JP7220021B2 - 水素化熱分解プロセスの制御のための共処理及びその生成物 - Google Patents
水素化熱分解プロセスの制御のための共処理及びその生成物 Download PDFInfo
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Images
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
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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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- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/1018—Biomass of animal origin
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/1022—Fischer-Tropsch products
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
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- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/307—Cetane number, cetane index
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- C10G2400/02—Gasoline
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
水素化熱分解プロセスは、水素及び脱酸素化触媒を含有する水素化熱分解反応容器において起こる水素化熱分解ステップを含む。本明細書に記載されているように、水素化熱分解は、一般に、水素、バイオマス含有供給原料、及び任意に共供給物を、高い温度及び圧力下で作動し、かつ脱酸素化触媒を(例えば、流動床として)含有する水素化熱分解反応容器に供給することを含む。少なくとも1つの非凝縮性ガス(例えば、CO、CO2、及び/またはCH4)、部分的に脱酸素化された水素化熱分解生成物、及びチャー粒子を含む水素化熱分解反応器生産物が生成される。代表的なプロセスは、任意にチャー粒子を除去した後(例えば、それからのそれらの溶出に続いて水素化熱分解反応容器の外部に)、水素化転化触媒を(例えば、固定床として)含有する少なくとも1つの水素化転化反応容器を含む水素化転化ゾーンにおいて部分的に脱酸素化された水素化熱分解生成物の少なくとも一部を水素化転化することをさらに含む。水素化熱分解反応容器に導入する代わりに、またはそれと組み合わせて、共供給物が水素化転化反応容器に任意に導入され得る。いずれの場合でも、水素化転化反応器生産物が生成され、その生産物から実質的に完全に脱酸素化された炭化水素液体及びガス混合物が回収され得る。
「バイオマス」は、任意の種類の木材または紙生成物を含む、任意の固体植物材料またはそのような植物材料の混合物を指す。代表的な木材としては、硬材(例えば、白色木材)、軟材、または硬材もしくは軟材の樹皮が挙げられる。また、エネルギー作物、または農業残渣(例えば、伐採残渣)もしくは他の種類の植物廃棄物もしくは植物由来の廃棄物を植物材料として使用してもよい。特定の例示的な植物材料としては、「意図的な」エネルギー作物、例えばスイッチグラス及びススキに加えて、コーンファイバー、コーンストーバー、トウゴマ豆茎、サトウキビバガス、及びモロコシが挙げられる。短輪作森林生成物、例えばエネルギー作物としては、ハンノキ、灰、南ブナ、カバノキ、ユーカリ、ポプラ、ヤナギ、カジノキ、オーストラリアブラックウッド、スズカケノキ、及びウスバギリの変種が挙げられる。好適なバイオマスの他の例としては、炭水化物(例えば、糖)、有機性廃棄物材料、例えば廃棄紙、建設、解体廃棄物、及びバイオスラッジが挙げられる。
代表的な実施形態では、脂肪族炭化水素前駆体は、この別の供給原料(または共供給物)を水素化熱分解反応容器、水素化転化反応容器、またはその両方に導入することによって上述の水素化熱分解プロセスにおいて共処理され、上述したように、これらの反応器の一方または両方の作動条件を改善し、及び/または水素化転化反応器から回収される完全に脱酸素化された炭化水素液体の特性を改善する。
n(CO+2H2)→(-CH2-)n+nH2O+熱
代表的な実施形態では、芳香族炭化水素前駆体は、この別の供給原料(または共供給物)を水素化熱分解反応容器、水素化転化反応容器、またはその両方に導入することによって上述の水素化熱分解プロセスにおいて共処理され、上述したように、これらの反応器の一方または両方の作動条件を改善し、及び/または水素化転化反応器から回収される完全に脱酸素化された炭化水素液体の特性を改善する。
上述の特定の脂肪族炭化水素前駆体及び芳香族炭化水素前駆体のいずれかに加えて、またはその代替として、他の共供給物も同様に、水素化熱分解反応容器、水素化転化反応容器、またはその両方に導入することによって上述の水素化熱分解プロセスにおいて共処理することができ、上述したように、これらの反応器の一方または両方の作動条件を改善し、及び/または水素化転化反応器から回収される完全に脱酸素化された炭化水素液体の特性を改善する。当業者は、本開示に従って、そのような共供給物のどれが、水素化熱分解プロセスにおいて所定の種類の炭化水素(例えば、脂肪族または芳香族炭化水素)に対する前駆体であるかを所与の共供給物の特定の分子構造が決定づけるであろうことを認識するであろう。
上述したように、脂肪族炭化水素前駆体及び/または芳香族炭化水素前駆体の共処理は、例えば、(例えば、分留または分別によって)この液体から得られた/分離された液体生成物を含む実質的に完全に脱酸素化された炭化水素液体の水素化熱分解プロセスの作動及び/または生成物特性の改善につながる。特に、水素化熱分解プロセスにおいて、そのような供給原料をバイオマス含有原料と共処理することに関連する数多くの利点が本明細書に記載されている。これらの利点のいくつかは、いくつかの実施形態によれば、水素化熱分解反応器及び/または水素化転化ゾーンの少なくとも1つの水素化転化反応器において、適度な水素分圧(例えば、約13.8barg(200psig)~約34.5barg(約500psig)の範囲)の使用に関する。水素化熱分解反応器の場合、この水素分圧は、流動触媒床と併せて、比較的乏しい品質のもの(例えば、固体不純物を含有する)を含む多様な共供給物が、水素化転化ゾーンにおいてさらなる処理のために好適にアップグレードされる環境を提供する。また、下流の処理において問題となるフリーラジカル及び多核芳香族化合物(PNA)を含有する高度に酸素含有酸性バイオ油の生成が有利に回避される。
上述したように、前処理ステップ、例えば、減少した非生物学的材料の含有量(例えば、全ての鉱物形態を含む、ガラス、金属、及び金属酸化物の含有量)、減少した平均粒径、減少した平均粒子空気力学的径、増加した平均粒子表面積対質量比、またはより均一な粒径などの少なくとも1つの特徴を改良するための物理的分類に供された後に得られる前処理された供給原料である共供給物のバイオマス含有供給原料を供給することも可能である。脱揮発された及び/または部分的に水素化熱分解された前処理された供給原料の場合、前反応器から得られる蒸気、すなわち、固体(例えば、チャーまたは触媒などの固体床材料)の除去後に得られる前反応器蒸気流または精製された前反応器蒸気流から得られた蒸気は、水素化熱分解反応容器に供給され得る。水素が前反応器において脱揮発及び/または限定された水素化熱分解を行うために最初に利用される場合、前反応器蒸気流または精製された前反応器蒸気流は水素を含有し得る。そのため、前反応器蒸気流、または精製された前反応器蒸気流は、水素化熱分解反応器に供給される水素の一部もしくは全部、または水素化熱分解用の化学的水素必要量の少なくとも一部及び場合によっては全てを提供し得る。
本開示の態様によれば、水素化熱分解プロセスは、(i)水素、(ii)バイオマス含有供給原料(例えば、脱揮発及び/または水素化熱分解後の前処理された供給原料を含む)、及び/または(iii)共供給物(例えば、脱揮発後の前処理された共供給物を含む)を水素化熱分解反応容器に供給することを含む。そのプロセスは、異なる供給原料を組み合わせ、共処理し、またはブレンドして、大幅に望ましい特性、割合、及び/または収率を有する液体炭化水素生成物を生成することを含み、これを以下により十分に記載する。
Claims (22)
- 液体炭化水素生成物を生成するためのプロセスであって、
a)水素及び脱酸素化触媒を含み、7barg(102psig)~55barg(798psig)の水素分圧で作動する水素化熱分解反応容器において、バイオマス含有供給原料を水素化熱分解して、少なくとも1つの非凝縮性ガス、部分的に脱酸素化された水素化熱分解生成物、及びチャー粒子を含む水素化熱分解反応器生産物を生成することと、
b)水素化転化触媒を含有する少なくとも1つの水素化転化反応容器を含む水素化転化反応ゾーンにおいて、前記部分的に脱酸素化された水素化熱分解生成物の少なくとも一部を水素化転化して、水素化転化反応器生産物を生成することと、
c)前記水素化転化反応器生産物から実質的に完全に脱酸素化された炭化水素液体及びガス混合物を回収することと、を含み、
前記実質的に完全に脱酸素化された炭化水素液体の特性が、前記水素化熱分解反応容器において、別の供給原料としての酸素含有プラスチックを共処理するおかげで改善し、
前記酸素含有プラスチックが、ポリ(メチルメタクリレート)またはポリアミドを含み、且つ、前記特性が(i)前記脱酸素化された炭化水素液体のディーゼル沸点範囲留分の改善したセタン価、(ii)前記脱酸素化された炭化水素液体のディーゼル沸点範囲留分の改善した収量、もしくは(iii)前記脱酸素化された炭化水素液体のジェット燃料沸点範囲留分の改善した収量である、又は、
前記酸素含有プラスチックが、ポリカーボネートまたはポリエチレンテレフタレートを含み、且つ、前記特性が(i)前記脱酸素化された炭化水素液体のガソリン沸点範囲留分の改善したオクタン価、もしくは(ii)前記脱酸素化された炭化水素液体のガソリン沸点範囲留分の改善した収量である、
プロセス。 - 前記酸素含有プラスチックが、ポリ(メチルメタクリレート)またはポリアミドを含み、且つ、前記酸素含有プラスチックの供給速度が、前記実質的に完全に脱酸素化された炭化水素液体のディーゼル沸点範囲留分の収量もしくはセタン価の測定された減少または所望の増大に応じて増大される、または、前記酸素含有プラスチックの供給速度が、前記実質的に完全に脱酸素化された炭化水素液体のディーゼル沸点範囲留分の収量もしくはセタン価の測定された増大または所望の減少に応じて減少される、または、
前記酸素含有プラスチックが、ポリカーボネートまたはポリエチレンテレフタレートを含み、且つ、前記酸素含有プラスチックの供給速度が、前記実質的に完全に脱酸素化された炭化水素液体のガソリン沸点範囲留分の収量もしくはオクタン価の測定された減少または所望の増大に応じて増大される、または、前記酸素含有プラスチックの供給速度が、前記実質的に完全に脱酸素化された炭化水素液体のガソリン沸点範囲留分の収量もしくはオクタン価の測定された増大または所望の減少に応じて減少される、プロセスであって、
水素化熱分解反応容器の触媒インベントリーの重量によって分割されるバイオマス含有供給原料及び酸素含有プラスチックの組み合わされた重量流量として計算される、水素化熱分解反応器の重量毎時空間速度(WHSV)が、0.1hr-1~10hr-1である、請求項1に記載のプロセス。 - 前記酸素含有プラスチックが、ポリ(メチルメタクリレート)またはポリアミドを含み、且つ、前記特性が、前記脱酸素化された炭化水素液体のディーゼル沸点範囲留分の改善したセタン価である、請求項1又は2に記載のプロセス。
- 前記酸素含有プラスチックが、ポリ(メチルメタクリレート)またはポリアミドを含み、且つ、前記特性が、前記脱酸素化された炭化水素液体のディーゼル沸点範囲留分の改善した収量である、請求項1又は2に記載のプロセス。
- 前記酸素含有プラスチックが、ポリ(メチルメタクリレート)またはポリアミドを含み、且つ、前記特性が、前記脱酸素化された炭化水素液体のジェット燃料沸点範囲留分の改善した収量である、請求項1又は2に記載のプロセス。
- 前記酸素含有プラスチックが、ポリカーボネートまたはポリエチレンテレフタレートを含み、且つ、前記特性が、前記脱酸素化された炭化水素液体のガソリン沸点範囲留分の改善したオクタン価である、請求項1又は2に記載のプロセス。
- 前記酸素含有プラスチックが、ポリカーボネートまたはポリエチレンテレフタレートを含み、且つ、前記特性が、前記脱酸素化された炭化水素液体のガソリン沸点範囲留分の改善した収量である、請求項1又は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反応器であり、前記水素化転化反応容器が固定床反応器であり、水素化転化ステップ(b)の前に前記部分的に脱酸素化された水素化熱分解生成物からチャー粒子が除去される、請求項1~7のいずれか一項に記載のプロセス。
- 水素化転化ステップ(b)の前に前記水素化転化触媒の毒が前記チャー粒子において除去される、請求項8に記載のプロセス。
- 前記酸素含有プラスチックが、ポリ(メチルメタクリレート)またはポリアミドを含む、請求項1又は2に記載のプロセス。
- 前記酸素含有プラスチックの供給速度が、実質的に完全に脱酸素化された炭化水素液体のディーゼル沸点範囲留分の収量もしくはセタン価の測定された減少または所望の増大に応じて増大される、または、前記酸素含有プラスチックの供給速度が、前記実質的に完全に脱酸素化された炭化水素液体のディーゼル沸点範囲留分の収量もしくはセタン価の測定された増大または所望の減少に応じて減少される、請求項10に記載のプロセス。
- 前記酸素含有プラスチックが、ポリカーボネートまたはポリエチレンテレフタレートを含む、請求項1又は2に記載のプロセス。
- 前記酸素含有プラスチックの供給速度が、実質的に完全に脱酸素化された炭化水素液体のガソリン沸点範囲留分の収量もしくはオクタン価の測定された減少または所望の増大に応じて増大される、または、前記酸素含有プラスチックの供給速度が、前記実質的に完全に脱酸素化された炭化水素液体のガソリン沸点範囲留分の収量もしくはオクタン価の測定された増大または所望の減少に応じて減少される、請求項12に記載のプロセス。
- 前記水素分圧が、13.8barg(200psig)~34.5barg(500psig)である、請求項1に記載のプロセス。
- 前記脱酸素化触媒が、耐火性無機酸化物を含む担持材料上の少なくとも1つのVIII族金属および少なくとも1つのVI族金属を含む、請求項1~14のいずれか一項に記載のプロセス。
- 前記酸素含有プラスチックが、都市固形廃棄物(MSW)中に存在する、請求項1~15のいずれか一項に記載のプロセス。
- 固体の前記バイオマス含有供給原料が、木材を含む、請求項1~16のいずれか一項に記載のプロセス。
- 前記ガス混合物の少なくとも一部を水蒸気改質し、改質した水素を生成することをさらに含む、請求項1~17のいずれか一項に記載のプロセス。
- 前記改質した水素の少なくとも一部を水素化熱分解反応容器にリサイクルすることをさらに含む、請求項18に記載のプロセス。
- 前記実質的に完全に脱酸素化された炭化水素液体が、2重量%未満の全酸素含有量を有する、請求項1~19のいずれか一項に記載のプロセス。
- 前記水素化転化反応容器からの水相水素化転化生成物を凝縮することをさらに含む、請求項1~20のいずれか一項に記載のプロセス。
- 前記水素化転化反応ゾーンが、水素化異性化反応容器をさらに含む、請求項1~21のいずれか一項に記載のプロセス。
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US20160312125A1 (en) | 2016-10-27 |
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