JP4211900B2 - Metal fine particle supported hydrocarbon reforming catalyst and method for producing the same - Google Patents
Metal fine particle supported hydrocarbon reforming catalyst and method for producing the same Download PDFInfo
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- JP4211900B2 JP4211900B2 JP08563798A JP8563798A JP4211900B2 JP 4211900 B2 JP4211900 B2 JP 4211900B2 JP 08563798 A JP08563798 A JP 08563798A JP 8563798 A JP8563798 A JP 8563798A JP 4211900 B2 JP4211900 B2 JP 4211900B2
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- 239000003054 catalyst Substances 0.000 title claims description 78
- 229910052751 metal Inorganic materials 0.000 title claims description 15
- 239000002184 metal Substances 0.000 title claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 11
- 229930195733 hydrocarbon Natural products 0.000 title claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 11
- 238000002407 reforming Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000010419 fine particle Substances 0.000 title description 3
- 238000000034 method Methods 0.000 claims description 14
- 229960001545 hydrotalcite Drugs 0.000 claims description 11
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 11
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- -1 hydrotalcite compound Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 32
- 239000010948 rhodium Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 238000006057 reforming reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/007—Mixed salts
Description
【０００１】
【発明の属する技術分野】
本発明は炭化水素の水蒸気及び炭酸ガス改質用触媒、特に高分散化した金属微粒子担持炭化水素改質用触媒に関する。
【０００２】
【従来の技術】
炭化水素の水蒸気改質用触媒としては、従来よりα−アルミナ等の耐熱性酸化物を担体として、これに触媒活性成分としてロジウム、ルテニウム等の貴金属或いは酸化ニッケルを担持したものが知られている。更に水蒸気改質については「化学工学論文集」第１６巻、第５号（１９９０）に報告があり、水蒸気改質ではＮｉ系触媒が既に実用化されており、J.R.Rostrup-Nielsen, in “Catalysis, Science and Technology" (Eds.J.R.Anderson and M.Boudart, Springer-Verlag:Berlin, 1984), Vol.5, 1-117に発表されている。
ＣＯ2 によるメタンの改質反応触媒としては、貴金属系ではA.T.Ashcroft, A.K.Cheetham, J.S.Foord, M.L.H.Green and P.D.F.Vemon, “Nature" 352, 225 (1991)に報告があり、Ｎｉ系触媒は、T.Osaki, T.Horiuchi, K.Suzuki and T.Mori, “J.Chem. Soc., Faraday Trans.", 92, 1627 (1997) に発表されている。
【０００３】
現在、合成ガスはこのような触媒を用いた天然ガスの水蒸気改質により製造されているが、この方法は大きな吸熱反応であると同時に触媒上での炭素質の析出を抑制するために多量の水蒸気を用いて操業せざるを得ず、エネルギー的には極めて不利なプロセスである。さらに生成する合成ガスのＣＯ／Ｈ2 比は１／３となり、後続するメタノール合成或いはＦ−Ｔ合成に適合させるためには、後段にシフト反応を組み合わせて調整する必要がある。また水蒸気に替わる反応として二酸化炭素によるメタン改質反応とメタンの部分酸化反応がある。
【０００４】
【発明が解決しようとする課題】
上記のような炭化水素の水蒸気又は二酸化炭素改質反応、例えば二酸化炭素のメタン改質反応及びメタンの部分酸化反応も現状触媒ではシンタリングやコーキングが顕著なため瞬時に劣化する問題を抱えている。これらの反応においては、操業中の炭素の析出（コーキング）を抑制するための高活性な触媒の開発が必須となる。
従って本発明は炭化水素の水蒸気及び二酸化炭素改質反応において触媒上での炭素の析出を抑制した高活性及び長寿命な金属微粒子担持触媒及びその製造方法を提供することを目的とする。
【０００５】
【課題を解決するための手段】
上記目的を達成するにあたり、従来から用いられている方法として、触媒成分を外部から付着させる含浸担持法では金属粒子径の制御及び触媒成分の強固な担持は困難である。そこで本発明者らは、触媒成分を内部から表面に染み出させることにより、金属超微粒子が高分散且つ強固に担持された金属担持触媒を製造する新規な触媒製造法（本方法を固相晶析法と呼ぶ。）を見いだし本発明を完成するに至った。
【０００６】
すなわち、本発明は、ハイドロタルサイト（構造式：Ｍa 2+Ｍb 3+（ＯＨ）2a+2b（Ｘ） ｂ／２ ・２Ｈ2Ｏ）の主構成元素として、Ｍa をＭｇ、Ｍb をＡｌ、ＸをＣＯ3 2- とし、Ａｌの全部がＳｃ及びＲｈ、又は、Ｙ及びＲｈに置換される組成となるように混合水溶液を調製し、該混合水溶液から得られる沈殿物を焼成し、ハイドロタルサイト化合物を得ることを特徴とする金属微粒子担持炭化水素改質用触媒の製造方法を提供することを目的とする。すなわち、ハイドロタルサイトのＡｌを以下のいずれかで置換するものである。
（１）ＳｃとＲｈ
（２）ＹとＲｈ
【０００７】
さらに本発明は、上記の製造方法により製造されることを特徴とする金属微粒子担持炭化水素改質用触媒を提供するものである。
【０００８】
【発明の実施の態様】
本発明において、構成元素の一部を貴金属又は遷移金属で置換する場合、置換する元素の価数が連合すれば、両者の混合による置換も可能であり、また、Ｍa 、Ｍb の一部を置換する場合、置換する割合は原子比で０．１〜５０％、特に０．１〜１０％が好ましい。置換濃度がこの範囲より低いと触媒活性が不適切であり、高過ぎると十分に置換されなくなるという問題が生じるのでこの範囲が好ましい。
本発明において、ハイドロタルサイトを製造するには、Ｍｇ、Ａｌ及びＲｈの硝酸塩等のような水溶性塩を適当な比率に混合して水に溶解し混合水溶液を調製し、Ｎａ2 ＣＯ3 やＮａＯＨのようなアルカリ水溶液を用いて好ましくはｐＨ６〜１２、特にｐＨ９〜１１の範囲に調整して沈殿を生成させることにより行う。次いで沈殿物は熟成、洗浄、焼成する。熟成は６０〜１００℃、特に７０〜９０℃、焼成は４００〜９００℃、特に６００〜９００℃で行うのが好ましい。 上記と同様にして、更に遷移金属、貴金属で適宜に置換したハイドロタルサイトを調製する。
【０００９】
上記の方法で得られるハイドロタルサイトは、一般式Ｍa 2+Ｍb 3+（ＯＨ）2a+2b （Ｘ） ｂ／２ ・２Ｈ2Ｏで表されるものであり（但しＭa ＝Ｍｇ、Ｍb ＝Ａｌ、Ｘ＝ＣＯ3 2- ）、これを前駆体として用いて、Ｍｇ及びＡｌのそれぞれ一部又は全部を貴金属又は遷移元素で置換された触媒を得る。上記工程における焼成段階において活性金属である貴金属及び遷移金属種が内部から表面に染み出して高分散化した金属微粒子を担持した触媒となり、特に炭化水素の水蒸気、ＣＯ2 改質、例えばメタンのＣＯ2 リフォーミング反応、メタンの部分酸化反応、ＣＯ及びＨ2 からメタンを合成するメタネーション反応、メタノールの改質あるいは分解反応による合成ガスの製造等に有効な触媒が得られる。以下、本固相晶析法による触媒調製法及び本触媒を用いた活性評価試験結果を実施例により詳細に説明する。
【００１０】
【実施例】
（実施例１）
触媒の調製Ｍｇ（ＮＯ3 ）2 ・６Ｈ2 Ｏ：７．５８３ｇ、Ａｌ2 （ＮＯ3 ）・９Ｈ2 Ｏ：２．３１１ｇ、Ｒｈ（ＮＯ3 ）3 ：０．１ｇを純水で２００ｍｌとし、金属の量論比の混合溶液を調製した。次に、Ｎａ2 ＣＯ3 ・１０Ｈ2 Ｏ：２．８２３ｇを秤量し、純粋で２０ｍｌとして四つ口フラスコに入れた。室温でＮａ2 ＣＯ3 溶液を攪拌しながらＭｇ／Ａｌ／Ｒｈ混合溶液に滴下した。この際、混合溶液のｐＨを１ＭのＮａＯＨ水溶液を用いて１０に保持した。滴下終了後、９０℃で４０分間攪拌を続けた。攪拌をやめ、９０℃で一晩熟成させた後、生成する混濁溶液を、吸収濾過し、過剰のイオン交換水で洗浄した。得られた沈殿物を、約１００℃で一晩乾燥させた。乾燥させた沈殿物を粉砕し、６５０℃で１４時間焼成し、次に８５０℃で５時間焼成させＡｌの一部をＲｈで置換した組成比Ｍｇ3 Ａｌ0.966 Ｒｈ0.034 を有するハイドロタルサイト型の参考触媒１を得た。なお、Ｒｈ（ＮＯ3 ）3 の量を半分にして組成比Ｍｇ3 Ａｌ 0.983 Ｒｈ0.017 （係数は原子比）を有する参考触媒２を得た。
【００１１】
次に、上記参考触媒１と同様な方法において、Ｒｈ（ＮＯ3 ）3 の代わりにＲｕＣｌ3 、Ｐｄ（ＮＨ3 ）2 Ｃｌ2 及びＮｉＣｌ2 ・６Ｈ2 Ｏを原料として各々のハイドロタルサイト型層状酸化物を得た。本触媒を参考触媒１と同様に焼成して各参考触媒を得た。本参考触媒は金属原子比でＭｇ3 Ａｌ0.966 Ｒｕ0.034 、Ｍｇ3 Ａｌ0.983Ｒｕ0.017 、Ｍｇ3 Ａｌ0.966 Ｐｄ0.034 、Ｍｇ3 Ａｌ0.983 Ｐｄ0.017 、Ｍｇ3 Ａｌ0.966 Ｎｉ0.034 、Ｍｇ3 Ａｌ0.983 Ｎｉ0.017 で表され、各々参考触媒３〜参考触媒８とする。また、参考触媒１においてＲｈ（ＮＯ3 ）の量を５倍、１０倍添加して参考触媒１と同様な方法にて調製し、組成比Ｍｇ3 Ａｌ0.828 Ｒｈ0.172 、Ｍｇ3Ａｌ0.67Ｒｈ0.33の参考触媒９、１０を得た。更に、参考触媒１０の調製法においてＡｌの代わりにＳｃ、Ｃｒ、Ｆｅ、Ｇａ、Ｙを選定し、各々金属硝酸塩を用いて参考触媒１０と同様の調製法にてＭｇ3 Ｆｅ0.67Ｒｈ0.33、Ｍｇ3 Ｃｒ0.67Ｒｈ0.33、Ｍｇ3 Ｇａ0.67Ｒｈ0.33、Ｍｇ3 Ｓｃ0.67Ｒｈ0.33、Ｍｇ3 Ｙ0.67Ｒｈ0.33を得た。本触媒を参考触媒１１、１２、１３、及び触媒１、２とする。
【００１２】
さらに、比較触媒として、参考触媒１の方法においてＲｈ（ＮＯ3 ）3 を添加せずに調製したＭｇ3 Ａｌのハイドロタルサイト型の層状化合物を調製し、参考触媒１と同様に焼成した。本触媒を比較触媒１とする。また、α−Ａｌ2 Ｏ3 にＲｈ（ＮＯ3 ）3 水溶液でＲｈを浸漬担持法で含浸させ、乾燥後、５００℃、５時間焼成した。本触媒を比較触媒２とする。さらに、参考触媒１にＲｈを浸漬担持法で含浸し、１０００℃で焼成した。本触媒を比較触媒３とする。
【００１３】
（参考例１）
メタンのＣＯ2 リフォーミング反応試験実施例１にて調製した触媒を用いてメタンのＣＯ2 リフォーミング反応を行った。反応器としては、円筒形反応器に触媒を固定床として保持した形式のものを用いた。反応条件を下記表１に示す。
【００１４】
【表１】
なお、活性、選択性は下記式により求めた。
ＣＨ4 転化率（％）＝（１−出口ＣＨ4 濃度／入口ＣＨ4 濃度）×１００
ＣＯ転化率（％）＝（１−出口ＣＯ濃度／入口ＣＯ濃度）×１００
ＣＯ選択率（％）＝（生成したＣＯ濃度／反応した（ＣＨ4 ＋ＣＯ2 ）濃度）×１００
Ｈ2 選択率（％）＝（生成したＨ2 濃度／反応したＣＨ4 濃度×２）×１００
【００１６】
【表２】
【表３】
表２に昇温反応におけるＣＯ2 によるメタン改質反応結果を示す。本結果より、参考触媒１〜８の固相晶析法による担持触媒は活性、選択性とも良好であり、ＣＯ、Ｈ2 の選択性は殆ど９０％以上を有した。一方、金属を担持していない比較触媒１や従来の含浸法により調製した比較触媒２は殆ど活性を示さないことがわかった。また、表３に７５０℃定温反応におけるＣＨ4 及びＣＯ2 の６時間後の転化率、選択性を、さらに図１〜図３には参考触媒２、４、６のＣＨ4 、ＣＯ2 の転化率の経時変化を示す。本結果より、参考触媒１、２、４、６はいずれも安定な高い活性を示すことがわかった。一方、比較触媒２は本条件においても殆ど活性を示さないことを確認した。更に参考触媒１〜８及び比較触媒１は８５０℃焼成後においても高比表面積を有することを確認した。
【００１９】
（参考例２）
メタンの部分酸化反応試験実施例１で調製した参考触媒を用いて、参考例１と同様の反応器中でメタンの部分酸化反応を行った。反応条件を下記表４に示す。
【００２０】
【表４】
なお、活性、選択性は下記式により求めた。
ＣＨ4 転化率（％）＝（１−出口ＣＨ4 濃度／入口ＣＨ4 濃度）×１００
Ｏ2 転化率（％）＝（１−出口Ｏ2 濃度／入口Ｏ2 濃度）×１００
ＣＯ選択率（％）＝（生成したＣＯ濃度／反応したＣＨ4 濃度）×１００
Ｈ2 選択率（％）＝（生成したＨ2 濃度／反応したＣＨ4 濃度×２）×１００
ＣＯ2 選択率（％）＝（生成したＣＯ2 濃度／反応したＣＨ4 濃度）×１００
【００２２】
【表５】
【表６】
表５、表６にＲｈ系の参考触媒及びＡｌ代替３価元素により調製した触媒のＣＨ4 の部分酸化反応結果（昇温反応）を示す。本結果より、参考触媒１、９〜１３及び本発明の触媒１、２はいずれも高いＣＨ4 の部分酸化活性を有し、ＣＨ4 が高選択率にてＣＯ、Ｈ2 に変換されることがわかった。
【００２５】
【発明の効果】
結晶性層状化合物（ハイドロタルサイト）を前駆体として、その構成元素の一部を活性金属である貴金属及び遷移金属元素で置換、焼成し、活性金属種を内部から表面に染み出させることにより得られる高分散化した金属微粒子担持触媒を用いて、メタンのＣＯ2 リフォーミング反応及びメタンの部分酸化反応を行った結果、本発明の触媒を用いることにより高活性を示し、高選択率でＣＯ、Ｈ2 への変換を可能とし、高温焼成後においても高表面積を有していることが示された。
【図面の簡単な説明】
【図１】図１は触媒２を用いたときのＣＨ4 、ＣＯ2 の転化率の経時変化を示す。
【図２】図２は触媒４を用いたときのＣＨ4 、ＣＯ2 の転化率の経時変化を示す。
【図３】図３は触媒６を用いたときのＣＨ4 、ＣＯ2 の転化率の経時変化を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrocarbon steam and carbon dioxide reforming catalyst, and more particularly to a highly dispersed metal fine particle-supported hydrocarbon reforming catalyst.
[0002]
[Prior art]
As a hydrocarbon steam reforming catalyst, a catalyst in which a heat-resistant oxide such as α-alumina is used as a carrier and a noble metal such as rhodium or ruthenium or nickel oxide is supported thereon as a catalyst active component is known. . Further, steam reforming has been reported in “Chemical Engineering Papers” Vol. 16, No. 5 (1990), and Ni-based catalysts have already been put to practical use in steam reforming. JRRostrup-Nielsen, in “Catalysis, Science and Technology "(Eds. JR Anderson and M. Boudart, Springer-Verlag: Berlin, 1984), Vol. 5, 1-117.
As a reforming reaction catalyst of methane by CO 2 , there are reports on ATAshcroft, AKCheetham, JSFoord, MLHGreen and PDFVemon, “Nature” 352, 225 (1991) for noble metals, and Ni-based catalysts are T. Osaki, T. Horiuchi, K. Suzuki and T. Mori, “J. Chem. Soc., Faraday Trans.”, 92, 1627 (1997).
[0003]
At present, synthesis gas is produced by steam reforming of natural gas using such a catalyst, but this method is a large endothermic reaction, and at the same time, a large amount of carbon dioxide is prevented from being deposited on the catalyst. This process is extremely disadvantageous in terms of energy because it must be operated using steam. Further, the CO / H 2 ratio of the synthesis gas to be produced is 1/3, and in order to adapt to the subsequent methanol synthesis or FT synthesis, it is necessary to adjust by combining the shift reaction in the subsequent stage. In addition, there are methane reforming reaction by carbon dioxide and partial oxidation reaction of methane as reaction instead of steam.
[0004]
[Problems to be solved by the invention]
Hydrocarbon steam or carbon dioxide reforming reactions such as those described above, such as methane reforming reaction of carbon dioxide and partial oxidation reaction of methane, have the problem of instant deterioration due to remarkable sintering and coking in current catalysts. . In these reactions, it is essential to develop a highly active catalyst for suppressing carbon deposition (coking) during operation.
Accordingly, an object of the present invention is to provide a highly active and long-life metal fine particle-supported catalyst that suppresses carbon deposition on the catalyst in a hydrocarbon steam and carbon dioxide reforming reaction, and a method for producing the same.
[0005]
[Means for Solving the Problems]
In order to achieve the above object, it is difficult to control the metal particle diameter and firmly support the catalyst component by the impregnation support method in which the catalyst component is attached from the outside as a conventionally used method. Therefore, the present inventors have developed a novel catalyst production method for producing a metal-supported catalyst in which ultrafine metal particles are highly dispersed and firmly supported by leaching the catalyst component from the inside to the surface (this method is a solid phase crystal). The present invention has been completed.
[0006]
That is, the present invention relates to hydrotalcite (structural formula: M a 2+ M b 3+ (OH) 2a + 2b (X) b / 2. As · 2H main constituent element of the 2 O), a M a and Mg, the M b Al, the X CO 3 2-a, all of Al, Sc and Rh, or, to be the composition which is substituted with Y and Rh An object of the present invention is to provide a method for producing a metal fine particle-supported hydrocarbon reforming catalyst, characterized in that a mixed aqueous solution is prepared and a precipitate obtained from the mixed aqueous solution is calcined to obtain a hydrotalcite compound. . That is, the hydrotalcite Al is substituted with any of the following.
(1) Sc and Rh
(2) Y and Rh
[0007]
Furthermore, the present invention provides a metal fine particle-supported hydrocarbon reforming catalyst produced by the production method described above .
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, when a part of the constituent elements is replaced with a noble metal or transition metal, if the valences of the elements to be replaced are combined, replacement by mixing both of them is possible, and part of M a and M b When substituting, the substitution ratio is 0.1 to 50%, particularly 0.1 to 10% in terms of atomic ratio. If the substitution concentration is lower than this range, the catalyst activity is inappropriate. If the substitution concentration is too high, there is a problem that the substitution is not sufficient.
In the present invention, in order to produce hydrotalcite, water-soluble salts such as Mg, Al and Rh nitrates are mixed in an appropriate ratio and dissolved in water to prepare a mixed aqueous solution, and Na 2 CO 3 or It is carried out by using an aqueous alkali solution such as NaOH, preferably by adjusting the pH in the range of 6 to 12, particularly in the range of pH 9 to 11, to generate a precipitate. The precipitate is then aged, washed and fired. The aging is preferably performed at 60 to 100 ° C, particularly 70 to 90 ° C, and the calcination is performed at 400 to 900 ° C, particularly 600 to 900 ° C. In the same manner as described above, a hydrotalcite further appropriately substituted with a transition metal or a noble metal is prepared.
[0009]
The hydrotalcite obtained by the above method is represented by the general formula M a 2+ M b 3+ (OH) 2a + 2b (X) b / 2 · 2H 2 O (where M a = Mg , M b = Al, X = CO 3 2− ), and using this as a precursor, a catalyst in which a part or all of Mg and Al is replaced with a noble metal or a transition element is obtained. In the calcination stage in the above process, the noble metal and transition metal species which are active metals exude to the surface from the inside and become a catalyst carrying highly dispersed metal fine particles, particularly hydrocarbon steam, CO 2 reforming, such as CO of methane 2 An effective catalyst can be obtained for reforming reaction, partial oxidation reaction of methane, methanation reaction for synthesizing methane from CO and H 2 , production of synthesis gas by reforming or decomposition reaction of methanol. Hereinafter, the catalyst preparation method by this solid-phase crystallization method and the activity evaluation test result using this catalyst will be described in detail by way of examples.
[0010]
【Example】
Example 1
Preparation of catalyst Mg (NO 3 ) 2 · 6H 2 O: 7.583 g, Al 2 (NO 3 ) · 9H 2 O: 2.311 g, Rh (NO 3 ) 3: 0.1 g to 200 ml with pure water, A mixed solution of metal stoichiometric ratio was prepared. Next, 2.823 g of Na 2 CO 3 .10H 2 O: was weighed and put into a four-necked flask as pure 20 ml. The Na 2 CO 3 solution was added dropwise to the Mg / Al / Rh mixed solution with stirring at room temperature. At this time, the pH of the mixed solution was maintained at 10 using 1M NaOH aqueous solution. After completion of dropping, stirring was continued at 90 ° C. for 40 minutes. After the stirring was stopped and the mixture was aged at 90 ° C. overnight, the resulting turbid solution was subjected to absorption filtration and washed with excess ion-exchanged water. The resulting precipitate was dried at about 100 ° C. overnight. The dried precipitate was pulverized, calcined at 650 ° C. for 14 hours, then calcined at 850 ° C. for 5 hours, and a part of Al was replaced with Rh. Hydrotalcite type composition having a composition ratio of Mg 3 Al 0.966 Rh 0.034 Reference catalyst 1 was obtained. Incidentally, Rh (NO 3) 3 amounts to half to the composition ratio Mg 3 A l 0.983 Rh 0.017 (coefficient atomic ratio) to obtain a reference catalyst 2 having a.
[0011]
Next, in the same method as the above-mentioned reference catalyst 1, each hydrotalcite type layered material is made from RuCl 3 , Pd (NH 3 ) 2 Cl 2 and NiCl 2 .6H 2 O instead of Rh (NO 3 ) 3. An oxide was obtained. This catalyst was calcined in the same manner as the reference catalyst 1 to obtain each reference catalyst. This reference catalyst is Mg 3 Al 0.966 Ru 0.034 , Mg 3 Al 0.983 Ru 0.017 , Mg 3 Al 0.966 Pd 0.034 , Mg 3 Al 0.983 Pd 0.017 , Mg 3 Al 0.966 Ni 0.034 , Mg 3 Al 0.983 Ni 0.017 in terms of metal atomic ratio. These are represented by reference catalyst 3 to reference catalyst 8, respectively. Further, 5 times the amount of the reference catalyst 1 Rh (NO 3), was added 10-fold was prepared in a similar manner to Reference Catalyst 1 method, the composition ratio Mg 3 Al 0.828 Rh 0.172, the Mg 3 Al 0.67 Rh 0.33 Reference catalysts 9 and 10 were obtained. Furthermore, Sc instead of Al in the preparation method of Reference catalyst 10, Cr, Fe, Ga, selected the Y, Mg 3 Fe 0.67 Rh 0.33 each using a metal nitrate in the same preparation method as in Reference catalyst 10, Mg 3 Cr 0.67 Rh 0.33, Mg 3 Ga 0.67 Rh 0.33, Mg 3 Sc 0.67 Rh 0.33, to obtain a Mg 3 Y 0.67 Rh 0.33. This catalyst is referred to as
[0012]
Furthermore, as a comparative catalyst, a hydrotalcite-type layered compound of Mg 3 Al prepared without adding Rh (NO 3 ) 3 in the method of Reference Catalyst 1 was prepared and calcined in the same manner as Reference Catalyst 1. This catalyst is referred to as Comparative Catalyst 1. Further, α - Al 2 O 3 was impregnated with Rh (NO 3 ) 3 aqueous solution by an immersion support method, dried, and then fired at 500 ° C. for 5 hours. This catalyst is referred to as Comparative Catalyst 2. Further, Rh was impregnated in the reference catalyst 1 by a dipping support method and calcined at 1000 ° C. This catalyst is referred to as Comparative Catalyst 3.
[0013]
( Reference Example 1)
Methane CO 2 reforming reaction test Using the catalyst prepared in Example 1, methane CO 2 reforming reaction was conducted. As the reactor, a cylindrical reactor in which the catalyst was held as a fixed bed was used. The reaction conditions are shown in Table 1 below.
[0014]
[Table 1]
In addition, activity and selectivity were calculated | required by the following formula.
CH 4 conversion (%) = (1−outlet CH 4 concentration / inlet CH 4 concentration) × 100
CO conversion rate (%) = (1−outlet CO concentration / inlet CO concentration) × 100
CO selectivity (%) = (concentrated CO concentration / reacted (CH 4 + CO 2 ) concentration) × 100
H 2 selectivity (%) = (H 2 concentration generated / CH 4 concentration reacted × 2) × 100
[0016]
[Table 2]
[Table 3]
Table 2 shows the methane reforming reaction result by CO 2 in the heated reaction. From these results, the supported catalysts obtained by the solid-phase crystallization method of Reference Catalysts 1 to 8 had both good activity and selectivity, and the selectivity of CO and H 2 was almost 90% or more. On the other hand, it was found that the comparative catalyst 1 not supporting a metal and the comparative catalyst 2 prepared by the conventional impregnation method showed almost no activity. Table 3 shows the conversion rate and selectivity of CH 4 and CO 2 after 6 hours in a constant temperature reaction at 750 ° C. Further, FIGS. 1 to 3 show the conversion of CH 4 and CO 2 of the
[0019]
( Reference Example 2)
Partial oxidation reaction test of methane Using the reference catalyst prepared in Example 1, a partial oxidation reaction of methane was carried out in the same reactor as in Reference Example 1. The reaction conditions are shown in Table 4 below.
[0020]
[Table 4]
In addition, activity and selectivity were calculated | required by the following formula.
CH 4 conversion (%) = (1−outlet CH 4 concentration / inlet CH 4 concentration) × 100
O 2 conversion (%) = (1−outlet O 2 concentration / inlet O 2 concentration) × 100
CO selectivity (%) = (concentrated CO concentration / reacted CH 4 concentration) × 100
H 2 selectivity (%) = (H 2 concentration generated / CH 4 concentration reacted × 2) × 100
CO 2 selectivity (%) = (CO 2 concentration produced / CH 4 concentration reacted) × 100
[0022]
[Table 5]
[Table 6]
Tables 5 and 6 show the CH 4 partial oxidation reaction results (temperature raising reaction) of the catalysts prepared using the Rh-based reference catalyst and the Al-substitute trivalent element. From these results, the reference catalysts 1, 9 to 13 and the catalysts 1 and 2 of the present invention all have high CH 4 partial oxidation activity, and CH 4 is converted to CO and H 2 with high selectivity. I understood.
[0025]
【The invention's effect】
Obtained by using a crystalline layered compound (hydrotalcite) as a precursor, replacing some of its constituent elements with precious metals and transition metal elements, which are active metals, and firing, and leaching active metal species from the inside to the surface. As a result of performing the CO 2 reforming reaction of methane and the partial oxidation reaction of methane using the highly dispersed metal fine particle supported catalyst obtained, the catalyst of the present invention shows high activity, with high selectivity, It was shown that it can be converted to H 2 and has a high surface area even after high temperature firing.
[Brief description of the drawings]
FIG. 1 shows changes with time in the conversion rate of CH 4 and CO 2 when a catalyst 2 is used.
FIG. 2 shows the change over time in the conversion rate of CH 4 and CO 2 when catalyst 4 is used.
FIG. 3 shows the change over time in the conversion rate of CH 4 and CO 2 when
Claims (2)
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