シータ‐酸化アルミニウム、アルファ‐酸化アルミニウム、LaAlO3、BaAl2O4、SrAl2O4、CoAl2O4、La‐安定化酸化アルミニウム、La‐安定化酸化水酸化アルミニウムからなる群より選択され、
前記ヘキサアルミネート含有触媒は、BET表面積が、2m2/gより大きく、好ましくは4m2/gより大きく、より好ましくは8m2/gより大きく、特に15m2/gより大きく、下記工程
(i)アルミニウム源、好ましくは微細化した酸化及び/又は水酸化変性アルミニウムを製造する工程、
(ii)微細化したアルミニウム源を、可融性又は溶解性のコバルト含有化合物と、Ba、La、Srからなる群より選択される少なくとも1種の更なる溶解性又は可融性金属塩と接触させる工程、
(iii)前記アルミニウム源と溶解した又は溶融した金属塩を混和する工程、
(iv)混合物を乾燥させる工程、
(v)混合物を低温焼成する工程、
(vi)造形又は成形する工程、及び
(vii)混合物を高温焼成する工程、
により製造される、ヘキサアルミネート含有触媒。 - 炭化水素及びCO2の改質用のヘキサアルミネート含有触媒の製造方法であって、下記;
(i)好ましくは一次粒子径が500nm以下の分散性一次粒子の形態であって、好ましくは粒子がベーマイトからなる、微細化した酸化アルミニウム源を、少なくとも溶解性又は可融性のコバルト‐及びランタン‐含有種を含む金属塩と接触させる工程と、
(ii)前記酸化アルミニウム源を、溶解した又は溶融した金属塩と混和する工程と、
(iii)混合物を乾燥させる工程と、
(iv)混合物を低温焼成する工程と、
(v)造形又は成形する工程と、
(vi)高温焼成する工程と、
を含む、ヘキサアルミネート含有触媒の製造方法。 - 前記高温焼成が、800〜1300℃、好ましくは850〜1200℃、特に900〜1100℃の範囲の温度で行われ、及び/又は、前記高温焼成の期間は、0.5時間より長く、好ましくは5時間より長く、より好ましくは10時間より長く、及び/又は、
前記低温焼成が550℃未満の温度、より好ましくは250℃以上550℃未満の温度で、0.1時間以上24時間以下行われる請求項11に記載のヘキサアルミネート含有触媒の製造方法。 - 前記造形又は成形(プロセス工程(vi))を乾燥工程(iv)の前に行い、及び/又は、乾燥工程(iv)を低温焼成工程(v)と一緒に行い、及び/又は、プロセス工程(i)〜(iii)のうち、少なくとも1つの工程を、種結晶の存在下で行い、前記種結晶の割合は、0.1質量%以上10質量%以下である請求項11又は請求項12に記載のヘキサアルミネート含有触媒の製造方法。
- CO2存在下で炭化水素、好ましくはメタンを改質するためのヘキサアルミネート含有触媒であって、
前記触媒は、ヘキサアルミネート含有相を含み、
前記ヘキサアルミネート含有触媒は、コバルトと、Ba、Sr、Laからなる群より選択される少なくとも1種の更なる金属とを含有し、
Coの含有量は、2〜15mol%の範囲、好ましくは3〜10mol%、より好ましくは4〜8mol%の範囲であり、
Ba、Sr、Laからなる群より選択される少なくとも1種の更なる金属の含有量は、2〜25mol%、好ましくは3〜15mol%、より好ましくは4〜10mol%の範囲であり、
Alの含有量は、70〜90mol%の範囲であり、
前記触媒は、酸化物第2相を、0〜50質量%、好ましくは3〜40質量%、より好ましくは5〜30質量%の範囲で有し、当該酸化物第2相は、シータ‐酸化アルミニウム、アルファ‐酸化アルミニウム、LaAlO3、BaAl2O4、SrAl2O4、CoAl2O4、La‐安定化酸化アルミニウム、La‐安定化酸化水酸化アルミニウムからなる群より好ましくは選択され、
前記ヘキサアルミネート含有触媒のBET表面積は、2m2/gより大きく、好ましくは4m2/gより大きく、より好ましくは8m2/gより大きく、特に15m2/gより大きいヘキサアルミネート含有触媒。 - コバルト対アルミニウムのモル比が0.05以上0.09以下の範囲であり、好ましくは0.06以上0.08以下の範囲であり、
Ba、Sr、Laからなる群より選択される少なくとも1種の元素(MBaSrLa)対アルミニウムのモル比が0.09以上0.25以下の範囲、好ましくは0.092以上0.20以下の範囲であり、
Co対Ba、Sr、Laからなる群より選択される少なくとも1種の元素(MBaSrLa)のモル比が、1.0以下0.3以上の範囲、好ましくは0.85以下0.40以上の範囲である請求項14に記載のヘキサアルミネート含有触媒。
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- 2013-02-07 EP EP13747145.4A patent/EP2812111A4/de active Pending
- 2013-02-07 CN CN201380006895.3A patent/CN104080530B/zh active Active
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JP2018528849A (ja) * | 2015-07-09 | 2018-10-04 | ユミコア アクチェンゲゼルシャフト ウント コンパニー コマンディートゲゼルシャフト | Nh3−scr活性、アンモニア酸化活性ならびに揮発性バナジウムおよびタングステン化合物のための吸着能を有する三元触媒 |
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Publication number | Publication date |
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CN104080530A (zh) | 2014-10-01 |
ZA201406561B (en) | 2016-08-31 |
CN104080530B (zh) | 2018-08-07 |
RU2631497C2 (ru) | 2017-09-25 |
WO2013118078A1 (de) | 2013-08-15 |
JP6238909B2 (ja) | 2017-11-29 |
CA2864063C (en) | 2021-06-01 |
RU2014136535A (ru) | 2016-04-10 |
KR20140126366A (ko) | 2014-10-30 |
CA2864063A1 (en) | 2013-08-15 |
EP2812111A4 (de) | 2015-11-18 |
EP2812111A1 (de) | 2014-12-17 |
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