JPH03273092A - Catalyst for hydrogenation of residual oil - Google Patents

Abstract

PURPOSE:To produce the title catalyst which has a high desulfurization activity and gives a product oil of which heavy fraction has preferable properties by supporting a specific active metal together with phosphorus and boron compounds on an alumina carrier so that the volume of pores having a specific average pore diameter may amount to a specific ratio. CONSTITUTION:The title catalyst is produced by supporting at least one active metal selected from the group consisting of Ni, Co, Mo, V and W in an amount of 1.0-20.0wt.% in terms of the oxide, a boron compound (e.g. orthoboric acid) and a phosphorus compound (e.g. phosphoric acid) each in an amount of 0.5-5.0wt.% in terms of the oxide on an alumina carrier so that the total surface area may be 100m<2>/g or more, the average pore diameter may be 100Angstrom or more, the total pore volume may be 0.4ml/g or more, and the volume wherein pores having an average pore diameter of 100-200Angstrom may account for at least 70% of the total pore volume. When the title catalyst is used in the hydrogenation of a residual oil, the catalyst exhibits a high desulfurization activity and gives a product oil of which heavy fraction has preferable properties.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a hydrotreating catalyst for removing sulfur content, nitrogen bones, and metal content such as nickel and vanadium contained in residual oil.

[Prior Art] Recent petroleum trends indicate that imported crude oil is becoming heavier. Therefore, after removing the useful light fraction, a large amount of heavy fraction, especially residual oil, is produced as a by-product. Therefore, processing this residual oil has become an important issue. This residual oil is enriched with sulfur, nitrogen bones, and metals, resulting in an extremely high concentration.

Hydrocracking, fluid catalytic cracking, etc. are methods of processing residual oil to make it lighter, but if residual oil containing high concentrations of sulfur, nitrogen bones, and metals is used as a raw material, product quality will deteriorate. Alternatively, it can cause catalyst poisoning, and furthermore, sulfur content and nitrogen bones can be a source of air pollution.

Therefore, a method of removing sulfur content, nitrogen bones, or metal content by hydrotreating residual oil as a pretreatment to lighten it is becoming increasingly important. Hydrotreating is the process of catalytically treating feedstock oil under hydrogen pressure in the presence of a catalyst, converting the sulfur content and nitrogen bones in the feedstock oil into hydrogen sulfide, ammonia, etc., and removing the metal content in the presence of a catalyst. This is a method to deposit and remove it.

Traditionally, indirect desulfurization mainly involves processing vacuum gas oil.
The metal content in the raw oil was low. However, as crude oil has recently become heavier worldwide, the content of metals such as sulfur, nickel, and vanadium in crude oil has increased, and direct desulfurization of residual oil is becoming increasingly popular. It became so.

By the way, the large amount of sulfur contained in residual oil cannot be desulfurized, so a high reaction temperature is required to achieve a high desulfurization rate, but a higher reaction temperature may increase the likelihood of coke formation. Are known. Another problem is the clogging of catalyst pores by metals and coke, which necessitates raising the reaction temperature to compensate for the decrease in catalyst activity, which hinders the operation of the device. In order to achieve stable operation, it is necessary to develop a long-life, highly active catalyst that can efficiently remove sulfur and metals contained in feedstock oil and maintain its activity over a long period of time.

At the same time, it is also necessary that the resulting product oil has good stability.

[Problems to be Solved by the Invention] Residual oil contains large amounts of metals such as vanadium and nickel, and also contains large molecules such as asphaltene, which cause coke formation. The active sites on the catalyst are covered and the pores are clogged by metals and coke, which causes the catalyst to deteriorate easily and shorten its lifespan.

Therefore, the reaction temperature is usually set high to improve the desulfurization rate and decomposition rate.
Denitrification rate, demetalization rate, etc. are improved. However, it is known that the properties of the products that are removed, especially those of fractions with a boiling point of 3BO°C or higher, deteriorate. In other words, this fraction tends to form sludge, causing trouble during operation, transportation, storage, etc. As for sludge, the quantification method is to measure the toluene insoluble content. This is 0.05vt%, preferably 03w
If it is below t%, there is no problem. When obtaining a high decomposition rate at high temperature using a normal catalyst, for example, the decomposition rate is 50 to 60%.
%, the toluene insoluble content is 0. It may be lvL%.

The product properties of the fraction are mainly determined by the toluene-insoluble content, and the greater the toluene-insoluble content, the less desirable the product is. Therefore, in order to hydrotreat heavy oil, the reaction temperature is low, the activity is high, and there is little coke formation.
There is also a need to develop catalysts that provide desirable product properties.

Many methods have been proposed for hydrotreating heavy oil. JP-A No. 61-4588 and JP-A No. 81-128198 disclose methods in which components such as boron and phosphorus are added to the carrier or the pores of the carrier are controlled.
No. 74455, JP-A-62-74455, JP-A-62-74455.
There are publications such as No. 25418. Addition of boron or phosphorus is said to be effective in improving hydrogenation activity and desulfurization activity. On the other hand, pore control is effective in prolonging service life by providing a suitable reaction field for residual oil and at the same time preventing blockages. However, to date, there has been no method that combines preferable additives and the effects of their addition with preferable pore structures, and furthermore, there is no method that takes into account the properties of the resulting product.

[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, the present inventors controlled the pores of the carrier to make the average pore diameter above a certain level, and added phosphorus as an additive. By adding a boron compound and a boron compound, we have discovered a catalyst that has high desulfurization activity and favorable product properties for the heavy fraction of produced oil in the hydrotreatment of residual oil.

That is, the present invention provides an alumina support with at least one active metal selected from nickel, cobalt, molybdenum, vanadium, and tungsten as an oxide of 1.0 to 20%.
．． 0 wt%, and 0.5 to 5.0 wt% of each of a boron compound and a phosphorus compound as oxides, the total surface area is 1ook, /g or more, and the average pore diameter is 100 Å.
Hydrogen in the residual oil, characterized in that the total pore volume is 0.4 d/g or more, and the volume occupied by pores with an average pore diameter of 100 to 200 is at least 70% of the total pore volume. The present invention provides a chemical treatment catalyst.

The alumina carrier used in the present invention can be prepared by a known method. For example, an aluminum salt such as aluminum sulfate is neutralized with an alkali such as ammonia, or an aluminate such as sodium aluminate, and an appropriate alkali is added to the resulting alumina hydrate to create an alumina hydrate thriller. Adjust the pH to a weak alkalinity of 8 to 0, and
Boehmite is produced by aging at ~150°C, and the boehmite is kneaded and molded into any desired shape by extrusion molding, etc.
It is obtained by drying at 200°C and firing at 300 to 600°C. However, if the aging is insufficient, the alumina carrier referred to in the present invention may not be obtained. It can also be obtained by using commercially available boehmite powder, peptizing it with an acid or the like, molding it, and then drying and firing it.

The active metal components used in the present invention are Ni, Co, and W.

It is sufficient to contain at least one selected from Mo and V, and in the case of compounding, Nl-Mo, Co-Mo.

Ni-Co-Mo, Nf-W, Co-W, NIC
o-W, N1-V, Co-V, Co-V-M.

etc. are possible. Co-MO is preferred.

Nl-Mo, Nl-Co-Mo, Co-W,
N1-W is mentioned. A small amount of active metals other than these may also be included. The amount of active metal supported is calculated as metal oxide based on the total weight of the catalyst, and is 1.0 to 30.0 νt.
%, preferably in the range of 5.0 to 20.0 wt%. In addition, in the case of composite, Co is 0.5 to 10.0 wt%
, N1 is 0.5~IO, Owt%, Mo is 2.0~20
．． Owt%, W is 2.0 to 20. Owt%,■ is 2.0
~20. A range of Owt% is preferred.

The boron compound used in the present invention may be either an inorganic compound or an organic compound of boron, which is converted into boron oxide when the catalyst is fired. for example,
Examples include boron, ammonium borate, orthoboric acid, tetraboric acid, ammonium diborate, diborane, methyl borate, butyl borate, tricyclohexyl borate, and the like.

The phosphorus compound used in the present invention may be either an inorganic compound or an organic compound of phosphorus, which can be converted into phosphorus oxide when the catalyst is fired. Examples include phosphoric acid, ammonium phosphate, ammonium phosphate, and the like.

In the present invention, the amount of each of the boron compound and the phosphorus compound added is 0.5 to 5.0 wt%, calculated as oxide based on the total weight of the catalyst. Preferably 1.0~
It is in the range of 5.0 wt%. If the amount of boron compounds and phosphorus compounds added is less than 0.5 wt%, there will be no effect;
When the amount exceeds 5.0 wt%, the desulfurization activity of the catalyst obtained does not change much, and there is a drawback that the pore diameter becomes small. Further, in the catalyst of the present invention, both the boron compound and the phosphorus compound must be contained as oxides at least 0.5 wt%, preferably at least 1.0 wt%, and high activity cannot be obtained with only one of them. . The addition ratio of each oxide is preferably 1:9 to 9:l (weight ratio)
The ratio is more preferably 1:4 to 4 to 1 (weight ratio).

In the present invention, the method of supporting the boron compound, phosphorus compound, and active metal component on the alumina support is not particularly limited. For example, each component may be supported separately or simultaneously. Furthermore, two components are initially supported,
The remaining components may be supported later. Furthermore, the order in which they are supported is not limited.

The catalyst of the invention has a surface area of at least 100 m/g1
Preferably 120 to 250 pores/g and an average pore diameter of 1.
The total pore volume is 0.4 d/g or more, preferably 0.5 d/g or more, and the average pore diameter is 100-200 pores. at least 70%, preferably 75% of the total pore volume
It has a pore distribution as follows. The surface area of the catalyst is 1ooTI1
．． If it is less than /g, sufficient activity will not be obtained. If the average pore diameter is less than 100A, pores are likely to be clogged and the lifespan will be shortened. When the total pore volume is less than 0.4 d/g, the amount of metal in the feedstock oil accumulated on the catalyst is small. In addition, if the pore distribution has an average pore diameter of 100 to 200 and the volume of pores is less than 70% of the total pore volume, the reaction field required for conversion of molecules such as residual oil is small and the activity is effectively expressed. do not.

The pore structure of the catalyst of the present invention is measured by a conventional nitrogen gas adsorption method, mercury intrusion method, or the like. In the present invention, a preferable pore structure is shown, and if the pore structure deviates from this, for example, if the pore diameter is small, the catalyst life will be short and the product properties will not be good.

If the pore diameter is too large, the activity will be low and a desirable decomposition rate or desulfurization activity cannot be expected. The catalyst of the present invention can be used in any desired shape, such as spherical, tablet, or cylindrical. Further, the catalyst of the present invention can be used in the form of a fixed bed, fluidized bed, or moving bed.

Although the catalyst of the present invention can be used alone by being packed in a reactor, a demetalization catalyst may be packed in the upper stage as a pretreatment catalyst. Moreover, the ratio is preferably 1:3 to 1:1 (weight ratio).

The residual oil referred to in the present invention is an oil that contains a large amount of heavy metal components such as vanadium and nickel, for example, 50 ppm or more, and also contains large molecules such as asphaltenes, and is obtained, for example, by normal pressure or reduced pressure distillation of crude oil. Examples include residual oil, residual oil obtained by normal pressure or vacuum distillation of crude oil extracted from oil sands or tar sands, and mixed oils thereof. In the present invention, vacuum distillation residual oil is preferably used.

Hydrotreating conditions using the catalyst of the present invention include a reaction pressure of 20
~20ONg/m, preferably 50-15ONg/ca
t.

Reaction temperature 300-500°C, preferably 350-450°C
°C, LHSVO, 1-2.0, preferably 0.1-1.
0, Hydrogen/raw oil ratio is 100-200ON J/N
It is J.

By cracking residual oil using the catalyst of the present invention, the cracking rate is 50 to 60%, and the yield of middle distillate is about 13 to 20%. Further, the toluene insoluble content of the fraction having a boiling point of 360° C. or higher is 0.05 wt% or less.

[Effects of the Invention] As shown above, the catalyst of the present invention has particularly high desulfurization activity, and by using this catalyst to hydrogenate vacuum residual oil, etc., large molecules in the residual oil can be removed inside the catalyst. At the same time, it is possible to suppress over-cracking and suppress the generation of naphtha and gas, making it possible to obtain a high cracking rate and a large amount of middle distillate.At the same time, the toluene insoluble content in the high boiling point fraction is small, making it stable. A product with good properties can be obtained.

[Example] Next, the present invention will be described in more detail with reference to Examples.

Example Boehmite powder was dispersed in distilled water and diluted nitric acid was added to adjust the pH.
was set as 1.0. Add ammonia water and adjust the pH to 7~
Neutralized with 8. The obtained alumina hydrate gel was thoroughly washed with distilled water, filtered, and mixed with heat in a kneader to reduce the water content to 75.
% of contaminants were obtained. After extrusion molding, it was heated to 110°C.
After drying for 8 hours at 550° C. for 3 hours, 80 g of an alumina carrier was obtained.

The alumina support prepared as above was impregnated in a solution of nickel nitrate, ammonium molybdate, citric acid, boric acid, and phosphoric acid dissolved in distilled water at 40 to 50°C for 2 hours while maintaining that temperature. did. Thereafter, the carrier was taken out, left to dry at room temperature day and night, further dried at 110°C for 3 hours, and calcined at 550°C for 3 hours to obtain catalyst A.

Comparative Example Catalyst B was obtained using the same alumina carrier as in the example and in exactly the same manner as in the example except that boric acid and phosphoric acid were not added.

Evaluation Example The properties of the catalyst A%B obtained are shown in Table 1. Each catalyst was packed into a microreactor with an inner diameter of 20 mm, and after sulfidation, it was hydrogenated using vacuum residual oil having the properties shown in Table 2 under the following conditions.

Temperature 400℃ LHS VO,2 Pressure I L5Kt / atr
G hydrogen/oil 70ONJ/NJ The reaction results are summarized in Table 3. Catalyst A of the present invention is
Compared to Catalyst B of Comparative Example, the desulfurization rate and metal removal rate are excellent, and the yield of middle distillate is also high. In addition, despite the high conversion rate, the high boiling point fraction contained only a small amount of toluene insoluble matter, making it desirable as a product.

Table 3 $1: Distillate below 170℃ *2: Distillate between 170 and 360℃ $3: Distillate above 360℃

Claims (1)

[Claims] 1. Nickel, cobalt, molybdenum on alumina carrier,
1.0 to 20.0 wt% of at least one active metal selected from vanadium and tungsten as an oxide, and 0.0 wt% of each of a boron compound and a phosphorus compound as an oxide.
5 to 5.0 wt%, and the total surface area is 100 m
^2/g or more, the average pore diameter is 100 Å or more, the total pore volume is 0.4 ml/g or more, and the average pore diameter is 100~
A resid hydroprocessing catalyst characterized in that the volume occupied by 200 Å pores is at least 70% of the total pore volume.