JPH04166232A - Production of catalyst for hydrogenation treatment - Google Patents

Abstract

PURPOSE:To obtain a catalyst for hydrogenation treatment having extremely high activity by depositing metals of group VI and group VIII on a catalyst carrier comprising a porous material, and adding a polyhydric alcohol to form a complex compd. of active metal. CONSTITUTION:A porous material such as alumina, silica, titania, zirconia, activated carbon is used as a catalyst carrier, on which metals of group VI (Mo or/and W) and group VIII (Co or/and Ni) are deposited as the active metal. Or, metals of group VI and group VIII and phorphorus are deposited. To the catalyst deposited, a polyhydric alcohol (ethyleneglycol, diethyleneglycol, triethyleneglycol, glycerine, 2,2-diethyl-1,3-propyleneglycol, etc.) is added by 0.3-5.0 times moles to the total mole of the active metal in the catalyst. Then the catalyst is dried at <=200 deg.C. By this method, the obtd. catalyst has extremely high activity and enables high-level hydrogenation treatment such as deep desulfurization of hydrocarbon oils.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a catalyst for hydrotreating hydrocarbon oil.

[Prior Art] Porous catalyst carriers such as alumina, titanium, silica, and activated carbon are used as catalysts used in hydroprocessing to hydrogenate, desulfurize, denitrify, and decompose hydrocarbon oils. Catalysts are used in which metals and Group VIII metals are supported as active metals. Generally, Mo and W are used for the 6th Flh metal and 1-1, and Ni and Co are used for the 8th group metal, but these active metals are supported in the form of oxides on the catalyst carrier. Shows no activity. Therefore, it is used as a catalyst in a sulfurized state after being subjected to an appropriate pre-sulfurization treatment.

By the way, in a hydrotreating catalyst, the active sites of the catalyst are formed on the surface of the active metal sulfide. Therefore, it is known that as the surface area of the metal sulfide increases, the number of active sites increases, resulting in a highly active catalyst. In order to increase the surface area of the sulfide, attempts have been made to make the metal sulfide fine and highly dispersed, and various methods have been disclosed. For example, JP 59-102442.59-69
No. 147 discloses a method in which a catalyst carrier such as alumina is impregnated with a mixed solution of a carboxylic acid such as citric acid or malic acid and an active metal, and then dried and calcined. These manufacturing methods aim to prevent active metal agglomeration by forming complex ions with active metals and carboxylic acids and supporting them, but in all methods, impregnation is performed at the final stage. However, because it is roasted, sufficient results are not always obtained.

[Problems to be Solved by the Invention] Recently, EP 0181035 (A2) discloses the use of nitrogen-containing organic compounds such as nidosoloacetic acid, ethylenediaminetetraacetic acid, and diethylenetriamine as complexing agents, and the interaction between these complexing agents and active metals. A method was disclosed in which a mixed solution is impregnated into an alumina carrier or a silica carrier, and then dried at 200° C. or lower without roasting. It is true that the activity of the catalyst produced by this method is higher than that of conventional products. However, according to a recently submitted report, it is required to reduce the sulfur content in diesel oil to 0.05% by weight or less due to stricter exhaust gas regulations. In order to meet this requirement, the above EP O]
The catalyst manufactured by the method disclosed in Publication No. 81035 (A2) is not sufficient, and since the complexing agent used in this method contains nitrogen, harmful gases such as hydrogen cyanide are generated during the pre-sulfurization treatment. The problem is that there is a strong possibility that

An object of the present invention is to provide a method for producing a highly active hydrotreating catalyst that does not have the above-mentioned drawbacks.

[Means for Solving the Problems] The method of the present invention for solving the above problems is based on a catalyst in which a metal of group 6 and a metal of group 8 of the periodic table are supported as active metals on a catalyst carrier, or After adding polyhydric alcohol in an amount of 03 to 50 times the total number of moles of active metals in the catalyst to a catalyst supporting a Group 6 metal, a Group 8 metal, and phosphorus in the rate table, the temperature was increased to 200°C. It is dried under
Preferably, after the catalyst carrier is impregnated with a solution containing a metal from group 6 and a metal from group 8 of the periodic table, or after the catalyst carrier contains a metal from group 6 and a metal from group 8 of the periodic table and also contains phosphorus. After impregnating with the solution, the impregnated product is dried at 200° C. or less to obtain a catalyst, and the amount of the impregnated product is 0.5% based on the total number of moles of active metal in the catalyst.
After adding 3 to 5.0 times the molar amount of polyhydric alcohol, 2
It is dried at temperatures below 00°C.

Examples of polyhydric alcohols that can be used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, glycerin, 2,2-diethyl-1,3-propylene glycol, butanediol, and the like.

[Function] The catalyst used in the present invention uses a porous material such as alumina, silica, titania, zirconia, activated carbon, etc. as a catalyst carrier, and metals from Group 6 and Group 8 of the periodic table as active metals. or one in which a group 6 metal of the periodic table, a group 8 metal, and phosphorus are supported. MO and/or W is used as the 6th group metal, and Co and/or Ni is used as the 8th group metal. The supported amount of each active metal is the value generally adopted as a catalyst for hydrotreating, that is, the amount of Group 6 metal supported as an oxide is 5 to 5.
It is preferable that the amount is 30% by weight, and the Group 8 metal is preferably 1 to 8% by weight as an oxide.

When supporting these metals, for example, molybdenum oxide and cobalt carbonate are suspended in water and then boiled to dissolve and impregnate them, but the impregnated material is dried at 2000C or less to prevent agglomeration of the active metals. It is preferable to do so.

In addition, phosphorus seems to act as a stabilizer during impregnation with active metals, further improving the activity. Therefore, phosphorus is P, 0. It is preferable that the phosphoric acid is mixed to contain 0.1 to 8% by weight, and various phosphoric acids such as orthophosphoric acid can be used as the phosphorus source.

In the hydrogenation catalyst of the present invention, the active metal forms a complex compound with the polyhydric alcohol, and is stably supported on the catalyst carrier. It is not clear why selecting a polyhydric alcohol as a complexing agent results in higher activity than when using the nitrogen-containing organic compound as a complexing agent. The present inventor discovered that basic compounds such as ammonia and amines generated by decomposition of nitrogen-containing organic compounds during presulfurization are not completely removed by the catalyst.
It is assumed that this is because the active sites are poisoned by these basic compounds, and because the active metal surface area of the catalyst produced by the method of the present invention is extremely large, the stability and decomposition behavior of the complex compound formed are affected. It is presumed that this prevents agglomeration during pre-sulfurization of active metals.

The reason why the drying temperature of the catalyst of the present invention is set to 200° C. or lower is to prevent the polyhydric alcohol, which is a complexing agent, from decomposing or volatilizing. Addition amount in moles is 0.3 of the total mole amount of active metal.
The reason why the amount should be ~5.0 times is that if it is less than 0.3 times, the active metal cannot be sufficiently complexed, and if it exceeds 5.0 times, the complexing agent will not be completely decomposed and removed during pre-sulfurization, and the carbon content will be reduced. This is because it precipitates on active metals and interferes with sulfidation, reducing activity.

[Example-1] Specific surface area 280 m2/g, pore volume 0°75 m1
7 g of γ-alumina support I Kg of molybdenum trioxide
Active metal aqueous solution 8 prepared from 193 g, cobalt carbonate 82 g, 85% phosphoric acid 61.5 g and water
00 ml was impregnated and dried at 110° C. for 10 hours. This process was repeated to obtain the required amount of dried material. Next, 250 g of the dried material was impregnated with the complexing agent shown in Table 1 according to the impregnation amount shown in the same table, and dried at 110°C for 10 hours. ,,E
SFSG, , H and catalysts ISJ, K, and L prepared by the method disclosed in EP 0181035 (A2) were prepared. Note that the amount of impregnation in Table 1 is the amount of MO contained in the catalyst.
It is a multiple of the total number of moles of Co and Co, and when this value is 1, it means that the same mole amount is impregnated.

Catalyst A, BSC, D, E, F, G, H, ISJ.

The Mo content of both K and L is 15% by weight as MoOa, the Co content of both is 4% by weight as CoO, and the P content of both is P2O.

The total content was 3% by weight.

These catalysts A, B, C, DSE, F, G, , H, I, J,
A hydrodesulfurization test was conducted on claate atmospheric gas oil having the following properties using L under the following conditions.

(Properties of Kraate atmospheric gas oil) Specific gravity (1574℃) 0.844 Sulfur (%
) 1.55 Distillation properties (initial boiling point)
C) 231 (50 Vo1% °C) 313 (End point °C) 3.90 (Test conditions) Catalyst amount (ml) 15 Raw material oil liquid hourly space velocity ()lr-') 2 Reaction hydrogen pressure (Kg/a
m″G) 30 Reaction degree (″C) 330 Hydrogen/oil flow rate ratio (Nl/1) 300 Oil passage time (hr)
88 The obtained hydrodesulfurization activity is expressed as a relative value of the reaction rate constant, and the rate constant was calculated assuming that the deflow reaction rate is proportional to the 1.75th power of the sulfur concentration of the atmospheric gas oil as the raw material. A conventional catalyst was used as a reference, and its rate constant was set to 100.

The obtained results are also shown in Table 1.

(Hereinafter in the margin of this page) Table 1 From Table 1, the activity of the catalyst prepared by the method of the present invention is as follows:
EP 0 is said to have the highest activity among conventional catalysts.
It can be seen that this is extremely high compared to catalysts ①, JSK, and L prepared by the method disclosed in Publication No. 181035 (A2).

[Example 21 200 g of pseudo-boehmite alumina carrier (A120.92.8% by weight), 357 g of molybdenum trioxide, 15.23 g of cobalt carbonate, 85% phosphoric acid 11.
150 ml of active metal aqueous solution prepared from 4 g and water
was impregnated with water and dried at 110°C for 5 hours. next,
100 g of the dried material was impregnated with diethylene glycol (catalyst M) and glycerin (catalyst N) according to the impregnation amounts shown in Table 1, and dried at 110° C. for 10 hours to obtain catalysts M and N according to the method of the present invention.

The Mo content of both catalysts M and N is 1 as MoOs.
5% by weight, and the Co content is Co.

The P content is 4% by weight as P2O,
It was 3% by weight.

A hydrodesulfurization test was conducted using this catalyst MSN in the same manner as in Example-1. The obtained results are also shown in Table 1.

From Table 1, catalysts M and N are also catalyst 1. It can be seen that the activity of J and L is significantly higher than that of L.

[Example-3] Silica-alumina carrier (10% by weight as SiO□, specific surface area 325 m2/g, pore volume 0.69 ml/
g) Impregnate 200 g with 160 ml of an active metal aqueous solution prepared from 38.5 g of molybdenum trioxide, 16.2 g of nickel carbonate, 12.3 g of 85% phosphoric acid, and water,
It was dried at 10° C. for 5 hours. Next, the dried product 100
g was impregnated with diethylene glycol (catalyst O) according to the impregnation amount shown in Table 1, and dried at 110° C. for 10 hours to obtain catalyst O according to the method of the present invention.

The Mo content of the catalyst O is Mo0. The content of Co was 4% by weight as Coo, and the content of P was 3% by weight as P2O.

Using this catalyst 0, a hydrodesulfurization test was conducted in the same manner as in Example-1. The obtained results are also shown in Table 1.

From Table 1, catalyst O and catalyst 1. It can be seen that the activity of J and L is significantly higher than that of L.

From the above, it can be seen that the activity of the catalyst prepared by the method of the present invention is extremely high, and among them, one impregnated with diethylene glycol is more preferable.

[Effects of the Invention] The activity of the catalyst produced by the method of the present invention is extremely high, and as a result, advanced hydroprocessing such as deep desulfurization and denitrification of hydrocarbon oil becomes possible.

Patent applicant: Sumitomo Metal Mining Co., Ltd.

Claims (4)

[Claims] (1) A catalyst in which group 6 metals and group 8 metals of the periodic table are supported as active metals on a catalyst carrier, 0.3 to 5.0 times the total number of moles of active metals in the catalyst. A method for producing a hydrogenation catalyst, which comprises adding a molar amount of polyhydric alcohol and then drying at 200°C or lower. (2) A catalyst in which Group 6 metals, Group 8 metals, and phosphorus are supported on a catalyst carrier, 0.3 to 5.0 times the mole of active metals in the catalyst. A method for producing a hydrotreating catalyst, which comprises adding a certain amount of polyhydric alcohol and then drying at 200°C or lower. (3) After impregnating a catalyst carrier with a solution containing metals from Group 6 and Group 8 of the periodic table, the impregnated product is dried at 200°C or less to obtain a catalyst, and the active metals in the catalyst are A method for producing a hydrogenation catalyst, which comprises adding polyhydric alcohol in an amount of 0.3 to 5.0 times the total number of moles, and then drying at 200°C or lower. (4) After impregnating the catalyst carrier with a solution containing Group 6 metals and Group 8 metals of the periodic table and containing phosphorus, the impregnated material is
After drying at 00°C or lower to obtain a catalyst, adding polyhydric alcohol in a molar amount of 0.3 to 5.0 times the total number of moles of active metals in the catalyst, drying at 200°C or lower. A method for producing a hydrotreating catalyst characterized by: