JPH0391591A - Hydrotreatment of heavy hydrocarbon oil - Google Patents
Hydrotreatment of heavy hydrocarbon oilInfo
- Publication number
- JPH0391591A JPH0391591A JP22838189A JP22838189A JPH0391591A JP H0391591 A JPH0391591 A JP H0391591A JP 22838189 A JP22838189 A JP 22838189A JP 22838189 A JP22838189 A JP 22838189A JP H0391591 A JPH0391591 A JP H0391591A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- atmospheric distillation
- hydrotreating
- hydrocarbon oil
- heavy hydrocarbon
- 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
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 35
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 35
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 32
- 238000004821 distillation Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims description 19
- 239000003921 oil Substances 0.000 abstract description 59
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 abstract description 21
- 239000011593 sulfur Substances 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000010779 crude oil Substances 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- -1 NiO-MoO2 or NiO-W2O3 Chemical class 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010457 zeolite Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 16
- 238000005984 hydrogenation reaction Methods 0.000 description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 9
- 230000023556 desulfurization Effects 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000011221 initial treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QLJVFHXULZBBSH-UHFFFAOYSA-N [Ni]=O.[W]=O Chemical compound [Ni]=O.[W]=O QLJVFHXULZBBSH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、硫黄、アスファルテン、及びニッケル、バナ
ジウム等の重金属分を含有する重質炭化水素油の水素化
処理方法に関し、さらに詳しくは、常圧蒸留残油を水素
化処理して得られる重質留分を単独に、又は常圧蒸留残
油と混合して、更に水素化処理する重質炭化水素油の水
素化処理方法に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for hydrotreating heavy hydrocarbon oil containing sulfur, asphaltenes, and heavy metals such as nickel and vanadium. The present invention relates to a method for hydrotreating heavy hydrocarbon oils, in which a heavy fraction obtained by hydrotreating a pressure distillation residue is further hydrotreated either alone or in combination with an atmospheric distillation residue.
近年、大気汚染防止から低硫黄重油の必要性はますます
高まっている。一方、世界的な原油の重質化に伴い硫黄
、アスファルテン、重金属分等の含有量が多い原油を処
理する傾向にあり１、常圧蒸留残渣を水素化処理して低
硫黄重油を得る条件は厳しくなっている。In recent years, the need for low-sulfur heavy oil has been increasing to prevent air pollution. On the other hand, as crude oil becomes heavier worldwide, there is a trend to process crude oil with a high content of sulfur, asphaltene, heavy metals, etc. 1, and the conditions for obtaining low-sulfur heavy oil by hydrotreating the atmospheric distillation residue are It's getting tougher.
このため、水素化処理して低硫黄重油の増産を図る目的
として、水素化処理触媒の高活性化、高寿命化に関する
研究も栄んである。実際には、常圧蒸留残渣の水素化処
理においても、触媒活性、触媒寿命に合わせ、原料油種
、処理量等の調整を行っている。For this reason, with the aim of increasing the production of low-sulfur heavy oil through hydrotreating, research into increasing the activation and longevity of hydrotreating catalysts is flourishing. In fact, even in the hydrogenation treatment of atmospheric distillation residues, the raw material oil type, processing amount, etc. are adjusted in accordance with the catalyst activity and catalyst life.
しかしながら、同一処理条件においては、軽質常圧蒸留
残渣では低硫黄重質炭化水素油を採取できるが、重質常
圧蒸留残渣では必要とする低硫黄重質炭化水素油が採取
できないケースが多い。この場合、反応温度を上げ、低
硫黄重質炭化水素油の採取を図ると、反応温度上昇によ
るカーボン発生を促進し、触媒劣化を早めることになり
、好ましくないという問題があった。However, under the same processing conditions, it is possible to extract low-sulfur heavy hydrocarbon oil from light atmospheric distillation residue, but in many cases the required low-sulfur heavy hydrocarbon oil cannot be extracted from heavy atmospheric distillation residue. In this case, if the reaction temperature is raised to collect a low-sulfur heavy hydrocarbon oil, the rise in reaction temperature will promote carbon generation and accelerate catalyst deterioration, which is not desirable.
そこで、本発明は、上記の従来技術の問題点を解決し、
反応温度を上昇せずに、重質常圧蒸留残渣から低硫黄重
質炭化水素油を採取する方法を提供することを目的とす
る。Therefore, the present invention solves the above-mentioned problems of the prior art, and
It is an object of the present invention to provide a method for extracting a low-sulfur heavy hydrocarbon oil from a heavy atmospheric distillation residue without increasing the reaction temperature.
上記目的を達成するために、本発明では、常圧蒸留残油
を水素化処理して得られる重質炭化水素油を単独に、又
は常圧蒸留残油と混合して、更に水素化処理することを
特徴とする重質炭化水素油の水素化処理方法としたもの
である。In order to achieve the above object, in the present invention, heavy hydrocarbon oil obtained by hydrotreating atmospheric distillation residual oil is further hydrotreated either alone or in combination with atmospheric distillation residual oil. This is a method for hydrotreating heavy hydrocarbon oil, which is characterized by the following.
本発明者らは、特に重質常圧蒸留残渣から低硫黄重質炭
化水素油を採取する方法について、種々検討を行った結
果、常圧蒸留残渣を一度水素化処理した重質炭化水素油
について、再度水素化処理することが有効な方法である
ことを見い出し、上記の本発明を完成するに至った。The present inventors have conducted various studies on methods for extracting low-sulfur heavy hydrocarbon oil from heavy atmospheric distillation residue, and have found that heavy hydrocarbon oil obtained by once hydrogenating atmospheric distillation residue They discovered that re-hydrogenation is an effective method and completed the above-mentioned present invention.
従来は、水素化処理方法については、−炭水素化処理し
た重質炭化水素油には、反応性の乏しい硫黄化合物が残
留し、再度の水素化処理により除かれる硫黄量が少な゛
いと考えられていたが、本発明者等は脱硫反応性の向上
に係わる多種多様な研究を進めたところ、必ずしも一度
水素化処理した重質炭化水素油の脱硫反応性は低下せず
、むしろ脱硫反応性が向上するという知見を得、本発明
を完成した。Conventionally, with regard to hydrotreating methods, it has been thought that sulfur compounds with poor reactivity remain in heavy hydrocarbon oils that have undergone hydrotreating, and that the amount of sulfur that can be removed by repeated hydrotreating is small. However, the present inventors conducted a wide variety of studies related to improving desulfurization reactivity, and found that the desulfurization reactivity of heavy hydrocarbon oil does not necessarily decrease once hydrotreated, but rather that the desulfurization reactivity increases. The present invention was completed based on the knowledge that the present invention was improved.
次に、本発明の詳細な説明する。Next, the present invention will be explained in detail.
本発明の常圧蒸留残油は、原油を常圧蒸留して得られる
残油をいう。使用される原油は、何んでも良いが、好ま
しくは、クェート原油、イラニアンヘビー原油、カフジ
原油、メキシコ原油、ベネズエラ原油等の重質原油を用
いるのが、より効果的である。The atmospheric distillation residual oil of the present invention refers to the residual oil obtained by atmospheric distillation of crude oil. Although any crude oil may be used, it is more effective to use heavy crude oil such as Kuwaiti crude oil, Iranian heavy crude oil, Khafji crude oil, Mexican crude oil, Venezuelan crude oil, etc.
常圧蒸留残油の水素化処理（以下、「−訳本素化処理」
という。）に際しては、特別な条件を設定する必要はな
く、通常の水素化処理条件を適用すればよい。Hydrogenation treatment of atmospheric distillation residual oil (hereinafter referred to as “-translation hydrogenation treatment”)
That's what it means. ), it is not necessary to set special conditions, and normal hydrogenation treatment conditions may be applied.
触媒としては、６ｂ族金属戒分及び／又は、８族金属底
分を多孔性の無機質酸化物のような担体に担持した、通
常の水素化処理触媒組成物が使用できる。すなわち、触
媒の例としては、酸化二−ツケルー酸化モリブデン系や
酸化ニッケルー酸化タングステン系などの触媒成分を、
アルミナ、シリカアルミナ、ゼオライト等に担持させた
ものを用いる。As the catalyst, a conventional hydrotreating catalyst composition in which a group 6b metal component and/or a group 8 metal component is supported on a carrier such as a porous inorganic oxide can be used. In other words, examples of catalysts include catalyst components such as di-oxide-molybdenum oxide and nickel oxide-tungsten oxide.
A material supported on alumina, silica alumina, zeolite, etc. is used.
反応条件としては反応温度的３４０〜４５０℃、好まし
くは約３５０〜４２０℃、水素分圧的４０〜２５０ｋｇ
／ａｍ２、好ましくは約７０〜２００ ｋｇ ／ ｃｍ
” 、水素ガス供給量的５００〜２０００ ＮＭ、／ｋ
ｊ？オ、Ｊ、びＬＨ３Ｖ （液空間速度）約０．１〜５
．０ｈ″−１の条件下で水素化処理を行う。又、−炭水
素化処理油は、−訳本素化処理後、蒸留装置において軽
質分をカットしたもので良い。Reaction conditions include reaction temperature of 340 to 450°C, preferably about 350 to 420°C, and hydrogen partial pressure of 40 to 250 kg.
/am2, preferably about 70-200 kg/cm
”, hydrogen gas supply amount 500-2000 NM, /k
j? E, J, and LH3V (liquid hourly velocity) approx. 0.1 to 5
．． Hydrogenation treatment is carried out under the condition of 0h''-1.The hydrocarbonization treated oil may be one in which the light components are removed in a distillation apparatus after the hydrogenation treatment.
一次水素化処理された重質炭化水素油も常圧蒸留残油と
の混合比率は、装置能力、低硫黄原油の必要量、常圧蒸
留残渣の生成量等を基に適宜決定すればよいが、一般に
は、重量で、１００：０から２：９８の間で自由な比率
で決定することができ、好ましくは１００：０から５：
９５の比率が良い。The mixing ratio of primary hydrocarbon oil and atmospheric distillation residue may be determined as appropriate based on the equipment capacity, the required amount of low-sulfur crude oil, the amount of atmospheric distillation residue produced, etc. , generally by weight, can be determined in any ratio between 100:0 and 2:98, preferably between 100:0 and 5:
A ratio of 95 is good.
一次水素化処理して得られる重質炭化水素油を単独に、
又は、常圧蒸留残油と混合して、更に水素化処理（以下
、「二次水素化処理」とい−う。）するための条件は、
−訳本素化処理条件と同じ範囲で使用できる。その範囲
内であれば、−訳本素化処理条件と、二次水素化処理条
件は同じ条件であってもよいし、異っていてもよい。Separately, heavy hydrocarbon oil obtained through primary hydrotreating,
Alternatively, the conditions for further hydrotreating (hereinafter referred to as "secondary hydrotreating") by mixing with the atmospheric distillation residual oil are as follows:
- Can be used within the same range as the translated text atomization processing conditions. As long as they are within that range, the primary treatment conditions and the secondary hydrogenation treatment conditions may be the same or different.
本発明方法は一次水素化処理よりも二次水素化処理の方
が脱硫活性が向上するため、むしろ、二次水素化処理条
件では、反応温度を低く押えることができる。In the method of the present invention, the desulfurization activity is improved more in the secondary hydrogenation treatment than in the primary hydrogenation treatment, so the reaction temperature can be kept low under the conditions of the secondary hydrogenation treatment.
二次水素化処理する方法としては、好ましくは、−炭水
素化処理油を一度タンクに貯蔵し、その後、タンク貯蔵
油を再度、単独で処理するか、あるいは他の常圧蒸留残
油とブレンドして処理する方法、又は、水素化処理装置
を２系列以上保有しいる場合は、一方の装置で一次水素
化処理を行い、他方の装置で単独又は、他の常圧蒸留残
油とブレンドして連続して二次水素化処理する方法等が
ある。The method of secondary hydrotreating preferably includes: - storing the hydrotreated oil once in a tank, and then processing the tank-stored oil again alone or blending it with other atmospheric distillation residues; Or, if you have two or more hydrotreating units, one unit performs the primary hydrotreating, and the other unit performs the primary hydrotreating process, and the other unit performs the primary hydrotreating process alone or blends it with other atmospheric distillation residues. There are methods such as continuous secondary hydrogenation treatment.
以下、本発明を実施例により具体的に説明するが、本発
明はこれらの実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
実施例は、次の水素化処理評価試験方法により評価した
。Examples were evaluated using the following hydrotreatment evaluation test method.
く水素化処理評価試験方法〉
装置は、Ｔ−アルミナ担体に酸化モリブデン１２．０％
、酸化ニッケル４．０％を担持させた平均細孔径８０人
の水素化脱硫触媒４００ｇを充填した固定床流通式反応
管を用いる。そして、原料油は高圧ポンプにより、また
水素ガスは圧縮機により所定の圧力に昇圧した原料油と
水素ガスを、混合して反応管に送り、反応管を出た油と
ガスを気液分離器でガスと油に分離した。Hydrotreating evaluation test method〉 The device uses 12.0% molybdenum oxide on a T-alumina carrier.
A fixed bed flow reaction tube filled with 400 g of a hydrodesulfurization catalyst having an average pore diameter of 80 and supporting 4.0% of nickel oxide is used. Then, the feedstock oil is pressurized to a specified pressure by a high-pressure pump, and the hydrogen gas is boosted to a predetermined pressure by a compressor.The feedstock oil and hydrogen gas are mixed and sent to a reaction tube, and the oil and gas exiting the reaction tube are passed through a gas-liquid separator. separated into gas and oil.
得られた生成油は、所定の方法で硫黄含有量を分析した
。反応条件は、反応温度を除き、全て次の条件で統一し
た。The resulting oil was analyzed for sulfur content using a prescribed method. All reaction conditions were unified as follows, except for reaction temperature.
圧力 １０５ ｋｇ／ ｃｍ２ＧＬＨ３Ｖ
Ｏ，２３ｈｒ−’水素ガス供給量 ８８
０ ＮＭ’／ｋＬ水素濃度 １００％
常圧蒸留残油の一次水素化処理、及び二次水素化処理に
おける脱硫反応性の評価試験は、初期の触媒活性の低下
時期を回避するため、表−１に示した常圧蒸留残渣（Ａ
）を用い、６０日間運転し、触媒活性が安定しているこ
とを確認した後、実施した。Pressure 105 kg/cm2GLH3V
O, 23hr-'Hydrogen gas supply amount 88
0 NM'/kL Hydrogen concentration 100% In order to avoid the initial stage of decline in catalyst activity, evaluation tests for desulfurization reactivity in the primary and secondary hydrotreating of atmospheric distillation residual oil were carried out using Table-1 The atmospheric distillation residue shown in (A
) was operated for 60 days and the catalyst activity was confirmed to be stable.
実施例１
原料油として表−１に示した常圧蒸留残渣（Ｂ）を用い
、反応温度３８０℃で処理した後、３３０℃より軽質の
炭化水素油を蒸留分離し、−炭水素化処理重質炭化水素
油（Ｄ）を得た。Example 1 The atmospheric distillation residue (B) shown in Table 1 was used as a raw material oil, and after treatment at a reaction temperature of 380°C, lighter hydrocarbon oils were separated by distillation from 330°C. A quality hydrocarbon oil (D) was obtained.
次に、−炭水素化処理重質炭化水素油（Ｄ）を反応温度
３７３℃で二次水素化処理した。Next, the -hydrohydrotreated heavy hydrocarbon oil (D) was subjected to secondary hydrogenation treatment at a reaction temperature of 373°C.
実施例２
実施例１の中間過程で得られる一次水素化処理重質炭化
水素油（Ｄ）と常圧蒸留残渣（Ｃ）を各々９０ｗｔ％及
び１０ｗｔ％で混合し、反応温度３７３℃で二次水素化
処理した。Example 2 The primary hydrotreated heavy hydrocarbon oil (D) obtained in the intermediate process of Example 1 and the atmospheric distillation residue (C) were mixed at 90 wt% and 10 wt%, respectively, and the secondary hydrocarbon oil was mixed at a reaction temperature of 373°C. Hydrogenated.
実施例３
実施例１の中間過程で得られる一次水素化処理重質炭化
水素油（Ｄ）と常圧蒸留残渣（Ｃ）を各々５０ｗｔ％及
び５０ｗｔ％で混合し、反応温度３７３℃で二次水素化
処理した。Example 3 The primary hydrotreated heavy hydrocarbon oil (D) obtained in the intermediate process of Example 1 and the atmospheric distillation residue (C) were mixed at 50 wt% and 50 wt%, respectively, and the secondary hydrocarbon oil was mixed at a reaction temperature of 373°C. Hydrogenated.
実施例４
実施例１の中間過程で得られる一次水素化処理重質炭化
水素油（Ｄ）と常圧蒸留残渣（Ｃ）を各々１０ｗｔ％及
び９０ｗｔ％で混合し、反応温度３７３℃で二次水素化
処理した。Example 4 The primary hydrotreated heavy hydrocarbon oil (D) obtained in the intermediate process of Example 1 and the atmospheric distillation residue (C) were mixed at 10 wt% and 90 wt%, respectively, and the secondary hydrocarbon oil was mixed at a reaction temperature of 373°C. Hydrogenated.
比較例１
常圧蒸留残渣（Ｂ）を反応温度３７３℃で水素化処理し
た。Comparative Example 1 The atmospheric distillation residue (B) was hydrogenated at a reaction temperature of 373°C.
比較例２
常圧蒸留残渣（Ｃ）と常圧蒸留残渣（Ｂ）各々５Ｑｗｔ
％ずつ混合し、反応温度３７３℃で水素化処理した。Comparative Example 2 Atmospheric distillation residue (C) and atmospheric distillation residue (B) 5Qwt each
% and hydrogenated at a reaction temperature of 373°C.
比較例３
常圧蒸留残渣（Ｂ）を用い、反応温度３８０℃で処理し
た後３３０℃より軽質の炭イヒ水素油を蒸留分離し、−
炭水素化処理重質炭化水素油（Ｄ）を得た。Comparative Example 3 Using the atmospheric distillation residue (B), after processing at a reaction temperature of 380°C, lighter hydrocarbon oil was distilled and separated from 330°C, and -
A hydrocarbonated heavy hydrocarbon oil (D) was obtained.
参考例１
比較例１において、触媒量を２倍にした（こ）場合、Ｌ
Ｈ３ＶＧ；！０．１１５となる。）以外は、同様の条件
で水素化処理した。Reference Example 1 In Comparative Example 1, when the amount of catalyst was doubled, L
H3VG;! It becomes 0.115. ) The hydrogenation treatment was carried out under the same conditions except for the following.
上記の実施例、比較例、参考例の結果を第２表に示す。The results of the above Examples, Comparative Examples, and Reference Examples are shown in Table 2.
注２） 実施例にあっては、二次水素化処理における原
料油中の硫黄分をいい、比
較例および参考例にあっては一次水素
化処理における原料油中の硫黄分をい
う。Note 2) In Examples, it refers to the sulfur content in the feed oil in the secondary hydrotreating, and in Comparative Examples and Reference Examples, it refers to the sulfur content in the feed oil in the primary hydrotreating.
注３） 実施例にあっては、二次水素化処理における生
成油中の硫黄分をいう。Note 3) In the examples, it refers to the sulfur content in the oil produced in secondary hydrotreating.
注４） 脱硫反応速度定数＝
ＬＨ３ＶＸ （１／生生皮硫黄分−１／原料油硫黄分）
注５） 生成油は、−炭水素化処理重質炭化水素油（Ｄ
）である。Note 4) Desulfurization reaction rate constant = LH3VX (1/rawhide sulfur content - 1/raw oil sulfur content) Note 5) The produced oil is - hydrocarbonized heavy hydrocarbon oil (D
).
実施例１及び比較例１から当該水素化処理方法によれば
、同一原油由来の常圧蒸留残油の一次処理に比して、明
らかに脱硫反応性が向上する。このため、反応温度を下
げて硫黄分の低い重質炭化水素油を採取できる。また、
実施例３の軽質常圧蒸留残渣油（Ｃ）との混合処理にお
いても、同様に優れた脱硫反応性を示し、ている。From Example 1 and Comparative Example 1, the hydrotreating method clearly improves the desulfurization reactivity compared to the primary treatment of atmospheric distillation residual oil derived from the same crude oil. Therefore, heavy hydrocarbon oil with low sulfur content can be extracted by lowering the reaction temperature. Also,
In the mixing treatment with the light atmospheric distillation residue oil (C) of Example 3, similarly excellent desulfurization reactivity was exhibited.
〔発明の゛効果］
上記の如く、常圧蒸留残油を一次水素化処理して得られ
た重質炭化水素油を単独に、又は常圧蒸留残油と混合し
て、二次水素化処理することにより、二次水素化処理に
おいて、脱硫の反応性は、−炭水素化処理の場合に比べ
て低下するどころか、むしろ向上するため、二次水素化
処理では反応温度を低く保持しつつ、低硫黄重質炭化水
素油の増産ができる。[Effects of the invention] As described above, the heavy hydrocarbon oil obtained by primary hydrotreating the atmospheric distillation residual oil can be subjected to secondary hydrogenation treatment either alone or in combination with the atmospheric distillation residual oil. By doing so, in the secondary hydrotreating, the reactivity of desulfurization is improved rather than decreased compared to the -hydrohydrotreating, so in the secondary hydrotreating, while keeping the reaction temperature low, It is possible to increase production of low-sulfur heavy hydrocarbon oil.
Claims (1)
素油を単独に、又は常圧蒸留残油と混合して、更に水素
化処理することを特徴とする重質炭化水素油の水素化処
理方法。1. A heavy hydrocarbon oil obtained by hydrotreating an atmospheric distillation residual oil, which is further hydrotreated either alone or in combination with an atmospheric distillation residual oil. Hydrotreating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22838189A JPH0391591A (en) | 1989-09-05 | 1989-09-05 | Hydrotreatment of heavy hydrocarbon oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22838189A JPH0391591A (en) | 1989-09-05 | 1989-09-05 | Hydrotreatment of heavy hydrocarbon oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0391591A true JPH0391591A (en) | 1991-04-17 |
Family
ID=16875577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22838189A Pending JPH0391591A (en) | 1989-09-05 | 1989-09-05 | Hydrotreatment of heavy hydrocarbon oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0391591A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4866105A (en) * | 1971-12-08 | 1973-09-11 | ||
| JPS4961204A (en) * | 1972-05-12 | 1974-06-13 | ||
| JPS5863786A (en) * | 1981-09-28 | 1983-04-15 | シエブロン・リサ−チ・コンパニ− | Hydrocarbon oil desulfurization and demetallization |
-
1989
- 1989-09-05 JP JP22838189A patent/JPH0391591A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4866105A (en) * | 1971-12-08 | 1973-09-11 | ||
| JPS4961204A (en) * | 1972-05-12 | 1974-06-13 | ||
| JPS5863786A (en) * | 1981-09-28 | 1983-04-15 | シエブロン・リサ−チ・コンパニ− | Hydrocarbon oil desulfurization and demetallization |
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