JPH02258893A - Two-stage hydrogenolysis of petroleum-based heavy oil - Google Patents
Two-stage hydrogenolysis of petroleum-based heavy oilInfo
- Publication number
- JPH02258893A JPH02258893A JP8065789A JP8065789A JPH02258893A JP H02258893 A JPH02258893 A JP H02258893A JP 8065789 A JP8065789 A JP 8065789A JP 8065789 A JP8065789 A JP 8065789A JP H02258893 A JPH02258893 A JP H02258893A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- petroleum
- heavy oil
- hydrogenolysis
- boiling point
- 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.)
- Granted
Links
- 239000000295 fuel oil Substances 0.000 title claims abstract description 24
- 239000003208 petroleum Substances 0.000 title claims abstract description 14
- 238000007327 hydrogenolysis reaction Methods 0.000 title abstract 6
- 239000003921 oil Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 17
- 238000009835 boiling Methods 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 239000010802 sludge Substances 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910017709 Ni Co Inorganic materials 0.000 abstract 1
- 229910003267 Ni-Co Inorganic materials 0.000 abstract 1
- 229910003296 Ni-Mo Inorganic materials 0.000 abstract 1
- 229910003262 Ni‐Co Inorganic materials 0.000 abstract 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- HMAMGXMFMCAOPV-UHFFFAOYSA-N 1-propylnaphthalene Chemical compound C1=CC=C2C(CCC)=CC=CC2=C1 HMAMGXMFMCAOPV-UHFFFAOYSA-N 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 241000219104 Cucurbitaceae Species 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【発明の詳細な説明】
（技術分野）
本発明は、石油系重質油を、２段階の水素化処理工程に
より水素化分解して軽質化炭化水素油を製造する方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a method for producing light hydrocarbon oil by hydrocracking petroleum heavy oil through a two-stage hydrotreating process.
（従来技術及びその問題点）
石油系重質油を２段階水素化処理工程によって処理する
方法は知られている（特開昭５３−９８３０８号等）、
シかし、従来の石油系重質油の２段階水素化処理法の多
くは、石油系重質油中に含まれる金属成分や、硫黄成分
及び窒素成分等の汚染物質を除去することを目的とした
もので１重質油の水素化分解を目的としたものではない
、このような２段階水素化処理においては１通常、第１
段の水素化処理工程は脱金属を目的とし、第２段の水素
化工程は脱硫を目的としている。(Prior art and its problems) A method of treating petroleum-based heavy oil by a two-stage hydrotreating process is known (Japanese Patent Application Laid-Open No. 53-98308, etc.).
However, most of the conventional two-stage hydrotreatment methods for petroleum-based heavy oil are aimed at removing pollutants such as metal components, sulfur components, and nitrogen components contained in petroleum-based heavy oil. In such a two-stage hydrotreating process, which is not intended for hydrocracking of heavy oil, the first
The hydrogenation step of the stage is aimed at demetallization, and the hydrogenation step of the second stage is aimed at desulfurization.
石油系重質油を水素化分解するために、平均細孔直径が
１４０Å以上の触媒を用い、水素加圧下、４１０−４９
０℃で重質油を水素化処理する方法は知られている（特
開昭５８−１７９２９１号）、シかし、このような−段
の水素化分解方法においては、水素化分解率を高めると
、触媒劣化が起りやすい上に、分解生成油中にドライス
ラッヂが生じ、分解生成油の安定性及び品質を悪化させ
るという問題を生起する。In order to hydrocrack petroleum-based heavy oil, a catalyst with an average pore diameter of 140 Å or more is used, and under hydrogen pressure, 410-49
A method of hydrotreating heavy oil at 0°C is known (Japanese Unexamined Patent Publication No. 179291/1983), but in such a one-stage hydrocracking method, it is possible to increase the hydrocracking rate. This causes a problem in that catalyst deterioration is likely to occur and dry sludge is generated in the decomposed oil, deteriorating the stability and quality of the decomposed oil.
（発明の課題）
本発明は１石油系重質油の水素化分解において見られる
前記問題を解決することをその課題とする。(Problem of the Invention) An object of the present invention is to solve the above-mentioned problems observed in the hydrocracking of petroleum heavy oil.
（課題を解決するための手段）
本発明者らは、前記課題を解決すべく鋭意研究を重ねた
結果、本発明を完成するに到った。(Means for Solving the Problems) The present inventors have completed the present invention as a result of intensive research to solve the above problems.
即ち１本発明によれば１石油系重質油を、平均細孔直径
が１５０Å以上である大細孔径の水素化触媒を用いて２
段階水素化処理することからなり、第１水素化処理工程
を、温度４００℃以下、水素圧１００ｋｇ／ａＪＧ以上
、及びヘキサン不溶でベンゼン可溶成分の減少率が９０
％以上及び沸点５４０℃以上の留分の分解率が１０気以
下の条件で行い、かつ第２水素化処理工程を、温度４０
０〜４６０℃、水素圧８０ｋｇ／ａＪＧ以上及び沸点５
４０℃以上の留分の全分解率が少なくとも６０％の条件
で行い、スラッジを実質的に含有しない水素化分解生成
油を得ることを特徴とする石油系重質油の２段階水素化
分解方法が提供される。That is, according to the present invention, 1 petroleum-based heavy oil is heated to 2 using a large pore hydrogenation catalyst having an average pore diameter of 150 Å or more.
The first hydrogenation step is carried out at a temperature of 400°C or less, a hydrogen pressure of 100kg/aJG or more, and a reduction rate of 90% in hexane-insoluble and benzene-soluble components.
% or more and the decomposition rate of the fraction with a boiling point of 540°C or more is 10 atmospheres or less, and the second hydrogenation step is carried out at a temperature of 40 degrees Celsius or less.
0 to 460℃, hydrogen pressure 80kg/aJG or more, and boiling point 5
A two-step hydrocracking method for petroleum heavy oil, which is carried out under conditions where the total cracking rate of fractions of 40° C. or higher is at least 60%, to obtain a hydrocracking oil that does not substantially contain sludge. is provided.
本発明で用いる石油系重質油としては、常圧残油、減圧
残油等が挙げられ、沸点５４０℃以上の成分を２０重量
％以上含み、ヘキサン不溶でベンゼン可溶成分を１通常
、２〜１８重量％含有するものである。Examples of the petroleum heavy oil used in the present invention include atmospheric residual oil, vacuum residual oil, etc., which contain 20% by weight or more of components with a boiling point of 540°C or higher, and usually contain 1 or 2% of components insoluble in hexane and soluble in benzene. It contains ~18% by weight.
本発明においては、このような重質油を原料油として用
い、これを水素化分解して軽質化油とするために、以下
に示すような２段階の水素化処理工程を行うものである
。In the present invention, such heavy oil is used as a feedstock oil, and in order to hydrocrack it to produce a light oil, a two-stage hydrotreating process as shown below is performed.
（第１水素化処理工程）
この第１水素化処理工程は、原料油を、温度４００℃以
下、好ましくは３５０−３９０℃、水素圧１００ｋｇ／
ａＪＧ以上、好ましくは１２０〜１５０ｋｇ／ａＪＧの
条件下、水素化触媒を用いて高度に水素化処理する工程
である。(First Hydrotreating Step) In this first hydrotreating step, the feedstock oil is treated at a temperature of 400°C or less, preferably 350-390°C, and a hydrogen pressure of 100kg/
This is a step of highly hydrogenating using a hydrogenation catalyst under conditions of aJG or more, preferably 120 to 150 kg/aJG.
この水素化工程で用いる水素化触媒は、芳香核への水素
添加を主目的としたもので、その水素化度は、ヘキサン
不溶でベンゼン可溶成分（以下、ＨＩ−ＢＳ成分という
）の減少割合が９０重量％以上、好ましくは９５〜１０
０重量での割合となるように行う、また、この第１段水
素化工程における重質油中の沸点５４０℃以上の留分の
分解率（ｆ（＋））（以下、単に分解率とも言う）は、
１０以下であり、通常５−１０ｇの範囲である。The hydrogenation catalyst used in this hydrogenation process is mainly intended for hydrogenation to aromatic nuclei, and its degree of hydrogenation is determined by the rate of decrease in hexane-insoluble and benzene-soluble components (hereinafter referred to as HI-BS components). is 90% by weight or more, preferably 95-10%
The decomposition rate (f(+)) of the fraction with a boiling point of 540°C or higher in the heavy oil in this first stage hydrogenation step (hereinafter also simply referred to as decomposition rate) )teeth,
10 or less, usually in the range of 5-10 g.
なお、本明細書で言うｌｌ−８５成分の減少率Ｒ及び分
解率ｆ（１）は次の式で定義される。Note that the reduction rate R and decomposition rate f(1) of the ll-85 component referred to in this specification are defined by the following equations.
−Ｂ
Ｒ＝Ｘ１００（１）
Ａ：重質油中のＨＩ−ＢＳ成分の重量％Ｂ：水素化生成
油中の）！ｌ−０５成分の１１−Ｄ
ｆ（Ｄ＝ ｘｌＯＯ（２）
Ｃ：原料重質油中の沸点５４０℃以上の留分の重量Ｘ
Ｄ：水素化生成油中の沸点５４０℃以上の留分の重量〆
この第１水素化処理工程で用いる水素化触媒は、多孔性
担体にＶ％Ｎｏ、Ｗ％Ｎｉ、Ｃｏ、 Ｐｄ、 Ｐｔ、
Ｒｅ、 Ｒｕ。-B R=X100 (1) A: Weight % of HI-BS component in heavy oil B: in hydrogenated oil)! 11-D f (D = xlOO(2) of l-05 component) C: Weight of the fraction with a boiling point of 540°C or higher in the raw material heavy oil Weight: The hydrogenation catalyst used in this first hydrogenation step contains V%No, W%Ni, Co, Pd, Pt,
Re, Ru.
Ｒｈ等の金属を担持させたものが用いられ、特に。Those on which metals such as Rh are supported are used, in particular.
Ｎ１−Ｇｏ、ＮＬ−Ｎｏ等の組合せを担持させたものを
用いるが好ましい、多孔性担体としては、アルミナ、シ
リカ、チタニア、アルミナシリカ、アルミナチタニア、
アルミナジルコニア、シリカマグネシア等の各種のもの
が用いられる。好ましい担体は。It is preferable to use a porous carrier supporting a combination of N1-Go, NL-No, etc., such as alumina, silica, titania, alumina-silica, alumina-titania,
Various materials such as alumina zirconia and silica magnesia are used. A preferred carrier is.
アルミナ、チタニ、ア等である。担持金属は通常。These include alumina, titanium, and alumina. Supported metals are normal.
激化物及び／又は硫化物の形で担体上に存在する。It is present on the carrier in the form of an intensifier and/or a sulfide.
この水素化処理工程で用いる触媒は、平均細孔直径が１
５０Å以上の細孔径を有するものが用いられる。The catalyst used in this hydrotreating step has an average pore diameter of 1
A material having a pore diameter of 50 Å or more is used.
（第２水素化工程）
この工程は、前記第１水素化処理工程で得られた水素化
生成油を、温度４００〜４６０℃、好ましくは４３０−
４５０℃、水素圧８０ｋｇ／ ｃｉ ０以上、好ましく
は１００ｋｇ／ａＪＧ以上の条件下において、水素化触
媒を用いて水素化処理する工程である。この水素化処理
工程は、脂肪族系炭化水素の水素化分解を主目的とする
もので、前記したように、その反応温度としては第水素
化処理工程よりも高い温度を用いる。(Second hydrogenation step) In this step, the hydrogenated oil obtained in the first hydrogenation step is heated at a temperature of 400 to 460°C, preferably 430-460°C.
This is a step of hydrogenating using a hydrogenation catalyst under conditions of 450° C. and a hydrogen pressure of 80 kg/ci 0 or higher, preferably 100 kg/aJG or higher. The main purpose of this hydrotreating step is the hydrocracking of aliphatic hydrocarbons, and as described above, the reaction temperature is higher than that in the first hydrotreating step.
この第２水素化処理工程における分解率ｆ （ＩＩ ’
）は、通常６０〜８０％であり、全分解率ｆ （Ｔ）は
５通常、７０〜９０％である。なお、分解率ｆ（ｎ）及
び全分解率ｆ（Ｔ）は次式で定義される。Decomposition rate f (II'
) is usually 60-80%, and the total decomposition rate f (T) is usually 70-90%. Note that the decomposition rate f(n) and the total decomposition rate f(T) are defined by the following equations.
−Ｅ
ｆ（ＩＩ）＝ Ｘ１００ （３）
Ｄ＝第１水素化生成油中の沸点５４０℃以上の留分の重
量％
Ｅ：第２水素化生成油中の沸点５４０℃以上の留分の重
量％
−Ｅ
ｆ（Ｔ）＝ Ｘ１００ （３）Ａ
：ｆｊＫ料重質油中の沸点５４０℃以上の留分の重量算
Ｅ：第２水素化生成油中の沸点５４０℃以上の留分の重
量％
この第２水素化処理触媒としては、前記第１水素化工程
で示したのと同様の性状を示すもの、即ち。−E f(II)=X100 (3)
D = Weight % of the fraction with a boiling point of 540°C or higher in the first hydrogenated oil E: Weight % of the fraction with a boiling point of 540°C or higher in the second hydrogenated oil -E f (T) = X100 (3 )A
: Weight calculation of the fraction with a boiling point of 540° C. or higher in the fjK feed heavy oil E: Weight % of the fraction with a boiling point of 540° C. or higher in the second hydrogenated oil 1 exhibiting properties similar to those shown in the hydrogenation step, ie.
多孔性担体としてアルミナ、シリカ、チタニア、アルミ
ナシリカ、アルミナチタニア、アルミナジルコニア、シ
リカマグネシア等の各種のものを用い、担体金属として
Ｖ、にｏ、 Ｗ、 Ｎｉ、Ｃｏ等の金属を用い、平均細
孔直径１５０Å以上の大細孔径を有する触媒が用いられ
る。特に好ましい触媒としては、担持金属として、 Ｎ
ｉ−Ｍｏや、 Ｎ１−Ｉｔを担持させたシリカアルミナ
等が用いられる。Various materials such as alumina, silica, titania, alumina silica, alumina titania, alumina zirconia, and silica magnesia are used as porous carriers, and metals such as V, Ni, W, Ni, and Co are used as carrier metals. A catalyst having a large pore diameter of 150 Å or more is used. Particularly preferred catalysts include N as a supported metal.
i-Mo, silica alumina supported with N1-It, etc. are used.
この第２水素化処理工程においては、全分解率を高める
とともにスラッジの生成を防止するために、芳香族性油
を反応液中に２〜２０重量％添加するのが好ましい、芳
香族性油としては、沸点２００〜４００℃の芳香族化合
物（例えば、メチルナフタレン。In this second hydrotreating step, in order to increase the total decomposition rate and prevent the formation of sludge, it is preferable to add 2 to 20% by weight of aromatic oil to the reaction liquid. is an aromatic compound with a boiling point of 200 to 400°C (for example, methylnaphthalene).
ナフタレン、エチルナフタレン、プロピルナフタレン等
）又はこれらを少なくとも５０重量％含むもの等が挙げ
られる。naphthalene, ethylnaphthalene, propylnaphthalene, etc.) or those containing at least 50% by weight of these.
（発明の効果）
本発明によれば、重質油を、大細孔径触媒を用い、第１
水素化処理工程で高度に水素化した後、水素化分解処理
することから、スラッジの生成を回避して重質油を高度
に水素化分解することができる１本発明で得られる生成
油（軽質化炭化水素油）は、スラッジを実質的に含まな
い高品質のもので、安定性の良いものである。(Effects of the Invention) According to the present invention, heavy oil is
The produced oil (light (carbonized hydrocarbon oil) is of high quality, substantially free of sludge, and has good stability.
（実施例） 次に本発明を実施例によりさらに詳細に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例
原料重質油として、アラビアンライト原油の減圧残渣油
を用いた。この減圧残渣油は、ヘキサン可溶（Ｈ３）成
分＝９１重量％、ヘキサン不溶でベンゼン可溶（ｌ（Ｉ
−ＢＳ）成分：９重量％、ベンゼン不溶（８Ｉ）成分：
０重量％からなるものであった。また、その沸点５４０
℃以上の留分の割合は９５重量％であった。Example As raw material heavy oil, vacuum residue oil of Arabian Light crude oil was used. This vacuum residue oil has a hexane-soluble (H3) component of 91% by weight, a hexane-insoluble and benzene-soluble (l(I)
-BS) component: 9% by weight, benzene insoluble (8I) component:
It consisted of 0% by weight. Also, its boiling point is 540
The fraction of fractions with a temperature of 95% by weight or higher was 95% by weight.
この原料油１０重量部をオートクレーブに入れ、水素化
処理触媒１重量部を添加し、温度＝３９０℃。10 parts by weight of this raw oil was put into an autoclave, 1 part by weight of a hydrotreating catalyst was added, and the temperature was 390°C.
水素圧：１５０ｋｇ／ａ＃Ｇで３時間反応を行った。そ
の反応結果を表−１に示す。The reaction was carried out at hydrogen pressure: 150 kg/a#G for 3 hours. The reaction results are shown in Table-1.
なお、この水素化処理工程で用いた水素化触媒は、 Ｎ
ｉＯ：１．０重量％、 ＭＯＯ３： ５．０重量％含む
シリカアルミナ触媒であり、比表面積：１４７ｒｒｒ／
ｇ、比細孔容積：０．７１ｍＱ／ｇ及び平均細孔直径：
１６８人を有するものであった。このものは、あらかじ
め５％Ｈ，Ｓを含む水素ガスを用い、３６０℃で６時間
予備硫化処理して用いた。The hydrogenation catalyst used in this hydrogenation process was N
A silica alumina catalyst containing iO: 1.0% by weight, MOO3: 5.0% by weight, specific surface area: 147rrr/
g, specific pore volume: 0.71 mQ/g and average pore diameter:
It had 168 people. This material was pre-sulfurized using hydrogen gas containing 5% H and S at 360° C. for 6 hours before use.
次に、前記で得た水素化生成油１０重量部をオートクレ
ーブに入れ、前記で示したのと同じ水素化触媒１重量部
を添加し、温度：４２０℃、水素圧：１５０ｋｇ／ｃｊ
Ｇで１時間反応を行った。その反応結果を表−１に示す
。Next, 10 parts by weight of the hydrogenated oil obtained above was put into an autoclave, 1 part by weight of the same hydrogenation catalyst as shown above was added, temperature: 420°C, hydrogen pressure: 150 kg/cj
The reaction was carried out at G for 1 hour. The reaction results are shown in Table-1.
表−１
実施例２
実施例１において、第２水素化処理工程における反応時
間を３時間とした以外は同様にして実験を行った。その
結果、全分解率（ｆ （Ｔ） ）７０％の成績が得られ
た。この場合、生成油中のスラッジの生成が極く微量認
められたが、生成油の品質は良好であると判断された。Table 1 Example 2 An experiment was conducted in the same manner as in Example 1 except that the reaction time in the second hydrogenation step was changed to 3 hours. As a result, a total decomposition rate (f(T)) of 70% was obtained. In this case, although a very small amount of sludge was observed in the produced oil, the quality of the produced oil was judged to be good.
実施例３
実施例１において、第２水素化処理工程における温度を
４４０℃とし、第１水素化生成油に対し１−メチルナフ
タレンを１０重量Ｘ添加した以外は同様にして実験を行
った。その結果、全分解率（ｆ（Ｔ））８１％の成績が
得られ、生成油中にはスラッジの生成は実質的に認めら
れなかった。Example 3 An experiment was conducted in the same manner as in Example 1 except that the temperature in the second hydrogenation step was 440° C. and 10 weight X of 1-methylnaphthalene was added to the first hydrogenated oil. As a result, a total decomposition rate (f(T)) of 81% was obtained, and virtually no sludge was observed in the produced oil.
比較例１
実施例１で示した原料重質油１０重量部をオートクレー
ブに入れ、実施例１で示した触媒１重量部を添加し１反
応温度４２０℃、水素圧：１５０ｋｇ／ａ＃Ｇで４時間
反応を行った。その結果１分解率７４瓢の成績が得られ
たが、この場合には多量のスラッジが生成した。Comparative Example 1 10 parts by weight of the raw material heavy oil shown in Example 1 was put into an autoclave, 1 part by weight of the catalyst shown in Example 1 was added, and the mixture was heated at a reaction temperature of 420°C and a hydrogen pressure of 150 kg/a#G. A time reaction was performed. As a result, a decomposition rate of 74 gourds was obtained, but in this case a large amount of sludge was produced.
比較例２
実施例１において、第１及び第２水素化処理工程におけ
る触媒として、ＮｉＯ：３．１重量％、 ＭｏＯ２：１
５重量％を含有するアルミナ触媒で、比表面積： ２７
３ ｒＩ？／ｇ、比細孔容積０．５２ｄ／ｇ、平均細孔
直径１００Å以下の性状を有するものをあらかじめ５％
Ｈ１Ｓを含む水素ガスを用い、３６０℃で６時間予ｍｖ
ｉｔ化処理して用いた以外は同様にして実験を行った。Comparative Example 2 In Example 1, NiO: 3.1% by weight, MoO2: 1 were used as catalysts in the first and second hydrogenation treatment steps.
Specific surface area: 27 with alumina catalyst containing 5% by weight
3 rI? /g, specific pore volume 0.52 d/g, average pore diameter 100 Å or less.
Premv at 360°C for 6 hours using hydrogen gas containing H1S
The experiment was conducted in the same manner except that it was subjected to IT processing.
その結果、全分解率（４（Ｔ））６３％省成績が得られ
たが、この場合には多量のスラッジの生成が認められた
。As a result, a total decomposition rate (4(T)) of 63% was obtained, but in this case, a large amount of sludge was observed to be produced.
特許出願人 千代田化工建設株式会社Patent applicant: Chiyoda Corporation
Claims (1)
ある大細孔径の水素化触媒を用いて２段階水素化処理す
ることからなり、第１水素化処理工程を、温度４００℃
以下、水素圧１００ｋｇ／ｃｍ＾２Ｇ以上、及びヘキサ
ン不溶でベンゼン可溶成分の減少率が９０％以上及び沸
点５４０℃以上の留分の分解率が１０％以下の条件で行
い、かつ第２水素化処理工程を、温度４００〜４６０℃
、水素圧８０ｋｇ／ｃｍ＾２Ｇ以上及び沸点５４０℃以
上の留分の全分解率が少なくとも６０％の条件で行い、
スラッジを実質的に含有しない水素化分解生成油を得る
ことを特徴とする石油系重質油の２段階水素化分解方法
。(1) Petroleum-based heavy oil is subjected to two-stage hydrogenation treatment using a large pore hydrogenation catalyst with an average pore diameter of 150 Å or more, and the first hydrogenation step is carried out at a temperature of 400°C.
Hereinafter, the hydrogen pressure was 100 kg/cm^2G or more, the reduction rate of hexane-insoluble and benzene-soluble components was 90% or more, the decomposition rate of the fraction with a boiling point of 540°C or more was 10% or less, and the second hydrogen The temperature of the chemical treatment process is 400 to 460℃.
, carried out under conditions where the total decomposition rate of the fraction with a hydrogen pressure of 80 kg/cm^2 G or more and a boiling point of 540° C. or more is at least 60%,
A two-step hydrocracking method for petroleum-based heavy oil, characterized in that a hydrocracking product oil containing substantially no sludge is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8065789A JP2740815B2 (en) | 1989-03-30 | 1989-03-30 | Two-stage hydrocracking method for petroleum heavy oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8065789A JP2740815B2 (en) | 1989-03-30 | 1989-03-30 | Two-stage hydrocracking method for petroleum heavy oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02258893A true JPH02258893A (en) | 1990-10-19 |
| JP2740815B2 JP2740815B2 (en) | 1998-04-15 |
Family
ID=13724428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8065789A Expired - Lifetime JP2740815B2 (en) | 1989-03-30 | 1989-03-30 | Two-stage hydrocracking method for petroleum heavy oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2740815B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012036186A1 (en) * | 2010-09-14 | 2012-03-22 | Ｊｘ日鉱日石エネルギー株式会社 | Aromatic hydrocarbon production process |
-
1989
- 1989-03-30 JP JP8065789A patent/JP2740815B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012036186A1 (en) * | 2010-09-14 | 2012-03-22 | Ｊｘ日鉱日石エネルギー株式会社 | Aromatic hydrocarbon production process |
| US9446997B2 (en) | 2010-09-14 | 2016-09-20 | Jx Nippon Oil & Energy Corporation | Method for producing aromatic hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2740815B2 (en) | 1998-04-15 |
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