JPH04210240A - Hydrogenation catalyst and its production - Google Patents
Hydrogenation catalyst and its productionInfo
- Publication number
- JPH04210240A JPH04210240A JP34105390A JP34105390A JPH04210240A JP H04210240 A JPH04210240 A JP H04210240A JP 34105390 A JP34105390 A JP 34105390A JP 34105390 A JP34105390 A JP 34105390A JP H04210240 A JPH04210240 A JP H04210240A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- activity
- carrier
- catalysts
- molybdenum
- 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 53
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract 2
- 230000000694 effects Effects 0.000 description 16
- 238000001035 drying Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005987 sulfurization reaction Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000007327 hydrogenolysis reaction Methods 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- YXOVIGZJPGLNGM-UHFFFAOYSA-N 5-methyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=C1C=CC=C2C YXOVIGZJPGLNGM-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017311 Mo—Mo Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- -1 metals changes Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は1重質炭化水素を原料として水素化処理を行い
、より軽質留分を得る場合に用いられる水素化処理用触
媒に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a hydrotreating catalyst used when hydrogenating a heavy hydrocarbon as a raw material to obtain a lighter fraction. .
[従来の技術]
近年、エネルギー問題、化石燃料の枯渇化にともなって
重中質油など炭化水素を原料とする水素化精製反応に関
する研究が精力的に行われている。[Prior Art] In recent years, with energy problems and the depletion of fossil fuels, research on hydrorefining reactions using hydrocarbons such as heavy and medium oils as raw materials has been actively conducted.
特に減圧残油、オイルシェール、オイルサンド。Especially vacuum residual oil, oil shale, and oil sands.
石炭などから得られる芳香族環を多く含有する重質油を
効率よく軽質化することについては、新燃料油の用途拡
大という見地からも新しい技術開発が強く望まれている
。Regarding the efficient lightening of heavy oil containing many aromatic rings obtained from coal, etc., there is a strong desire for the development of new technology from the perspective of expanding the uses of new fuel oil.
また、より良い環境を目指して排ガス処理技術と並行し
て燃料のより一層のクリーン化が求められており新しい
高性能触媒の開発が必要となっている。In addition, in order to create a better environment, there is a need for even cleaner fuels as well as exhaust gas treatment technology, necessitating the development of new high-performance catalysts.
このような重質炭化水素の水素化処理反応に用いられる
触媒としては、無機塩から調製したモリブデン、タング
ステン、コバルト、ニッケル、鉄などの単独あるいは組
み合わせたものをアルミナ。Catalysts used in the hydrogenation reaction of heavy hydrocarbons include molybdenum, tungsten, cobalt, nickel, iron, etc., prepared from inorganic salts, singly or in combination with alumina.
チタニア、シリカなどの担体に担持し触媒として用いら
れてきた。これら触媒は、活性金属を担体に担持し乾燥
した後、空気中400〜600℃の温度で焼成すること
により調製されている。調製された酸化物触媒は反応に
先だって硫化処理し硫化物触媒として水素化処理反応に
もちいている。It has been used as a catalyst by being supported on a carrier such as titania or silica. These catalysts are prepared by supporting an active metal on a carrier, drying it, and then calcining it in air at a temperature of 400 to 600°C. The prepared oxide catalyst is sulfurized prior to the reaction and used as a sulfide catalyst in the hydrogenation reaction.
[発明が解決しようとする課題]
しかしながら、400〜600℃の温度で焼成した触媒
は、乾燥、焼成および硫化過程で、活性金属であるコバ
ルト、ニッケル、モリブデン、タングステン、鉄などの
分散状態が大きく変化する。[Problems to be Solved by the Invention] However, in the catalyst calcined at a temperature of 400 to 600°C, active metals such as cobalt, nickel, molybdenum, tungsten, and iron are largely dispersed during the drying, calcining, and sulfurizing processes. Change.
また、活性金属が担体成分と複合酸化物を形成する問題
もある。このため、必要な反応選択性。There is also the problem that the active metal forms a composite oxide with the carrier component. For this reason, the required reaction selectivity.
活性などが得られず、高活性を有し、水素化活性。It has high activity and hydrogenation activity.
水素化分解活性など触媒の基本機能の制御が可能な新し
い触媒系の開発が期待されている。The development of new catalyst systems that can control the basic functions of catalysts, such as hydrocracking activity, is expected.
そこで本発明では2重質炭化水素類を水素化処理するこ
とにより、効率よく改質あるいは軽質化する場合に用い
る触媒の調製方法を提供することをその課題とする。す
なわち、触媒調製において従来法の空気雰囲気下で乾燥
、焼成し、酸化物触媒を経由し硫化処理により硫化物触
媒とする工程を経ずに、乾燥後、直接に硫化物触媒とす
ることを特徴とする。Therefore, an object of the present invention is to provide a method for preparing a catalyst that can be used to efficiently reform or lighten heavy hydrocarbons by hydrotreating them. That is, the catalyst is prepared by drying and calcining the catalyst in an air atmosphere, passing through an oxide catalyst, and then converting it into a sulfide catalyst by sulfurization, without going through the process of preparing the catalyst, and directly converting it into a sulfide catalyst after drying. shall be.
具体的には、活性金属種を含浸担持後、焼成することな
しに乾式で硫化し硫化物触媒とする方法である。Specifically, after impregnating and supporting the active metal species, dry sulfurization is performed without calcination to form a sulfide catalyst.
本方法によれば、触媒表面上における活性金属の分散状
態を制御できること、担体と活性金属種が複合酸化物を
形成せず活性金属種が触媒表面上に有効に分散されるこ
と、容易に活性金属種が硫化されること、など触媒の高
性能化に向けて多くの利点が考えられる。このため、従
来の触媒機能と異なった新しい触媒の開発が期待できる
。According to this method, the dispersion state of the active metal on the catalyst surface can be controlled, the carrier and the active metal species do not form a composite oxide and the active metal species are effectively dispersed on the catalyst surface, and the active metal species can be easily activated. There are many advantages that can be considered for improving the performance of catalysts, such as sulfurization of metal species. Therefore, we can expect the development of new catalysts that differ from conventional catalyst functions.
すなわち、触媒表面に担持されている金属塩を酸化物に
することなく還元雰囲気中で加熱脱水および硫化処理を
することにより、従来の触媒と異なった表面構造を有し
、新機能を示す触媒の開発が期待できる。In other words, by heating and dehydrating and sulfurizing the metal salts supported on the catalyst surface in a reducing atmosphere without converting them into oxides, we can create catalysts with a surface structure different from conventional catalysts and exhibiting new functions. We can expect development.
[W題を解決するための手段]
本発明者らは、前記課題を解決するために種々研究を重
ねた結果、従来法の触媒調製において乾燥、焼成過程に
おいてニッケル、コバルト、モリブデン、タングステン
、鉄などの金属の分散状態あるいは酸化還元状態が変化
し、その結果、目的とする触媒活性が得られず反応選択
性も低くなるなどの事実がわかった。そこでこれらの課
題を解決するための研究を行いその過程において本発明
による乾式調製法が優れていることを見いだし本発明に
至った。[Means for Solving Problem W] As a result of various studies to solve the above problem, the present inventors have found that nickel, cobalt, molybdenum, tungsten, and iron are It was found that the dispersion state or oxidation-reduction state of metals such as metals changes, and as a result, the desired catalytic activity cannot be obtained and the reaction selectivity decreases. Therefore, we conducted research to solve these problems, and in the process discovered that the dry preparation method of the present invention is superior, leading to the present invention.
すなわち9本発明の触媒は従来の触媒と比べではるかに
高い水素化分解活性が得られる。水素化分解活性の向上
にはモリブデン、タングステン等の原子ががある程度集
合している状態をとることが必要であり2本発明の触媒
は従来の触媒との比べてモリブデンの集合形態は明らか
に異なり低温による乾式調製法を用いればモリブデンが
水素化分解活性の向上に寄与していることがEXAFS
(X線吸収端微細構造)の測定結果よりわかった。In other words, the catalyst of the present invention has much higher hydrocracking activity than conventional catalysts. In order to improve the hydrogenolysis activity, it is necessary that the atoms of molybdenum, tungsten, etc. are aggregated to some extent.2 The catalyst of the present invention has a clearly different aggregated form of molybdenum compared to conventional catalysts. EXAFS shows that molybdenum contributes to improving hydrogenolysis activity when dry preparation method at low temperature is used.
(X-ray absorption edge fine structure) measurement results.
[実施例] 以下、実施例に基づき、本発明を更に詳細に説明する。[Example] Hereinafter, the present invention will be explained in more detail based on Examples.
実施例1 触媒の調製 触媒担体はγ−アルミナ(直径: 1/32インチ。Example 1 Preparation of catalyst The catalyst carrier was γ-alumina (diameter: 1/32 inch).
柱状、細孔径 80人2表面積 240m+” / g
)を選定し用いた。活性金属としてモリブデン、コバ
ルト、ニッケル、タングステンあるいはこれらを組み合
わせた触媒を調製条件を変え調製した。各種触媒の組成
の一例は21.7警t%MoO,/A Q 203.3
.5tit%Ni0−15.0すt%Mob、 / A
Q 20. 、3.5wt%Coo/A Q 203
、および1 、75wt%Ni0−1.75wt%Co
o−15wt%Mob。Columnar shape, pore size 80 people 2 surface area 240m+”/g
) was selected and used. Catalysts using molybdenum, cobalt, nickel, tungsten, or a combination of these as active metals were prepared under different preparation conditions. An example of the composition of various catalysts is 21.7% MoO, /A Q 203.3
.. 5tit%Ni0-15.0st%Mob, /A
Q20. , 3.5wt%Coo/A Q 203
, and 1, 75wt%Ni0-1.75wt%Co
o-15wt% Mob.
/AQ20.(各種触媒間で活性金属の原子数を揃えた
)である。/AQ20. (The number of active metal atoms was the same among the various catalysts.)
具体的な触媒調製の手法は、まずモリブデン酸アンモニ
ウム、硝酸ニッケル、硝酸コバルトをアンモニア水(2
8%)に溶解し、上記組成になるように溶液濃度を調製
した。ついで当該溶液にγ−アルミナを浸しく含浸法)
上記組成の触媒とした。得られた含浸成型物は4通りの
方法で乾燥および焼成した。A法は大気中で12時間、
B法は110℃で2時間各々乾燥させた。CおよびD法
は110℃で2時間乾燥させた後、300℃(C法)お
よび550℃(D法)で1時間焼成した。The specific catalyst preparation method is to first mix ammonium molybdate, nickel nitrate, and cobalt nitrate with aqueous ammonia (2
8%), and the solution concentration was adjusted to have the above composition. Then, γ-alumina is soaked in the solution (impregnation method)
A catalyst having the above composition was prepared. The obtained impregnated molded products were dried and fired in four ways. Method A is for 12 hours in the atmosphere.
In Method B, each sample was dried at 110°C for 2 hours. Methods C and D were dried at 110°C for 2 hours and then fired at 300°C (method C) and 550°C (method D) for 1 hour.
実施例2
触媒活性の評価
調製した触媒は5ν01%H2S/)I2の硫化水素含
有ガスにより400℃、1時間の硫化処理を行い各種水
素化処理反応に用いた。活性の評価はモデル化合物を用
い、水素化(HY)活性、水素化分解(HC)活性につ
いて行った。用いたモデル化合物は1−メチルナフタレ
ン(1−MN)であり。Example 2 Evaluation of Catalytic Activity The prepared catalyst was subjected to a sulfiding treatment at 400°C for 1 hour using a hydrogen sulfide-containing gas of 5v01% H2S/)I2, and was used in various hydrogenation reactions. The activity was evaluated using model compounds in terms of hydrogenation (HY) activity and hydrogenolysis (HC) activity. The model compound used was 1-methylnaphthalene (1-MN).
1.5−メチルテトラリンの収率をもってHY活性とし
た。さらにジフェニルメタン(DPM)を用いて、ベン
ゼンとトルエンの収率をもってHC活性とした。反応は
、オートクレーブ(内容積50cm3)を用い、触媒0
.3g、モデル化合物10011 、水素初圧 70k
g/c、m2.反応温度 310℃(HY活性)、40
0℃(HC活性)2反応時間1時間である。The yield of 1,5-methyltetralin was defined as HY activity. Further, using diphenylmethane (DPM), the yield of benzene and toluene was determined as HC activity. The reaction was carried out using an autoclave (inner volume 50 cm3) with 0 catalyst.
.. 3g, model compound 10011, hydrogen initial pressure 70k
g/c, m2. Reaction temperature: 310°C (HY activity), 40
0°C (HC activity) 2 reaction time 1 hour.
反応生成物の分析はキャピラリーガスクロを用いた。Capillary gas chromatography was used to analyze the reaction products.
A法(大気中 12h乾燥) B法(110℃ 2h乾燥) D法(110℃ 2h乾燥。Method A (drying in the atmosphere for 12 hours) Method B (drying at 110°C for 2 hours) Method D (drying at 110°C for 2 hours.
300℃ 1h焼成) D法(100℃ 2h乾燥。Baking at 300℃ for 1 hour) Method D (drying at 100°C for 2 hours.
550℃ 1h焼成)
この結果、焼成過程を経ることなしに乾式で硫化処理し
た触媒が焼成後硫化した触媒と比べ、高い水素化分解活
性を示すことがわかった。また。550°C for 1 hour) As a result, it was found that the catalyst that was dry sulfurized without undergoing a calcination process exhibited higher hydrocracking activity than the catalyst that was sulfurized after calcination. Also.
活性金属種の組合せ、担持量を変えた触媒でも同様の結
果が得られた。Similar results were obtained using catalysts with different combinations of active metal species and different supported amounts.
実施例3
EXAFSによりMo−5すなわちMOの周りのSの配
位数を測定した。理論上はMOが完全に硫化された場合
。Example 3 The coordination number of Mo-5, ie, S around MO, was measured by EXAFS. Theoretically, if MO is completely sulfurized.
Mo原子の周りにはSは6個配位する。従って、 A、
B法はC,D法に比へてこの数値が大きな値を示すこと
から触媒の硫化が進行しているという事がわかる。また
、 Mo−Moについては、 Mo原子の周りのM。Six S atoms are coordinated around the Mo atom. Therefore, A,
It can be seen that the sulfurization of the catalyst is progressing in Method B because this value is larger than that in Methods C and D. Also, for Mo-Mo, M around Mo atoms.
について測定したもので理論値は6個である。この値の
違いにより、 MoS2の集合形態が異なることがわか
る。表の結果から、触媒はMoS2結晶が焼成過程を経
た触媒と比較し、適度に成長し、この結果水素化分解活
性が向上したことがわかる。The theoretical value is 6. It can be seen that the aggregation form of MoS2 differs depending on the difference in this value. From the results in the table, it can be seen that the catalyst grew moderately in comparison to the catalyst in which MoS2 crystals underwent a calcination process, and as a result, the hydrogenolysis activity was improved.
以上の結果2本発明の低温による乾式、硫化処理による
触媒調製法は、 Noの硫化が容易に進行し。As a result of the above, 2. In the catalyst preparation method using dry sulfurization treatment at low temperature according to the present invention, sulfurization of No proceeds easily.
一方では結晶化がおさえられるため、高い水素化分解活
性が得られた。On the other hand, high hydrogenolysis activity was obtained because crystallization was suppressed.
Claims (2)
コバルト、ニッケル、鉄などを、単独または複数種類組
み合わせて担体に担持し、焼成過程を経ずに乾式で硫化
処理をして水素化処理触媒として用いる方法。(1) Molybdenum, tungsten as catalytically active metals,
A method in which cobalt, nickel, iron, etc., singly or in combination, are supported on a carrier, and then dry sulfurized without going through a calcination process and used as a hydrogenation catalyst.
化処理触媒およびその製造方法。(2) A method for producing a catalyst, a hydrotreating catalyst, and a method for producing the same, according to claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34105390A JPH04210240A (en) | 1990-11-30 | 1990-11-30 | Hydrogenation catalyst and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34105390A JPH04210240A (en) | 1990-11-30 | 1990-11-30 | Hydrogenation catalyst and its production |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04210240A true JPH04210240A (en) | 1992-07-31 |
Family
ID=18342803
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP34105390A Pending JPH04210240A (en) | 1990-11-30 | 1990-11-30 | Hydrogenation catalyst and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04210240A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5468709A (en) * | 1992-11-18 | 1995-11-21 | Sumitomo Metal Mining Co., Ltd. | Catalysts for hydrotreating hydrocarbon oils and method of preparing the same |
JP2002536166A (en) * | 1999-02-15 | 2002-10-29 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Manufacture of hydrotreating catalyst |
JP2004344725A (en) * | 2003-05-20 | 2004-12-09 | National Institute Of Advanced Industrial & Technology | Impregnating solution for hydrogenation catalyst, and hydrogenation catalyst using the same |
JP2005262063A (en) * | 2004-03-17 | 2005-09-29 | National Institute Of Advanced Industrial & Technology | Hydrogenation catalyst |
KR100636432B1 (en) * | 2000-09-25 | 2006-10-18 | 차이나 페트로리움 앤드 케미컬 코포레이션 | A guard catalyst and a process for its preparation |
CN109569635A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | For Tar production fuel oil hydrogenation catalysts |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6214946A (en) * | 1985-07-08 | 1987-01-23 | ユニリ−バ− ナ−ムロ−ゼ ベンノ−トシヤ−プ | Manufacture of catalyst |
JPS6411645A (en) * | 1987-07-02 | 1989-01-17 | Sumitomo Metal Mining Co | Manufacture of catalyst for hydrogenation of hydrocarbons |
-
1990
- 1990-11-30 JP JP34105390A patent/JPH04210240A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6214946A (en) * | 1985-07-08 | 1987-01-23 | ユニリ−バ− ナ−ムロ−ゼ ベンノ−トシヤ−プ | Manufacture of catalyst |
JPS6411645A (en) * | 1987-07-02 | 1989-01-17 | Sumitomo Metal Mining Co | Manufacture of catalyst for hydrogenation of hydrocarbons |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5468709A (en) * | 1992-11-18 | 1995-11-21 | Sumitomo Metal Mining Co., Ltd. | Catalysts for hydrotreating hydrocarbon oils and method of preparing the same |
JP2002536166A (en) * | 1999-02-15 | 2002-10-29 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Manufacture of hydrotreating catalyst |
KR100636432B1 (en) * | 2000-09-25 | 2006-10-18 | 차이나 페트로리움 앤드 케미컬 코포레이션 | A guard catalyst and a process for its preparation |
JP2004344725A (en) * | 2003-05-20 | 2004-12-09 | National Institute Of Advanced Industrial & Technology | Impregnating solution for hydrogenation catalyst, and hydrogenation catalyst using the same |
JP4646500B2 (en) * | 2003-05-20 | 2011-03-09 | 独立行政法人産業技術総合研究所 | Hydrotreating catalyst using impregnation solution for hydrotreating catalyst |
JP2005262063A (en) * | 2004-03-17 | 2005-09-29 | National Institute Of Advanced Industrial & Technology | Hydrogenation catalyst |
CN109569635A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | For Tar production fuel oil hydrogenation catalysts |
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