JPS63310641A - Catalyst for hydrogenation of hydrocarbon and method for activating same - Google Patents
Catalyst for hydrogenation of hydrocarbon and method for activating sameInfo
- Publication number
- JPS63310641A JPS63310641A JP14514387A JP14514387A JPS63310641A JP S63310641 A JPS63310641 A JP S63310641A JP 14514387 A JP14514387 A JP 14514387A JP 14514387 A JP14514387 A JP 14514387A JP S63310641 A JPS63310641 A JP S63310641A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- group
- metal
- hydrogenation
- acid
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229930195733 hydrocarbon Natural products 0.000 title claims description 19
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 12
- 230000003213 activating effect Effects 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- UIJGNTRUPZPVNG-UHFFFAOYSA-N benzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=CC=C1 UIJGNTRUPZPVNG-UHFFFAOYSA-N 0.000 claims abstract description 6
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 230000000737 periodic effect Effects 0.000 claims description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 125000000446 sulfanediyl group Chemical group *S* 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000004913 activation Effects 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000005987 sulfurization reaction Methods 0.000 description 7
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920001021 polysulfide Polymers 0.000 description 6
- 239000005077 polysulfide Substances 0.000 description 6
- 150000008117 polysulfides Polymers 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000007788 liquid Substances 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は活性化処理が容易な炭化水素油の水素化処理触
媒とその活性化処理方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a catalyst for hydrotreating hydrocarbon oil that is easy to activate and a method for activating the same.
炭化水素油を水素の存在下で水添、脱硫、脱窒素、分解
等を行う所謂水素化処理には、アルミナ、シリカ−アル
ミナ、チタニア等の無機酸化物担体に、周期律表第6族
金属及び第8族金属から選ばれる少な(とも1種の金属
を水素化活性成分として担持せしめた触媒が用いられ、
第6族金属としてはMo及びW、第8族金属としてはG
o及びNiが良く用いられている。In so-called hydrogenation treatment, in which hydrocarbon oil is hydrogenated, desulfurized, denitrified, decomposed, etc. in the presence of hydrogen, a group 6 metal of the periodic table is used on an inorganic oxide carrier such as alumina, silica-alumina, or titania. and a catalyst supporting a small amount of metal selected from Group 8 metals as a hydrogenation active component,
Mo and W are Group 6 metals, and G is Group 8 metals.
o and Ni are often used.
これらの金属は通常酸化動態で担持されておりそのまま
では活性がないため、水素化処理反応に供するには酸化
動態から硫化動態に変換して活性化する予備硫化が必要
である。These metals are usually supported with oxidation dynamics and are not active as they are, so pre-sulfidation is required to convert the oxidation dynamics into sulfuration dynamics and activate them in order to use them for the hydrogenation reaction.
この予備硫化は従来、炭化水素油の水素化処理を行う反
応器に触媒を充填した後、この触媒層に硫化剤を水素と
共に通過せしめて行うのが一般的である。予備硫化の操
作条件は、水素化処理プロセスによって又使用する硫化
剤によって種々に異なるが、硫化水素による場合は水素
中に0.5〜5容量%程度含有せしめ、これを触媒II
!当り標準温度、圧力に換算し”i’1.000〜3,
000 j!、温度180℃以上(通常は250℃以上
)で行っており、二硫化炭素、ノルマルブチルメルカプ
タン、硫化ジメチル、二硫化ジメチル等を用いる場合は
これらを軽質炭化水素油で希釈して供し、温度250〜
350℃、圧力20〜100賭/−2液空間速度0.5
〜2 hr−’、水素/油圧200〜100ONl/I
tで行っている。Conventionally, this pre-sulfurization is generally carried out by filling a catalyst in a reactor for hydrogenating hydrocarbon oil and then passing a sulfurizing agent together with hydrogen through the catalyst bed. The operating conditions for pre-sulfiding vary depending on the hydrotreating process and the sulfurizing agent used, but when hydrogen sulfide is used, it is contained in hydrogen at about 0.5 to 5% by volume, and this is added to catalyst II.
! Convert to standard temperature and pressure "i'1.000~3,
000j! When using carbon disulfide, n-butyl mercaptan, dimethyl sulfide, dimethyl disulfide, etc., these are diluted with light hydrocarbon oil and used at a temperature of 250 °C or higher. ~
350℃, pressure 20-100/-2 liquid space velocity 0.5
~2 hr-', hydrogen/hydraulic pressure 200-100 ONl/I
I'm doing it with t.
このような予備硫化操作を行った後実際に処理すべき原
料油に切り替え、水素化処理操業が開始される。After performing such a pre-sulfiding operation, the raw material oil to be actually treated is switched to, and the hydrotreating operation is started.
ところで上記予備硫化操作は以後の水素化処理の成否を
左右するので、使用資材の適切な選択と慎重な操作が要
求される。例えば希釈剤を用いた場合、希釈剤にオレフ
ィン類が含有されていると重合生成物が触媒を被毒する
ためオレフィン類を含有しない炭化水素油を用いる必要
があり、又粘性が高いと触媒表面の湿潤効果が乏しく重
質油では不適当なため結局軽質留出物を用いざるを得な
い。このような軽質油の使用はコスト高を招く。By the way, since the above-mentioned pre-sulfurization operation influences the success or failure of the subsequent hydrogenation treatment, appropriate selection of the materials used and careful operation are required. For example, when using a diluent, if the diluent contains olefins, the polymerization product will poison the catalyst, so it is necessary to use a hydrocarbon oil that does not contain olefins, and if the diluent has high viscosity, the catalyst surface Since heavy oil is not suitable due to its poor moisturizing effect, light distillates have no choice but to be used. Use of such light oil results in increased costs.
又、触媒金属が高温で水素と反応して還元されると不働
態化するのでこれを防止するため硫化剤を多口に用いる
必要があり、硫化剤と水素の割合を適正に維持しなけれ
ばならない、更にこのような予備硫化は数日間にわたっ
て行うのが通常であるが、この操作は一時的なものであ
るため自動化されていないことが多く、通常と異なる煩
雑な操作が要求されるため操作員の負担が極めて大きい
。In addition, when the catalyst metal reacts with hydrogen at high temperatures and is reduced, it becomes passivated, so in order to prevent this, it is necessary to use a large amount of sulfurizing agent, and the ratio of sulfurizing agent and hydrogen must be maintained properly. Moreover, such pre-sulfurization is normally carried out over several days, but since this operation is temporary, it is often not automated, and requires unusual and complicated operations. The burden on staff is extremely heavy.
このため予備硫化を省略するか、少なくとも操作の煩雑
さを軽減することが課題になっていた。Therefore, it has been a challenge to eliminate presulfurization or at least reduce the complexity of the operation.
最近に至り、このような要請に応え得る方法が提案され
た。Recently, a method has been proposed that can meet these demands.
その方法は活性金属が担持された触媒に一般式%式%
R′は水素原子、又は1背当たり1〜150個の炭素原
子を有する有機基)で表わされる多硫化物を含浸せしめ
、水素ガスの不存在下、65〜275℃、0.5〜70
バールの圧力下で前記触媒を熱処理するものである(特
開昭61−111144号公fり0この方法によれば触
媒に含浸された多硫化物が熱処理によって活性金属を硫
化するので、反応器内で予備硫化する場合は硫化剤及び
希釈剤が不要となるため操作が容易になり、又反応器外
での予備硫化も可能で、その場合は予備硫化した触媒を
反応器に充填すれば直ちに水素化処理操業を開始できる
。The method involves impregnating a catalyst on which an active metal is supported with a polysulfide represented by the general formula % (R' is a hydrogen atom or an organic group having 1 to 150 carbon atoms per back), and hydrogen gas is in the absence of, 65-275°C, 0.5-70
According to this method, the polysulfide impregnated in the catalyst sulfurizes the active metal by heat treatment, so that the catalyst is heat-treated under the pressure of bar. Pre-sulfiding inside the reactor eliminates the need for a sulfurizing agent and diluent, making the operation easier, and pre-sulfurizing outside the reactor is also possible. Hydrotreating operations can be started.
上記多硫化物の使用量は、後で触媒中の活性金属酸化物
(例えばNtO+ Mo5s)全体を硫化するために必
要な化学量論量であり、適切な有機溶媒に希釈して触媒
に含浸する。したがって、活性金属担持量の多い触媒に
含浸する場合には、高濃度の上記多硫化物溶液を用いる
ことが必要となる。ところが上記多硫化物は高粘度であ
るために高濃度溶液では触媒細孔内部への浸透が困難に
なるという問題がある。The amount of the polysulfide used is the stoichiometric amount required to later sulfurize the entire active metal oxide (e.g. NtO+Mo5s) in the catalyst, which is diluted in a suitable organic solvent and impregnated into the catalyst. . Therefore, when impregnating a catalyst with a large amount of active metal supported, it is necessary to use a highly concentrated polysulfide solution. However, since the polysulfide has a high viscosity, there is a problem that it becomes difficult to penetrate into the catalyst pores in a highly concentrated solution.
本発明者らは多硫化物より取り扱い易い硫化剤による予
備硫化方法を種々研究した結果、チオ酸が適当であるこ
とを見出して本発明に到達した。The present inventors conducted various studies on presulfurization methods using sulfurizing agents that are easier to handle than polysulfides, and as a result, they discovered that thioacids were suitable and arrived at the present invention.
即ち、本発明は、無機酸化物担体に周期律表第6族金属
及び第8族金属から選ばれる少くとも1種の金属の酸化
物を担持セしめた触媒に、チオ酸を含浸せしめた点に特
徴がある炭化水素油の水素化処理用触媒と、このチオ酸
を含浸せしめた触媒を水素の存在下で室温〜400℃の
温度で処理する点に特徴がある活性化方法である。That is, the present invention is characterized in that a catalyst comprising an oxide of at least one metal selected from Group 6 metals and Group 8 metals of the periodic table supported on an inorganic oxide carrier is impregnated with thioic acid. This activation method is characterized in that a catalyst for hydrotreating hydrocarbon oil, which is characterized by the above, and a catalyst impregnated with this thioic acid are treated in the presence of hydrogen at a temperature of room temperature to 400°C.
従来よりよく知られているように無機酸化物担体として
は、アルミナ又はシリカ・アルミナが代表的なものであ
る。また従来から知られているように活性金属として担
持される周期律表第6族金属成分としてはMo及び/ま
たはWの酸化物が好ましく、第8族金属成分としてはC
o及び/またはNiの酸化物が好ましい。第6族金属成
分と第8族金属成分は単独で或いは混合して用いられる
。As is well known in the art, alumina or silica-alumina is typical as the inorganic oxide carrier. Further, as is conventionally known, the Group 6 metal component of the periodic table supported as an active metal is preferably an oxide of Mo and/or W, and the Group 8 metal component is C.
Oxides of o and/or Ni are preferred. The Group 6 metal component and the Group 8 metal component may be used alone or in combination.
チオ酸は、一般式R−CO3II (式中、Rは一価
の炭化水素基を示す)で表わされ、チオ酢酸(CHaC
OSH) 、チオ安息香酸(C,H5COSH)などを
好ましい例として挙げることができる。Thioacid is represented by the general formula R-CO3II (wherein R represents a monovalent hydrocarbon group) and is thioacetic acid (CHaC
(OSH), thiobenzoic acid (C,H5COSH), and the like can be mentioned as preferred examples.
これらは、アルコール等の有機溶媒に溶解して無機酸化
物担体に周期律表第6族金属成分、第8族金属成分の少
なくとも一つを酸化物として含む触媒に含浸法により担
持させる。These are dissolved in an organic solvent such as alcohol and supported on an inorganic oxide carrier by an impregnation method on a catalyst containing at least one of a group 6 metal component and a group 8 metal component of the periodic table as an oxide.
チオ酸の担持量は、周期律表第6族金属及び第8族金属
が水素化反応に於いて高活性を示す硫化形態(例えばM
o5z、 WSzt CoS、 N15)を形成するに
必要な硫黄量の1〜3当量倍が好ましい。担持量がこれ
以下では活性の低下をまねき、またこれ以上を使用して
もそれほど活性の向上が望めるわけではないので不経済
である。The supported amount of thioacid is determined by the sulfurized form of group 6 metals and group 8 metals of the periodic table that exhibit high activity in hydrogenation reactions (for example, M
The amount of sulfur is preferably 1 to 3 times the amount of sulfur required to form O5z, WSzt CoS, N15). If the amount supported is less than this, the activity will decrease, and if more than this amount is used, no significant improvement in activity can be expected, so it is uneconomical.
チオ酸を担持した触媒は、場合によってはチオ酸を溶解
するのに使用した溶媒を乾燥除去した後に水素の存在下
で室温〜400℃の温度で処理され活性化される。溶媒
の除去は、水素の存在下での活性化時に起こっても良く
、活性化の前に特に乾燥操作が必要ということではない
。水素の存在下での活性化処理では、周期律表第6族金
属及び/または第8族金属に配位したチオ酸が水素化分
解し、上記金属成分は水素化反応での活性種である硫化
物へと変化する。水素の存在下での活性化処理では反応
圧力に制限はなく、且つ炭化水素が混在していても良い
、従って、該活性化処理は触媒が使用される炭化水素の
水素化処理用の反応器とは別の処理装置で行うことも、
水素化処理用の反応器に装填してから行うことも可能で
ある。The thioacid-supported catalyst is activated by treatment in the presence of hydrogen at temperatures from room temperature to 400° C., optionally after drying off the solvent used to dissolve the thioacid. Removal of the solvent may occur during activation in the presence of hydrogen, and no specific drying operation is required prior to activation. In the activation treatment in the presence of hydrogen, the thioacid coordinated to the Group 6 metal and/or Group 8 metal of the periodic table undergoes hydrogenolysis, and the above metal components are the active species in the hydrogenation reaction. Changes to sulfide. In the activation treatment in the presence of hydrogen, there is no restriction on the reaction pressure, and hydrocarbons may be mixed. It can also be done with a separate processing device,
It is also possible to carry out the treatment after loading it into a reactor for hydrotreating.
活性化は室温〜400℃の温度で、好ましくは100〜
300℃の温度で行なわれる。400℃より高い温度で
は、処理した触媒の水素化活性が低下するので好ましく
ない。Activation is at a temperature between room temperature and 400°C, preferably between 100°C and 400°C.
It is carried out at a temperature of 300°C. Temperatures higher than 400°C are not preferred because the hydrogenation activity of the treated catalyst decreases.
〔作 用〕
本発明で調製された触媒は、炭化水素油の水素化脱硫反
応において従来技術によって硫化された触媒と同等以上
の活性を示す。その理由は定かではないが、チオ酸が周
期律表第6族金属及び/または第8族金属と配位化合物
を形成して担持されることがその後行なわれる水素の存
在下での活性化処理時に好ましい金属硫化物体を形成す
るのに効果的に働くためと考えられる。[Function] The catalyst prepared according to the present invention exhibits an activity equal to or higher than that of a catalyst sulfurized by the prior art in the hydrodesulfurization reaction of hydrocarbon oil. Although the reason is not clear, the thioic acid forms a coordination compound with a metal from Group 6 and/or a metal from Group 8 of the periodic table and is supported during the subsequent activation treatment in the presence of hydrogen. This is thought to be because it works effectively to form metal sulfide objects, which are sometimes desirable.
以下本発明の実施例及び比較例を示す。 Examples and comparative examples of the present invention will be shown below.
実施例
γ−アルミナを担体とし、Mo5sを17重量%、Co
Oを4重量%含有する市販触媒(日本ケッチェン■社製
KF−707)30gに、チオ酢酸12.7gまたはチ
オ安息香酸23. Ogを含むエタノール溶液15ml
を全量含浸した後、80℃で16時間乾燥し触媒A、B
を得た。Example γ-alumina was used as a carrier, Mo5s was 17% by weight, Co
12.7 g of thioacetic acid or 23.7 g of thiobenzoic acid was added to 30 g of a commercially available catalyst (KF-707, manufactured by Nippon Ketchen ■) containing 4% by weight of O. 15ml of ethanol solution containing Og
After impregnating the entire amount of catalysts, catalysts A and B were dried at 80°C for 16 hours.
I got it.
触媒A、B、でのチオ酸の担持量はMo、 CoがMo
5t、 CoSになるのに必要な硫黄の理論量に換算し
て、1.8倍である。The amount of thio acid supported on catalysts A and B is Mo, Co is Mo
5t, which is 1.8 times the theoretical amount of sulfur required to form CoS.
該触媒A、Bをステンレス製固定床流通反応管に装填し
、次の条件で活性化処理した。The catalysts A and B were loaded into a stainless steel fixed bed flow reaction tube and activated under the following conditions.
触媒量 : 3ml
圧 力 二 大気圧
温度:200℃
水素流量: 4BNl/hr
時間:3hr
上記の条件下で活性化処理された触媒を用いて、クェー
ト常圧軽油の水素化脱硫反応を行った。反応に用いた常
圧軽油の性状は次の通りであった。Catalyst amount: 3ml Pressure 2 Atmospheric pressure Temperature: 200°C Hydrogen flow rate: 4BNl/hr Time: 3hr Using the catalyst activated under the above conditions, a hydrodesulfurization reaction of Kuwait atmospheric gas oil was carried out. The properties of the atmospheric gas oil used in the reaction were as follows.
比重(15/4℃):0.848
硫黄 :1.61重量%
窒素 :157重量ppm
蒸留性状(初留点): 211℃
〃(50vd%):340℃
〃 (終点’) : 406℃反応は流通式反
応装置を用い次の反応条件で行うた。Specific gravity (15/4℃): 0.848 Sulfur: 1.61% by weight Nitrogen: 157ppm by weight Distillation properties (initial boiling point): 211℃ 〃 (50vd%): 340℃ 〃 (End point'): 406℃ Reaction was carried out using a flow reactor under the following reaction conditions.
触媒量 : 3aal
原料油液空間速度 : 2.0hr−’反応圧力(水
素圧) : 30kg/cj反応温度 :330
℃
水素/油化 : 30ONt’/l’通油時間
: 8hr
処理油は2時間毎にサンプリングし硫黄含有量を測定し
、脱硫率を求めた。4時間目、6時間目、8時間目にサ
ンプリングした処理油の硫黄含有量から求めた脱硫率の
平均値を第1表に示す。Catalyst amount: 3aal Raw material oil/liquid space velocity: 2.0hr-'Reaction pressure (hydrogen pressure): 30kg/cj Reaction temperature: 330
°C Hydrogen/oil conversion: 30ONt'/l' Oil passage time: 8 hr The treated oil was sampled every 2 hours, the sulfur content was measured, and the desulfurization rate was determined. Table 1 shows the average value of the desulfurization rate determined from the sulfur content of the treated oil sampled at the 4th hour, 6th hour, and 8th hour.
比較例
実施例で使用したMOO,/COO触媒を、流通式反応
装置に装填し、次の条件で硫化処理した後、そのまま実
施例と同様にしてクェート常圧軽油の水素化脱硫反応を
行った。Comparative Example The MOO, /COO catalyst used in the example was loaded into a flow reactor and subjected to sulfurization under the following conditions, and then the hydrodesulfurization reaction of Kuwait atmospheric gas oil was carried out in the same manner as in the example. .
硫化油:3重量%n−ブチルメルカプタン/クェート常
圧軽油
触媒量 :3cal
原料油液空間速度 : 2.0hr−’反応圧力
: 30kg/cd反応温度 : 3
16℃
水素/油化 : 30ONg71通油時間
: 8hr
4時間目、6時間目、8時間目にサンプリングした処理
油の硫黄含有量から求めた脱硫率の平均値を第1表に示
す。Sulfurized oil: 3% by weight n-butyl mercaptan/Kuwaite normal pressure gas oil Catalyst amount: 3cal Raw material oil liquid hourly space velocity: 2.0hr-'Reaction pressure
: 30kg/cd Reaction temperature : 3
16℃ Hydrogen/oil conversion: 30ONg71 oil passage time
: 8 hr Table 1 shows the average value of the desulfurization rate determined from the sulfur content of the treated oil sampled at the 4th hour, 6th hour, and 8th hour.
Mo/Co系の触媒で、チオ酢酸、チオ安息香酸を担持
した触媒は、3重量%のn−ブチルメルカプタンを混合
したクェート常圧軽油を用いて硫化した触媒と同等以上
の活性を示すことが分る。A Mo/Co-based catalyst supporting thioacetic acid and thiobenzoic acid can exhibit activity equal to or higher than a catalyst sulfurized using Kuwait atmospheric gas oil mixed with 3% by weight of n-butyl mercaptan. I understand.
第1表 ト常圧軽油を用いた硫化法。Table 1 A sulfurization method using normal pressure light oil.
本発明は、周期律表第6族金属成分、第8族金属成分の
少なくとも一つを酸化物として含み、その活性種が上記
金属の硫化物であるあらゆる炭化水素の水素化処理触媒
に適用可能である。The present invention is applicable to any hydrocarbon hydrotreating catalyst that contains at least one of a Group 6 metal component and a Group 8 metal component of the periodic table as an oxide, and whose active species is a sulfide of the above metal. It is.
本発明によれば、従来技術の硫化法よりも簡略化された
操作で、優れた性能を有する炭化水素の水素化処理触媒
を得ることができる。According to the present invention, a hydrocarbon hydrotreating catalyst having excellent performance can be obtained with a simpler operation than the conventional sulfurization method.
特許出願人 住友金属鉱山株式会社 手続補正書(自発) 昭和62年9月2日Patent applicant: Sumitomo Metal Mining Co., Ltd. Procedural amendment (voluntary) September 2, 1986
Claims (6)
、第8族金属成分の少なくとも一つを酸化物として含む
触媒に、チオ酸を含浸せしめたことを特徴とする炭化水
素の水素化処理用触媒。(1) A hydrocarbon characterized by impregnating a catalyst using an inorganic oxide as a carrier and containing at least one of a group 6 metal component and a group 8 metal component of the periodic table as an oxide with thioacid. Hydrotreating catalyst.
であり、第8族金属がCo、Niの少なくとも一つであ
る特許請求の範囲第(1)項記載の炭化水素の水素化処
理用触媒。(2) Hydrogen in the hydrocarbon according to claim (1), wherein the Group 6 metal of the periodic table is at least one of Mo and W, and the Group 8 metal is at least one of Co and Ni. Catalyst for chemical treatment.
ある特許請求の範囲第(1)項または第(2)項記載の
炭化水素の水素化処理用触媒。(3) The catalyst for hydrogenation of hydrocarbons according to claim (1) or (2), wherein the thioacid is thioacetic acid and/or thiobenzoic acid.
、第8族金属成分の少なくとも一つを酸化物として含む
触媒に、チオ酸を含浸せしめた炭化水素の水素化処理用
触媒を、水素の存在下で室温〜400℃の温度で処理す
ることを特徴とする炭化水素の水素化処理用触媒の活性
化方法。(4) A catalyst for hydrogenation of hydrocarbons in which a catalyst containing an inorganic oxide as a carrier and containing at least one of a group 6 metal component and a group 8 metal component of the periodic table as an oxide is impregnated with thioacid. 1. A method for activating a catalyst for hydrogenation of hydrocarbons, which comprises treating at a temperature of room temperature to 400°C in the presence of hydrogen.
あり、第8族金属がCo、Niの少くとも一つである特
許請求の範囲第(4)項記載の炭化水素の水素化処理用
触媒の活性化方法。(5) The hydrocarbon according to claim (4), wherein the Group 6 metal of the periodic table is at least one of Mo and W, and the Group 8 metal is at least one of Co and Ni. A method for activating a hydrotreating catalyst.
ある特許請求の範囲第(4)項または第(5)項記載の
炭化水素の水素化処理用触媒の活性化方法。(6) The method for activating a catalyst for hydrogenation of hydrocarbons according to claim (4) or (5), wherein the thioacid is thioacetic acid and/or thiobenzoic acid.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14514387A JPS63310641A (en) | 1987-06-12 | 1987-06-12 | Catalyst for hydrogenation of hydrocarbon and method for activating same |
EP19920201346 EP0506206A1 (en) | 1987-04-22 | 1988-04-21 | A catalyst for hydrotreating hydrocarbons and methods of activating the same |
EP88303592A EP0289211B1 (en) | 1987-04-22 | 1988-04-21 | Catalysts for hydrotreating hydrocarbons and method of activating the same |
DE88303592T DE3884451T2 (en) | 1987-04-22 | 1988-04-21 | Catalysts for the hydrogenating treatment of hydrocarbons and their activation. |
US07/184,958 US4845068A (en) | 1987-04-22 | 1988-04-22 | Catalysts for hydrotreating hydrocarbons and method of activating the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14514387A JPS63310641A (en) | 1987-06-12 | 1987-06-12 | Catalyst for hydrogenation of hydrocarbon and method for activating same |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63310641A true JPS63310641A (en) | 1988-12-19 |
Family
ID=15378410
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14514387A Pending JPS63310641A (en) | 1987-04-22 | 1987-06-12 | Catalyst for hydrogenation of hydrocarbon and method for activating same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63310641A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0271844A (en) * | 1988-09-08 | 1990-03-12 | Sumitomo Metal Mining Co Ltd | Catalyst for hydrogenation treatment of hydrocarbon and production thereof |
-
1987
- 1987-06-12 JP JP14514387A patent/JPS63310641A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0271844A (en) * | 1988-09-08 | 1990-03-12 | Sumitomo Metal Mining Co Ltd | Catalyst for hydrogenation treatment of hydrocarbon and production thereof |
JPH0549340B2 (en) * | 1988-09-08 | 1993-07-26 | Sumitomo Metal Mining Co |
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