JP4629435B2 - 微結晶蝋及び中間蒸留物燃料の製造方法 - Google Patents
微結晶蝋及び中間蒸留物燃料の製造方法 Download PDFInfo
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- JP4629435B2 JP4629435B2 JP2004522491A JP2004522491A JP4629435B2 JP 4629435 B2 JP4629435 B2 JP 4629435B2 JP 2004522491 A JP2004522491 A JP 2004522491A JP 2004522491 A JP2004522491 A JP 2004522491A JP 4629435 B2 JP4629435 B2 JP 4629435B2
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- fischer
- weight
- middle distillate
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- wax
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Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/42—Refining of petroleum waxes
- C10G73/44—Refining of petroleum waxes in the presence of hydrogen or hydrogen-generating compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S208/00—Mineral oils: processes and products
- Y10S208/95—Processing of "fischer-tropsch" crude
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Steroid Compounds (AREA)
Description
SX100等級、又はASTM D938で測定した凝固点が85〜120℃の範囲にある類似の商用フィッシャー・トロプシュ誘導等級の欠点は、硬すぎるため、幾つかの用途には使用できないことである。蝋の硬度は、IP 376法で測定できる。市販のフィッシャー・トロプシュ誘導SX100蝋について、この方法を用いて得られる43℃でのPEN値は、通常、0.2〜0.6mmの範囲である。
Sie S T等,“Conversion of natural gas to transportation fuels via the Shell Middle distillate synthesis process(SMDS)”,Catalysis Today,Amsterdam,第8巻,1991年,371−394頁には、フィッシャー・トロプシュ生成物の穏やかな水素化分解により中間蒸留物を得ることが記載されている。
前記提案に開示されたSMDS法と殆ど同様な方法が、最近公開されたWO−A−0174969に開示されている。この方法では、フィッシャー・トロプシュ生成物に低転化率で水素化処理工程を行なう。この刊行物の実施例で得られた蝋状生成物は、ASTM D−1321の針入度値を特徴とする。この値の測定温度は示されていないので、これら生成物の柔軟性の評価はできない。更に融点について述べているが、この特性の測定法を示していない。
(a)フィッシャー・トロプシュ生成物中の炭素原子数60以上の化合物と炭素原子数30以上の化合物との重量比が少なくとも0.4で、かつフィッシャー・トロプシュ生成物中の化合物の30重量%以上が炭素原子数30以上の化合物である該フィッシャー・トロプシュ生成物を水素化分解/水素化異性化する工程(但し、該工程での転化率は25〜70重量%の範囲である)、及び
(b)工程(a)の流出流に対し1つ以上の蒸留物分離を行って、中間蒸留物燃料フラクション及び初期沸点範囲が500〜600℃の微結晶蝋を得る工程、
による微結晶蝋及び中間蒸留物燃料の製造方法。
以上の方法で得られる柔らかな微結晶蝋のASTM D938で測定した凝固点は、85〜120℃、好ましくは95〜120℃の範囲であり、IP 376で測定した43℃でのPENは、0.8mmを超え、好ましくは1mmを超える。この蝋は、好ましくは芳香族化合物が1重量%未満、ナフテン化合物が10重量%未満であり、更に好ましくはナフテン化合物が5重量%未満であることを更に特徴とする。蝋中の分岐パラフィンのモル割合は、C13 NMRで測定して、好ましくは33モル%を超え、更に好ましくは45モル%を超え、80モル%未満である。この方法は、蝋の平均分子量を測定し、引き続き、各分子は2つ以上の分岐を持たないという条件で、メチル分岐を有する分子、エチル分岐を有する分子、C3分岐を有する分子及びC4+分岐を有する分子のモル%を測定する。分岐パラフィンのモル%は、これら個々の%の合計である。この方法は、蝋中の、分岐が1つだけの平均的分子のモル%を算出する。実際には、2つ以上の分岐を有するパラフィン分子が存在する可能性がある。したがって、他の方法で測定した分岐パラフィンの含有量は、異なる値になってもよい。
本発明を以下の非限定的実施例により説明する。
WO−A−9934917の実施例IIIの触媒を用いて実施例VIIで得られたフィッシャー・トロプシュ生成物のC5〜C750℃+フラクションを連続的に水素化分解工程(工程(a))に供給した。この原料は、C30+生成物を約60重量%含有し、C60+/C30+比は、約0.55である。水素化分解工程では、このフラクションは、EP−A−532118の実施例1の水素化分解触媒と接触させた。
工程(a)の流出流を連続的に蒸留し、軽質分、燃料及び沸点370℃以上の残留物“R”を得た。新しい原料に対するガス油フラクションの収率は、43重量%であった。得られたガス油の特性を第1表に示す。残留物“R”の大部分は、工程(a)に再循環し、残部は、真空蒸留により第2表に示す微結晶蝋に分離した。得られた微結晶蝋のフラクションは、真空蒸留した原料に対し63.2重量%であった。
水素化分解工程(a)の条件は、新しい原料重量の時間当り空間速度(WHSV)=1.02kg/l.h、再循環原料のWHSV=0.31kg/l.h、水素ガス速度=1000Nl/kg、全圧=40バール、反応器温度=329℃である。
Claims (1)
- (a)フィッシャー・トロプシュ生成物中の炭素原子数60以上の化合物と炭素原子数30以上の化合物との重量比が少なくとも0.4で、かつフィッシャー・トロプシュ生成物中の化合物の30重量%以上が炭素原子数30以上の化合物である該フィッシャー・トロプシュ生成物を水素化分解/水素化異性化する工程(但し、該工程での転化率は25〜70重量%の範囲である)、及び
(b)工程(a)の流出流に対し1つ以上の蒸留物分離を行って、中間蒸留物燃料フラクション及び初期沸点範囲が500〜600℃の微結晶蝋を得る工程、及び
(c)工程(b)で得られた蝋に対し、更に脱油工程を行って、油含有量が0.1〜2重量%の範囲の蝋を得る工程、
による微結晶蝋及び中間蒸留物燃料の製造方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02077921 | 2002-07-18 | ||
PCT/EP2003/007785 WO2004009739A2 (en) | 2002-07-18 | 2003-07-17 | Process to prepare a microcrystalline wax and a middle distillate fuel |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005537344A JP2005537344A (ja) | 2005-12-08 |
JP4629435B2 true JP4629435B2 (ja) | 2011-02-09 |
Family
ID=30470285
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004522491A Expired - Fee Related JP4629435B2 (ja) | 2002-07-18 | 2003-07-17 | 微結晶蝋及び中間蒸留物燃料の製造方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US7300565B2 (ja) |
EP (1) | EP1534802B1 (ja) |
JP (1) | JP4629435B2 (ja) |
AT (1) | ATE310066T1 (ja) |
AU (1) | AU2003255058A1 (ja) |
BR (1) | BR0312667B1 (ja) |
DE (1) | DE60302366T2 (ja) |
ES (1) | ES2254973T3 (ja) |
WO (1) | WO2004009739A2 (ja) |
ZA (1) | ZA200500155B (ja) |
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-
2003
- 2003-07-17 US US10/521,668 patent/US7300565B2/en not_active Expired - Fee Related
- 2003-07-17 AT AT03765027T patent/ATE310066T1/de not_active IP Right Cessation
- 2003-07-17 EP EP03765027A patent/EP1534802B1/en not_active Expired - Lifetime
- 2003-07-17 ES ES03765027T patent/ES2254973T3/es not_active Expired - Lifetime
- 2003-07-17 DE DE60302366T patent/DE60302366T2/de not_active Expired - Lifetime
- 2003-07-17 WO PCT/EP2003/007785 patent/WO2004009739A2/en active Search and Examination
- 2003-07-17 AU AU2003255058A patent/AU2003255058A1/en not_active Abandoned
- 2003-07-17 BR BRPI0312667-6A patent/BR0312667B1/pt not_active IP Right Cessation
- 2003-07-17 JP JP2004522491A patent/JP4629435B2/ja not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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ZA200500155B (en) | 2006-07-26 |
WO2004009739A3 (en) | 2004-03-25 |
BR0312667B1 (pt) | 2012-11-27 |
ATE310066T1 (de) | 2005-12-15 |
ES2254973T3 (es) | 2006-06-16 |
WO2004009739A2 (en) | 2004-01-29 |
JP2005537344A (ja) | 2005-12-08 |
DE60302366T2 (de) | 2006-08-03 |
BR0312667A (pt) | 2005-04-26 |
AU2003255058A1 (en) | 2004-02-09 |
US20050247601A1 (en) | 2005-11-10 |
US7300565B2 (en) | 2007-11-27 |
EP1534802B1 (en) | 2005-11-16 |
EP1534802A2 (en) | 2005-06-01 |
DE60302366D1 (de) | 2005-12-22 |
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