JP2580278B2 - Hydrotreating catalyst and method for producing the same - Google Patents
Hydrotreating catalyst and method for producing the sameInfo
- Publication number
- JP2580278B2 JP2580278B2 JP63218197A JP21819788A JP2580278B2 JP 2580278 B2 JP2580278 B2 JP 2580278B2 JP 63218197 A JP63218197 A JP 63218197A JP 21819788 A JP21819788 A JP 21819788A JP 2580278 B2 JP2580278 B2 JP 2580278B2
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- nickel
- weight
- cobalt
- catalyst
- 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.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 46
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 7
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 238000001420 photoelectron spectroscopy Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 45
- 229910052759 nickel Inorganic materials 0.000 description 25
- 230000000694 effects Effects 0.000 description 10
- 150000004645 aluminates Chemical class 0.000 description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- -1 nickel forms aluminate Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005987 sulfurization 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
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YXOVIGZJPGLNGM-UHFFFAOYSA-N 5-Methyltetralin Natural products C1CCCC2=C1C=CC=C2C YXOVIGZJPGLNGM-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000012438 extruded product Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000002186 photoelectron spectrum Methods 0.000 description 2
- 102200118166 rs16951438 Human genes 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- APBBTKKLSNPFDP-UHFFFAOYSA-N 1-methyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2C(C)CCCC2=C1 APBBTKKLSNPFDP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、水素化処理触媒、特に炭化水素油の水素化
処理に好適な触媒、およびその製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a hydrotreating catalyst, particularly a catalyst suitable for hydrotreating a hydrocarbon oil, and a method for producing the same.
従来、原油から得られる油状留分、石炭から選ばれる
油状留分等の炭化水素油の水素化処理工程では、アルミ
ナ担体にニッケル、モリブデン、タングステン等の活性
金属を担持した触媒が用いられている。これらの触媒
は、通常、アルミナ水和物を成形後、300〜600℃程度で
焼成してγ−アルミナ担体としたものにニッケル塩水溶
液を含浸し、再度300〜600℃程度で焼成することにより
製造されている。Conventionally, in the hydrotreating process of hydrocarbon oils such as oily fractions obtained from crude oil and oily fractions selected from coal, a catalyst in which an active metal such as nickel, molybdenum, and tungsten is supported on an alumina carrier is used. . These catalysts are usually formed by molding alumina hydrate, and then calcined at about 300 to 600 ° C. to obtain a γ-alumina carrier, impregnated with a nickel salt aqueous solution, and calcined again at about 300 to 600 ° C. Being manufactured.
こうして得られる触媒においては、ニッケル、モリブ
デン、タングステン等が酸化物態で担持されているので
そのままでは活性が示されない。そこで、通常、水素化
処理に供する際には、水素化処理を行う反応器に該触媒
を充填した後に触媒層に水素とともに硫化剤を流通させ
ることにより担持ニッケルを硫化物態に転換する予備硫
化処理を施し、しかる後に水素化処理を実施する。In the catalyst thus obtained, nickel, molybdenum, tungsten, etc., are supported in an oxide state, so that the catalyst does not show activity as it is. Therefore, usually, when subjected to hydrotreating, the catalyst is charged into a reactor for hydrotreating, and then a sulfide is passed through the catalyst layer together with hydrogen to convert the supported nickel into a sulfide state. Treatment, followed by hydrogenation.
ところで、上記の製造方法においては、ニッケル塩水
溶液を含浸後にγ−アルミナ担体を焼成する段階で、担
持されたニッケル、モリブデン、タングステン等の活性
金属成分の多くがγ−アルミナと反応してアルミネート
を形成する。しかし、アルミネートは予備硫化工程にお
いて硫化物態に転換されないため触媒活性に寄与しな
い。したがって、上記の方法によって得られる触媒で
は、活性金属成分担持量に見合うだけの触媒活性を引き
出すことができないという問題がある。特に、ニッケル
・モリブデン系やニッケル・タングステン系の触媒で
は、ニッケル硫化物とモリブデンまたはタングステン硫
化物との最適な組み合わせ割合、あるいは両者の相互作
用が触媒活性、選択性の向上に必要不可欠と考えられて
いるが、ニッケルが担体とアルミネートを形成すると両
者の組み合わせによる活性発現が阻害される。By the way, in the above-mentioned production method, at the stage of baking the γ-alumina carrier after impregnating the nickel salt aqueous solution, most of the supported active metal components such as nickel, molybdenum, and tungsten react with γ-alumina and aluminate. To form However, aluminate does not contribute to the catalytic activity because it is not converted to the sulfide form in the pre-sulfurization step. Therefore, there is a problem that the catalyst obtained by the above-described method cannot bring out the catalytic activity corresponding to the amount of the active metal component carried. In particular, for nickel-molybdenum-based or nickel-tungsten-based catalysts, the optimal combination ratio of nickel sulfide and molybdenum or tungsten sulfide, or the interaction of both, is considered to be indispensable for improving catalytic activity and selectivity. However, when nickel forms aluminate with the carrier, the activity expression by the combination of both is inhibited.
そこで、本発明の目的は、前記従来の水素化処理触媒
の問題点を解決し、ニッケルの硫化状態の制御あるいは
ニッケルとモチブデンもしくはタングステンとの配位状
態を制御することにより、主たる担持金属活性成分であ
るニッケルが有する潜在的な触媒活性発現機能を十分に
引き出すことができる、高活性の水素化処理触媒、およ
びその製造方法を提供することにある。Therefore, an object of the present invention is to solve the problems of the conventional hydrotreating catalyst and control the sulfuration state of nickel or the coordination state of nickel and motibdenum or tungsten to form the main supported metal active component. It is an object of the present invention to provide a highly active hydrotreating catalyst capable of fully exploiting the potential catalytic activity expressing function of nickel, and a method for producing the same.
本発明は、かかる目的を達成する手段として、 （ａ） δ−アルミナおよびθ−アルミナの少なくとも
１種を10重量％以上含有するアルミナ ……20〜95重量％、 （ｂ） コバルトアルミネート ……コバルト含有量がCoO換算で１〜20重量％であ
り、そのうち前記コバルアルミネートとしての含有量が
光電子分光法により測定される782eVにおけるピーク強
度（I782）と777eVにおけるピーク強度（I777）との関
係が I782／I777≧1.0 となる量、 および （ｃ） 酸化ニッケル、酸化モリブデンおよび酸化タン
グステンから選ばれる少なくとも１種 ……１重量％以上 を含有してなる水素化処理触媒を提供するものである。The present invention provides means for achieving the above object by: (a) alumina containing at least one of δ-alumina and θ-alumina in an amount of 10% by weight or more: 20 to 95% by weight; (b) cobalt aluminate: The cobalt content is 1 to 20% by weight in terms of CoO, and the content as the cobalaluminate is a peak intensity at 782 eV (I 782 ) and a peak intensity at 777 eV (I 777 ) measured by photoelectron spectroscopy. providing a quantity relationship is I 782 / I 777 ≧ 1.0, and (c) nickel oxide, hydrotreating catalyst which comprises at least one ...... 1 wt% or more selected from molybdenum oxide and tungsten oxide Things.
本発明の触媒において担体（ａ）を構成するアルミナ
は、δ−アルミナおよびθ−アルミナから選ばれる少な
くとも１種を必須成分として含むもので、その含有量
は、10重量％以上、好ましくは、40重量％以上である。
これらのδ−アルミナおよびθ−アルミナはニッケルと
アルミネートを形成しにくいので、ニッケルのアルミネ
ート化の抑制、触媒活性の向上に寄与する。このアルミ
ナ担体には、δ−アルミナおよびθ−アルミナ以外のア
ルミナ、すなわちγ−アルミナおよびα−アルミナが含
まれてもよいが、γ−アルミナは、ニッケルアルミネー
トを形成しやすいという難点があり、また、α−アルミ
ナは比表面積が極端に小さいためこれの含有量が増すと
担体の比表面積が著しく低下してしまい、活性金属成分
であるニッケルの担持量が著しく減少する不利が生じ
る。したがって、所要の触媒活性を得るためには、δ−
アルミナおよび／またはθ−アルミナの含有量は、10重
量％以上であることが必要である。The alumina constituting the support (a) in the catalyst of the present invention contains at least one selected from δ-alumina and θ-alumina as an essential component, and its content is 10% by weight or more, preferably 40% by weight or more. % By weight or more.
Since these δ-alumina and θ-alumina hardly form aluminate with nickel, they contribute to suppression of aluminate conversion of nickel and improvement of catalytic activity. The alumina carrier may contain alumina other than δ-alumina and θ-alumina, that is, γ-alumina and α-alumina, but γ-alumina has a disadvantage that nickel aluminate is easily formed, Further, since the specific surface area of α-alumina is extremely small, when the content thereof is increased, the specific surface area of the carrier is remarkably reduced, so that there is a disadvantage that the carried amount of nickel as an active metal component is significantly reduced. Therefore, in order to obtain the required catalytic activity, δ-
The content of alumina and / or θ-alumina needs to be 10% by weight or more.
本発明の触媒においては、コバルトアルミネート
（ｂ）が生成しているために、後述する製造方法の説明
からも明らかなように、ニッケルアルミネートの形成が
これによっても抑制される。コバルトは、アルミネート
以外の形態、特に酸化物の形態でも存在しうるが、コバ
ルト分は、CoO換算で１〜20重量％、好ましくは４〜10
重量％である。In the catalyst of the present invention, since cobalt aluminate (b) is produced, formation of nickel aluminate is also suppressed by this, as is clear from the description of the production method described later. Cobalt may be present in a form other than aluminate, particularly in the form of an oxide. The cobalt content is 1 to 20% by weight in terms of CoO, preferably 4 to 10% by weight.
% By weight.
光分子分光法によると、コバルトアルミネートは782e
Vにコバルトの光電子スペクトル固有のピークを示し、C
oOは777eVにコバルト固有のピークを示す。触媒中にお
けるコバルトアルミネートの含有量は、782eVにおける
ピーク強度（I782）と777eVにおけるピーク強度
（I777）との比である、I782／I777の値が、1.0以上と
なる量であることが必要で、特に1.5以上であることが
好ましい。According to photomolecular spectroscopy, cobalt aluminate is 782e
V shows a peak unique to the photoelectron spectrum of cobalt, and C
oO shows a peak unique to cobalt at 777 eV. The content of cobalt aluminate in the catalyst is such that the value of I 782 / I 777 , which is the ratio of the peak intensity at 782 eV (I 782 ) to the peak intensity at 777 eV (I 777 ), is 1.0 or more. And it is particularly preferable that the ratio be 1.5 or more.
コバルトの総含有量が１重量％未満であったり、ある
いはI782／I777の比が、1.0未満であると、活性金属と
して担持されるニッケルのアルミネート化を効果的に抑
制できない。なお、コバルトの総含有量が20重量％を超
えてももはや触媒活性のそれ以上の向上は期待困難であ
るばかりか、経済的に不利である。If the total content of cobalt is less than 1% by weight or the ratio of I 782 / I 777 is less than 1.0, it is not possible to effectively suppress the aluminaation of nickel supported as an active metal. Even if the total content of cobalt exceeds 20% by weight, further improvement of the catalytic activity is not only expected but also economically disadvantageous.
本発明の触媒における酸化ニッケル、酸化モリブデン
および酸化タングステンから選ばれる少なくとも１種
（ｃ）ha、予備硫化工程により硫化されて活性化される
ものであり、１重量％以上、通常１〜20重量％担持され
る。担持量が１重量％未満であると、得られる触媒活性
が不十分である。乗っけるは部分的にアルミネート化し
た状態で存在してもよいが、大部分は酸化物の状態で存
在する。ニッケルアルミネートは、856eVにニッケルの
光電子スペクトル固有のピークを示し、NiOは851eVに固
有のピークを示すが、ニッケルアルミネートの含有量
は、これらの強度比が、 I856／I851≦0.8 となる範囲であることが好ましい。At least one kind (c) ha selected from nickel oxide, molybdenum oxide and tungsten oxide in the catalyst of the present invention, which is activated by being sulfided in a preliminary sulfidation step, and is 1% by weight or more, usually 1 to 20% by weight. It is carried. When the supported amount is less than 1% by weight, the obtained catalyst activity is insufficient. The rider may exist in a partially aluminate state, but mostly exists in an oxide state. Nickel aluminate shows a peak unique to the photoelectron spectrum of nickel at 856 eV, and NiO shows a unique peak at 851 eV, but the content of nickel aluminate is such that their intensity ratio is I 856 / I 851 ≦ 0.8. It is preferable that it is in the range.
担持金属は、ニッケル、モリブデンおよびタングステ
ンの少なくとも１種でよいが、好ましくはニッケル・モ
リブデン系、およびニッケル・タングステン系が好まし
い。このとき、それぞれの担持量は酸化物換算で、NiO
２〜10重量％、MoO3もしくはWO3 ５〜25重量％の範
囲から、目的に応じて選ばれる。The supported metal may be at least one of nickel, molybdenum and tungsten, but is preferably nickel-molybdenum-based or nickel-tungsten-based. At this time, each supported amount is NiO
2-10 wt%, from a range of MoO 3 or WO 3 5 to 25 wt%, are selected according to the purpose.
本発明の触媒は、例えば、γ−アルミナ担体にコバル
ト塩を担持させ、 次に、該担体を600〜1,100℃で焼成し、 次に、該担体に、ニッケル塩、モリブデン塩およびタ
ングステン塩から選ばれる少なくとも１種を担持させた
後300〜600℃で焼成する工程からなる方法により製造す
ることができる。The catalyst of the present invention, for example, a cobalt salt is supported on a γ-alumina carrier, then the carrier is calcined at 600 to 1,100 ° C., and then the carrier is selected from a nickel salt, a molybdenum salt and a tungsten salt. And carrying out baking at 300 to 600 [deg.] C. after supporting at least one of the above.
この方法に用いられるγ−アルミナ担体は、従来用い
られているものと同様であり、特に限定されず、例え
ば、アルミナ水和物を成形後300〜600℃程度で焼成して
得られるもの、市販のものなど使用できる。γ−アルミ
ナ担体にコバルト塩を担持させる方法も、通常の方法で
よく、例えば、コバルトの硝酸塩、炭酸塩等の水溶液に
担体を浸漬後、乾燥させればよい。こうしてコバルト塩
が担持されたγ−アルミナ担体は、次に、600〜1,100
℃、好ましくは800〜1,100で焼成される。雰囲気は、酸
素含有ガス、代表的には空気の気流中などであり、時間
は温度にもよるが、大体１〜４時間程度でよい。この焼
成処理によりアルミナの結晶形態は、γ−相からδ−相
へ、温度が高いとさらにθ−相へ、場合によってはさら
にα−相へと変化が進行する。したがって、焼成の温度
と時間によって異なるが、一般に、数種の結晶形態の混
成状態となる。しかし、焼成温度が600℃未満である
と、δ−相、θ−相の生成が困難であり、1,100℃を超
えると、δ−相、θ−相が減少し、比表面積の小さいα
−相が大量に生成して触媒担体としての機能を低下させ
る。600〜1,100℃で焼成することにより、δ−アルミナ
および／またはθ−アルミナが約10重量％以上生成した
アルミナ担体となり、しかも担持されたコバルト塩はア
ルミナと反応してアルミネートを形成する結果担体は一
層安定化し、次工程においてニッケルのアルミネート化
は一層抑止される。The γ-alumina carrier used in this method is the same as that conventionally used, and is not particularly limited.For example, those obtained by molding alumina hydrate and firing at about 300 to 600 ° C., commercially available Can be used. The method of supporting the cobalt salt on the γ-alumina carrier may be a conventional method. For example, the carrier may be immersed in an aqueous solution of cobalt nitrate, carbonate or the like and then dried. The γ-alumina support on which the cobalt salt is supported in this manner is then 600 to 1,100
C., preferably at 800-1,100. The atmosphere is an oxygen-containing gas, typically in a stream of air, and the time depends on the temperature, but may be about 1 to 4 hours. By this calcination treatment, the crystal form of alumina progresses from the γ-phase to the δ-phase, further to the θ-phase at a high temperature, and further to the α-phase in some cases. Therefore, although it depends on the firing temperature and time, generally, it is a hybrid state of several crystal forms. However, when the firing temperature is lower than 600 ° C., it is difficult to generate a δ-phase and a θ-phase, and when the firing temperature is higher than 1,100 ° C., the δ-phase and the θ-phase decrease and α having a small specific surface area is used.
-A large amount of phase is formed and reduces its function as a catalyst support. By firing at 600 to 1,100 ° C, δ-alumina and / or θ-alumina become about 10% by weight or more of alumina support, and the supported cobalt salt reacts with alumina to form aluminate. Is further stabilized, and the conversion of nickel to aluminate in the next step is further suppressed.
この焼成処理の後、ニッケル、モリブデン、タングス
テン等を担持させ、300〜600℃で焼成する工程は、従来
と同様に行われる。ニッケル、タングステン、モリブデ
ン等の担持は、例えば、硝酸ニッケル、モリブデン酸ア
ンモニウム、タングステン酸アンモニウム等の水溶液に
前記焼成処理後の担体を浸漬した後乾燥し、次いで空気
中で300〜600℃で焼成すればよい。焼成温度が、300℃
未満であると、ニッケル分が酸化物態に転換されがた
く、600℃を超えると担体と複合酸化物を形成するため
好ましくない。なおこの工程で、ニッケルの一部がアル
ミネート化するが、その割合は極めて小さい。After this baking treatment, the step of carrying nickel, molybdenum, tungsten or the like and baking at 300 to 600 ° C. is performed in the same manner as in the related art. For supporting nickel, tungsten, molybdenum, etc., for example, the carrier after the calcination treatment is immersed in an aqueous solution of nickel nitrate, ammonium molybdate, ammonium tungstate, etc., dried, and then calcined at 300 to 600 ° C. in air. I just need. Firing temperature is 300 ℃
If it is less than the above, it is difficult to convert the nickel component to an oxide state, and if it exceeds 600 ° C., a composite oxide is formed with the carrier, which is not preferable. In this step, a part of nickel is aluminate, but the ratio is extremely small.
次に、本発明を実施例により具体的に説明する。 Next, the present invention will be specifically described with reference to examples.
実施例 市販のγ−アルミナ円筒型押出成形態100gに、硝酸コ
バルト17.1g（酸化コバルト換算で4.17gのもの）を水に
溶解して調製した含浸液84mlを含浸し、100℃で16時間
乾燥した後、1,000℃で２時間焼成して担体を得た。こ
の担体100gに、硝酸ニッケル45.6g（酸化ニッケル換算
で11.1gのもの）及び水から調製した含浸液84mlを含浸
し、100℃で16時間乾燥した後、500℃で２時間焼成して
酸化物換算で酸化ニッケル10重量％、酸化コバルト４重
量％、残部がアルミナの組成を有する触媒を得た。Example 100 g of a commercially available γ-alumina cylindrical extruded form was impregnated with 84 ml of an impregnating liquid prepared by dissolving 17.1 g of cobalt nitrate (4.17 g in terms of cobalt oxide) in water, and dried at 100 ° C. for 16 hours. After that, the mixture was calcined at 1,000 ° C. for 2 hours to obtain a carrier. 100 g of the carrier is impregnated with 45.6 g of nickel nitrate (11.1 g in terms of nickel oxide) and 84 ml of an impregnating liquid prepared from water, dried at 100 ° C. for 16 hours, and calcined at 500 ° C. for 2 hours to obtain an oxide. A catalyst having a composition of 10% by weight of nickel oxide, 4% by weight of cobalt oxide and the balance being alumina was obtained.
得られた触媒のアルミナ分をＸ線解折により分析した
ところ、次の組成からなることがわかった。When the alumina content of the obtained catalyst was analyzed by X-ray diffraction, it was found that the catalyst had the following composition.
δ−アルミナ 10重量％ θ−アルミナ 80重量％ また、触媒中のコバルトを光電子分光法により測定し
たところ、次の結果が得られた。δ-alumina 10% by weight θ-alumina 80% by weight Further, when the cobalt in the catalyst was measured by photoelectron spectroscopy, the following results were obtained.
I782／I777＝2.8 比較例１ 市販のγ−アルミナ円筒型押出成形体を1,000℃で２
時間焼成して得られた担体100gに、硝酸コバルト19.1g
および硝酸ニッケル47.7gを水に溶解して調製した含浸
液84mlを含浸し、100℃で16時間乾燥した後、600℃で２
時間焼成して酸化ニッケル10重量％、酸化コバルト４重
量％、残部がアルミナである触媒を得た。I 782 / I 777 = 2.8 Comparative Example 1 A commercially available γ-alumina cylindrical extruded product was prepared at 1,000 ° C.
To the carrier 100 g obtained by firing for 1 hour, cobalt nitrate 19.1 g
And 84 ml of an impregnating solution prepared by dissolving 47.7 g of nickel nitrate in water, dried at 100 ° C for 16 hours, and then dried at 600 ° C for 2 hours.
After calcining for 10 hours, a catalyst was obtained in which nickel oxide was 10% by weight, cobalt oxide was 4% by weight, and the balance was alumina.
比較例２ 市販のγ−アルミナ円筒型押出成形体100gに硝酸コバ
ルト19.1gおよび硝酸ニッケル47.7gを水に溶解して調製
した含浸液84mlを含浸し、100℃で16時間乾燥した後500
℃で２時間焼成して、酸化ニッケル10重量％、酸化コバ
ルト４重量％、残部がアルミナである触媒を得た。Comparative Example 2 A commercially available γ-alumina cylindrical extruded product (100 g) was impregnated with 84 ml of an impregnating solution prepared by dissolving 19.1 g of cobalt nitrate and 47.7 g of nickel nitrate in water, and dried at 100 ° C. for 16 hours.
The mixture was calcined at 2 ° C. for 2 hours to obtain a catalyst containing 10% by weight of nickel oxide, 4% by weight of cobalt oxide, and the balance being alumina.
水素化活性の評価 実施例、比較例で調製した触媒を、下記の条件で予備
硫化に供した後、水素化活性を評価した。Evaluation of hydrogenation activity After the catalysts prepared in Examples and Comparative Examples were subjected to preliminary sulfurization under the following conditions, the hydrogenation activity was evaluated.
（１） 予備硫化 容量10mlの反応管に触媒1.5gを充填し、H2Sを５容量
％含有するH2S／H2混合ガスを、流量100ml/min、温度40
0℃、圧力70kg/cm2の条件で２時間流通させた。(1) Preliminary sulfurization A reaction tube having a capacity of 10 ml was filled with 1.5 g of the catalyst, and a mixed gas of H 2 S / H 2 containing 5% by volume of H 2 S was supplied at a flow rate of 100 ml / min and a temperature of 40 ml.
The mixture was allowed to flow at 0 ° C. and a pressure of 70 kg / cm 2 for 2 hours.
（２） 水素化活性の測定 内容量50mlのマイクロオートクレーブ内に、予備硫化
処理を施した触媒0.5gと、１−メチルナフタレン10mlを
仕込み、さらに水素ガスを初圧70kg/cm2で導入し、400
℃に１時間保持した。その後、１−メチルテトラリンお
よび５−メチルテトラリンの生成量をガスクロマトグラ
フィーで測定し、１−メチルナフタレンの転化率から触
媒の水素化活性を求めた。(2) Measurement of hydrogenation activity In a micro autoclave having a content of 50 ml, 0.5 g of the presulfurized catalyst and 10 ml of 1-methylnaphthalene were charged, and hydrogen gas was introduced at an initial pressure of 70 kg / cm 2 . 400
C. for 1 hour. Thereafter, the production amounts of 1-methyltetralin and 5-methyltetralin were measured by gas chromatography, and the hydrogenation activity of the catalyst was determined from the conversion of 1-methylnaphthalene.
結果を次表に示す。触媒 水素化活性 実施例 21.3％ 比較例１ 12.7％ 比較例２ 8.1％ 〔発明の効果〕 本発明の水素化処理触媒は、活性金属として担持され
ているニッケル、モリブデン、タングステン、特にニッ
ケルのアルミネート化が抑制され、酸化物質の形で担持
されている。そのため、水素化処理前に施される予備硫
化工程においてほとんどすべてのニッケル分が活性化さ
れるので、従来の水素化処理用ニッケル・モリブデン系
あるいはニッケル・タングステン系触媒に比しより高い
活性を示す。The results are shown in the following table. Example of catalytic hydrogenation activity 21.3% Comparative example 1 12.7% Comparative example 2 8.1% [Effect of the Invention] The hydrotreating catalyst of the present invention is nickel, molybdenum, tungsten supported as an active metal, particularly nickel aluminate. Oxidization is suppressed, and is carried in the form of an oxidized substance. For this reason, almost all nickel components are activated in the pre-sulfurization step performed before the hydrogenation treatment, so that they exhibit higher activity than the conventional nickel-molybdenum-based or nickel-tungsten-based catalysts for hydrogenation. .
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ１０Ｇ 45/48 9547−4Ｈ Ｃ１０Ｇ 45/48 (72)発明者 葭村 雄二 茨城県つくば市東１丁目１番地 工業技 術院化学技術研究所内 (72)発明者 島田 広道 茨城県つくば市東１丁目１番地 工業技 術院化学技術研究所内 (72)発明者 松林 信行 茨城県つくば市東１丁目１番地 工業技 術院化学技術研究所内 審査官 新居田 知生──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical indication location // C10G 45/48 9547-4H C10G 45/48 (72) Inventor Yuji Yoshimura East of Tsukuba City, Ibaraki Prefecture 1-1 chome, Institute of Chemical Technology, Industrial Technology Institute (72) Inventor Hiromichi Shimada 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Tomio Niida, Examiner, Chemical Technology Research Institute, Industrial Technology Institute
Claims (2)
の少なくとも１種を10重量％以上含有するアルミナ ……20〜95重量％、 （ｂ） コバルトアルミネート ……コバルト含有量がCoO換算で１〜20重量％であり、
そのうち前記コバルトアルミネートとしての含有量が光
電子分光法により測定される782eVにおけるピーク強度
（I782）と777eVにおけるピーク強度（I777）との関係
が I782／I777≧1.0 となる量、 および （ｃ） 酸化ニッケル、酸化モリブデンおよび酸化タン
グステンから選ばれる少なくとも１種 ……１重量％以上 を含有してなる水素化処理触媒。(1) Alumina containing at least one of δ-alumina and θ-alumina in an amount of 10% by weight or more: 20 to 95% by weight; (b) Cobalt aluminate: The cobalt content is calculated as CoO. 1 to 20% by weight,
Wherein the content of the cobalt aluminate is such that the relationship between the peak intensity at 782 eV (I 782 ) measured by photoelectron spectroscopy (I 782 ) and the peak intensity at 777 eV (I 777 ) is I 782 / I 777 ≧ 1.0, and (C) A hydrotreating catalyst comprising at least one selected from nickel oxide, molybdenum oxide and tungsten oxide: 1% by weight or more.
せ、次に、該担体を600〜1,100℃で焼成し、次に、該担
体に、ニッケル塩、酸化モリブデンおよび酸化タングス
テンから選ばれる少なくとも１種を担持させた後300〜6
00℃で焼成することからなる特許請求の範囲第１項記載
の水素化処理触媒の製造方法。2. A γ-alumina carrier, on which a cobalt salt is supported, the carrier is calcined at 600 to 1,100 ° C., and then the carrier is provided with at least one selected from a nickel salt, molybdenum oxide and tungsten oxide. 300 ~ 6 after supporting seed
The method for producing a hydrotreating catalyst according to claim 1, wherein the method is calcined at 00 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63218197A JP2580278B2 (en) | 1988-08-31 | 1988-08-31 | Hydrotreating catalyst and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63218197A JP2580278B2 (en) | 1988-08-31 | 1988-08-31 | Hydrotreating catalyst and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0268142A JPH0268142A (en) | 1990-03-07 |
| JP2580278B2 true JP2580278B2 (en) | 1997-02-12 |
Family
ID=16716137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63218197A Expired - Lifetime JP2580278B2 (en) | 1988-08-31 | 1988-08-31 | Hydrotreating catalyst and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP2580278B2 (en) |
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|---|---|---|---|---|
| US7253136B2 (en) * | 2003-04-11 | 2007-08-07 | Exxonmobile Research And Engineering Company | Preparation of titania and cobalt aluminate catalyst supports and their use in Fischer-Tropsch synthesis |
| CN110368947A (en) * | 2019-08-09 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of preparation method of dimethyl maleate hydrogenation catalyst |
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1988
- 1988-08-31 JP JP63218197A patent/JP2580278B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH0268142A (en) | 1990-03-07 |
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