JPS60202738A - Catalyst for denitrifying hydrocarbonic oil by hydrogenation - Google Patents

Abstract

PURPOSE:To obtain the titled catalyst for hydrogenating and denitrifying hydrocarbonic oil having high activity and long service life by depositing a metal or the compd. of the metal selected from a group consisting of group VIa and VIIIelements in the periodic table on a carrier obtained by incorporating chromia into alumina and titania. CONSTITUTION:A carrier consisting of a composite oxide is prepared by adding 5-50wt% chromia, as the third component, to 20wt% alumina and 5-50wt% titania or 20wt% alumina and 5-50wt% zirconia. And >=1 kind of metal (e.g., Mo and Ni) or the compd. of the metal selected from a group consisting of group VIa or VIII elements in the periodic table is deposited on the carrier. The catalyst is effective for the denitrification by hudrogenation and the hydrodesulfurization of hydrocarbonic oil. The catalyst exhibits an excellent effect on the hydrogenation treatment of hydrocarbonic oil such as shale oil contg. a high content of nitrogen.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a hydrotreating catalyst for effectively removing all formula compounds and sulfur compounds contained in hydrocarbon oil.

[Background of the invention]

Hydrocarbon oils such as petroleum crude oil, rock oil, liquefied coal oil, and tar sant bitumen contain large amounts of impurities such as nitrogen and sulfur compounds. In particular, rock oil contains a larger amount of nitrogen compounds than petroleum-based crude oil, and the nitrogen content is known to be as high as 1 to 2% by weight. Nitrogen compounds generally contained in hydrocarbon oils include basic nitrogen compounds such as pyridines, quinolines, amines and amides, and weakly acidic nitrogen compounds such as virols and indoles. If hydrocarbon oil containing these nitrogen compounds is used as fuel oil, it will cause air pollution.
LTtUnfavorable in terms of environmental hygiene. In addition, nitrogen compounds completely reduce the hue, stability, etc. of the product hydrocarbon oil and cause the formation of sludge and the like. On the other hand, when such hydrocarbon oils are subjected to catalytic cracking or catalytic reforming, nitrogen compounds also cause a significant reduction in the activity of the catalyst.

Conventionally, in order to remove nitrogen compounds and sulfur compounds from hydrocarbon oil, a method of hydrotreating hydrocarbon oil at high temperature and high pressure in the presence of hydrogen is widely known. It is also known that nitrogen compounds in hydrocarbon oil have extremely low reactivity compared to coexisting sulfur compounds. Therefore, many researchers are conducting research and making several proposals to develop denitrification catalysts with higher activity and longer life.

For example, in U.S. Patent No. 5.778.565, Y
- Catalysts consisting of zeolite and nickel-tungsten, nickel-molybdenum, or zinc-tungsten, etc., pretreated with ammonia are said to be effective for hydrodenitrogenation and hydrocracking of shale oil. -! U.S. Pat. No. 4,128,505 discloses a catalyst in which Via group metals and Vm group metals are supported on a titania-zirconia or titania-zirconia-alumina support to hydrodenitrogenate and desulfurize hydrocarbon oil. Proposed. US Pat. No. 4,159,492 states that a catalyst prepared by impregnating an alumina or alguna-silica support with a borohydrofluoric acid solution of Vta group and II group metals is effective for hydrodenitrogenation. U.S. Patent No. 4,139.
No. 495 states that catalysts such as cobalt-molybdenum/silica-alumina or nickel-molybdenum/silica-alumina prepared by an ion conversion method are effective for the hydrodenitrogenation of hydrocarbon oils. Unexamined publication [56-
No. 1, No. 0452 proposes a catalyst in which Vta group and Vl group metals and phosphorus or boron are supported on titanium oxide as a hydrodenitrification catalyst for hydrocarbon oil.

However, although all of these catalysts have been devised to effectively remove nitrogen compounds from hydrocarbon oil, they are still not sufficient.

[Structure of the invention]

The present inventors have conducted extensive research to develop a catalyst for hydrotreating hydrocarbon oil that has excellent hydrodesulfurization activity in addition to hydrodesulfurization activity, and as a result, has arrived at the present invention.

In the present invention, at least one metal selected from the group consisting of Group Vla and Group III of the periodic table or a compound thereof is supported on a composite oxide in which chromia is completely added as a third component to alumina-titania or alumina-zirconia. It is a catalyst for hydrodenitrification of hydrocarbon oil. In this case, the metals of Group Via and Group II of the periodic table used as supported metals include chromium, molybdenum, tungsten, iron, cobalt, nickel, ruthenium, rhodium, palladium, osminium,
Iridium and platinum, particularly preferably nickel-molybdenum, nickel-tungsten or nickel-molybdenum.
This is a combination of Kono(rutho) and molybdenum. There are no particular restrictions on the method of supporting these metals, and any known method such as impregnation or spraying can be used.

The composite oxide used in the present invention can be prepared by a commonly used coprecipitation method or gel mixing method. That is, the respective metal salts (e.g. aluminum nitrate, chromium nitrate,
Aqueous ammonia is added to a mixed aqueous solution of zirconyl nitrate, titanium chloride, etc.) and hydrolyzed to obtain a coprecipitated substance. Hydrogels of each metal are prepared in advance by a known method such as a coprecipitation method, a homogeneous precipitation method, an unrestricted precipitation method, etc. A gel mixing method is employed in which each hydrogel is prepared separately and then these hydrogels are kneaded. After adjusting the moisture content, the coprecipitate or mixed substance obtained by the above method is molded into a desired shape by any method such as transfer granulation, compression molding, extrusion molding, etc., dried, and then heated at 400 to 600 °C. Calcinate at a temperature of 2 to 5 hours and serve as a carrier.

The catalyst according to the present invention is effective for hydrodenitrogenation and hydrodesulfurization of hydrocarbon oil. %, it exhibits excellent effects in the hydrogenation treatment of hydrocarbon oils with high phoneme content, such as rock oil. Although the cause of this is not clear, it is presumed that the addition of chromia, the third component, modifies the active site of the F catalyst, resulting in high elimination element activity and its sustained action.

The catalyst can be used in a conventional reaction format such as fixed bed or moving bed. Hydrogenation conditions were as follows: temperature: 100 to 500°C, pressure: 10 to 300 kg/crn2, liquid hourly space velocity: 11 to 10 hr-'', and supply ratio of hydrogen to feedstock hydrocarbon: 1.
It is preferable to carry out within the range of 00 to 3000 Nt/l.

Next, a more detailed explanation will be given based on all examples of the present invention and comparative examples.

Comparative Example 1 A commercially available alumina carrier was impregnated with a predetermined amount of an ammonia water bath solution of nickel nitrate and ammonium paramolybdate, left to stand for 6 hours, and then dried at 120° C. for 4 hours. This 1
Catalyst A was obtained by calcining at 550°C for 5 hours.

Comparative Example 2 5% ammonia water was gradually added to a 10% aluminum nitrate aqueous solution and a 10% zirconyl nitrate aqueous solution at room temperature with complete stirring until the pH reached 9VC, and the precipitate was overwashed to obtain Vigor 4 alumina hydrogel and zirconia hydrogel. I got money. This alumina hydrogel and zirconia hydrogel on an anhydrous oxide basis are 90:10i1? : After adjusting the moisture content and kneading well with a kneader,
It was molded into a cylindrical shape of 1.6 mφ using an extrusion molding machine.

This molded body was dried at 120° C. for 2 hours and further calcined at 550° C. for 3 hours to obtain an alumina-zirconia support. A predetermined amount of nickel and molybdenum was supported on this carrier by the same impregnation method as in Comparative Example 1 to obtain catalyst Bi.

Comparative Example 6 5 tons of ammonia water was gradually added to 1 ton of ice-cooled 10% titanium chloride water bath solution, hydrolyzed with stirring, and washed with precipitation to obtain a titania hydrogel. This titania hydrogel was mixed with alumina hydrogel obtained in the same manner as in Comparative Example 2 at a ratio of 10:90 based on anhydrous oxide. For the subsequent preparations, the same operations as in Comparative Example 2 were repeated to obtain catalyst C.

Example 1 Add 6 of gold to 4 tons of 1.5 t of chromium nitrate aqueous solution,
The entire chromia hydrogel was obtained by hydrolysis. This chromia hydrogel, alumina hydrogel and zirconia hydrogel obtained in the same manner as in Comparative Example 2, and a total anhydrous oxide base of 1
Mix the hydrogel mixture at a ratio of 0:80:10 to 1#'fc. The subsequent catalyst preparation was carried out in the same manner as in Comparative Example 2 to obtain Catalyst #D.

Example 2 The alumina hydrogel and zirconia hydrogel obtained in Comparative Example 2 were mixed with the chromia hydrogel obtained in Example 1 in a ratio of 70:10:20 based on anhydrous oxide.

This hydrogel mixture was subjected to all the same operations as in Comparative Example 2,
Catalyst E was obtained.

Example 6 Alumina hydrogel, titania hydrogel, and chromia hydrogel obtained in Comparative Example 2, Comparative Example 3, and Example 1 were mixed in a ratio of 80:10:10 based on total anhydrous oxide. This hydrogel mixture was subjected to all the same operations as in Comparative Example 2 to obtain catalyst F.

Example 4 The alumina hydrogel, titania hydrogel and chromia hydrogel obtained in Comparative Example 2, Comparative Example 6 and Example 1 were mixed into Process 9 in a ratio of 70:ID:20 based on anhydrous oxide. This hydrogel mixture was subjected to the same operation as in Comparative Example 2 to obtain a catalyst Gi.

Example 5 The compositions, specific surface areas, and pore volumes of the catalysts prepared in Comparative Examples 1 to 3 and Examples 1 to 4 are all shown in Table 1. Three types of catalysts of comparative examples (A, B, 0) and four types of catalysts of examples (D,
E, F, G), each catalyst was packed in a fixed bed flow reactor at 50% capacity, pre-sulfurized the catalyst, and then processed under the reaction conditions shown in Table 2 with the properties shown in Table 5. A hydrotreatment experiment was conducted on produced rock oil, and the produced oil was collected and analyzed 50 hours after the start of oil flow. As a result't-
Shown in Table 1. Among the catalysts of the ternary composite oxide carrier containing chromia, the catalyst (D) of Example 1 was different from the catalyst C of Comparative Example 2.
It is clearly more active than B). Further, in Example 2, the chromia ratio was increased compared to Example 1, but the denitrification rate remained unchanged.

Claims (1)

[Scope of Claims] 1. On a carrier called V, which is a composite oxide prepared by adding chromia as a third component to alumina-titania or alumina-zirconia, a group Vla group of the periodic table and a group KVI group P of the periodic table are prepared.
A hydrodenitrifying agent catalyst for hydrocarbon oil, which supports at least one metal selected from the group consisting of: 2. The composite oxide is at least 20% alumina by weight,
Catalyst according to claim 1, comprising from 5 to 50% by weight of titania and from 5 to 50% by weight of chromia. (v) alumina containing at least 20% by weight of the composite oxide;
Catalyst according to claim 1, comprising 5 to 50% by weight of zirconia and 5 to 50% by weight of chromia. 4. The catalyst according to claim 1, 2 or 6, wherein the supported metal is at least one metal selected from the group consisting of molybdenum, tungsten, cobalt and nickel.