JP2007502899A - A method for improving the quality of kerosene and gas oil from naphthenic and aromatic crudes. - Google Patents
A method for improving the quality of kerosene and gas oil from naphthenic and aromatic crudes. Download PDFInfo
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- 239000003350 kerosene Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims description 21
- 125000003118 aryl group Chemical group 0.000 title description 17
- 239000003921 oil Substances 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 30
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 19
- 239000003208 petroleum Substances 0.000 claims abstract description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000779 smoke Substances 0.000 claims abstract description 14
- 239000010779 crude oil Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000009835 boiling Methods 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 210000003918 fraction a Anatomy 0.000 claims 1
- 239000003209 petroleum derivative Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 41
- 239000002994 raw material Substances 0.000 description 29
- 239000000446 fuel Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 239000002283 diesel fuel Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000013058 crude material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Fats And Perfumes (AREA)
Abstract
ワトソン特性係数Ｋ値が１２．０以下の原油から石油誘導ケロシンフラクション及び石油誘導ガス油フラクションを単離し（但し、ケロシンフラクション中のナフタレン含有量が３容量％未満で、かつガス油フラクションのセタン価が５０未満又は密度が８４５ｋｇ／ｍ３を超える場合、ケロシンフラクションの煙点は２５又は１９ｍｍ未満）、該ケロシンフラクションに、得られる混合物中のナフタレン含有量が３容量％未満の場合、混合物の煙点が２５又は１９ｍｍを超えるような量のフィッシャー・トロプシュ誘導ケロシンフラクションを添加し、次いで該石油誘導ガス油フラクションに、混合物のセタン価が５１を超えるような量のフィッシャー・トロプシュ誘導ガス油フラクションを添加する前記製造法。
【選択図】なし
Oil-derived kerosene fraction and petroleum-derived gas oil fraction are isolated from crude oil having Watson characteristic coefficient K value of 12.0 or less (however, the naphthalene content in kerosene fraction is less than 3% by volume and the cetane number of gas oil fraction Is less than 50 or the density is greater than 845 kg / m 3 , the smoke point of the kerosene fraction is less than 25 or 19 mm), and if the kerosene fraction contains less than 3% by volume of naphthalene in the resulting mixture, the smoke of the mixture Add an Fischer-Tropsch derived kerosene fraction in an amount such that the point is greater than 25 or 19 mm, and then add to the petroleum derived gas oil fraction an Fischer-Tropsch derived gas oil fraction in an amount such that the cetane number of the mixture exceeds 51. The said manufacturing method to add.
[Selection figure] None
Description
発明の分野
ワトソン（Ｗａｔｓｏｎ）特性係数Ｋ値が１２以下を特徴とするナフテン系及び芳香族系原油からの低品質のケロシン及びガス油の品質向上法。
FIELD OF THE INVENTION A method for improving the quality of low quality kerosene and gas oil from naphthenic and aromatic crudes characterized by a Watson characteristic coefficient K value of 12 or less.
発明の背景
ワトソン特性係数Ｋ値が１１〜１２を特徴とする原油は、“ナフテン系”粗原料とも言われている。Ｋ値が１１未満の粗原料は、“芳香族系”粗原料とも言われている。炭化水素についてのワトソン特性係数Ｋは、ＡＰＩ技術データブック（セクション２ 特徴化）に定義されている。
BACKGROUND OF THE INVENTION Crude oil characterized by a Watson characteristic coefficient K value of 11-12 is also referred to as a “naphthenic” crude feed. A crude material having a K value of less than 11 is also referred to as an “aromatic” crude material. The Watson characteristic factor K for hydrocarbons is defined in the API technical data book (section 2 characterization).
ナフテン系又は芳香族系粗原料から蒸留した生ナフサフラクションは、接触改質により容易に高オクタン価改質物に転化できるので、高オクタン自動車ガソリン成分を製造するのに極めて好適である。しかし、ナフテン系及び／又は芳香族系粗原料から製造した生ケロシン及び生ガス油は、種々の地域及び市場において、ますます増加する多数の立法府により要求される特定の環境保護に関する駆動燃料規格に適合するには不適当な特定の品質特性を特徴としている。 The raw naphtha fraction distilled from a naphthenic or aromatic raw material can be easily converted to a high octane number reformed product by catalytic reforming, and thus is extremely suitable for producing a high octane automobile gasoline component. However, raw kerosene and raw gas oils made from naphthenic and / or aromatic raw materials are driving fuel standards for specific environmental protection required by an increasing number of legislatures in various regions and markets. It is characterized by specific quality characteristics that are inappropriate for conformance.
蒸留及び処理によりナフテン系及び／又は芳香族系粗原料から製造した航空機用ケロシンは、通常、共同操作システム（Ｊｏｉｎｔｌｙ Ｏｐｅｒａｔｅｄ Ｓｙｓｔｅｍ）用航空機燃料品質要件（ＡＦＱＲＪＯＳ）の照合表Ｎｏ．１９の航空機タービン燃料（Ａｖｔｕｒ）に設定された所要国際規格（最小２５ｍｍ）よりも遥かに煙点が低いか、或いはケロシン中のナフテン含有量が３容量％未満の場合の代替規格である最大煙点（最小１９ｍｍ）に適合しない。これら粗原料から製造したケロシンでは、ケロシンの最終沸点が高い場合、時にはナフタレン水準が高すぎることがある。最小合計酸価０．０１５ｍｇＫＯＨ／ｇ、最大特定芳香族水準２５容量％及び熱安定性要件（ＪＦＴＯＴ）のような、航空機用ケロシンに設定されたその他の規格もナフテン系及び／又は芳香族系粗原料から直接蒸留したケロシンでは適合困難である。 Aircraft kerosene produced from naphthenic and / or aromatic raw materials by distillation and processing is usually referred to in the reference table No. of Aircraft Fuel Quality Requirements (AFQRJOS) for Jointly Operated Systems. Maximum smoke, which is an alternative standard when the smoke point is much lower than the required international standard (minimum 25 mm) set for 19 aircraft turbine fuels (Avtur) or when the naphthene content in kerosene is less than 3% by volume Does not fit point (minimum 19mm). In kerosene produced from these raw materials, the naphthalene level is sometimes too high when the final boiling point of kerosene is high. Other standards set for aircraft kerosene, such as a minimum total acid number of 0.015 mg KOH / g, a maximum specified aromatic level of 25% by volume and a thermal stability requirement (JFTOT) are also naphthenic and / or aromatic crude It is difficult to adapt with kerosene distilled directly from the raw material.
このようなナフテン系又は芳香族系粗原料から製造したディーゼル品質のガス油は、通常、低セタン価（ＣＮ）を特徴とする。通常、このセタン価は、ディーゼル等級に設定された所要の国際セタン価規格より低い３５〜５０の範囲である。国際的には、ディーゼル燃料のセタン価を上げて、自動車排出物を減少させる、きれいな駆動燃料（ａ ｄｒｉｖｅ）がある。例えばヨーロッパディーゼル規格（ＥＮ ５９０）の最小セタン価要件は、Ｅｕｒｏ ＩＩＩ燃料用のＥＵ燃料指針９８／７０に設定されたヨーロッパディーゼル燃料・排出物要件に適合させるため、２０００年以降、５１の最小値に上げられた。地球規模の自動車メーカーは、２００２年のＷｏｒｌｄ Ｗｉｄｅ Ｆｕｅｌ Ｃｈａｒｔｅｒで発表したように、ディーゼル燃料セタン価要件を更に最小５５までも上げることを要望している。 Diesel quality gas oils made from such naphthenic or aromatic raw materials are usually characterized by low cetane number (CN). Typically, this cetane number is in the range of 35-50, which is lower than the required international cetane number standard set for diesel grade. Internationally, there is a clean drive fuel that increases the cetane number of diesel fuel and reduces automobile emissions. For example, the minimum cetane number requirement of the European Diesel Standard (EN 590) is a minimum value of 51 since 2000 to meet the European diesel fuel and emissions requirements set in the EU Fuel Guidelines 98/70 for Euro III fuel Was raised. Global automakers want to raise diesel fuel cetane number requirements to a minimum of 55, as announced at the 2002 World Wide Fuel Charter.
ナフテン系又は芳香族系粗原料から製造したガス油は、高密度も特徴としている。国際的ディーゼル品質の最大密度限界は、現在、ディーゼル自動車排出物要件に適合させるため低下しつつある。またＥＵでは、ＥＵ ５９０のディーゼル燃料用の最大規格は、２０００年にはＥＵ燃料指針９８／７０に設定されるように、８４５ｋｇ／ｍ３の最大値に低下した。 Gas oils produced from naphthenic or aromatic raw materials are also characterized by high density. The maximum density limit for international diesel quality is currently falling to meet diesel vehicle emissions requirements. Also in the EU, the maximum standard for diesel fuel of EU 590 has been reduced to a maximum value of 845 kg / m 3 in 2000, as set in EU fuel guidelines 98/70.
これら排出物駆動燃料要件の結果から、ナフテン系又は芳香族系粗原料から製造した中間蒸留物燃料は、Ａｖｔｕｒ及びディーゼルに設定された厳しい環境保護上の駆動燃料規格要件に適合するには不適当かも知れない。その結果、これら粗原料がいわゆる水素化スキミング（ｈｙｄｒｏｓｋｉｍｍｉｎｇ）製油所で処理されていれば、“規格外”のディーゼル品質又はケロシン品質となる。水素化スキミング製油所は、粗原料の蒸留及び水素化処理工程からなる比較的簡単な製油所である。 As a result of these emissions-driven fuel requirements, middle distillate fuels produced from naphthenic or aromatic raw materials are not suitable to meet the stringent environmental drive fuel standard requirements set for Avtur and diesel. May. As a result, if these raw materials are processed at a so-called hydroskimming refinery, “non-standard” diesel quality or kerosene quality results. The hydroskimming refinery is a relatively simple refinery consisting of crude raw material distillation and hydroprocessing steps.
これら粗原料から製造した蒸留物の品質を向上して、特定の製品品質に適合させるには、前記製油所は下記２つの選択肢を有する。
１）第一の選択肢として、低蒸留物品質の更なる向上は、更に厳しい水素化処理又は水素化分解を施すことにより達成できる。しかし、このような選択肢はこれらの処理ユニットを備えていない製油所に高価な投資を必要とする可能性がある。
In order to improve the quality of distillates produced from these raw materials and to meet specific product quality, the refinery has the following two options.
1) As a first option, further improvement in low distillate quality can be achieved by applying more severe hydrotreating or hydrocracking. However, such options may require expensive investments in refineries that do not have these processing units.
ＵＳ−Ａ−３６０７７２９に記載されるようなケロシンフラクション中のナフテン系成分の接触開環による方法では、ケロシンフラクションの煙点を改良できる。またガス油のセタン価もこれら方法の水素化反応及び開環反応により向上できる。 The method by catalytic ring opening of naphthenic components in the kerosene fraction as described in US-A-3607729 can improve the smoke point of the kerosene fraction. Moreover, the cetane number of gas oil can also be improved by the hydrogenation reaction and ring-opening reaction of these methods.
ＵＳ−Ａ−３７７５２９７には、ナフテン系粗原料から単離したガス油を潤滑基油及び自動車ガソリンに転化する方法が記載されている。
更にＵＳ−Ａ−５１０７０５６に記載の最近の発展は、望ましくないナフテン系化合物を膜分離により油から除去する方法である。
US-A-3775297 describes a method for converting gas oil isolated from naphthenic raw materials into lubricating base oil and automobile gasoline.
Furthermore, a recent development described in US-A-51007056 is a method for removing undesirable naphthenic compounds from oil by membrane separation.
２）ケロシン及びガス油の特性を向上する第二の選択肢は、これら低品質種のナフテン系及び芳香族系粗原料を多種のパラフィン系粗原料とブレンドし、共同処理することである。この粗原料ブレンドの最終蒸留物の収率は、各粗原料から得られる蒸留物の収率を掛けた粗原料ブレンド比から計算できる。 2) A second option to improve the properties of kerosene and gas oil is to blend these low quality species of naphthenic and aromatic raw materials with various paraffinic raw materials and co-process them. The yield of the final distillate of this raw material blend can be calculated from the raw material blend ratio multiplied by the yield of the distillate obtained from each raw material.
パラフィン系粗原料とのブレンドによる欠点は、これらの粗原料が必ずしも製油所の地域で入手できないか、或いは非常に高価なことである。他の欠点は、ケロシン及びガス油の特性と蒸留物の需要量との両者をそれぞれ規定量で品質に適合するようにブレンドするパラフィン系粗原料が必ずしも見い出せないことである。 The disadvantage of blending with paraffinic raw materials is that these raw materials are not always available in the refinery area or are very expensive. Another drawback is that it is not always possible to find a paraffinic raw material that blends both the characteristics of kerosene and gas oil and the demand for distillate in a specified amount to match the quality.
普通、粗原料のブレンドは、品質の不合格（ｇｉｖｅ−ａｗａｙ）を生じ、例えばこれら粗原料をブレンド後、煙点、それぞれセタン価規格に適合するケロシンブレンド又はガス油ブレンドのいずれかである。その他のブレンドは、規格値を超える特性値を有するが、この特性値は、規格に更に近い特性を有するブレンドと同じか近い。このようないわゆる品質の不合格は、自明の理由から好ましくは避けるべきである。けれども、前述のように、製油所のブレンド環境において、ケロシン及びガス油の両製品を最適化する際、このような品質の不合格は、必ずしも避けられない。またパラフィン系粗原料の共同処理は、多量の粗原料の貯蔵、取り扱い、ブレンド、粗原料の蒸留及び処理を必要とすることにもなる。 Usually, the blend of raw materials results in a quality-away, for example, after blending these raw materials, the smoke point, either a kerosene blend or a gas oil blend, each meeting cetane number specifications. Other blends have a characteristic value that exceeds the specification value, but this characteristic value is the same as or close to a blend that has characteristics closer to the specification. Such so-called quality failures should preferably be avoided for obvious reasons. However, as mentioned above, such quality failures are not necessarily avoided when optimizing both kerosene and gas oil products in a refinery blending environment. The joint processing of paraffinic raw materials also requires storage, handling, blending, distillation and processing of the raw materials in large quantities.
Ｃｏｏｋｓｏｎ Ｄａｖｉｄ Ｊ等、“Ｏｂｓｒｅｖｅｄ ａｎｄ ｐｒｅｄｉｃｔｅｄ ｐｒｏｐｅｒｔｉｅｓ ｏｆ ｊｅｔ ａｎｄ ｄｉｅｓｅｌ ｆｕｅｌ ｆｏｒｍｕｌａｔｅｄ ｆｒｏｍ ｃｏａｌ ｌｉｑｕｅｆａｃｔｉｏｎ ａｎｄ Ｆｉｓｃｈｅｒ−Ｔｒｏｐｓｃｈ ｆｅｅｄｓｔｏｃｋ”，Ｅｎｅｒｇｙ Ｆｕｅｌｓ １９９２，６，ｐ５８１−５８５には、非粗原料、即ち、コール液化法で得られたケロシン及びガス油フラクションをそれぞれフィッシャー・トロプシュ誘導ケロシン及びガス油とブレンドする方法が記載されている。
本発明の目的は、製品品質の不合格が低減されると共に、ナフテン系又は芳香族系炭化水素含有量を減少させる特別な処置を必要としない、ナフテン系又は芳香族系粗原料からのケロシン及びガス油の製造方法を得ることである。 The object of the present invention is to provide kerosene from naphthenic or aromatic raw materials, which reduces product quality rejection and does not require special treatment to reduce naphthenic or aromatic hydrocarbon content. It is to obtain a method for producing gas oil.
発明の概要
この目的は、以下の方法により達成される。（ａ）ワトソン特性係数Ｋ値が１２．０以下の原油から石油誘導ケロシンフラクション及び石油誘導ガス油フラクションを単離する工程であって、該ケロシンフラクション中のナフタレン含有量が３容量％未満であり、かつ該ガス油フラクションのセタン価が５０未満か又は該ガス油フラクションの密度が８４５ｋｇ／ｍ３を超える場合、石油誘導ケロシンフラクションの煙点は２５ｍｍ未満又は１９ｍｍ未満である該工程、（ｂ）該石油誘導ケロシンフラクションに、得られる混合物中のナフタレン含有量が３容量％未満である場合、該混合物の煙点値が２５ｍｍを超えるか又は１９ｍｍを超えるような量のフィッシャー・トロプシュ誘導ケロシンフラクションを添加する工程、及び（ｃ）該石油誘導ガス油フラクションに、得られる混合物のセタン価が５１を超えるような量のフィッシャー・トロプシュ誘導ガス油フラクションを添加する工程、による前記原油からのケロシン及びガス油製品の製造法。
SUMMARY OF THE INVENTION This object is achieved by the following method. (A) a step of isolating a petroleum-derived kerosene fraction and a petroleum-derived gas oil fraction from crude oil having a Watson characteristic coefficient K value of 12.0 or less, wherein the naphthalene content in the kerosene fraction is less than 3% by volume And when the gas oil fraction has a cetane number of less than 50 or the density of the gas oil fraction is greater than 845 kg / m 3 , the smoke point of the petroleum-derived kerosene fraction is less than 25 mm or less than 19 mm, (b) If the petroleum-derived kerosene fraction has a naphthalene content in the resulting mixture of less than 3% by volume, an amount of Fischer-Tropsch derived kerosene fraction such that the smoke point value of the mixture is greater than 25 mm or greater than 19 mm. The step of adding, and (c) the resulting mixture to the petroleum-derived gas oil fraction Adding a Fischer-Tropsch derived gas oil fraction in an amount such that the cetane number of the product exceeds 51, to produce kerosene and gas oil products from said crude oil.
本発明方法は、パラフィン系粗原料の共同処理の必要性を回避しながら、所望の特性を有するケロシン及びガス油製品を得る簡単な方法を提供する。フレンド成分としてフィッシャー・トロプシュ生成物を使用することにより、ナフテン系及び芳香族系種の粗原料から蒸留した生（ｖｉｒｇｉｎ）ケロシン及び生ガス油も容易に使用できる。こうして、通常、これらフラクション中のナフテン又は芳香族含有量の低下に利用される水素化処理工程の必要性を低減するか、更には該工程を回避できる。 The method of the present invention provides a simple way to obtain kerosene and gas oil products having the desired properties while avoiding the need for joint processing of paraffinic raw materials. By using the Fischer-Tropsch product as a friend component, raw kerosene and raw gas oil distilled from crude raw materials of naphthenic and aromatic species can also be easily used. In this way, the need for a hydrotreatment step, usually used to lower the naphthene or aromatic content in these fractions, can be reduced or even avoided.
更なる利点は、ケロシンの他の製品特性が向上することである。例えば該ケロシンの高い熱量のため、水素含有量が増大する。また熱安定性も向上する。 A further advantage is that other product properties of kerosene are improved. For example, the high heat content of the kerosene increases the hydrogen content. Thermal stability is also improved.
また生ナフテン系ガス油をフィッシャー・トロプシュ誘導ガス油とブレンド後、セタン価以外の他のガス油特性も同様に向上する。例えば熱安定性が向上し、密度が低下し、また硫黄及び芳香族含有量は、カテゴリー４のディーゼル等級用の自動車メーカーによるＷｏｒｌｄ Ｗｉｄｅ Ｆｕｅｌ Ｃｈａｒｔｅｒ（２００２年改訂版）の要求どおりに低下する。 Also, after blending raw naphthenic gas oil with Fischer-Tropsch derived gas oil, other gas oil properties other than cetane number are improved as well. For example, thermal stability is improved, density is reduced, and sulfur and aromatic content is reduced as required by World Wide Fuel Charter (revised 2002) by Category 4 diesel grade automakers.
原油は、１２．０以下のワトソン特性係数Ｋ値を特徴とする。このＫ値はＡＰＩ技術データブック（セクション２ 特徴化）に記載の式及びノモグラムに従って計算される。このような低Ｋ値を有する原油の例は、西アフリカ粗原料、例えばＦｏｒｃａｄｏｓ及びＮｉｇｅｒｉａｎ Ｌｉｇｈｔ，Ｆａｒ Ｅａｓｔ粗原料、例えばＣｈａｍｐｉｏｎ Ｅｘｐｏｒｔ，Ｌａｂｕａｎ ａｎｄ Ｍｉｒｉ Ｌｉｇｈｔ，北海粗原料、例えばデンマーク（ＤＵＣ），Ｔｒｏｌｌ，Ｇｒｙｐｈｏｎ及びＡｌｂａ粗原料、南米粗原料、例えばＴｉａ Ｊｕａｎａ Ｐｅｓａｄｏ，Ｎａｃｈｅｑｕｅｒｏ及びＭａｙａである。本発明方法で得られるガス油及びケロシン製品は、Ｋ値が１２．０以下の粗原料に対し、好ましくは５０重量％を超え、更に好ましくは７０重量％を超え、最も好ましくは９０重量％である。 Crude oil is characterized by a Watson characteristic coefficient K value of 12.0 or less. This K value is calculated according to the formula and nomogram described in the API technical data book (section 2 characterization). Examples of crude oils having such low K values include West African crudes such as Forcados and Nigerian Light, Far East crudes such as Champion Export, Labuan and Miri Light, North Sea crudes such as Denmark (DUC), Troll, Gryphon. And Alba crude materials, South American crude materials such as Tia Juana Pesado, Naquequero and Maya. The gas oil and kerosene product obtained by the method of the present invention is preferably more than 50% by weight, more preferably more than 70% by weight, and most preferably 90% by weight with respect to the crude material having a K value of 12.0 or less. is there.
原油からは、好ましくは蒸留により、石油誘導ケロシン及びガス油が単離される。この種の蒸留は、製油所操作に精通する当業者に周知の方法により常圧蒸留塔で行うことが好ましい。蒸留により単離され、他の転化処理を行っていないフラクションは、生蒸留物フラクションと言う。 Petroleum-derived kerosene and gas oil are isolated from the crude oil, preferably by distillation. This type of distillation is preferably carried out in an atmospheric distillation column by methods well known to those skilled in the art of refinery operations. The fraction isolated by distillation and not subjected to other conversion treatments is called the raw distillate fraction.
この石油誘導ケロシンフラクションのＡＳＴＭ Ｄ８６のＩＢＰは好ましくは、１４０〜２００℃の範囲で、最終沸点は２００〜最大３００℃の範囲である。
石油誘導ガス油フラクションのＡＳＴＭ Ｄ８６のＩＢＰは好ましくは、２５０〜３００℃の範囲で、ＦＢＰは３４０〜３８０℃の範囲である。
The petroleum-derived kerosene fraction ASTM D86 IBP is preferably in the range of 140-200 ° C and the final boiling point is in the range of 200-up to 300 ° C.
The IBP of the petroleum-derived gas oil fraction ASTM D86 is preferably in the range of 250-300 ° C and the FBP is in the range of 340-380 ° C.
フィッシャー・トロプシュ誘導ケロシン及びガス油フラクションは、好適には（水素化分解した）フィッシャー・トロプシュ合成生成物から得られる。フィッシャー・トロプシュ誘導ケロシン及びガス油については、ＥＰ−Ａ−５８３８３６、ＷＯ−Ａ−９７１４７６８、ＷＯ−Ａ−９７１４７６９、ＷＯ−Ａ−０１１１１６、ＷＯ−Ａ−０１１１１７、ＷＯ−Ａ−０１８３４０６、ＷＯ−Ａ−０１８３６４８、ＷＯ−Ａ−０１８３６４７、ＷＯ−Ａ−０１８３６４１、ＷＯ−Ａ−００２０５３５、ＷＯ−Ａ−００２０５３４、ＥＰ−Ａ−１１０１８１３、ＵＳ−Ａ−５３７８３４８及びＵＳ−Ａ−６２０４４２６に記載されている。 Fischer-Tropsch derived kerosene and gas oil fractions are preferably obtained from (hydrocracked) Fischer-Tropsch synthesis products. For Fischer-Tropsch derived kerosene and gas oil, see EP-A-58383, WO-A-9714768, WO-A-9714769, WO-A-011116, WO-A-011117, WO-A-0183406, WO-A. -0183648, WO-A-0183647, WO-A-01833641, WO-A-0020535, WO-A-0020534, EP-A-1101813, US-A-5378348 and US-A-6204426.
フィッシャー・トロプシュ誘導ケロシンは、好適には９０重量％以上、更に好ましくは９５重量％以上のイソ及び線状パラフィンからなる。イソパラフィンとノーマルパラフィンとの重量比は、好適には０．３を超える。この比は１２以下である。この比は好適には２〜６の範囲である。この比の実際の値は、フィッシャー・トロプシュ合成生成物からフィッシャー・トロプシュ誘導ケロシン又はガス油を製造するために用いた水素化転化法により部分的に測定される。若干の環式パラフィンが存在してもよい。 Fischer-Tropsch derived kerosene is preferably composed of 90 wt% or more, more preferably 95 wt% or more of iso and linear paraffin. The weight ratio of isoparaffin to normal paraffin is preferably above 0.3. This ratio is 12 or less. This ratio is preferably in the range of 2-6. The actual value of this ratio is measured in part by the hydroconversion process used to produce Fischer-Tropsch derived kerosene or gas oil from the Fischer-Tropsch synthesis product. Some cyclic paraffin may be present.
フィッシャー・トロプシュ誘導ケロシンの煙点は２５ｍｍを超え、好ましくは５０ｍｍを超え、ＡＳＴＭ Ｄ８６蒸留曲線は、大部分が通常のケロシン沸点範囲である約１５０〜２００℃の範囲にあり、密度は１５℃で約７４０ｋｇ／ｍ３であり、また硫黄及び芳香族の水準はゼロ（検出限界未満）である。 Fischer-Tropsch derived kerosene has a smoke point of greater than 25 mm, preferably greater than 50 mm, and the ASTM D86 distillation curve is in the range of about 150-200 ° C., mostly the normal kerosene boiling range, and the density is 15 ° C. It is about 740 kg / m 3 and the sulfur and aromatic levels are zero (below the detection limit).
フィッシャー・トロプシュ誘導ガス油は、好適には９０重量％以上、更に好ましくは９５重量％以上のイソ及び線状パラフィンからなる。イソパラフィンとノーマルパラフィンとの重量比は、好適には０．３を超える。この比は１２以下である。この比は好適には２〜６の範囲である。この比の実際の値は、フィッシャー・トロプシュ合成生成物からフィッシャー・トロプシュ誘導ケロシン又はガス油を製造するために用いた水素化転化法により部分的に測定される。若干の環式パラフィンが存在してもよい。 The Fischer-Tropsch derived gas oil is preferably composed of 90% by weight or more, more preferably 95% by weight or more of iso and linear paraffin. The weight ratio of isoparaffin to normal paraffin is preferably above 0.3. This ratio is 12 or less. This ratio is preferably in the range of 2-6. The actual value of this ratio is measured in part by the hydroconversion process used to produce Fischer-Tropsch derived kerosene or gas oil from the Fischer-Tropsch synthesis product. Some cyclic paraffin may be present.
フィッシャー・トロプシュ誘導ガス油のセタン価は６０を超え、好ましくは７０を超え、ＡＳＴＭ Ｄ８６蒸留曲線は、大部分が通常のガス油沸点範囲である約２００〜４００℃の範囲にある。フィッシャー・トロプシュ誘導ガス油のＴ９０容量％は３００〜４００℃の範囲であり、密度は１５℃で約０．７６〜０．７９ｇ／ｃｍ３の範囲にあり、また粘度は４０℃で約２．５〜４．０ｃＳｔの範囲である。 The cetane number of Fischer-Tropsch derived gas oil is greater than 60, preferably greater than 70, and the ASTM D86 distillation curve is in the range of about 200-400 ° C., which is mostly the normal gas oil boiling range. Fischer-Tropsch derived gas oil has a T90 volume% in the range of 300-400 ° C., a density in the range of about 0.76-0.79 g / cm 3 at 15 ° C., and a viscosity of about 2. It is in the range of 5 to 4.0 cSt.
ブレンドは、いわゆるインラインブレンド、オンラインブレンド又はバッチ式ブレンドのいずれかで実施できる。これは自動化の水準に依存する。バッチ式ブレンドでは、石油誘導フラクションとフィッシャー・トロプシュ誘導フラクションとのブレンドは、まず混合し、次いで貯蔵容器に供給してから、この最終ブレンドを船、鉄道、自動車、その他の輸送手段に供給する。貯蔵容器への供給物の所望の製品品質、即ち、煙点又はセタン価を測定し、品質の不合格を最小化するため、この特性値が所定範囲内に維持されるように、これらブレンド成分を調節する。 The blending can be done either in so-called in-line blending, online blending or batch blending. This depends on the level of automation. In a batch blend, a blend of petroleum derived fractions and Fischer-Tropsch derived fractions are first mixed and then fed to a storage vessel before the final blend is fed to a ship, rail, car, or other vehicle. In order to measure the desired product quality of the feed to the storage container, i.e. smoke point or cetane number, and minimize the quality failure, these blend components are maintained so that this property value is maintained within a predetermined range. Adjust.
インラインブレンドを適用する場合、中間の貯蔵容器は利用するが、ブレンド比／容量は品質測定器（ＱＭＩ）により自動的にインラインで調節され、ブレンドは直接、船、鉄道又は自動車に放出する。ブレンドの品質又は性能の測定及び管理は周知技術、例えば近赤外線（ＮＩＲ）により実施できる。好適な方法はＷＯ−Ａ−０２０６９０５に記載されている。
本発明を以下の非限定的実施例により説明する。これらの実施例は公知のブレンド公式を用いた計算に基づく。
When applying an in-line blend, an intermediate storage vessel is utilized, but the blend ratio / capacity is automatically adjusted in-line by a quality meter (QMI) and the blend is released directly to the ship, rail or car. Measurement and control of blend quality or performance can be performed by well-known techniques such as near infrared (NIR). A suitable method is described in WO-A-0206905.
The invention is illustrated by the following non-limiting examples. These examples are based on calculations using known blend formulas.
例１
ＵＯＰＫ値１１．５のナフテン系粗原料を蒸留し、ナフサフラクション、ケロシンフラクション及びガス油フラクションを得た。これら異なるフラクションの特性を第１表に示す。
Example 1
A naphthenic crude material having a UOPK value of 11.5 was distilled to obtain a naphtha fraction, a kerosene fraction, and a gas oil fraction. The characteristics of these different fractions are shown in Table 1.
例２
例１を繰り返した。更に、ワトソンＫ特性係数値が１２．３のパラフィン系粗原料を蒸留して、第１表に示すケロシン及びガス油の特性を改良するブレンド成分を得た。使用したパラフィン系粗原料の量は、第１表の各フラクションを所望の規格に適合させて、ケロシンとガス油との混合物を得るのに十分な量とした。これらブレンドの特性を第２表に示す。
Example 2
Example 1 was repeated. Further, the paraffinic raw material having a Watson K characteristic coefficient value of 12.3 was distilled to obtain a blend component for improving the characteristics of kerosene and gas oil shown in Table 1. The amount of the crude paraffinic raw material used was an amount sufficient to obtain a mixture of kerosene and gas oil by adapting each fraction in Table 1 to a desired standard. The properties of these blends are shown in Table 2.
第２表から判るように、品質の不合格は、ブレンドから製造したケロシンの煙点や、セタン価及び密度のような若干のガス油品質で観察された。
As can be seen from Table 2, quality failures were observed with some gas oil qualities such as the smoke point and cetane number and density of kerosene made from the blend.
例３
例１を繰り返した。第１表のケロシン及びガス油フラクションにフィッシャー・トロプシュケロシン及びガス油をそれぞれ、煙点及びセタン価規格に適合するのに十分な量で添加した。得られた特性を第４表に示す。
Example 3
Example 1 was repeated. Fischer-Tropsch kerosene and gas oil were added to the kerosene and gas oil fractions in Table 1 in amounts sufficient to meet smoke point and cetane number specifications, respectively. The obtained characteristics are shown in Table 4.
Claims (6)
The method according to any one of claims 1 to 5, wherein the Fischer-Tropsch derived kerosene has an isoparaffin to normal paraffin weight ratio in the range of 2-6.
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| PCT/EP2004/050819 WO2004104142A1 (en) | 2003-05-22 | 2004-05-17 | Process to upgrade kerosenes and a gasoils from naphthenic and aromatic crude petroleum sources |
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2004
- 2004-05-17 AT AT04741581T patent/ATE380855T1/en not_active IP Right Cessation
- 2004-05-17 JP JP2006530200A patent/JP5478806B2/en not_active Expired - Lifetime
- 2004-05-17 DK DK04741581T patent/DK1627028T3/en active
- 2004-05-17 US US10/557,870 patent/US20070021636A1/en not_active Abandoned
- 2004-05-17 DE DE602004010648T patent/DE602004010648T2/en not_active Expired - Lifetime
- 2004-05-17 CN CNB2004800140603A patent/CN100362085C/en not_active Expired - Lifetime
- 2004-05-17 EP EP04741581A patent/EP1627028B1/en not_active Expired - Lifetime
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009520854A (en) * | 2005-12-22 | 2009-05-28 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Fuel composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5478806B2 (en) | 2014-04-23 |
| CN1795258A (en) | 2006-06-28 |
| EP1627028B1 (en) | 2007-12-12 |
| ATE380855T1 (en) | 2007-12-15 |
| DE602004010648T2 (en) | 2008-12-11 |
| DK1627028T3 (en) | 2008-03-17 |
| WO2004104142A1 (en) | 2004-12-02 |
| CN100362085C (en) | 2008-01-16 |
| US20070021636A1 (en) | 2007-01-25 |
| DE602004010648D1 (en) | 2008-01-24 |
| EP1627028A1 (en) | 2006-02-22 |
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