JP5611252B2 - 白金/スズ触媒を用いる酢酸からのエタノールの直接且つ選択的な製造 - Google Patents
白金/スズ触媒を用いる酢酸からのエタノールの直接且つ選択的な製造 Download PDFInfo
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Description
「選択率」は、転化した酢酸を基準とするモル%として表す。例えば、転化率が50モル%であり、転化した酢酸の50モル%がエタノールに転化している場合には、本発明者らはエタノール選択率が50%であると言う。選択率は、ガスクロマトグラフィー(GC)のデータから下式:
触媒金属の重量%は、金属の重量、並びに金属及び担体の合計乾燥重量に基づく。
反応は、次の化学式:
本発明によれば、酢酸のエタノールへの転化は、例えば、所望の場合には層状固定床であってよい単一の反応区域内のような種々の形態で行うことができる。断熱反応器を用いることができ、或いは熱伝達媒体を備えたシェルアンドチューブ反応器を用いることができる。固定床には、異なる触媒粒子又はここで更に記載する複数の触媒を含む触媒粒子の混合物を含ませることができる。固定床にはまた、反応物質のための混合区域を構成する粒子状材料の層を含ませることもできる。酢酸、水素、及び場合によっては不活性キャリアガスを含む反応混合物を、混合区域への加圧流として床に供給する。この流れは、次に(差圧を用いて)反応区域又は層に供給される。反応区域は、好適な水素化触媒を含む触媒組成物を含み、ここで酢酸が水素化されてエタノールが生成する。反応器のタイプ、処理量の要求などに応じて、任意の好適な粒径を用いることができる。
規定した特性を有する炭素担体を製造するために好ましい熱処理手順は、順番に、(1)炭素を不活性雰囲気中900℃〜3300℃の温度で加熱し(2)炭素を300℃〜1200℃の温度で酸化し(3)不活性雰囲気中900℃〜3000℃の温度で加熱する;ことを含む。
不活性ガス中の加熱の継続時間は重要ではない。炭素において必要な変化を生起させるためには、炭素を必要な最高温度に加熱するのに必要な時間で十分である。
酸化剤の供給速度は、好ましくは所望の重量損失が少なくとも2時間、より好ましくは少なくとも4時間で起こるようなものである。
上述したように、白金及びスズの装填レベルは、一般に白金の含量及びPt/Snの重量比を基準とし、約0.1〜2の範囲である。したがって、Pt/Snの重量比が0.1である場合には、白金の量は0.1又は1重量%であってよく、1又は10重量%のスズが触媒担体上に存在する。より好ましくは、Pt/Snの重量比は約0.5であり、触媒担体上の白金の量は0.5又は1重量%のいずれかであってよく、スズの量は1又は2重量%のいずれかである。より好ましくは、Pt/Snの重量比は1である。担体上の白金の量は、0.5、1、又は2重量%であり、スズの量も、0.5、1、又は2重量%である。しかしながら、より低いPt/Snの重量比を用いることもできる。例えば、0.2のPt/Snの重量比を用いることもできる。かかる場合においては、担体上の白金の量は0.5又は1重量%であってよく、これに対して2.5又は5重量%のスズを用いる。
一般に、本発明の活性触媒は、シリカ上に担持されている白金及びスズを含み、白金及びスズの装填量がそれぞれ1重量%である非促進触媒である。本発明の実施によれば、これらの触媒を用いて、酢酸を、約90%の転化率、並びに少なくとも90%のエタノール選択率、より好ましくは少なくとも95%のエタノールへの選択率で転化させることができる。
反応は、気体状態又は液体状態において、広範囲の条件下で行うことができる。好ましくは、反応は気相中で行う。例えば約200℃〜約300℃、好ましくは約225℃〜約275℃の範囲の反応温度を用いることができる。圧力は一般に反応に対して重要ではなく、大気圧以下、大気圧、又は大気圧以上の圧力を用いることができる。しかしながら、殆どの場合においては、反応圧は約1〜30絶対気圧の範囲であり、最も好ましくは反応区域の圧力は約10〜25絶対気圧の範囲である。
実施例A
黒鉛上1重量%白金/1重量%スズの製造:
約0.2mmの均一な粒径分布の粉末化し篩別した黒鉛(100g)を、オーブン内、窒素雰囲気下で120℃において一晩乾燥し、次に室温に冷却した。これに、蒸留水(16mL)中の硝酸白金(Chempur)(1.64g)の溶液、及び希硝酸(1N、8.5mL)中のシュウ酸スズ(Alfa Aesar)(1.74g)の溶液を加えた。得られたスラリーを、オーブン内で110℃に徐々に加熱(>2時間、10℃/分)して乾燥した。次に、含浸した触媒混合物を400℃においてカ焼した(6時間、1℃/分)。
高純度低表面積シリカ上0.5重量%白金/5重量%スズの製造:
約0.2mmの均一な粒径分布の粉末化し篩別した高純度で低表面積のシリカ(100g)を、オーブン内、窒素雰囲気下で120℃において一晩乾燥し、次に室温に冷却した。これに、蒸留水(8mL)中の硝酸白金(Chempur)(0.82g)の溶液、及び希硝酸(1N、43.5mL)中のシュウ酸スズ(Alfa Aesar)(8.7g)の溶液を加えた。得られたスラリーを、オーブン内で110℃に徐々に加熱(>2時間、10℃/分)して乾燥した。次に、含浸した触媒混合物を500℃においてカ焼した(6時間、1℃/分)。
高純度低表面積シリカ上1重量%白金/1重量%スズの製造:
蒸留水(16mL)中の硝酸白金(Chempur)(1.64g)の溶液、及び希硝酸(1N、8.5mL)中のシュウ酸スズ(Alfa Aesar)(1.74g)の溶液を用いた他は、実施例Bの手順を実質的に繰り返した。
ケイ酸カルシウム上1重量%白金/1重量%スズの製造:
蒸留水(16mL)中の硝酸白金(Chempur)(1.64g)の溶液、及び希硝酸(1N、8.5mL)中のシュウ酸スズ(Alfa Aesar)(1.74g)の溶液を用い、触媒担体としてケイ酸カルシウムを用いた他は、実施例Bの手順を実質的に繰り返した。
高純度低表面積シリカ上0.5重量%白金/0.5重量%スズ/0.2重量%コバルトの製造:
約0.2mmの均一な粒径分布の粉末化し篩別した高純度で低表面積のシリカ(100g)を、オーブン内、窒素雰囲気下で120℃において一晩乾燥し、次に室温に冷却した。これに、蒸留水(8mL)中の硝酸白金(Chempur)(0.82g)の溶液、及び希硝酸(1N、4.5mL)中のシュウ酸スズ(Alfa Aesar)(0.87g)の溶液を加えた。得られたスラリーを、オーブン内で110℃に徐々に加熱(>2時間、10℃/分)して乾燥した。次に、含浸した触媒混合物を500℃においてカ焼した(6時間、1℃/分)。このカ焼し冷却した材料に、蒸留水(2mL)中の硝酸コバルト6水和物(0.99g)の溶液を加えた。得られたスラリーを、オーブン内で110℃に徐々に加熱(>2時間、10℃/分)して乾燥した。次に、含浸した触媒混合物を500℃においてカ焼した(6時間、1℃/分)。
高純度低表面積シリカ上0.5重量%スズの製造:
約0.2mmの均一な粒径分布の粉末化し篩別した高純度で低表面積のシリカ(100g)を、オーブン内、窒素雰囲気下で120℃において一晩乾燥し、次に室温に冷却した。これに、希硝酸(1N、8.5mL)中のシュウ酸スズ(Alfa Aesar)(1.74g)の溶液を加えた。得られたスラリーを、オーブン内で110℃に徐々に加熱(>2時間、10℃/分)して乾燥した。次に、含浸した触媒混合物を500℃においてカ焼した(6時間、1℃/分)。
オンラインGCによって生成物の分析を行った。1つの炎イオン化検出器(FID)及び2つの熱伝導度型検出器(TCD)を備えた3チャンネルの小型GCを用いて、反応物質及び生成物を分析した。フロントチャンネルには、FID及びCP-Sil 5(20m)+WaxFFap(5m)カラムを取り付け、これを用いて
アセトアルデヒド;
エタノール;
アセトン;
酢酸メチル;
酢酸ビニル;
酢酸エチル;
酢酸;
エチレングリコールジアセテート;
エチレングリコール;
エチリデンジアセテート;
パラアルデヒド;
を定量した。
CO2;
エチレン;
エタン;
を定量した。
ヘリウム;
水素;
窒素;
メタン;
一酸化炭素;
を定量した。
用いた触媒は、実施例Cの手順にしたがって製造したシリカ上1重量%白金/1重量%スズであった。
用いた触媒は、実施例Dの手順にしたがって製造したケイ酸カルシウム上1重量%白金/1重量%スズであった。
用いた触媒は、実施例Fの手順にしたがって製造した低表面積高純度シリカ上1重量%スズであった。
(1)酢酸及び水素を含む供給流を、昇温温度において、好適な触媒担体上の白金及びスズの組み合わせ、並びに場合によっては該担体上に担持されている第3の金属を含み、第3の金属が、パラジウム、ロジウム、ルテニウム、レニウム、イリジウム、クロム、銅、モリブデン、タングステン、バナジウム、及び亜鉛からなる群から選択される好適な水素化触媒と接触させることを含む、酢酸からエタノールを選択的且つ直接に生成する方法。
(2)触媒担体が、シリカ、アルミナ、シリカ−アルミナ、ケイ酸カルシウム、炭素、ジルコニア、及びチタニアからなる群から選択される、(1)に記載の方法。
(3)触媒担体がシリカである、(2)に記載の方法。
(4)触媒担体が高純度シリカである、(3)に記載の方法。
(5)触媒担体がケイ酸カルシウムである、(2)に記載の方法。
(6)触媒担体が炭素である、(2)に記載の方法。
(7)触媒担体が黒鉛である、(6)に記載の方法。
(8)触媒担体が高表面積の黒鉛化炭素である、(7)に記載の方法。
(9)触媒担体が、約0.1〜2の範囲のPt/Snの重量比の白金及びスズの組み合わせを含む、(1)に記載の方法。
(10)白金の装填量が約0.5重量%であり、スズの装填量が約0.5重量%であり、触媒担体が、シリカ、黒鉛、シリカ−アルミナ、又はケイ酸カルシウムである、(9)に記載の方法。
(11)白金の装填量が約1重量%であり、スズの装填量が約1重量%であり、触媒担体が、シリカ、黒鉛、シリカ−アルミナ、又はケイ酸カルシウムである、(9)に記載の方法。
(12)白金の装填量が約0.5重量%であり、スズの装填量が約2.5重量%であり、触媒担体が、シリカ、黒鉛、シリカ−アルミナ、又はケイ酸カルシウムである、(9)に記載の方法。
(13)白金の装填量が約1重量%であり、スズの装填量が約5重量%であり、触媒担体が、シリカ、黒鉛、シリカ−アルミナ、又はケイ酸カルシウムである、(9)に記載の方法。
(14)消費された酢酸を基準とするエタノールへの選択率が少なくとも60%である、(1)に記載の方法。
(15)消費された酢酸を基準とするエタノールへの選択率が少なくとも80%である、(1)に記載の方法。
(16)消費された酢酸を基準とするエタノールへの選択率が少なくとも90%である、(1)に記載の方法。
(17)消費された酢酸を基準とするエタノールへの選択率が少なくとも95%である、(1)に記載の方法。
(18)エタノールへの水素化を、気相中、約200℃〜300℃の範囲の温度において行う、(1)に記載の方法。
(19)エタノールへの水素化を、気相中、約225℃〜275℃の範囲の温度において行う、(18)に記載の方法。
(20)供給流が不活性キャリアガスを含む、(18)に記載の方法。
(21)反応物質が、約100:1〜1:100の範囲のモル比の酢酸及び水素から構成され、反応区域の温度が約200℃〜300℃の範囲であり、反応区域の圧力が約1〜30絶対気圧の範囲である、(18)に記載の方法。
(22)反応物質が、約1:20〜1:2の範囲のモル比の酢酸及び水素から構成され、反応区域の温度が約225℃〜275℃の範囲であり、反応区域の圧力が約10〜25絶対気圧の範囲である、(18)に記載の方法。
(23)酢酸及び水素を含む供給流を、昇温温度において、好適な触媒担体上の約0.5重量%〜約1重量%の白金及び0.5重量%〜約5重量%のスズ、並びに場合によっては該担体上に担持されている第3の金属を含み、第3の金属が、コバルト、ルテニウム、及びパラジウムからなる群から選択される好適な水素化触媒と接触させることを含む、酢酸からエタノールを選択的且つ直接に生成する方法。
(24)触媒担体が白金及びスズをそれぞれ約1重量%の装填レベルで含む、(23)に記載の方法。
(25)触媒担体がシリカである、(23)に記載の方法。
(26)反応物質が、約1:20〜1:5の範囲のモル比の酢酸及び水素から構成され、反応区域の温度が約225℃〜275℃の範囲であり、反応区域の圧力が約10〜25絶対気圧の範囲である、(23)に記載の方法。
Claims (13)
- 炭素源からエタノールを選択的且つ直接に生成する方法であって、
(a)炭素源を酢酸に転化させること;及び
(b)蒸気形態の酢酸及び水素を含む供給流を、200℃〜300℃の温度において、触媒担体上の0.1〜2のPt/Snの重量比の白金及びスズの組み合わせを含む水素化触媒と接触させること;
を含み、
ここで、水素化触媒が、0.5重量%〜1重量%の白金、及び0.5重量%〜5重量%のスズを含み、
少なくとも80重量%の消費された酢酸がエタノールへ転化される、上記方法。 - 触媒担体が、シリカ、アルミナ、シリカ−アルミナ、ケイ酸カルシウム、炭素、ジルコニア、チタニア、及びこれらの組み合わせからなる群から選択される、請求項1に記載の方法。
- 炭素源が、天然ガス、石油、及び石炭からなる群から選択される、請求項1に記載の方法。
- 炭素源がバイオマスである、請求項1に記載の方法。
- バイオマスを酢酸に転化させる工程が、
(i)バイオマスを、シンガスを含む第1の流れに転化させること;
(ii)シンガスの少なくとも一部を、メタノールを含む第2の流れに触媒的に転化させること;
(iii)一部のシンガスを、水素及び一酸化炭素に分離させること;及び
(iv)一部の一酸化炭素を伴う少なくとも一部のメタノールを、酢酸を含む第3の流れに触媒的に転化させること;
を含み、
ここで、接触させる工程が、少なくとも一部の酢酸を一部の水素とともに、エタノールを含む第4の流れへ還元させることを含む、請求項4に記載の方法。 - 炭素源をメタノールに転化させること、及びメタノールを酢酸に転化させることをさらに含み、
ここで、接触させる工程が、少なくとも一部の酢酸をエタノールへ還元させることを含む、請求項1に記載の方法。 - 炭素源をシンガスに転化させること、少なくとも一部のシンガスをメタノールに転化させること、及びメタノールを酢酸に転化させることをさらに含み、
ここで、接触させる工程が、少なくとも一部の酢酸をエタノールへ還元させることを含む、請求項1に記載の方法。 - 炭素源をシンガスに転化させること、一部のシンガスを水素流と一酸化炭素流に分離させること、及び一部の一酸化炭素流をメタノールとともに酢酸まで反応させることをさらに含み、
ここで、接触させる工程が、少なくとも一部の酢酸を一部の水素流とともに、エタノールへ還元させることを含む、請求項1に記載の方法。 - 炭素源をシンガスに転化させること、一部のシンガスを水素流と一酸化炭素流に分離させること、少なくとも一部のシンガスをメタノールに転化させること、及び一部の一酸化炭素流をメタノールとともに酢酸まで反応させることをさらに含み、
ここで、接触させる工程が、少なくとも一部の酢酸を一部の水素流とともに、エタノールへ還元させることを含む、請求項1に記載の方法。 - 反応物質が、100:1〜1:100の範囲のモル比の酢酸及び水素から構成され、反応区域の圧力が1〜30絶対気圧の範囲である、請求項1に記載の方法。
- 水素化触媒が、パラジウム、ロジウム、レニウム、イリジウム、クロム、銅、モリブデン、タングステン、バナジウム、及び亜鉛からなる群から選択される第3の金属をさらに含有する、請求項1に記載の方法。
- 水素化触媒が、ロジウム、イリジウム、銅、モリブデン、及び亜鉛からなる群から選択される第3の金属をさらに含有する、請求項1に記載の方法。
- 水素化触媒が、パラジウム、及びコバルトからなる群から選択される第3の金属をさらに含有する、請求項1に記載の方法。
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