JP2013245294A - Adsorptive desulfurization method of heavy oil - Google Patents
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 40
- 230000023556 desulfurization Effects 0.000 title claims abstract description 40
- 239000000295 fuel oil Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000000274 adsorptive effect Effects 0.000 title claims abstract description 18
- 239000003245 coal Substances 0.000 claims abstract description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 18
- 150000002898 organic sulfur compounds Chemical class 0.000 claims abstract description 16
- 239000003463 adsorbent Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010742 number 1 fuel oil Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000011593 sulfur Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000011280 coal tar Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011338 soft pitch Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004058 oil shale Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007841 coal based oil Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
本発明は、硫黄化合物を含有する重質油の吸着脱硫方法に関し、特に、硫黄化合物を含有する石炭系重質油に適した吸着脱硫方法に関する。 The present invention relates to an adsorptive desulfurization method for heavy oil containing a sulfur compound, and more particularly to an adsorptive desulfurization method suitable for coal-based heavy oil containing a sulfur compound.
石油、石炭などの化石資源を原料とする燃料油中に含まれる硫黄化合物類は、燃焼に際して大気環境汚染の原因となる硫黄酸化物を生成するため、燃料油中からの除去が必須である。そのため、燃料油中に含まれる硫黄化合物の除去を目的とする脱硫技術については、従来より積極的に開発が進められてきており、現在、石油系燃料の脱硫法としては、一般的に、触媒の存在下に水素化処理を行う水素化脱硫方法が採用されている。
Sulfur compounds contained in fuel oils made from fossil resources such as petroleum and coal produce sulfur oxides that cause air pollution during combustion, and therefore must be removed from the fuel oil. Therefore, desulfurization technology aimed at removing sulfur compounds contained in fuel oil has been actively developed. Conventionally, as a desulfurization method for petroleum-based fuels, a catalyst is generally used. A hydrodesulfurization method in which hydrotreating is carried out in the presence of is used.
また、別の脱硫方法としては、吸着脱硫法、バイオ脱硫法、および、酸化脱硫法などが検討されている。
吸着脱硫法は、無機物または有機物の吸着剤に、燃料油中の有機硫黄化合物を吸着することにより燃料油中から除去する方法である。この吸着脱硫方法によれば、燃料油中の有機硫黄化合物類を、吸着剤に化学吸着および物理吸着させることにより燃料油から効率的に分離・除去することができる。
例えば、特許文献１には、比表面積５００ｃｍ2／ｇ以上の炭素材料から構成された吸着脱硫剤を用いることによって、石油留分に含まれる有機硫黄化合物を吸着除去することが記載されている。
また、特許文献２には、炭化水素油とニッケルと亜鉛を含む多孔質脱硫剤とを、水素存在下で、接触させる炭化水素油の脱硫方法が記載されている。
As other desulfurization methods, an adsorption desulfurization method, a biodesulfurization method, an oxidative desulfurization method, and the like have been studied.
The adsorptive desulfurization method is a method of removing an organic sulfur compound in a fuel oil by adsorbing the organic sulfur compound in an inorganic or organic adsorbent. According to this adsorptive desulfurization method, organic sulfur compounds in the fuel oil can be efficiently separated and removed from the fuel oil by causing the adsorbent to perform chemical adsorption and physical adsorption.
For example, Patent Document 1 describes that an organic sulfur compound contained in a petroleum fraction is adsorbed and removed by using an adsorptive desulfurization agent composed of a carbon material having a specific surface area of 500 cm 2 / g or more.
Patent Document 2 describes a hydrocarbon oil desulfurization method in which a hydrocarbon oil and a porous desulfurization agent containing nickel and zinc are contacted in the presence of hydrogen.
石炭系重質油の高度利用のためには、石油系の場合と同様、硫黄分含有率の低減が必須である。しかし、近年、低硫黄含有率の高品位な石炭が枯渇傾向にあるため高硫黄分の低品位な石炭を用いざるを得ない状況になってきており、石炭系重質油の脱硫技術の開発が喫緊の課題となっている。
しかしながら、石炭タール等の石炭系重質油は、多環芳香族炭化水素類が主成分であるため、その中に含まれる硫黄化合物類は、上記の水素化脱硫法では効率的に除去することは出来ない。
In order to use coal-based heavy oil at a high level, it is essential to reduce the sulfur content as in the case of petroleum-based heavy oil. In recent years, however, high-grade coal with a low sulfur content has been depleted, so it has been forced to use low-grade coal with a high sulfur content. Is an urgent issue.
However, since coal-based heavy oils such as coal tar are mainly composed of polycyclic aromatic hydrocarbons, sulfur compounds contained therein must be efficiently removed by the hydrodesulfurization method described above. I can't.
一方、石炭系重質油については、硫黄化合物類を吸着することにより除去する吸着脱硫方法が有効であると考えられる。すなわち、この吸着脱硫法によれば、石炭系重質油中の硫黄化合物類を吸着剤に吸着させることにより、石炭系重質油から効率的に分離・除去することができると考えられる。 On the other hand, for coal-based heavy oils, an adsorptive desulfurization method that removes sulfur compounds by adsorbing them is considered effective. That is, according to this adsorptive desulfurization method, it is considered that sulfur compounds in coal-based heavy oil can be efficiently separated and removed from coal-based heavy oil by adsorbing the adsorbent to the adsorbent.
現時点において、石炭系重質油の効率的かつ経済的な脱硫法は存在しないため、新規脱硫技術の開発が望まれている。
本発明は、こうした現状を鑑みてなされたものであって、石炭系重質油中に含まれている有機硫黄化合物類を、選択的かつ効率的に吸着・除去できる、実用的な吸着脱硫方法を提供することを目的とするものである。
At present, there is no efficient and economical method for desulfurization of heavy coal-based oil, so the development of new desulfurization technology is desired.
The present invention has been made in view of the current situation, and is a practical adsorptive desulfurization method capable of selectively and efficiently adsorbing and removing organic sulfur compounds contained in coal-based heavy oil. Is intended to provide.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、石炭系重質油を溶解できる有機溶媒中において、水素存在下、金属担持吸着剤で処理することにより、石炭系重質油中に含まれる硫黄化合物類を選択的かつ効率的に吸着・除去できるという知見を得た。 As a result of intensive studies to achieve the above-mentioned object, the present inventors, in an organic solvent capable of dissolving coal-based heavy oil, by treating with a metal-supported adsorbent in the presence of hydrogen, coal-based heavy It was found that sulfur compounds contained in oil can be selectively adsorbed and removed selectively.
本発明はこれらの知見に基づいて完成に至ったものであり、本発明によれば、以下の発明が提供される。
［１］硫黄化合物を含有する石炭系重質油を、有機溶媒中において、水素存在下、金属担持吸着剤で処理すること特徴とする石炭系重質油の吸着脱硫方法。
［２］前記担持金属が、白金（Ｐｔ）又はパラジウム（Ｐｄ）であることを特徴とする［１］に記載の重質油の酸化脱硫方法。
［３］前記有機溶媒が、テトラヒドロフランであることを特徴とする［１］又は［２］に記載の石炭系重質油の酸化脱硫方法。
［４］前記硫黄化合物が、有機硫黄化合物であることを特徴とする［１］〜［３］のいずれかに記載の石炭系重質油の吸着脱硫方法。
The present invention has been completed based on these findings, and according to the present invention, the following inventions are provided.
[1] A method for adsorptive desulfurization of heavy coal oil, characterized in that a heavy coal oil containing a sulfur compound is treated with a metal-supported adsorbent in the presence of hydrogen in an organic solvent.
[2] The heavy oil oxidative desulfurization method according to [1], wherein the supported metal is platinum (Pt) or palladium (Pd).
[3] The method for oxidative desulfurization of heavy coal oil according to [1] or [2], wherein the organic solvent is tetrahydrofuran.
[4] The adsorptive desulfurization method for heavy coal oil according to any one of [1] to [3], wherein the sulfur compound is an organic sulfur compound.
本発明によれば、硫黄化合物、特に有機硫黄化合物を含有する重質油を、テトラヒドロフラン等の有機溶剤中において、水素存在下、金属担持吸着剤で処理することにより、有機硫黄化合物を吸着剤に吸着し、重質油中から除去、すなわち、脱硫することができ、特に、本発明の脱硫方法は、従来から知られている水素化反応を利用する脱硫法では脱硫することが不可能であった石炭系重質油の脱硫を可能とするものである。 According to the present invention, a heavy oil containing a sulfur compound, particularly an organic sulfur compound, is treated with a metal-supported adsorbent in the presence of hydrogen in an organic solvent such as tetrahydrofuran, thereby converting the organic sulfur compound into an adsorbent. It can be adsorbed and removed from heavy oil, that is, desulfurized. In particular, the desulfurization method of the present invention cannot be desulfurized by a conventionally known desulfurization method using a hydrogenation reaction. This makes it possible to desulfurize coal-based heavy oil.
本発明において、石炭系重質油とは、石炭由来の重質油を意味するが、石炭に限らず、石油、オイルサンド、オイルシェール、及びオリマルジョン等の有機化石資源由来の重質油であっても差し支えない。
この具体例を挙げると、石炭系としては、コールタール等が、石油系としては、重油等が、石油類似資源では、オイルサンド、オイルシェール、オリマルジョン等からの抽出物等がある。
In the present invention, coal-based heavy oil means heavy oil derived from coal, but is not limited to coal, and is heavy oil derived from organic fossil resources such as petroleum, oil sands, oil shale, and olimarsion. There is no problem.
Specific examples include coal tar as coal-based, heavy oil as petroleum-based, and oil-like resources such as extracts from oil sands, oil shale, orimulsion.
重質油中に含まれる硫黄化合物としては、無機硫黄化合物及び有機硫黄化合物が包含される。
有機硫黄化合物としては、芳香族炭化水素の置換基として骨格中に硫黄原子を含む複素環化合物、たとえば、チオフェン類、ベンゾチオフェン類、ジベンゾチオフェン類等、および、炭素鎖中に硫黄原子を含有する基を有する化合物、たとえば、チオフェノール類、チオアニソール類等、さらに、脂肪族炭化水素を構成する炭素鎖中に硫黄原子を含有する化合物、たとえばチオール類、チオエーテル類等を挙げることができる。
そして、これらの有機硫黄化合物は、多環芳香族炭化水素類などの炭化水素を主成分とする重質油中に含有されているものである。
As a sulfur compound contained in heavy oil, an inorganic sulfur compound and an organic sulfur compound are included.
Organic sulfur compounds include heterocyclic compounds containing a sulfur atom in the skeleton as a substituent of an aromatic hydrocarbon, such as thiophenes, benzothiophenes, dibenzothiophenes, etc., and a sulfur atom in the carbon chain Examples thereof include compounds having a group, such as thiophenols and thioanisole, and compounds having a sulfur atom in the carbon chain constituting the aliphatic hydrocarbon, such as thiols and thioethers.
These organic sulfur compounds are contained in heavy oils mainly composed of hydrocarbons such as polycyclic aromatic hydrocarbons.
重質油中に含まれる硫黄化合物の割合は、適宜選択することができるが、通常、有機硫黄化合物の含有量は、硫黄として０.０１〜１０重量％であることが好ましい。
本発明においては、前記した硫黄化合物好ましくは有機硫黄化合物を含有する重質油を、テトラヒドロフラン中において、水素存在下、金属担持吸着剤で処理して、重質油から分離・除去することを特徴としている。
The ratio of the sulfur compound contained in the heavy oil can be selected as appropriate, but usually the content of the organic sulfur compound is preferably 0.01 to 10% by weight as sulfur.
In the present invention, the heavy oil containing the above-described sulfur compound, preferably an organic sulfur compound, is treated with a metal-supported adsorbent in tetrahydrofuran in the presence of hydrogen, and separated and removed from the heavy oil. It is said.
本発明において用いられる有機溶媒には、石炭系重質油を可溶化できる溶媒が用いられるが、中でも、テトラヒドロフラン（ＴＨＦ）が好ましく用いられる。また、用いる有機溶媒の量は、石炭系重質油を可溶化できる量であれば、限定されない。 As the organic solvent used in the present invention, a solvent capable of solubilizing coal-based heavy oil is used, and among them, tetrahydrofuran (THF) is preferably used. Further, the amount of the organic solvent to be used is not limited as long as it is an amount capable of solubilizing the heavy coal oil.
また、本発明に用いる担持金属としては、Ｐｔ、Ｐｄ等を使用するのが好ましい。
これらの担持金属は、水素存在下において、有機硫黄化合物類を選択的に化学吸着すると考えられ、反応液の脱硫が可能となる。
さらに、担体としては、アルミナ（Ａｌ2Ｏ3）、シリカ（ＳｉＯ2）等の無機系担体が好ましく用いられる。なお、担体として活性炭を用いた場合には、石炭系重質油（多環芳香族類）の活性炭への物理吸着によると思われる収率の低下が認められた。
Moreover, it is preferable to use Pt, Pd or the like as the supported metal used in the present invention.
These supported metals are considered to selectively chemisorb organic sulfur compounds in the presence of hydrogen, and the reaction solution can be desulfurized.
Furthermore, as the carrier, an inorganic carrier such as alumina (Al 2 O 3 ) or silica (SiO 2 ) is preferably used. In addition, when activated carbon was used as a support | carrier, the fall of the yield considered to be due to the physical adsorption | suction to coal activated heavy oil (polycyclic aromatics) was recognized.
本発明は、水素ガス存在下で行うのが有効であるが、必ずしも水素分圧が１００％である必要はない。 Although it is effective to perform the present invention in the presence of hydrogen gas, the hydrogen partial pressure is not necessarily 100%.
反応温度は、反応液が液状を保持できる温度であれば適宜設定することができる。このようなことから１０〜７０℃で行うことができる。 The reaction temperature can be appropriately set as long as the reaction solution can maintain a liquid state. Therefore, it can be performed at 10 to 70 ° C.
以下に、本発明の内容を実施例により具体的に説明する。しかしながら、以下に示す、実施例は一例であり、本発明はこれらの実施例により限定されるものではない。
（実施例１）
内容積１００ｍＬのガラス製反応器中に、石炭系重質油である石炭タール軟ピッチ（硫黄分０.３６ｗｔ％）０.１５ｇのＴＨＦ溶液５０ｍＬをとり、さらに、吸着剤として５ｗｔ％Ｐｔ／Ａｌ2Ｏ3 ０.９８ｇ（Ｐｔ、２５０μｍｏｌ）を添加する。反応器に還流冷却器を設置し、反応器内を窒素ガス、続いて水素ガスで置換後、水素ガス流量を５ｍL/分とし、反応器を６０℃に保たれている油浴中に浸すことにより、吸着反応を開始した。反応時間は５時間とした。反応終了後、吸着剤をロ別し、ＴＨＦを留去することにより、脱硫試料を得た。
脱硫試料の硫黄分析結果を以下の表１に示す。
反応処理後の硫黄分が０.２３ｗｔ％（脱硫率３６％）へと大きく減少したことから、本発明による吸着脱硫法が、石炭タール軟ピッチの脱硫法として有効に作用することがわかる。
Hereinafter, the contents of the present invention will be specifically described with reference to examples. However, the following examples are merely examples, and the present invention is not limited to these examples.
Example 1
In a glass reactor having an internal volume of 100 mL, 50 mL of THF solution of 0.15 g of coal tar soft pitch (sulfur content 0.36 wt%), which is a coal-based heavy oil, is taken, and further 5 wt% Pt / Al as an adsorbent. 0.98 g of 2 O 3 (Pt, 250 μmol) is added. A reflux condenser is installed in the reactor, and after the inside of the reactor is replaced with nitrogen gas and subsequently with hydrogen gas, the hydrogen gas flow rate is set to 5 mL / min, and the reactor is immersed in an oil bath maintained at 60 ° C. The adsorption reaction was started. The reaction time was 5 hours. After completion of the reaction, the adsorbent was separated and the THF was distilled off to obtain a desulfurized sample.
The sulfur analysis results of the desulfurized sample are shown in Table 1 below.
Since the sulfur content after the reaction treatment was greatly reduced to 0.23 wt% (desulfurization rate 36%), it is understood that the adsorptive desulfurization method according to the present invention works effectively as a desulfurization method for coal tar soft pitch.
（比較例１）
窒素ガス存在下、水素ガスを用いない他は、実施例１と同じ条件下に、反応を行った。
反応処理後の硫黄分は、０.３６％（脱硫率０％）であり、硫黄分の低下は認められなかった。
(Comparative Example 1)
The reaction was carried out under the same conditions as in Example 1 except that hydrogen gas was not used in the presence of nitrogen gas.
The sulfur content after the reaction treatment was 0.36% (desulfurization rate 0%), and no decrease in the sulfur content was observed.
（実施例２）
吸着剤として５ｗｔ％Ｐｔ／Ａｌ2Ｏ3 １.９６ｇ（Ｐｔ、５００μｍｏｌ）を用いた他は、実施例１と同じ条件下に反応を行った。
反応処理後の硫黄分は、０.１８ｗｔ％（脱硫率５０％）へと大きく減少し、吸着脱硫の効果が認められた。
(Example 2)
The reaction was conducted under the same conditions as in Example 1 except that 1.96 g (Pt, 500 μmol) of 5 wt% Pt / Al 2 O 3 was used as the adsorbent.
The sulfur content after the reaction treatment was greatly reduced to 0.18 wt% (desulfurization rate 50%), and the effect of adsorptive desulfurization was recognized.
（比較例２）
窒素ガス存在下、水素ガスを用いない他は、実施例２と同じ条件下に、反応を行った。
反応処理後の硫黄分は、０.３５％（脱硫率３％）であり、硫黄分の低下はほとんど認められなかった。
(Comparative Example 2)
The reaction was carried out under the same conditions as in Example 2 except that hydrogen gas was not used in the presence of nitrogen gas.
The sulfur content after the reaction treatment was 0.35% (desulfurization rate 3%), and almost no decrease in the sulfur content was observed.
（実施例３）
吸着剤として５ｗｔ％Ｐｄ／Ａｌ2Ｏ3 １.０６ｇ（Ｐｄ、５００μｍｏｌ）を用いた他は、実施例１と同じ条件下に反応を行った。
反応処理後の硫黄分は、０.２６ｗｔ％（脱硫率２８％）へと大きく減少し、吸着脱硫の効果が認められた。
(Example 3)
The reaction was performed under the same conditions as in Example 1 except that 1.06 g (Pd, 500 μmol) of 5 wt% Pd / Al 2 O 3 was used as the adsorbent.
The sulfur content after the reaction treatment was greatly reduced to 0.26 wt% (desulfurization rate 28%), and the effect of adsorptive desulfurization was recognized.
（比較例３）
窒素ガス存在下、水素ガスを用いない他は、実施例３と同じ条件下に、反応を行った。
反応処理後の硫黄分は、０.３６％（脱硫率３％）であり、硫黄分の低下は認められなかった。
(Comparative Example 3)
The reaction was carried out under the same conditions as in Example 3 except that hydrogen gas was not used in the presence of nitrogen gas.
The sulfur content after the reaction treatment was 0.36% (desulfurization rate 3%), and no decrease in the sulfur content was observed.
以上の実施例１〜３及び比較例１〜３における石炭タール軟ピッチ（硫黄分、０.３６ｗｔ％）の吸着脱硫結果を表１にまとめて記載する。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5747387A (en) * | 1980-07-07 | 1982-03-18 | Mobil Oil Corp | Hydrogenating treatment of heavy hydrocarbon oil |
| JPS63243196A (en) * | 1987-03-30 | 1988-10-11 | Nippon Oil Co Ltd | Conversion f heavy oil to light oil |
| JP2002294256A (en) * | 2001-03-29 | 2002-10-09 | Cosmo Oil Co Ltd | Adsorbent for sulfur compound in hydrocarbon oil and method for removing sulfur compound from hydrocarbon oil |
| JP2002363574A (en) * | 2001-06-06 | 2002-12-18 | Idemitsu Kosan Co Ltd | Method for desulfurizing hydrocarbon oil and method for producing hydrogen for fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5747387A (en) * | 1980-07-07 | 1982-03-18 | Mobil Oil Corp | Hydrogenating treatment of heavy hydrocarbon oil |
| JPS63243196A (en) * | 1987-03-30 | 1988-10-11 | Nippon Oil Co Ltd | Conversion f heavy oil to light oil |
| JP2002294256A (en) * | 2001-03-29 | 2002-10-09 | Cosmo Oil Co Ltd | Adsorbent for sulfur compound in hydrocarbon oil and method for removing sulfur compound from hydrocarbon oil |
| JP2002363574A (en) * | 2001-06-06 | 2002-12-18 | Idemitsu Kosan Co Ltd | Method for desulfurizing hydrocarbon oil and method for producing hydrogen for fuel cell |
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