JPH09263775A - Production of heavy oil base material - Google Patents
Production of heavy oil base materialInfo
- Publication number
- JPH09263775A JPH09263775A JP7662896A JP7662896A JPH09263775A JP H09263775 A JPH09263775 A JP H09263775A JP 7662896 A JP7662896 A JP 7662896A JP 7662896 A JP7662896 A JP 7662896A JP H09263775 A JPH09263775 A JP H09263775A
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- Prior art keywords
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- oil
- content
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- hydrotreated
- Prior art date
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、重油基材の製造法
に関する。TECHNICAL FIELD The present invention relates to a method for producing a heavy oil base stock.
【0002】[0002]
【従来の技術】従来、我国における重油は硫黄含有量の
少ない原油を常圧蒸留装置で処理しナフサ、灯油、軽油
といった軽質炭化水素を除去することにより得られる硫
黄含有量の低い常圧蒸留残査物や、この低硫黄常圧蒸留
残査物を更に減圧蒸留装置で処理して減圧軽油を除去す
ることにより得られる低硫黄減圧蒸留残査物を主な基材
とし、これにさらに粘度等の調整に灯油、軽油などを混
合することで製造されてきた。2. Description of the Related Art Conventionally, heavy oil in Japan has a low sulfur-containing atmospheric distillation residue obtained by removing crude hydrocarbons such as naphtha, kerosene and light oil by treating crude oil having a low sulfur content with an atmospheric distillation apparatus. And a low-sulfur vacuum distillation residue obtained by further treating the low-sulfur atmospheric distillation residue with a reduced-pressure distillation apparatus to remove reduced-pressure gas oil. It has been manufactured by mixing kerosene, light oil, etc. in the adjustment of.
【0003】一方、低硫黄原油の供給不足や硫黄含有量
の多い原油から得られる常圧または減圧蒸留残査物の有
効利用、更に粘度調整用の灯油、軽油等の中間留分の増
産といった観点から、硫黄含有量の多い原油から得られ
る常圧または減圧蒸留残査物を高温高水素分圧下で水素
化触媒と接触させて脱硫、脱窒素、分解反応を進めるこ
とで、低硫黄かつ低粘度の重油基材を製造する水素化処
理プロセスが開発され、商業運転されている。この水素
化処理プロセスの代表的な運転条件は、反応温度350
〜450℃、反応塔入口の水素分圧9.8〜19.6M
Pa、液空間速度0.1〜5.0h-1、反応塔入口の水
素/油比250〜1700Nm3 /m3 である。[0003] On the other hand, low supply of low-sulfur crude oil, effective utilization of atmospheric or reduced-pressure distillation residue obtained from crude oil having a high sulfur content, and increase in production of middle distillates such as kerosene and gas oil for viscosity adjustment. From low-sulfur and low-viscosity by contacting the atmospheric or reduced pressure distillation residue obtained from crude oil with high sulfur content with a hydrogenation catalyst under high temperature and high hydrogen partial pressure to promote desulfurization, denitrification and cracking reaction Hydroprocessing processes to produce heavy oil bases have been developed and are in commercial operation. Typical operating conditions for this hydrotreating process are a reaction temperature of 350
~ 450 ° C, hydrogen partial pressure 9.8 ~ 19.6M at the inlet of the reaction tower
Pa, liquid space velocity 0.1 to 5.0 h -1 , and hydrogen / oil ratio of 250 to 1700 Nm 3 / m 3 at the inlet of the reaction tower.
【0004】これらの水素化処理プロセスは上述したと
おり、低硫黄原油の供給不足や硫黄含有量の多い原油か
ら得られる常圧または減圧蒸留残査物の有効利用、更に
粘度調整用の灯油、軽油等の中間留分の増産といった観
点から、非常に有意義なものであるが、反応温度を高く
する等の苛酷度の高い運転条件で蒸留残査物を水素化処
理すると、生成物中の重質分、コークス質が増加し、反
応器下流の熱交換器などの管表面に付着することにより
圧力損失の増加、ひいては管閉塞を引き起こす場合があ
る。圧力損失が増加すると管の清掃のために装置全体を
停止しなければならないため多大な損失をもたらす。As described above, these hydrotreating processes effectively utilize the atmospheric pressure or reduced pressure distillation residue obtained from a low-sulfur crude oil supply shortage or a crude oil having a high sulfur content, and further kerosene or light oil for viscosity adjustment. It is very significant from the viewpoint of increasing the production of middle distillates, etc., but when the distillation residue is hydrotreated under severe operating conditions such as increasing the reaction temperature, the heavy products in the product will be As a result, the quality of coke increases and adheres to the surface of a tube such as a heat exchanger downstream of the reactor, which may cause an increase in pressure loss and eventually blockage of the tube. Increased pressure loss results in significant losses because the entire system must be shut down to clean the tubes.
【0005】したがってこれまでは、水素化処理プロセ
スの運転において、下流の管の圧力損失上昇を引き起こ
さない反応温度を上限とするような運転条件の制約を受
けざるを得なかった。Therefore, until now, in the operation of the hydrotreating process, there was no choice but to be restricted by the operating conditions such that the upper limit is the reaction temperature that does not cause an increase in the pressure loss of the downstream pipe.
【0006】また、蒸留残査物の水素化処理で用いられ
る水素化触媒は通常運転時間と共に脱硫、脱窒素、分解
反応の活性が低下するため、運転中の触媒活性の低下を
補償するための反応温度の昇温を考慮して運転初期の反
応温度を決めるが、運転期間中の原油タイプに代表され
る原料油種の変更や生成油硫黄含有量の目標値の変更等
により触媒活性の低下が予想以上に進み、運転の途中で
運転末期の設計反応温度に到達してしまうことがある。[0006] Further, the hydrogenation catalyst used in the hydrotreatment of the distillation residue usually decreases in activity of desulfurization, denitrification, and decomposition reaction with the operation time, so that it is necessary to compensate for the decrease in catalyst activity during operation. The reaction temperature at the initial stage of operation is determined in consideration of the increase in the reaction temperature, but the catalytic activity decreases due to changes in the type of feed oil represented by crude oil type during operation and changes in the target value of the sulfur content of produced oil. May go beyond expectations and reach the design reaction temperature at the end of operation during operation.
【0007】したがってたとえ運転初期の反応温度を下
流の管の圧力損失上昇を引き起こさない温度以下に設定
しても、運転途中に運転末期の設計反応温度に到達する
と下流の管の圧力損失上昇が発生するため、それ以降は
脱硫、脱窒素、分解反応の転化率を下げる、厳しい反応
条件が要求される減圧蒸留残査物の処理比率を下げる、
または反応条件の緩やかな常圧蒸留残査物のみを処理す
る、あるいはその処理量を下げるといった制限を受けて
いた。Therefore, even if the reaction temperature in the initial stage of operation is set to a temperature below the temperature at which the pressure loss in the downstream pipe does not increase, if the design reaction temperature in the final stage of operation is reached during the operation, the pressure loss in the downstream pipe will increase. Therefore, after that, the conversion rate of desulfurization, denitrification, and decomposition reactions is reduced, and the treatment rate of the vacuum distillation residue, which requires severe reaction conditions, is reduced.
Alternatively, there has been a limitation that only the atmospheric distillation residue under mild reaction conditions is treated, or the treatment amount is reduced.
【0008】[0008]
【発明が解決しようとする課題】本発明は、水素化反応
塔の下流の管の閉塞を引き起こさずに、常圧蒸留装置ま
たは減圧蒸留装置などより得られる硫黄含有量の比較的
高い原料油から硫黄含有量の低い重油基材を経済的に製
造する方法を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention uses a feed oil having a relatively high sulfur content obtained from an atmospheric distillation apparatus or a vacuum distillation apparatus without causing clogging of a pipe downstream of a hydrogenation reaction column. An object of the present invention is to provide a method for economically producing a heavy oil base material having a low sulfur content.
【0009】[0009]
【課題を解決するための手段】上記のように硫黄含有量
の多い原油から得られる常圧または減圧蒸留残査物を反
応温度を高くするなどの苛酷度の高い運転条件で水素化
処理すると、生成油中の重質分、コーク質が増加し、反
応器下流の熱交換器などの管表面に付着することにより
圧力損失の増加、ひいては管閉塞を引き起こす場合があ
る。このような管閉塞を引き起こす原因物質としては原
料油中の重質分が重合したもの、アスファルテンのよう
な多環芳香族のうち脂肪族側鎖が失われより芳香族性が
増したものが考えられる。本発明者らは上記のような管
閉塞を引き起こす原因物質についてさらに研究したとこ
ろ、トルエン不溶分含有量と管の圧力損失上昇によい相
関があることを見いだした。そして本発明者らは硫黄含
有量の比較的多い石油蒸留残査物を苛酷な条件で水素化
処理して低硫黄含有量の重油基材を得る際に起こる上記
問題点を解決すべく研究を重ねた結果、原料油を特定さ
れた条件で2段階で水素化処理することにより、硫黄含
有量およびトルエン不溶分含有量の低い重油基材が得ら
れることを見い出し、本発明を完成するに至った。[Means for Solving the Problems] When hydrotreating the atmospheric distillation residue or vacuum distillation residue obtained from crude oil having a high sulfur content as described above under high operating conditions such as increasing reaction temperature, Heavy components and coke in the produced oil may increase and adhere to the surface of tubes such as heat exchangers downstream of the reactor to increase pressure loss and eventually to block the tubes. As the causative substance that causes such pipe blockage, it is considered that the heavy components in the feedstock are polymerized, or the polycyclic aromatic compounds such as asphaltene that have lost the aliphatic side chain and have higher aromaticity. To be The present inventors further studied the causative substances causing the above-mentioned tube clogging, and found that there was a good correlation between the toluene insoluble content and the increase in the pressure loss of the tube. And the present inventors have conducted research to solve the above-mentioned problems that occur when a petroleum distillation residue having a relatively high sulfur content is hydrotreated under severe conditions to obtain a heavy oil base material having a low sulfur content. As a result of repeated experiments, it was found that a heavy oil base material having a low sulfur content and a toluene insoluble content content can be obtained by hydrotreating a feed oil in two stages under specified conditions, and the present invention was completed. It was
【0010】本発明は、ドライスラッジ含有量が0〜
5.0質量%で硫黄含有量が1.0〜10質量%である
原料油を、水素化触媒を充填した第1段階において、加
圧下、触媒床中の最高温度が390〜450℃で水素化
処理して、硫黄含有量が原料油の硫黄含有量の30%以
下、トルエン不溶分含有量が10質量ppm以上の水素
化処理油を得、引き続き第1段階の水素化処理油を、水
素化触媒を充填した第2段階において、加圧下、触媒床
中の最高温度が第1段階の最高温度よりも10℃以上低
く、かつ410℃以下で水素化処理して、硫黄含有量が
原料油の硫黄含有量の30%以下、トルエン不溶分含有
量が第1段階のトルエン不溶分含有量の50%以下の水
素化処理油を得ることを特徴とする重油基材の製造方法
を提供するものである。以下、本発明の内容について詳
細に説明する。The present invention has a dry sludge content of 0 to
In the first stage in which a feed oil having a sulfur content of 5.0% by mass and a sulfur content of 1.0 to 10% by mass was filled with a hydrogenation catalyst, hydrogen was added under pressure at a maximum temperature in the catalyst bed of 390 to 450 ° C. To obtain a hydrotreated oil having a sulfur content of 30% or less of the sulfur content of the raw material oil and a toluene insoluble content of 10 mass ppm or more, and then continuously treating the hydrotreated oil of the first stage with hydrogen. In the second stage filled with the hydrogenation catalyst, the maximum temperature in the catalyst bed is 10 ° C. or more lower than the maximum temperature in the first stage under pressure, and the hydrotreating process is performed at 410 ° C. or less, so that the sulfur content is higher than that of the feed oil. To obtain a hydrotreated oil having a sulfur content of 30% or less and a toluene insoluble content of 50% or less of the toluene insoluble content of the first stage. Is. Hereinafter, the contents of the present invention will be described in detail.
【0011】[0011]
【発明の実施の形態】本発明の重油基材の製造方法にお
ける原料油としては、具体的には例えば、石油蒸留残査
物が挙げられる。これら石油蒸留残査物としては、具体
的には例えば、常圧蒸留装置より得られる、通常、蒸留
温度300℃以上の留分を70質量%以上、好ましくは
90質量%以上、より好ましくは95質量%以上含む常
圧蒸留残査物;減圧蒸留装置より得られる、通常、蒸留
温度400℃以上の留分を70質量%以上、好ましくは
90質量%以上、より好ましくは95質量%以上含む減
圧蒸留残査物;これら常圧蒸留残査物と減圧蒸留残査物
を任意の割合で混合した残査油;これら常圧蒸留残査
物、減圧蒸留残査物またはそれらの混合物を水素化処理
して得られる硫黄分や窒素分等が減少した生成油;また
はこれらの混合物などが挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of the feedstock in the method for producing a heavy oil base material of the present invention include petroleum distillation residue. Specific examples of these petroleum distillation residues include, for example, 70% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass of a fraction obtained at a distillation temperature of 300 ° C. or higher, which is obtained from an atmospheric distillation apparatus. Atmospheric pressure distillation residue containing at least mass%; reduced pressure containing a fraction obtained at a distillation temperature of 400 ° C. or more, usually 70 mass% or more, preferably 90 mass% or more, more preferably 95 mass% or more, obtained from a vacuum distillation apparatus. Distillation residue; Residue oil obtained by mixing these atmospheric distillation residue and vacuum distillation residue at any ratio; Hydrogenation of these atmospheric distillation residue, vacuum distillation residue or mixture thereof The product oil obtained by reducing the sulfur content, the nitrogen content, and the like; or a mixture of these.
【0012】なお、本発明でいう蒸留温度とは、JIS
K 2254に規定する「石油製品−蒸留試験方法」
の「6.減圧法蒸留試験方法」に準拠して測定される温
度を意味する。以降、本発明における石油留分の蒸留温
度とは、すべて上記方法により測定される値を意味す
る。The distillation temperature in the present invention means JIS
"Petroleum products-Distillation test method" specified in K 2254
Means the temperature measured in accordance with “6. Hereinafter, the distillation temperature of the petroleum fraction in the present invention means a value measured by the above method.
【0013】また本発明の原料油としては、これら石油
蒸留残査物100重量部に対して、接触分解装置(FC
C)から得られる分解重質軽油(ヘビーサイクル油)や
スラリー油を40重量部以下、好ましくは20重量部以
下配合したような混合油なども好ましく用いることがで
きる。Further, as the feedstock of the present invention, the catalytic cracking unit (FC
A cracked heavy oil (heavy cycle oil) obtained from C) or a mixed oil obtained by mixing 40 parts by weight or less, preferably 20 parts by weight or less of a slurry oil can also be preferably used.
【0014】さらに本発明の原料油としては、後述する
第2段階の水素化処理工程における出口油の一部をリサ
イクルして、上記の石油蒸留残査物や混合油100重量
部に対してこのリサイクル油を50重量部以下、好まし
くは30重量部以下配合した混合油なども、また好まし
く用いることができる。Further, as the feedstock of the present invention, a part of the outlet oil in the second-stage hydrotreating step described later is recycled to obtain 100 parts by weight of the above petroleum distillation residue or mixed oil. A mixed oil containing 50 parts by weight or less, preferably 30 parts by weight or less of recycled oil can also be preferably used.
【0015】本発明でいうドライスラッジとは、一般に
1.0μm以上の径を有するアスファルテン分子を主体
とする油中で固形の粒子である。本発明における原料油
のドライスラッジ含有量の下限値は0質量%であり、一
方、その上限値は5.0質量%、好ましくは1.0質量
%である。ドライスラッジ含有量の上限値が5.0質量
%を超える場合は、水素化処理工程における原料油供給
系統でのストレーナーやバルブの閉塞、熱交換器や加熱
炉のファウリングによる伝熱効率の低下等の問題を生じ
る恐れがあるため好ましくない。The dry sludge in the present invention is a solid particle in oil mainly composed of asphaltene molecules having a diameter of 1.0 μm or more. The lower limit of the dry sludge content of the feedstock in the present invention is 0% by mass, while the upper limit thereof is 5.0% by mass, preferably 1.0% by mass. If the upper limit of the dry sludge content exceeds 5.0% by mass, the strainer or valve in the feedstock feed system in the hydrotreating process is blocked, and the heat transfer efficiency is reduced due to fouling of the heat exchanger or heating furnace. This is not preferable because it may cause the problem described above.
【0016】なお本発明におけるドライスラッジ含有量
とは、ASTM D 4870-92に規定する”Standard Test Meth
od for Determination of Total Sediment in Residual
Fuels”に準拠して測定される全沈降物量を意味する。
以降、本発明におけるドライスラッジ含有量とは、すべ
てこの方法により測定される値を意味する。The dry sludge content in the present invention means "Standard Test Meth" defined in ASTM D 4870-92.
od for Determination of Total Sediment in Residual
It means the total amount of sediment measured according to Fuels ”.
Hereinafter, the dry sludge content in the present invention means a value measured by this method.
【0017】またこの石油蒸留残査物の硫黄含有量の下
限値は1.0質量%、好ましくは2.0質量%であり、
一方、その上限値は10質量%、好ましくは6.0質量
%である。硫黄含有量が1.0質量%未満の場合は本発
明のような2段階の工程での水素化処理を要さずとも重
油基材を製造することが可能であり、エネルギーコスト
的に不利である。また硫黄含有量が10質量%を超える
場合は、得られる重油基材の硫黄含有量が高くなり、ボ
イラー燃料として用いた場合に燃焼排ガス中の硫黄酸化
物量の増大をもたらしてしまう。また得られる重油基材
の硫黄含有量をより低下させるためには、反応塔や周辺
機器等の建設費が急激に上昇したり、多量のカッター材
を必要とするため、それぞれ好ましくない。The lower limit of the sulfur content of the petroleum distillation residue is 1.0% by mass, preferably 2.0% by mass,
On the other hand, the upper limit value is 10% by mass, preferably 6.0% by mass. When the sulfur content is less than 1.0% by mass, it is possible to manufacture a heavy oil base without the need for hydrotreatment in a two-stage process as in the present invention, which is disadvantageous in energy cost. is there. Further, when the sulfur content exceeds 10% by mass, the sulfur content of the obtained heavy oil base material becomes high, and when used as a boiler fuel, the amount of sulfur oxides in the combustion exhaust gas increases. Further, in order to further reduce the sulfur content of the obtained heavy oil base material, the construction cost of the reaction tower, peripheral equipment and the like rapidly increases, and a large amount of cutter material is required.
【0018】なお、本発明における硫黄含有量とは、JI
S K 2541-1992 に規定する「原油及び石油製品−硫黄分
試験方法」の「6.放射線式励起法」に準拠して測定さ
れる硫黄含有量を意味する。以降、本発明における硫黄
含有量とは、すべて上記方法により測定される値を意味
する。The sulfur content in the present invention means JI
It means the sulfur content measured according to “6. Radiation excitation method” of “Crude oil and petroleum products-Sulfur content test method” specified in SK 2541-1992. Hereinafter, the sulfur content in the present invention means all values measured by the above method.
【0019】本発明においては、これら原料油に対して
まず水素化触媒を充填した第1段階において加圧、昇温
下で水素化処理を行う。第1段階の触媒床中の温度は下
限値が好ましくは340℃以上、さらに好ましくは37
0℃以上であり、一方、その上限値が好ましくは450
℃、さらに好ましくは430℃である。さらに本発明で
は第1段階の触媒床中の最高温度は下限値が390℃以
上、好ましくは400℃以上、一方、その上限値が45
0℃、好ましくは430℃に維持される必要がある。第
1段階の触媒床中の温度の下限値が340℃未満または
最高温度が390℃未満の場合は触媒活性が十分に発揮
されないため脱硫、脱窒素および分解反応が実用の領域
まで進まず、一方、その水素化処理温度が450℃を超
える場合はコーキング反応が激しくなり、触媒上にコー
クが堆積して触媒活性が急速に低下し、触媒寿命が短く
なるため、それぞれ好ましくない。本発明における触媒
床中の最高温度とは、触媒床が原料油の流通方向に対し
て温度勾配を持つ場合は触媒床中で温度が最も高い点の
温度を指し、触媒床が等温系の場合は触媒床の平均温度
を指す。また第1段階の水素化処理工程における温度以
外の他の条件は任意である。In the present invention, these feedstock oils are first subjected to hydrotreating under pressure and temperature rise in the first stage in which the hydrogenation catalyst is filled. The lower limit of the temperature in the catalyst bed of the first stage is preferably 340 ° C. or higher, more preferably 37
0 ° C. or higher, on the other hand, the upper limit thereof is preferably 450
C., more preferably 430.degree. Further, in the present invention, the maximum temperature in the first stage catalyst bed has a lower limit value of 390 ° C. or higher, preferably 400 ° C. or higher, while its upper limit value is 45 ° C. or higher.
It should be maintained at 0 ° C, preferably 430 ° C. When the lower limit of the temperature in the catalyst bed of the first stage is less than 340 ° C or the maximum temperature is less than 390 ° C, the catalytic activity is not sufficiently exhibited, so desulfurization, denitrification and decomposition reactions do not proceed to the practical range. However, if the hydrotreating temperature exceeds 450 ° C., the coking reaction becomes vigorous, coke is deposited on the catalyst, the catalytic activity is rapidly reduced, and the catalyst life is shortened, which is not preferable. The maximum temperature in the catalyst bed in the present invention refers to the temperature of the highest temperature in the catalyst bed when the catalyst bed has a temperature gradient with respect to the flow direction of the feed oil, when the catalyst bed is an isothermal system Refers to the average temperature of the catalyst bed. The conditions other than the temperature in the first stage hydrotreatment process are arbitrary.
【0020】第1段階の入口の圧力は水素分圧は、通
常、下限値が好ましくは8. 0MPa、より好ましくは
9.8MPaであり、一方、上限値が好ましくは25.
0MPa、より好ましくは19.6MPaの範囲であ
る。水素分圧が8.0MPa未満の場合は触媒上のコー
ク生成が激しくなり触媒寿命が極端に短くなる懸念があ
り、一方、その水素分圧が25.0MPaを越える場合
は反応塔や周辺機器等の建設費が急激に上昇し、経済的
に実用性が失われる懸念がある。The hydrogen partial pressure of the inlet in the first stage is usually such that the lower limit value is preferably 8.0 MPa, more preferably 9.8 MPa, while the upper limit value is preferably 25.
The range is 0 MPa, and more preferably 19.6 MPa. If the hydrogen partial pressure is less than 8.0 MPa, there is a concern that coke formation on the catalyst will become violent and the life of the catalyst will be extremely shortened. On the other hand, if the hydrogen partial pressure exceeds 25.0 MPa, the reaction tower, peripheral equipment, etc. There is a concern that the construction cost of the project will rise sharply, and its economic utility will be lost.
【0021】第1段階での原料油の液空間速度(LHS
V)は、通常、下限値が好ましくは0.05h-1、より
好ましくは0.1h-1であり、一方、上限値が好ましく
は5.0h-1、より好ましくは2.0h-1の範囲であ
る。液空間速度(LHSV)が0.05h-1未満の場合
は、反応塔の建設費が莫大になり経済的に実用性が失わ
れる懸念があり、一方、液空間速度(LHSV)が5.
0h-1を越える場合は触媒活性が十分に発揮されず、脱
硫、脱窒素および分解反応が実用の領域まで進まない懸
念がある。Liquid hourly space velocity (LHS) of the feedstock in the first stage
V) is normally the lower limit of preferably 0.05 h -1, more preferably 0.1 h -1, whereas the upper limit is preferably from 5.0 h -1, more preferably 2.0 h -1 It is a range. When the liquid hourly space velocity (LHSV) is less than 0.05 h -1 , there is a concern that the construction cost of the reaction tower becomes enormous and economically impractical. On the other hand, the liquid hourly space velocity (LHSV) is 5.
If it exceeds 0 h -1 , there is a concern that the catalytic activity will not be sufficiently exhibited and that desulfurization, denitrification and decomposition reactions will not proceed to the practical range.
【0022】第1段階の入口の水素/油比は、通常、下
限値が好ましくは250Nm3 /m3 、より好ましくは
600Nm3 /m3 であり、一方、上限値が好ましくは
1700Nm3 /m3 、より好ましくは1500Nm3
/m3 の範囲である。水素/油比が250Nm3 /m3
未満の場合は触媒上のコーク生成が激しくなり触媒寿命
が極端に短くなる懸念があり、一方、水素/油比が17
00Nm3 /m3 を超える場合は、反応塔や周辺機器等
の建設費が急激に上昇し、経済的に実用性が失われる懸
念がある。The hydrogen / oil ratio at the inlet of the first stage, usually, the lower limit is preferably 250 Nm 3 / m 3, more preferably from 600 Nm 3 / m 3, whereas the upper limit is preferably 1700 nm 3 / m 3 , more preferably 1500 Nm 3
The range is / m 3 . Hydrogen / oil ratio of 250 Nm 3 / m 3
If it is less than the above, coke formation on the catalyst may become severe and the life of the catalyst may be extremely shortened, while the hydrogen / oil ratio may be 17 or less.
If it exceeds 00 Nm 3 / m 3 , there is a concern that the construction cost of the reaction tower, peripheral equipment and the like will rise sharply, and economically impractical.
【0023】第1段階での水素化処理の操作は、油とガ
スを並行で下降流または上昇流で行うことができ、ま
た、油とガスを向流で行うこともできる。また、第1段
階の水素化処理として触媒を充填して使用される反応塔
は、単独の反応塔または連続した複数の反応塔のどちら
で構成されていてもよい。更に反応塔内は、単独の触媒
床または複数の触媒床のどちらで構成されていてもよ
い。The hydrotreating operation in the first stage can be carried out in parallel with oil and gas in a downflow or upflow, or can be carried out with oil and gas in countercurrent. Further, the reaction tower used by being filled with a catalyst for the first-stage hydrotreatment may be either a single reaction tower or a plurality of continuous reaction towers. Further, the inside of the reaction tower may be constituted by either a single catalyst bed or a plurality of catalyst beds.
【0024】第1段階の水素化処理における各反応塔の
間や各触媒床の間に、後続の反応塔や触媒床の入口の反
応温度を調節する目的で、気体、液体または液体と気体
の混合物を注入することも可能である。A gas, a liquid, or a mixture of liquid and gas is used between the reaction towers in the first stage hydrotreatment or between the catalyst beds for the purpose of adjusting the reaction temperature at the inlet of the subsequent reaction tower or catalyst bed. It is also possible to inject.
【0025】ここでいう気体は、通常、水素;例えばメ
タン、エタン、プロパン、ブタン、ペンタン、ヘキサン
等の炭素数1〜6のパラフィン系炭化水素およびこれら
の混合物など、注入する温度、圧力で気体として存在で
きる炭化水素;または水素とこれら炭化水素との混合
物;が好ましく用いられるが、例えば硫化水素、アンモ
ニア、窒素など、注入する温度、圧力で気体として存在
できる他の物質を含んでいてもよい。The gas referred to herein is usually hydrogen; for example, methane, ethane, propane, butane, pentane, hexane, and other paraffinic hydrocarbons having 1 to 6 carbon atoms, and mixtures thereof. Is preferably used, but a mixture of hydrogen and these hydrocarbons is preferably used, but it may contain other substances such as hydrogen sulfide, ammonia, and nitrogen, which can exist as a gas at the temperature and pressure of injection. .
【0026】また、ここでいう液体は、通常、例えば、
灯油、直留軽油、減圧軽油などの石油蒸留物;石油蒸留
残査物;石油蒸留物や石油蒸留残査物などの水素化処理
油;石油蒸留物や石油蒸留残査物などの熱分解油;石油
蒸留物や石油蒸留残査物などの接触分解油;またはこれ
らの混合物;など、注入する温度、圧力で液体として存
在できる炭化水素が好ましく用いられるが、後述する第
2段階の水素化処理工程における出口油の一部をリサイ
クルして使用するのが更に好ましい。The liquid referred to here is usually, for example,
Petroleum distillates such as kerosene, straight-run gas oil and vacuum gas oil; petroleum distillation residues; hydrotreated oils such as petroleum distillates and petroleum distillation residues; pyrolysis oils such as petroleum distillates and petroleum distillation residues Hydrocarbons that can be present as a liquid at the temperature and pressure of injection, such as catalytically cracked oils such as petroleum distillates and petroleum distillation residues; or mixtures thereof, are preferably used, but the second stage hydrotreatment described below. It is more preferable to recycle and use a part of the outlet oil in the process.
【0027】第1段階において各反応塔の間や各触媒床
の間に気体や液体を注入する場合、それらの注入量は任
意であるが、通常、気体を注入する場合は注入量が気体
/油比で1700Nm3 /m3 以下の範囲で行うことが
でき、液体を注入する場合は注入量が液体/油比で1m
3 /m3 以下の範囲で行うことができる。When gas or liquid is injected between the reaction towers or between the catalyst beds in the first stage, the injection amount thereof is arbitrary, but when the gas is injected, the injection amount is usually gas / oil ratio. Can be performed in the range of 1700 Nm 3 / m 3 or less. When injecting a liquid, the injection amount is 1 m in terms of liquid / oil ratio.
3 / m 3 or less.
【0028】なお、第1段階の水素化処理工程において
複数の反応塔または触媒床を使用する場合、本発明にお
ける触媒床中の最高温度とは、各反応塔の間や各触媒床
の間への気体、液体または液体と気体の混合物の注入の
有無にかかわらず、またさらに反応塔の数に関係なく、
第1段階のすべての触媒床を対象にして、温度が最も高
い点の温度を指す。When a plurality of reaction towers or catalyst beds are used in the first stage hydrotreating step, the maximum temperature in the catalyst bed in the present invention means the gas between the reaction towers and the catalyst beds. , With or without injection of a liquid or a mixture of liquid and gas, and further regardless of the number of reaction columns,
For all catalyst beds of the first stage, it refers to the temperature at the highest temperature.
【0029】また、第1段階の水素化処理工程における
水素化処理触媒としては、従来公知の任意の水素化処理
触媒が使用可能である。具体的には例えば、アルミナ、
シリカ、チタニア、ジルコニア、マグネシア、アルミナ
−シリカ、アルミナ−ボリア、アルミナ−チタニア、ア
ルミナ−ジルコニア、アルミナ−マグネシア、アルミナ
−シリカ−ジルコニア、アルミナ−シリカ−チタニア、
各種ゼオライト、セピオライト、モンモリロナイト等の
各種粘土鉱物などの多孔性無機酸化物を担体とし、これ
に水素化活性金属を担持した物を好ましく用いることが
できる。As the hydrotreating catalyst in the first stage hydrotreating step, any conventionally known hydrotreating catalyst can be used. Specifically, for example, alumina,
Silica, titania, zirconia, magnesia, alumina-silica, alumina-boria, alumina-titania, alumina-zirconia, alumina-magnesia, alumina-silica-zirconia, alumina-silica-titania,
A porous inorganic oxide such as various zeolites, sepiolite, various clay minerals such as montmorillonite, which is used as a carrier, and a hydrogenation-active metal is supported thereon can be preferably used.
【0030】該担持金属としては、通常、周期律表第V
IA、VA、VB、およびVIII族の金属から選ばれ
る少なくとも1種の水素化活性金属種が好ましく用いら
れ、特にコバルト、モリブデン、ニッケルをそれぞれ単
独で、または、コバルト、モリブデン、ニッケルを2種
あるいは3種組み合わせて多孔性無機酸化物に担持した
触媒がより好ましく用いられる。なお、本発明の第1段
階の水素化処理工程で用いる水素化処理触媒は、通常市
販されている水素化処理触媒でも十分目的が達成可能で
あり、本発明は触媒の種類によって何ら制限されるもの
ではない。The metal to be supported is usually V
At least one hydrogenation-active metal species selected from the group IA, VA, VB, and VIII metals is preferably used. In particular, cobalt, molybdenum, and nickel are each used alone, or two or more of cobalt, molybdenum, and nickel are used. A catalyst supported on a porous inorganic oxide in combination of three types is more preferably used. The hydrotreating catalyst used in the hydrotreating step of the first stage of the present invention can be achieved even if it is a commercially available hydrotreating catalyst, and the present invention is not limited by the kind of the catalyst. Not a thing.
【0031】第1段階の水素化処理で得られる水素化処
理油のトルエン不溶分含有量は10質量ppm以上とな
る。より一般的には、20質量ppm以上の値となる。
本発明でいうトルエン不溶分とは試料中のトルエンに不
溶な成分を指し、トルエン不溶分含有量は試料中のトル
エンに不溶な成分と試料の重量比で表される。トルエン
不溶分含有量の測定方法としては試料適量を十分なトル
エンに溶解した後、十分目の細かいフィルターで濾過
し、フィルター上のろ滓の質量を測定する方法が挙げら
れる。この方法においては通常50〜150gの試料が
用いられ、これをトルエンに溶解して全量を500〜1
500ccにした後、フィルターで濾過する。フィルタ
ーの孔径としては0.2μmまたはそれ以下のものが好
ましい。またフィルターの材質は試料、トルエンによっ
て変質しないものであれば任意であり、メンブレンフィ
ルターなどが用いられる。The content of toluene-insoluble matter in the hydrotreated oil obtained in the first stage hydrotreatment is 10 mass ppm or more. More generally, the value is 20 mass ppm or more.
In the present invention, the toluene insoluble component refers to a component insoluble in toluene in the sample, and the content of the toluene insoluble component is represented by a weight ratio between the component insoluble in the sample and the sample. Examples of the method for measuring the content of toluene insolubles include a method in which an appropriate amount of a sample is dissolved in sufficient toluene, filtered with a filter having a sufficiently fine mesh, and the mass of the filter cake on the filter is measured. In this method, a sample of 50 to 150 g is usually used, and this is dissolved in toluene to make a total amount of 500 to 1
After adjusting to 500 cc, it is filtered with a filter. The filter preferably has a pore size of 0.2 μm or less. The material of the filter is arbitrary as long as it is not changed by the sample or toluene, and a membrane filter or the like is used.
【0032】第1段階の水素化処理では、通常、実質的
に原料油の脱硫反応、脱窒素反応および分解反応の大部
分が達成される。第1段階の水素化処理で得られる水素
化処理油の硫黄含有量は原料中の硫黄含有量の30%以
下、好ましくは20%以下である。脱硫率としては70
%以上、好ましくは80%以上である。通常、原料油中
の硫黄含有量の下限値は0.01質量%、好ましくは
0.1質量%であり、一方、その上限値は2.0質量
%、好ましくは1.0質量%である。第1段階の水素化
処理工程で得られる水素化処理油の窒素含有量も何ら規
定しないが、通常、その下限値は好ましくは0.01質
量%、より好ましくは0.1質量%であり、一方、その
上限値は好ましくは1.0質量%、より好ましくは0.
5質量%が一般的である。In the first-stage hydrotreatment, substantially all of the desulfurization reaction, denitrification reaction and cracking reaction of the feedstock are substantially achieved. The sulfur content of the hydrotreated oil obtained by the first stage hydrotreatment is 30% or less, preferably 20% or less, of the sulfur content in the raw material. Desulfurization rate is 70
% Or more, preferably 80% or more. Usually, the lower limit of the sulfur content in the feed oil is 0.01% by mass, preferably 0.1% by mass, while the upper limit thereof is 2.0% by mass, preferably 1.0% by mass. . Although the nitrogen content of the hydrotreated oil obtained in the first stage hydrotreatment step is not specified at all, the lower limit thereof is preferably 0.01% by mass, more preferably 0.1% by mass, On the other hand, the upper limit thereof is preferably 1.0% by mass, more preferably 0.
5% by weight is common.
【0033】なお、本発明における窒素含有量とは、JI
S K 2609-1990 に規定する「原油及び石油製品−窒素分
試験方法」の「7.化学発光法」に準拠して測定される
窒素含有量を意味する。以降、本発明における窒素含有
量とは、すべて上記方法により測定される値を意味す
る。The nitrogen content in the present invention means JI
It means the nitrogen content measured according to "7. Chemiluminescence method" of "Crude oil and petroleum products-Nitrogen content test method" specified in SK 2609-1990. Hereinafter, the nitrogen content in the present invention means all values measured by the above method.
【0034】本発明では第1段階の水素化処理油を、さ
らに水素化触媒を充填した第2段階において、加圧、昇
温下で水素化処理を行う。第2段階の触媒床中の温度は
下限値が好ましくは150℃、さらに好ましくは200
℃であり、一方、その上限値が好ましくは410℃、さ
らに好ましくは400℃である。第2段階の触媒床の温
度が150℃未満の場合は触媒活性が十分に発揮されな
いためトルエン不溶分の水素化反応が実用の領域まで進
まない。一方、その水素化処理温度が410℃を超える
場合はトルエン不溶分の水素化が進まずに、逆にトルエ
ン不溶分が増加してしまうため好ましくない。In the present invention, the hydrotreated oil of the first stage is subjected to the hydrotreatment under pressure and temperature rise in the second stage in which the hydrotreated catalyst is further filled. The lower limit of the temperature in the catalyst bed in the second stage is preferably 150 ° C., more preferably 200 ° C.
On the other hand, the upper limit thereof is preferably 410 ° C, more preferably 400 ° C. When the temperature of the catalyst bed in the second stage is lower than 150 ° C., the catalytic activity is not sufficiently exhibited, and the hydrogenation reaction of the toluene insoluble matter does not proceed to a practical range. On the other hand, if the hydrogenation temperature exceeds 410 ° C., the hydrogenation of the toluene-insoluble matter will not proceed, and the toluene-insoluble matter will increase, which is not preferable.
【0035】さらに本発明では第2段階の水素化におい
て、触媒床中の最高温度を第1段階の触媒床中の最高温
度より低い値に設定して水素化処理を実施することが重
要である。第2段階の触媒床中の最高温度は、第1段階
での触媒床中の最高温度より10℃以上低く、より好ま
しくは20℃以上低く維持される必要がある。本発明に
おいて、第2段階の最高温度が第1段階の最高温度と同
一または第1段階の水素化処理温度より高い場合は、ト
ルエン不溶分の水素化が進まずに、逆にトルエン不溶分
が増加してしまうため好ましくない。Further, in the present invention, in the second stage hydrogenation, it is important to set the maximum temperature in the catalyst bed to a value lower than the maximum temperature in the first stage catalyst bed to carry out the hydrotreatment. . The maximum temperature in the catalyst bed of the second stage should be kept 10 ° C. or more lower than the maximum temperature in the catalyst bed of the first stage, more preferably 20 ° C. or more lower. In the present invention, when the maximum temperature of the second stage is the same as the maximum temperature of the first stage or higher than the hydrotreating temperature of the first stage, the hydrogenation of the toluene insoluble matter does not proceed, and conversely, the toluene insoluble matter is It is not preferable because it increases.
【0036】また第2段階の水素化処理における温度以
外の他の条件は任意である。第2段階の触媒床入口の圧
力は水素分圧として、通常、下限値が好ましくは1.0
MPaであり、一方、上限値が好ましくは25.0MP
a、より好ましくは19.6MPaの範囲である。触媒
床入口の水素分圧が1.0MPa未満の場合は触媒活性
が十分に発揮されず、トルエン不溶分の水素化反応が実
用の領域まで進まない懸念があり、一方、その水素分圧
が25.0MPaを越える場合は反応塔や周辺機器等の
建設費が急激に上昇し、経済的に実用性が失われる懸念
がある。The conditions other than the temperature in the second stage hydrotreatment are arbitrary. The pressure at the catalyst bed inlet in the second stage is a hydrogen partial pressure, and the lower limit is usually preferably 1.0.
MPa, while the upper limit is preferably 25.0MP
a, more preferably in the range of 19.6 MPa. If the hydrogen partial pressure at the catalyst bed inlet is less than 1.0 MPa, the catalytic activity may not be sufficiently exhibited, and the hydrogenation reaction of the toluene insoluble matter may not proceed to a practical range. If it exceeds 0.0 MPa, the construction cost of the reaction tower, peripheral equipment, and the like will rise sharply, and there is a concern that it will be economically impractical.
【0037】第2段階での原料油(第1段階の水素化処
理を経た水素化処理油)の液空間速度(LHSV)は、
通常、下限値が好ましくは0.1-1、より好ましくは
0.2h-1であり、一方、上限値が好ましくは10
h-1、より好ましくは4.0h-1の範囲である。液空間
速度(LHSV)が0.1h-1未満の場合は、反応塔の
建設費が莫大になり経済的に実用性が失われる懸念があ
り、一方、液空間速度(LHSV)が10h-1を越える
場合は触媒活性が十分に発揮されず、トルエン不溶分の
水素化反応が実用の領域まで進まない懸念がある。The liquid hourly space velocity (LHSV) of the feedstock in the second stage (hydrotreated oil after the first stage hydrotreatment) is
Usually, the lower limit is preferably 0.1 -1 , more preferably 0.2 h -1 , while the upper limit is preferably 10 1.
h -1, more preferably in the range of 4.0 h -1. When the liquid hourly space velocity (LHSV) is less than 0.1 h -1 , there is a concern that the construction cost of the reaction tower becomes enormous and economically impractical. On the other hand, the liquid hourly space velocity (LHSV) is 10 h -1. If it exceeds, the catalytic activity may not be sufficiently exhibited, and there is a concern that the hydrogenation reaction of the toluene-insoluble portion may not proceed to a practical range.
【0038】第2段階の入口の水素/油比は、通常、下
限値が好ましくは250Nm3 /m3 、より好ましくは
600Nm3 /m3 であり、一方、上限値が好ましくは
1700Nm3 /m3 、より好ましくは1500Nm3
/m3 の範囲である。水素/油比が250Nm3 /m3
未満の場合は、触媒上のコーク生成が激しくなり触媒寿
命が極端に短くなる懸念があり、一方、水素/油比が1
700Nm3 /m3 を超える場合は、反応塔や周辺機器
等の建設費が急激に上昇し、経済的に実用性が失われる
懸念がある。The hydrogen / oil ratio at the inlet of the second stage, usually, the lower limit is preferably 250 Nm 3 / m 3, more preferably from 600 Nm 3 / m 3, whereas the upper limit is preferably 1700 nm 3 / m 3 , more preferably 1500 Nm 3
The range is / m 3 . Hydrogen / oil ratio of 250 Nm 3 / m 3
If it is less than 1, there is a concern that coke formation on the catalyst will become severe and the life of the catalyst will be extremely short, while the hydrogen / oil ratio will be 1
If it exceeds 700 Nm 3 / m 3 , there is a concern that the construction cost of the reaction tower, peripheral equipment, etc. will rise sharply, and economically impractical.
【0039】第2段階での水素化処理の操作は、油とガ
スを並行で下降流または上昇流で行うことができ、ま
た、油とガスを向流で行うこともできる。また、第2段
階の水素化処理工程として触媒を充填して使用される反
応塔は、単独の反応塔または連続した複数の反応塔のど
ちらで構成されていてもよい。更に、反応塔内は、単独
の触媒床または複数の触媒床のどちらで構成されていて
もよい。The operation of hydrotreating in the second stage can be carried out in parallel with oil and gas in a downflow or upflow, or can be carried out with oil and gas in countercurrent. Further, the reaction tower used by being filled with a catalyst in the second stage hydrotreating step may be composed of either a single reaction tower or a plurality of continuous reaction towers. Further, the inside of the reaction tower may be constituted by either a single catalyst bed or a plurality of catalyst beds.
【0040】第2段階の水素化処理における各反応塔の
間や各触媒床の間に、後続の反応塔や触媒床の入口の反
応温度を調節する目的で、気体、液体または液体と気体
の混合物を注入することも可能である。A gas, a liquid or a mixture of liquid and gas is used between the reaction columns in the second stage hydrotreatment or between the catalyst beds for the purpose of controlling the reaction temperature at the inlet of the subsequent reaction column or catalyst bed. It is also possible to inject.
【0041】ここでいう気体は、通常、水素;例えばメ
タン、エタン、プロパン、ブタン、ペンタン、ヘキサン
等の炭素数1〜6のパラフィン系炭化水素およびこれら
の混合物など、注入する温度、圧力で気体として存在で
きる炭化水素;または水素とこれら炭化水素との混合
物;が好ましく用いられるが、例えば硫化水素、アンモ
ニア、窒素など、注入する温度、圧力で気体として存在
できる他の物質を含んでいてもよい。The gas referred to herein is usually hydrogen; for example, methane, ethane, propane, butane, pentane, hexane, and other paraffinic hydrocarbons having 1 to 6 carbon atoms, and mixtures thereof. Is preferably used, but a mixture of hydrogen and these hydrocarbons is preferably used, but it may contain other substances such as hydrogen sulfide, ammonia, and nitrogen, which can exist as a gas at the temperature and pressure of injection. .
【0042】また、ここでいう液体は、通常、例えば、
灯油、直留軽油、減圧軽油などの石油蒸留物;石油蒸留
残査物;石油蒸留物や石油蒸留残査物などの水素化処理
油;石油蒸留物や石油蒸留残査物などの熱分解油;石油
蒸留物や石油蒸留残査物などの接触分解油;またはこれ
らの混合物;など、注入する温度、圧力で液体として存
在できる炭化水素が好ましく用いられるが、第2段階の
水素化処理工程における出口油の一部をリサイクルして
使用するのが更に好ましい。The liquid mentioned here is usually, for example,
Petroleum distillates such as kerosene, straight-run gas oil and vacuum gas oil; petroleum distillation residues; hydrotreated oils such as petroleum distillates and petroleum distillation residues; pyrolysis oils such as petroleum distillates and petroleum distillation residues Hydrocarbons that can be present as a liquid at the temperature and pressure of injection, such as catalytically cracked oils such as petroleum distillates and petroleum distillation residues; or mixtures thereof, are preferably used, but in the second stage hydrotreatment step It is more preferable to recycle a part of the outlet oil for use.
【0043】第2段階において各反応塔の間や各触媒床
の間に気体や液体を注入する場合、それらの注入量は任
意であるが、通常、気体を注入する場合は注入量が気体
/油比で1700Nm3 /m3 以下の範囲で行うことが
でき、液体を注入する場合は注入量が液体/油比で1m
3 /m3 以下の範囲で行うことができる。When injecting a gas or a liquid between the reaction towers or between the catalyst beds in the second stage, the injection amounts are arbitrary, but when injecting the gas, the injection amount is usually the gas / oil ratio. Can be performed in the range of 1700 Nm 3 / m 3 or less. When injecting a liquid, the injection amount is 1 m in terms of liquid / oil ratio.
3 / m 3 or less.
【0044】第2段階の水素化処理において複数の反応
塔または触媒床を使用する場合、本発明における触媒床
中の最高温度とは、各反応塔の間や各触媒床の間への気
体、液体または液体と気体の混合物の注入の有無にかか
わらず、またさらに反応塔の数に関係なく、第2段階の
すべての触媒床を対象にして、温度が最も高い点の温度
を指す。When a plurality of reaction towers or catalyst beds are used in the second stage hydrotreatment, the maximum temperature in the catalyst bed in the present invention means the gas, liquid or gas between the reaction towers and the catalyst beds. It refers to the temperature of the highest temperature for all catalyst beds of the second stage, with or without injection of a mixture of liquid and gas, and also regardless of the number of reaction columns.
【0045】第2段階の水素化処理で用いる水素化処理
触媒としては、従来公知の任意の水素化処理触媒が使用
可能である。具体的には例えば、アルミナ、シリカ、チ
タニア、ジルコニア、マグネシア、アルミナ−シリカ、
アルミナ−ボリア、アルミナ−チタニア、アルミナ−ジ
ルコニア、アルミナ−マグネシア、アルミナ−シリカ−
ジルコニア、アルミナ−シリカ−チタニア、各種ゼオラ
イト、セピオライト、モンモリロナイト等の各種粘土鉱
物などの多孔性無機酸化物を担体とし、これに水素化活
性金属を担持した物を好ましく用いることができる。As the hydrotreating catalyst used in the second stage hydrotreating, any conventionally known hydrotreating catalyst can be used. Specifically, for example, alumina, silica, titania, zirconia, magnesia, alumina-silica,
Alumina-Boria, Alumina-Titania, Alumina-Zirconia, Alumina-Magnesia, Alumina-Silica-
Porous inorganic oxides such as zirconia, alumina-silica-titania, various zeolites, various clay minerals such as sepiolite and montmorillonite are used as a carrier, and a substance having a hydrogenation-active metal supported thereon can be preferably used.
【0046】該担持金属としては、通常、周期律表第V
IA、VA、VB、およびVIII族の金属から選ばれ
る少なくとも1種の水素化活性金属種が好ましく用いら
れ、特にコバルト、モリブデン、ニッケルをそれぞれ単
独で、または、コバルト、モリブデン、ニッケルを2種
あるいは3種組み合わせて多孔性無機酸化物に担持した
触媒がより好ましく用いられる。なお、本発明の第2段
階の水素化処理工程で用いる水素化処理触媒は、通常市
販されている水素化処理触媒でも十分目的が達成可能で
あり、本発明は触媒の種類によって何ら制限されるもの
ではない。As the supported metal, usually, the periodic table V
At least one hydrogenation-active metal species selected from the group IA, VA, VB, and VIII metals is preferably used. In particular, cobalt, molybdenum, and nickel are each used alone, or two or more of cobalt, molybdenum, and nickel are used. A catalyst supported on a porous inorganic oxide in combination of three types is more preferably used. The hydrotreating catalyst used in the hydrotreating step of the second step of the present invention can be achieved by using a commercially available hydrotreating catalyst, and the present invention is not limited by the kind of the catalyst. Not a thing.
【0047】本発明においては、第1段階と第2段階の
水素化処理を、一つの反応塔の中で行ってもよく、ある
いは分離した2基以上の反応塔を用いて行ってもよい。
また反応塔の中は複数個の触媒床に分かれていても良
い。In the present invention, the first stage and second stage hydrotreating may be carried out in one reaction tower or may be carried out using two or more separated reaction towers.
Further, the inside of the reaction tower may be divided into a plurality of catalyst beds.
【0048】本発明において、第2段階の水素化処理温
度を第1段階の水素化処理温度より下げる方法は特に限
定されるものでなく、任意の方法を採用することができ
る。具体的には従来公知の方法、例えば、低温の気体、
液体、あるいは気体と液体の両方を注入する方法、また
は熱交換器による低温流体との熱交換の方法などを用い
ることができる。In the present invention, the method of lowering the second stage hydrotreating temperature below the first stage hydrotreating temperature is not particularly limited, and any method can be adopted. Specifically, a conventionally known method, for example, a low temperature gas,
A method of injecting a liquid, or both a gas and a liquid, a method of heat exchange with a cryogenic fluid by a heat exchanger, or the like can be used.
【0049】なおここでいう気体は、通常、水素;例え
ばメタン、エタン、プロパン、ブタン、ペンタン、ヘキ
サン等の炭素数1〜6のパラフィン系炭化水素およびこ
れらの混合物など、注入する温度、圧力で気体として存
在できる炭化水素;または水素とこれら炭化水素との混
合物;が好ましく用いられるが、例えば硫化水素、アン
モニア、窒素など、注入する温度、圧力で気体として存
在できる他の物質を含んでいてもよい。The gas referred to herein is usually hydrogen; for example, methane, ethane, propane, butane, pentane, hexane, and other paraffinic hydrocarbons having 1 to 6 carbon atoms, and mixtures thereof at the temperature and pressure for injection. Hydrocarbons that can exist as a gas; or a mixture of hydrogen and these hydrocarbons; are preferably used, but may also contain other substances that can exist as a gas at the injection temperature and pressure, such as hydrogen sulfide, ammonia, and nitrogen. Good.
【0050】また、ここでいう液体は、通常、例えば、
灯油、直留軽油、減圧軽油などの石油蒸留物;石油蒸留
残査物;石油蒸留物や石油蒸留残査物などの水素化処理
油;石油蒸留物や石油蒸留残査物などの熱分解油;石油
蒸留物や石油蒸留残査物などの接触分解油;またはこれ
らの混合物;など、注入する温度、圧力で液体として存
在できる炭化水素が好ましく用いられるが、第2段階の
水素化処理工程における出口油の一部をリサイクルして
使用するのが更に好ましい。The liquid referred to here is usually, for example,
Petroleum distillates such as kerosene, straight-run gas oil and vacuum gas oil; petroleum distillation residues; hydrotreated oils such as petroleum distillates and petroleum distillation residues; pyrolysis oils such as petroleum distillates and petroleum distillation residues Hydrocarbons that can be present as a liquid at the temperature and pressure of injection, such as catalytically cracked oils such as petroleum distillates and petroleum distillation residues; or mixtures thereof, are preferably used, but in the second stage hydrotreatment step It is more preferable to recycle a part of the outlet oil for use.
【0051】本発明における第1段階の水素化処理と第
2段階の水素化処理は連続的操作に限定されるわけでは
なく、第1段階の操作と第2段階の操作を個別に実施し
てもよい。なお両段階の操作を個別に実施する場合、第
1段階と第2段階の間の条件は特に限定されるものでは
ない。The first-stage hydrotreatment and the second-stage hydrotreatment in the present invention are not limited to the continuous operation, and the first-stage operation and the second-stage operation are carried out individually. Good. When the operations in both stages are individually performed, the conditions between the first stage and the second stage are not particularly limited.
【0052】第2段階の水素化処理で得られる水素化処
理油の硫黄含有量は原料中の硫黄含有量の30%以下、
好ましくは20%以下である。脱硫率としては70%以
上、好ましくは80%以上である。通常、原料油中の硫
黄含有量の下限値は0.01質量%、好ましくは0.1
質量%であり、一方、その上限値は2.0質量%、好ま
しくは1.0質量%である。トルエン不溶分含有量が第
1段階の水素化処理工程の出口でのトルエン不溶分含有
量の50%以下、好ましくは40%以下である。このよ
うに本発明において、以上の2段階の水素化処理によ
り、第1段階の水素化処理工程で高温処理したにもかか
わらずトルエン不溶分含有量が低く、かつ硫黄含有量が
低められた重油基材が得られる。The sulfur content of the hydrotreated oil obtained in the second stage hydrotreatment is 30% or less of the sulfur content in the raw material,
It is preferably 20% or less. The desulfurization rate is 70% or more, preferably 80% or more. Usually, the lower limit of the sulfur content in the feed oil is 0.01% by mass, preferably 0.1%.
On the other hand, the upper limit is 2.0% by mass, preferably 1.0% by mass. The toluene insoluble content is 50% or less, preferably 40% or less, of the toluene insoluble content at the outlet of the first stage hydrotreatment process. As described above, in the present invention, by the above-described two-stage hydrotreatment, heavy oil having a low toluene-insoluble content and a low sulfur content despite the high-temperature treatment in the first-stage hydrotreatment process A substrate is obtained.
【0053】なお、本発明における脱硫反応の達成率は
次式1で示される値を意味する。以降、本発明における
脱硫反応の達成率とは、すべてこの式1により計算され
る値を意味する。The achievement rate of the desulfurization reaction in the present invention means the value represented by the following formula 1. Hereinafter, the achievement rate of the desulfurization reaction in the present invention means all values calculated by the formula 1.
【0054】[0054]
【数1】 [Equation 1]
【0055】また得られる重油基材の窒素含有量も何ら
規定されるものではないが、通常、原料油に対する脱窒
素反応の達成率が10%以上、好ましくは30%以上で
あるのが一般的である。Further, the nitrogen content of the obtained heavy oil base material is not specified at all, but usually, the achievement rate of the denitrification reaction with respect to the feed oil is 10% or more, preferably 30% or more. Is.
【0056】なお、本発明における脱窒素反応の達成率
は次式2で示される値を意味する。以降、本発明におけ
る脱窒素反応の達成率とは、すべてこの式2により計算
される値を意味する。The achievement rate of the denitrification reaction in the present invention means the value represented by the following equation 2. Hereinafter, the achievement rate of the denitrification reaction in the present invention means all values calculated by the equation 2.
【0057】[0057]
【数2】 [Equation 2]
【0058】また本発明における2段階の水素化処理に
よる全体での分解反応達成率は任意であるが、通常20
%以上、好ましくは40%以上であるのが一般的であ
る。なお、本発明における分解反応の達成率は次式3で
示される値を意味する。以降、本発明における分解反応
の達成率とは、すべてこの式3により計算される値を意
味する。In the present invention, the overall achievement rate of the decomposition reaction by the two-stage hydrotreatment is arbitrary, but usually 20
% Or more, preferably 40% or more. The achievement rate of the decomposition reaction in the present invention means a value represented by the following formula 3. Hereinafter, the achievement rate of the decomposition reaction in the present invention means all values calculated by the equation 3.
【0059】[0059]
【数3】 (Equation 3)
【0060】また本発明においては、通常、第1段階の
水素化処理での脱硫反応達成率が、第2段階の水素化処
理工程も含めた全体の水素化処理での脱硫反応達成率の
70%以上、好ましくは80%以上、より好ましくは9
0%以上を占めることが望ましい。In the present invention, the desulfurization reaction achievement rate in the first-stage hydrotreatment is usually 70% of the desulfurization reaction achievement rate in the entire hydrotreatment including the second-stage hydrotreatment step. % Or more, preferably 80% or more, more preferably 9
It is desirable to occupy 0% or more.
【0061】また本発明においては、通常、第1段階の
水素化処理での脱窒素反応達成率が、第2段階の水素化
処理工程も含めた全体の水素化処理での脱窒素反応達成
率の好ましくは50%以上、より好ましくは80%以
上、特に好ましくは90%以上を占めることが望まし
い。In the present invention, the denitrification reaction achievement rate in the first-stage hydrotreatment is usually the denitrification reaction achievement rate in the entire hydrotreatment including the second-stage hydrotreatment step. Is preferably 50% or more, more preferably 80% or more, particularly preferably 90% or more.
【0062】さらに本発明においては、通常、第1段階
の水素化処理工程での分解反応達成率が、第2段階の水
素化処理工程も含めた全体の水素化処理での分解反応達
成率の好ましくは75%以上、より好ましくは85%以
上、特に好ましくは90%以上を占めることが望まし
い。Further, in the present invention, usually, the decomposition reaction achievement rate in the first stage hydrotreating step is smaller than the decomposition reaction achievement rate in the entire hydrotreating step including the second stage hydrotreating step. It is desirable to occupy preferably 75% or more, more preferably 85% or more, particularly preferably 90% or more.
【0063】本発明により得られる重油基材は、単独で
も製品重油として使用可能である。また、具体的には例
えば、石油蒸留残査物;灯油;直留軽油;減圧軽油;石
油蒸留残査物を熱分解して得られる軽油や残油およびこ
れらの水素化処理油;接触分解装置より得られる軽質軽
油(ライトサイクル油)、重質軽油(ヘビーサイクル
油)、スラリー油;等の他の重油基材を適宜配合して、
製品重油とすることもできる。The heavy oil base material obtained by the present invention can be used alone as a heavy oil product. Also, specifically, for example, petroleum distillation residue; kerosene; straight-run gas oil; vacuum gas oil; gas oil or residue obtained by pyrolyzing petroleum distillation residue and their hydrotreated oils; Other light oil base materials such as light oil (light cycle oil), heavy oil (heavy cycle oil), and slurry oil obtained from
Product heavy oil can also be used.
【0064】[0064]
【実施例】次に実施例および比較例により本発明をさら
に詳細に説明するが、本発明はこれらの例によって何ら
限定されるものではない。Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
【0065】(実施例1)アルミナ担体にNiO 3質
量%とMoO3 11質量%を含有する市販脱硫触媒を、
直列に配した第1段階の水素化処理用ステンレス製反応
塔および第2段階の水素化処理用のステンレス製反応塔
にそれぞれ充填後、触媒を予備硫化した。次いで表1の
性状を有する減圧蒸留残査油を原料油とし、この反応塔
を用いて表2に示す反応条件で連続的に水素化処理を行
った。このとき図1に示すように第1段階の水素化処理
温度を原料油の入口から出口にかけて徐々に上昇させ
た。具体的には上部を370℃、中部を400℃、下部
を430℃とした。第1段階および第2段階の反応条件
および第1段階および第2段階の反応塔出口より得られ
た水素化処理油の性状(トルエン不溶分含有量、ドライ
スラッジ含有量、硫黄含有量、窒素含有量、蒸留565
℃留分)を表2に併記した。またこのときの反応器出口
からセパレーターまでの圧力損失の経時変化を図2に示
す。Example 1 A commercial desulfurization catalyst containing 3 % by mass of NiO and 11% by mass of MoO 3 on an alumina carrier was used.
The catalyst was pre-sulphurized after being filled in the stainless steel reaction tower for the first stage hydrotreatment and the stainless steel reaction tower for the second stage hydrotreatment, which were arranged in series. Next, a vacuum distillation residue oil having the properties shown in Table 1 was used as a raw material oil, and a hydrogenation treatment was continuously performed using this reaction tower under the reaction conditions shown in Table 2. At this time, as shown in FIG. 1, the hydrotreating temperature of the first stage was gradually increased from the feedstock inlet to the feedstock outlet. Specifically, the upper part was 370 ° C., the middle part was 400 ° C., and the lower part was 430 ° C. First-stage and second-stage reaction conditions and properties of hydrotreated oil obtained from the first-stage and second-stage reaction tower outlets (toluene insoluble content, dry sludge content, sulfur content, nitrogen content Quantity, distillation 565
(° C fraction) is also shown in Table 2. Further, FIG. 2 shows the change over time in the pressure loss from the reactor outlet to the separator at this time.
【0066】(実施例2)実施例1と同一の原料油およ
び脱硫触媒を使用し、第1段階の最高温度、すなわち第
1段階下部の温度を420℃に変更して水素化処理を行
った。第2段階の水素化処理温度は実施例1と同一とし
た。第1段階および第2段階の反応条件および第1段階
および第2段階の反応塔出口より得られた水素化処理油
の性状(トルエン不溶分含有量、ドライスラッジ含有
量、硫黄含有量、窒素含有量、蒸留565℃留分)を表
2に併記した。またこのときの反応器出口からセパレー
ターまでの圧力損失の経時変化を図2に示す。(Example 2) Using the same feedstock and desulfurization catalyst as in Example 1, the maximum temperature of the first stage, that is, the temperature of the lower part of the first stage was changed to 420 ° C to carry out the hydrotreatment. . The second stage hydrotreatment temperature was the same as in Example 1. First-stage and second-stage reaction conditions and properties of hydrotreated oil obtained from the first-stage and second-stage reaction tower outlets (toluene insoluble content, dry sludge content, sulfur content, nitrogen content The amount and the distillation fraction (565 ° C. fraction) are also shown in Table 2. Further, FIG. 2 shows the change over time in the pressure loss from the reactor outlet to the separator at this time.
【0067】(比較例1)第2段階の反応塔の低温処理
効果を明確にするため、実施例1と同一の原料油および
脱硫触媒を使用し、第2段階の水素化処理温度を第1段
階の最高温度と等しくして水素化処理を行った。このと
きの水素化処理温度の分布を図1に併記した。第1段階
および第2段階の反応条件および第1段階および第2段
階の反応塔出口より得られた水素化処理油の性状(トル
エン不溶分含有量、ドライスラッジ含有量、硫黄含有
量、窒素含有量、蒸留565℃留分)を表2に併記し
た。またこのときの反応器出口からセパレーターまでの
圧力損失の経時変化を図2に示す。(Comparative Example 1) In order to clarify the effect of the low temperature treatment of the second stage reaction tower, the same feed oil and desulfurization catalyst as in Example 1 were used, and the second stage hydrotreating temperature was changed to the first stage. The hydrotreatment was carried out at a temperature equal to the maximum temperature of the step. The distribution of the hydrotreating temperature at this time is also shown in FIG. First-stage and second-stage reaction conditions and properties of hydrotreated oil obtained from the first-stage and second-stage reaction tower outlets (toluene insoluble content, dry sludge content, sulfur content, nitrogen content The amount and the distillation fraction (565 ° C. fraction) are also shown in Table 2. Further, FIG. 2 shows the change over time in the pressure loss from the reactor outlet to the separator at this time.
【0068】[0068]
【表1】 [Table 1]
【0069】[0069]
【表2】 [Table 2]
【0070】表2の結果から明らかなとおり、本発明の
方法によれば、硫黄含有量の比較的高い石油蒸留残査物
を原料油として用いた場合でも、第1段階の苛酷な水素
化処理条件によって硫黄含有量が原料油より低められ、
かつ第2段階の低温水素化処理によりトルエン不溶分含
有量が低い重油基材を得ることが可能である。このため
図2に示すように装置の圧力損失上昇をさけて長期間運
転することが可能である。さらに得られる重油基材は原
料油より窒素含有量も低められ、また蒸留温度565℃
以上の留分の含有量も大きく低下していることが判る。
それに対して第2段階の水素化処理温度を第1段階の最
高温度と等しくして水素化処理を行った比較例1では、
実施例1と同程度に硫黄含有量、窒素含有量が低めら
れ、かつ蒸留温度565℃以上の留分が減少しているも
のの、第2段階の反応塔出口より得られた水素化処理油
のトルエン不溶分含有量が550質量ppmと実施例と
比較して非常に高い。このため装置の圧力損失が急激に
上昇し早期に装置の停止を余儀なくされた。As is clear from the results shown in Table 2, according to the method of the present invention, even when the petroleum distillation residue having a relatively high sulfur content is used as the feedstock, the first stage of severe hydrotreatment is carried out. Depending on the conditions, the sulfur content is lower than that of the stock oil,
Moreover, it is possible to obtain a heavy oil base material having a low toluene insoluble content by the second-stage low-temperature hydrotreatment. Therefore, as shown in FIG. 2, it is possible to operate for a long period of time without increasing the pressure loss of the device. Further, the heavy oil base material obtained has a lower nitrogen content than the feed oil, and the distillation temperature is 565 ° C.
It can be seen that the contents of the above fractions are also greatly reduced.
On the other hand, in Comparative Example 1 in which the hydrotreatment temperature of the second stage was made equal to the maximum temperature of the first stage to perform the hydrotreatment,
Although the sulfur content and the nitrogen content were reduced to the same extent as in Example 1 and the fraction at the distillation temperature of 565 ° C. or higher was reduced, the hydrotreated oil obtained from the outlet of the reaction tower in the second stage was The toluene insoluble content is 550 mass ppm, which is very high as compared with the examples. For this reason, the pressure loss of the device rapidly increased, and the device had to be stopped early.
【0071】[0071]
【発明の効果】本発明の方法によれば、比較的硫黄含有
量の多い石油蒸留残査物を原料油とした場合でも、水素
化処理を特定条件のもとで2段階で行うことにより、最
終的に硫黄含有量およびトルエン不溶分含有量が低い重
油基材を得ることができる。このため、通常行われる水
素化処理で受ける運転条件の制約、例えばトルエン不溶
分が析出しない反応温度の上限や、反応圧力の下限とい
った運転条件の制約を大幅に緩和でき、装置建設の経済
性を大幅に向上できる。According to the method of the present invention, even when a petroleum distillation residue with a relatively high sulfur content is used as a feedstock, the hydrotreatment is carried out in two stages under specific conditions. Finally, a heavy oil base material having a low sulfur content and a toluene insoluble content can be obtained. For this reason, it is possible to greatly relax the operating condition constraints that are usually received in hydrotreatment, such as the upper limit of the reaction temperature at which toluene insoluble matter does not precipitate and the lower limit of the reaction pressure. Can be greatly improved.
【図1】 反応塔内の水素化処理温度と反応塔内の位置
の関係を示すグラフである。FIG. 1 is a graph showing the relationship between the hydrotreating temperature in the reaction tower and the position in the reaction tower.
【図2】 反応塔出口からセパレーターまでの圧力損失
の経時変化を示すグラフである。FIG. 2 is a graph showing changes over time in pressure loss from the outlet of the reaction tower to the separator.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤山 優一郎 神奈川県横浜市中区千鳥町8番地 日本石 油株式会社中央技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuichiro Fujiyama 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Nippon Oil & Oil Co., Ltd. Central Technology Research Institute
Claims (1)
%で硫黄含有量が1.0〜10質量%である原料油を、
水素化触媒を充填した第1段階において、加圧下、触媒
床中の最高温度が390〜450℃で水素化処理して、
硫黄含有量が原料油の硫黄含有量の30%以下、トルエ
ン不溶分含有量が10質量ppm以上の水素化処理油を
得、引き続き第1段階の水素化処理油を、水素化触媒を
充填した第2段階において、加圧下、触媒床中の最高温
度が第1段階の最高温度よりも10℃以上低く、かつ4
10℃以下で水素化処理して、硫黄含有量が原料油の硫
黄含有量の30%以下、トルエン不溶分含有量が第1段
階のトルエン不溶分含有量の50%以下の水素化処理油
を得ることを特徴とする重油基材の製造方法。1. A raw material oil having a dry sludge content of 0 to 5.0 mass% and a sulfur content of 1.0 to 10 mass%,
In the first stage filled with a hydrogenation catalyst, under the pressure, the maximum temperature in the catalyst bed is hydrotreated at 390 to 450 ° C.,
A hydrotreated oil having a sulfur content of 30% or less of the sulfur content of the feedstock and a toluene insoluble content of 10 mass ppm or more was obtained, and subsequently the hydrotreated oil of the first stage was filled with a hydrogenation catalyst. In the second stage, under pressurization, the maximum temperature in the catalyst bed is 10 ° C. or more lower than the maximum temperature in the first stage, and 4
A hydrotreated oil having a sulfur content of 30% or less of the sulfur content of the feedstock and a toluene insoluble content of 50% or less of the toluene insoluble content of the first stage is hydrotreated at 10 ° C or less. A method for producing a heavy oil base material, which comprises:
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007521343A (en) * | 2003-07-09 | 2007-08-02 | インステイチユート メキシカノ デル ペトロレオ | Method of catalytic hydrotreating heavy petroleum hydrocarbons |
WO2012161019A1 (en) * | 2011-05-26 | 2012-11-29 | Jx日鉱日石エネルギー株式会社 | C heavy oil composition and method for producing same |
US9862897B2 (en) | 2013-02-21 | 2018-01-09 | Jx Nippon Oil & Energy Corporation | Method for producing monocyclic aromatic hydrocarbon |
US10087376B2 (en) | 2010-01-20 | 2018-10-02 | Jx Nippon Oil & Energy Corporation | Method for producing monocyclic aromatic hydrocarbons |
-
1996
- 1996-03-29 JP JP07662896A patent/JP3608095B2/en not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007521343A (en) * | 2003-07-09 | 2007-08-02 | インステイチユート メキシカノ デル ペトロレオ | Method of catalytic hydrotreating heavy petroleum hydrocarbons |
US10087376B2 (en) | 2010-01-20 | 2018-10-02 | Jx Nippon Oil & Energy Corporation | Method for producing monocyclic aromatic hydrocarbons |
WO2012161019A1 (en) * | 2011-05-26 | 2012-11-29 | Jx日鉱日石エネルギー株式会社 | C heavy oil composition and method for producing same |
JP2012246356A (en) * | 2011-05-26 | 2012-12-13 | Jx Nippon Oil & Energy Corp | C heavy oil composition and method of producing the same |
US9862897B2 (en) | 2013-02-21 | 2018-01-09 | Jx Nippon Oil & Energy Corporation | Method for producing monocyclic aromatic hydrocarbon |
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