JPH04247239A - Production of catalyst for hydrogenation treatment of hydrocarbon oil - Google Patents

Abstract

PURPOSE:To offer the production of presulfide-type hydrogenation treatment catalyst which has high activity at least almost equal to that of a presulfide type hydrogenation treatment catalyst using mercaptocarboxylic acid, and moreover, produces no corrosive material when heated for activation. CONSTITUTION:A catalyst carrier essentially comprising one or both of inorg. oxide and its hydrate is used. To this carrier, group VI metal by 5-30wt.% in terms of oxide, group VIII metal by 1-8wt.% in terms of oxide, and phosphoric acid by 1-8wt.% as P2O5 are deposited as the active metal. Also, there are added carboxylic acid such as citric acid, tartaric acid, etc., by the amt. 0.05-3.5 times as the total mol. number of the active metal, and beta-thioglycol by 0.3-2.5 times as the amt. required to make sulfide of the active metal. After these components are added, kneaded and molded, the molded body is dried at <=200 deg.C to obtain the catalyst. Thus, the presulfide-type hydrogenation treatment catalyst can easily be obtd. which can be used for high-level hydrogenation treatment such as desulfurization and denitrification.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a catalyst for hydrotreating hydrocarbon oil, which can perform high-level desulfurization and denitrification of hydrocarbon oil.

0002

[Prior Art] Porous catalyst carriers such as alumina, titania, silica, and activated carbon are used as catalysts for hydrogenation, desulfurization, denitrification, decomposition, etc. of hydrocarbon oil. Catalysts are used in which group 6 and group 8 metals are supported as active metals. Generally, molybdenum and tungsten are used as Group 6 metals, and nickel and cobalt are used as Group 8 metals, but these active metals are supported in the form of oxides on catalyst carriers. The activity is low because it is Therefore, when used as a catalyst, it is necessary to perform an appropriate preliminary sulfurization treatment to convert it into a sulfide form. As a pre-sulfiding treatment method for this purpose, a conventional hydrotreating equipment is filled with an oxide catalyst to form a catalyst layer, and hydrocarbon oil with a sulfurizing agent dissolved in this catalyst layer is placed in the presence of hydrogen. The so-called on-site sulfurization method, in which sulfur is sulfurized to a sulfide form by raising the temperature and passing through the sulfide, is generally widely used. However, in this on-site sulfiding method, the pre-sulfiding operation determines the success or failure of the subsequent hydrotreating process, so appropriate selection of materials 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. Highly viscous hydrocarbon oils such as oil are unsuitable because they have poor wettability to the catalyst surface. Furthermore, when the active metal component reacts with hydrogen at high temperatures and is reduced, it becomes passivated and the catalyst activity decreases, so it is necessary to use an excessive amount of the sulfiding agent. As described above, in the on-site sulfurization method, the preliminary sulfurization treatment is extremely complicated and requires careful operation in all respects. Therefore, it is desired to omit or at least simplify this presulfiding step, and various methods have been proposed.

One method is to add a sulfiding agent to a sulfide-form hydrotreating catalyst in advance to make the active metal into a sulfide or sulfide precursor, and fill this into a hydrotreating apparatus to form a catalyst layer. A so-called off-site sulfurization method has been proposed in which hydrocarbons are passed through this in the presence of hydrogen and heated. The hydrotreating catalyst used in this off-site sulfidation process is characterized by the fact that the required amount of sulfur is already supported in the catalyst matrix. is not required for off-site sulfidation methods.

As the sulfurizing agent used in this off-site sulfurizing method, for example, US Pat. No. 4,636,487 discloses mercapto alcohols, and US Pat. No. 4,7255 discloses mercapto alcohols.
No. 71 contains dialkyl polysulfide (general formula R-
S(n)-R) is disclosed, and JP-A-2-90948 discloses dithiocarbamic acid, dimercaptothiadiazole, thiourea, ammonium thiocyanate, dimethyl sulfoxide, dothiaadipic acid, and dithiodiethanol.

[0005] However, in recent years, there has been a movement toward stricter exhaust gas regulations, and there has been a demand for further reductions in the sulfur content in fuel oil. As a result, there has been a demand for catalysts that not only enable the omission or simplification of pre-sulfurization treatment, but also have higher activity than conventional catalysts. The off-site catalysts described above are not necessarily sufficient to meet this requirement. This is because, although these catalysts do not require pre-sulfurization treatment, their activity is not much different from conventional products, and the sulfurizing agents used are all expensive, leading to high costs.

[0006] In order to meet the above requirements, the present applicant has previously disclosed a pre-sulfurization type hydrotreating catalyst using mercaptocarboxylic acid and a method for producing the same (Japanese Patent Application No. 1992-3).
No. 02240 and Japanese Patent Application No. 1-302241).

[0007]

[Problems to be Solved by the Invention] However, catalysts using mercaptocarboxylic acids as sulfiding agents decompose during activation at elevated temperatures and generate corrosive carboxylic acids.
This poses a problem in that it corrodes and deteriorates the device material, resulting in a major practical drawback.

[0008] The present invention provides a pre-sulfiding hydrogenation catalyst which has at least as high activity as a pre-sulfiding hydrogenation catalyst using mercaptocarboxylic acid and which does not generate corrosive substances upon activation at elevated temperatures. The object of the present invention is to provide a method for producing a treated catalyst.

[0009]

[Means for Solving the Problems] As a result of repeated research in order to solve the above problems and achieve the above objects, the present inventors have discovered that instead of using mercaptocarboxylic acid, β-thiodiglycol is used as a catalyst carrier. After supporting, kneading and molding, 200℃
The present invention was completed by discovering that the object can be achieved by using a drying method as described below. That is,
In the present invention, an aqueous solution containing metal ions of Groups 6 and 8 of the periodic table, carboxylic acid and/or phosphoric acid, and β-thiodiglycol is added to a catalyst carrier, and the mixture is kneaded and shaped. , a method for producing a catalyst for hydrotreating hydrocarbon oil, which is dried at a temperature of 200° C. or lower.

[0010] As the catalyst carrier in the present invention, one whose main component is an oxide such as alumina, titania, silica, zirconia, etc. and/or a hydrate thereof can be used.

[0011] The active metal of Group 6 of the periodic table includes at least one of molybdenum and tungsten.
type, and the amount added is 5 to 5 as MoO3 or WO3.
The Group 8 metal is at least one of cobalt and nickel, and the amount added is 1 to 8% by weight as CoO or NiO.
Hold it so that it becomes

0012

[Operation] In the present invention, carboxylic acid and/or phosphoric acid are added, but this is because a small amount of active metal remains undissolved in the aqueous solution for impregnating an active metal. Mineral acids such as nitric acid, sulfuric acid, and hydrochloric acid can also be used, but these mineral acids generate corrosive substances when activating the catalyst. This is because it is undesirable because it may remain in the catalyst after activation and cause a decrease in activity. However,
Examples of the carboxylic acid include citric acid, tartaric acid, glycolic acid, malonic acid, gluconic acid, glyceric acid, and malic acid, and at least one of these is used. The amount added depends on the acidity of the acid, and the stronger the acidity, the smaller the amount needed, but it is 0.05 to 3.5 of the total number of moles of the active metal.
A double range is preferred. In addition, commercially available phosphoric acid can be used,
The amount added is preferably 1 to 8% by weight as P2O5 in the catalyst. The addition of these acids not only has the effect of dissolving the above-mentioned inert metal salts, but also can improve the catalytic activity by adding an optimum amount.

[0013] The reason why high activity is obtained when β-thiodiglycol is used is not clear, but in the pre-sulfurized hydrogen-treated catalyst obtained by the present invention, the active metal is supported in a highly dispersed state even after activation. This is believed to be due to the fact that it can be assumed that the number of hydrogenation active sites has increased significantly since this has been proven by X-ray diffraction, chemisorption experiments, BET specific surface area measurements, TEM observations, etc. The amount of β-thiodiglycol added is molybdenum,
MoS2, WS2, CoS, and Ni each have active metals such as tungsten, cobalt, and nickel.
0.3 to 2.5 of the amount necessary to form a sulfide such as S
It is preferable to double the amount. The reason why 0.3 times the amount is sufficient is that the sulfur content contained in the hydrocarbon oil used for activation helps in sulfurizing the active metal. Furthermore, if too much β-thiodiglycol is added, carbonaceous matter will precipitate during activation and remain in the catalyst, clogging the pores of the catalyst, making it impossible to develop sufficient activity.
Since this shortens the catalyst life, it is preferably 2.5 times or less.

[0014] These components are supported on a catalyst carrier, kneaded and molded, and then dried at 200°C or lower. this is,
This is because β-thiodiglycol decomposes when dried at a temperature of 200°C or higher, but the decomposition products of β-thiodiglycol generated upon activation of the catalyst obtained by the present invention are methane, ethane, etc. It is a lower hydrocarbon and ethanol and does not generate any corrosive substances such as carboxylic acid.

[0015]

[Example] Next, an example of the present invention will be described. Example 1 1000 g of alumina hydrate (water content 60% by weight), 124 g of molybdenum trioxide, 36 g of cobalt carbonate, 85%
400ml of an aqueous solution prepared from 27g of phosphoric acid, 36.6g of citric acid, 390g of β-thiodiglycol, and water
1 was added, the mixture was heated and kneaded at 80° C., and then molded into a 1.6 mm straight cylinder shape using an extrusion molding machine. Thereafter, the molded product was dried at 100° C. for 16 hours to obtain catalyst A.

The metal content of catalyst A is such that molybdenum is Mo
The amount of cobalt is 22% by weight in terms of O3, the amount of cobalt is 4% by weight in terms of CoO, and the amount of phosphorus is 3% by weight in terms of P2O5. The amount of β-thiodiglycol added is 1.5 times the amount required for molybdenum and cobalt to form MoS2 and CoS, respectively, and the amount of citric acid added is 0 times the amount of molybdenum and cobalt required to form MoS2 and CoS, respectively. .15 times.

Furthermore, the activity of the obtained catalyst was tested by hydrodesulfurization reaction of Kuwait atmospheric gas oil. The properties of the atmospheric gas oil used in the reaction were as follows.

Specific gravity (15/4°C)
0.844 Sulfur
Yellow (wt%)
1.55 Distillation properties (initial boiling point, °C)
231
(50vol%, °C) 313
(End point, °C)
The 390 reaction was carried out using a flow reactor under the following reaction conditions.

[0019] Catalyst amount (ml)
15 Raw material oil liquid space velocity (hr-1)
2 reaction hydrogen pressure (kg/c
m2G) 30 reaction temperature (℃)
330
Hydrogen/oil flow ratio (Nl/l)
300 oil passing time (hr)
88 Hydrodesulfurization activity shall be expressed as a relative value of the reaction rate constant calculated assuming that the desulfurization reaction rate is proportional to the 1.75th power of the sulfur concentration of the feedstock atmospheric gas oil,
Table 1 shows the relative reaction rate constant values calculated by setting the reaction rate constant of the catalyst obtained in Comparative Example 2 as 100. Example 2 Catalyst B was obtained in the same manner as in Example 1, except that the amount of β-thiodiglycol used was 182 g. The metal content of catalyst B is 22% by weight of molybdenum in terms of MoO3,
Cobalt is 4% by weight in terms of CoO, phosphorus is P2O5
The amount was 3% by weight. In addition, the amount of β-thiodiglycol added is as follows: molybdenum and cobalt are respectively MoS
2. The amount of citric acid added is 0.7 times the amount required to form CoS, and the amount of citric acid added is 0.1 times the total number of moles of molybdenum and cobalt.
It was 5 times more. Furthermore, an activity test was conducted in the same manner as in Example 1. The results are shown in Table 1. Example 3 Catalyst C was obtained in the same manner as in Example 1, except that the amount of β-thiodiglycol used was 130 g. The metal content of catalyst C is 22% by weight of molybdenum in terms of MoO3,
Cobalt is 4% by weight in terms of CoO, phosphorus is P2O5
The amount was 3% by weight. In addition, the amount of β-thiodiglycol added is as follows: molybdenum and cobalt are respectively MoS
2. The amount of citric acid added is 0.5 times the amount required to form CoS, and the amount of citric acid added is 0.1 times the total number of moles of molybdenum and cobalt.
It was 5 times more. Furthermore, an activity test was conducted in the same manner as in Example 1. The results are shown in Table 1. Example 4 1000 g of the alumina hydrate, 11 molybdenum trioxide
Catalyst D was obtained in the same manner as in Example 1, except that 9 g of nickel carbonate, 35 g of tartaric acid, and 125 g of β-thiodiglycol were used. The metal content of catalyst D is as follows: molybdenum is 22% by weight in terms of MoO3, and nickel is NiO3.
The amount was 4% by weight. In addition, the amount of β-thiodiglycol added is as follows: molybdenum and nickel are respectively MoS
2. The amount of tartaric acid added was 0.5 times the amount required to form NiS, and the amount of tartaric acid added was 0.2 times the total number of moles of molybdenum and nickel. Furthermore, an activity test was conducted in the same manner as in Example 1. The results are shown in Table 1. Example 5 1000 g of the alumina hydrate, 11 molybdenum trioxide
Catalyst E was obtained in the same manner as in Example 1, except that 9 g of nickel carbonate, 35 g of nickel carbonate, 27 g of acetic acid, and 250 g of β-thiodiglycol were used. The metal content of Catalyst E was 22% by weight of molybdenum in terms of MoO3, and 4% by weight of nickel in terms of NiO. In addition, the amount of β-thiodiglycol added is as follows: molybdenum and nickel are respectively MoS2
The amount of acetic acid added was 0.4 times the total number of moles of molybdenum and nickel. Furthermore, an activity test was conducted in the same manner as in Example 1, and the results are shown in Table 1. Example 6 870 g of silica-alumina hydrate (10
(wt% content, moisture content 54 wt%), molybdenum trioxide 1
Catalyst F was obtained in the same manner as in Example 1, except that 19 g of cobalt carbonate, 35 g of acetic acid, and 125 g of β-thiodiglycol were used. The metal content of catalyst F is as follows: molybdenum is 22% by weight in terms of MoO3, cobalt is CoO
The amount was 4% by weight. In addition, the amount of β-thiodiglycol added is as follows: molybdenum and cobalt are respectively MoS
2. The amount of acetic acid added was 0.5 times the amount required to form CoS, and the amount of acetic acid added was 0.3 times the total number of moles of molybdenum and cobalt. Furthermore, an activity test was conducted in the same manner as in Example 1, and the results are shown in Table 1. Example 7 The amount of citric acid used in Example 1, 36.6g, was changed to 73.6g.
2g, and the amount of β-thiodiglycol used is 390g.
Catalyst G was obtained in the same manner as in Example 1 except that the amount was 30 g. The metal content of Catalyst G was 22% by weight of molybdenum in terms of MoO3, 4% by weight of cobalt in terms of CoO, and 3% by weight of phosphorus in terms of P2O5. or,
The amount of β-thiodiglycol added is 0.5 times the amount required for molybdenum and cobalt to form MoS2 and CoS, respectively, and the amount of citric acid added is 0.3 times the total number of moles of molybdenum and cobalt. Met. Furthermore, an activity test was conducted in the same manner as in Example 1, and the results are shown in Table 1. Example 8 1000 g of the above alumina, 124 g of molybdenum trioxide,
Catalyst H was obtained in the same manner as in Example 1, except that 36 g of cobalt carbonate, 27 g of 85% phosphoric acid, and 260 g of β-thiodiglycol were used. The metal content of catalyst H is as follows: molybdenum is 22% by weight in terms of MoO3, cobalt is CoO
The amount of phosphorus was 4% by weight in terms of P2O5, and 3% by weight in terms of P2O5. Further, the amount of β-thiodiglycol added was 1.0 times the amount of molybdenum and cobalt required to form MoS2 and CoS, respectively. Furthermore, Example 1
Table 1 shows the results of an activity test conducted in the same manner as above. Comparative Example 1 1000 g of the alumina hydrate, 12 molybdenum trioxide
Catalyst I was obtained in the same manner as in Example 1, except that 4 g of cobalt carbonate, 36 g of cobalt carbonate, 27 g of 85% phosphoric acid, and 264 g of mercaptoacetic acid were used. The metal content of catalyst I was as follows: molybdenum was 22% by weight in terms of MoO3, and cobalt was 22% by weight in terms of MoO3.
The amount of phosphorus was 4% by weight in terms of P2O5, and 3% by weight in terms of P2O5. Further, the amount of mercaptoacetic acid added was 1.35 times the amount necessary for molybdenum and cobalt to form MoS2 and CoS. Furthermore, an activity test was conducted in the same manner as in Example 1, and the results are shown in Table 1. Comparative Example 2 Using a commercially available catalyst, Ketjenfine KF-742 catalyst (a typical alumina supported, cobalt, molybdenum catalyst, the active metal loading is 4.15 wt% as CoO and MoO, respectively), An activity test was conducted in the same manner as in Example 1. The reaction rate constant of this catalyst was set as 100, and the reaction rate constants of other catalysts were determined as relative values.

[0020]

[Table 1] From these results, catalysts A to H prepared according to the present invention
has at least the same or higher activity than High Activity Catalyst I using mercaptoacetic acid as a sulfiding agent, and furthermore, even if β-thiodiglycol decomposes during activation at elevated temperature, carboxylic acids etc. It is clear from gas analysis that no corrosive substances are generated, and it is recognized that the catalyst has extremely high activity compared to the KF-742 catalyst. This shows that β-thiodiglycol is an excellent sulfiding agent that contributes to the activation of the hydrogenation catalyst like mercaptocarboxylic acid and does not generate corrosive substances.

[0021]

Effects of the Invention The present invention involves adding an active metal, a carboxylic acid and/or a phosphoric acid, and β-thiodiglycol to a catalyst carrier, kneading and molding the carrier, and then drying the carrier at 200°C or lower. Therefore, it is possible to produce a hydrotreating catalyst that can perform advanced hydrotreating such as advanced desulfurization and denitrification very easily, and extremely excellent effects are recognized.

Claims (1)

[Claims] Claim 1: A catalyst carrier containing metal ions of Groups 6 and 8 of the periodic table, carboxylic acid and/or phosphoric acid, and β-
Add an aqueous solution containing thiodiglycol and knead.
A method for producing a catalyst for hydrotreating hydrocarbon oil, which comprises molding and then drying at a temperature of 200° C. or lower.