JP5789596B2 - 高品質液体燃料を製造するためのバイオマスの水素化熱分解 - Google Patents
高品質液体燃料を製造するためのバイオマスの水素化熱分解 Download PDFInfo
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Description
ガラスセラミック触媒は、非常に強力且つ耐摩耗性であり、熱含浸された(すなわち担持された)触媒としてまたはバルク触媒として調製することができる。硫化されたNiMo、Ni/NiO、またはCoベースのガラスセラミック触媒として使用する場合、得られる触媒は、容易に入手可能であるが柔らかい従来のNiMo、Ni/NiO、またはCoベースの触媒の耐摩耗型である。硫化されたNiMo、Ni/NiO、またはCoベースのガラスセラミック触媒は、従来の担持触媒の触媒作用を提供することができ、はるかに強固で耐摩耗性の形態であるため、高温流動床中での使用に特に適している。更に、触媒の耐摩耗性により、反応容器内で水素化熱分解反応が進行するにつれてバイオマスとチャーは同時により小さい粒子へと粉砕される。したがって、触媒の強度および耐摩耗性が非常に高いため、最終的に回収されるチャーに触媒からの触媒混入物が実質的に含まれない。触媒の摩耗速度は、典型的には、標準的な高速ジェットカップ摩耗試験(high velocity jet cup attrition test)指数試験による測定で、約2重量%/時間未満、好ましくは1重量%/時間未満である。
リン化Ni触媒は、作用するために硫黄を必要としないため、硫黄を含まない環境中でも、H2S、COS、およびその他の硫黄含有化合物を含む環境中と同じように活性である。したがって、この触媒は、硫黄がほとんどまたは全く存在しないバイオマスに対しても、硫黄を含むバイオマス(例えばトウモロコシ茎葉)の場合と同じように活性である。この触媒は、別個の触媒として炭素に含浸されてもよく、バイオマス供給原料自体に直接含浸されてもよい。
ボーキサイトは非常に安価な材料であるため、使い捨て触媒として使用することができる。ボーキサイトはNi、Mo等のその他の材料と含浸されてもよく、硫化されてもよい。
市販のNiMoまたはCoMo触媒は通常、固定床または沸騰床中で使用するための1/8〜1/16の大サイズのタブレットとして提供されている。本発明の場合には、NiMoが噴霧乾燥シリカアルミナ触媒に含浸され、流動床中で使用される。この触媒は、従来のNiMo触媒よりもNiMoの充填量が少なく低い活性を示すが、流動床中での使用に適したサイズである。
Claims (20)
- バイオマスから液体生成物を製造するプロセスであって、
a)前記バイオマスを、分子状水素および脱酸素触媒を含む水素化熱分解反応容器中で水素化熱分解し、CO2、CO、およびC1〜C 4 ガス、部分的に脱酸素された水素化熱分解生成物、チャー、および第1ステージ熱を含んでなる水素化熱分解反応産物を生成する工程、
b)前記水素化熱分解反応産物から前記チャーを除去する工程、
c)前記工程a)で生成したCO2、CO、およびC1〜C 4 ガスの存在下で、水素化転化触媒を用いて水素化転化反応容器中で前記部分的に脱酸素された水素化熱分解生成物を水素化転化し、完全に脱酸素された水素化熱分解生成物と、CO、CO2、および軽質炭化水素ガス(C1〜C 4 )を含んでなるガス状混合物と、第2ステージ熱とを生成する工程、
d)前記ガス状混合物の少なくとも一部を水蒸気改質し、改質された分子状水素を生成する工程、および
e)前記改質された分子状水素を、前記バイオマスを水素化熱分解する前記反応容器中に導入する工程、
を含んでなり、
前記工程a)およびc)が、前記バイオマス中の酸素の40〜60%がH2Oに転化され且つ前記酸素の40〜60%がCOおよびCO2に転化される条件下で行われる、プロセス。 - 前記水素化転化触媒が、水性ガスシフト反応および水素化転化の両方を触媒する、請求項1に記載のプロセス。
- 前記工程a)、c)、およびd)が、実質的に同じ圧力で行われる、請求項1に記載のプロセス。
- 前記圧力が、2.07MPa〜5.52MPa(約300〜約800psig)である、請求項3に記載のプロセス。
- 前記水素化熱分解が、427℃〜510℃(約800〜約950°F)の温度で行われ、前記水素化転化が、316℃〜427℃(約600〜約800°F)の温度で行われる、請求項4に記載のプロセス。
- 前記水素化転化が、0.3〜0.7の液空間速度で行われる、請求項1に記載のプロセス。
- 前記完全に脱酸素された水素化熱分解生成物が、輸送燃料としての使用に適したディーゼル留分およびガソリン留分に分離される、請求項1に記載のプロセス。
- 前記水素化熱分解反応容器が、流動床を含む流動床反応器であり、前記水素化熱分解反応容器中でのガス滞留時間が1分未満である、請求項1に記載のプロセス。
- 前記流動床の上方から、前記チャーが、前記流動床反応器から除去される、請求項8に記載のプロセス。
- 前記完全に脱酸素された水素化熱分解生成物の高沸点部分を用いた再循環液体中で前記水素化熱分解によるガス産物を泡立たせることで、前記水素化熱分解反応産物からチャーが除去される、請求項1に記載のプロセス。
- 前記プロセスの産物が、液体生成物およびCO2から本質的になる、請求項1に記載のプロセス。
- 前記脱酸素触媒が、粒状化されており且つ前記チャーを摩耗させるような十分な耐摩耗性を有し、それにより、前記流動床の上方から前記チャーを前記流動床反応器から除去することが可能になる、請求項8に記載のプロセス。
- バイオマスから液体生成物を製造するプロセスであって、
H2および脱酸素触媒の存在下にて反応容器中で前記バイオマスを熱分解し、部分的に脱酸素された水素化熱分解生成物、チャー、および第1の熱部分を含んでなる熱分解プロセス産物を生成する工程、
前記熱分解プロセス産物から前記チャーを分離する工程、
前記部分的に脱酸素された水素化熱分解生成物を水素化転化触媒の存在下で水素化転化し、完全に脱酸素された水素化熱分解生成物と、COおよびC1〜C 4 軽質炭化水素ガスを含んでなるガス状混合物と、第2の熱部分とを生成する工程、
前記ガス状混合物の少なくとも一部を水蒸気改質し、改質されたH2を生成する工程、および
前記バイオマスの前記熱分解の前記反応容器中に前記改質されたH2を再循環させる工程、
を含んでなり、
前記バイオマス中の酸素の40〜60%が、H2Oに転化され、前記酸素の40〜60%が、COおよびCO2に転化される、プロセス。 - 前記水素化転化触媒が、水性ガスシフト反応および水素化転化の両方を触媒する、請求項13に記載のプロセス。
- 前記水素化熱分解工程および前記水素化転化工程が、同じ圧力で行われる、請求項13に記載のプロセス。
- 前記圧力が、2.07MPa〜5.52MPa(約300〜約800psig)である、請求項15に記載のプロセス。
- 前記水素化熱分解工程が、427℃〜510℃(約800〜約950°F)の水素化熱分解温度で行われ、前記水素化転化工程が、316℃〜427℃(約600〜約800°F)の水素化転化温度で行われる、請求項13に記載のプロセス。
- 前記完全に脱酸素された水素化熱分解生成物が、輸送燃料としての使用に適したディーゼル留分およびガソリン留分に分離される、請求項13に記載のプロセス。
- 前記反応容器が、流動床を含む流動床反応器である、請求項13に記載のプロセス。
- 前記プロセスの産物が、液体生成物およびCO2から本質的になる、請求項13に記載のプロセス。
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