JP5521031B2 - 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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- JP5521031B2 JP5521031B2 JP2012504670A JP2012504670A JP5521031B2 JP 5521031 B2 JP5521031 B2 JP 5521031B2 JP 2012504670 A JP2012504670 A JP 2012504670A JP 2012504670 A JP2012504670 A JP 2012504670A JP 5521031 B2 JP5521031 B2 JP 5521031B2
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Description
本願は、2009年4月7日付で提出された同時係属中の同出願人による米国特許出願第12/419,535号の一部係属出願である。
ガラスセラミックス触媒は、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インチという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またはCoMo触媒よりも高い強度を示し、流動床中での使用に適したサイズである。
Claims (43)
- 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)分子状の水素および脱酸素触媒を含む水素化熱分解反応器中でバイオマスを水素化熱分解して、CO2、CO、およびC1〜C3ガス、部分的に脱酸素された水素化熱分解生成物、およびチャー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)前記部分的に脱酸素された水素化熱分解生成物を、前記工程a)で生成したCO2、CO、およびC1〜C3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水素化転化し、実質的に完全に脱酸素された炭化水素液体と、CO、CO2、および軽質炭化水素ガス(C1〜C3)を含んでなるガス状混合物とを生成する工程、
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、前記バイオマスの水素化熱分解のために前記反応器中に導入する工程であって、前記工程a)およびc)が、前記バイオマス中の酸素の30〜70%がH2Oに転化され且つ前記酸素の30〜70%がCOおよびCO2に転化される条件下で行われる工程、
を含んでなる、プロセス。 - 前記工程c)で生成された前記実質的に完全に脱酸素された炭化水素液体の一部が、前記水素化熱分解反応容器または前記水素化転化反応容器へとリサイクルされてその中の温度が調整される、請求項1に記載のプロセス。
- 前記脱酸素触媒および前記水素化転化触媒の少なくとも1つが、ガラスセラミック材料である、請求項1に記載のプロセス。
- 前記水素化転化反応容器の上流、下流、内部、および並行しての少なくとも1つに水素化分解触媒が配置される、請求項1に記載のプロセス。
- 前記水素化分解触媒が、水素化作用および酸性作用の両方を提供する酸性の金属含有触媒である、請求項4に記載のプロセス。
- 前記水素化転化触媒が、水素化分解触媒で置換されている、請求項1に記載のプロセス。
- 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)の全てが、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。
- 前記工程a)、c)、およびd)の全てが、実質的に同じ圧力で行われる、請求項4に記載のプロセス。
- 前記圧力が、0.69〜5.5MPaである、請求項8に記載のプロセス。
- 前記圧力が、0.69〜5.5MPaである、請求項9に記載のプロセス。
- 前記水素化熱分解が、260〜537.8℃の温度で行われ、前記水素化転化が、260〜454.4℃の温度で行われる、請求項1に記載のプロセス。
- 前記水素化熱分解が、0.2〜10gm(バイオマス)/gm(触媒)/hrの重量空間速度で行われる、請求項1に記載のプロセス。
- 前記水素化転化が、0.2〜3gm(バイオマス)/gm(触媒)/hrの重量空間速度で行われる、請求項1に記載のプロセス。
- 前記実質的に完全に脱酸素された炭化水素液体が、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2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。
- 実質的に前記流動床の上方からのみ、前記チャーが、前記流動床反応器から除去される、請求項16に記載のプロセス。
- 前記工程b)が、実質的に完全に脱酸素された炭化水素液体の高沸点部分を含む再循環液体中で前記水素化熱分解反応器によるガス産物を泡立たせることを含む、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、実質的に前記流動床の上方からのみ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17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、前記チャーが、慣性プロセス、静電プロセス、および磁気プロセスの少なくとも1つを用いるエネルギー的チャー分離によって前記流動床反応器から除去される、請求項1に記載のプロセス。
- 前記脱酸素触媒が、ガラスセラミック材料である、請求項21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、水素化熱分解反応容器中で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およびチャーを含んでなる水素化熱分解プロセス産物を生成する工程、
水素化転化反応容器中で、水素化転化触媒存在下、0.69〜5.5MPaの水素化転化圧にて、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、実質的に完全に脱酸素された炭化水素液体と、COおよびC1〜C3軽質炭化水素ガスを含んでなるガス状混合物とを生成する工程、および
前記ガス状混合物の少なくとも一部を水蒸気改質し、前記バイオマスを水素化熱分解すするのに十分な量の改質されたH2を生成する工程、
を含んでなる、プロセス。 - 前記バイオマス中の酸素の30〜70%が、H2Oに転化され、前記酸素の30〜70%が、COおよびCO2に転化される、請求項23に記載のプロセス。
- 前記水素化転化反応容器の上流、下流、内部、および並行しての少なくとも1つに水素化分解触媒が配置される、請求項23に記載のプロセス。
- 前記水素化分解触媒が、水素化作用および酸性作用の両方を提供する酸性の金属含有触媒である、請求項25に記載のプロセス。
- 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23に記載のプロセス。
- 前記水素化熱分解工程が、260〜537.8℃の水素化熱分解温度で行われ、前記水素化転化工程が、260〜454.4℃の水素化転化温度で行われる、請求項23に記載のプロセス。
- 前記実質的に完全に脱酸素された炭化水素液体が、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23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23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23に記載のプロセス。
- 前記水素化転化触媒が、水素化分解触媒によって完全に置換されている、請求項23に記載のプロセス。
- 前記脱酸素触媒が、水素化分解触媒によって完全に置換されている、請求項23に記載のプロセス。
- 前記工程d)において、改質された分子状の水素が、前記バイオマスを水素化熱分解するのに十分な量で生成される、請求項1に記載のプロセス。
- 前記水蒸気改質工程d)が、前記工程a)および工程c)において生成した水を用いて行われ、改質された分子状の水素が生成される、請求項1に記載のプロセス。
- 前記水素化転化圧が、0.69〜3.45MPaの範囲である、請求項23に記載のプロセス。
- 前記水素化熱分解プロセス産物から前記チャーを分離する工程をさらに含む、請求項23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、
a)H2および脱酸素触媒の存在下、水素化熱分解反応器中で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およびチャーを含んでなる水素化熱分解反応産物を生成する工程、
b)水素化転化反応容器中で、水素化転化触媒存在下、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、実質的に完全に脱酸素された炭化水素液体と、COおよびC1〜C3軽質炭化水素ガスを含んでなるガス状混合物とを生成する工程、
c)前記ガス状混合物の少なくとも一部を、前記工程a)および工程b)において生成した水を用いて水蒸気改質し、改質されたH 2 を生成する工程、および
d)前記改質されたH2を前記水素化熱分解反応器に導入する工程、
を含んでなる、プロセス。 - 前記工程a)およびb)において生成した水が、実質的に完全に脱酸素された炭化水素液体から分離される、請求項38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、
a)H2および脱酸素触媒の存在下、水素化熱分解反応器中で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およびチャーを含んでなる水素化熱分解反応産物を生成する工程、
b)水素化転化反応容器中で、水素化転化触媒存在下、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、実質的に完全に脱酸素された炭化水素液体と、COおよびC1〜C3軽質炭化水素ガスを含んでなるガス状混合物とを生成する工程、
c)前記ガス状混合物の少なくとも一部を水蒸気改質して、改質されたH2を生成する工程、および
d)前記改質されたH2を前記水素化熱分解反応器に導入する工程、
を含んでなる、プロセス。 - 前記水素化転化触媒の上流に水素化分解触媒が設けられてなる、請求項40に記載のプロセス。
- 前記水素化転化触媒の下流に水素化分解触媒が設けられてなる、請求項40に記載のプロセス。
- 前記水素化転化反応容器と並行して運転される個別の水素化分解反応容器中に水素化分解触媒が配置されている、請求項40に記載のプロセス。
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US12/419,535 US20100251600A1 (en) | 2009-04-07 | 2009-04-07 | Hydropyrolysis of biomass for producing high quality liquid fuels |
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US12/685,352 US8492600B2 (en) | 2009-04-07 | 2010-01-11 | Hydropyrolysis of biomass for producing high quality fuels |
US12/685,352 | 2010-01-11 | ||
PCT/US2010/001020 WO2010117437A1 (en) | 2009-04-07 | 2010-04-05 | Hydropyrolysis of biomass for producing high quality liquid fuels |
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R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |