JP2010077170A - Desulfurization method of hydrocarbon oil, and hydrocarbon resin - Google Patents
Desulfurization method of hydrocarbon oil, and hydrocarbon resin Download PDFInfo
- Publication number
- JP2010077170A JP2010077170A JP2008243604A JP2008243604A JP2010077170A JP 2010077170 A JP2010077170 A JP 2010077170A JP 2008243604 A JP2008243604 A JP 2008243604A JP 2008243604 A JP2008243604 A JP 2008243604A JP 2010077170 A JP2010077170 A JP 2010077170A
- Authority
- JP
- Japan
- Prior art keywords
- hydrocarbon oil
- hydrocarbon
- sulfur
- acid
- ppm
- 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.)
- Pending
Links
Abstract
Description
本発明は、炭化水素油（特に、ナフサから得られた成分を主体とし、キシレン、スチレン、ビニルトルエン、ジシクロペンタジエン、インデン、ナフタレン等の芳香族炭化水素油又は当該芳香族炭化水素を含有する炭化水素油）の脱硫方法に関する。 The present invention is a hydrocarbon oil (especially an aromatic hydrocarbon oil such as xylene, styrene, vinyltoluene, dicyclopentadiene, indene, naphthalene, or the like, mainly composed of components obtained from naphtha or the aromatic hydrocarbon. The present invention relates to a desulfurization method of hydrocarbon oil).
キシレン、スチレン、ビニルトルエン、ジシクロペンタジエン、インデン、ナフタレン等の芳香族炭化水素は、ナフサから分離することによって得られるが、いずれも不純物として硫黄化合物を含有している。これら芳香族炭化水素は各種石油化学製品あるいは石油化学製品の中間原料の基礎原料として使用されるが、これらの製品或いは中間原料を製造する際に、硫黄化合物は触媒毒となるので、脱硫処理が必要となる場合が多い。 Aromatic hydrocarbons such as xylene, styrene, vinyltoluene, dicyclopentadiene, indene and naphthalene are obtained by separation from naphtha, but all contain sulfur compounds as impurities. These aromatic hydrocarbons are used as basic raw materials for various petrochemical products or intermediate raw materials for petrochemical products. When these products or intermediate raw materials are produced, sulfur compounds become catalyst poisons. Often required.
しかしながら、これら芳香族炭化水素に含まれる硫黄化合物はチオフェン類や、ベンゾチオフェン類、ジベンゾチオフェン類等の芳香族硫黄化合物であって、沸点その他の性状が類似していることから、蒸留で精密に分離することは容易ではない。 However, the sulfur compounds contained in these aromatic hydrocarbons are aromatic sulfur compounds such as thiophenes, benzothiophenes, dibenzothiophenes, etc. and have similar boiling points and other properties. It is not easy to separate.
そこで、炭化水素油を蒸留し、得られた蒸留留分に酸触媒を加えて重合し、脱硫を行う方法が提案されている（特許文献１参照）。当該方法によれば、硫黄化合物の含有量を低減できるものの、その効果は十分ではなく、また重合成分から炭化水素油を分離するために蒸留工程が必要であり、そのための蒸留設備が必要となり、また、蒸留のために時間を要する等の問題を有していた。また、反応を伴わない物理吸着剤で硫黄化合物を吸着除去する方法（特許文献２参照）も検討されているが、その効果は十分ではなかった。 Then, the method of distilling hydrocarbon oil, adding an acid catalyst to the obtained distillation fraction, polymerizing, and desulfurizing is proposed (refer patent document 1). According to the method, although the content of the sulfur compound can be reduced, the effect is not sufficient, and a distillation step is required to separate the hydrocarbon oil from the polymerization component, and a distillation facility for that purpose is required. In addition, there is a problem that it takes time for distillation. Moreover, although the method (refer patent document 2) of adsorbing and removing a sulfur compound with the physical adsorption agent which does not accompany reaction is also examined, the effect was not enough.
本発明は、容易に、炭化水素油中に含まれる硫黄化合物を微量濃度まで低減する方法を提供すること、また、硫黄化合物の含有量を低減した炭化水素油を用いて硫黄化合物の含有量が低減された炭化水素樹脂を提供することを課題とする。 The present invention provides a method for easily reducing a sulfur compound contained in a hydrocarbon oil to a trace concentration, and the content of the sulfur compound is reduced using a hydrocarbon oil with a reduced content of the sulfur compound. It is an object of the present invention to provide a reduced hydrocarbon resin.
本発明者は、上記課題を解決するために鋭意研究を進めた結果、不純物として硫黄化合物を含むナフサから得られた炭化水素油の一部を重合し、必要に応じて得られた重合物含有炭化水素油から重合物を除去する工程を経て、炭化水素油に特定の吸着剤を接触させることにより、硫黄化合物の含有量を低減した炭化水素油が得られることを見出し、本発明を完成させた。 As a result of diligent research to solve the above problems, the present inventors polymerized a part of hydrocarbon oil obtained from naphtha containing a sulfur compound as an impurity, and contained a polymer obtained as necessary. Through the process of removing the polymer from the hydrocarbon oil, it was found that a hydrocarbon oil with a reduced content of sulfur compounds can be obtained by bringing the hydrocarbon oil into contact with a specific adsorbent, thereby completing the present invention. It was.
すなわち、本発明は、ナフサから得られた沸点１００℃〜２５０℃の成分を主体とし、不純物として硫黄化合物を含有する炭化水素油に、（１）酸性触媒を加え、炭化水素油全体の０．０１〜３０重量％の範囲内で重合反応を行う工程、（２）必要に応じて得られた重合物含有炭化水素油から重合物を除去する工程を経て、（３）炭化水素油に、活性白土、酸性白土及び酸性イオン交換樹脂からなる群から選ばれる少なくとも一種の吸着剤を接触させる工程を有することを特徴とする炭化水素油の脱硫方法；当該方法で脱硫処理を行った炭化水素油を重合処理することにより得られた硫黄含有量が１６０ｐｐｍ以下の炭化水素樹脂に関するものである。 That is, the present invention comprises (1) an acidic catalyst added to a hydrocarbon oil mainly containing a component having a boiling point of 100 ° C. to 250 ° C. obtained from naphtha and containing a sulfur compound as an impurity. A step of performing a polymerization reaction within a range of 01 to 30% by weight; (2) a step of removing the polymer from the polymer-containing hydrocarbon oil obtained as necessary; and (3) an activity on the hydrocarbon oil. A hydrocarbon oil desulfurization method comprising a step of contacting at least one adsorbent selected from the group consisting of clay, acidic clay and acidic ion exchange resin; The present invention relates to a hydrocarbon resin having a sulfur content of 160 ppm or less obtained by polymerization.
本発明によれば、容易に炭化水素油中に含まれる硫黄化合物を微量濃度まで低減することができる。また、硫黄化合物の含有量を低減した炭化水素油を重合処理することにより硫黄化合物の含有量が低減された炭化水素樹脂を提供することができる。 According to the present invention, the sulfur compound contained in the hydrocarbon oil can be easily reduced to a very small concentration. Moreover, the hydrocarbon resin by which content of the sulfur compound was reduced can be provided by polymerizing the hydrocarbon oil which reduced content of the sulfur compound.
本発明は、ナフサから得られた沸点１００℃〜２５０℃の成分を主体とし、不純物として硫黄化合物を含有する炭化水素油に、（１）酸性触媒を加え、炭化水素油全体の０．０１〜３０重量％の範囲内で重合反応を行う工程、（２）必要に応じて得られた重合物含有炭化水素油から重合物を除去する工程を経て、（３）炭化水素油に、活性白土、酸性白土及び酸性イオン交換樹脂からなる群から選ばれる少なくとも一種の吸着剤を接触させる工程を有することを特徴とする。 The present invention mainly comprises a component having a boiling point of 100 ° C. to 250 ° C. obtained from naphtha, and a hydrocarbon oil containing a sulfur compound as an impurity. A step of performing a polymerization reaction within a range of 30% by weight, (2) a step of removing the polymer from the polymer-containing hydrocarbon oil obtained as necessary, and (3) an activated clay, It has the process of making the at least 1 sort (s) of adsorption agent chosen from the group which consists of acidic clay and acidic ion exchange resin contact.
本発明の脱硫方法が好適に適用できる炭化水素油としては、特に、ナフサから得られた沸点１００℃〜２５０℃（好ましくは１４０℃〜２００℃）の成分を主体とし、キシレン、スチレン、ビニルトルエン、ジシクロペンタジエン、インデン、ナフタレン等の芳香族炭化水素油又は前記芳香族炭化水素を含んだ炭化水素油が挙げられる。なお、当該硫黄を含有する炭化水素油中に含まれる硫黄分量は、限定されないが、通常、５０〜５００ｐｐｍ程度含有する場合に、脱硫効率が向上するため、特に好ましい。なお、硫黄の含有量は、蛍光Ｘ線による値である。 The hydrocarbon oil to which the desulfurization method of the present invention can be suitably applied is mainly composed of components having a boiling point of 100 ° C. to 250 ° C. (preferably 140 ° C. to 200 ° C.) obtained from naphtha, and xylene, styrene, vinyl toluene. And aromatic hydrocarbon oils such as dicyclopentadiene, indene and naphthalene, or hydrocarbon oils containing the aromatic hydrocarbons. In addition, although the sulfur content contained in the hydrocarbon oil containing the said sulfur is not limited, Since a desulfurization efficiency improves normally when it contains about 50-500 ppm normally, it is especially preferable. Note that the sulfur content is a value by fluorescent X-rays.
本発明で使用する酸性触媒は、炭化水素油中の硫黄化合物同士及び／又は硫黄化合物と芳香族炭化水素との反応（すなわち、チオフェン環とベンゼン環の反応など）を触媒して重質な硫黄化合物の生成を促進するものである。 The acidic catalyst used in the present invention catalyses the reaction between sulfur compounds in hydrocarbon oils and / or the reaction between sulfur compounds and aromatic hydrocarbons (that is, the reaction between thiophene ring and benzene ring, etc.) It promotes the formation of compounds.
酸性触媒として具体的には、ブレンステッド酸、ルイス酸、固体酸などが用いられる。これらの具体例としては、三フッ化ホウ素及びその錯体、硫酸、リン酸、塩酸、硝酸、塩化アルミニウム、活性白土、酸性白土、酸性イオン交換樹脂などを挙げることができる。 Specifically, a Bronsted acid, a Lewis acid, a solid acid, or the like is used as the acidic catalyst. Specific examples thereof include boron trifluoride and its complex, sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, aluminum chloride, activated clay, acidic clay, and acidic ion exchange resin.
酸性触媒と炭化水素油とを接触させる方法は、特に限定されず公知の方法を採用することができる。具体的には、たとえば、回分式（バッチ式）でも流通式でも良い。流通式の場合、容器に成形された固体酸触媒を充填して炭化水素油を流通する流通式でも良い。
脱硫処理を行う温度は、固体酸触媒の場合、重質な硫黄化合物を生成する硫黄化合物同士及び／又は硫黄化合物と芳香族炭化水素との反応を伴うので若干高めが好ましく１０〜２００℃程度、特には３０〜１００℃が好ましい。遷移金属酸化物担持活性炭の場合、反応は期待できないが、物理吸着能に優れているので、物理吸着に適する１５０℃以下の温度が好ましく、特には０〜８０℃が好ましい。なお、接触時間は特に限定されないが、通常、５分〜３時間程度である。なお、酸性触媒の使用量は特に限定されないが、通常、炭化水素油１００重量部に対し、０．１〜５０重量部程度である。
A method for bringing the acidic catalyst into contact with the hydrocarbon oil is not particularly limited, and a known method can be adopted. Specifically, for example, a batch type (batch type) or a distribution type may be used. In the case of a circulation type, a circulation type in which a solid acid catalyst formed in a container is filled and hydrocarbon oil is circulated may be used.
In the case of a solid acid catalyst, the temperature at which the desulfurization treatment is performed is preferably slightly higher because it involves a reaction between sulfur compounds that produce heavy sulfur compounds and / or sulfur compounds and aromatic hydrocarbons. In particular, 30 to 100 ° C. is preferable. In the case of transition metal oxide-supported activated carbon, no reaction can be expected, but since the physical adsorption ability is excellent, a temperature of 150 ° C. or less suitable for physical adsorption is preferable, and 0 to 80 ° C. is particularly preferable. The contact time is not particularly limited, but is usually about 5 minutes to 3 hours. In addition, although the usage-amount of an acidic catalyst is not specifically limited, Usually, it is about 0.1-50 weight part with respect to 100 weight part of hydrocarbon oils.
重合は、通常、重合物の量が、炭化水素油全体の０．０１〜３０重量％となるまで行う。重合物の量は、ゲルパーメーションクロマトグラフィー法（ＧＰＣ法）によるポリスチレン換算値により決定される。また、得られた重合物を再沈や、蒸留精製することにより重量を算出する方法等を用いることができる。 The polymerization is usually performed until the amount of the polymer becomes 0.01 to 30% by weight of the entire hydrocarbon oil. The amount of the polymer is determined by the polystyrene conversion value by gel permeation chromatography method (GPC method). In addition, a method of calculating the weight by reprecipitation or distillation purification of the obtained polymer can be used.
重合反応工程を終えた炭化水素油は、そのまま、吸着剤に接触させてもよいが、必要に応じて蒸留もしくは再沈等の方法により、得られた重合物含有炭化水素油から重合物を除去する工程を設けてもよい。使用する吸着剤としては、活性白土、酸性白土及び酸性イオン交換樹脂が用いられる。なお、吸着剤は、前処理として、吸着している微量の水分を予め除去することが好ましい。水分が吸着していると、硫黄化合物の吸着を阻害するばかりか、炭化水素油の導入開始直後に吸着剤から脱離した水分が炭化水素に混入するためである。吸着剤の使用量は特に限定されないが、通常、炭化水素油１００重量部に対し、０．１〜５０重量部程度である。 The hydrocarbon oil that has undergone the polymerization reaction step may be contacted with the adsorbent as it is, but if necessary, the polymer is removed from the resulting polymer-containing hydrocarbon oil by distillation or reprecipitation. You may provide the process to do. As the adsorbent used, activated clay, acidic clay and acidic ion exchange resin are used. Note that the adsorbent preferably removes a small amount of adsorbed moisture in advance as a pretreatment. This is because moisture adsorbed not only inhibits adsorption of sulfur compounds, but also desorbs moisture from the adsorbent immediately after the start of introduction of hydrocarbon oil. Although the usage-amount of an adsorbent is not specifically limited, Usually, it is about 0.1-50 weight part with respect to 100 weight part of hydrocarbon oils.
炭化水素油と吸着剤を接触させる方法としては特に限定されず公知の方法を採用することができる。具体的には、回分式反応器に炭化水素油と吸着剤を加え混合する方法又は固定床を使用した流通式反応器で、固定床として吸着剤を用い、炭化水素油を流通させる方法などが挙げられる。炭化水素油と吸着剤を接触させる際の温度は特に限定されないが、通常、０〜１００℃程度であり、接触時間は、５分〜３時間程度である。 The method for bringing the hydrocarbon oil and the adsorbent into contact is not particularly limited, and a known method can be employed. Specifically, there are a method of adding hydrocarbon oil and adsorbent to a batch reactor and mixing them, or a method of circulating hydrocarbon oil using an adsorbent as a fixed bed in a flow reactor using a fixed bed. Can be mentioned. Although the temperature at the time of making hydrocarbon oil and an adsorbent contact is not specifically limited, Usually, it is about 0-100 degreeC, and contact time is about 5 minutes-3 hours.
前記方法で処理された炭化水素油を、公知の方法により吸着剤をろ別することにより、硫黄分の含有量が低減された炭化水素油を得ることができる。このようにして得られた炭化水素油に含まれる硫黄分は、原料として使用する炭化水素油に含まれる硫黄分の量、重合時間や吸着材の使用量を変更することにより制御することができるが、通常、１２０ｐｐｍ程度以下にすることが好ましい。 By separating the adsorbent from the hydrocarbon oil treated by the above method by a known method, a hydrocarbon oil having a reduced sulfur content can be obtained. The sulfur content contained in the hydrocarbon oil thus obtained can be controlled by changing the amount of sulfur contained in the hydrocarbon oil used as a raw material, the polymerization time and the amount of adsorbent used. However, it is usually preferable to set it to about 120 ppm or less.
このようにして得られた脱硫炭化水素油は、さらに重合処理することにより炭化水素樹脂とすることができる。炭化水素樹脂は、公知の方法により得ることができる。通常は、該脱硫炭化水素油に三フッ化ホウ素等のカチオン重合性触媒を添加し、重合すればよい。たとえば、特開平１−２１３３０５号公報に記載の方法を採用できる。当該方法により得られる炭化水素樹脂は、硫黄含有量が、通常、１６０ｐｐｍ以下である。 The desulfurized hydrocarbon oil obtained in this way can be converted into a hydrocarbon resin by further polymerization treatment. The hydrocarbon resin can be obtained by a known method. Usually, the desulfurized hydrocarbon oil may be polymerized by adding a cationic polymerizable catalyst such as boron trifluoride. For example, the method described in JP-A-1-213305 can be employed. The hydrocarbon resin obtained by this method usually has a sulfur content of 160 ppm or less.
以下、本発明を実施例により、さらに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。なお、硫黄分の含有量は、Ｒｉｇａｋｕ製波長分散型蛍光Ｘ線分析装置ＺＳＸ−１００ｅを用い、ＳＱＸ計算により決定した。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. The sulfur content was determined by SQX calculation using a wavelength dispersive X-ray fluorescence spectrometer ZSX-100e manufactured by Rigaku.
実施例１
ナフサから得られ、硫黄を１５９ｐｐｍ含有する沸点１４０℃〜２００℃の炭化水素油１００ｇに対し、活性白土０．５ｇ（炭化水素油に対し、０．５重量％）を加え、１２０℃で３０分間攪拌し重合反応を行った。活性白土をろ別した後に、炭化水素油の硫黄量を測定したところ１５０ｐｐｍであった。また、重合反応により生成した樹脂成分は炭化水素油全体の２．０％であった。このろ液２０ｇに対し０．１ｇ（０．５重量％）の活性白土を加え、室温で１時間攪拌し、吸着処理を行った。活性白土をろ別した後に得られた炭化水素油の硫黄量を測定したところ、１１５ｐｐｍであった。
Example 1
To 100 g of hydrocarbon oil having a boiling point of 140 ° C. to 200 ° C. obtained from naphtha and containing 159 ppm of sulfur, 0.5 g of activated clay (0.5% by weight based on hydrocarbon oil) is added, and 120 ° C. for 30 minutes. The polymerization reaction was carried out with stirring. After the activated clay was filtered off, the sulfur content of the hydrocarbon oil was measured and found to be 150 ppm. Moreover, the resin component produced | generated by the polymerization reaction was 2.0% of the whole hydrocarbon oil. 0.1 g (0.5% by weight) of activated clay was added to 20 g of the filtrate, and the mixture was stirred at room temperature for 1 hour for adsorption treatment. The sulfur content of the hydrocarbon oil obtained after filtering off the activated clay was measured and found to be 115 ppm.
実施例２
吸着処理した活性白土の量を０．４ｇ（２重量％）とした以外は実施例１と同様の方法で脱硫処理を行った。得られた炭化水素油の硫黄量は１１１ｐｐｍであった。
Example 2
A desulfurization treatment was performed in the same manner as in Example 1 except that the amount of the activated clay subjected to the adsorption treatment was changed to 0.4 g (2% by weight). The obtained hydrocarbon oil had a sulfur content of 111 ppm.
比較例１
ナフサから得られ、硫黄を１５９ｐｐｍ含有する沸点１４０℃〜２００℃の炭化水素油１００ｇに対し、０．５ｇ（０．５重量％）の活性白土を加え、室温で１時間攪拌し、吸着処理を行った。活性白土をろ別した後に得られた炭化水素油の硫黄量を測定したところ、１５４ｐｐｍであった。
Comparative Example 1
To 100 g of hydrocarbon oil having a boiling point of 140 ° C. to 200 ° C. obtained from naphtha and containing 159 ppm of sulfur, 0.5 g (0.5 wt%) of activated clay is added and stirred at room temperature for 1 hour to perform the adsorption treatment. went. When the sulfur content of the hydrocarbon oil obtained after filtering off the activated clay was measured, it was 154 ppm.
実施例３
ナフサから得られ、硫黄を１５９ｐｐｍ含有する沸点１４０℃〜２００℃の炭化水素油１００ｇに対し、活性白土０．５ｇ（炭化水素油に対し、０．５重量％）を加え、９０℃で３０分間攪拌し重合反応を行った。活性白土をろ別した後に、炭化水素油の硫黄量を測定したところ１３４ｐｐｍであった。また、重合反応により生成した樹脂成分は炭化水素油全体の１．０重量％であった。このろ液２０ｇに対し０．１ｇ（０．５重量％）の活性白土を加え、１時間攪拌し、吸着処理を行った。活性白土をろ別した後に得られた炭化水素油の硫黄量を測定したところ、１２０ｐｐｍであった。
Example 3
Activated clay 0.5g (0.5% by weight with respect to hydrocarbon oil) is added to 100g of hydrocarbon oil having a boiling point of 140 ° C to 200 ° C and containing 159ppm of sulfur, which is obtained from naphtha, at 90 ° C for 30 minutes. The polymerization reaction was carried out with stirring. After the activated clay was filtered off, the sulfur content of the hydrocarbon oil was measured and found to be 134 ppm. Moreover, the resin component produced | generated by the polymerization reaction was 1.0 weight% of the whole hydrocarbon oil. 0.1 g (0.5% by weight) of activated clay was added to 20 g of the filtrate, and the mixture was stirred for 1 hour to perform an adsorption treatment. The sulfur content of the hydrocarbon oil obtained after filtering off the activated clay was measured and found to be 120 ppm.
実施例４
吸着処理した活性白土の量を０．４ｇ（２重量％）とした以外は実施例３と同様の方法で脱硫処理を行った。得られた炭化水素油の硫黄量は１０３ｐｐｍであった。
Example 4
A desulfurization treatment was performed in the same manner as in Example 3 except that the amount of the activated clay subjected to the adsorption treatment was changed to 0.4 g (2% by weight). The resulting hydrocarbon oil had a sulfur content of 103 ppm.
実施例５
ナフサから得られ、硫黄を１５９ｐｐｍ含有する沸点１４０℃〜２００℃の炭化水素油１００ｇに対し、活性白土０．５ｇ（炭化水素油に対し、０．５重量％）を加え、６０℃で３０分間攪拌し重合反応を行った。活性白土をろ別した後に、炭化水素油の硫黄量を測定したところ１１６ｐｐｍであった。重合反応により生成した樹脂成分は炭化水素油全体の０．５重量％であった。このろ液２０ｇに対し０．１ｇ（０．５重量％）の活性白土を加え、１時間攪拌し、吸着処理を行った。活性白土をろ別した後に得られた炭化水素油の硫黄量を測定したところ、１０１ｐｐｍであった。
Example 5
Activated clay 0.5g (0.5% by weight with respect to hydrocarbon oil) is added to 100g of hydrocarbon oil obtained from naphtha and having a boiling point of 140 ° C to 200 ° C and containing 159ppm of sulfur, and 30 minutes at 60 ° C. The polymerization reaction was carried out with stirring. After the activated clay was filtered off, the sulfur content of the hydrocarbon oil was measured and found to be 116 ppm. The resin component produced by the polymerization reaction was 0.5% by weight of the total hydrocarbon oil. 0.1 g (0.5% by weight) of activated clay was added to 20 g of the filtrate, and the mixture was stirred for 1 hour to perform an adsorption treatment. The sulfur content of the hydrocarbon oil obtained after filtering off the activated clay was measured and found to be 101 ppm.
実施例６
吸着処理した活性白土の量を０．４ｇ（２重量％）とした以外は実施例５と同様の方法で脱硫処理を行った。得られた炭化水素油の硫黄量は８７ｐｐｍであった。
Example 6
A desulfurization treatment was performed in the same manner as in Example 5 except that the amount of the activated clay subjected to the adsorption treatment was changed to 0.4 g (2% by weight). The resulting hydrocarbon oil had a sulfur content of 87 ppm.
比較例２
ナフサから得られた硫黄を１５９ｐｐｍ含有する炭化水素油を特開平１−２１３３０５号公報に記載された方法と同様の方法で重合反応を行い、炭化水素樹脂を得た。得られた炭化水素樹脂の硫黄量を測定したところ、２３３ｐｐｍであった。
Comparative Example 2
A hydrocarbon oil containing 159 ppm of sulfur obtained from naphtha was subjected to a polymerization reaction in the same manner as described in JP-A-1-213305 to obtain a hydrocarbon resin. When the amount of sulfur of the obtained hydrocarbon resin was measured, it was 233 ppm.
実施例７
実施例１で得られた硫黄を１１５ｐｐｍ含む炭化水素油を用いた以外は比較例２と同様の方法にて重合反応を行い、炭化水素樹脂を得た。得られた炭化水素樹脂の硫黄量を測定したところ、１５８ｐｐｍであった。
Example 7
A hydrocarbon resin was obtained by performing a polymerization reaction in the same manner as in Comparative Example 2 except that the hydrocarbon oil containing 115 ppm of sulfur obtained in Example 1 was used. When the amount of sulfur of the obtained hydrocarbon resin was measured, it was 158 ppm.
実施例８
実施例２で得られた硫黄を１１１ｐｐｍ含む炭化水素油を用いた以外は比較例２と同様の方法にて重合反応を行い、炭化水素樹脂を得た。得られた炭化水素樹脂の硫黄量を測定したところ、１５１ｐｐｍであった。
Example 8
A polymerization reaction was performed in the same manner as in Comparative Example 2 except that the hydrocarbon oil containing 111 ppm of sulfur obtained in Example 2 was used to obtain a hydrocarbon resin. When the amount of sulfur of the obtained hydrocarbon resin was measured, it was 151 ppm.
比較例３
比較例１で得られた硫黄を１５４ｐｐｍ含む炭化水素油を用いた以外は比較例２と同様の方法にて重合反応を行い、炭化水素樹脂を得た。得られた炭化水素樹脂の硫黄量を測定したところ、２１５ｐｐｍであった。
Comparative Example 3
A polymerization reaction was performed in the same manner as in Comparative Example 2 except that the hydrocarbon oil containing 154 ppm of sulfur obtained in Comparative Example 1 was used to obtain a hydrocarbon resin. When the amount of sulfur of the obtained hydrocarbon resin was measured, it was 215 ppm.
実施例９
実施例３で得られた硫黄を１２０ｐｐｍ含む炭化水素油を用いた以外は比較例２と同様の方法にて重合反応を行い、炭化水素樹脂を得た。得られた炭化水素樹脂の硫黄量を測定したところ、１５９ｐｐｍであった。
Example 9
A polymerization reaction was performed in the same manner as in Comparative Example 2 except that the hydrocarbon oil containing 120 ppm of sulfur obtained in Example 3 was used to obtain a hydrocarbon resin. When the amount of sulfur of the obtained hydrocarbon resin was measured, it was 159 ppm.
実施例１０
実施例４で得られた硫黄を１０３ｐｐｍ含む炭化水素油を用いた以外は比較例２と同様の方法にて重合反応を行い、炭化水素樹脂を得た。得られた炭化水素樹脂の硫黄量を測定したところ、１４０ｐｐｍであった。
Example 10
A polymerization reaction was performed in the same manner as in Comparative Example 2 except that the hydrocarbon oil containing 103 ppm of sulfur obtained in Example 4 was used to obtain a hydrocarbon resin. When the amount of sulfur of the obtained hydrocarbon resin was measured, it was 140 ppm.
実施例１１
実施例５で得られた硫黄を１０１ｐｐｍ含む炭化水素油を用いた以外は比較例２と同様の方法にて重合反応を行い、炭化水素樹脂を得た。得られた炭化水素樹脂の硫黄量を測定したところ、１３８ｐｐｍであった。
Example 11
A polymerization reaction was performed in the same manner as in Comparative Example 2 except that the hydrocarbon oil containing 101 ppm of sulfur obtained in Example 5 was used to obtain a hydrocarbon resin. When the amount of sulfur of the obtained hydrocarbon resin was measured, it was 138 ppm.
実施例１２
実施例６で得られた硫黄を８７ｐｐｍ含む炭化水素油を用いた以外は比較例２と同様の方法にて重合反応を行い、炭化水素樹脂を得た。得られた炭化水素樹脂の硫黄量を測定したところ、１１９ｐｐｍであった。
Example 12
A polymerization reaction was performed in the same manner as in Comparative Example 2 except that the hydrocarbon oil containing 87 ppm of sulfur obtained in Example 6 was used to obtain a hydrocarbon resin. When the amount of sulfur of the obtained hydrocarbon resin was measured, it was 119 ppm.
Claims (7)
A hydrocarbon resin having a sulfur content of 160 ppm or less obtained by polymerizing a hydrocarbon oil that has been desulfurized by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008243604A JP2010077170A (en) | 2008-09-24 | 2008-09-24 | Desulfurization method of hydrocarbon oil, and hydrocarbon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008243604A JP2010077170A (en) | 2008-09-24 | 2008-09-24 | Desulfurization method of hydrocarbon oil, and hydrocarbon resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2010077170A true JP2010077170A (en) | 2010-04-08 |
Family
ID=42207989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008243604A Pending JP2010077170A (en) | 2008-09-24 | 2008-09-24 | Desulfurization method of hydrocarbon oil, and hydrocarbon resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2010077170A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289728A (en) * | 2012-03-03 | 2013-09-11 | 辽宁石油化工大学 | Straight-run diesel oil desulfurating method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2002322483A (en) * | 2001-04-24 | 2002-11-08 | Idemitsu Kosan Co Ltd | Method for desulfurization of liquid oil containing organic sulfur compound |
| JP2007537332A (en) * | 2004-05-14 | 2007-12-20 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Method for removing sulfur from naphtha |
| JP2008133377A (en) * | 2006-11-29 | 2008-06-12 | Sekiyu Combinat Kodo Togo Unei Gijutsu Kenkyu Kumiai | Method for producing low-sulfur hydrocarbon oil |
-
2008
- 2008-09-24 JP JP2008243604A patent/JP2010077170A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2002322483A (en) * | 2001-04-24 | 2002-11-08 | Idemitsu Kosan Co Ltd | Method for desulfurization of liquid oil containing organic sulfur compound |
| JP2007537332A (en) * | 2004-05-14 | 2007-12-20 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Method for removing sulfur from naphtha |
| JP2008133377A (en) * | 2006-11-29 | 2008-06-12 | Sekiyu Combinat Kodo Togo Unei Gijutsu Kenkyu Kumiai | Method for producing low-sulfur hydrocarbon oil |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289728A (en) * | 2012-03-03 | 2013-09-11 | 辽宁石油化工大学 | Straight-run diesel oil desulfurating method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ania et al. | Importance of structural and chemical heterogeneity of activated carbon surfaces for adsorption of dibenzothiophene | |
| KR101759351B1 (en) | Method for Hydro-cracking Heavy Hydrocarbon Fractions Using Supercritical Solvents | |
| KR20100076965A (en) | Solid acid, process for producing the solid acid, method for desulfurizing hydrocarbon oil using solid acid as desulfurizing agent | |
| CN1394230A (en) | Process for removing mercury from liquid hydrocarbon | |
| JP2005522530A5 (en) | ||
| JP4366583B2 (en) | Integrated process for desulfurization of effluents from hydrocarbon cracking or steam cracking processes | |
| JP2010077170A (en) | Desulfurization method of hydrocarbon oil, and hydrocarbon resin | |
| CN1267536C (en) | Desulfurizing method for distillate | |
| JP2008534752A (en) | Method for removing colored bodies from hydrocarbon fuels using activated carbon | |
| CN1891792A (en) | Petroleum solvent oil refining adsorbent, and its preparing method and use | |
| CN101054529A (en) | Method of refining solvent oil | |
| JPS6247852B2 (en) | ||
| EP4105298A1 (en) | Method for removing chlorine from high chlorine content waste oil using solid acid substances | |
| CN103752271A (en) | Mineral spirit refining adsorbent and preparation method thereof | |
| EP4281516A1 (en) | Process for hydrodepolymerization of polymeric waste material | |
| JP4787598B2 (en) | Processing method of plastic decomposition oil | |
| US2745793A (en) | Deleading gasoline | |
| JP4863186B2 (en) | Process for producing olefin polymer | |
| JP2008537758A (en) | Method for removing colored bodies from hydrocarbon fuels using activated carbon | |
| US11118118B2 (en) | Process for reducing nitrogen content of hydrocarbon feed | |
| CN103275252B (en) | Method for purification treatment on styrene polymerization recovered liquid | |
| JP2819178B2 (en) | Purification method of dicyclopentadiene | |
| JPH11181447A (en) | Removal of mercury from hydrocarbon oil | |
| JP6393235B2 (en) | Adsorption removal of anilines from catalytic cracking gasoline | |
| CA3110400C (en) | Process for removing sulfur in crude oil using microwaves |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110807 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120911 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130228 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130306 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20130627 |