JPH1088153A - Production of low-sulfur diesel light oil - Google Patents
Production of low-sulfur diesel light oilInfo
- Publication number
- JPH1088153A JPH1088153A JP24075396A JP24075396A JPH1088153A JP H1088153 A JPH1088153 A JP H1088153A JP 24075396 A JP24075396 A JP 24075396A JP 24075396 A JP24075396 A JP 24075396A JP H1088153 A JPH1088153 A JP H1088153A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- hue
- catalyst
- sulfur content
- hydrogen
- 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
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は石油蒸留留出油原料
油から低硫黄分で、かつ色相および色相安定性も良好な
ディーゼル軽油を経済的に製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for economically producing a diesel light oil having a low sulfur content and a good hue and hue stability from a petroleum distillate feedstock.
【０００２】[0002]
【従来の技術】従来、我が国でのディーゼル軽油は、主
に直留軽油を一般的な脱硫反応装置で処理した脱硫直留
軽油留分に直留軽油留分、直留灯油留分、分解装置から
得られる軽油留分等を調合して硫黄分０．４〜０．５重
量％の範囲に調製して製造してきた。しかし、昨今の国
内環境問題に端を発し、ディーゼル車排ガス中のＮＯｘ
および粒子状物質の削減が要求され、このため、ディー
ゼル軽油中の硫黄分はすでに０．２重量％に引き下げら
れ、さらに平成９年には０．０５重量％へ引き下げられ
ることが決定している。また、色相の規格は規定されて
いないが、石油各社は独自にセーボルト色、ＡＳＴＭ
色、ＡＰＨＡ色等による一定の色相基準値を定め品質管
理をしている。とくに、軽油基材としての需要が今後大
幅に増加する見込みの分解軽油は色相が著しく悪いた
め、色相の改善も要求される。2. Description of the Related Art Conventionally, diesel gas oil in Japan is mainly composed of a straight gas oil fraction, a straight gas oil fraction, and a cracker, which are mainly obtained by treating a straight gas oil with a general desulfurization reactor. And a sulfur fraction in the range of 0.4 to 0.5% by weight. However, starting with recent domestic environmental problems, NOx in diesel exhaust gas
And the reduction of particulate matter is required. For this reason, it has been decided that the sulfur content in diesel gas oil has already been reduced to 0.2% by weight, and further reduced to 0.05% by weight in 1997. . Hue standards are not specified, but petroleum companies have their own Saybolt color, ASTM
A certain hue reference value based on color, APHA color, and the like is determined and quality control is performed. In particular, cracked light oil, whose demand as a light oil base material is expected to increase significantly in the future, has a remarkably poor hue, so that an improvement in hue is also required.
【０００３】ディーゼル軽油中の硫黄を０．２重量％以
下にするための一つの方法として、二段階水素化処理方
法が提案されている（方法−１：特開平３−８６７９３
号公報）。しかしながら、この方法の反応条件（第１段
の圧力１０〜４０ｋｇ／ｃｍ2 、温度２８０〜３７０
℃、ＬＨＳＶ０．５〜５．０ｈ-1）では硫黄分０．０５
重量％を達成することは困難である。さらに、色相が不
良な分解軽油を原料油に使用した場合特に顕著である
が、第二反応塔圧力４０ｋｇ／ｃｍ2 以下では第一反応
塔において、硫黄分０．０５重量％を達成するために、
より高温で処理された脱硫油の色相改善は極めて困難で
ある。As one method for reducing the sulfur in diesel gas oil to 0.2% by weight or less, a two-stage hydrotreating method has been proposed (method-1: Japanese Patent Laid-Open No. 3-86793).
No.). However, the reaction conditions of this method (first stage pressure 10-40 kg / cm 2 , temperature 280-370)
° C, LHSV 0.5-5.0 h -1 ), sulfur content 0.05
It is difficult to achieve weight percent. Furthermore, this is particularly remarkable when cracked gas oil having a poor hue is used as a feedstock oil. However, in order to achieve a sulfur content of 0.05% by weight in the first reaction tower at a pressure of the second reaction tower of 40 kg / cm 2 or less. ,
Improving the hue of desulfurized oils treated at higher temperatures is extremely difficult.
【０００４】炭化水素化合物の色相や酸化安定性を改善
するための一つの方法として、二段階水素化処理方法が
提案されている（方法−２：米国特許第４，７５５，２
８０号明細書）。しかしながら、この方法は炭化水素化
合物の色相および酸化反応性を改善する目的の第二反応
塔触媒にＦｅ系触媒を用いており、Ｆｅ系触媒は硫化物
等により容易に被毒されるため（特開昭６２−８４１８
２号公報）、その水素化活性を維持するために第二反応
塔供給物中の硫化水素等の硫黄化合物やアンモニア等の
窒素化合物を第二反応塔供給以前に１０ｐｐｍ以下に低
減させる必要がある。As one method for improving the hue and oxidation stability of hydrocarbon compounds, a two-stage hydrotreating method has been proposed (Method-2: US Pat. No. 4,755,2).
No. 80). However, in this method, an Fe-based catalyst is used as the second reaction tower catalyst for the purpose of improving the hue and oxidation reactivity of the hydrocarbon compound, and the Fe-based catalyst is easily poisoned by sulfides and the like. Kaisho 62-8418
No. 2), in order to maintain the hydrogenation activity, it is necessary to reduce sulfur compounds such as hydrogen sulfide and nitrogen compounds such as ammonia in the feed to the second reactor to 10 ppm or less before feeding to the second reactor. .
【０００５】炭化水素化合物の色相および臭気を改善す
るための一つの方法として、二段階水素化処理法が提案
されている（方法−３：米国特許第３，８４１，９９５
号明細書）。しかしながら、この方法は炭化水素化合物
の色相および臭気を改善する目的の第二反応塔にＰｔ等
の貴金属系触媒を用いており、Ｐｔ等の貴金属系触媒は
硫化水素等により容易に被毒されるため、その水素化活
性を維持するために第二反応塔供給物中の硫化水素等の
硫黄化合物やアンモニア等の窒素化合物を第二反応塔供
給以前に事実上すべて除去する必要がある。As one method for improving the hue and odor of hydrocarbon compounds, a two-stage hydrotreating method has been proposed (Method-3: US Pat. No. 3,841,995).
Specification). However, this method uses a noble metal catalyst such as Pt in the second reaction tower for the purpose of improving the hue and odor of the hydrocarbon compound, and the noble metal catalyst such as Pt is easily poisoned by hydrogen sulfide or the like. Therefore, in order to maintain the hydrogenation activity, it is necessary to remove virtually all sulfur compounds such as hydrogen sulfide and nitrogen compounds such as ammonia in the feed to the second reaction tower before feeding to the second reaction tower.
【０００６】上記の方法−２、方法−３のように、第二
反応塔供給物中の硫化水素等の硫黄化合物やアンモニア
等の窒素化合物を第二反応塔以前に除去するためには、
たとえば、気液分離のセパレーターや液状物質中に溶存
する硫化水素、アンモニア除去のためのストリッパーお
よびガス状物質中に存在する硫化水素、アンモニア除去
のための洗浄塔等の設備が必要である。このため、これ
らの方法では設備投資額の増大およびランニングコスト
の増加を余儀なくされるという商業上非常に好ましくな
い重大な欠点がある。In order to remove sulfur compounds such as hydrogen sulfide and nitrogen compounds such as ammonia in the feed of the second reaction tower before the second reaction tower as in the above-mentioned method-2 and method-3,
For example, facilities such as a separator for gas-liquid separation, a stripper for removing hydrogen sulfide and ammonia dissolved in a liquid substance, and a washing tower for removing hydrogen sulfide and ammonia present in a gaseous substance are required. For this reason, these methods have serious disadvantages, which are commercially unfavorable in that they require an increase in capital investment and an increase in running costs.
【０００７】しかしながら、触媒の寿命、および生成油
の色相安定性（色相の貯蔵安定性）についてはまだ十分
に満足できるものではない。[0007] However, the life of the catalyst and the hue stability (storage stability of hue) of the produced oil are not yet sufficiently satisfactory.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、原料
油である硫黄分０．１〜２．０重量％の範囲にある石油
蒸留留出油から硫黄分０．０５重量％以下で、かつ色相
および色相安定性も良好なディーゼル軽油を経済的に製
造する方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a distillate from a petroleum distillate having a sulfur content of 0.1 to 2.0% by weight with a sulfur content of 0.05% by weight or less, Another object of the present invention is to provide a method for economically producing diesel light oil having good hue and good hue stability.
【０００９】[0009]
【課題を解決するための手段】本発明者らは前記の問題
を解決するため鋭意研究した結果、原料油である石油蒸
留留出油を特定の条件で二段水素化処理することにより
低硫黄分で、かつ色相および色相安定性も良好なディー
ゼル軽油を製造できることを見出し本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, low-sulfur distillate, which is a feed oil, is subjected to two-stage hydrotreatment under specific conditions. It has been found that a diesel light oil can be produced with good hue and good hue stability in just minutes.
【００１０】すなわち、本発明は原料油である硫黄分
０．１〜２．０重量％、沸点１５０〜４００℃の範囲に
ある石油蒸留留出油を水素化処理触媒の存存下、温度３
３０〜４５０℃、圧力４５〜１００ｋｇ／ｃｍ2 の条件
で水素と接触させて、硫黄分が０．０５重量％以下、か
つ色相がセーボルト色値で−１０を超える生成油を得る
第一工程と、前記生成油を水素化処理触媒の存在下、温
度２００〜３２０℃、圧力４５〜１００ｋｇ／ｃｍ2 の
条件で水素と接触させて、色相が前記第一工程の色相の
セーボルト色値を超える生成油を得る第二工程とからな
ることを特徴とする低硫黄ディーゼル軽油の製造方法を
提供するものである。That is, in the present invention, a petroleum distillate having a sulfur content of 0.1 to 2.0% by weight and a boiling point of 150 to 400 ° C. in the range of 3 to 3 wt.
A first step of contacting with hydrogen under the conditions of 30 to 450 ° C. and a pressure of 45 to 100 kg / cm 2 to obtain a product oil having a sulfur content of 0.05% by weight or less and a hue exceeding -10 in Saybolt color value; Contacting the product oil with hydrogen under the conditions of a temperature of 200 to 320 ° C. and a pressure of 45 to 100 kg / cm 2 in the presence of a hydrotreating catalyst, so that the hue exceeds the Saybolt color value of the hue of the first step. And a second step of obtaining an oil.
【００１１】[0011]
【発明の実施の形態】本発明で用いる原料油は、硫黄分
０．１〜２．０重量％、沸点１５０〜４００℃の範囲に
ある石油蒸留留出油である。好ましくは硫黄分０．５〜
２．０重量％、沸点２００〜４００℃の範囲にある石油
蒸留留出油である。石油蒸留留出油としては、例えば原
油の常圧あるいは減圧蒸留により得られる留出油（ＬＧ
Ｏ）、流動接触分解（ＦＣＣ）油の蒸留により得られる
留出油（ＬＣＯ）、熱分解油の蒸留により得られる留出
油等が挙げられる。これらの石油蒸留留出油は単独また
は混合物の形で用いることができる。DETAILED DESCRIPTION OF THE INVENTION The feedstock oil used in the present invention is a petroleum distillate having a sulfur content of 0.1 to 2.0% by weight and a boiling point of 150 to 400 ° C. Preferably sulfur content 0.5 to
It is a petroleum distillate having a boiling point of 2.0% by weight and a boiling point of 200 to 400 ° C. As the petroleum distillate, for example, a distillate obtained by normal or reduced pressure distillation of crude oil (LG
O), distillate (LCO) obtained by distillation of fluid catalytic cracking (FCC) oil, distillate obtained by distillation of pyrolysis oil, and the like. These petroleum distillates can be used alone or in a mixture.
【００１２】本発明では原料油として流動接触分解によ
り得られる留出油と原油の常圧蒸留により得られる留出
油の混合物で、沸点１５０〜４００℃の範囲にある留出
油が好ましく用いられ、さらに好ましくは、沸点２００
〜４００℃の範囲にある留出油が用いられる。In the present invention, a mixture of a distillate obtained by fluid catalytic cracking and a distillate obtained by atmospheric distillation of crude oil is preferably used as a feed oil, and a distillate having a boiling point of 150 to 400 ° C. is used. And more preferably a boiling point of 200
Distillate oils in the range of ４００400 ° C. are used.
【００１３】流動接触分解油の蒸留により得られる留出
油あるいは熱分解油の蒸留により得られる留出油と原油
の常圧あるいは減圧蒸留により得られる留出油を混合す
る場合の混合比率は１：９９〜９９：１で、好ましくは
５：９５〜５０：５０である。The mixing ratio of the distillate obtained by distillation of fluidized catalytic cracking oil or the distillate obtained by distillation of pyrolysis oil and the distillate obtained by distillation of crude oil at normal pressure or reduced pressure is 1 : 99 to 99: 1, preferably 5:95 to 50:50.
【００１４】本発明においては、第一工程では主として
石油蒸留留出油原料油の水素化脱硫が行われ、第二工程
では事実上水素化脱硫は起こらず第一工程の脱硫生成油
の色相改善および色相安定性改善が行われる。In the present invention, in the first step, hydrodesulfurization of a petroleum distillate feedstock is mainly performed, and in the second step, virtually no hydrodesulfurization occurs and the hue of the desulfurized product oil in the first step is improved. And hue stability improvement.
【００１５】第一工程の水素化処理温度は３３０〜４５
０℃、好ましくは３４０〜４００℃、さらに好ましくは
３５０〜３９０℃の範囲である。３３０℃より低い場合
には硫黄分０．０５重量％を達成することは困難であ
る。４５０℃より高い場合には第一工程の触媒の寿命が
短くなり経済的でない。なお、本発明において第一工程
の水素化処理温度とは触媒層の最高温度のことである。
通常、触媒層出口の温度が最高温度となる。The hydrotreating temperature in the first step is from 330 to 45.
0 ° C, preferably 340-400 ° C, more preferably 350-390 ° C. If the temperature is lower than 330 ° C., it is difficult to achieve a sulfur content of 0.05% by weight. When the temperature is higher than 450 ° C., the life of the catalyst in the first step is shortened, which is not economical. In the present invention, the hydrogenation temperature in the first step is the maximum temperature of the catalyst layer.
Usually, the temperature at the outlet of the catalyst layer is the highest temperature.
【００１６】第一工程の水素化処理圧力は４５〜１００
ｋｇ／ｃｍ2 、好ましくは５０〜７０ｋｇ／ｃｍ2 の範
囲である。なお、本発明において第一工程の水素化処理
圧力とは水素分圧のことである。The hydrotreating pressure in the first step is 45 to 100.
kg / cm 2, preferably in the range of 50~70kg / cm 2. In the present invention, the hydrotreating pressure in the first step is a hydrogen partial pressure.
【００１７】第一工程の原料油の供給量（液空間速度）
（ＬＨＳＶ）は１〜１０ｈ-1が好ましく、特に２〜６ｈ
-1が好ましい範囲である。Supply amount of feedstock oil in first step (liquid hourly space velocity)
(LHSV) is preferably 1 to 10 h -1 , particularly 2 to 6 h -1
-1 is a preferred range.
【００１８】第一工程の水素／油比は好ましくは２００
〜５０００ｓｃｆ／ｂｂｌ、特に好ましくは５００〜３
０００ｓｃｆ／ｂｂｌ、さらに特に好ましくは６００〜
２００ｓｃｆ／ｂｂｌの範囲である。The hydrogen / oil ratio in the first step is preferably 200
-5000 scf / bbl, particularly preferably 500-3
000 scf / bbl, more preferably 600 to
It is in the range of 200 scf / bbl.
【００１９】また本発明において、第一工程に必要に応
じて冷却などのために水素をクエンチすることが好まし
い。本発明において使用する水素としては純粋な水素で
もよいし、製油所で通常使用可能なガス状の炭化水素を
含んだ水素でもよい。本発明において、第一工程の水素
化処理触媒は多孔性無機酸化物担体に水素化活性金属と
してクロム、モリブデン、タングステンのうち少なくと
も１種の金属およびコバルト、ニッケルのうち少なくと
も１種の金属を担持した触媒である。In the present invention, it is preferable to quench hydrogen for cooling or the like as required in the first step. The hydrogen used in the present invention may be pure hydrogen or hydrogen containing a gaseous hydrocarbon which can be used in a refinery. In the present invention, the hydrotreating catalyst of the first step supports at least one metal of chromium, molybdenum and tungsten and at least one metal of cobalt and nickel as a hydrogenation active metal on a porous inorganic oxide carrier. It is a catalyst.
【００２０】水素化活性金属としては特にコバルト−モ
リブデンあるいはニッケル−モリブデンが好ましい。こ
れらの金属は担体上に金属状、酸化物、硫化物またはそ
れらの混合物の形態で存在できる。The hydrogenation active metal is particularly preferably cobalt-molybdenum or nickel-molybdenum. These metals can be present on the support in the form of metals, oxides, sulfides or mixtures thereof.
【００２１】多孔性無機酸化物担体としては、例えば、
アルミナ、シリカ、チタニア、ボリア、ジルコニア、シ
リカ−アルミナ、シリカ−マグネシア、アルミナ−マグ
ネシア、アルミナ−チタニア、シリカ−チタニア、アル
ミナ−ボリア、アルミナ−ジルコニア等が挙げられる。
特にアルミナ、シリカ−アルミナが好ましい。Examples of the porous inorganic oxide carrier include:
Examples thereof include alumina, silica, titania, boria, zirconia, silica-alumina, silica-magnesia, alumina-magnesia, alumina-titania, silica-titania, alumina-boria, and alumina-zirconia.
Particularly, alumina and silica-alumina are preferable.
【００２２】これらの触媒は通常石油蒸留留出油の水素
化脱硫に用いられている触媒であり、耐硫黄性が高い。
本発明では、第一工程の触媒には特にアルミナ担体にコ
バルト−モリブデン、ニッケル−モリブデンの活性金属
を担持した触媒を用いることが好ましい。These catalysts are usually used for hydrodesulfurization of petroleum distillate and have high sulfur resistance.
In the present invention, it is preferable to use a catalyst in which an active metal such as cobalt-molybdenum or nickel-molybdenum is supported on an alumina carrier, as the catalyst in the first step.
【００２３】活性金属の担持方法としては含浸法、共沈
法等の公知の方法を用いることができる。該活性金属の
担持量はそれぞれ酸化物として１〜３０重量％の範囲が
好ましく、特に３〜２０重量％の範囲が好ましい。該触
媒の形状は粒状、錠剤状、円柱形のいずれでもよい。As a method for supporting the active metal, known methods such as an impregnation method and a coprecipitation method can be used. The loading amount of the active metal is preferably in the range of 1 to 30% by weight as an oxide, and particularly preferably in the range of 3 to 20% by weight. The shape of the catalyst may be any of granular, tablet, and columnar.
【００２４】第一工程の水素化処理触媒は水素化処理に
用いる前に公知の方法で予備硫化して用いることが好ま
しい。第一工程の水素化処理反応塔の形式は固定床、流
動床、膨張床のいずれでもよいが、特に固定床が好まし
い。第一工程の反応塔での水素、石油蒸留留出油および
触媒の接触は並流上昇流、並流下降流、向流のいずれの
方式を採用してもよい。The hydrotreating catalyst in the first step is preferably preliminarily sulfurized by a known method before use in the hydrotreating. The type of the hydrotreating reaction tower in the first step may be any of a fixed bed, a fluidized bed and an expanded bed, but a fixed bed is particularly preferred. The contact between the hydrogen, the petroleum distillate and the catalyst in the reaction column in the first step may be any of cocurrent upflow, cocurrent downflow, and countercurrent.
【００２５】本発明の第一工程において、原料油である
石油蒸留留出油を前記の水素化処理条件で水素化処理し
て硫黄分が０．０５重量％以下の生成油を得る。しかし
ながら、本発明では第一工程の生成油の硫黄分が著しく
低くなる条件で反応を行うと第一工程の触媒の寿命が短
くなり経済的でない。また後述するように本発明の方法
では第二工程の触媒に耐硫黄性の高い水素化処理触媒を
用いるため、第一工程の生成油の硫黄分を著しく低める
必要がない。したがって第一工程の生成油の硫黄分の下
限値を、好ましくは０．００５重量％以上、より好まし
くは０．００６重量％、特に好ましくは０．００８重量
％以上にすることが好ましい。In the first step of the present invention, a petroleum distillate, which is a feed oil, is hydrotreated under the above-mentioned hydrotreating conditions to obtain a product oil having a sulfur content of 0.05% by weight or less. However, in the present invention, if the reaction is carried out under the condition that the sulfur content of the oil produced in the first step is extremely low, the life of the catalyst in the first step is shortened, which is not economical. Further, as described later, in the method of the present invention, since a hydrotreating catalyst having high sulfur resistance is used as the catalyst in the second step, it is not necessary to significantly reduce the sulfur content of the oil produced in the first step. Therefore, the lower limit of the sulfur content of the oil produced in the first step is preferably at least 0.005% by weight, more preferably at least 0.006% by weight, particularly preferably at least 0.008% by weight.
【００２６】また本発明の第一工程において、生成油の
色相をセーボルト色値で−１０を超え（セーボルト値で
−１０を含まず、−１０より明るい色）、好ましくは−
５以上（セーボルト値で−５と同等または−５より明る
い色）、より好ましくは０以上にする。第一工程の生成
油の色相がセーボルト色値で−１０以下（セーボルト色
値で−１０と同等または−１０より暗い色）の場合に
は、第二工程で色相改善を行った生成油の色相安定性が
低下する。また、第一工程の生成油の色相がセーボルト
値で−１０以下になる場合には、第一工程の触媒の寿命
が短くなり経済的でない。In the first step of the present invention, the hue of the produced oil is more than -10 in Saybolt color value (excluding -10 in Saybolt value and lighter than -10), preferably-
5 or more (color equivalent to or lighter than -5 in Saybolt value), more preferably 0 or more. When the hue of the oil produced in the first step is -10 or less in Saybolt color value (a color equivalent to or darker than -10 in the Saybolt color value), the hue of the oil produced by improving the hue in the second step Stability decreases. Further, when the hue of the oil produced in the first step is -10 or less in Saybolt value, the life of the catalyst in the first step is shortened, which is not economical.
【００２７】本発明では第一工程で水素化処理した後、
第一工程で水素化処理して得た生成物（液状物質および
ガス状物質を含む）の実質全部を第二工程に供給して水
素化処理を行う。つまり第一工程で水素化処理して得た
生成物をセパレーター等で液状物質とガス状物質に気液
分離しないで、また液状物質およびガス状物質中に含有
する硫化水素等の硫黄化合物やアンモニア等の窒素化合
物をストリッピング等の繰作で除去しないで、そのまま
第二工程に供給し水素化処理を行う。In the present invention, after the hydrogenation treatment in the first step,
Substantially all of the products (including liquid substances and gaseous substances) obtained by the hydrogenation treatment in the first step are supplied to the second step to perform the hydrogenation treatment. In other words, the product obtained by the hydrogenation treatment in the first step is not separated into a liquid substance and a gaseous substance by gas-liquid separation using a separator or the like, and a sulfur compound such as hydrogen sulfide or ammonia contained in the liquid substance or the gaseous substance is not used. Without removing the nitrogen compounds such as by stripping or the like, the nitrogen compounds are supplied to the second step as they are and subjected to a hydrogenation treatment.
【００２８】本発明の第二工程の水素化処理温度は第一
工程の水素化処理温度より低く、２００〜３２０℃、好
ましくは２１０〜２９０℃、さらに好ましくは２２０〜
２８０℃、もっとも好ましくは２２０〜２６０℃であ
る。２００℃より低い場合には第二工程での色相の改善
が十分でない。３２０℃よりも高い場合は生成油の色相
がセーボルト色値で−１０を超える生成油を得ることは
困難である。なお、本発明において第二工程の水素化処
理温度とは触媒層出口の温度のことである。The hydrogenation temperature in the second step of the present invention is lower than the hydrogenation temperature in the first step, 200 to 320 ° C., preferably 210 to 290 ° C., more preferably 220 to 290 ° C.
280 ° C, most preferably 220-260 ° C. If the temperature is lower than 200 ° C., the hue in the second step is not sufficiently improved. If the temperature is higher than 320 ° C., it is difficult to obtain a product oil having a hue of the product oil exceeding −10 in Saybolt color value. In the present invention, the hydrogenation temperature in the second step refers to the temperature at the outlet of the catalyst layer.
【００２９】第二工程の水素化処理圧力は４５〜１００
ｋｇ／ｃｍ2 、好ましくは５０〜７０ｋｇ／ｃｍ2 範囲
である。なお、本発明において第二工程の水素化処理圧
力とは水素分圧のことである。The hydrotreating pressure in the second step is 45 to 100.
kg / cm 2, preferably 50~70kg / cm 2 range. In the present invention, the hydrotreating pressure in the second step is a hydrogen partial pressure.
【００３０】第二工程の供給油の供給量（液空間速度）
（ＬＨＳＶ）は１〜１５ｈ-1が好ましく、特に４〜１２
ｈ-1が好ましい範囲である。第二工程の水素／油比は２
００〜５０００ｓｃｆ／ｂｂｌが好ましく、より好まし
くは５００〜３０００ｓｃｆ／ｂｂｌ、特に好ましくは
６００〜２０００ｓｃｆ／ｂｂｌの範囲である。第二工
程で水素化処理に必要な水素は第一工程から供給される
水素で賄うが足りない場合には新たに水素を第二工程に
供給することもできる。Supply amount of supply oil (liquid space velocity) in the second step
(LHSV) is preferably 1 to 15 h -1 , and particularly preferably 4 to 12 h -1.
h -1 is a preferred range. The hydrogen / oil ratio in the second step is 2
It is preferably in the range of 00 to 5000 scf / bbl, more preferably in the range of 500 to 3000 scf / bbl, and particularly preferably in the range of 600 to 2000 scf / bbl. Hydrogen required for the hydrotreating in the second step can be supplied by the hydrogen supplied from the first step, but if it is not enough, hydrogen can be newly supplied to the second step.
【００３１】本発明において、第二工程の水素化処理触
媒は多孔性無機酸化物担体に水素化活性金属としてクロ
ム、モリブデン、タングステンのうち少なくとも１種の
金属およびコバルト、ニッケルのうち少なくとも１種の
金属を担持した触媒である。水素化活性金属としては特
にコバルト−モリブデンあるいはニッケル−モリブデン
が好ましい。これらの金属は担体上に金属状、酸化物、
硫化物またはそれらの混合物の形態で存在できる。In the present invention, the hydrotreating catalyst in the second step is a method in which at least one metal selected from chromium, molybdenum, and tungsten and at least one selected from cobalt and nickel are used as a hydrogenation active metal on a porous inorganic oxide carrier. It is a catalyst that carries a metal. As the hydrogenation active metal, cobalt-molybdenum or nickel-molybdenum is particularly preferred. These metals are metal-like, oxide,
It can be in the form of a sulfide or a mixture thereof.
【００３２】多孔性無機酸化物担体としては、例えば、
アルミナ、シリカ、チタニア、ボリア、ジルコニア、シ
リカ−アルミナ、シリカ−マグネシア、アルミナ−マグ
ネシア、アルミナ−チタニア、シリカ−チタニア、アル
ミナ−ボリア、アルミナ−ジルコニア等が挙げられる。
特にアルミナ、シリカ−アルミナが好ましい。As the porous inorganic oxide carrier, for example,
Examples thereof include alumina, silica, titania, boria, zirconia, silica-alumina, silica-magnesia, alumina-magnesia, alumina-titania, silica-titania, alumina-boria, and alumina-zirconia.
Particularly, alumina and silica-alumina are preferable.
【００３３】これらの触媒は通常石油蒸留留出油の水素
化脱硫に用いられている触媒であり、耐硫黄性が高い。
本発明では、第二工程の触媒には特にアルミナ担体にコ
バルト−モリブデン、ニッケルーモリブデンの活性金属
を担持した触媒を用いることが好ましい。These catalysts are usually used for hydrodesulfurization of petroleum distillate and have high sulfur resistance.
In the present invention, it is preferable to use a catalyst in which an active metal such as cobalt-molybdenum or nickel-molybdenum is supported on an alumina carrier, as the catalyst in the second step.
【００３４】活性金属の担持方法としては含浸法、共沈
法等の公知の方法を用いることができる。該活性金属の
担持量はそれぞれ酸化物として１〜３０重量％の範囲が
好ましく、特に３〜２０重量％の範囲が好ましい。該触
媒の形状は粒状、錠剤状、円柱形のいずれでもよい。As a method for supporting the active metal, known methods such as an impregnation method and a coprecipitation method can be used. The loading amount of the active metal is preferably in the range of 1 to 30% by weight as an oxide, and particularly preferably in the range of 3 to 20% by weight. The shape of the catalyst may be any of granular, tablet, and columnar.
【００３５】第二工程の水素化処理触媒としては第一工
程で用いたものと同じ触媒を用いることができるし、ま
た異なる触媒を用いることもできる。例えば、第一工程
で活性金属としてコバルト−モリブデンを用いた場合に
は、第二工程ではニッケル−モリブデンを用い、第一工
程で活性金属としてニッケル−モリブデンを用いた場合
には第二工程ではコバルト−モリブデンを用いることが
できる。As the hydrotreating catalyst in the second step, the same catalyst as that used in the first step can be used, or a different catalyst can be used. For example, when cobalt-molybdenum is used as the active metal in the first step, nickel-molybdenum is used in the second step, and when nickel-molybdenum is used as the active metal in the first step, cobalt is used in the second step. -Molybdenum can be used.
【００３６】第二工程の水素化処理触媒は水素化処理に
用いる前に公知の方法で予備硫化して用いることが好ま
しい。第二工程の水素化処理反応塔の形式は固定床、流
動床、膨脹床のいずれでもよいが、特に固定床が好まし
い。第二工程の水素、供給油および触媒の接触は並流上
昇流、並流下降流、向流のいずれの方式を採用してもよ
い。The hydrotreating catalyst in the second step is preferably preliminarily sulfurized by a known method before use in the hydrotreating. The type of the hydrotreating reaction tower in the second step may be any of a fixed bed, a fluidized bed and an expanded bed, but a fixed bed is particularly preferred. The contact between the hydrogen, the supply oil and the catalyst in the second step may be any of cocurrent upflow, cocurrent downflow, and countercurrent.
【００３７】本発明は第一工程と第二工程を直列に使用
するが、連続的操作に限定したものではなく、第一工程
相当の操作と第二工程相当の操作を個別に実施すること
もできる。本発明の第二工程では、第二工程の生成油の
色相を第一工程の生成油の色相のセイボルト色値を超え
たものにする。そして生成油の色相をセイボルト色値で
好ましくは０以上、さらに好ましくは＋５以上、特に好
ましくは＋１０以上、さらに特に好ましくは＋１５以
上、最も好ましくは＋２０以上にする。In the present invention, the first step and the second step are used in series. However, the present invention is not limited to the continuous operation, and the operation corresponding to the first step and the operation corresponding to the second step may be performed individually. it can. In the second step of the present invention, the hue of the oil produced in the second step is made to exceed the Saybolt color value of the hue of the oil produced in the first step. The hue of the resulting oil is preferably at least 0, more preferably at least +5, particularly preferably at least +10, particularly preferably at least +15, most preferably at least +20 in Saybolt color value.
【００３８】本発明の第二工程では事実上水素化脱硫は
起こらずに、第一工程の生成油の色相改善および色相安
定性改善が行われる。したがって硫黄分は事実上第一工
程の生成油と同じく０．０５重量％以下を保持する。In the second step of the present invention, virtually no hydrodesulfurization occurs, and the hue and hue stability of the oil produced in the first step are improved. Therefore, the sulfur content is maintained at substantially 0.05% by weight or less as in the oil produced in the first step.
【００３９】第二工程で水素化処理した後、生成油はセ
パレーターで気液分離し、液状物質はストリッピングし
て、硫化水素等の硫黄化合物やアンモニア等の窒素化合
物等の軽質分を分離して製品とする。また、本発明によ
る低硫黄軽油においては、その低温流動性の改善効果に
優れるという点から、水素化処理軽油の他に水素化精製
灯油を配合しても良い。After the hydrogenation treatment in the second step, the produced oil is gas-liquid separated by a separator, and the liquid substance is stripped to separate light components such as sulfur compounds such as hydrogen sulfide and nitrogen compounds such as ammonia. Product. In addition, the low sulfur gas oil according to the present invention may be blended with hydrorefined kerosene in addition to the hydrotreated gas oil because of its excellent effect of improving low temperature fluidity.
【００４０】[0040]
【実施例】本発明を実施例によりさらに詳細に説明する
が、本発明は実施例の範囲に限定されるものではない。 （実施例１）原料油として、硫黄分１．２重量％、色相
がセーボルト色値で＋１０の沸点１５０〜４００℃の範
囲にある原油の常圧蒸留により得られる留出油（ＬＧ
Ｏ）を用いて、表１に示す触媒及び処理条件で二段階水
素化処理を行った。第一工程の水素化処理触媒にはアル
ミナ担体にＣｏＯ５重量％とＭｏＯ3 １８重量％を担持
した市販触媒を用いた。第二工程の水素化処理触媒には
第一工程に用いた触媒と同じ市販触媒を用いた。該触媒
は公知の方法で予備硫化した。第一工程と第二工程は直
列に配し連続的に水素化処理を行った。この際、第一工
程で水素化処理した後、生成した液状物質およびガス状
物質はそのまま第二工程に供給し水素化処理を行った。
また第一工程、第二工程とも処理温度は等温とした。得
られた生成油の色相安定性を下記の方法で試験した結
果、および二段階水素化処理触媒の寿命を下記の方法で
実験した結果を表１に示す。EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to the scope of the examples. (Example 1) A distillate (LG) obtained by atmospheric distillation of a crude oil having a sulfur content of 1.2% by weight and a hue of +10 and a boiling point of 150 to 400 ° C with a Saybolt color value of +10 as a raw material oil.
Using O), a two-stage hydrogenation treatment was performed under the catalysts and treatment conditions shown in Table 1. As the hydrotreating catalyst in the first step, a commercially available catalyst having 5 wt% of CoO and 18 wt% of MoO 3 supported on an alumina carrier was used. As the hydrotreating catalyst in the second step, the same commercially available catalyst as the catalyst used in the first step was used. The catalyst was presulfurized in a known manner. The first step and the second step were arranged in series, and a hydrogenation treatment was continuously performed. At this time, after the hydrogenation treatment in the first step, the generated liquid substance and gaseous substance were supplied to the second step as they were to carry out the hydrogenation treatment.
In both the first step and the second step, the processing temperature was set to be isothermal. Table 1 shows the results of testing the hue stability of the obtained product oil by the following method and the results of experimenting the life of the two-stage hydrotreating catalyst by the following method.
【００４１】（実施例２）原料油として、硫黄分０．８
重量％、色相がセーボルト値で＋４の沸点１５０〜４０
０℃の範囲にある混合油［流動接触分解により得られる
留出油（ＬＣＯ）と原油の常圧蒸留により得られる留出
油（ＬＧＯ）の混合油（混合比率２０：８０）］を用い
て、表１に示す触媒（実施例１と同じ）及び処理条件で
実施例１と同様に二段階水素化処理を行った。得られた
生成油の色相安定性および二段階水素化処理触媒の寿命
を同様にして試験した結果を表１に示す。Example 2 As a feed oil, a sulfur content of 0.8 was used.
% By weight, boiling point 150 to 40 with hue of +4 in Saybolt value
Using a mixed oil in the range of 0 ° C. [a mixed oil of a distillate (LCO) obtained by fluid catalytic cracking and a distillate (LGO) obtained by atmospheric distillation of crude oil (mixing ratio: 20:80)] A two-stage hydrogenation treatment was performed in the same manner as in Example 1 using the catalysts (same as in Example 1) and processing conditions shown in Table 1. Table 1 shows the results of similar tests conducted on the hue stability of the resulting oil and the life of the two-stage hydrotreating catalyst.
【００４２】（実施例３）第二工程の水素化処理触媒に
アルミナ担体にＮｉＯ５重量％とＭｏＯ3 １８重量％を
担持した市販触媒を用いて、表１に示す触媒（第一工程
は実施例１と同じ）、原料油（実施例１と同じ）及び処
理条件で実施例１と同様に二段階水素化処理を行った。
得られた生成油の色相安定性を同様にして試験した結果
を表１に示す。Example 3 A commercially available catalyst having 5% by weight of NiO and 18% by weight of MoO 3 supported on an alumina carrier was used as the hydrotreating catalyst in the second step. 1), a feed oil (same as in Example 1) and processing conditions, and a two-stage hydrogenation treatment was performed in the same manner as in Example 1.
Table 1 shows the results of similar tests conducted on the hue stability of the obtained product oil.
【００４３】（実施例４）第一工程および第二工程の触
媒にアルミナ担体にＮｉＯ５重量％とＭｏＯ3 １８重量
％を担持した市販触媒を用いて、表１に示す原料油（実
施例１と同じ）及び処理条件で実施例１と何様に二段階
水素化処理を行った。得られた生成油の色相安定性を同
様にして試験した結果を表１に示す。[0043] (Example 4) using a commercially available catalyst supporting NiO5 wt% and MoO 3 18 wt% alumina carrier in the catalyst of the first step and the second step, the raw material oil are shown in Table 1 (Example 1 The same two-stage hydrogenation treatments as in Example 1 were carried out under the same conditions and processing conditions. Table 1 shows the results of similar tests conducted on the hue stability of the obtained product oil.
【００４４】[0044]
【表１】 [Table 1]
【００４５】（比較例１）比較例１では第一工程の生成
油の色相が本発明の条件を満たさない場合の比較実験を
行った。表２に示す原料油（実施例１と同じ）、触媒
（実施例１と同じ）及び処理条件で実施例１と同様に二
段階水素化処理を行った。得られた生成油の色相安定性
および二段階水素化処理触媒の寿命を同様にして試験し
た結果を表２に示す。Comparative Example 1 In Comparative Example 1, a comparative experiment was conducted in the case where the hue of the oil produced in the first step did not satisfy the conditions of the present invention. A two-stage hydrogenation treatment was carried out in the same manner as in Example 1 using the feedstock (same as in Example 1), the catalyst (same as in Example 1) and the processing conditions shown in Table 2. Table 2 shows the results of similar tests conducted on the hue stability of the resulting oil and the life of the two-stage hydrotreating catalyst.
【００４６】（比較例２）比較例２では第一工程の生成
油の色相が本発明の条件を満たさない場合の比較実験を
行った。表２に示す原料油（実施例２と同じ混合油）、
触媒（実施例２と同じ）及び処理条件で実施例１と同様
に二段階水素化処理を行った。得られた生成油の色相安
定性および二段階水素化処理触媒の寿命を同様にして試
験した結果を表２に示す。Comparative Example 2 In Comparative Example 2, a comparative experiment was conducted in the case where the hue of the oil produced in the first step did not satisfy the conditions of the present invention. Raw oil shown in Table 2 (the same mixed oil as in Example 2),
A two-stage hydrogenation treatment was carried out in the same manner as in Example 1 using a catalyst (same as in Example 2) and processing conditions. Table 2 shows the results of similar tests conducted on the hue stability of the resulting oil and the life of the two-stage hydrotreating catalyst.
【００４７】（比較例３）比較例３では処理圧力が本発
明の条件を満たさない場合の比較実験を行った。表２に
示す原料油（実施例１と同じ）、触媒（実施例１と同
じ）及び処理条件で実施例１と同様に二段階水素化処理
を行った。得られた生成油の色相安定性および二段階水
素化処理触媒の寿命を同様にして試験した結果を表２に
示す。Comparative Example 3 In Comparative Example 3, a comparative experiment was performed in the case where the processing pressure did not satisfy the conditions of the present invention. A two-stage hydrogenation treatment was carried out in the same manner as in Example 1 using the feedstock (same as in Example 1), the catalyst (same as in Example 1) and the processing conditions shown in Table 2. Table 2 shows the results of similar tests conducted on the hue stability of the resulting oil and the life of the two-stage hydrotreating catalyst.
【００４８】[0048]
【表２】 [Table 2]
【００４９】（生成油の色相安定性試験）実施例１〜
４、比較例１〜３の二段階水素化処理して得た生成油
を、３０℃の暗所で２カ月間保存した。保存後の生成油
の色相を表１及び表２に示した。(Hue Stability Test of Produced Oil)
4. The product oil obtained by the two-stage hydrogenation treatment of Comparative Examples 1 to 3 was stored in a dark place at 30 ° C. for 2 months. The hue of the resulting oil after storage is shown in Tables 1 and 2.
【００５０】（二段階水素化処理触媒寿命実験）実施例
１、２および比較例１〜３の実験を継続して触媒寿命実
験を行った。触媒の劣化に伴い生成油の硫黄分が増大す
るが、生成油の硫黄分を０．０４重量％になるように反
応温度を徐々に上昇させた。反応開始時の反応温度から
２０℃高い温度になるまでの期間を触媒寿命と定義し
た。(Two-Step Hydrogenation Catalyst Life Experiment) A catalyst life experiment was conducted by continuing the experiments of Examples 1 and 2 and Comparative Examples 1 to 3. Although the sulfur content of the produced oil increases with the deterioration of the catalyst, the reaction temperature was gradually increased so that the sulfur content of the produced oil was 0.04% by weight. The period from the reaction temperature at the start of the reaction to a temperature 20 ° C. higher was defined as the catalyst life.
【００５１】表１から判るように、実施例１、２では７
２０日後でも２０℃上昇しなかったが、表２に示したよ
うに、比較例１〜３ではそれぞれ９０日後、７５日後、
４０日後に２０℃上昇した。表１および表２から明らか
なように、実施例１〜４は比較例１〜３に比べて生成油
の色相が良好であり、色相安定性に優れている。さらに
触媒寿命も著しく長い。As can be seen from Table 1, in Examples 1 and 2, 7
Although the temperature did not increase by 20 ° C. even after 20 days, as shown in Table 2, in Comparative Examples 1 to 3, 90 days and 75 days, respectively.
After 40 days the temperature rose by 20 ° C. As is clear from Tables 1 and 2, Examples 1 to 4 have better hue of the produced oil and better hue stability than Comparative Examples 1 to 3. Furthermore, the catalyst life is significantly longer.
【００５２】[0052]
【発明の効果】本発明の二段階水素化処理方法は、原料
油である硫黄分が０．１〜２．０重量％の範囲にある石
油蒸留留出油から硫黄分０．０５重量％以下で、かつ色
相が良好で、色相安定性が優れたディーゼル軽油を製造
することができる。また、本発明の方法は触媒寿命が長
く、該ディーゼル軽油を経済的に製造することができ
る。また、本発明の二段階水素化処理方法に用いる触媒
は耐硫黄性が高く、従来の鉄、Ｐｔ等の触媒を用いた二
段階水素化処理に比べて硫化水素等による触媒被毒を考
慮する必要がないので、セパレーター、ストリッパーお
よび洗浄塔などの除去設備が不必要である。従って、よ
り簡素な設備でもって低硫黄ディーゼル軽油を製造する
ことができるので、設備投資額の低減およびランニング
コストの減少を達成でき非常に経済的である。According to the two-stage hydrotreating method of the present invention, the sulfur content of the feed oil is from 0.05 to 2.0% by weight from a petroleum distillate having a sulfur content of 0.05% by weight or less. A diesel light oil having excellent hue and excellent hue stability can be produced. Further, the method of the present invention has a long catalyst life and can economically produce the diesel gas oil. Further, the catalyst used in the two-stage hydrotreating method of the present invention has a high sulfur resistance, and takes into account catalyst poisoning due to hydrogen sulfide and the like as compared with the conventional two-stage hydrotreating using a catalyst such as iron or Pt. Since there is no need, removal equipment such as a separator, a stripper and a washing tower is unnecessary. Therefore, low-sulfur diesel gas oil can be manufactured with simpler equipment, and the cost of equipment and the running cost can be reduced, which is very economical.
Claims (3)
％、沸点１５０〜４００℃の範囲にある石油蒸留留出油
を水素化処理触媒の存存下、温度３３０〜４５０℃、圧
力４５〜１００ｋｇ／ｃｍ2 の条件で水素と接触させ
て、硫黄分が０．０５重量％以下、かつ色相がセーボル
ト色値で−１０を超える生成油を得る第一工程と、前記
生成油を水素化処理触媒の存在下、温度２００〜３２０
℃、圧力４５〜１００ｋｇ／ｃｍ2 の条件で水素と接触
させて、色相が前記第一工程の色相のセーボルト色値を
超える生成油を得る第二工程とからなることを特徴とす
る低硫黄ディーゼル軽油の製造方法。A petroleum distillate having a sulfur content of 0.1 to 2.0% by weight and a boiling point of 150 to 400 ° C. in the presence of a hydrotreating catalyst at a temperature of 330 to 450 ° C. A first step of contacting with hydrogen under conditions of a pressure of 45 to 100 kg / cm 2 to obtain a product oil having a sulfur content of 0.05% by weight or less and a hue exceeding -10 in Saybolt color value; At a temperature of 200 to 320 in the presence of a hydrotreating catalyst.
A low-sulfur diesel comprising contacting with hydrogen at a temperature of 45 ° C. and a pressure of 45 to 100 kg / cm 2 to obtain a product oil whose hue exceeds the Saybolt color value of the hue of the first step. Manufacturing method of light oil.
タングステンのうち少なくとも一種の金属およびコバル
ト、ニッケルのうち少なくとも一種の金属を多孔性無機
酸化物担体に担持したものである請求項１記載の低硫黄
ディーゼル軽油の製造方法。2. The hydrotreating catalyst is chromium, molybdenum,
The method for producing a low-sulfur diesel light oil according to claim 1, wherein at least one metal of tungsten and at least one metal of cobalt and nickel are supported on a porous inorganic oxide carrier.
カ−アルミナである請求項２記載の低硫黄ディーゼル軽
油の製造方法。3. The method according to claim 2, wherein the porous inorganic oxide is alumina or silica-alumina.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24075396A JPH1088153A (en) | 1996-09-11 | 1996-09-11 | Production of low-sulfur diesel light oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24075396A JPH1088153A (en) | 1996-09-11 | 1996-09-11 | Production of low-sulfur diesel light oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1088153A true JPH1088153A (en) | 1998-04-07 |
Family
ID=17064206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24075396A Pending JPH1088153A (en) | 1996-09-11 | 1996-09-11 | Production of low-sulfur diesel light oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1088153A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041064A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Deep-desulfurization method of diesel distillate |
-
1996
- 1996-09-11 JP JP24075396A patent/JPH1088153A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041064A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Deep-desulfurization method of diesel distillate |
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