JP4943522B2 - High viscosity base oil and method for producing high viscosity base oil - Google Patents

High viscosity base oil and method for producing high viscosity base oil Download PDF

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JP4943522B2
JP4943522B2 JP2010027273A JP2010027273A JP4943522B2 JP 4943522 B2 JP4943522 B2 JP 4943522B2 JP 2010027273 A JP2010027273 A JP 2010027273A JP 2010027273 A JP2010027273 A JP 2010027273A JP 4943522 B2 JP4943522 B2 JP 4943522B2
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欣之 森島
憲司 藤野
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Jx日鉱日石エネルギー株式会社
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02Petroleum fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G53/00Treatment of hydrocarbon oils in the absence of hydrogen, by two or more refining processes
    • C10G53/02Treatment of hydrocarbon oils in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04Treatment of hydrocarbon oils in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C10G53/06Treatment of hydrocarbon oils in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/30Physical properties of feedstocks or products
    • C10G2300/301Boiling range
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/30Physical properties of feedstocks or products
    • C10G2300/302Viscosity
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/30Physical properties of feedstocks or products
    • C10G2300/304Pour point, cloud point, cold flow properties
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/44Solvents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10Lubricating oil

Description

本発明は、天然ゴム又は合成ゴムに添加するプロセス油並びに高粘度基油及びこれらの製造方法に関し、特に、多環芳香族化合物の含有量が少ないことにより毒性及び発ガン性がなく、取り扱いが容易なゴムプロセス油及びその製造方法に関するものである。   The present invention relates to process oils and high-viscosity base oils added to natural rubber or synthetic rubber, and methods for producing them, and in particular, because of the low content of polycyclic aromatic compounds, there is no toxicity and carcinogenicity, and handling The present invention relates to an easy rubber process oil and a method for producing the same.
ゴムプロセス油は、ゴムポリマー組織に対する浸透性を用いて、混練、押出し、成形などのゴム製造操作を容易にするために用いられる。又、ゴム製品の物理的性質を改善するためにも用いられる。このようなゴムプロセス油には、ゴムに対する好適な親和性を有することが必要である。一方、加工するゴムには天然ゴム及び合成ゴムがあり、合成ゴムには様々な種類のものがある。このようなもののうち、特に天然ゴム及びスチレン−ブタジエンゴム(SBR)が多量に用いられており、これらには芳香族炭化水素を多量に含みゴムに高い親和性を有するゴムプロセス油が一般的に用いられる。   Rubber process oils are used to facilitate rubber manufacturing operations such as kneading, extrusion, molding, etc., using their permeability to rubber polymer structures. It is also used to improve the physical properties of rubber products. Such rubber process oils must have a suitable affinity for rubber. On the other hand, the rubber to be processed includes natural rubber and synthetic rubber, and there are various types of synthetic rubber. Of these, natural rubber and styrene-butadiene rubber (SBR) are used in large quantities, and rubber process oils containing a large amount of aromatic hydrocarbons and having high affinity for rubber are generally used. Used.
このようなゴムプロセス油を得るために、原油の減圧蒸留によって得られる潤滑油留分や、または減圧蒸留残油を脱瀝した後、必要に応じて脱ろう処理や水素化精製処理することによって得られる油を芳香族炭化水素に親和性を有する溶剤で油を抽出処理することによって得られる油が用いられる。この様にして得られるゴムプロセス油は、カラムクロマトグラフィによれば70〜99%の芳香族化合物を含有し、環分析(ASTM D2140)によれば%CA値は20〜50%であり、イギリス石油協会の規定による多環芳香族化合物(PCA)の含量に相当するジメチルスルホキシド(DMSO)抽出分を5〜25質量%含有する。 In order to obtain such a rubber process oil, the lubricating oil fraction obtained by vacuum distillation of crude oil or the vacuum distillation residual oil is defoamed and then dewaxed or hydrorefined as necessary. Oil obtained by subjecting the obtained oil to extraction treatment with a solvent having affinity for aromatic hydrocarbons is used. Rubber process oil obtained in this way contains 70 to 99 percent of the aromatic compound according to the column chromatography according to the% C A value ring analysis (ASTM D 2140) is 20-50%, United Kingdom It contains 5 to 25% by mass of a dimethyl sulfoxide (DMSO) extract corresponding to the content of polycyclic aromatic compound (PCA) as defined by the Petroleum Institute of Japan.
しかし、近年、PCAの発ガン性が重要視され、ヨーロッパでは、3%以上のDMSO抽出分を含有する油などには有毒表示が義務づけられ、使用を規制する動きがある。従って、ゴムプロセス油のDMSO抽出分を3%未満に減量することが急務となっている。   However, in recent years, the carcinogenicity of PCA has been regarded as important, and in Europe, oil containing 3% or more of DMSO extract is obliged to be toxic and there is a movement to regulate its use. Therefore, there is an urgent need to reduce the DMSO extract of rubber process oil to less than 3%.
DMSO抽出分が3%未満のゴムプロセス油については、特表平6−505524号公報は、減圧蒸留残留分を脱瀝処理し、得られた油を脱ろう処理してDMSO抽出分を3%未満に減少させたゴムプロセス油を製造するプロセスを開示する。上述の油のDMSO抽出分はより低くなっているが、アニリン点が高い。アニリン点は芳香族炭化水素の含量の指標となり、アニリン点が高いことは芳香族炭化水素含量が低いことを意味する。しかし、油中の芳香族炭化水素含量が減少すると、油のゴムに対する親和性が減少する。故に、上記公報に開示されるものでは、ゴムプロセス油に必要な性質、つまり、ゴムポリマーに対するゴムプロセス油の浸透性が低下する。又、最終ゴム製品の物理的状態を満足なものとするのが困難になる。   Regarding rubber process oil having a DMSO extract of less than 3%, Japanese Patent Publication No. 6-505524 discloses dewaxing the residue under reduced pressure distillation and dewaxing the resulting oil to obtain a DMSO extract of 3%. Disclosed is a process for producing a reduced rubber process oil. The DMSO extract of the above oil is lower but has a higher aniline point. The aniline point is an indicator of the aromatic hydrocarbon content, and a high aniline point means a low aromatic hydrocarbon content. However, as the aromatic hydrocarbon content in the oil decreases, the affinity of the oil for rubber decreases. Therefore, in what is disclosed in the above publication, the property required for the rubber process oil, that is, the permeability of the rubber process oil to the rubber polymer is lowered. In addition, it becomes difficult to satisfy the physical state of the final rubber product.
又、特表平7−501346号公報は、非発ガン性ブライトストック抽出物及び/又は脱瀝油並びにその精製プロセスを開示し、変異原性指数(MI)を1以下にするために、MIと相関のある特性を精製の指標とすることを提案している。これにおいては真空蒸留カラム中の残渣の脱瀝によって得られる油又は脱瀝油の抽出処理によって芳香族化合物が減少した油あるいはその脱ろう処理によって得られる油が使用されている。ただし、DMSO抽出分は3%以上と推定される。このような脱瀝油のMIとDMSO抽出分の関係については該特許では発表されてはいない。   In addition, JP 7-501346 A discloses a non-carcinogenic bright stock extract and / or demineralized oil and a purification process thereof, and in order to reduce the mutagenicity index (MI) to 1 or less, MI It has been proposed to use a property that correlates with the above as an index of purification. In this, the oil obtained by dewaxing the residue in the vacuum distillation column, the oil in which the aromatic compound is reduced by the extraction treatment of the defoamed oil, or the oil obtained by the dewaxing treatment thereof is used. However, the DMSO extract is estimated to be 3% or more. The relationship between MI and DMSO extract of such deoiled oil is not disclosed in the patent.
特表平6−505524号公報JP-T 6-505524 特表平7−501346号公報JP 7-501346 A
本発明は、この様な従来技術の問題を解決するためになされたもので、本発明の課題は、安全性が高く、ゴムポリマーに対する浸透性が高い、DMSO抽出分3%未満のゴムプロセス油を製造するための新規でしかも経済性に優れたプロセスを提供することである。
併せて、前記プロセス油の製造工程でプロセス油として有用なエキストラクトと高粘度基油として有用なラフィネートを得て、後者のラフィネートから高粘度基油を製造する方法及び該高粘度基油を提供することである。
The present invention has been made in order to solve such problems of the prior art, and the object of the present invention is to provide a rubber process oil having a high safety and high permeability to a rubber polymer and having a DMSO extract of less than 3%. Is to provide a new and economical process for producing
In addition, an extract useful as a process oil and a raffinate useful as a high-viscosity base oil are obtained in the process oil production process, and a method for producing a high-viscosity base oil from the latter raffinate and the high-viscosity base oil are provided. It is to be.
上記目的を達成するために、本発明者らは鋭意研究を重ねた結果、特定の蒸留・溶剤精製条件下でDMSO抽出分が3%未満になることを見いだし、本発明に至った。
上記知見に基づく本発明は、
.プロセス油として有用なエキストラクトと高粘度基油として有用なラフィネートを溶剤精製で製造する工程において、減圧蒸留を留出油の終点が常圧換算580℃以上となる条件にておこない、得られた残渣油を脱瀝油の残留炭素分が1.6%以下になる条件で脱瀝し、脱瀝油を溶剤精製に供して、溶剤としてフルフラール、フェノール及びN−メチル−2−ピロリドンから1つあるいはそれ以上を選択し用い、エキストラクト収率が35〜60%になる条件で行うことにより得たラフィネートの脱鑞後に得られる40℃の動粘度400mm2/s以上700mm2/s以下である高粘度基油の流動点が−5℃以下、粘度指数が95以上であることを特徴とする高粘度基油の製造方法、
.減圧蒸留を留出油の終点が常圧換算580℃以上となる条件にておこない、得られた残渣油を脱瀝油の残留炭素分が1.6%以下になる条件で脱瀝し、脱瀝油を溶剤精製に供して、溶剤としてフルフラール、フェノール及びN−メチル−2−ピロリドンから1つあるいはそれ以上を選択し用い、エキストラクト収率が35〜60%になる条件で行うことにより得られたラフィネートの脱鑞後に得られる40℃の動粘度400mm2/s以上700mm2/s以下であり、流動点が−5℃以下、粘度指数が95以上である高粘度基油、
を提供するものである。
In order to achieve the above object, the present inventors have conducted extensive research and found that the DMSO extract is less than 3% under specific distillation / solvent refining conditions, leading to the present invention.
The present invention based on the above findings
1 . In the process of producing an extract useful as a process oil and a raffinate useful as a high-viscosity base oil by solvent refining, vacuum distillation was performed under conditions where the end point of the distillate oil was 580 ° C. or higher in terms of atmospheric pressure. The residual oil is degassed under the condition that the residual carbon content of the deoiled oil is 1.6% or less, the deoiled oil is subjected to solvent refining, and one of furfural, phenol and N-methyl-2-pyrrolidone is used as a solvent. Alternatively, the kinematic viscosity at 40 ° C. obtained after defatting of the raffinate obtained by selecting and using it under the condition that the extract yield is 35 to 60% is 400 mm 2 / s to 700 mm 2 / s. A high viscosity base oil having a pour point of −5 ° C. or less and a viscosity index of 95 or more,
2 . Distillation under reduced pressure is carried out under the condition that the end point of the distillate is 580 ° C. or higher in terms of atmospheric pressure, and the resulting residual oil is dewaxed under the condition that the residual carbon content of the deoiled oil is 1.6% or less. It is obtained by subjecting camellia oil to solvent refining, selecting one or more of furfural, phenol and N-methyl-2-pyrrolidone as the solvent and using it under conditions where the extract yield is 35-60%. A high-viscosity base oil having a kinematic viscosity at 40 ° C. of 400 mm 2 / s or more and 700 mm 2 / s or less obtained after degassing of the obtained raffinate, a pour point of −5 ° C. or less, and a viscosity index of 95 or more;
Is to provide.
本発明の製造方法によって、安全性が高くゴムポリマーに対する浸透性が高いプロセス油と、高粘度基油とを同時にしかも経済的に得ることができる。   According to the production method of the present invention, a process oil having high safety and high permeability to a rubber polymer and a high viscosity base oil can be obtained simultaneously and economically.
以下、本発明をさらに詳細に説明する。プロセス油は、一般に、原油から得られる潤滑油留分を原料として調製することができる。潤滑油留分は、原油を常圧蒸留した後の残留油を減圧蒸留した留分として、あるいは、原油を減圧蒸留した残留油を脱瀝した脱瀝油として得ることができる。潤滑油留分から各構成成分を分離する方法として溶剤抽出があり、油の溶剤抽出において、芳香族炭化水素化合物に選択的親和性を有する溶剤を用いれば、芳香族炭化水素を潤滑油留分から分離することができる。しかし、芳香族炭化水素化合物に選択的親和性を有する溶剤は、多環芳香族化合物(PCA)に対する親和性がより高いので、一般的な抽出操作によって芳香族炭化水素化合物を抽出すると、多量のPCAが含まれることになる。この抽出油からPCAを除去することができれば、好適なプロセス油が得られるが、一般には困難で、経済的でない。本願発明者らは、PCAの量が少ない油の製造プロセスについて研究した結果、特定の減圧蒸留条件及び溶剤精製条件を組み合わせることによって効果的に製造できることを見出した。   Hereinafter, the present invention will be described in more detail. Process oils can generally be prepared from a lubricating oil fraction obtained from crude oil. The lubricating oil fraction can be obtained as a fraction obtained by distilling the residual oil after atmospheric distillation of the crude oil, or as a degassed oil obtained by removing the residual oil obtained by distilling the crude oil under reduced pressure. Solvent extraction is a method for separating each component from the lubricating oil fraction. If a solvent having a selective affinity for aromatic hydrocarbon compounds is used in the solvent extraction of oil, the aromatic hydrocarbon is separated from the lubricating oil fraction. can do. However, a solvent having a selective affinity for an aromatic hydrocarbon compound has a higher affinity for a polycyclic aromatic compound (PCA). Therefore, when an aromatic hydrocarbon compound is extracted by a general extraction operation, a large amount of the solvent is used. PCA will be included. If PCA can be removed from this extracted oil, a suitable process oil can be obtained, but it is generally difficult and not economical. As a result of studying a process for producing an oil having a small amount of PCA, the present inventors have found that it can be effectively produced by combining specific vacuum distillation conditions and solvent purification conditions.
本発明のゴムプロセス油の製造方法は、減圧蒸留によって原油から得られる蒸留残油の脱瀝によって得られる脱瀝油留分を、芳香族炭化水素に対して親和性を有する溶剤で処理し、溶剤と抽出物(エキストラクト)とを分離回収するものである。なお、この場合の溶剤抽出の際に分離されるラフィネートについては、必要に応じて水素化処理・脱ろう処理を行い高粘度基油として利用できる。   The method for producing a rubber process oil according to the present invention comprises treating a defoamed oil fraction obtained by defoaming a distillation residue obtained from crude oil by distillation under reduced pressure with a solvent having affinity for aromatic hydrocarbons, A solvent and an extract (extract) are separated and recovered. In addition, about the raffinate isolate | separated in the case of solvent extraction in this case, a hydrogenation process and a dewaxing process can be performed as needed and it can utilize as a high-viscosity base oil.
本発明の特定の製造方法によって得られるプロセス油は、多環芳香族化合物の含量は少なく芳香族炭化水素は豊富なゴムプロセス油として最も好適なものである。本願において用いられるDMSO抽出分は、イギリス石油協会の規定によるIP346法に従ってDMSO(ジメチルスルホキシド)により抽出される芳香族化合物の含量を言う。従来のPCAの規定には3つ以上の環を有する芳香族化合物を言うものもあるが、IP346法は油材のPCA含量の決定法として認められた一般的且つ標準的な方法である。   The process oil obtained by the specific production method of the present invention is most suitable as a rubber process oil having a low content of polycyclic aromatic compounds and abundant aromatic hydrocarbons. The DMSO extract used in the present application refers to the content of aromatic compounds extracted with DMSO (dimethyl sulfoxide) according to the IP346 method defined by the British Petroleum Institute. Although some conventional PCA regulations refer to aromatic compounds having three or more rings, the IP346 method is a recognized and standard method for determining the PCA content of oils.
本発明で得られるゴムプロセス油は、多環芳香族化合物の含量は極めて低いが、クロマトで測定される芳香族炭化水素含量は従来のゴムプロセス油とくらべてもほとんど低下していないので、SBRゴム、天然ゴムなどのゴムに対する浸透性が高くゴムの加工性が低下しない。加えて、本発明のゴムプロセス油は、多量のPCAを含んだ従来のプロセス油で処理して得られるゴム製品とほぼ同レベルの物理的特性を発揮可能なゴムを得るに十分な材料である。   The rubber process oil obtained in the present invention has a very low content of polycyclic aromatic compounds, but the aromatic hydrocarbon content measured by chromatography is hardly decreased as compared with the conventional rubber process oil. High penetrability to rubber such as rubber and natural rubber. In addition, the rubber process oil of the present invention is a material sufficient to obtain a rubber that can exhibit almost the same physical properties as a rubber product obtained by processing with a conventional process oil containing a large amount of PCA. .
以下に、本発明の製造方法の実施形態を詳細に説明する。本発明のゴムプロセス油を生成するために、原油の常圧蒸留残渣を所定の条件の下に減圧蒸留した減圧蒸留残渣の脱瀝によって得られる脱瀝油留分を、芳香族炭化水素に対して選択的親和性を有する溶剤で処理し、ラフィネートを除去することによって、エキストラクトを溶剤との混合物の形態で得る。この溶剤を除くことによりゴムプロセス油が得られる。   Hereinafter, embodiments of the production method of the present invention will be described in detail. In order to produce the rubber process oil of the present invention, a degassed oil fraction obtained by degassing a vacuum distillation residue obtained by subjecting a crude oil atmospheric distillation residue to vacuum distillation under a predetermined condition is used as an aromatic hydrocarbon. The extract is obtained in the form of a mixture with the solvent by treating with a solvent having a selective affinity and removing the raffinate. By removing this solvent, a rubber process oil can be obtained.
原油としては、パラフィン原油、ナフテン原油などのような種々の原油を用いることができ、あらゆる種類の原油の常圧蒸留残渣を減圧蒸留した減圧蒸留残渣の脱瀝によって得られる脱瀝油を用いることができる。   As crude oil, various crude oils such as paraffin crude oil, naphthenic crude oil, etc. can be used, and defoamed oil obtained by desulfurization of vacuum distillation residue obtained by distilling atmospheric distillation residue of all kinds of crude oil under reduced pressure. Can do.
減圧蒸留は、留出油の終点が常圧換算580℃以上となる条件あるいは残渣の初留が450℃以上となる条件にて行う。終点がこの温度より低いと、得られたエキストラクトのDMSO抽出分が高くなるため好ましくない。   The distillation under reduced pressure is carried out under conditions where the end point of the distillate is 580 ° C. or higher in terms of atmospheric pressure, or under conditions where the initial distillation of the residue is 450 ° C. or higher. When the end point is lower than this temperature, the DMSO extract of the obtained extract becomes high, which is not preferable.
次に、減圧蒸留で得られた残渣油を脱瀝油の残留炭素分が1.6%以下になる条件で脱瀝する。残留炭素分が1.6%を超えるとエキストラクト中のPCAが増加する他、得られる高粘度基油の酸化安定性に悪影響を及ぼすため好ましくない。   Next, the residual oil obtained by distillation under reduced pressure is degassed under the condition that the residual carbon content of the degassed oil is 1.6% or less. If the residual carbon content exceeds 1.6%, the PCA in the extract increases, and the oxidation stability of the resulting high viscosity base oil is adversely affected.
上記の方法で得られた脱瀝油を芳香族炭化水素に親和性を有する溶剤で抽出する溶剤精製処理を行う。芳香族炭化水素に選択的親和性を有する溶剤としては、フルフラール、フェノール及びN−メチル−2−ピロリドンから1つあるいはそれ以上を選択して用いることができる。   A solvent refining process is performed in which the deoiled oil obtained by the above method is extracted with a solvent having affinity for aromatic hydrocarbons. As the solvent having selective affinity for the aromatic hydrocarbon, one or more selected from furfural, phenol and N-methyl-2-pyrrolidone can be used.
この溶剤精製工程においてはエキストラクトの収率が35〜60%となる条件で行う。エキストラクト収率が35%未満となる条件では、DMSO抽出分が3%未満にならず、一方、エキストラクト収率が60%を超えると、エキストラクト中の芳香族分が減少する他、ラフィネートとして得られる高粘度基油の収率が低くなり経済性が悪くなるため好ましくない。   In this solvent refining process, the extract yield is 35 to 60%. When the extract yield is less than 35%, the DMSO extract is not less than 3%. On the other hand, when the extract yield exceeds 60%, the aromatic content in the extract is reduced and raffinate. Since the yield of the high-viscosity base oil obtained as the above becomes low and the economic efficiency deteriorates, it is not preferable.
エキストラクト収率を上記の範囲とするための具体的な抽出条件は、脱瀝油組成にもよるため一義的に決めることはできないが、溶剤比、圧力、温度等によって調整することが可能である。一般的には、温度60℃以上、好ましくは60〜155℃、溶剤/油比(容積比)=2/1〜7/1程度で溶剤と接触させ、ラフィネートを除去する。このラフィネートは、さらに必要に応じて水素化処理・脱ろう工程を行うことによって高粘度潤滑基油として使用することができる。   The specific extraction conditions for bringing the extract yield within the above range cannot be determined uniquely because it depends on the deoiled oil composition, but can be adjusted by the solvent ratio, pressure, temperature, etc. is there. In general, the raffinate is removed by contacting with a solvent at a temperature of 60 ° C. or higher, preferably 60 to 155 ° C., solvent / oil ratio (volume ratio) = 2/1 to 7/1. The raffinate can be used as a high-viscosity lubricating base oil by performing a hydrotreating / dewaxing step as necessary.
本発明においてプロセス油として有用なエキストラクトは、100℃の動粘度50〜100mm2/s、%CA(ASTM D2140)15〜35%、DMSO抽出分(IP346)3%未満、アニリン点90℃以下、クロマトによる芳香族分60重量%〜95重量%、Mw(重量平均分子量)が650以上のものである。また変異原性指数MIが1.0未満のものである。 The extract useful as a process oil in the present invention has a kinematic viscosity at 100 ° C. of 50 to 100 mm 2 / s,% C A (ASTM D2140) 15 to 35%, DMSO extract (IP346) less than 3%, aniline point 90 ° C. Hereinafter, the aromatic content is 60 wt% to 95 wt% by chromatography, and the Mw (weight average molecular weight) is 650 or more. The mutagenicity index MI is less than 1.0.
100℃の動粘度が100mm2/sを超えるとプロセス油として使用する場合の作業性が低下するとともにプロセス油としてのゴムに対する粘度低下効果が十分でなくなる。一方、100℃の動粘度が50mm2/s未満では、DMSO抽出分を3%未満にすることが著しく困難になり、精製工程の経済性が悪くなるため好ましくない。 When the kinematic viscosity at 100 ° C. exceeds 100 mm 2 / s, workability when used as a process oil is lowered and the effect of reducing the viscosity of the rubber as the process oil is not sufficient. On the other hand, if the kinematic viscosity at 100 ° C. is less than 50 mm 2 / s, it is extremely difficult to make the DMSO extract less than 3%, and the economical efficiency of the purification process is deteriorated.
また、%CA(ASTM D2140)が15%未満の場合、ゴムプロセス油を用いてゴムを製造することが困難になったりゴム製品の物理特性が低下する恐れがある。他方、%CA(ASTM D2140)が35%を超える場合、やはりゴム製品の物理特性が低下する恐れがあり、また、DMSO抽出分を3%未満にすることが著しく困難になり、精製工程の経済性が悪くなるため好ましくない。 Further, when% C A (ASTM D2140) is less than 15%, it may be difficult to produce rubber using the rubber process oil, or physical properties of the rubber product may be deteriorated. On the other hand, if% C A (ASTM D2140) exceeds 35%, the physical properties of the rubber product may also deteriorate, and it will be extremely difficult to make the DMSO extract less than 3%. This is not preferable because the economy is deteriorated.
DMSO抽出分(IP346)については、既に説明したように3%以上となると発ガン性の危険があるとしてEUの規制対象になることから、3%未満になるようにする。   The DMSO extract (IP 346) is less than 3% because it is subject to EU regulation if there is a risk of carcinogenicity if it exceeds 3% as already explained.
アニリン点が90℃を超えると、ゴムとの相溶性が低下するため好ましくない。   If the aniline point exceeds 90 ° C., the compatibility with the rubber decreases, which is not preferable.
また、クロマトによる芳香族分が60%未満の場合、ゴムプロセス油を用いてゴムを製造することが困難になったりゴム製品の物理特性が低下する恐れがある。他方、クロマトによる芳香族分が95%を超える場合、やはりゴム製品の物理特性が低下する恐れがあり、また、DMSO抽出分を3%未満にすることが著しく困難になり、精製工程の経済性が悪くなるため好ましくない。   Moreover, when the aromatic content by chromatography is less than 60%, it may be difficult to produce rubber using the rubber process oil, or the physical characteristics of the rubber product may be deteriorated. On the other hand, if the aromatic content by chromatography exceeds 95%, the physical properties of the rubber product may also deteriorate, and it will be extremely difficult to make the DMSO extract less than 3%. Is not preferable because of worsening.
Mw(重量平均分子量)が650未満であるとやはりDMSO抽出分を3%未満にすることが著しく困難になり、精製工程の経済性が悪くなるため好ましくない。変異原性指数MIが1.0以上と発ガン性の可能性が生じるので好ましくない。   If the Mw (weight average molecular weight) is less than 650, it will be extremely difficult to make the DMSO extract less than 3%, and the economical efficiency of the purification process will be unfavorable. A mutagenicity index MI of 1.0 or more is not preferable because of the possibility of carcinogenicity.
また、DSCで測定したガラス転移点はゴム製品への低ロス付与性能が向上することから、−70℃以上が好ましい。また、低温性能の点から−20℃以下が好ましい。   Further, the glass transition point measured by DSC is preferably −70 ° C. or higher because the low loss imparting performance to rubber products is improved. Moreover, -20 degrees C or less is preferable from the point of low-temperature performance.
また、溶剤精製工程によって得られるラフィネートはさらに必要に応じて水添・脱ろう工程を行うことにより、流動点−5℃以下、粘度指数95以上、動粘度(40℃)400mm2/s以上700mm2/s以下である高粘度基油を得ることができる。 In addition, the raffinate obtained by the solvent refining process is further subjected to a hydrogenation / dewaxing process, if necessary, so that the pour point is −5 ° C. or less, the viscosity index is 95 or more, and the kinematic viscosity (40 ° C.) is 400 mm 2 / s or more and 700 mm. A high viscosity base oil of 2 / s or less can be obtained.
本発明の製造方法を用いた場合、1段の溶剤抽出によって得られるエキストラクトを直接製品として用いることができるので、2段溶剤抽出、または水素化処理などの2次処理を行う方法に比べて製造コストが削減される。また、非発ガン性のプロセス油と粘度指数が通常より高い高粘度基油を同時に得ることができるため、経済性にも優れている。   When the production method of the present invention is used, the extract obtained by the first-stage solvent extraction can be directly used as a product. Therefore, compared to the method of performing the second-stage solvent extraction or the secondary treatment such as hydrogenation. Manufacturing costs are reduced. Further, since non-carcinogenic process oil and high viscosity base oil having a viscosity index higher than usual can be obtained at the same time, it is excellent in economic efficiency.
以下、実施例・比較例に基づいて本発明について詳細に説明するが、本発明は実施例に限定されるものではない。本発明における測定項目は、以下の方法によって定めた。
[多環芳香族化合物(PCA)濃度(DMSO抽出分)の測定]DMSO抽出分は、IP346(1992年版)試験法によって決定した。
[環分析]環分析値%CAは、ASTM D 2140−97に従って算出した。
[動粘度]JIS K2283−1993の規定に従って測定した。
[アニリン点]JIS K2256−1998の規定に従って測定した。
[Mw(重量平均分子量)]MwはMw=ΣMi2Ni/ΣMiNi(Mi:分子量、Ni:分子数)で定義され、一般的にはGPC(ゲルパーミエーションクロマトグラフィー)などで測定される。
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to an Example. The measurement items in the present invention were determined by the following method.
[Measurement of Polycyclic Aromatic Compound (PCA) Concentration (DMSO Extract)] The DMSO extract was determined by the IP346 (1992 version) test method.
[Ring Analysis ring analysis% C A was calculated according to ASTM D 2140-97.
[Kinematic Viscosity] Measured according to JIS K2283-1993.
[Aniline point] Measured according to JIS K2256-1998.
[Mw (weight average molecular weight)] Mw is defined by Mw = ΣMi 2 Ni / ΣMiNi (Mi: molecular weight, Ni: number of molecules), and is generally measured by GPC (gel permeation chromatography) or the like.
今回は以下の条件でGPCによりMw(ポリスチレン換算)を測定した。
溶剤:テトラヒドロフラン
カラム温度:50℃
流速:1.0ml/Min
カラム:Shodex GPC KF−805L
検出器:Shimadzu RID−6A
[流動点]JIS C2101−1999の規定に従って測定した。
[粘度指数]JIS K2283−1993の規定に従って算出した。
[窒素分]JIS K2609−1998の規定に従って算出した。
[硫黄分]JIS K2541−1996の規定に従って測定した。
[クロマトによる芳香族分]ASTM D2007−98の規定に従って測定した。
[変異原性指数(MI)]ASTM E1687−98の規定に従って測定した。
[ガスクロ蒸留]ASTM D2887−97aの規定に従って測定した。
[残留炭素分]JIS K2270−1998の規定に従って測定した。
(実施例1)
アラビアンライト原油を終点が(ガスクロ蒸留FBP)600℃となるように減圧蒸留して残った残渣を残留炭素分が1.3%となるように、プロパン脱瀝し(溶剤比は700%、圧力は3.3MPaG、反応塔72℃)、溶剤にフルフラールを使用して溶剤比を400%とし、エキストラクト収率42%となるように溶剤抽出を行った。ラフィネートは、さらにニッケル3重量%、モリブデン12重量%担持したアルミナ系触媒を使用して水素化精製(水素圧力:6.5MPaG、液空間速度(LHSV):2.5h-1、温度:315℃、脱硫率48%)を行い、軽質分を除去した後、溶剤脱蝋(メチルエチルケトン:トルエン=1:1、溶剤比330%、−20℃まで冷却、収率84%)を行い、動粘度(40℃)508.4mm2/s、流動点−10℃、粘度指数101の高粘度基油を得た。IP346法により測定されたエキストラクトのDMSO抽出分は2.7質量%、%CAは25.3%、動粘度(100℃)は65.26mm2/s、アニリン点は72℃、クロマトによる芳香族分は84重量%、Mwは785であった。
(比較例1)
アラビアンライト原油を終点が(ガスクロ蒸留FBP)600℃となるように減圧蒸留して残った残渣を残留炭素分が1.3%となるように、プロパン脱瀝し(溶剤比は700%、圧力は3.3MPaG、反応塔温度72℃)、溶剤にフルフラールを使用して溶剤比を350%とし、エキストラクト収率30%となるように溶剤抽出を行った。IP346法により測定されたエキストラクトのDMSO抽出分は4.0質量%、%CAは28.6%、動粘度(100℃)は80.24mm2/s、アニリン点は63℃、クロマトによる芳香族分は86重量%、Mwは730であった。
(比較例2)
アラビアンライト原油を終点が(ガスクロ蒸留FBP)600℃となるように減圧蒸留して残った残渣を残留炭素分が1.3%となるように、プロパン脱瀝し(溶剤比は700%、圧力は3.3MPaG、反応塔72℃)、溶剤にフルフラールを使用して溶剤比を280%とし、エキストラクト収率20%となるように溶剤抽出を行った。IP346法により測定されたエキストラクトのDMSO抽出分は5.3質量%、%CAは33.5%、動粘度(100℃)は110.6mm2/s、アニリン点は51℃、クロマトによる芳香族分は86重量%、Mwは645であった。
(比較例3)
アラビアンライト原油を留出点が(ガスクロ蒸留FBP)560℃となるように減圧蒸留して残った残渣を残留炭素分が1.3%となるように、プロパン脱瀝し(溶剤比は700%、圧力は3.3MPaG、反応塔72℃)、溶剤にフルフラールを使用して溶剤比を280%とし、エキストラクト収率25%となるように溶剤抽出を行った。IP346法により測定されたエキストラクトのDMSO抽出分は9.9質量%、%CAは33.6%、動粘度(100℃)は58.33mm2/s、アニリン点は55℃、クロマトによる芳香族分は86重量%、Mwは601であった。
This time, Mw (polystyrene conversion) was measured by GPC under the following conditions.
Solvent: Tetrahydrofuran Column temperature: 50 ° C
Flow rate: 1.0ml / Min
Column: Shodex GPC KF-805L
Detector: Shimadzu RID-6A
[Pour point] Measured according to JIS C2101-1999.
[Viscosity index] The viscosity index was calculated in accordance with JIS K2283-1993.
[Nitrogen content] Calculated according to JIS K2609-1998.
[Sulfur content] Measured according to JIS K2541-1996.
[Aromatic content by chromatography] Measured in accordance with ASTM D2007-98.
[Mutagenicity index (MI)] Measured according to ASTM E1687-98.
[Gas chromatographic distillation] Measured according to ASTM D2887-97a.
[Residual carbon content] Measured according to JIS K2270-1998.
Example 1
The residue obtained by distilling Arabian light crude oil under reduced pressure so that the end point is (gas chromatographic distillation FBP) 600 ° C. is propane-dehydrated so that the residual carbon content is 1.3% (solvent ratio is 700%, pressure Was 3.3 MPaG, reaction tower 72 ° C.), furfural was used as a solvent, the solvent ratio was set to 400%, and the solvent was extracted so that the extract yield was 42%. The raffinate was further hydrorefined using an alumina catalyst supported by 3% by weight of nickel and 12% by weight of molybdenum (hydrogen pressure: 6.5 MPaG, liquid space velocity (LHSV): 2.5 h −1 , temperature: 315 ° C. , Desulfurization rate 48%), light components were removed, solvent dewaxing (methyl ethyl ketone: toluene = 1: 1, solvent ratio 330%, cooled to -20 ° C., yield 84%), kinematic viscosity ( 40 ° C.) A high viscosity base oil having 508.4 mm 2 / s, a pour point of −10 ° C., and a viscosity index of 101 was obtained. DMSO extractables measured extract by IP346 method 2.7 wt.%,% C A is 25.3%, a kinematic viscosity (100 ° C.) is 65.26mm 2 / s, aniline point 72 ° C., by chromatography The aromatic content was 84% by weight and Mw was 785.
(Comparative Example 1)
The residue obtained by distilling Arabian light crude oil under reduced pressure so that the end point is (gas chromatographic distillation FBP) 600 ° C. is propane-dehydrated so that the residual carbon content is 1.3% (solvent ratio is 700%, pressure Was 3.3 MPaG, the reaction tower temperature was 72 ° C.), the solvent ratio was 350% using furfural as the solvent, and the solvent extraction was performed so that the extract yield was 30%. DMSO extractables measured extract by IP346 method 4.0 wt.%,% C A is 28.6%, a kinematic viscosity (100 ° C.) is 80.24mm 2 / s, aniline point 63 ° C., by chromatography The aromatic content was 86% by weight and Mw was 730.
(Comparative Example 2)
The residue obtained by distilling Arabian light crude oil under reduced pressure so that the end point is (gas chromatographic distillation FBP) 600 ° C. is propane-dehydrated so that the residual carbon content is 1.3% (solvent ratio is 700%, pressure Was 3.3 MPaG, reaction tower 72 ° C.), furfural was used as the solvent, the solvent ratio was 280%, and the solvent was extracted so that the extract yield was 20%. DMSO extractables measured extract by IP346 method 5.3 wt.%,% C A is 33.5%, a kinematic viscosity (100 ° C.) is 110.6mm 2 / s, aniline point 51 ° C., by chromatography The aromatic content was 86% by weight and Mw was 645.
(Comparative Example 3)
The residue remaining after distilling Arabian light crude oil under reduced pressure so that the distilling point is 560 ° C (gas chromatographic distillation FBP) is propane-dehydrated so that the residual carbon content is 1.3% (solvent ratio is 700% The pressure was 3.3 MPaG, the reaction tower was 72 ° C.), and the solvent ratio was 280% using furfural as the solvent, and the solvent was extracted so that the extract yield was 25%. DMSO extractables measured extract by IP346 method 9.9 wt.%,% C A is 33.6%, a kinematic viscosity (100 ° C.) is 58.33mm 2 / s, aniline point 55 ° C., by chromatography The aromatic content was 86% by weight and Mw was 601.
実施例及び比較例の溶剤精製条件、得られたエキストラクト及びラフィネートを溶剤脱蝋して得られた高粘度基油の性状を併せて表1に示す。   Table 1 shows the solvent refining conditions of Examples and Comparative Examples, and the properties of the high-viscosity base oils obtained by solvent dewaxing of the obtained extract and raffinate.

Claims (2)

  1. プロセス油として有用なエキストラクトと高粘度基油として有用なラフィネートを溶剤精製で製造する工程において、減圧蒸留を留出油の終点が常圧換算580℃以上となる条件にておこない、得られた残渣油を脱瀝油の残留炭素分が1.6%以下になる条件で脱瀝し、脱瀝油を溶剤精製に供して、溶剤としてフルフラール、フェノール及びN−メチル−2−ピロリドンから1つあるいはそれ以上を選択し用い、エキストラクト収率が35〜60%になる条件で行うことにより得たラフィネートの脱鑞後に得られる40℃の動粘度400mm2/s以上700mm2/s以下である高粘度基油の流動点が−5℃以下、粘度指数が95以上であることを特徴とする高粘度基油の製造方法。 In the process of producing useful raffinate in solvent refining useful extract and a high viscosity base oil as a process oil, subjected to vacuum distillation end point of distillate is Te a condition to be normal pressure terms 580 ° C. or higher, obtained The residual oil was degassed under the condition that the residual carbon content of the deoiled oil was 1.6% or less, the deoiled oil was subjected to solvent refining, and 1 from furfural, phenol and N-methyl-2-pyrrolidone as a solvent. The kinematic viscosity at 40 ° C. obtained after the defatting of the raffinate obtained by performing selection under the condition that the extract yield is 35 to 60% is selected from one or more and from 400 mm 2 / s to 700 mm 2 / s. A method for producing a high-viscosity base oil, wherein a pour point of a high-viscosity base oil is −5 ° C. or less and a viscosity index is 95 or more.
  2. 減圧蒸留を留出油の終点が常圧換算580℃以上となる条件にておこない、得られた残渣油を脱瀝油の残留炭素分が1.6%以下になる条件で脱瀝し、脱瀝油を溶剤精製に供して、溶剤としてフルフラール、フェノール及びN−メチル−2−ピロリドンから1つあるいはそれ以上を選択し用い、エキストラクト収率が35〜60%になる条件で行うことにより得たラフィネートの脱鑞後に得られる40℃の動粘度400mm2/s以上700mm2/s以下であり、流動点が−5℃以下、粘度指数が95以上である高粘度基油。 It performs a vacuum distillation end point of distillate is Te in conditions that the atmospheric pressure in terms of 580 ° C. or higher, the residual carbon content of the resulting residual oil deasphalted oil is deasphalted with conditions to be 1.6% or less, By subjecting the deoiled oil to solvent refining and selecting one or more of furfural, phenol and N-methyl-2-pyrrolidone as the solvent and performing the extraction yield under conditions of 35-60%. A high-viscosity base oil having a kinematic viscosity at 40 ° C. of 400 mm 2 / s or more and 700 mm 2 / s or less, a pour point of −5 ° C. or less, and a viscosity index of 95 or more obtained after deraising of the obtained raffinate.
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