JP2013006918A - Purification method of aromatic hydrocarbon oil - Google Patents
Purification method of aromatic hydrocarbon oil Download PDFInfo
- Publication number
- JP2013006918A JP2013006918A JP2011139135A JP2011139135A JP2013006918A JP 2013006918 A JP2013006918 A JP 2013006918A JP 2011139135 A JP2011139135 A JP 2011139135A JP 2011139135 A JP2011139135 A JP 2011139135A JP 2013006918 A JP2013006918 A JP 2013006918A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic hydrocarbon
- aromatic
- hydrocarbon oil
- boiling point
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
本発明は、芳香族炭化水素を主成分とする芳香族炭化水素油の芳香族性を低下させることなく、主成分の芳香族炭化水素と同等の沸点範囲を有する芳香族オレフィンを除去・低減することを特徴とする芳香族炭化水素油の精製方法である。 The present invention removes and reduces aromatic olefins having a boiling range equivalent to that of the main component aromatic hydrocarbon without lowering the aromaticity of the aromatic hydrocarbon oil containing the main component of the aromatic hydrocarbon. This is a method for refining an aromatic hydrocarbon oil.
石油精製工業や石油化学工業において生産される沸点１００〜２５０℃の芳香族炭化水素を主成分とする炭化水素油は、汎用の芳香族溶剤の原料として、塗料、インキ、ゴム、粘着剤、接着剤、金属の脱脂洗浄、反応溶剤等多方面で使用されている。特に、芳香族溶剤は脂肪族溶剤に比較して溶解性に優れており、多種類の物質を良く溶解することから好んで使用される溶剤である。しかるに芳香族溶剤はしばしば高温において使用されることが多く、高温でも安定であることが求められる。
一方で、石油精製工業や石油化学工業や石炭化学工業において生産される沸点１００〜２５０℃の芳香族オレフィンを含有する沸点１００〜２５０℃の芳香族炭化水素を主成分とする炭化水素油は、熱安定性が低い等の理由から上記の汎用の芳香族溶剤として使用することが難しく、主に燃料用に供されている。
Hydrocarbon oils mainly composed of aromatic hydrocarbons with a boiling point of 100-250 ° C produced in the petroleum refining industry and petrochemical industry are used as raw materials for general-purpose aromatic solvents, such as paints, inks, rubbers, adhesives and adhesives It is used in various fields such as chemicals, degreasing cleaning of metals, and reaction solvents. In particular, the aromatic solvent is excellent in solubility as compared with the aliphatic solvent, and is preferably used because it dissolves many kinds of substances well. However, aromatic solvents are often used at high temperatures and are required to be stable at high temperatures.
On the other hand, a hydrocarbon oil mainly containing an aromatic hydrocarbon having a boiling point of 100 to 250 ° C. containing an aromatic olefin having a boiling point of 100 to 250 ° C. produced in the petroleum refining industry, petrochemical industry, and coal chemical industry, It is difficult to use as the above-mentioned general-purpose aromatic solvent because of its low thermal stability, and is mainly used for fuel.
炭化水素油からオレフィンを除去・低減する方法として、蒸留法、吸着分離法、抽出法、錯形成剤を用いた抽出法、水素化法、膜分離法などが知られている。
これら従来の方法では、芳香族炭化水素を主成分とする炭化水素油から、産業上有用な当該炭化水素油の芳香族性を低下させることなく、主成分の芳香族炭化水素と同等の沸点範囲を有する芳香族オレフィンの９０％以上を除去することはできない。
Known methods for removing and reducing olefins from hydrocarbon oils include distillation, adsorption separation, extraction, extraction using a complexing agent, hydrogenation, and membrane separation.
In these conventional methods, the boiling point range equivalent to the aromatic hydrocarbon of the main component can be obtained from a hydrocarbon oil mainly composed of the aromatic hydrocarbon without reducing the aromaticity of the industrially useful hydrocarbon oil. It is not possible to remove 90% or more of the aromatic olefins having
例えば、特許文献１には、銅化合物によるエチルベンゼン／スチレン混合物からのスチレンの分離方法が記されているが、スチレンの９０％以上が除去されたエチルベンゼンを得るまでには至っていない。
特許文献２には、分離膜を用いたオレフィンの分離方法が記されているが、芳香族オレフィンの分離能があるか否かは定かではない。
特許文献３には、分離膜を用いたパラフィンとの混合物からオレフィンを分離する方法が記されているが、芳香族炭化水素と芳香族オレフィンとの分離能があるかは不明である。
また、パラフィンとオレフィンの混合物からオレフィンを吸着分離する工程で使用される分子ふるいの活性部位を芳香族炭化水素が非活性化することが知られている（特許文献４）。
For example, Patent Document 1 describes a method for separating styrene from an ethylbenzene / styrene mixture using a copper compound, but has not yet reached ethylbenzene from which 90% or more of styrene has been removed.
Patent Document 2 describes a method for separating olefins using a separation membrane, but it is not clear whether aromatic olefins are separated or not.
Patent Document 3 describes a method of separating olefins from a mixture with paraffin using a separation membrane, but it is unclear whether aromatic hydrocarbons and aromatic olefins can be separated.
In addition, it is known that aromatic hydrocarbons deactivate the active sites of molecular sieves used in the process of adsorbing and separating olefins from a mixture of paraffin and olefin (Patent Document 4).
本発明の課題は、石油精製工業または石油化学工業または石炭化学工業において生産される沸点１００〜２５０℃の芳香族炭化水素を主成分として、沸点１００〜２５０℃の芳香族オレフィンを含有する芳香族炭化水素油を汎用の芳香族溶剤の原料として供することである。すなわち、当該芳香族炭化水素油から、産業上有用な芳香族炭化水素を損失することなく、当該芳香族オレフィンの９０％以上を除去することによって、当該芳香族炭化水素油を汎用の芳香族溶剤の原料として供することである。 An object of the present invention is an aromatic containing an aromatic olefin having a boiling point of 100 to 250 ° C. based on an aromatic hydrocarbon having a boiling point of 100 to 250 ° C. produced in the petroleum refining industry, petrochemical industry or coal chemical industry. It is to provide hydrocarbon oil as a raw material for general-purpose aromatic solvents. That is, by removing 90% or more of the aromatic olefin from the aromatic hydrocarbon oil without losing industrially useful aromatic hydrocarbons, the aromatic hydrocarbon oil is removed from a general-purpose aromatic solvent. It is to serve as a raw material.
上記課題を解決するために、本発明者らは鋭意研究を行った結果、芳香族オレフィンを含有する沸点１００〜２５０℃の芳香族炭化水素を主成分とする芳香族炭化水素油に酸触媒を加えて重合処理を行った後に、蒸留して当該芳香族炭化水素を回収することによって、産業上有用な芳香族炭化水素の損失がなく、しかも、芳香族オレフィンの９０％以上が除去された芳香族炭化水素油を得ることができることを見出し、本発明を完成するに至った。 In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, an acid catalyst is added to an aromatic hydrocarbon oil mainly containing an aromatic hydrocarbon having a boiling point of 100 to 250 ° C. and containing an aromatic olefin. In addition, after the polymerization treatment, the aromatic hydrocarbon is recovered by distillation, so that there is no loss of industrially useful aromatic hydrocarbons, and more than 90% of the aromatic olefins are removed. It discovered that a group hydrocarbon oil could be obtained, and came to complete this invention.
すなわち本発明は、沸点１００〜２５０℃の芳香族炭化水素を主成分とし、沸点１００〜２５０℃の芳香族オレフィンを含有する芳香族炭化水素油に酸触媒を加えて重合処理を行う工程と、この重合処理された芳香族炭化水素油を蒸留して沸点１００〜２５０℃の芳香族炭化水素を回収する蒸留処理工程とを含むことを特徴とする芳香族炭化水素油の精製方法である。 That is, the present invention comprises a step of carrying out a polymerization treatment by adding an acid catalyst to an aromatic hydrocarbon oil containing an aromatic hydrocarbon having a boiling point of 100 to 250 ° C as a main component and an aromatic olefin having a boiling point of 100 to 250 ° C; And a distillation process step of recovering the aromatic hydrocarbon having a boiling point of 100 to 250 ° C. by distilling the polymerized aromatic hydrocarbon oil, and a method for purifying the aromatic hydrocarbon oil.
また本発明は、芳香族炭化水素油が、石油精製工業または石油化学工業または石炭化学工業において生産される炭素数８から炭素数１０の芳香族炭化水素を主成分とする芳香族炭化水素油であることを特徴とする前記記載の芳香族炭化水素油の精製方法である。 The present invention also relates to an aromatic hydrocarbon oil mainly comprising an aromatic hydrocarbon having 8 to 10 carbon atoms produced in the petroleum refining industry, petrochemical industry or coal chemical industry. The method for refining an aromatic hydrocarbon oil as described above, wherein
また本発明は、重合処理で使用する酸触媒が固体酸であり、この酸触媒の使用量が芳香族炭化水素油に対して０．１〜５０重量％であり、反応温度が０〜３００℃の範囲であることを特徴とする前記記載の芳香族炭化水素油の精製方法である。 In the present invention, the acid catalyst used in the polymerization treatment is a solid acid, the amount of the acid catalyst used is 0.1 to 50% by weight with respect to the aromatic hydrocarbon oil, and the reaction temperature is 0 to 300 ° C. The method for refining an aromatic hydrocarbon oil as described above, wherein
さらに本発明は、芳香族オレフィンの９０％以上が重合することを特徴とする前記記載の芳香族炭化水素油の精製方法である。 Furthermore, the present invention is the above-described method for purifying an aromatic hydrocarbon oil, wherein 90% or more of the aromatic olefin is polymerized.
本発明の方法により、芳香族オレフィンを含有する沸点１００〜２５０℃の芳香族炭化水素を主成分とする芳香族炭化水素油から、産業上有用な芳香族炭化水素を損失することなく、芳香族オレフィンの９０％以上が除去された芳香族炭化水素油を得ることができる。 According to the method of the present invention, an aromatic hydrocarbon oil containing an aromatic olefin and having a boiling point of 100 to 250 ° C. as a main component is aromatic without losing industrially useful aromatic hydrocarbons. An aromatic hydrocarbon oil from which 90% or more of the olefin has been removed can be obtained.
以下に本発明について説明する。
本発明の精製方法に供される芳香族炭化水素油（以下、原料炭化水素という。）は、沸点１００〜２５０℃の芳香族炭化水素を主成分とし、沸点１００〜２５０℃の芳香族オレフィンを含有する芳香族炭化水素油である。かかる原料炭化水素としては、石油の流動接触分解装置や熱分解装置で生成する分解軽油、芳香族炭化水素樹脂を製造する際に得られる未反応油、石炭乾留において生産される軽油などの石油精製工業または石油化学工業または石炭化学工業にて生産される芳香族炭化水素を主成分として芳香族オレフィンを含有する芳香族炭化水素油が挙げられ、これらは所望に応じて２種類のものを混合したり、成分や組成を適宜調整して使用することもできる。
以下では、原料炭化水素に酸触媒を加えて重合処理を行った後を重合油と言い、重合油を蒸留して原料炭化水素から芳香族オレフィン分を除去して得られる芳香族炭化水素を精製油という。
The present invention will be described below.
The aromatic hydrocarbon oil (hereinafter referred to as raw material hydrocarbon) to be used in the purification method of the present invention comprises an aromatic hydrocarbon having a boiling point of 100 to 250 ° C. as a main component and an aromatic olefin having a boiling point of 100 to 250 ° C. It is an aromatic hydrocarbon oil to be contained. Such raw material hydrocarbons include petroleum refining such as cracked light oil produced by fluid catalytic cracking equipment and thermal cracking equipment of petroleum, unreacted oil obtained when producing aromatic hydrocarbon resins, and light oil produced in coal dry distillation. Examples include aromatic hydrocarbon oils containing aromatic olefins as a main component of aromatic hydrocarbons produced in industry, petrochemical industry or coal chemical industry. These are mixed in two kinds as desired. In addition, components and compositions can be appropriately adjusted and used.
In the following, after adding an acid catalyst to the raw material hydrocarbon and carrying out the polymerization treatment, it is referred to as polymerized oil, and the aromatic hydrocarbon obtained by distilling the polymerized oil to remove aromatic olefins from the raw material hydrocarbon is purified. Called oil.
原料炭化水素の沸点は１００〜２５０℃であり、好ましくは１４０℃以上、２００℃以下である。沸点の下限が１００℃未満の場合や、沸点の上限が２５０℃を超えると目的とする芳香族炭化水素の含有量が少なくなるため、経済性が成り立たない。 The boiling point of the raw material hydrocarbon is 100 to 250 ° C, preferably 140 ° C or higher and 200 ° C or lower. When the lower limit of the boiling point is less than 100 ° C., or when the upper limit of the boiling point exceeds 250 ° C., the content of the target aromatic hydrocarbon is reduced, so that economic efficiency is not realized.
原料炭化水素における芳香族炭化水素（芳香族オレフィン分を含む）の含有割合は５０容量％以上であることが好ましく、より好ましくは８０容量％以上である。芳香族炭化水素の含有割合が５０容量％未満の場合は、精製油の溶解力が低いために汎用の芳香族溶剤の原料として供することができない。
また、原料炭化水素の芳香族炭化水素としては、炭素数８〜１０のものを主成分とすることが好ましい。
The content ratio of the aromatic hydrocarbon (including the aromatic olefin component) in the raw material hydrocarbon is preferably 50% by volume or more, more preferably 80% by volume or more. When the content ratio of the aromatic hydrocarbon is less than 50% by volume, the refined oil has a low dissolving power and cannot be used as a raw material for a general-purpose aromatic solvent.
Moreover, as an aromatic hydrocarbon of raw material hydrocarbon, it is preferable to mainly have a C8-10 thing.
また原料炭化水素における芳香族オレフィンの含有割合は５０容量％以下であることが好ましく、より好ましくは２０容量％未満である。芳香族オレフィンの含有割合が５０容量％よりも多くなると目的とする芳香族炭化水素の回収量が少ないため経済性が成り立たない。また、芳香族オレフィンの含有割合が２容量％未満の場合は、精製処理する必要性に乏しく経済性が成り立たない。 Moreover, it is preferable that the content rate of the aromatic olefin in raw material hydrocarbon is 50 volume% or less, More preferably, it is less than 20 volume%. If the content ratio of the aromatic olefin is more than 50% by volume, the target aromatic hydrocarbon recovery amount is small and the economic efficiency is not realized. Moreover, when the content rate of an aromatic olefin is less than 2 volume%, the necessity for refinement | purification processing is scarce and economical efficiency is not realized.
なお、原料炭化水素の臭素価は、２０ｇＢｒ２／１００ｇ未満であることが好ましい。 The bromine number of the raw material hydrocarbon is preferably less than 20 gBr 2/100 g.
本発明の方法における重合処理工程では、上記した原料炭化水素に酸触媒を加え、原料炭化水素中の芳香族オレフィンの重合を行う。
本発明における重合処理とは、原料炭化水素に含まれるビニルトルエン、メチルスチレン、アリルベンゼン、インデン等の芳香族オレフィンの９０％以上、好ましくは９５％以上が重合することをいう。芳香族オレフィンの重合率が９０％未満の場合は、精製油の熱安定性が低いために汎用の芳香族溶剤の原料として供することができない。
In the polymerization treatment step in the method of the present invention, an acid catalyst is added to the raw material hydrocarbon described above, and the aromatic olefin in the raw material hydrocarbon is polymerized.
The polymerization treatment in the present invention means that 90% or more, preferably 95% or more of an aromatic olefin such as vinyltoluene, methylstyrene, allylbenzene, and indene contained in the raw material hydrocarbon is polymerized. When the polymerization rate of the aromatic olefin is less than 90%, the heat stability of the refined oil is low, so that it cannot be used as a raw material for a general-purpose aromatic solvent.
重合処理に使用する酸触媒としては、例えば、硫酸、燐酸、塩酸、硝酸等のブレンステッド酸、三弗化硼素およびその錯体、塩化アルミニウム等のルイス酸、および、酸性白土、活性白土、酸性イオン交換樹脂等の固体酸等を挙げることができる。 Examples of the acid catalyst used in the polymerization treatment include Bronsted acid such as sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid, boron trifluoride and its complex, Lewis acid such as aluminum chloride, and acid clay, activated clay, and acidic ion. Examples thereof include solid acids such as exchange resins.
重合処理条件は、原料炭化水素の種類や使用する酸触媒の種類等によって異なるが、酸触媒の使用量は原料炭化水素に対して０．１〜５０重量％が好ましく、より好ましくは０．１〜３０重量％の範囲である。また反応温度は０〜３００℃が好ましく、より好ましくは２０〜２８０℃の範囲である。反応時間としては０．１〜４８時間が好ましく、より好ましくは０．１〜２４時間の範囲である。 The polymerization treatment conditions vary depending on the type of raw material hydrocarbon, the type of acid catalyst used, etc., but the amount of acid catalyst used is preferably 0.1 to 50% by weight, more preferably 0.1%, based on the raw material hydrocarbon. It is in the range of ˜30% by weight. Moreover, 0-300 degreeC of reaction temperature is preferable, More preferably, it is the range of 20-280 degreeC. The reaction time is preferably from 0.1 to 48 hours, more preferably from 0.1 to 24 hours.
重合処理後、重合油を蒸留処理して精製油を回収する。
蒸留処理は、常圧、減圧のいずれでもよいが、重合物の分解を抑制するために減圧が好ましい。この蒸留処理で採取する精製油の沸点温度範囲は、常圧換算で１００〜２５０℃の範囲、好ましくは１５０〜２００℃の範囲である。沸点温度の下限が１００℃未満の場合は、精製油の引火点が低くなるために汎用の芳香族溶剤の原料として供することができない。また、沸点温度の上限が２５０℃を超えると、精製油の粘度が高くなるために汎用の芳香族溶剤の原料として供することができない。
After the polymerization treatment, the purified oil is recovered by distillation of the polymerized oil.
The distillation treatment may be performed at normal pressure or reduced pressure, but reduced pressure is preferred in order to suppress decomposition of the polymer. The boiling point temperature range of the refined oil collected by this distillation treatment is in the range of 100 to 250 ° C., preferably in the range of 150 to 200 ° C. in terms of normal pressure. When the lower limit of the boiling point temperature is less than 100 ° C., the flash point of the refined oil is lowered, so that it cannot be used as a raw material for general-purpose aromatic solvents. Moreover, since the viscosity of refined oil will become high when the upper limit of boiling point temperature exceeds 250 degreeC, it cannot use as a raw material of a general purpose aromatic solvent.
以上のような重合処理および蒸留処理により精製した芳香族炭化水素油は、無色透明で熱安定性に優れており、汎用の芳香族溶剤の原料として用いることができる。 The aromatic hydrocarbon oil refined by the above-described polymerization treatment and distillation treatment is colorless and transparent and excellent in thermal stability, and can be used as a raw material for general-purpose aromatic solvents.
以下に実施例により本発明の内容を具体的に説明するが、本発明はそれらの実施例に限定されるものではない。 EXAMPLES The content of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
（実施例１）
容量３０ｍＬのスクリュー管瓶に原料炭化水素油Ａ（沸点：１７０〜１９０℃、炭素数：９〜１０、臭素価：１１．２ｇＢｒ２／１００ｇ、芳香族濃度：９７．０容量％（芳香族オレフィン濃度：１１容量％））１０ｇと活性白土２．５ｇを入れて、２５℃にてマグネチックスターラーを用いて２４時間攪拌後に静置した。上澄み液の組成をガスクロマトグラフィーで分析し、芳香族オレフィンの代表例としてアリルベンゼンの転化率を求め、その結果を表１に示す。
なお、転化率は以下の式により算出した。
転化率（％）=｛１−（上澄み液中のアリルベンゼン濃度／原料炭化水素油Ａ中のアリルベンゼン濃度）｝×１００
Example 1
Screw tube bottle feedstock hydrocarbon oil A (the boiling point of the capacitor 30 mL: 170 to 190 ° C., the number of carbon atoms: 9-10, bromine number: 11.2gBr 2 / 100g, aromatic concentration: 97.0% by volume (aromatic olefins Concentration: 11% by volume))) and 10 g of activated clay were added, and the mixture was allowed to stand after stirring for 24 hours at 25 ° C. using a magnetic stirrer. The composition of the supernatant liquid was analyzed by gas chromatography, and the conversion rate of allylbenzene was determined as a representative example of the aromatic olefin. The results are shown in Table 1.
The conversion rate was calculated by the following formula.
Conversion (%) = {1- (Allylbenzene concentration in the supernatant / Allylbenzene concentration in the raw material hydrocarbon oil A)} × 100
（比較例１〜６）
活性白土を各種触媒に変更した以外は実施例１と同様にして、アリルベンゼンの転化率を求めた。その結果を表１に示す。
(Comparative Examples 1-6)
The conversion rate of allylbenzene was determined in the same manner as in Example 1 except that the activated clay was changed to various catalysts. The results are shown in Table 1.
（実施例２）
活性白土を２０ｍＬ充填したチューブリアクターに、２２０℃にて原料炭化水素油Ａを毎時１１８ｍＬの速さで４時間通油して、４４２ｍＬ（４０１ｇ）の生成油を得た。生成油の組成をガスクロマトグラフィーで分析した。アリルベンゼンの転化率は１００％であった。
この生成油１００ｍＬ（９０．７ｇ）を常圧蒸留試験器を用いて単蒸留し、初留から１８０℃までの留分５６．１ｇを得た。得られた留分の臭素指数を測定した。臭素指数は４３５ｍｇＢｒ２／１００ｇであった。また、組成をガスクロマトグラフィーで分析した。芳香族濃度は９７．０容量％であった。
(Example 2)
The raw hydrocarbon oil A was passed through a tube reactor filled with 20 mL of activated clay at a rate of 118 mL / hour for 4 hours at 220 ° C. to obtain 442 mL (401 g) of product oil. The composition of the product oil was analyzed by gas chromatography. The conversion rate of allylbenzene was 100%.
100 mL (90.7 g) of this product oil was simply distilled using an atmospheric distillation tester to obtain 56.1 g of a fraction from the initial distillation to 180 ° C. The bromine index of the obtained fraction was measured. Bromine Index was 435mgBr 2 / 100g. The composition was analyzed by gas chromatography. The aromatic concentration was 97.0% by volume.
（実施例３）
活性白土を１１０ｍＬ充填したチューブリアクターに、２４０℃にて原料炭化水素油Ａを毎時６６０ｍＬの速さで１６時間通油して、１０Ｌ（９．１ｋｇ）の生成油を得た。生成油の組成をガスクロマトグラフィーで分析した。アリルベンゼンの転化率は９６．８％であった。この操作を３回行って得た生成油３０Ｌ（２７ｋｇ）を理論段数３０段の回分式常圧蒸留塔を用いて精密蒸留し、１６０℃から１８０℃までの留分１７１５ｋｇを得た。得られた留分の臭素指数を測定した。臭素指数は４７３ｍｇＢｒ２／１００ｇであった。また、組成をガスクロマトグラフィーで分析した。芳香族濃度は９７．０容量％であった。
(Example 3)
The raw hydrocarbon oil A was passed through a tube reactor filled with 110 mL of activated clay at 240 ° C. at a speed of 660 mL / hour for 16 hours to obtain 10 L (9.1 kg) of product oil. The composition of the product oil was analyzed by gas chromatography. The conversion of allylbenzene was 96.8%. 30 L of product oil (27 kg) obtained by performing this operation three times was subjected to precision distillation using a batch-type atmospheric distillation tower having 30 theoretical plates to obtain 1715 kg of a fraction from 160 ° C. to 180 ° C. The bromine index of the obtained fraction was measured. Bromine Index was 473mgBr 2 / 100g. The composition was analyzed by gas chromatography. The aromatic concentration was 97.0% by volume.
本発明により、沸点１００〜２５０℃の芳香族炭化水素を主成分とし、沸点１００〜２５０℃の芳香族オレフィンを含有する芳香族炭化水素油を、汎用の芳香族溶剤の原料として供することが可能となった。 INDUSTRIAL APPLICABILITY According to the present invention, an aromatic hydrocarbon oil containing an aromatic hydrocarbon having a boiling point of 100 to 250 ° C. as a main component and an aromatic olefin having a boiling point of 100 to 250 ° C. can be used as a raw material for a general-purpose aromatic solvent. It became.
（実施例３）
活性白土を１１０ｍＬ充填したチューブリアクターに、２４０℃にて原料炭化水素油Ａを毎時６６０ｍＬの速さで１６時間通油して、１０Ｌ（９．１ｋｇ）の生成油を得た。生成油の組成をガスクロマトグラフィーで分析した。アリルベンゼンの転化率は９６．８％であった。この操作を３回行って得た生成油３０Ｌ（２７ｋｇ）を理論段数３０段の回分式常圧蒸留塔を用いて精密蒸留し、１６０℃から１８０℃までの留分１７ｋｇを得た。得られた留分の臭素指数を測定した。臭素指数は４７３ｍｇＢｒ２／１００ｇであった。また、組成をガスクロマトグラフィーで分析した。芳香族濃度は９７．０容量％であった。
(Example 3)
The raw hydrocarbon oil A was passed through a tube reactor filled with 110 mL of activated clay at 240 ° C. at a speed of 660 mL / hour for 16 hours to obtain 10 L (9.1 kg) of product oil. The composition of the product oil was analyzed by gas chromatography. The conversion of allylbenzene was 96.8%. 30 L of product oil (27 kg) obtained by performing this operation three times was subjected to precision distillation using a batch-type atmospheric distillation tower having 30 theoretical plates, thereby obtaining 17 kg of a fraction from 160 ° C. to 180 ° C. The bromine index of the obtained fraction was measured. Bromine Index was 473mgBr 2 / 100g. The composition was analyzed by gas chromatography. The aromatic concentration was 97.0% by volume.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011139135A JP5841357B2 (en) | 2011-06-23 | 2011-06-23 | Aromatic hydrocarbon oil purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011139135A JP5841357B2 (en) | 2011-06-23 | 2011-06-23 | Aromatic hydrocarbon oil purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013006918A true JP2013006918A (en) | 2013-01-10 |
| JP5841357B2 JP5841357B2 (en) | 2016-01-13 |
Family
ID=47674537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011139135A Active JP5841357B2 (en) | 2011-06-23 | 2011-06-23 | Aromatic hydrocarbon oil purification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5841357B2 (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4932845B2 (en) * | 1971-08-06 | 1974-09-03 | ||
| JPS53119902A (en) * | 1977-03-29 | 1978-10-19 | Nippon Petrochemicals Co Ltd | Treatment of byyproducts from thermal cracking |
| JPS55115830A (en) * | 1979-02-19 | 1980-09-06 | Huels Chemische Werke Ag | Manufacture of 11phenyll1*3*33trimethylindan |
| JPS59117585A (en) * | 1982-11-19 | 1984-07-06 | Nippon Petrochem Co Ltd | Treatment of thermally cracked oil |
| JPS63308092A (en) * | 1987-06-09 | 1988-12-15 | Nippon Steel Chem Co Ltd | Desulfurization of hydrocarbon oil |
| JPH01213305A (en) * | 1988-02-23 | 1989-08-28 | Nippon Steel Chem Co Ltd | Production of hydrogenated hydrocarbon resin |
| US5034562A (en) * | 1990-06-08 | 1991-07-23 | Phillips Petroleum Company | Acid-sulfolance catalyzed production of cyclic alkylated compounds |
| JPH10324878A (en) * | 1997-04-09 | 1998-12-08 | Haldor Topsoee As | Method for removing aromatic compound from hydrocarbon mixture |
-
2011
- 2011-06-23 JP JP2011139135A patent/JP5841357B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4932845B2 (en) * | 1971-08-06 | 1974-09-03 | ||
| JPS53119902A (en) * | 1977-03-29 | 1978-10-19 | Nippon Petrochemicals Co Ltd | Treatment of byyproducts from thermal cracking |
| JPS55115830A (en) * | 1979-02-19 | 1980-09-06 | Huels Chemische Werke Ag | Manufacture of 11phenyll1*3*33trimethylindan |
| JPS59117585A (en) * | 1982-11-19 | 1984-07-06 | Nippon Petrochem Co Ltd | Treatment of thermally cracked oil |
| JPS63308092A (en) * | 1987-06-09 | 1988-12-15 | Nippon Steel Chem Co Ltd | Desulfurization of hydrocarbon oil |
| JPH01213305A (en) * | 1988-02-23 | 1989-08-28 | Nippon Steel Chem Co Ltd | Production of hydrogenated hydrocarbon resin |
| US5034562A (en) * | 1990-06-08 | 1991-07-23 | Phillips Petroleum Company | Acid-sulfolance catalyzed production of cyclic alkylated compounds |
| JPH10324878A (en) * | 1997-04-09 | 1998-12-08 | Haldor Topsoee As | Method for removing aromatic compound from hydrocarbon mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5841357B2 (en) | 2016-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5327485B2 (en) | Method for separating 1,3-butadiene from crude C4 fraction using acetylene conversion | |
| TWI745381B (en) | Production method of isopropanol and isopropanol with reduced impurities | |
| TWI679186B (en) | Method for producing hexafluoro-1,3-butadiene | |
| JP2004500970A (en) | Method for isolating the source of concentration of conductive polymer precursor | |
| KR20090016561A (en) | Process for hydrogen peroxide production including step for regeneration of working solution | |
| RU2014108327A (en) | METHOD FOR PRODUCING OLEFINS AND AROMATIC HYDROCARBONS | |
| JP5946960B2 (en) | Preparation of polymers of thiophene, benzothiophene, and their alkylated derivatives | |
| JP5841357B2 (en) | Aromatic hydrocarbon oil purification method | |
| CN103865625A (en) | Method for solvent extraction regeneration of waste engine oil | |
| WO2007107202A1 (en) | Method for preparing linear alpha-olefins with removal of aromatic by-products and reactor system therefor | |
| JP2014177416A (en) | Method for purifying carbonate | |
| JP4592529B2 (en) | Process for producing refined naphthalene absorption oil | |
| CN105693455B (en) | A kind of synthetic method of 1,5,9- cyclodoecatrienes | |
| CN115340437A (en) | Extractive distillation method of hexafluorobutadiene | |
| CN110606798A (en) | Method for preparing benzyl alcohol by using microchannel reactor without alkali | |
| JP2006335715A (en) | High-quality vinylbenzoic acid tertiary butyl ester and method for producing the same | |
| EP2123353B1 (en) | Extraction of boron trifluoride or complexes thereof from a mixture of reaction products by using hydrofluorocarbon or oxygenic hydrofluorocarbon as the extraction solvent | |
| RU2810167C1 (en) | Method of separation and isolation of boron trifluoride and its complexes in reaction of olefins polymerization | |
| JP2987230B2 (en) | Desulfurization purification method of aromatic hydrocarbon | |
| JP2019006724A (en) | Tetrahydropyran and method of purifying tetrahydropyran | |
| JP5481270B2 (en) | Method for reducing sulfur compounds in hydrocarbon oils | |
| JP4286529B2 (en) | Methods for recovering and recycling boron trifluoride or its complexes | |
| US20050256350A1 (en) | Hydrocarbon mixtures comprising modified polycyclic aromatic hydrocarbons | |
| JP2009007288A (en) | Cleaning method for solid matter and purification method for meta-cresol | |
| JP2007302766A (en) | Method and apparatus for treating plastic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140613 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150312 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150331 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150522 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20151027 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20151113 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5841357 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |