JPS6229095B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hydrotreating catalyst for effectively removing nitrogen compounds and sulfur compounds contained in hydrocarbon oil. More specifically, crude oil containing nitrogen compounds and sulfur compounds, atmospheric distillate oil, atmospheric distillation residual oil, vacuum distillation distillate oil, vacuum distillation residual oil, pyrolysis oil, deasphalted oil, tar sand bitumen, The present invention relates to a catalyst for effectively hydrodenitrogenizing and desulfurizing rock oil and the like, and particularly to a catalyst having extremely high activity for hydrodenitrogenizing reactions. In general, hydrocarbon oils contain nitrogen compounds such as pyridines, pyrroles, quinolines, carbazoles, amines, polyphyllins, and nitriles, and sulfur compounds such as mercaptans, sulfides, disulfides, Contains thiophenes, benzothiophenes, dibenzothiophenes, etc. When hydrocarbon oil containing these is used as a fuel oil, nitrogen compounds and sulfur compounds cause air pollution, which is undesirable. Furthermore, nitrogen compounds in particular worsen the hue and stability of the product hydrocarbon oil, and also cause a significant decrease in catalytic activity when the hydrocarbon oil is subjected to catalytic cracking or catalytic reforming. Conventionally, hydrorefining, that is, a method of catalytically hydrotreating feedstock hydrocarbon oil under high temperature and high pressure reaction conditions in the presence of hydrogen, has been known as a method for removing these nitrogen compounds and sulfur compounds from hydrocarbon oil. . The hydrodesulfurization method, which has already been widely practiced industrially, is one of these hydrorefining methods, in which a catalyst consisting of a group A metal of the periodic table and a group metal supported on a support made of alumina or alumina-silica is used. Commonly used. However, although these catalysts exhibit high activity for hydrodesulfurization reactions, they do not exhibit sufficient activity for hydrodenitrogenation reactions. That is, under commonly used hydrodesulfurization conditions, the hydrodenitrogenation activity is extremely low compared to the hydrodesulfurization activity.
Therefore, in order to sufficiently carry out the hydrodenitrogenation reaction using a hydrodesulfurization catalyst, it is necessary to perform the treatment at high temperature and pressure or at a low space velocity. When actually hydrotreating feedstock hydrocarbon oil under such conditions, although satisfactory results regarding hydrodenitrogenation may be obtained, on the other hand, desulfurization, hydrogenation, and further lightening may be performed unnecessarily. As a result, hydrogen consumption increases and it becomes difficult to obtain a product with the desired fraction distribution. This is not economically desirable and is not practical. Therefore, in order to remove not only sulfur compounds but also nitrogen compounds by hydrotreating hydrocarbon oil, in addition to the hydrodesulfurization activity of the conventionally known hydrodesulfurization catalyst, it is necessary to have high hydrodenitrogenation. There is a need for catalysts that also have activity. Therefore, many researchers have investigated catalysts that meet these requirements, and several proposals have also been made. For example, US Pat. No. 3,434,964 proposes a catalyst in which metals such as molybdenum, nickel, and cobalt are supported on fluorine-treated alumina or alumina-silica for hydrodenitrifying hydrocarbon oil. In addition, US Patent No. 3,444,074 discloses a catalyst for hydrodenitrogenation in which group A and group metals are supported on a silica-zirconia support, and metal fluorides such as bismuth, aluminum, gallium, indium, thallium, and rare earth metals are added. is proposed. U.S. Pat. No. 3,446,730 states that an activated alumina carrier supporting group A and group metals and further adding phosphorus, silicon, barium, etc. is effective for the hydrodenitrogenation reaction of petroleum fractions. US Patent No. 3749664
No. 1 also states that catalysts in which group A and group metals and phosphorus are supported on alumina, silica-alumina, etc. are effective for hydrodenitrogenation reactions. US Patent No.
No. 3,536,604 states that a catalyst containing alumina-silica and zeolite and group A and group metals, as well as titanium, zirconium, thorium, and hafnium, is effective in the hydrodenitrogenation reaction of hydrocarbon oils. U.S. Patent No. 3954670, Japanese Unexamined Patent Publication No. 51-100983
No. 53-3306 filed by the applicant is a.
It is stated that catalysts consisting of group metals and group metals, alumina, and boria are effective in hydrodenitrogenation reactions. In general, many catalysts for hydrotreating, including those disclosed in these patents and published patent publications, have alumina or silica as a main component, and improved versions of these catalysts are used in hydrodenitrogenation reactions. However, in order to provide the catalysts proposed in the above-mentioned literature with high denitrification activity in the hydrotreating reaction, various efforts have been made, but they have not yet become sufficient. In order to obtain a hydrotreating catalyst having higher hydrodenitrogenation activity, the inventors conducted repeated tests on possible combinations of solid acid carriers and catalytic metals, leading to the development of the present invention. That is, titanium oxide is used as a carrier, and at least one or more of each of group A and group metals of the periodic table, and phosphorus or/and
A catalyst in which a catalytic component consisting of alumina and boron is supported is more effective in hydrodenitrogenation treatment than a conventional catalyst in which a catalytic metal is supported on a support mainly made of alumina or silica. It was discovered that this compound exhibits extremely high activity. Until now, there have been few examples of using titanium oxide as a catalyst carrier, and only a few
There are only examples of its use as a catalyst for NOx treatment and a catalyst for the production of carboxylic acid. When investigating catalysts using titanium oxide as a carrier, the inventors first used these conventionally known titanium oxide carriers to support various catalytic metals and investigated the denitrification activity. The carrier does not have desirable physical properties for hydrotreating hydrocarbon oils, such as having an extremely small specific surface area, so not only its hydrodenitrogenation activity but also its hydrodesulfurization activity is extremely low, making it very impractical. It wasn't worth it. Therefore, the inventors reexamined titanium oxide carriers and produced a new titanium oxide carrier without being restricted by conventional ones.If the specific surface area could be maintained to a certain extent, the catalytic activity would be significant. After discovering that improvements can be expected, and after studying combinations with various catalyst metals, we have arrived at the development of the present invention. In other words, the titanium oxide support manufactured by paying attention to the firing conditions so as not to cause a decrease in the specific surface area has a
Hydrodenitrogenation in which a catalytic metal is supported on a conventionally known alumina or silica-based carrier by supporting at least one each of group metals and phosphorus and/or boron. Even though the specific surface area is still smaller than that of the catalyst, it has exhibited substantially the same level of hydrodesulfurization activity and dramatically improved hydrodenitrogenation activity. In this case, the supported catalyst components must simultaneously support at least one of each of Group A and Group metals of the periodic table, and three types of components: phosphorus and/or boron. In cases where even species are missing, no dramatic improvement in denitrification activity was observed, even though activity comparable to that of conventionally known catalysts could be obtained. This is probably because the catalytic activity of these three components exerts a mutual effect with the titanium oxide used as a carrier, resulting in a dramatic improvement in activity. The group A and group metals of the periodic table used as catalyst components are chromium, molybdenum, tungsten, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, and molybdenum or tungsten is particularly preferable as the group A metal. with either one of
A combination with cobalt or/and nickel as a group metal. For combinations of these metals, phosphorus or/
and boron are the preferred catalyst components. Next, the most preferred combinations of catalyst components will be listed. Molybdenum, nickel, boron; molybdenum, cobalt, boron; molybdenum, nickel,
Phosphorus; molybdenum, nickel, cobalt, boron; molybdenum, nickel, cobalt, phosphorus. In the case of group A metals, the content of the catalyst component is 5 to 25% by weight based on the total weight of the catalyst as a metal oxide;
For group metals it is 0.5-15% by weight. Boron and phosphorus are also represented as B ₂ O ₃ and P ₂ O _5.
It is 0.5-30% by weight. The minimum limit of each supported amount is the minimum limit at which the required activity can be expressed, and the upper limit indicates the point at which the effect of increasing the amount added starts to decrease when the relationship between the amount added and the activity is determined. In other words, the upper limit is the point at which an effect proportional to the added amount cannot be obtained by adding a larger amount. These metal compounds are usually dissolved in water in the form of water-soluble salts, added, and calcined to form oxides. Before use, it is sulfurized if necessary to convert it into a sulfide form. Boron and phosphorus, which are other catalyst components, are added in the form of an aqueous solution of boric acid and its salts, or phosphoric acid and its salts. As a method for effectively adding boron or phosphorus,
There is a method in which boric acid and phosphoric acid are supported using salts of the catalyst metals, such as nickel phosphate, cobalt phosphate, phosphotungstic acid, phosphomolybdic acid, and nickel borate. This method has the advantage that it is not necessary to repeat the supporting treatment many times and the manufacturing process can be simplified. Various oxide forms of titanium oxide can be used as the carrier. That is, basic titanium monoxide TiO, weakly basic dititanium trioxide Ti ₂ O ₃ ,
Amphoteric titanium dioxide TiO ₂ , acidic titanium trioxide
Any form such as TiO ₃ may be used, but titanium dioxide TiO ₂
is the most stable and practical. Titanium dioxide has
There are anatase type, rutile type, and amorphous type, but any of them may be used, or a mixture thereof may be used. As mentioned above, the catalyst according to the present invention is required to have a larger specific surface area than the conventional catalyst using titanium oxide as a carrier. In general, it is said that the larger the specific surface area and pore volume, the better from the point of view of catalyst activity and life, and there is a strong demand for this as a catalyst for hydrotreating hydrocarbon oils. However, due to its physical properties, titanium oxide Alternatively, it is difficult to obtain a large specific surface area compared to an alumina-silica catalyst, and moreover, the specific surface area tends to decrease due to the firing treatment after supporting the catalyst component. In order to maintain the required denitrification rate, the catalyst of the present invention has a specific surface area of 50 m ² /g or more and a pore volume of 0.1 cc/g.
It has been experimentally confirmed that an average pore diameter of 50 to 150 Å is desirable. All of the above physical properties
This is a value measured using a mercury intrusion porosimeter manufactured by AMINOCO. Next, an example of a method for producing a catalyst according to the present invention will be explained. There are two methods: the first method is to prepare a carrier made of titanium oxide and support the catalyst component on it, and the second method is to knead the catalyst component into hydrous titanium oxide and mold it to form a catalyst. It's a method. Hydrous titanium oxide, which is the raw material, is titanium chloride TiCl ₄
Alternatively, titanium oxide can be produced by hydrolyzing the sulfate TiOSO ₄ or by adding alkali such as ammonia, caustic soda, or caustic potash to these, or by the sulfuric acid method to produce titanium pigment industrially from ilmenite ore, high titanium slag, etc. Obtained as an intermediate product in the manufacturing process. In any of these methods, for the purpose of the present invention, it is desirable that the obtained hydrous titanium oxide be sufficiently washed to remove as much of the coexisting salts as possible. After adjusting the water content of the hydrated titanium oxide by air drying or the like, it is formed into a desired shape by any method such as extrusion molding, rolling granulation, molding granulation in oil, etc., and then dried. Drying is carried out at a temperature of 80-150° C. for 1-10 hours, followed by air-drying at room temperature if necessary. After drying, the carrier is further calcined at a temperature of 150 to 600°C for 1/6 to 5 hours, more preferably at a temperature of 400 to 600°C for 1/6 to 3 hours. The above-mentioned catalyst component is supported on the carrier thus obtained by a conventional method such as an impregnation method or a spray method. In addition, when adopting the second method, the catalyst components are supported on thoroughly washed hydrous titanium oxide by coprecipitation, spraying, kneading, etc., and after air drying, catalyst molded bodies are formed in the same manner as in carrier manufacturing. All you have to do is get it. The catalyst according to the present invention is effective for hydrotreating hydrocarbon oils, particularly for hydrodenitrogenation and hydrodesulfurization. There is no particular restriction on the method of use, and it can be used in a conventional manner in various known reactors such as fixed bed and moving bed systems. The reaction conditions are also not particularly limited; reaction pressure 10 to 300 Kg/cm ² G; reaction temperature 250 to 450°C; liquid hourly space velocity 0.1 to 10 Hr ^-1 ; supply ratio of hydrogen to raw material hydrocarbon oil 100 to 3000 N/. Select and set within the range depending on the properties of the raw material hydrocarbon. In order to explain the present invention in more detail, the production of the catalyst and the use of the catalyst will be explained below based on Examples and Comparative Examples. Comparative Example 1 A catalyst was prepared according to the method described in Japanese Patent Application No. 53-3306 as follows. 80g of commercially available alumina carrier, 18g of nickel sulfate,
After sprinkling 96 g of a solution of 19 g of ammonium molybdate dissolved in 15N ammonia water and leaving it for 3 hours,
Dry at 120℃ for 5 hours, then heat in an electric oven at 550℃.
It was baked for 4 hours. Next, take this in a flask and
91.1 g of an aqueous orthoboric acid solution containing 10% by weight of boron oxide (B ₂ O ₃ ) was added, and the mixture was boiled to evaporate water. This was then transferred to a porcelain crucible and evaporated to dryness.
Catalyst A was obtained by calcining at 550°C for 4 hours. Comparative Example 2 100g of commercially available titanium oxide carrier, 18.4g of ammonium paramolybdate and 19.5g of nickel nitrate at 25%
Dissolve in ammonia water, sprinkle the entire amount of this liquid,
After being left for 3 hours, it was dried at 120°C for 5 hours.
This dried material was impregnated with a solution of 8.9 g of orthoboric acid dissolved in deionized water and left for 1 hour. After that, it was transferred to a porcelain crucible, dried at 120℃ for 2 hours, and further baked at 500℃ for 30 minutes.
Catalyst B was obtained. Catalyst composition TiO ₂ 80% by weight; MoO ₃ 12% by weight;
NiO4% by weight; B ₂ O ₃ 4% by weight Specific surface area 34m ² /g Pore volume 0.32cc/g Denitrification rate 35% Desulfurization rate 62% Example 1 Titanium tetrachloride was gradually dissolved in water in a draft.
An aqueous solution containing 500 g/TiCl ₄ was prepared. Next, 14 pieces of deionized water was placed in a 60 glass reaction vessel that could be heated and stirred and heated to 95°C. The titanium tetrachloride aqueous solution 7 was gradually added to the reaction vessel with stirring, and after confirming that the liquid temperature was 95° C. or higher, 15% aqueous ammonia 9 was further added gradually. Thereafter, the mixture was further boiled for 1 hour while stirring. Deionized water was added to the hydrous titanium oxide obtained in the above operation, and the mixture was filtered using a vacuum filter, and the washing was repeated until chlorine ions were no longer detected in the silver nitrate aqueous solution.
In this way, a 5.8 kg hydrated titanium oxide cake was obtained. The solid content concentration in this hydrous titanium oxide cake is
After baking at 500°C for 1 hour, the content was 25% by weight (hereinafter referred to as hydrous titanium oxide cake). Take 4kg of hydrous titanium oxide cake and make it into 1mmφ using an extrusion molding machine.
After forming a cylindrical molded product, it was dried at 120°C for 3 hours to obtain 1.25 kg of dried product. Furthermore, 1Kg of this dried material is 500
C. for 1 hour to obtain 0.8 kg of a titanium oxide molded carrier. Next, 200 g of titanium oxide carrier was impregnated with the entire solution of 36.8 g of ammonium paramolybdate and 39.0 g of nickel nitrate dissolved in 25% ammonia water.
After being left for an hour, it was dried at 120°C for 5 hours. This dried carrier was divided into two equal parts, and one side was made with orthoboric acid.
One was immersed in a solution of 8.9 g of orthophosphoric acid dissolved in deionized water, and the other was immersed in a solution of 6.9 g of orthophosphoric acid dissolved in deionized water, and left for one hour. After that, each was transferred to a porcelain crucible, dried at 120℃ for 2 hours, and then heated to 500℃.
The catalyst was obtained by firing for 30 minutes. The catalysts obtained here are designated as C and D, respectively. Example 2 To 100 g of the titanium oxide support obtained in Example 1, 18.4 g of ammonium paramolybdate and cobalt nitrate were added.
The whole sample was impregnated with a solution of 19.4 g dissolved in 25% aqueous ammonia, left to stand for 3 hours, and then dried at 120°C for 5 hours. Next, 8.9 g of orthoboric acid was dissolved in deionized water, and the entire amount was impregnated into this dried product. After being left for 1 hour, it was transferred to a porcelain crucible and dried again at 120° C. for 2 hours. The catalyst thus obtained was calcined at 500°C for 30 minutes to obtain catalyst E. Example 3 The types and amounts of metal salts dissolved in 25% aqueous ammonia were compared with ammonium paramolybdate.
18.4g, nickel nitrate 4.9g, cobalt nitrate 14.6g
Dissolve orthoboric acid in deionized water using
Catalyst F was obtained by repeating the method of Example 2, except that 8.9 g was used. Example 4 100 g of the titanium oxide support obtained in Example 1 was impregnated with the entire solution of 17.8 g of tungstic acid and 19.5 g of nickel nitrate dissolved in deionized water, left for 3 hours, and then dried at 120°C for 5 hours. did. This dried product was impregnated with a solution of 8.9 g of orthoboric acid dissolved in deionized water, left for 1 hour, transferred to a porcelain crucible, dried at 120°C for 2 hours, and further heated at 500°C.
Catalyst G was obtained by firing for 30 minutes. Example 5 18.4 g of ammonium paramolybdate and nickel nitrate were added to 100 g of the titanium oxide support obtained in Example 1.
It was impregnated with the entire solution of 19.5 g dissolved in 25% aqueous ammonia, left to stand for 3 hours, and then dried at 120°C for 5 hours. Next, the entire surface was impregnated with a solution of 6.7 g of orthoboric acid dissolved in deionized water, allowed to stand for 1 hour, and then dried at 120° C. for 3 hours. Furthermore, the dry material was again impregnated with the entire solution of 1.7 g of orthophosphoric acid dissolved in deionized water, and after being left for 1 hour, it was transferred to a porcelain crucible and heated at 120°C.
After drying for 2 hours, Catalyst H was obtained by calcining at 500°C for 30 minutes. Example 6 18.4 g of ammonium paramolybdate and cobalt nitrate were added to 100 g of the titanium oxide support obtained in Example 1.
The whole sample was impregnated with a solution of 19.4 g dissolved in 25% aqueous ammonia, left to stand for 3 hours, and then dried at 120°C for 5 hours. Next, 6.9 g of orthophosphoric acid was dissolved in deionized water, the entire amount was impregnated into the dried product, and after being left for 1 hour, it was transferred to a porcelain crucible and dried again at 120° C. for 2 hours. The catalyst thus obtained was calcined at 500°C for 30 minutes to obtain catalyst I. Example 7 The composition, specific surface area, and pore volume in terms of oxides prepared in Comparative Example and Examples 1 to 6 are shown in Table 1 below. A, B, C, D, E, F, G, H, The hydrodenitrogenation desulfurization reaction activity of nine types of catalysts I was tested under the following conditions. Using a fixed bed flow reactor, Middle Eastern vacuum gas oil containing 0.18% by weight of nitrogen and 1.92% by weight of sulfur was reacted at a reaction temperature of 360℃ and a pressure of 80Kg/ ^cm2 .
G, liquid space velocity 2Hr ^-1 hydrogen to vacuum gas oil supply ratio 600N
Hydrorefining treatment was carried out under the conditions of /, and the nitrogen and sulfur contents in the produced oil were analyzed 50 hours after the start of the reaction to determine the denitrification rate and desulfurization rate. The results are also listed in Table-1. The nitrogen content was analyzed using a microcoulometric titration device (manufactured by Dohrmann), and the sulfur content was measured using a non-dispersive fluorescence X-ray analyzer (manufactured by Horiba, Ltd.).

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Claims (1)

[Claims] 1 Titanium oxide is used as a carrier, and periodic table a
1. A catalyst for hydrodenitrogenization of hydrocarbon oil, characterized in that it supports a catalyst component consisting of at least one of each of group metals and group metals, and phosphorus and/or boron. The catalyst according to claim 1, having a specific surface area of 250 m ² /g or more and a pore volume of 0.1 cc/g or more. 3. Claim 1 or 2, wherein the Group A metal of the periodic table is molybdenum or tungsten, and the Group metal is nickel and/or cobalt.
Catalysts as described in section. 4. The catalyst according to claim 3, wherein the catalyst components consist of molybdenum, nickel, and boron. 5. The catalyst according to claim 3, wherein the catalyst components consist of molybdenum, cobalt and boron. 6. The catalyst according to claim 3, wherein the catalyst components consist of molybdenum, nickel, and phosphorus. 7. The catalyst according to claim 3, wherein the catalyst components consist of molybdenum, cobalt, and phosphorus. 8. The catalyst according to claim 3, wherein the catalyst components consist of molybdenum, nickel, cobalt and boron. 9. The catalyst according to claim 3, wherein the catalyst components consist of molybdenum, nickel, cobalt and phosphorus.