JP4118503B2 - Process for producing hydrocarbons in the presence of carbon dioxide - Google Patents

Description

【００３２】
〔連鎖成長確率（α）〕
炭素数ｎの炭化水素の生成物中の質量分率をＭｎ、連鎖成長確率をαとした場合、シュルツ・フローリー分布に従うと、下式のような関係が成り立つ。従って、ｌｏｇ（Ｍｎ／ｎ）とｎをプロットしたときの傾きｌｏｇ αからα値を知ることができる。
【００３３】
【数２】

【００３４】
【実施例】
以下、実施例および比較例によりさらに具体的に本発明を説明するが、本発明はこれらの実施例に限定されるものではない。
なお、以下の実施例において、ＣＯおよびＣＨ₄の分析には、Active Carbon (60/80mesh) を分離カラムに用い熱伝導度型ガスクロマトグラフ(TCD-GC)で行った。なお、Ａｒを内部標準として１０ｖｏｌ．％添加した合成ガスを用いた。なお、ＣＯおよびＣＨ₄のピーク位置、ピーク面積をＡｒと比較することで定性および定量分析した。Ｃ₁〜Ｃ₆炭化水素類の分析には、Capillary Column（Ａｌ₂Ｏ₃／ＫＣｌ ＰＬＯＴ）を分離カラムに用い水素炎イオン化検出型ガスクロマトグラフ(FID-GC)を用い、ＴＣＤ−ＧＣ共通に分析できるＣ₁（メタン）と比較して該炭化水素類の定性、定量を行った。さらに、Ｃ₅〜Ｃ₄₀炭化水素類の分析にはCapillary Column(TC-1)を備えたＦＩＤ−ＧＣを用い、軽質炭化水素（Ｃ₁〜Ｃ₆）と共通に分析できるＣ₅およびＣ₆と比較して該炭化水素類の定性、定量を行った。触媒（担体を含む）比表面積の測定は自動表面積測定装置（ベルソープ２８、日本ベル製）を用い窒素をプローブ分子に用いてＢＥＴ法で測定した。触媒の化学成分の同定はＩＣＰ（CQM-10000P、島津製作所製）により、粒度分布はレーザー光散乱法による粒度測定装置（Mastersizer MSX-46型、マルバーン製）で求めた。
【００３５】
実施例１
予め乾燥した酸化マンガン粉末30g に純水をビュレットから滴下し、飽和吸水量を求めた。この時の飽和吸水量は0.26ml/gだった。炭酸ナトリウム(Na Assay 43質量%)0.31g にイオン交換水( 以下水と略記) を加え8ml とし、撹拌して溶解した。この溶液全量を30g の酸化マンガン粉末に含浸させ、約3 時間放置した後、空気中、温度110℃で数時間乾燥した。塩化ルテニウム(Ru Assay 35質量%)0.09ｇに水を加えて8ml とし、撹拌して溶解した。この溶液の全量をNa含浸酸化マンガン粉末に含浸させ、約３時間放置した後、空気中、温度110℃で数時間乾燥した。これをメノウ乳鉢に移して粉砕し、触媒粒子径分布0.5 〜150 μm に篩い分けして触媒Ａを得た。なお粒子径分布はレーザー光散乱法によって求めた。この触媒の平均粒子径は20μm 、嵩密度は2.3 だった。ICP を用いて組成分析を行った結果、Ru換算で 0.1質量% 、Na換算で0.45質量% 、残り酸化マンガンであった。また、比表面積は 4m²/gであった。触媒Ａ12g を容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄(ノルマルヘキサデカン)40g を加えた後、水素分圧 20kg/cm²(1.96MPa) 、温度170℃ 、流量100ml/min (STP: standard temperature and pressure) で接触させ24時間還元した後、直ちにヘリウムガスでパージし200℃ まで昇温した。さらに、ヘリウムを流通させながら系内を 20kg/cm² (1.96MPa) とし、次いでアルゴン10vol.% 、一酸化炭素30vol.% 、残り水素の混合ガス（Ｈ₂／Ｃ０比 2）に切り替えFT反応を開始し、20時間経過後に二酸化炭素を0.2kg/cm²(0.0196MPa) の分圧で導入してGHSV(gas hourly space velocity)2400 で接触させた。48時間後のワンパスCO転化率は69% 、連鎖成長確率は0.90、Ｃ３
中のオレフィン／パラフィン比は７だった。
【００３６】
実施例２
実施例１に示した調製手法によってRu換算 1質量% 、Na換算0.45質量% 、残り酸化マンガン、比表面積 8m²/g 、触媒粒子径分布0.5-120 μm 、平均粒子径20μm 、嵩密度2.1 の触媒Ｂを得た。触媒Ｂ12g を容積100ml の反応器に充填し、実施例１と同様の還元処理およびFT反応を行った。二酸化炭素はFT反応開始20時間後に2kg/cm²(0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は80% 、連鎖成長確率は0.90、Ｃ₃中のオレフィン／パラフィン比は６だった。
【００３７】
実施例３
実施例１に示した調製手法によってRu換算 1質量% 、K 換算0.45質量%(Ｋ₂ＣＯ₃を用いNa担持方法と同様) 、残り酸化マンガン、比表面積 8m²/g、触媒粒子径分布0.5-150 μm 、平均粒子径20μm 、嵩密度2.1 の触媒Ｃを得た。触媒Ｃ12ｇを容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄（ノルマルヘキサデカン）40gを加えた後、水素分圧 20kg/cm² (1.96MPa) 、温度170℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし270℃ まで昇温した。次いでアルゴン10vol.% 、一酸化炭素30vol.% 、残り水素の混合ガス（Ｈ₂／Ｃ０比 2.0）に切り替えFT反応を開始し、20時間経過後に二酸化炭素を2kg/cm²(0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は83.5% 、連鎖成長確率は0.89、Ｃ₃中のオレフィン／パラフィン比は７だった。
【００３８】
実施例４
実施例３に示した調製手法によってRu換算 2質量% 、Na換算 0.1質量% 、残り酸化マンガン、比表面積 8m²/g、触媒粒子径分布0.5-150 μm 、平均粒子径20μm 、嵩密度2.1 の触媒Ｄを得た。触媒Ｄ12g を容積100ml の反応器に充填し、実施例３と同様の還元処理およびFT反応を行った。二酸化炭素はFT反応開始20時間後に2kg/cm² (0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は83% 、連鎖成長確率は0.89、Ｃ₃中のオレフィン／パラフィン比は６だった。
【００３９】
実施例５
実施例３に示した調製手法によってRu換算 2質量% 、Na換算0.45質量% 、残り酸化マンガン、比表面積 8m²/g、触媒粒子径分布1.0-150 μm 、平均粒子径20μm 、嵩密度2.1 の触媒Ｅを得た。触媒Ｅ12ｇを容積100ml の反応器に充填し、実施例３と同様の還元処理およびFT反応を行った。二酸化炭素はFT反応開始20時間後に2kg/cm²(0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は85.5% 、連鎖成長確率は0.88、Ｃ₃中のオレフィン／パラフィン比は６だった。
【００４０】
実施例６
実施例３に示した調製手法によってRu換算 2質量% 、Ca換算0.45質量%(Ｃａ（ＮＯ₃）₂・４Ｈ₂Ｏを用いNa担持方法と同様) 、残り酸化マンガン、比表面積 8m²/g、触媒粒子径分布1.0-150 μm 、平均粒子径20μm 、嵩密度2.1 の触媒Ｆを得た。触媒Ｆ12ｇを容積100ml の反応器に充填し、実施例３と同様の還元処理およびFT反応を行った。二酸化炭素はFT反応開始20時間後に2kg/cm²(0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は84.5% 、連鎖成長確率は0.88、Ｃ₃中のオレフィン／パラフィン比は６だった。
【００４１】
実施例７
実施例１に示した調製手法によってRu換算 2質量% 、K 換算0.45質量% 、残り酸化マンガン、比表面積 8m²/g、触媒粒子径分布1.0-150 μm 、平均粒子径20μm 、嵩密度2.1 の触媒Ｇを得た。触媒Ｇ12ｇを容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄（ノルマルヘキサデカン）40gを加えた後、水素分圧 20kg/cm² (1.96MPa) 、温度170℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし290℃ まで昇温した。次いでアルゴン10vol.% 、一酸化炭素30vol.% 、残り水素の混合ガス（Ｈ₂／ＣＯ比 2.0）に切り替えFT反応を開始し、20時間経過後に二酸化炭素を2kg/cm² (0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は86.5% 、連鎖成長確率は0.88、Ｃ₃中のオレフィン／パラフィン比は６だった。
【００４２】
実施例８
実施例１に示した調製手法によってRu換算 5質量% 、Na換算0.45質量% 、残り酸化マンガン、比表面積 8m²/g、触媒粒子径分布0.5-150 μm 、平均粒子径20μm 、嵩密度2.1 の触媒Ｈを得た。触媒Ｈ 6ｇを容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄（ノルマルヘキサデカン）24g を加えた後、水素分圧 50kg/cm² (4.9MPa)、温度170℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし300℃ まで昇温した。さらに、ヘリウムを流通させながら系内を 15kg/cm² (1.47MPa) まで降圧し、次いでアルゴン10vol.% 、一酸化炭素36vol.% 、残り水素の混合ガス（Ｈ₂／ＣＯ比 1.5）に切り替えFT反応を開始し20時間後に二酸化炭素を3kg/cm²(0.294MPa)の分圧で導入し、GHSV12000 で接触させた。反応開始48時間後のワンパスCO転化率は80.2% 、連鎖成長確率は0.88、Ｃ₃中のオレフィン／パラフィン比は７だった。
【００４３】
実施例９
実施例１に示した調製手法によってRu換算20質量% 、Na換算10質量% 、残り酸化マンガン、比表面積 100m²/g、触媒粒子径分布0.5-150 μm 、平均粒子径40μm 、嵩密度1.0 の触媒Ｉを得た。触媒Ｉ 2ｇを容積100ml の反応器に充填し、水素分圧50kg/cm² (4.9MPa)、温度140℃ 、流量100ml/min(STP)で触媒に接触させ12時間還元した後、直ちにヘリウムガスでパージし300℃ まで昇温した。その後、ヘリウムを通気下、分散媒としてn-Ｃ₁₆Ｈ₃₄(ノルマルヘキサデカン)40gを圧送し、撹拌した。さらに、ヘリウムを流通させながら系内を 15kg/cm²(1.47MPa)まで降圧し、次いでアルゴン10vol.% 、一酸化炭素39.1.vol% 、残り水素の混合ガス（Ｈ₂／ＣＯ比 1.3）に切り替えFT反応を開始し20時間後に二酸化炭素を5kg/cm² (0.49MPa) の分圧で導入し、GHSV12000 で接触させた。反応開始48時間後のワンパスCO転化率は79.5% 、連鎖成長確率は0.89、Ｃ₃中のオレフィン／パラフィン比は７だった。
【００４４】
実施例１０
実施例１に示した調製手法によってRu換算30質量% 、K 換算15質量% 、残り酸化マンガン、比表面積 120m²/g、触媒粒子径分布0.5-150 μm 、平均粒子径50μm 、嵩密度0.7 の触媒Ｊを得た。触媒Ｊ 2ｇを容積100ml の反応器に充填し、水素分圧 60kg/cm² (5.88MPa) 、温度200℃ 、流量100ml/min(STP)で触媒に接触させ12時間還元した後、直ちにヘリウムガスでパージし300℃ まで昇温した。その後、ヘリウムを流通下、分散媒としてn-Ｃ₁₆Ｈ₃₄(ノルマルヘキサデカン)67gを圧送し、撹拌した。ヘリウムで系内を 10kg/cm² (0.98MPa) まで降圧し、次いでアルゴン10vol.% 、一酸化炭素45vol.% 、残り水素の混合ガス（Ｈ₂／ＣＯ比 1.0）に切り替えFT反応を開始し20時間後に二酸化炭素を2kg/cm² (0.196MPa)の分圧で導入し、GHSV16000 で接触させた。反応開始48時間後のワンパスCO転化率は74.5% 、連鎖成長確率は0.88、Ｃ₃中のオレフィン／パラフィン比は５だった。
【００４５】
実施例１１
実施例１に示した調製手法によってRu換算50質量% 、Ca換算20質量% 、残り酸化マンガン、比表面積 200m²/g、触媒粒子径分布0.5-150 μm 、平均粒子径60μm 、嵩密度0.7 の触媒Ｋを得た。触媒Ｋ 0.5ｇを容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄（ノルマルヘキサデカン）50g を加えた後、水素分圧100kg/cm² (9.8MPa)、温度200℃、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし300℃まで昇温した。さらに、ヘリウムを流通させながら系内を 10kg/cm² (0.98MPa) まで降圧し、次いでアルゴン10vol.% 、一酸化炭素50vol.%、残り水素の混合ガス（Ｈ₂／ＣＯ比 0.8）に切り替えFT反応を開始し20時間後に二酸化炭素を6kg/cm²(0.588MPa)の分圧で導入し、GHSV24000 で接触させた。反応開始48時間後のワンパスCO転化率は90.1% 、連鎖成長確率は0.86、Ｃ₃中のオレフィン／パラフィン比は３だった。
【００４６】
比較例１
実施例１に示した調製手法によってRu換算 2質量% 、Na換算0.45質量% 、残り酸化マンガン、比表面積 8m²/g、触媒粒子径分布1.0-105 μm 、平均粒子径20μm 、嵩密度2.1 の触媒Ｌを得た。触媒Ｌ12g を容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄（ノルマルヘキサデカン）40g を加えた後、水素分圧 20kg/cm² (1.96MPa) 、温度170℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし270℃ まで昇温した。次いでアルゴン10vol.% 、一酸化炭素30vol.% 、残り水素の混合ガス（Ｈ₂／ＣＯ比 ２）に切り替えGHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は75.0% 、連鎖成長確率は0.9 、Ｃ₃中のオレフィン／パラフィン比は６だった。このように、FT反応中に二酸化炭素が存在しないとCO転化率( 実施例５と比較) が低下し、生産性が劣る可能性が高くなる。
【００４７】
比較例２
実施例１に示した調製手法によってRu換算 2質量% 、残り酸化マンガン、比表面積10m²/g、触媒粒子径分布1.0-150 μm 、平均粒子径20μm 、嵩密度2.1g/ml の触媒Ｍを得た。触媒Ｍ12g を容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄（ノルマルヘキサデカン）40g を加えた後、水素分圧 20kg/cm² (1.96MPa) 、温度170℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし270℃ まで昇温した。次いでアルゴン10vol.% 、一酸化炭素30vol.% 残り水素の混合ガス（Ｈ₂／Ｃ０比 ２）に切り替え、FT反応を開始し20時間後に二酸化炭素を2kg/cm² (0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は40% 、連鎖成長確率は0.9 、Ｃ₃中のオレフィン／パラフィン比は５だった。このように、アルカリ（土類）金属化合物を添加しない触媒でFT反応中に二酸化炭素を共存させるとCO転化率( 実施例５と比較) は急激に低下し、生産性が極端に劣る可能性が高くなる。
【００４８】
比較例３
予め、乾燥機で充分に乾燥させたアルミナに、ビュレットを用いて蒸留水を滴下し、飽和吸水量0.89ml/gを求めた。塩化ルテニウム（ＲｕＣｌ₃・ｎＨ₂Ｏ）5gを蒸留水78.5mlに溶解し、塩化ルテニウム水溶液を調製した。アルミナ40g にこの水溶液35.7mlを滴下して、塩化ルテニウムを含浸し、2 時間放置し水分を除去した。Ru換算 2質量% 、残りアルミナ、比表面積 250m²/g 、触媒粒子径分布1.0-150 μｍ、平均粒子径20μm 、嵩密度1g/ml の触媒Ｎを得た。触媒Ｎ 9ｇを容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄（ノルマルヘキサデカン）30g を加えた後、水素分圧 20kg/cm²(1.96MPa) 、温度170℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし270℃ まで昇温した。さらに、ヘリウムを流通させながら系内を 20kg/cm² (1.96MPa) とし、次いでアルゴン10vol.% 、一酸化炭素30vol.% 残り水素の混合ガス（Ｈ₂／ＣＯ比 ２）に切り替え、FT反応を開始し20時間後に二酸化炭素を2kg/cm² (0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は45% 、連鎖成長確率は0.80、Ｃ₃中のオレフィン／パラフィン比は３だった。反応結果は、実施例５に比べ二酸化炭素の添加効果は見られず不満足な結果であった。
【００４９】
比較例４
比較例３と同じアルミナ40g に、炭酸ナトリウム1gを蒸留水80.9mlに溶解した水溶液35.6mlを滴下して炭酸ナトリウムを含浸した。15時間静置した後、マッフル炉を用いて、600℃ で３時間焼成した。得られた担体に40g に、比較例３と同じ塩化ルテニウム水溶液35.6mlを滴下し、比較例３と同様にルテニウムを担持した。Ru換算 2質量% 、Na換算0.45質量% 、残りアルミナ、比表面積 250m²/g、触媒粒子径分布1.0-105 μｍ、平均粒子径20μm 、嵩密度1g/ml の触媒Ｏを得た。触媒Ｏ 9ｇを容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄（ノルマルヘキサデカン）30gを加えた後、水素分圧 20kg/cm² (1.96MPa) 、温度170℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし270℃ まで昇温した。さらに、ヘリウムを流通させながら系内を 20kg/cm² (1.96MPa) とし、次いでアルゴン10vol.% 、一酸化炭素30vol.% 残り水素の混合ガス（Ｈ₂／ＣＯ比 ２）に切り替え、FT反応を開始し20時間後に二酸化炭素を2kg/ｃｍ² (0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は47% 、連鎖成長確率は0.80、Ｃ₃中のオレフィン／パラフィン比は３だった。反応結果は、実施例5 に比べ二酸化炭素の添加効果は見られず不満足な結果であった。
【００５０】
比較例５
アルミナゾル(Al含有量７質量%)500gとシリカゾル(Si含有量３質量%)500gをホモジナイザーで３時間撹拌混合した後、フィルタープレスで水分を除去し、300℃で乾燥してシリカ−アルミナ担体を得た。得られたシリカ−アルミナ担体(Si 30質量%)の飽和吸水量は1.05ml/gであった。得られた担体40g に、比較例３と同じ塩化ルテニウム水溶液を滴下し、比較例３と同様にルテニウムを担持した。Ru換算２質量% 、残りシリカ−アルミナ、比表面積 240m²/g、触媒粒子径分布1.0-105 μｍ、平均粒子径20μm 、嵩密度1g/ml の触媒Ｐを得た。触媒Ｐ 9ｇを容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄（ノルマルヘキサデカン）30ｇを加えた後、水素分圧 20kg/cm² (1.96MPa) 、温度170℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし270℃ まで昇温した。さらに、ヘリウムを流通させながら系内を 20kg/cm² (1.96MPa) とし、次いでアルゴン10vol.% 、一酸化炭素30vol.% 残り水素の混合ガス（Ｈ₂／ＣＯ比 ２）に切り替え、FT反応を開始し20時間後に二酸化炭素を2kg/cm² (0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は46% 、連鎖成長確率は0.80、Ｃ₃中のオレフィン／パラフィン比は３だった。反応結果は、実施例５に比べ二酸化炭素の添加効果は見られず不満足な結果であった。
【００５１】
比較例６
比較例５と同様な手法でシリカ−アルミナ担体(Si 30質量%)を調製した。得られた担体40g に炭酸ナトリウム1gを蒸留水80.9mlに溶解した水溶液35.6mlを滴下して炭酸ナトリウムを含浸した。15時間静置した後、マッフル炉を用いて、600℃で３時間焼成した。得られた担体40g に、比較例３と同じ塩化ルテニウム水溶液35.6mlを滴下し、比較例３と同様にルテニウムを担持した。Ru換算２質量% 、Na換算0.45質量% 、残りシリカ−アルミナ、比表面積 240m²/g、触媒粒子径分布1.0-105 μｍ、平均粒子径20μm 、嵩密度1g/ml の触媒Ｑを得た。触媒Ｑ 9ｇを容積100ml の反応器に充填し、分散媒としてn-Ｃ₁₆Ｈ₃₄（ノルマルヘキサデカン）30gを加えた後、水素分圧 20kg/cm² (1.96MPa) 、温度170℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし270℃まで昇温した。さらに、ヘリウムを流通させながら系内を 20kg/cm² (1.96MPa)とし、次いでアルゴン10vol.% 、一酸化炭素30vol.% 残り水素の混合ガス（Ｈ₂／ＣＯ比 ２）に切り替え、FT反応を開始し20時間後に二酸化炭素を2kg/cm²(0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は48% 、連鎖成長確率は0.80、Ｃ₃中のオレフィン／パラフィン比は３だった。反応結果は、実施例５に比べ二酸化炭素の添加効果は見られず不満足な結果であった。
【００５２】
比較例７
予め、乾燥機で充分に乾燥させたシリカに、ビュレットを用いて蒸留水を滴下し、飽和吸水量1.35ml/gを求めた。硝酸コバルト（Ｃｏ（ＮＯ₃）₂・６Ｈ₂Ｏ）100g を蒸留水71.4mlに溶解し、硝酸コバルト水溶液を調製した。シリカ40g にこの水溶液54mlを滴下して、硝酸コバルトを含浸し、２時間放置し水分を除去した後、マッフル炉を用いて500℃ で３時間焼成した。次に、オキシ硝酸ジルコニウム水和物（ＺｒＯ（ＮＯ₃）₂・２Ｈ₂Ｏ）2.4gを蒸留水106ml に溶解し、硝酸ジルコニウム水溶液を調製した。コバルトを担持した前駆体に、この水溶液54mlを滴下して硝酸ジルコニウムを含浸し、２時間放置し水分を除去した後、マッフル炉を用いて500℃ で３時間焼成した。Co換算16質量% 、Zr換算 １質量% 、残りシリカ、比表面積 306m²/g、触媒粒子径分布1.0-105 μｍ、平均粒子径40μm 、嵩密度0.8g/ml の触媒Ｒを得た。触媒Ｒ 9ｇを容積100ml の反応器に充填し、水素分圧 20kg/cm² (1.96MPa) 、温度360℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし270℃ まで降温した。その後、ヘリウムを流通させながら、分散媒としてn-Ｃ₁₆Ｈ₃₄ (ノルマルヘキサデカン)30gを圧送し撹拌した。次いでアルゴン10vol.% 、一酸化炭素30vol.% 残り水素の混合ガス（Ｈ₂／ＣＯ比 ２）に切り替え、FT反応を開始し20時間後に二酸化炭素を2kg/cm² (0.196MPa)の分圧で導入し、GHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は48% 、連鎖成長確率は0.85、Ｃ₃中のオレフィン／パラフィン比は３だった。反応結果は、実施例５に比べ二酸化炭素の添加効果は見られず不満足な結果であった。
【００５３】
比較例８
比較例７に示した調製手法によってシリカ40g にCo30質量% 担持した後、塩化ルテニウム(Ru Assay 35質量%)4.6gを蒸留水103ml に溶解し、塩化ルテニウム水溶液を調製した。この水溶液54mlをCo担持前駆体に滴下して含浸し、２時間放置し水分を除去した後、空気中、110℃ で数時間乾燥した。比表面積 112m²/g、触媒粒子径分布1-105 μm 、平均粒子径75μm 、嵩密度1g/ml の触媒Ｓを得た。触媒Ｓ 9ｇを容積100ml の反応器に充填し、水素分圧 20kg/cm² (1.96MPa) 、温度360℃ 、流量100ml/min(STP)で触媒に接触させ24時間還元した後、直ちにヘリウムガスでパージし270℃ まで降温した。その後、ヘリウムを流通させながら、分散媒としてn-Ｃ₁₆Ｈ₃₄ (ノルマルヘキサデカン)30gを圧送し撹拌した。次いでアルゴン10vol.% 、一酸化炭素30vol.% 残り水素の混合ガス（Ｈ₂／ＣＯ比 ２）に切り替えGHSV6000で接触させた。反応開始48時間後のワンパスCO転化率は50% 、連鎖成長確率は0.85、Ｃ₃中のオレフィン／パラフィン比は0.5 だった。反応開始後４８時間後のワンパスＣＯ転化率は５０％、連鎖成長率は０．８５、Ｃ３中のオレフィン／パラフィン比は０．５だった。反応結果は、実施例５と比べ二酸化炭素の添加効果は見られず不満足な結果であった。
【００５４】
【表１】

【００５５】
【表２】

【００５６】
【発明の効果】
本発明の炭化水素類の製造方法によれば、二酸化炭素の共存下に、連鎖成長確率が高く、かつオレフィン選択性に優れ、触媒活性が高く、優れた一酸化炭素の転化率、改善された触媒寿命で、なおかつヒートスポットの発生など来たすことなく安定して円滑にＦＴ反応を行うことができる。本発明方法は、生成したワックス分の水素化分解、生成したオレフィンの二量化、三量化等により、灯軽油留分の増産に大きく寄与できると共に、ＦＴ反応に先立つ原料合成ガス中の二酸化炭素除去のための脱炭酸工程を簡略化もしくは省略することにより、灯軽油留分の製造コストの低減に大きく寄与できる方法である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing hydrocarbons from a mixed gas containing hydrogen and carbon monoxide as main components (hereinafter referred to as “synthesis gas”). More specifically, the synthesis gas is brought into contact with a ruthenium-based catalyst using manganese oxide dispersed in liquid hydrocarbons in the presence of carbon dioxide as a carrier, so that it can be easily applied to hydrocarbons, particularly kerosene oil fraction. The present invention relates to a process for producing hydrocarbons rich in olefins together with convertible waxes.
[0002]
[Prior art]
As a method for synthesizing hydrocarbons from synthesis gas, Fischer-Tropsch reaction (Fischer-Tropsch reaction), methanol synthesis reaction and the like are well known. The Fischer-Tropsch reaction is an iron-based catalyst such as iron, cobalt, ruthenium, etc., and the methanol synthesis reaction is a copper-based catalyst. ₂ Oxygen-containing (ethanol, acetaldehyde) synthesis is known to proceed with rhodium-based catalysts, and the catalytic ability of the catalysts used to synthesize these hydrocarbons has the ability to dissociatively adsorb carbon monoxide. (For example, “Homogeneous and heterogeneous catalysts”, published by Koshiki, Kyo Ichikawa, Maruzen, published in 1983).
[0003]
By the way, in recent years, gas oil with low sulfur content has been desired from the viewpoint of the preservation of the air environment, and this trend is expected to become stronger in the future. In addition, from the viewpoint that crude oil resources are limited, the development of alternative energy sources is desired, and it is expected that this will become more and more strongly desired in the future. As a technology to meet these demands, so-called GTL (gas to liquid) is a technology for synthesizing liquid fuel such as kerosene from natural gas (main component methane) which is said to have recoverable reserves equivalent to crude oil in terms of energy. There is. Natural gas does not contain sulfur, or hydrogen sulfide (H ₂ S) and mercaptans (CH _Three Since the obtained liquid fuel such as kerosene oil has almost no sulfur content and can be used for high-performance diesel fuel having a high cetane number, this GTL is In recent years, more and more attention has been paid.
[0004]
As part of the GTL, methods for producing hydrocarbons from synthesis gas by the Fischer-Tropsch reaction (hereinafter referred to as “FT reaction”) (hereinafter referred to as “FT method”) have been actively studied. In order to increase the yield of kerosene fraction when producing hydrocarbons by this FT method, C _Ten ~ C ₁₆ It is important to efficiently synthesize considerable hydrocarbons. In general, the carbon number distribution of hydrocarbon products in the FT reaction is supposed to follow the Shultz-Flory law, and the chain growth establishment α value greatly decreases as the reaction temperature increases under the Schultz-Flory law. In other words, when the reaction temperature rises, the carbon number of the generated hydrocarbons tends to decrease greatly. In the old days, it seems that technology development such as catalyst development was actively carried out with the issue of how to remove the Schulz-Flory law and how to selectively synthesize hydrocarbons with a specific carbon number, No technology has yet been proposed that has sufficiently solved this problem. In recent years, rather than removing the Schulz-Flory law, the yield of fractions that can be easily made into kerosene fractions by hydrocracking of waxes, etc. has been increased, and the wax content etc. The idea of increasing the yield of kerosene oil fraction as a result of hydrocracking has become common. However, the current chain growth probability is around 0.85, and how to increase this is one of the recent technical problems. Nonetheless, if the chain growth probability is increased too much, the generated hydrocarbons will be mostly waxy, which in turn causes problems in process operation, and the general performance of the catalyst also indicates chain growth. The probability is considered to be a practical upper limit of around 0.95.
[0005]
Therefore, in order to further increase the yield of kerosene fraction, in addition to improving the yield of kerosene fraction by hydrocracking, it also produces lower olefins and dimerizes them. Also, it is necessary to consider the generation of kerosene oil fraction by trimerization. It is considered that further improvement in the yield of this kerosene fraction can be achieved by carrying out an FT reaction having a high chain growth probability and excellent olefin selectivity in the produced lower hydrocarbon.
[0006]
In addition, when looking at the synthesis gas that is a raw material for the production of hydrocarbons by the FT method in the GTL process, the synthesis gas mainly consists of natural gas modified by autothermal reforming or steam reforming. In this reforming, in addition to the reforming reaction of the following formula (I), in addition to the reforming reaction of the following formula (II), it is obtained by reforming into a mixed gas mainly composed of hydrogen and carbon monoxide. Since the water gas shift reaction occurs in parallel, the resultant synthesis gas necessarily contains carbon dioxide. Furthermore, many unused natural gas fields contain carbon dioxide. If natural gas containing such carbon dioxide is used as a raw material, the carbon dioxide content of the resultant synthesis gas is further increased.
[0007]
CH _Four + H ₂ O = 3H ₂ + CO (I)
CO + H ₂ O = H ₂ + CO ₂ (II)
[0008]
In the FT reaction, liquid hydrocarbons are synthesized from synthesis gas as shown by the following formula (III). However, when carbon dioxide gas is contained in the reaction system, the tendency of the synthesis of hydrocarbons to be hindered increases. (Suzuki et al. The 63rd Annual Meeting of the Chemical Society of Japan 3C432 1992). Further, when the carbon dioxide content is increased, the hydrogen partial pressure in the reaction system is lowered in addition to the carbon dioxide reaction inhibition, which is also unfavorable for the FT reaction.
[0009]
nCO + 2nH ₂ = (CH ₂ ) _n + NH ₂ O (III)
[0010]
Therefore, conventionally, in the GTL process, it is essential to incorporate a decarbonation step of removing carbon dioxide in the synthesis gas between the step of producing synthesis gas from natural gas and the step of synthesizing liquid hydrocarbons from synthesis gas. It becomes. In this decarboxylation step, usually amine absorption or pressure swing adsorption (PSA) is used, but anyway, such decarboxylation step is preferable because it causes an increase in construction cost and operation cost. Absent. If the FT reaction can be suitably performed in the coexistence of carbon dioxide gas and the decarboxylation step can be simplified or omitted, it can greatly contribute to the reduction of the production cost of the liquid hydrocarbon in the GTL process.
[0011]
[Problems to be solved by the invention]
However, at present, a catalyst and a process capable of performing an FT reaction that has a high chain growth probability and excellent olefin selectivity and can sufficiently achieve the further improvement in the kerosene fraction yield have not been proposed. Absent. Conventionally, various catalysts for FT reaction have been proposed. As a catalyst aiming at high selectivity to olefins, a catalyst in which ruthenium is supported on a manganese oxide carrier, a third catalyst is further added to this ruthenium supported catalyst. Ruthenium-based catalysts such as catalysts with components added have been proposed (Japanese Patent Publication Nos. 3-70691 and 3-70692). However, the FT method using these ruthenium-based catalysts cannot sufficiently achieve further improvement in the kerosene oil fraction yield. That is, the ruthenium catalyst is a catalyst developed mainly for use in a fixed bed type, and the fixed bed type FT method using this ruthenium catalyst also has a chain growth probability of the ruthenium catalyst. Moreover, in the fixed bed type reaction mode, when a large amount of wax is generated, the generated wax adheres to and covers the active sites of the catalyst, and the catalyst activity is reduced. There is a problem in that a problem such as the occurrence of a heat spot that overheats the local area is likely to occur, and the reaction cannot be performed stably and smoothly.
[0012]
In addition, in the presence of carbon dioxide gas, a catalyst capable of performing an FT reaction that has a high chain growth probability as described above, has excellent olefin selectivity, and can sufficiently achieve further improvement in the kerosene fraction yield. The process has not yet been proposed.
[0013]
In view of the above situation, the object of the present invention is to have a high chain growth probability, excellent olefin selectivity, high catalytic activity, and stable and smooth reaction without causing heat spots. It is possible to provide an FT method that can perform such a desired reaction in the presence of carbon dioxide gas, and another object is to hydrocrack the produced wax, dimerize the produced olefin, trimerize, etc. As a result, the FT can contribute significantly to the increase in the production of kerosene oil fractions, and can greatly contribute to the reduction of the production cost of kerosene oil fractions by simplifying or omitting the decarbonation process for removing carbon dioxide in the synthesis gas. To provide a law.
[0014]
[Means for Solving the Problems]
Among the above-mentioned purposes, the FT method has a high probability of chain growth in the first half, excellent olefin selectivity, high catalytic activity, and stable and smooth reaction without causing heat spots. Regarding the provision, the present inventors previously used a catalyst having a certain physical property and having a certain amount of ruthenium supported on a manganese oxide support as a catalyst as a result of various studies. Then, after the reduction treatment in advance, it is dispersed in a liquid hydrocarbon at a constant concentration to form a dispersed state, and the mixed gas containing hydrogen and carbon monoxide as main components is brought into contact with the catalyst in this dispersed state, thereby obtaining the desired It is found that an FT method capable of performing a suitable reaction of (a) a catalyst mixed with a raw material mixed gas in a state where the catalyst is dispersed in liquid hydrocarbons at a constant concentration. According to the specific reaction mode, the reduction of the catalytic activity due to the adhesion of the wax to the catalytic activity point can be sufficiently prevented and the occurrence of heat spots can be suppressed even when the amount of wax in the reaction mixture becomes large. (B) In this specific reaction mode, the catalyst having specific physical properties most suitable for realizing an FT reaction having a high desired chain growth probability and excellent olefin selectivity is found. c) And the necessity of a prior reduction treatment for fully exhibiting the catalytic ability of the catalyst was found, and based on these findings, the following method for producing hydrocarbons was invented and a patent application was filed. That is, a specific surface area of 4 to 200 m, in which ruthenium is supported on a manganese oxide support in an amount of 0.1 to 50% by mass on a catalyst basis. ² / G, a catalyst having a catalyst particle size distribution of 0.5 to 150 μm is subjected to a reduction treatment in advance, and then dispersed in liquid hydrocarbons at a concentration of 1 to 50% by mass, and hydrogen and carbon monoxide are added to the catalyst. A patent application was invented for a method for producing hydrocarbons in which a mixed gas containing as a main component is brought into contact at a reaction temperature of 170 to 300 ° C. under pressure (Japanese Patent Application No. 2000-251185).
[0015]
As a result, the inventors of the present invention further studied to achieve the above object. As a result, in the above-described method for producing hydrocarbons as described above, as a catalyst, a manganese oxide support was used in addition to ruthenium. When a catalyst carrying a compound of at least one metal selected from a certain amount of alkali metal and alkaline earth metal is used, (a) the conversion of carbon monoxide is further improved and the catalyst life is also improved. (B) a desired and suitable reaction can be performed in the presence of a certain amount of carbon dioxide gas, that is, carbon dioxide, and (c) the reaction is performed in the presence of a certain amount of carbon dioxide, thereby The present inventors have found that the carbon conversion rate is further improved as compared with the case where the reaction is carried out in the absence of carbon dioxide, and the present invention has been completed based on these findings.
[0016]
That is, in order to achieve the above object, the present invention supports a manganese oxide support with 0.1 to 20% by mass of a compound of at least one metal selected from alkali metals and alkaline earth metals based on the catalyst. Furthermore, a specific surface area of 4 to 200 m carrying 0.1 to 50% by mass of ruthenium based on the catalyst. ² / G, a catalyst having a catalyst particle size distribution of 0.5 to 150 μm is subjected to a reduction treatment in advance, and then dispersed in liquid hydrocarbons at a concentration of 1 to 50% by mass, and hydrogen and carbon monoxide are added to the catalyst. Carbonization in which a mixed gas mainly containing hydrogen is contacted at a pressure of 1 to 10 MPa and a reaction temperature of 200 to 350 ° C. in the presence of 0.5 to 50% of carbon dioxide with respect to the total pressure of hydrogen and carbon monoxide. A method for producing hydrogen is provided.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The invention is described in detail below.
In the method of the present invention, at least one metal compound selected from alkali metals and alkaline earth metals (hereinafter referred to as “alkali (earth) metal compound”) and ruthenium are supported on a manganese oxide support as a catalyst. A catalyst having a variety of physical properties of the supported amount of alkali (earth) metal compound and ruthenium, specific surface area, and catalyst particle size distribution described below is used. The bulk density of the catalyst used in the present invention is suitably 0.5 to 2.5 g / cc.
[0018]
In the catalyst used in the present invention, the supported amount of alkali (earth) metal compound and ruthenium is related to the number of active sites. The supported amount of the alkali (earth) metal compound of the catalyst used in the present invention is 0.1 to 20% by mass, preferably 0.2 to 10% by mass, more preferably 0.2 to 3% by mass based on the catalyst. %. Moreover, the load of ruthenium is 0.1-50 mass% on a catalyst basis, preferably 0.1-20 mass%, more preferably 0.5-5 mass%. If the supported amounts of the alkali (earth) metal compound and ruthenium are less than the above ranges, the number of active sites may be insufficient and sufficient catalytic activity may not be obtained, and alkali (earth) metal species and support components (manganese) ) And synergistic effects are not obtained, and there is a lack of deterioration gradient and catalyst stability (lifetime). In addition, when the amount of each of the alkali (earth) metal compound and ruthenium exceeds the above range, the alkali (earth) metal compound and ruthenium are not sufficiently supported on the carrier, resulting in a decrease in dispersibility and carrier components. An alkali (earth) metal species or a ruthenium species that does not interact with each other is expressed, so that there is a tendency that a decrease in activity and a decrease in selectivity are observed, which is not preferable. The chemical composition of the catalyst was determined by inductively coupled plasma mass spectrometry (ICP method).
[0019]
The specific surface area of the catalyst used in the present invention is 4 to 200 m. ² / G, preferably 4 to 120 m ² / G, more preferably 5 to 100 m ² / G. Specific surface area is 4m ² If it is less than / g, the dispersibility of the alkali (earth) metal compound and ruthenium may decrease, which is not preferable. Regarding the upper limit of the specific surface area, in general, when handling a solid catalyst, the larger the surface area, the higher the gas-liquid solid contact frequency. However, the practical upper limit of the specific surface area of manganese oxide alone is 200 to 250 m. ² / G, it is about 200 m at maximum for the catalyst supporting an alkali (earth) metal compound and a ruthenium compound. ² / G or so. The specific surface area of the catalyst was determined by the BET method (Braunauer-Emett-Tailor method) using high purity nitrogen as a probe.
[0020]
Moreover, the distribution range of the catalyst particle diameter of the catalyst used in the present invention is 0.5 to 150 μm, preferably 0.5 to 120 μm, and more preferably 1.0 to 105 μm. In the present invention, since the catalyst is used in a dispersed state by being dispersed in liquid hydrocarbons, it is necessary to consider its particle size distribution. Particles that are too fine, such as less than 0.5 μm, pass through a filter and overflow to the downstream side, so the catalyst concentration in the reaction vessel decreases and it becomes difficult to maintain the catalyst concentration, or downstream equipment There is a high possibility of problems such as being damaged by catalyst fine particles. In some cases, the filter may be clogged, preventing continuous operation. Large particles exceeding 150 μm are difficult to uniformly disperse in liquid hydrocarbons throughout the reaction vessel, and the slurry in which the catalyst is dispersed becomes non-uniform, which increases the possibility that the reaction activity will decrease. It is not preferable.
[0021]
Even a catalyst having a particle size distribution within the above-mentioned fixed range may cause a deviation in dispersion when dispersed in liquid hydrocarbons. In such a case, it is desirable to consider the average particle size in order to uniformly disperse the catalyst particles in the liquid hydrocarbons without causing a bias. The average particle size of the catalyst used in the present invention is preferably 10 to 100 μm, more preferably 10 to 60 μm, still more preferably 10 to 50 μm. When the average particle diameter is out of the upper and lower limits in the range of 10 to 100 μm, the dispersion of the catalyst particles in the liquid hydrocarbons becomes non-uniform, and the reaction activity may be lowered.
[0022]
The catalyst used in the present invention can be prepared according to a conventionally known method for preparing a supported catalyst. First, as the manganese oxide of the carrier used for the preparation of the catalyst, various manganese oxides conventionally used as a carrier can be appropriately selected and used, by heat transfer by heating in air or by hydrothermal transfer. Or CO, H ₂ Various manganese oxide forms can be obtained by the reduction by. As an example, MnO ₂ , Mn ₂ O _Three , Mn _Three O _Four , MnO and the like are preferable. Further, a salt other than an oxide such as manganese sulfate can be used as a starting material, and a manganese oxide obtained therefrom can be used. For example, γ-type MnO obtained by anodizing thermally acidic manganese sulfate using a graphite electrode (carbon electrode) ₂ Etc. can be preferably used. Among the various manganese oxides, manganese oxides having a high charge number such as trivalent or tetravalent are preferably used. This is because it is presumed that charge transfer is caused in the manganese oxide of the carrier in order to keep the ruthenium oxidation state constant during the FT reaction. The specific surface area of manganese oxide is generally 6m ² / G or more is desirable, and the upper limit is not particularly limited, but is 200 to 250 m as described above. ² / G is a realistic upper limit. In addition, as the manganese oxide of the carrier, those having any shape such as powder, granule, tableted molded product, and extruded molded product can be used.
[0023]
When supporting the alkali (earth) metal compound and ruthenium on the manganese oxide of the carrier, first, the alkali (earth) metal compound is supported, moisture is removed, and then firing is performed. Next, ruthenium is supported, and after moisture is removed, it is sufficiently dried. In addition, the support of the alkali (earth) metal compound or ruthenium on the manganese oxide of the support is performed by, for example, immersing the support in a solution of a catalyst seed compound such as an alkali (earth) metal compound or ruthenium compound. The seed compound is adsorbed on the support, deposited by ion exchange, deposited by adding a precipitant such as alkali, the solution is evaporated to dryness, or the catalyst seed compound solution is dropped onto the support. For example, by contacting the support with a catalyst seed compound solution. At this time, the amounts of the alkali (earth) metal compound and the ruthenium compound to be contained in the support are adjusted so that the supported amount of the alkali (earth) metal compound and ruthenium in the target catalyst to be obtained is the predetermined amount. . Examples of the alkali (earth) metal compound used for the support include chlorides such as sodium, potassium, lithium, calcium, and magnesium, carbonates, nitrates, and ammonium salts. Moreover, as a ruthenium compound, the various ruthenium compounds conventionally used for preparation of a ruthenium carrying | support catalyst can be selected suitably, and can be used. Preferred examples thereof include water-soluble ruthenium salts such as ruthenium chloride, ruthenium nitrate, ruthenium acetate and hexaammonium ruthenium, and ruthenium compounds soluble in organic solvents such as ruthenium carbonyl and ruthenium acetylacetonate. The support manganese oxide containing the alkali (earth) metal compound and the ruthenium compound as described above is dried. This drying can generally be performed by holding at room temperature to 300 ° C. for 10 to 48 hours. Each dried catalyst seed compound-containing manganese oxide is appropriately pulverized and classified as necessary to obtain a predetermined catalyst particle size distribution, more preferably a powder with a predetermined average particle size. A catalyst having predetermined physical properties to be used can be obtained.
[0024]
In the method for producing hydrocarbons of the present invention, the catalyst prepared as described above is subjected to reduction treatment (activation treatment) in advance before being subjected to the FT reaction. By this reduction treatment, the catalyst is activated so as to exhibit a desired catalytic activity in the FT reaction. If this reduction treatment is not performed, the alkali (earth) metal species and ruthenium species supported on the manganese oxide are not sufficiently reduced, and the desired catalytic activity is not exhibited in the FT reaction. This reduction treatment is preferably performed by a method in which the catalyst is brought into contact with the reducing gas in a slurry state dispersed in liquid hydrocarbons, or a method in which the reducing gas is simply vented and brought into contact with the catalyst without using hydrocarbons. it can. As the liquid hydrocarbons for dispersing the catalyst in the former method, various hydrocarbons such as olefins, alkanes, alicyclic hydrocarbons, aromatic hydrocarbons can be used as long as they are liquid under the processing conditions. Can be used. Further, it may be a hydrocarbon containing a hetero element such as oxygen-containing or nitrogen-containing. The number of carbons of these hydrocarbons is not particularly limited as long as they are liquid under the processing conditions. ₆ ~ C ₄₀ Are preferred, C ₉ ~ C ₄₀ Is more preferred, C ₉ ~ C ₃₅ Is most preferred. C ₆ If the hydrocarbon is lighter than the above hydrocarbons, the vapor pressure of the solvent will be high, and the range of processing conditions will be limited. C ₄₀ If they are heavier than the above hydrocarbons, the solubility of the reducing gas is lowered, and there is a concern that sufficient reduction treatment cannot be performed. The amount of the catalyst dispersed in the hydrocarbon is suitably 1 to 50% by mass, preferably 3 to 40% by mass, more preferably 5 to 35% by mass. If the amount of catalyst is less than 1% by mass, the reduction efficiency of the catalyst decreases. As a method of preventing a reduction in the reduction efficiency of the catalyst, there is a method of reducing the reducing gas flow rate. When the reducing gas flow rate is reduced, gas (reducing gas) -liquid (solvent) -solid (catalyst) ) Is not preferable because dispersion of On the other hand, when the amount of the catalyst exceeds 50% by mass, the viscosity of the slurry in which the catalyst is dispersed in hydrocarbons becomes too high, the bubble dispersion becomes worse, and the catalyst is not sufficiently reduced, which is not preferable. The reduction treatment temperature is preferably 140 to 310 ° C, more preferably 150 to 250 ° C, and most preferably 160 to 220 ° C. Below 140 ° C., ruthenium is not sufficiently reduced and sufficient reaction activity cannot be obtained. Further, at a high temperature exceeding 310 ° C., the phase transition of the manganese oxide of the support, the change of the oxidation state, etc. proceed to form a complex with ruthenium, or the catalyst is sintered and activated. The possibility of incurring a decrease is increased. For this reduction treatment, a reducing gas mainly containing hydrogen can be preferably used. The reducing gas to be used may contain a certain amount of components other than hydrogen, for example, water vapor, nitrogen, rare gas, etc. within a range that does not hinder the reduction. This reduction treatment is influenced by the hydrogen partial pressure and the treatment time together with the treatment temperature, but the hydrogen partial pressure is 1 to 100 kg / cm. ² (0.098 to 9.8 MPa) is preferable, 5 to 60 kg / cm ² (0.49-5.88 MPa) is more preferable, 10-50 kg / cm ² (0.98 to 4.9 MPa) is most preferable. The reduction treatment time varies depending on the amount of catalyst, the amount of hydrogen flow, etc., but is generally preferably 0.1 to 72 hours, more preferably 1 to 48 hours, and most preferably 5 to 48 hours. When the treatment time is less than 0.1 hour, the activation of the catalyst becomes insufficient. Further, even if the reduction treatment is performed for a long time exceeding 72 hours, there is no adverse effect on the catalyst, but there is an undesirable problem such as an increase in the processing cost although no improvement in catalyst performance is observed.
[0025]
The catalyst reduced as described above is used for the FT reaction, that is, the synthesis reaction of hydrocarbons. The FT reaction in the present invention is a dispersed state in which the catalyst is dispersed in liquid hydrocarbons, and the synthesis gas is brought into contact with the dispersed catalyst in the presence of carbon dioxide. At this time, as the hydrocarbons in which the catalyst is dispersed, the same hydrocarbons used in the reduction treatment performed in advance can be used. That is, if it is liquid under the reaction conditions, it contains olefins, alkanes, alicyclic hydrocarbons, various hydrocarbons including aromatic hydrocarbons, and hetero elements such as oxygen and nitrogen. Hydrocarbon or the like can be used, and the number of carbons does not need to be particularly limited. ₆ ~ C ₄₀ Are preferred, C ₉ ~ C ₄₀ Is more preferred, C ₉ ~ C ₃₅ Is most preferred. C ₆ If it is lighter than these hydrocarbons, the vapor pressure of the solvent will be high, and the reaction condition range will be limited. C ₄₀ If they are heavier than the above hydrocarbons, the solubility of the synthesis gas as the raw material is lowered, and the reaction activity may be lowered. In the reduction treatment performed in advance, in the case where a method in which the catalyst is dispersed in liquid hydrocarbons is employed, the liquid hydrocarbons used in the reduction treatment can be used as they are in this FT reaction. The amount of the catalyst dispersed in the hydrocarbon is 1 to 50% by mass, preferably 3 to 40% by mass, more preferably 5 to 35% by mass. If the amount of catalyst is less than 1% by mass, the activity decreases. As a method of preventing the decrease in activity, there is a method of reducing the aeration amount of synthesis gas. However, when the aeration amount of synthesis gas is reduced, dispersion of gas (synthesis gas) -liquid (solvent) -solid (catalyst) is impaired. Therefore, it is not preferable. On the other hand, when the amount of the catalyst exceeds 50% by mass, the viscosity of the slurry in which the catalyst is dispersed in hydrocarbons becomes too high, resulting in poor bubble dispersion and insufficient reaction activity, which is not preferable.
[0026]
The synthesis gas used for the FT reaction only needs to contain hydrogen and carbon monoxide as main components, and may contain other components that do not interfere with the FT reaction. Since the rate (k) of the FT reaction depends on the hydrogen partial pressure in the first order, the partial pressure ratio of hydrogen and carbon monoxide (H ₂ / CO molar ratio) is preferably 0.6 or more. Since this reaction is a reaction accompanied by volume reduction, it is preferable that the total value of the partial pressures of hydrogen and carbon monoxide is higher. The upper limit of the partial pressure ratio of hydrogen and carbon monoxide is not particularly limited, but a practical range of this partial pressure ratio is suitably 0.6 to 2.7, preferably 0.8 to 2.5, More preferably, it is 1 to 2.3. When the partial pressure ratio is less than 0.6, the yield of the generated hydrocarbons decreases, and when the partial pressure ratio exceeds 2.7, the light hydrocarbons tend to increase in the generated hydrocarbons. Further, the components other than hydrogen and carbon monoxide contained in the synthesis gas are not particularly limited as long as they do not interfere with the reaction. ₂ O, N ₂ , CH _Four Etc.
[0027]
As carbon dioxide to be coexisted, for example, those obtained from a reforming reaction of petroleum products or natural gas can be used without any problem, and other components that do not interfere with the FT reaction may be mixed. It may be one containing steam, partially oxidized nitrogen or the like, such as a product coming out of a steam reforming reaction. The carbon dioxide can be positively added to synthesis gas containing no carbon dioxide, and can be obtained by reforming natural gas by a self-thermal reforming method or a steam reforming method. In addition, carbon dioxide in the synthesis gas containing carbon dioxide can be used, that is, the synthesis gas containing carbon dioxide can be directly subjected to the FT reaction without being decarboxylated. If the synthesis gas containing carbon dioxide is subjected to the FT reaction as it is, the equipment construction cost and operation cost required for the decarboxylation treatment can be reduced, and the production cost of hydrocarbons obtained by the FT reaction can be reduced. it can. The amount of carbon dioxide to be coexisted is 0.5 to 50%, preferably 0.5 to 30%, more preferably 1 to the total pressure of hydrogen and carbon monoxide in the synthesis gas used for the FT reaction. -10%. When the partial pressure of carbon dioxide in the synthesis gas (mixed gas) to be subjected to the FT reaction is a low one that is less than the above range, the effect of promoting the FT reaction by carbon dioxide cannot be obtained, and the high pressure exceeds the above range. In this case, the partial pressures of hydrogen and carbon monoxide in the synthesis gas (mixed gas) subjected to the FT reaction are lowered, and the yield of hydrocarbons is lowered, which is economically disadvantageous. Although the carbon dioxide may coexist in the reaction system from the beginning of the FT reaction, in order to improve the carbon monoxide conversion rate more effectively by demonstrating the FT reaction promoting effect of carbon dioxide. Is preferably introduced into the reaction system within 10 to 100 hours after the start of the FT reaction.
[0028]
Thus, the total pressure of the synthesis gas (mixed gas) to be subjected to the FT reaction (total value of partial pressures of all components) is preferably 1 to 10 MPa, more preferably 1.5 to 6 MPa, and 1.8 to 4.5 MPa. Is even more preferred. If it is less than 1 MPa, chain growth is insufficient, and the yield of gasoline, kerosene, wax, etc. tends to decrease, which is not preferable. In terms of equilibrium, the higher the partial pressure of hydrogen and carbon monoxide, the more advantageous. However, the higher the partial pressure, the higher the construction cost of the plant and the higher the operating cost due to the increase in size of the compressor required for compression. From the industrial point of view, the upper limit of the partial pressure is regulated.
[0029]
In this FT reaction, in general, synthesis gas H ₂ If the / CO molar ratio is the same, the lower the reaction temperature, the more chain growth proceeds and the higher the olefin selectivity, but the lower the CO conversion. On the contrary, if the reaction temperature is high, chain growth and olefin selectivity are low, but CO conversion is high. H ₂ The higher the / CO ratio, the higher the CO conversion, the lower the chain growth and olefin selectivity, ₂ The opposite is true when the / CO ratio is low. The effect of these factors on the reaction varies depending on the type of catalyst used, but in the present invention, the reaction temperature is preferably 200 ° C to 350 ° C, more preferably 220 to 310 ° C, and more preferably 250 to 290 ° C. Is even more preferred.
[0030]
According to the method for producing hydrocarbons of the present invention described above, if hydrocarbons are synthesized in the coexistence of carbon dioxide from a mixed gas containing hydrogen and carbon monoxide as main components, the CO conversion can be reduced to once through. conversion) is 60% or more, the chain growth probability (α) is 0.88 to 0.92, and the olefin / paraffin ratio in the lower hydrocarbon is, for example, C _Three For hydrocarbons, good results of 3-7 are obtained. Further, by providing the synthesis gas containing carbon dioxide as it is to the FT reaction, it is possible to reduce the equipment construction cost and operation cost required for the decarboxylation treatment, and from the poor natural gas containing a large amount of carbon dioxide. An induced synthesis gas containing a large amount of carbon dioxide can also be used as a raw material.
The CO conversion rate and chain growth probability (α) are defined by the following formulas. [CO conversion rate]
[0031]
[Expression 1]

[0032]
[Probability of chain growth (α)]
When the mass fraction in the product of hydrocarbons having n carbon atoms is Mn and the chain growth probability is α, the following relationship is established according to the Schulz-Flory distribution. Therefore, the α value can be obtained from the slope log α when log (Mn / n) and n are plotted.
[0033]
[Expression 2]

[0034]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
In the following examples, CO and CH _Four The analysis was performed by thermal conductivity gas chromatography (TCD-GC) using Active Carbon (60 / 80mesh) as a separation column. In addition, 10 vol. % Added synthesis gas was used. CO and CH _Four Qualitative and quantitative analysis was performed by comparing the peak position and the peak area of Ar with those of Ar. C ₁ ~ C ₆ For analysis of hydrocarbons, Capillary Column (Al ₂ O _Three / KCl PLOT) as a separation column and flame ionization detection type gas chromatograph (FID-GC), C that can be analyzed in common with TCD-GC ₁ The hydrocarbons were qualitatively and quantitatively compared with (methane). In addition, C _Five ~ C ₄₀ For analysis of hydrocarbons, FID-GC equipped with a Capillary Column (TC-1) was used, and light hydrocarbons (C ₁ ~ C ₆ C that can be analyzed in common with _Five And C ₆ Qualitative and quantitative determination of the hydrocarbons was performed. The specific surface area of the catalyst (including support) was measured by the BET method using nitrogen as a probe molecule using an automatic surface area measuring apparatus (Bell Soap 28, manufactured by Nippon Bell). The chemical component of the catalyst was identified by ICP (CQM-10000P, manufactured by Shimadzu Corporation), and the particle size distribution was determined by a particle size measuring device (Mastersizer MSX-46 type, manufactured by Malvern) using a laser light scattering method.
[0035]
Example 1
Pure water was added dropwise from 30 to 30 g of the previously dried manganese oxide powder, and the saturated water absorption was determined. The saturated water absorption at this time was 0.26 ml / g. Ion exchange water (hereinafter abbreviated as water) was added to 0.31 g of sodium carbonate (Na Assay 43% by mass) to make 8 ml, and dissolved by stirring. The total amount of this solution was impregnated with 30 g of manganese oxide powder, allowed to stand for about 3 hours, and then dried in air at a temperature of 110 ° C. for several hours. Water was added to 0.09 g of ruthenium chloride (Ru Assay 35% by mass) to make 8 ml, and dissolved by stirring. The total amount of this solution was impregnated with Na-impregnated manganese oxide powder, allowed to stand for about 3 hours, and then dried in air at a temperature of 110 ° C. for several hours. This was transferred to an agate mortar, pulverized, and sieved to a catalyst particle size distribution of 0.5 to 150 μm to obtain catalyst A. The particle size distribution was determined by a laser light scattering method. This catalyst had an average particle size of 20 μm and a bulk density of 2.3. As a result of composition analysis using ICP, it was 0.1% by mass in terms of Ru, 0.45% by mass in terms of Na, and the remaining manganese oxide. The specific surface area is 4m ² / g. A reactor with a capacity of 100 ml was charged with 12 g of catalyst A, and n-C was used as a dispersion medium. ₁₆ H ₃₄ After adding 40 g of (normal hexadecane), hydrogen partial pressure 20 kg / cm ² (1.96 MPa), contacted at a temperature of 170 ° C. and a flow rate of 100 ml / min (STP: standard temperature and pressure), reduced for 24 hours, immediately purged with helium gas, and heated to 200 ° C. Furthermore, 20 kg / cm in the system while circulating helium ² (1.96MPa), then mixed gas of argon 10vol.%, Carbon monoxide 30vol.%, Remaining hydrogen (H ₂ / C0 ratio 2) Switch to FT reaction, start carbon dioxide after 20 hours, 0.2kg / cm ² It was introduced at a partial pressure of (0.0196 MPa) and contacted with GHSV (gas hourly space velocity) 2400. 48-hour one-pass CO conversion is 69%, chain growth probability is 0.90, C3
The olefin / paraffin ratio in it was 7.
[0036]
Example 2
According to the preparation method shown in Example 1, Ru equivalent 1% by mass, Na equivalent 0.45% by mass, remaining manganese oxide, specific surface area 8m ² catalyst B having a catalyst particle size distribution of 0.5 to 120 μm, an average particle size of 20 μm and a bulk density of 2.1 was obtained. A reactor having a capacity of 100 ml was charged with 12 g of catalyst B, and the same reduction treatment and FT reaction as in Example 1 were carried out. Carbon dioxide is 2kg / cm 20 hours after the start of FT reaction ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 80%, the chain growth probability is 0.90, C _Three The olefin / paraffin ratio in it was 6.
[0037]
Example 3
According to the preparation method shown in Example 1, 1 mass% in terms of Ru and 0.45 mass% in terms of K (K ₂ CO _Three ), The remaining manganese oxide, specific surface area 8m ² catalyst C having a catalyst particle size distribution of 0.5 to 150 μm, an average particle size of 20 μm, and a bulk density of 2.1 was obtained. A reactor with a capacity of 100 ml is charged with 12 g of catalyst C, and n-C is used as a dispersion medium. ₁₆ H ₃₄ After adding 40g (normal hexadecane), hydrogen partial pressure 20kg / cm ² (1.96 MPa) The temperature was 170 ° C., contacted with the catalyst at a flow rate of 100 ml / min (STP), reduced for 24 hours, then immediately purged with helium gas and heated to 270 ° C. Next, a mixed gas of argon 10vol.%, Carbon monoxide 30vol.% And the remaining hydrogen (H ₂ / C0 ratio 2.0) FT reaction started and carbon dioxide was 2kg / cm after 20 hours ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 83.5%, the chain growth probability is 0.89, C _Three The olefin / paraffin ratio in it was 7.
[0038]
Example 4
According to the preparation method shown in Example 3, 2 mass% in terms of Ru, 0.1 mass% in terms of Na, remaining manganese oxide, specific surface area 8 m ² catalyst D having a catalyst particle size distribution of 0.5 to 150 μm, an average particle size of 20 μm and a bulk density of 2.1 was obtained. The catalyst D12g was charged into a reactor having a volume of 100 ml, and the same reduction treatment and FT reaction as in Example 3 were performed. Carbon dioxide is 2kg / cm 20 hours after the start of FT reaction ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 83%, the chain growth probability is 0.89, C _Three The olefin / paraffin ratio in it was 6.
[0039]
Example 5
According to the preparation method shown in Example 3, 2 mass% in terms of Ru, 0.45 mass% in terms of Na, remaining manganese oxide, specific surface area 8 m ² catalyst E having a catalyst particle size distribution of 1.0 to 150 μm, an average particle size of 20 μm and a bulk density of 2.1 was obtained. A reactor having a capacity of 100 ml was charged with 12 g of the catalyst E, and the same reduction treatment and FT reaction as in Example 3 were performed. Carbon dioxide is 2kg / cm 20 hours after the start of FT reaction ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 85.5%, the chain growth probability is 0.88, C _Three The olefin / paraffin ratio in it was 6.
[0040]
Example 6
According to the preparation method shown in Example 3, 2 mass% in terms of Ru and 0.45 mass% in terms of Ca (Ca (NO _Three ) ₂ ・ 4H ₂ Same as Na loading method using O), remaining manganese oxide, specific surface area 8m ² / g, catalyst F having a catalyst particle size distribution of 1.0-150 μm, an average particle size of 20 μm and a bulk density of 2.1 was obtained. A reactor having a capacity of 100 ml was charged with 12 g of catalyst F, and the same reduction treatment and FT reaction as in Example 3 were carried out. Carbon dioxide is 2kg / cm 20 hours after the start of FT reaction ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 84.5%, the chain growth probability is 0.88, C _Three The olefin / paraffin ratio in it was 6.
[0041]
Example 7
According to the preparation method shown in Example 1, 2 mass% in terms of Ru, 0.45 mass% in terms of K, remaining manganese oxide, specific surface area 8 m ² catalyst G having a catalyst particle size distribution of 1.0 to 150 μm, an average particle size of 20 μm and a bulk density of 2.1 was obtained. A reactor with a capacity of 100 ml is charged with 12 g of catalyst G, and n-C is used as a dispersion medium. ₁₆ H ₃₄ After adding 40g (normal hexadecane), hydrogen partial pressure 20kg / cm ² (1.96 MPa) The temperature was 170 ° C., contacted with the catalyst at a flow rate of 100 ml / min (STP), reduced for 24 hours, then immediately purged with helium gas and heated to 290 ° C. Next, a mixed gas of argon 10vol.%, Carbon monoxide 30vol.% And the remaining hydrogen (H ₂ / CO ratio 2.0) FT reaction started and carbon dioxide was 2kg / cm after 20 hours ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 86.5%, the chain growth probability is 0.88, C _Three The olefin / paraffin ratio in it was 6.
[0042]
Example 8
According to the preparation method shown in Example 1, 5 mass% in terms of Ru, 0.45 mass% in terms of Na, remaining manganese oxide, specific surface area 8 m ² / g, catalyst H having a catalyst particle size distribution of 0.5 to 150 μm, an average particle size of 20 μm and a bulk density of 2.1 was obtained. A reactor with a capacity of 100 ml is charged with 6 g of catalyst H, and n-C is used as a dispersion medium. ₁₆ H ₃₄ After adding 24 g (normal hexadecane), hydrogen partial pressure 50 kg / cm ² (4.9 MPa), temperature 170 ° C., flow rate 100 ml / min (STP), contacted with the catalyst and reduced for 24 hours, immediately purged with helium gas and heated to 300 ° C. Furthermore, 15 kg / cm in the system while circulating helium ² (1.47MPa), then argon 10vol.%, Carbon monoxide 36vol.%, Remaining hydrogen mixed gas (H ₂ / CO ratio 1.5) Switch to FT reaction and start carbon dioxide 3kg / cm 20 hours later ² It was introduced at a partial pressure of (0.294 MPa) and contacted with GHSV12000. 48 hours after the start of the reaction, the one-pass CO conversion is 80.2%, the chain growth probability is 0.88, C _Three The olefin / paraffin ratio in it was 7.
[0043]
Example 9
According to the preparation method shown in Example 1, 20 mass% in terms of Ru, 10 mass% in terms of Na, remaining manganese oxide, specific surface area 100 m ² catalyst I having a catalyst particle size distribution of 0.5-150 μm, an average particle size of 40 μm and a bulk density of 1.0 was obtained. A reactor with a capacity of 100 ml is charged with 2 g of catalyst I, and the hydrogen partial pressure is 50 kg / cm. ² (4.9 MPa), temperature 140 ° C., flow rate 100 ml / min (STP), contacted the catalyst and reduced for 12 hours, then immediately purged with helium gas and heated to 300 ° C. After that, helium is vented and n-C is used as a dispersion ₁₆ H ₃₄ 40 g (normal hexadecane) was pumped and stirred. Furthermore, 15 kg / cm in the system while circulating helium ² (1.47MPa), then argon 10vol.%, Carbon monoxide 39.1.vol%, remaining hydrogen mixed gas (H ₂ / CO ratio 1.3) FT reaction started and carbon dioxide was 5kg / cm 20 hours later ² It was introduced at a partial pressure of (0.49 MPa) and contacted with GHSV12000. 48 hours after the start of the reaction, the one-pass CO conversion is 79.5%, the chain growth probability is 0.89, C _Three The olefin / paraffin ratio in it was 7.
[0044]
Example 10
According to the preparation method shown in Example 1, Ru equivalent 30% by mass, K equivalent 15% by mass, remaining manganese oxide, specific surface area 120m ² catalyst J having a catalyst particle size distribution of 0.5-150 μm, an average particle size of 50 μm, and a bulk density of 0.7 was obtained. 2 g of catalyst J is charged into a 100 ml reactor and the hydrogen partial pressure is 60 kg / cm. ² (5.88 MPa), contacted with the catalyst at a temperature of 200 ° C. and a flow rate of 100 ml / min (STP), reduced for 12 hours, immediately purged with helium gas, and heated to 300 ° C. After that, n-C as a dispersion medium under helium circulation ₁₆ H ₃₄ 67 g (normal hexadecane) was pumped and stirred. 10kg / cm in the system with helium ² (0.98MPa), then argon 10vol.%, Carbon monoxide 45vol.%, Remaining hydrogen mixed gas (H ₂ / CO ratio 1.0) FT reaction started and carbon dioxide was 2kg / cm 20 hours later ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV16000. 48 hours after the start of the reaction, the one-pass CO conversion is 74.5%, the chain growth probability is 0.88, C _Three The olefin / paraffin ratio in it was 5.
[0045]
Example 11
According to the preparation method shown in Example 1, 50 mass% in terms of Ru, 20 mass% in terms of Ca, remaining manganese oxide, specific surface area 200 m ² catalyst K having a catalyst particle size distribution of 0.5 to 150 μm, an average particle size of 60 μm and a bulk density of 0.7 was obtained. A reactor with a capacity of 100 ml is charged with 0.5 g of catalyst K, and n-C is used as a dispersion medium. ₁₆ H ₃₄ After adding 50 g of (normal hexadecane), hydrogen partial pressure 100 kg / cm ² The catalyst was brought into contact with the catalyst at a temperature of (9.8 MPa), a temperature of 200 ° C., and a flow rate of 100 ml / min (STP) for 24 hours, then immediately purged with helium gas and heated to 300 ° C. Furthermore, 10 kg / cm in the system while circulating helium ² (0.98MPa), then argon 10vol.%, Carbon monoxide 50vol.%, Remaining hydrogen mixed gas (H ₂ / CO ratio 0.8) FT reaction started and carbon dioxide was 6kg / cm 20 hours later ² It was introduced at a partial pressure of (0.588 MPa) and contacted with GHSV24000. 48 hours after the start of the reaction, the one-pass CO conversion is 90.1%, the chain growth probability is 0.86, C _Three The olefin / paraffin ratio in it was 3.
[0046]
Comparative Example 1
According to the preparation method shown in Example 1, 2 mass% in terms of Ru, 0.45 mass% in terms of Na, remaining manganese oxide, specific surface area 8 m ² catalyst L having a catalyst particle size distribution of 1.0-105 μm, an average particle size of 20 μm and a bulk density of 2.1 was obtained. A reactor with a capacity of 100 ml is charged with 12 g of catalyst, and n-C is used as a dispersion medium. ₁₆ H ₃₄ After adding 40g of (normal hexadecane), hydrogen partial pressure 20kg / cm ² (1.96 MPa) The temperature was 170 ° C., contacted with the catalyst at a flow rate of 100 ml / min (STP), reduced for 24 hours, then immediately purged with helium gas and heated to 270 ° C. Next, a mixed gas of argon 10vol.%, Carbon monoxide 30vol.% And the remaining hydrogen (H ₂ Switched to / CO ratio 2) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 75.0%, the chain growth probability is 0.9, C _Three The olefin / paraffin ratio in it was 6. Thus, if no carbon dioxide is present during the FT reaction, the CO conversion rate (compared with Example 5) is lowered, and the possibility of poor productivity is increased.
[0047]
Comparative Example 2
According to the preparation method shown in Example 1, 2% by mass in terms of Ru, remaining manganese oxide, specific surface area 10 m ² catalyst M having a catalyst particle size distribution of 1.0-150 μm, an average particle size of 20 μm, and a bulk density of 2.1 g / ml was obtained. The catalyst M12g is charged into a reactor with a capacity of 100 ml, and n-C is used as a dispersion medium. ₁₆ H ₃₄ After adding 40g of (normal hexadecane), hydrogen partial pressure 20kg / cm ² (1.96 MPa) The temperature was 170 ° C., contacted with the catalyst at a flow rate of 100 ml / min (STP), reduced for 24 hours, then immediately purged with helium gas and heated to 270 ° C. Next, mixed gas of argon 10vol.%, Carbon monoxide 30vol.% Remaining hydrogen (H ₂ / C0 ratio 2) Switch to 2), start FT reaction, and after 20 hours carbon dioxide is 2kg / cm ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 40%, the chain growth probability is 0.9, C _Three The olefin / paraffin ratio in it was 5. Thus, when carbon dioxide coexists during the FT reaction with a catalyst to which no alkali (earth) metal compound is added, the CO conversion rate (compared with Example 5) is drastically decreased and the productivity may be extremely inferior. Becomes higher.
[0048]
Comparative Example 3
Distilled water was added dropwise to alumina that had been sufficiently dried with a dryer in advance using a burette to obtain a saturated water absorption of 0.89 ml / g. Ruthenium chloride (RuCl _Three ・ NH ₂ O) 5 g was dissolved in 78.5 ml of distilled water to prepare an aqueous ruthenium chloride solution. 35.7 ml of this aqueous solution was dropped into 40 g of alumina, impregnated with ruthenium chloride, and left for 2 hours to remove moisture. Ru equivalent 2% by mass, remaining alumina, specific surface area 250m ² catalyst N having a catalyst particle size distribution of 1.0-150 μm, an average particle size of 20 μm and a bulk density of 1 g / ml was obtained. A reactor with a capacity of 100 ml is charged with 9 g of catalyst N, and n-C is used as a dispersion medium. ₁₆ H ₃₄ After adding 30g (normal hexadecane), hydrogen partial pressure 20kg / cm ² (1.96 MPa) The temperature was 170 ° C., contacted with the catalyst at a flow rate of 100 ml / min (STP), reduced for 24 hours, then immediately purged with helium gas and heated to 270 ° C. Furthermore, 20 kg / cm in the system while circulating helium ² (1.96MPa), then argon 10vol.%, Carbon monoxide 30vol.% Residual hydrogen mixed gas (H ₂ / CO ratio 2), FT reaction is started, and carbon dioxide is 2kg / cm 20 hours later ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. One-pass CO conversion 48 hours after the start of the reaction is 45%, chain growth probability is 0.80, C _Three The olefin / paraffin ratio in it was 3. The reaction results were unsatisfactory as compared with Example 5 because the effect of adding carbon dioxide was not observed.
[0049]
Comparative Example 4
To 40 g of the same alumina as in Comparative Example 3, 35.6 ml of an aqueous solution prepared by dissolving 1 g of sodium carbonate in 80.9 ml of distilled water was added dropwise to impregnate with sodium carbonate. After standing for 15 hours, it was calcined at 600 ° C. for 3 hours using a muffle furnace. To the obtained carrier, 35.6 ml of the same ruthenium chloride aqueous solution as in Comparative Example 3 was added dropwise to 40 g, and ruthenium was supported as in Comparative Example 3. Ru conversion 2% by mass, Na conversion 0.45% by mass, remaining alumina, specific surface area 250m ² Catalyst O having a catalyst particle size distribution of 1.0-105 μm, an average particle size of 20 μm, and a bulk density of 1 g / ml was obtained. 9 g of catalyst O is packed in a 100 ml reactor and n-C is used as a dispersion medium. ₁₆ H ₃₄ After adding 30g (normal hexadecane), hydrogen partial pressure 20kg / cm ² (1.96 MPa) The temperature was 170 ° C., contacted with the catalyst at a flow rate of 100 ml / min (STP), reduced for 24 hours, then immediately purged with helium gas and heated to 270 ° C. Furthermore, 20 kg / cm in the system while circulating helium ² (1.96MPa), then argon 10vol.%, Carbon monoxide 30vol.% Residual hydrogen mixed gas (H ₂ / CO ratio 2), FT reaction is started, and carbon dioxide is 2kg / cm after 20 hours ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 47%, the chain growth probability is 0.80, C _Three The olefin / paraffin ratio in it was 3. The reaction result was unsatisfactory as compared with Example 5 because the effect of adding carbon dioxide was not observed.
[0050]
Comparative Example 5
500g of alumina sol (Al content 7% by mass) and 500g of silica sol (Si content 3% by mass) were stirred and mixed with a homogenizer for 3 hours, then water was removed with a filter press and dried at 300 ° C to obtain a silica-alumina carrier. Obtained. The saturated water absorption of the obtained silica-alumina carrier (Si 30% by mass) was 1.05 ml / g. The same ruthenium chloride aqueous solution as in Comparative Example 3 was added dropwise to 40 g of the obtained carrier, and ruthenium was supported in the same manner as in Comparative Example 3. 2% by mass in terms of Ru, remaining silica-alumina, specific surface area 240m ² catalyst P having a catalyst particle size distribution of 1.0-105 μm, an average particle size of 20 μm, and a bulk density of 1 g / ml was obtained. A reactor with a capacity of 100 ml was charged with 9 g of catalyst P, and n-C was used as a dispersion medium. ₁₆ H ₃₄ After adding 30g (normal hexadecane), hydrogen partial pressure 20kg / cm ² (1.96 MPa) The temperature was 170 ° C., contacted with the catalyst at a flow rate of 100 ml / min (STP), reduced for 24 hours, then immediately purged with helium gas and heated to 270 ° C. Furthermore, 20 kg / cm in the system while circulating helium ² (1.96MPa), then argon 10vol.%, Carbon monoxide 30vol.% Residual hydrogen mixed gas (H ₂ / CO ratio 2), FT reaction is started, and carbon dioxide is 2kg / cm 20 hours later ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 46%, the chain growth probability is 0.80, C _Three The olefin / paraffin ratio in it was 3. The reaction results were unsatisfactory as compared with Example 5 because the effect of adding carbon dioxide was not observed.
[0051]
Comparative Example 6
A silica-alumina carrier (Si 30% by mass) was prepared in the same manner as in Comparative Example 5. To 40 g of the obtained carrier, 35.6 ml of an aqueous solution prepared by dissolving 1 g of sodium carbonate in 80.9 ml of distilled water was added dropwise to impregnate with sodium carbonate. After leaving still for 15 hours, it baked at 600 degreeC for 3 hours using the muffle furnace. The same ruthenium chloride aqueous solution 35.6 ml as in Comparative Example 3 was added dropwise to 40 g of the obtained carrier, and ruthenium was supported in the same manner as in Comparative Example 3. 2% by mass in terms of Ru, 0.45% by mass in terms of Na, remaining silica-alumina, specific surface area 240m ² catalyst Q having a catalyst particle size distribution of 1.0-105 μm, an average particle size of 20 μm, and a bulk density of 1 g / ml was obtained. 9g of catalyst Q is packed into a 100ml reactor and n-C is used as a dispersion medium. ₁₆ H ₃₄ After adding 30g (normal hexadecane), hydrogen partial pressure 20kg / cm ² (1.96 MPa) At a temperature of 170 ° C., contacted with the catalyst at a flow rate of 100 ml / min (STP) and reduced for 24 hours, immediately purged with helium gas and heated up to 270 ° C. Furthermore, 20 kg / cm in the system while circulating helium ² (1.96MPa), then argon 10vol.%, Carbon monoxide 30vol.% Residual hydrogen mixed gas (H ₂ / CO ratio 2), FT reaction is started, and carbon dioxide is 2kg / cm 20 hours later ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 48%, the chain growth probability is 0.80, C _Three The olefin / paraffin ratio in it was 3. The reaction results were unsatisfactory as compared with Example 5 because the effect of adding carbon dioxide was not observed.
[0052]
Comparative Example 7
Distilled water was dropped onto silica that had been sufficiently dried in advance using a burette to obtain a saturated water absorption of 1.35 ml / g. Cobalt nitrate (Co (NO _Three ) ₂ ・ 6H ₂ O) 100 g was dissolved in 71.4 ml of distilled water to prepare an aqueous cobalt nitrate solution. 54 ml of this aqueous solution was dropped into 40 g of silica, impregnated with cobalt nitrate, allowed to stand for 2 hours to remove moisture, and then calcined at 500 ° C. for 3 hours using a muffle furnace. Next, zirconium oxynitrate hydrate (ZrO (NO _Three ) ₂ ・ 2H ₂ O) 2.4 g was dissolved in 106 ml of distilled water to prepare an aqueous zirconium nitrate solution. 54 ml of this aqueous solution was dropped into a precursor supporting cobalt and impregnated with zirconium nitrate, left standing for 2 hours to remove moisture, and then calcined at 500 ° C. for 3 hours using a muffle furnace. Co conversion 16% by mass, Zr conversion 1% by mass, remaining silica, specific surface area 306m ² catalyst R having a catalyst particle size distribution of 1.0-105 μm, an average particle size of 40 μm, and a bulk density of 0.8 g / ml was obtained. 9 g of catalyst R is charged into a 100 ml reactor and the hydrogen partial pressure is 20 kg / cm. ² The catalyst was brought into contact with the catalyst at a temperature of 360 ° C. and a flow rate of 100 ml / min (STP) for 24 hours, immediately purged with helium gas, and the temperature was lowered to 270 ° C. Then, while circulating helium, n-C as a dispersion medium ₁₆ H ₃₄ 30 g (normal hexadecane) was pumped and stirred. Next, mixed gas of argon 10vol.%, Carbon monoxide 30vol.% Remaining hydrogen (H ₂ / CO ratio 2), FT reaction is started, and carbon dioxide is 2kg / cm 20 hours later ² It was introduced at a partial pressure of (0.196 MPa) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 48%, the chain growth probability is 0.85, C _Three The olefin / paraffin ratio in it was 3. The reaction results were unsatisfactory as compared with Example 5 because the effect of adding carbon dioxide was not observed.
[0053]
Comparative Example 8
After 30 mass% of Co was supported on 40 g of silica by the preparation method shown in Comparative Example 7, 4.6 g of ruthenium chloride (Ru Assay 35 mass%) was dissolved in 103 ml of distilled water to prepare an aqueous ruthenium chloride solution. 54 ml of this aqueous solution was dropped onto a Co-supporting precursor, impregnated, left for 2 hours to remove moisture, and then dried in air at 110 ° C. for several hours. Specific surface area 112m ² Catalyst S having a catalyst particle size distribution of 1 to 105 μm, an average particle size of 75 μm, and a bulk density of 1 g / ml was obtained. 9g of catalyst S is packed in a 100ml reactor and hydrogen partial pressure is 20kg / cm. ² The catalyst was brought into contact with the catalyst at a temperature of 360 ° C. and a flow rate of 100 ml / min (STP) for 24 hours, immediately purged with helium gas, and the temperature was lowered to 270 ° C. Then, while circulating helium, n-C as a dispersion medium ₁₆ H ₃₄ 30 g (normal hexadecane) was pumped and stirred. Next, mixed gas of argon 10vol.%, Carbon monoxide 30vol.% Remaining hydrogen (H ₂ Switched to / CO ratio 2) and contacted with GHSV6000. 48 hours after the start of the reaction, the one-pass CO conversion is 50%, the chain growth probability is 0.85, C _Three The olefin / paraffin ratio in the medium was 0.5. 48 hours after the start of the reaction, the one-pass CO conversion was 50%, the chain growth rate was 0.85, and the olefin / paraffin ratio in C3 was 0.5. The reaction result was unsatisfactory as compared with Example 5 with no added effect of carbon dioxide.
[0054]
[Table 1]

[0055]
[Table 2]

[0056]
【The invention's effect】
According to the method for producing hydrocarbons of the present invention, in the presence of carbon dioxide, the chain growth probability is high, the olefin selectivity is excellent, the catalytic activity is high, the conversion rate of carbon monoxide is improved, and the improvement is achieved. The FT reaction can be carried out stably and smoothly with the catalyst life and without the occurrence of heat spots. The method of the present invention can greatly contribute to an increase in the production of kerosene oil fractions by hydrocracking the produced wax, dimerizing and trimerizing the produced olefin, and removing carbon dioxide in the raw syngas prior to the FT reaction. This is a method that can greatly contribute to the reduction of the production cost of the kerosene oil fraction by simplifying or omitting the decarbonation step for.

Claims (1)

A manganese oxide support is loaded with 0.1 to 20% by mass of a compound of at least one metal selected from alkali metals and alkaline earth metals on a catalyst basis, and further ruthenium is 0.1 to 50 on a catalyst basis. A catalyst having a specific surface area of 4 to 200 m ² / g and a catalyst particle size distribution of 0.5 to 150 μm supported by mass% is subjected to reduction treatment in advance, and then in a liquid hydrocarbon at a concentration of 1 to 50 mass%. The mixed gas mainly containing hydrogen and carbon monoxide is dispersed in the catalyst in the presence of 0.5 to 50% carbon dioxide with respect to the total pressure of the hydrogen and carbon monoxide, and the pressure is 1 to 10 MPa. The manufacturing method of hydrocarbons made to contact at reaction temperature 200-350 degreeC.