JPS6033154B2 - Method for improving low temperature fluidity of fuel oil - Google Patents
Method for improving low temperature fluidity of fuel oilInfo
- Publication number
- JPS6033154B2 JPS6033154B2 JP56095074A JP9507481A JPS6033154B2 JP S6033154 B2 JPS6033154 B2 JP S6033154B2 JP 56095074 A JP56095074 A JP 56095074A JP 9507481 A JP9507481 A JP 9507481A JP S6033154 B2 JPS6033154 B2 JP S6033154B2
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- fluidity
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Description
【発明の詳細な説明】
本発明は石油の中・重質留分から調製される燃料油の低
温流動性を改良する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for improving the cold flow properties of fuel oils prepared from medium and heavy fractions of petroleum.
周知のとおり原油を蒸留して得られる留分の中で、特に
中・車質留分と呼ばれる沸点が約150〜450o○の
留分は燈油、軽油、重油として国民のエネルギー源とし
て極めて重要な地位を占めている。その中で軽油や重油
は、冬期等の低温度下において、油に含有されるワック
ス分の析出のために流動性が箸るしく低下し、重大な問
題を生じることがある。たとえば冬期の寒冷状態下で軽
油中に含有されるワックス分の析出のために、ディーゼ
ルエンジンに燃料油を供給する回路の途中に設けてある
炉過器(ストレーナ−)が目詰まりを起し燃料油の供給
を停止させたり、さらに低温下では完全に流動性を失な
ったりしてディーゼルエンジンの作動ができなくなった
事例が数多くあった。重油の場合も同様のワックス析出
のために、漁船のエンジン停止や、ハウス栽培用ボイラ
ーの燃焼障害などのトラブル発生例があり、人命や資産
等に重大な影響を与えることがある。As is well known, among the fractions obtained by distilling crude oil, the fractions with a boiling point of approximately 150 to 450 o○, called medium-quality fractions, are particularly important as kerosene, light oil, and heavy oil as energy sources for the nation. occupies a position. Among these, the fluidity of light oils and heavy oils is significantly reduced at low temperatures such as in winter due to the precipitation of wax contained in the oil, which can cause serious problems. For example, in cold winter conditions, the wax contained in diesel oil precipitates, causing the strainer installed in the circuit that supplies fuel oil to diesel engines to become clogged. There have been many cases where diesel engines have been unable to operate due to oil supply being cut off or even completely losing fluidity at low temperatures. In the case of heavy oil, similar problems such as the engine shutdown of fishing boats and combustion problems in greenhouse cultivation boilers have occurred due to similar wax precipitation, which can have a serious impact on human life and property.
このためこの種の油の低温度下での流動性を改良するた
めに種々の方法がなされている。For this reason, various methods have been used to improve the fluidity of this type of oil at low temperatures.
たとえば比較的低温における流動性にすぐれた燈油用留
分を混合希釈することによって軽油や重油の流動性を改
善する方法がある。For example, there is a method of improving the fluidity of light oil and heavy oil by mixing and diluting a kerosene fraction that has excellent fluidity at relatively low temperatures.
しかし燈油のような比較的軽い蟹分は価格的に軽油や重
油よりも高価であり経済的方法と言えない。また原油自
体が車質化する一方では軽質蟹分の必要性が増大しつつ
ある今日の状況下、石油資源の有効活用の観点からも好
ましい方法とは言えない。別の方法として流動性向上剤
を添加する方法があり、その向上剤の殆んどは化学合成
品が使用されている。However, relatively light oil such as kerosene is more expensive than light oil or heavy oil, so it is not an economical method. In addition, in today's situation where crude oil itself is becoming more refined and the need for light crab is increasing, this method cannot be said to be a preferable method from the viewpoint of effective utilization of petroleum resources. Another method is to add a fluidity improver, and most of these improvers are chemically synthesized products.
流動性向上剤の役割りは、析出ワックスの巨大化を防ぎ
、微少結晶として安定化させることにより流動性を改良
せんとするものである。流動性向上剤の種類は数多く提
案されており、また実際に燃料油に添加されて大きな効
果を発揮している。代表的な流動性向上剤には、エチレ
ンーェチレン性不飽和ェステル共重合体、ポリアクリレ
ート、アルキルナフタリン、アルケニルコハク酸および
その譲導体などがよく知られている。The role of the fluidity improver is to improve fluidity by preventing the deposited wax from becoming too large and stabilizing it as microcrystals. Many types of fluidity improvers have been proposed, and they are actually added to fuel oil with great effect. Typical fluidity improvers include ethylene-ethylene unsaturated ester copolymers, polyacrylates, alkylnaphthalenes, alkenylsuccinic acids and derivatives thereof.
なかでもエチレンとエチレン性二重結合を有するカルボ
ン酸ェステルとの共重合体の流動性向上剤としての利用
に関する提案は数多〈あり、例えば特公昭39一200
6y号、特公昭48−23165号、特公昭50一76
05号および特関昭55−4829び号公報などに記載
されている。上記共重合体のなかでも特にエチレン−酢
酸ピニル共重合体は通常燃料油の流動点を降下させるだ
けでなく、低温炉過器目詰まり点の降下作用にすぐれる
ことから、近年その使用量は急速に伸びつつある。Among them, there are many proposals regarding the use of copolymers of ethylene and carboxylic acid esters having ethylenic double bonds as fluidity improvers; for example, Japanese Patent Publication No. 39-200
No. 6y, Special Publication No. 1986-23165, Special Publication No. 1976-1976
No. 05 and Tokusekki No. 55-4829, etc. Among the above copolymers, ethylene-pinyl acetate copolymer in particular not only lowers the pour point of normal fuel oil, but also has an excellent effect of lowering the clogging point of the filter in low temperature furnaces, so its usage has increased in recent years. It is growing rapidly.
しかし特殊な燃料油にしか有効でなかったり、比較的高
価であるにもかかわらず大量の添加を必要としたりして
、必ずしも満足できるものではない。本発明者らは燃料
油の低温流動性改良のため高価な上記のエチレンとエチ
レン性不飽和基を有するカルボン酸ェステルとの共重合
体の使用量を少なくし、かつ効果の大きい改良方法につ
いて鋭意検討の結果、上記共重合体と残澄油の組合せが
著しく有効であることを見い出し本発明に至った。However, they are not always satisfactory, as they are only effective for special fuel oils, and require a large amount of addition despite being relatively expensive. The present inventors have made efforts to reduce the amount of the expensive copolymer of ethylene and a carboxylic acid ester having an ethylenically unsaturated group in order to improve the low-temperature fluidity of fuel oil, and to develop a highly effective improvement method. As a result of studies, it was discovered that the combination of the above-mentioned copolymer and residual oil was extremely effective, leading to the present invention.
すなわち、本発明は石油の中質または/および車質油留
分からなる燃料油に残湾油およびエチレンとエチレン性
二重結合を有するカルボン酸ェステルとの共重合体を添
加することを特徴とする燃料油の低温流動性改良方法を
提供する。本発明においては燃料油の低温流動性改良、
すなわち流動点および低温炉過目詰まり点を低下させる
ことに関し残澄油と上記エチレン共重合体の組合せによ
り、各々の単独使用からは予想されない相乗的な効果が
得られる。That is, the present invention is characterized in that residual Gulf oil and a copolymer of ethylene and a carboxylic acid ester having an ethylenic double bond are added to a fuel oil consisting of a medium oil fraction and/or a car oil fraction. A method for improving the low-temperature fluidity of fuel oil is provided. In the present invention, the low temperature fluidity improvement of fuel oil,
That is, in terms of lowering the pour point and low temperature furnace over-clogging point, the combination of the resid oil and the above-mentioned ethylene copolymer provides a synergistic effect that would not be expected from the use of each alone.
さらに、本発明においては低温流動性改良のため高価な
エチレン共重合体の添加量を極力少なくする一方非常に
安価な残酒油を使用するのでその経済的効果も大きい。
以下本発明について詳細に説明する。本発明において使
用の石油の中質または/および重質蟹分とは原油を常圧
または減圧で蒸留して得られるもので常圧に換算した蒸
留点が約130℃〜約450oCの範囲の蟹分であり、
一般に、軽油、A重油等が含まれる。Furthermore, in the present invention, the amount of expensive ethylene copolymer added is minimized in order to improve low-temperature fluidity, and at the same time very cheap residual alcohol is used, which has a great economic effect.
The present invention will be explained in detail below. The medium and/or heavy crab content of petroleum used in the present invention is obtained by distilling crude oil at normal pressure or reduced pressure, and has a distillation point in the range of about 130°C to about 450°C when converted to normal pressure. minutes,
Generally, light oil, A heavy oil, etc. are included.
本発明において使用されるエチレンとエチレン性二重結
合を有するカルボン酸ェステルとの共重合体(以下エチ
レン共重合体と略す。)は公知の方法で製造することが
できる。たとえばフリーラジカル塊状重合、乳化重合ま
たは溶液重合によって製造することができる。なかでも
工業的に有利な方法は、多量の溶剤などを使用せずにで
きる連続式高圧重合方法があげられる。この方法は連続
式高圧重合装置を用いて圧力500〜4,000k9/
地、温度100〜30000の条件下で酸素または有機
過酸化物の触媒およびプロパン、ブタン、プロピレン、
ブテン、プロピオンアルデヒド、メチルエチルケトン、
テトラヒドロフラン、n−プチルアルデヒド、アセトン
またはシクロヘキサノンなどの重合調節剤の存在下でエ
チレンとエチレン性二重結合を有するカルボン酸ェステ
ル単量体を共重合する方法である。本発明で用いられる
エチレン性二重結合を有するカルポン酸ェステル単量体
は下記に示す化合物が例示され、その1種または2種以
上が用いられる。The copolymer of ethylene and a carboxylic acid ester having an ethylenic double bond (hereinafter abbreviated as ethylene copolymer) used in the present invention can be produced by a known method. For example, they can be produced by free radical bulk polymerization, emulsion polymerization or solution polymerization. Among them, the industrially advantageous method is a continuous high-pressure polymerization method that can be carried out without using a large amount of solvent. This method uses a continuous high-pressure polymerization device at a pressure of 500 to 4,000 k9/
Oxygen or organic peroxide catalyst and propane, butane, propylene,
butene, propionaldehyde, methyl ethyl ketone,
This is a method of copolymerizing ethylene and a carboxylic acid ester monomer having an ethylenic double bond in the presence of a polymerization regulator such as tetrahydrofuran, n-butyraldehyde, acetone, or cyclohexanone. The carboxylic acid ester monomer having an ethylenic double bond used in the present invention is exemplified by the compounds shown below, and one or more of them may be used.
すなわち酢酸ビニル、プロピオン酸ビニル、酪酸ビニル
、オクタン酸ビニル、ステアリン酸ビニル等の脂肪族ヱ
ステルまたはアクリル酸メチル、メタクリル酸メチル、
アクリル酸エチル、メタクリル酸エチル、アクリル酸ブ
チル、メタクリル酸ブチル、アクリル酸オクチル、メタ
クリル酸オクチル、アクリル酸ドデシル、メタクリル酸
ドデシル、アクリル酸ステアリル、メタクリル酸ステア
リル等のアクリル酸ェステルまたはメタクリル酸ェステ
ルなどである。エチレン英重合体は1種類でもよく、ま
た製造条件を変えて物性を変化させせた種類のものとの
併用もしくは混合物でもよい。上記のエチレン共重合体
の中で工業的に入手が容易であり、価格の点から、さら
には低温流動性改良性能の点からエチレン−酢酸ビニル
共重合体(以下EVAと記す)が好ましい。That is, aliphatic esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl stearate, methyl acrylate, methyl methacrylate,
Acrylic esters or methacrylic esters such as ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, etc. be. One type of ethylene polymer may be used, or a combination or a mixture of types with different physical properties by changing manufacturing conditions may be used. Among the above-mentioned ethylene copolymers, ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) is preferred because it is industrially easily available, is inexpensive, and further has the ability to improve low-temperature fluidity.
上記エチレン共重合体のエチレン性二重結合を有するカ
ルボン酸ェステルの含有量は特に限定されないが好まし
くは5〜4の重量%の範囲であり、また数平均分子量は
700〜7000の範囲が好ましい。The content of the carboxylic acid ester having an ethylenic double bond in the ethylene copolymer is not particularly limited, but is preferably in the range of 5 to 4% by weight, and the number average molecular weight is preferably in the range of 700 to 7,000.
特にEVAにおいて述べれば酢酸ビニル含量が5〜25
重量%で数平均分子量が1,000〜5,000のもの
が低温流動性改良の効果および効果の経時変化が少ない
ので特に好ましい。Especially when talking about EVA, the vinyl acetate content is 5 to 25.
Particularly preferred is one having a number average molecular weight of 1,000 to 5,000 in terms of weight percent, since the effect of improving low-temperature fluidity and the change in effect over time are small.
エチレン共重合体の添加量は石油の中・童質蟹分に対し
て重量で10〜2,000脚が適当である。The appropriate amount of the ethylene copolymer to be added is 10 to 2,000 units by weight based on the weight of the oil.
さらに好ましくは30〜1,00■血である。IQ側禾
満の添加量では誤差範囲内での添加効果しか期待できな
いし、また2,000弧肌を超えて添加しても効果はそ
れ以上に向上せず、経済的に不利となるので好ましくな
い。また、本発明に使用される残糟油について述べると
、残檀油とは石油精製プロセロにおいて蒸留塔の底部よ
り抜き出される重質油を総称し、蟹出油と対比される。More preferably, it is 30 to 1,00 cm of blood. It is preferable because the addition amount on the IQ side can only be expected to have an addition effect within the error range, and even if it is added in excess of 2,000 arcs, the effect will not be further improved and it will be economically disadvantageous. do not have. Regarding the residual oil used in the present invention, residual oil is a general term for heavy oil extracted from the bottom of a distillation column in a petroleum refining process, and is contrasted with crab oil.
具体的には常圧残燈油、減圧残澄油、分解残澄油等に区
別できる。常圧残澄油は原油を常圧蒸留装置で処理した
際の重質ボトム油であり、通称ロングレシデューと呼ば
れている。また減圧残澄油は常圧残澄油を減圧蒸留装置
で処理した際の超重質ボトム油であり、通称ショートレ
シデューと呼ばれている。分解残簿油は接触分解装置等
の関連設備から得られるものであるが精製プロセスでは
これらは常圧蒸留装置、減圧蒸留装置等に戻される場合
もある。なかでも量的な安定確保、取り扱い性、石油の
中・重質留分との相溶性などを考慮すると常圧残澄油が
好ましい。Specifically, it can be classified into atmospheric residual oil, vacuum residual oil, cracked residual oil, etc. Atmospheric residual oil is heavy bottom oil obtained when crude oil is processed in an atmospheric distillation apparatus, and is commonly called long residue. Vacuum residue oil is an ultra-heavy bottom oil obtained by processing normal pressure residue oil in a vacuum distillation apparatus, and is commonly called short residue oil. Cracked residual oil is obtained from related equipment such as catalytic cracking equipment, but in the refining process, it may be returned to atmospheric distillation equipment, vacuum distillation equipment, etc. Among these, atmospheric residual oil is preferred in consideration of ensuring quantitative stability, ease of handling, and compatibility with medium and heavy fractions of petroleum.
残櫨油の成分は原油の種類や蒸留等の操作条件などによ
り一定ではないが、大別するとアスフアルテン分、レジ
ン分、油分である。The components of residual cane oil vary depending on the type of crude oil and operating conditions such as distillation, but they can be roughly divided into asphaltenes, resins, and oils.
成分がそれぞれ異なるので、燃料油に添加した場合流動
性改良効果はおのずと変わるのでこれを考慮して添加量
を下記の範囲で適宜決めればよい。すなわち残澄油の添
加量は石油の中・軍質蟹分に対して重量で500〜20
,000柳の範囲が好ましい。残澄油は前述のエチレン
共重合体と共に、石油の中・重質蟹分に加えられるが、
50瓜岬未満の添加量では誤差範囲内での効果しか期待
できないし、20,000跡以上の添加量ではスラッジ
発生量が多くなり、製品価値が低下するので好ましくな
い。Since the components are different, the fluidity improving effect will naturally change when added to fuel oil, so the amount to be added may be appropriately determined within the range shown below, taking this into consideration. In other words, the amount of residual oil added is 500 to 20% by weight based on the oil content.
,000 willow range is preferred. Residue oil is added to the medium and heavy oil fraction along with the ethylene copolymer mentioned above,
If the amount of addition is less than 50 melons, the effect can only be expected within the error range, and if the amount of addition is more than 20,000, the amount of sludge generated will increase and the product value will decrease, which is not preferable.
添加方法に特に制限はなく、残澄油とエチレン共重合体
とを予め混合後石油の中・重質留分に添加してもよく、
またはそれぞれ別に添加してもよい。There are no particular restrictions on the method of addition, and the residual oil and ethylene copolymer may be mixed in advance and then added to the medium and heavy fractions of petroleum.
Alternatively, they may be added separately.
またこれらは適当な溶剤の濃厚溶液の形で添加してもよ
い。また残澄油を石油の中・車質蟹分と混合した後にエ
チレン共重合体をそのまま、または適当な溶剤に溶かし
た濃度液の形で添加することも何ら差し支えない。溶剤
としては脂肪族炭化水素、芳香族炭化水素等が使用でき
る。またその際に石油蟹分燃料油に対して通常加えられ
る防錆剤、酸化防止剤、静電気防止剤あるいは防食剤な
どの添加剤と併用したり、必要に応じて他の流動点降下
剤と併用してもよい。They may also be added in the form of concentrated solutions in suitable solvents. There is also no problem in adding the ethylene copolymer as it is or in the form of a concentrated liquid dissolved in a suitable solvent after mixing the residual oil with the petroleum oil or carcass substance. As the solvent, aliphatic hydrocarbons, aromatic hydrocarbons, etc. can be used. In addition, at that time, it is used in combination with additives such as rust inhibitors, antioxidants, antistatic agents, or anticorrosive agents that are normally added to petroleum fuel oil, or in combination with other pour point depressants as necessary. You may.
以下に本発明を実施例および比較例により具体的に説明
するが本発明はこれらに限定されるものではない。EXAMPLES The present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited thereto.
ここで流動性の評価方法としては流動点と低温炉過目詰
まり点を示すがこれらは次の方法で測定した。Here, as methods for evaluating fluidity, pour point and low temperature furnace overclogging point are shown, and these were measured by the following method.
流 動 点:JISK−2269に準拠して測定した。Pour point: Measured according to JISK-2269.
低温炉過目詰まり点:IP一309/1976英国(C
old Filter Pluggng Point
ofdistmatef雌ls)に準拠して測定した。
,実施例1および2、比較例1〜6
高圧連続重合反応器を用いて圧力700k9/c液、温
度22300の条件で重合開始剤として3級ブチルパー
オキシベンゾェートおよび連鎖移動剤としてプロパンを
用いることにより製造した酢酸ビニル含有量21重量%
、数平均分子量1,670のEVAと石油精製装置の常
圧蒸留塔から抜きだした比重(4000)0.9571
、動粘度(5000)720センチストークス、残留炭
素分10.5重量%、アスフアルテン分2.電車量%の
残澄油を表2に示す量表1に示した性状の燃料油A,B
に添加し、流動点および低温ロ過目詰まり点を測定した
。Low temperature furnace overclogging point: IP-309/1976 UK (C
Old Filter Plugging Point
ofdistmatef female ls).
, Examples 1 and 2, Comparative Examples 1 to 6 A high-pressure continuous polymerization reactor was used at a pressure of 700 k9/c and a temperature of 22,300, using tertiary butyl peroxybenzoate as a polymerization initiator and propane as a chain transfer agent. Vinyl acetate content 21% by weight
, EVA with a number average molecular weight of 1,670 and a specific gravity (4000) of 0.9571 extracted from the atmospheric distillation column of an oil refinery.
, kinematic viscosity (5000) 720 centistokes, residual carbon content 10.5% by weight, asphaltene content 2. Fuel oil A, B with the properties shown in Table 1, with the amount of residual oil shown in Table 2 in % of the train volume
The pour point and low temperature filtration clogging point were measured.
結果を表2に示す。表1表2
表2の結果から明らかなように、燃料油にEVAを添加
した場合または残澄油を添加した場合の流動点降下温度
または低温ロ過目語まり点降下温度の代数和に比較し、
EVAと残澄油の両方を添加した場合が、少なくとも流
動点または低温ロ過目詰まり点のいずれかが大きな温度
降下を示している。The results are shown in Table 2. Table 1 Table 2 As is clear from the results in Table 2, compared to the algebraic sum of pour point depression temperature or low temperature pour point depression temperature when EVA is added to fuel oil or when residual oil is added. ,
The addition of both EVA and residual oil shows a large temperature drop in at least either the pour point or the low temperature filtration plugging point.
実施例3および4、比較例7〜12
高圧連続重合装置を用いて圧力700kg/の、温度2
25qoの条件で重合開始剤として3級ブチルパーキシ
ベンゾェートおよび連鎖移動剤としてプロパンを用いる
ことにより製造した酢酸ビーニル含有量16重量%、数
平均分子量2,470のEVAと石油精製装置の常圧蒸
留塔から抜き出した比重(40℃)0.9110、動粘
度(5000)89センチストークス、残留炭素分4.
匁重量%、ァスフアルデン分0.5重量%の残燈油を表
3に示す量燃料油A,Bに添加して評価した。Examples 3 and 4, Comparative Examples 7 to 12 Using a high-pressure continuous polymerization apparatus, the pressure was 700 kg/, the temperature 2
EVA with a vinyl acetate content of 16% by weight and a number average molecular weight of 2,470 produced by using tertiary butyl perxybenzoate as a polymerization initiator and propane as a chain transfer agent under the conditions of 25 qo and the normal pressure of an oil refinery. The specific gravity (40°C) extracted from the distillation column was 0.9110, the kinematic viscosity (5000) was 89 centistokes, and the residual carbon content was 4.
Residual oil with momme weight % and asphaldane content of 0.5 weight % was added to fuel oils A and B in the amounts shown in Table 3 for evaluation.
結果を表3に示す。表3
表3の結果は実施例1の場合と同様EVAと残燈油の併
用系が流動点および低温ロ過目まり点が最も低くなり、
低温流動性の改良効果を示している。The results are shown in Table 3. Table 3 The results in Table 3 show that, as in Example 1, the combination system of EVA and residual oil had the lowest pour point and low temperature overflow point;
This shows the effect of improving low-temperature fluidity.
実施例5および6、比較例13〜16
実施例1で使用したEVAと残澄油の添加量を表4に示
すとおりに変えた以外は実施例1と同様に実施した。Examples 5 and 6, Comparative Examples 13 to 16 Examples were carried out in the same manner as in Example 1, except that the amounts of EVA and residual oil used in Example 1 were changed as shown in Table 4.
結果を表4に示す。表4
表4の結果はEVAまたは残澄油単独で添加するより併
用した方が、流動点および低温ロ過目詰まり点が最も低
くなり、低温流動性の改良効果を示している。The results are shown in Table 4. Table 4 The results in Table 4 show that the pour point and low-temperature filtration clogging point are the lowest when EVA or residual oil is used together rather than when added alone, indicating the effect of improving low-temperature fluidity.
実施例7、比較例17〜19
高圧連続反応器を用いて圧力700k9/欲、温度22
3ooの条件で重合開始剤として3級ブチルパーオキシ
ベンゾェートおよび連鎖移動剤としてプロパンを用いる
ことにより製造した酢酸ビニル単位含量21重量%、数
平均分子量1,670のEVAと石油精製装置の常圧蒸
留塔から抜きだした比重(40℃)0.9571、動粘
度(50午0)720センチストースス、残留炭素分1
0.5重量%、アスフアルテン分2.母重量%の残済油
を、表1に示した性状の燃料油Aに添加し、流動点およ
び低温ロ過目語まり点を測定した。Example 7, Comparative Examples 17 to 19 Using a high-pressure continuous reactor, the pressure was 700k9/temperature 22
EVA with a vinyl acetate unit content of 21% by weight and a number average molecular weight of 1,670 produced by using tertiary butyl peroxybenzoate as a polymerization initiator and propane as a chain transfer agent under conditions of 3OO and normal pressure of an oil refinery. Specific gravity (40°C) taken out from the distillation column: 0.9571, kinematic viscosity (50°C): 720 centistosus, residual carbon content: 1
0.5% by weight, asphaltene content 2. The remaining oil in the amount of % by weight of the fuel oil was added to fuel oil A having the properties shown in Table 1, and the pour point and low temperature sluggish point were measured.
なお各成分を調合後5000で10分間の前処理を与え
て完全に溶解し、室温で10〜30分振とうの後測定し
、一部残った試料は室温で1週間保存後、麓拝によりよ
く混合し加温処理なしで再測定した。EVAおよび残澄
油の添加量と低温特性を表5に示す。After each component was prepared, it was pretreated at 5,000 °C for 10 minutes to completely dissolve it, shaken at room temperature for 10 to 30 minutes, and then measured. Some of the remaining samples were stored at room temperature for one week, and then washed at the foot of the mountain. Mix well and measure again without heating. Table 5 shows the amounts of EVA and residual oil added and the low temperature characteristics.
表5実施例 8〜10
高圧連続反応器を用いて圧力700k9/c髭、温度2
2300の条件で重合開始剤として第3級ブチルパーオ
キシベンゾェートおよび連鎖移動剤としてプロパンを用
いることにより製造した酢酸ビニル単位含量16重量%
、数平均分子量2,240のEVAと石油精製装置の常
圧蒸留塔から抜き出した比重(40oo)0.9351
、動粘度(50qo)308センチストークス、残留炭
素分9.2重量%、、アスフアルテン分2.の重量%の
残澄油を表6に示す量燃料油Bに添加し、実施例1に従
がつて測定した結果表6の結果を得た。Table 5 Examples 8 to 10 Using a high pressure continuous reactor, pressure 700k9/c, temperature 2
Vinyl acetate unit content 16% by weight produced by using tertiary butyl peroxybenzoate as a polymerization initiator and propane as a chain transfer agent under the conditions of 2300
, EVA with a number average molecular weight of 2,240 and a specific gravity (40oo) of 0.9351 extracted from an atmospheric distillation column of an oil refinery.
, kinematic viscosity (50 qo) 308 centistokes, residual carbon content 9.2% by weight, asphaltene content 2. % by weight of residual oil was added to fuel oil B in the amount shown in Table 6, and the results shown in Table 6 were obtained as a result of measurements according to Example 1.
表6
実施例 11
実施例1の方法において、重合温度を24000に変え
て製造した酢酸ビニル単位含量11重量%、数平均分子
量1,750のEVAを使用した以外は実施例1の方法
に従がつて低温流動性を測定した。Table 6 Example 11 The method of Example 1 was followed except that EVA with a vinyl acetate unit content of 11% by weight and a number average molecular weight of 1,750, which was produced by changing the polymerization temperature to 24,000, was used. The low temperature fluidity was measured.
Claims (1)
油に残渣油およびエチレンとエチレン性二重結合を有す
るカルボン酸エステルと共重合体を、該燃料油に対して
それぞれ5×10^−^2〜2重量%および10×10
^−^4〜2×10^−^1重量%添加することを特徴
とする燃料油の低温流動性改良方法。 2 残渣油が常圧残渣油である特許請求の範囲第1項記
載の方法。 3 エチレンとエチレン性二重結合を有するカルボン酸
エステルとの共重合体がエチレン−酢酸ビニル共重合体
である特許請求の範囲第1項に記載の方法。 4 エチレン−酢酸ビニル共重合体が数平均分子量1,
000〜5,000で酢酸ビニル単位を5〜25重量%
含む特許請求の範囲第1項記載の方法。[Claims] 1. Adding residual oil and ethylene, a carboxylic acid ester having an ethylenic double bond, and a copolymer to a fuel oil consisting of medium and/or heavy oil fractions of petroleum. 5×10^-^2-2% by weight and 10×10 respectively
A method for improving the low-temperature fluidity of fuel oil, characterized by adding ^-^4 to 2 x 10^-^1% by weight. 2. The method according to claim 1, wherein the residual oil is an atmospheric residual oil. 3. The method according to claim 1, wherein the copolymer of ethylene and a carboxylic acid ester having an ethylenic double bond is an ethylene-vinyl acetate copolymer. 4 The ethylene-vinyl acetate copolymer has a number average molecular weight of 1,
000-5,000 and 5-25% by weight of vinyl acetate units
The method of claim 1 comprising:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56095074A JPS6033154B2 (en) | 1981-06-18 | 1981-06-18 | Method for improving low temperature fluidity of fuel oil |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56095074A JPS6033154B2 (en) | 1981-06-18 | 1981-06-18 | Method for improving low temperature fluidity of fuel oil |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57209995A JPS57209995A (en) | 1982-12-23 |
JPS6033154B2 true JPS6033154B2 (en) | 1985-08-01 |
Family
ID=14127825
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56095074A Expired JPS6033154B2 (en) | 1981-06-18 | 1981-06-18 | Method for improving low temperature fluidity of fuel oil |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6033154B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0662964B2 (en) * | 1986-10-31 | 1994-08-17 | 住友化学工業株式会社 | Fuel oil composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5491504A (en) * | 1977-12-20 | 1979-07-20 | Ici Ltd | Agent for improving low temperature flow property of fuel*and petroleum containing same |
JPS5652953A (en) * | 1979-10-04 | 1981-05-12 | Toshiba Corp | Deciding circuit |
-
1981
- 1981-06-18 JP JP56095074A patent/JPS6033154B2/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5491504A (en) * | 1977-12-20 | 1979-07-20 | Ici Ltd | Agent for improving low temperature flow property of fuel*and petroleum containing same |
JPS5652953A (en) * | 1979-10-04 | 1981-05-12 | Toshiba Corp | Deciding circuit |
Also Published As
Publication number | Publication date |
---|---|
JPS57209995A (en) | 1982-12-23 |
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