JP4664380B2 - 超純粋流体 - Google Patents
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- JP4664380B2 JP4664380B2 JP2007551265A JP2007551265A JP4664380B2 JP 4664380 B2 JP4664380 B2 JP 4664380B2 JP 2007551265 A JP2007551265 A JP 2007551265A JP 2007551265 A JP2007551265 A JP 2007551265A JP 4664380 B2 JP4664380 B2 JP 4664380B2
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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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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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Description
5,612,422; 5,853,566; 6,084,140; 6,136,181; 6,197,721; 6,264,826; 6,280,608; 6,281,397; 6,417,287; 6,432,297; 6,579,444; 及び 2003/0173252。
による電子顕微鏡写真で観察されるチャンネル間の反復距離a0に関連するものである。電子回折パターンで観測されるこのd100スペーシングは適当な担持体材料のX線回折パターンの低角度ピークのdスペーシングに該当する。これまでに得られた適当な担持体材料での最も高度に秩序のある調剤は、電子回折パターンで20−40の明確な点が観測されるものであった。これらのパターンは、100, 110, 200,210などの独特の反射を持つ六角形hkOサブセット及びそれらと対称の関係にある反射によって指標付けすることが出来る。
以下の例は本発明の説明のために記載するものである。これらは多くの修飾及び変更が可能であり、本発明は本明細書に記載された方法以外にも、特許請求の範囲の発明の範囲内において実施可能であることを理解すべきである。
好ましい芳香族飽和触媒が以下の実施例で使用され、65重量%の、孔直径が約40ÅのMCM-41を含む担持体、及び35重量%のアルミナバインダーよりなる。担持体は以下に述べる様に、0.9重量%パラジウム及び0.3重量%プラチナにより被覆されている。MCM-41構造にアルミニウムを組み込むことにより、更なる改善が見られ、以下の表1に示すように、MCM-41成分の孔の直径を低減させ、貴金属の搭載量を減少させる。
好ましい芳香族飽和触媒は以下の例で用いられ、約40Åの孔直径を持つMCM-41を65重量%、及びアルミナバインダーを35重量%含む担持体より成る。上に述べた様に、担持体は、0.9重量%パラジウム及び0.3重量%プラチナにより被覆されている。455 − 515 °Fからの蒸留カットを代表するC12-C15炭化水素を含む脂肪族流が試験された。原料Aは市販製品として製造され、まず従来のCoMo触媒上で水素化処理をし、その後460-506°F(238-263℃)の所望の実際のカットに分画し、約2ppmの硫黄及び25重量%芳香族を持つ原料とした。原料Bは市販製品として製造され、原料Aを従来のNiMo触媒上で処理をし、約1ppmの硫黄及び20重量%の芳香族を持つ原料とした。原料Cはパイロットプラントにおいて、原料Aを従来のニッケル触媒上で処理をし、検知可能な量の硫黄は無く、及び約10重量%の芳香族を持つ原料とした。これらの原料はその後好ましいし触媒上で、純粋H2を用いて23バールの全圧で処理をした。その結果は図3に示す。
原料Dは主にC16-C19炭化水素を含む流体であり、540-590°Fからの実際のカットを含み、更に2重量%の芳香族を含むもので、実施例5に記載の触媒上で処理された。
原料Eは主にC13-C15炭化水素を含む流体であり、480-510 °Fからの実際のカット、更に0.4重量%の芳香族を含むもので、実施例5に記載の触媒上で処理された。ジベンゾチオフェン(dibenzothiophene)がこの原料に加えられ、原料流中の硫黄の、超低量の芳香族炭化水素流製品を生成する能力に対する効果が評価された。
好ましい触媒と従来のニッケルを用いた比較試験を行い、150−156°F (約65-69℃)の実際のカットを含み、更に約20ppm酸素含有物を含むC6が大半を占める異性体原料を用いて酸素含有物の除去状態を評価した。パイロットプラントの運転は各触媒が1.7hr-1のLHSV、温度266°F(約130℃)及び約1000 scf/bblの純粋水素を用いた全圧力が335psigで行った。ニッケル触媒を用いて生産した製品の酸素含有物の含有量は原料の酸素含有物の量と同等であったが、好ましい触媒で生産した製品では検出されなかった。
カラム:HP-5 (30m x .32mm ID, .25μD df); LowOx (10m, 0.53mm ID, .10 μm df)
射出機:250℃、スプリット(split)He キャリアー、全フロー49.1ml/分、35℃のヘッド圧力22.0psig, 2.0μLサンプル注入
FID検出器:250℃, 40 cc/分 水素, 450 cc/分 エアー; 範囲 0
MSD:SIM モード, ソース温度 230℃, Quad 温度 150℃
炉:初期温度40℃を4分保持、温度を20℃/分の割合で40℃から200℃まで上昇させた。300℃までは5℃/分の割合で上昇させ15分間保持。
(II) 本発明のプロセスにより生成された少なくとも5℃の沸点範囲を持つC5-C25の炭化水素流の使用であり、前記プロセスは、半導体の製造、水処理、溶媒抽出、鉱石の抽出、金属圧延、又はポリオレフィン製造での加工助剤、掘削流体の剤形、印刷インク、農業用製剤、又はシリコン封止剤、着色剤、又はこれらの組み合わせを含む組成物;例えば、以下の使用:樹脂、着色剤、及び前記炭化水素流を含む塗料組成物での使用;前記炭化水素流と接触する大豆を含む溶媒抽出プロセス中での使用;炭化水素流、及び殺虫剤、植物成長調整剤、及びこれらの混合物から選択される少なくとも一つの材料を含む農業用製剤での使用、を含み、及びまた
(III)無機、多孔性、非積層、結晶性、約0.10−0.25重量%の Pt 及び約0.30-0.75重量%のPdを組み入れたメソ多孔性MCM-41を含む触媒であり、前記メソ多孔性MCM-41は少なくともアルミニウム及びシリカを含む枠組みを持ち、及びシリカとアルミニウムの比率が約l0:1 から約100: 1、平均孔直径が約15から約100Å未満の範囲であり;又は触媒は以下の特徴を持つ:更にアルミナーシリカバインダーを含み、前記MCM-41はシリカとアルミニウムとの比率が約100:1 から約: l0:1、好ましくは約60:1から約20:1及びより好ましくは約40:1から約20:1であり;前記枠組みは平均孔直径が約15から約50Å未満の範囲であり、好ましくは約20から約40Åである、ことを含み;及びまた(IV)本明細書に記載の組成物、特に本明細書に記載のプロセスにより生成され、又は得られる組成物を含み:本発明のプロセスにより生成されるC9-C25の炭化水素流におけるものであり、これは、ある実施の形態においては、改良点が、前記炭化水素流は100ppm未満の芳香族、ASTM D-5453による硫黄が10ppm未満、及びFIDによる酸素含有物が1ppm未満であることを含み、更に具体的に言えば、前記流体の沸点範囲は5℃から50℃に範囲であり、及び蒸留カット及び芳香族含有量がそれぞれ、(a) 157-207℃及び100ppm未満の芳香族;(b) 196-235℃及び100ppm未満の芳香族;(c) 238-263℃及び100ppm未満の芳香族;及び(d) 282-311℃及び300ppm未満の芳香族よりなる群れから選択され、及び/又はASTM D-5453による硫黄が検出されず、及び炎イオン化検出器(flame ionization detector(FID))による酸素含有物が検出されない特徴を持ち;また組成物は、本発明によるプロセスにより生成された炭化水素流、主にC6(ヘキサン)を含む炭化水素流である特徴があり、更にUV分光計による芳香族含有量が1ppm未満であり、ASTM D-5453による硫黄が検出されないレベルであり、及びFIDによる酸素含有物が検出されない特徴を持ち、及び本発明により生成された、C7(ヘプタン)を主に含む炭化水素流はまた、UV分光計による芳香族含有量が1ppm未満であり、ASTM D-5453による硫黄が検出されないレベルであり、及びFIDによる酸素含有物が検出されない。
Claims (18)
- プロセスであって、ACN (Atmospheric Crude Naptha)、HVN(Heavy Virgin Naputha)、灯油、ジーゼル油、LGO(Light Gas Oils)、PGO(Process Gas Oils)、化学プロセスで生成されるオリゴマー、GTLプロセスに由来する原料流、及びこれらの混合物より選択される第一の原料流を水素化し及び/又は水素化精製して、少なくとも5℃の沸点を持ち、少なくとも500ppmの芳香族含有量を持つC5-C19の炭化水素流を含む第二の原料流を得るステップ、そして
前記第二の原料流を、少なくとも5℃の沸点を持ち、100ppm未満の芳香族を含む炭化水素流を含む蒸留分画製品を生成するのに効果的な芳香族飽和条件で、水素を含む処理気体の存在下で、芳香族飽和触媒と接触させるステップを含み、前記芳香族飽和条件が232℃未満の温度及び水素分圧が1000psig未満であることを含み、前記芳香族飽和触媒はMCM−41に担持されたPtとPdの重量比率が1:2から1:4の範囲のPt及びPdを含む水素化−脱水素化成分を含み、前記か焼された結晶性担持体の孔サイズは15から40Åであり、そして蒸留分画製品を回収するステップを含む、前記プロセス。 - 前記蒸留分画製品がヘキサンを主に含む炭化水素流であり、更にUV分光計による芳香族含有量が1ppm未満であり、ASTM D-5453による硫黄が検出されないレベルであり、及びFIDによる酸素含有物が検出されない、請求項1のプロセス。
- 前記蒸留分画製品がヘプタンを主に含む炭化水素流であり、更にASTM D-5453による硫黄が検出されないレベルであり、及びFIDによる酸素含有物が検出されない、請求項1のプロセス。
- 前記製品の沸点範囲は前記原料流の沸点範囲と同じである請求項1または2のプロセス。
- 前記製品が前記原料流から異性化されなかった請求項1乃至4のいずれか1項のプロセス。
- 前記製品が、前記水素化―脱水素化成分と接触することによる異性化又は分解に起因する種を検出できる程度に含まない、請求項1乃至5のいずれか1項のプロセス。
- 前記製品は10ppm以下の芳香族含有量を含む、請求項1乃至6のいずれか1項のプロセス。
- 前記製品が10ppm未満の酸素含有物を含む、請求項1乃至7のいずれか1項のプロセス。
- 前記製品が5ppm未満の酸素含有物を含む、請求項1乃至7のいずれか1項のプロセス。
- 前記製品がFIDにより検出されるレベルの酸素含有物を含まない、請求項1乃至7のいずれか1項のプロセス。
- 前記製品がASTM D- 5453により検出されるレベルの硫黄を含まない、請求項1乃至10のいずれか1項のプロセス。
- 前記製品が60-150℃の蒸留カットであり、及び5から10の炭素原子を持つ、請求項1乃至11のいずれか1項のプロセス。
- 前記製品が6−8の炭素原子を持つ、請求項12のプロセス。
- 前記製品が150-315℃の蒸留カットであり、沸点範囲は5から40℃を持ち、9から19の炭素原子を持つ請求項1乃至11のいずれか1項のプロセス。
- 前記効果的な芳香族飽和条件が、水素分圧が300psigから1000psigであることを含む、請求項1乃至14のいずれか1項のプロセス。
- 前記芳香族飽和条件が180-220℃の温度を含む、請求項1のプロセス。
- 前記触媒がAlを含むバインダーを含む、請求項1のプロセス。
- 前記第一原料流を水素化し及び/又は水素化精製するステップは、第二の芳香族原料流を生成するためにNiMo又はNiに接触させることにより、そして前記第二の原料流はさらに硫黄の含有量が1ppm以下である、請求項1のプロセス。
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US64417805P | 2005-01-14 | 2005-01-14 | |
PCT/US2005/045918 WO2006078389A1 (en) | 2005-01-14 | 2005-12-19 | Ultra pure fluids |
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JP2008527140A JP2008527140A (ja) | 2008-07-24 |
JP4664380B2 true JP4664380B2 (ja) | 2011-04-06 |
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US (2) | US8163171B2 (ja) |
EP (1) | EP1846538A1 (ja) |
JP (1) | JP4664380B2 (ja) |
KR (1) | KR20070091330A (ja) |
CN (2) | CN102229816A (ja) |
BR (1) | BRPI0519808B1 (ja) |
CA (1) | CA2593533C (ja) |
SG (1) | SG158840A1 (ja) |
WO (1) | WO2006078389A1 (ja) |
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WO2008045565A1 (en) * | 2006-10-12 | 2008-04-17 | Idaho Research Foundation , Inc. | Biodiesel/diesel blend level detection using absorbance |
TWI435765B (zh) * | 2007-12-27 | 2014-05-01 | Exxonmobil Res & Eng Co | 芳族氫化作用之催化劑及方法 |
US20090299113A1 (en) * | 2008-05-28 | 2009-12-03 | E. I. Dupont De Nemours And Company | Process for preparing alkane liquids for use in immersion lithography |
WO2011061576A1 (en) * | 2009-11-20 | 2011-05-26 | Total Raffinage Marketing | Process for the production of hydrocarbon fluids having a low aromatic content |
WO2011061575A1 (en) * | 2009-11-20 | 2011-05-26 | Total Raffinage Marketing | Process for the production of hydrocarbon fluids having a low aromatic content |
FR3013357B1 (fr) * | 2013-11-18 | 2016-09-16 | Total Marketing Services | Procede de production de fluides hydrocarbures a basse teneur en aromatiques |
FR3015514B1 (fr) | 2013-12-23 | 2016-10-28 | Total Marketing Services | Procede ameliore de desaromatisation de coupes petrolieres |
JP7308061B2 (ja) * | 2019-03-29 | 2023-07-13 | コスモ石油株式会社 | ヘキサン溶剤の製造方法 |
JP7308062B2 (ja) * | 2019-03-29 | 2023-07-13 | コスモ石油株式会社 | ヘキサン溶剤の製造方法 |
WO2024068800A1 (en) * | 2022-09-28 | 2024-04-04 | Totalenergies Onetech | Process for the production of fluids from pyrolysis oil derived from plastic recycling |
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- 2005-12-19 SG SG200908686-9A patent/SG158840A1/en unknown
- 2005-12-19 CN CN2011101471592A patent/CN102229816A/zh active Pending
- 2005-12-19 CA CA2593533A patent/CA2593533C/en not_active Expired - Fee Related
- 2005-12-19 WO PCT/US2005/045918 patent/WO2006078389A1/en active Application Filing
- 2005-12-19 BR BRPI0519808-9A patent/BRPI0519808B1/pt not_active IP Right Cessation
- 2005-12-19 JP JP2007551265A patent/JP4664380B2/ja not_active Expired - Fee Related
- 2005-12-19 CN CN2005800479994A patent/CN101115821B/zh not_active Expired - Fee Related
- 2005-12-19 KR KR1020077015906A patent/KR20070091330A/ko not_active Application Discontinuation
- 2005-12-19 EP EP05854597A patent/EP1846538A1/en not_active Withdrawn
- 2005-12-19 US US11/311,005 patent/US8163171B2/en not_active Expired - Fee Related
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2012
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Also Published As
Publication number | Publication date |
---|---|
JP2008527140A (ja) | 2008-07-24 |
CA2593533A1 (en) | 2006-07-27 |
US20120184442A1 (en) | 2012-07-19 |
CN101115821A (zh) | 2008-01-30 |
US8163171B2 (en) | 2012-04-24 |
KR20070091330A (ko) | 2007-09-10 |
CN102229816A (zh) | 2011-11-02 |
US20060161031A1 (en) | 2006-07-20 |
EP1846538A1 (en) | 2007-10-24 |
BRPI0519808A2 (pt) | 2009-03-17 |
CN101115821B (zh) | 2011-07-20 |
SG158840A1 (en) | 2010-02-26 |
WO2006078389A1 (en) | 2006-07-27 |
CA2593533C (en) | 2012-07-10 |
BRPI0519808B1 (pt) | 2015-08-04 |
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