JPS63278553A - Hydrocarbon conversion catalyst - Google Patents

Abstract

PURPOSE:To control a decrease in the coke yield and activation by forming the title catalyst consisting of specified amts. of crystalline aluminosilicate zeolite and a matrix consisting of alumina, magnesia, and phosphite. CONSTITUTION:A hydrocarbon conversion catalyst contg. 3-40wt.% crystalline aluminosilicate zeolite and 60-97wt.% matrix consisting of alumina, magnesia, and phosphia is formed. In this case, the alumina content in the matrix is controlled to 40-90wt.%, the magnesia content to 2-50wt.%, and the phosphia content to 0.1-30wt.%. In addition, the 10-70wt.% of alumina must be formed from the alumina via pseudo-boehmite. Furthermore, the total pore volume of the catalyst is controlled to 0.25-1.0cc/g, the volume of the pores having <=600Angstrom diameter is adjusted to 0.2-0.7cc/g, and the volume of the pores having <=600Angstrom is regulated to >=70% of the total pore volume.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a hydrocarbon conversion catalyst, and in particular to a catalyst for converting hydrocarbons, in particular a catalyst containing at least nickel and vanadium in the total amount of heavy metals such as nickel, vanadium, iron and copper. The present invention relates to a novel hydrocarbon conversion catalyst that exhibits remarkable effects as a fluid catalytic cracking catalyst for catalytically cracking heavy oil containing more than 0.0 sppm to obtain light oil such as gasoline and kerosene.

[Technical background of the invention and its problems] In ordinary catalytic cracking, petroleum hydrocarbons are cracked by contacting them with a catalyst to obtain a large amount of light valves such as LPG and gasoline and a small amount of cracked light oil, etc. The coke deposited on the catalyst is burned off with air and the catalyst is recycled and reused. In this case, so-called distillate oils such as light gas oil (LGO), heavy gas oil (HGO) from atmospheric distillation towers, vacuum gas oil (VGO) from vacuum distillation towers, etc. are traditionally used as feedstock oils. .

However, in recent years, as crude oil has become heavier worldwide and the demand structure has changed in Japan, there has been a tendency for heavy oils to be in surplus from both the supply and demand perspective. It has become necessary to also cover the following.

However, heavy oil containing distillation residue contains far more metals such as nickel, vanadium, iron, copper, and sodium than distillate oil, and these metals are not present on the catalyst. It is known that it accumulates and significantly inhibits the activity and selectivity of degradation. In other words, as metals accumulate on the catalyst, the decomposition rate decreases, making it virtually impossible to achieve the desired decomposition rate, while the amount of hydrogen and coke generated increases significantly, making it difficult to operate the equipment. While making it difficult,
The yield of the desired liquid product is reduced.

[Problems to be Solved by the Invention] An object of the present invention is to provide a catalyst suitable for a conversion reaction of hydrocarbon oil. In addition, in particular, it contains 0.5 ppm of heavy metals such as nickel, vanadium, iron, etc. When cracking IXX heavy oil, it is possible to suppress the amount of hydrogen and coke produced without reducing the yield of gasoline and middle distillates. The purpose of the present invention is to provide a catalytic cracking catalyst with high properties.

The present inventors have previously discovered that a catalyst consisting of crystalline aluminosilicate zeolite and an alumina-magnesia matrix serves as a catalytic cracking catalyst with high metal resistance (Japanese Patent Application Laid-Open No. 150539/1983). The catalyst can be obtained by mixing alumina-magnesia hydrogel and zeolite, drying and calcining the mixture. At this time, by preparing the alumina-magnesia hydrogel by a coprecipitation method in a pH range of 8.5 or higher, a catalyst with high metal resistance can be obtained. However, it was still unsatisfactory as a fluid catalytic cracking catalyst.

On the other hand, by depositing magnesia or alumina-magnesia on pseudo-boehmite, a highly wear-resistant catalyst can be obtained. However, the metal resistance of the catalyst thus prepared was inferior to that of the catalyst prepared by coprecipitation.

It is already known that a catalyst having a matrix consisting of alumina, magnesia, and alumina phosphate has excellent metal resistance (U.S. Pat. No. 4,222,899).
No. 6, No. 4,407,730, No. 4,407,732
issue). However, none of these patents contain alumina via pseudo-boehmite, so they have a drawback of poor wear resistance.

The present invention has been researched and developed to improve the above-mentioned drawbacks.

[Structure of the Invention] That is, the present invention is a catalyst containing a matrix consisting of 3 to 40 wt% of crystalline aluminosilicate zeolite and 60 to 97 wt% of alumina, magnesia, and phosphere, and (1) the alumina content in the matrix is 40-90
wt%, magnesia content is 2 to 50 wt%, phosphere content is 0.1 to 30 wt%, ■ 10 to 70 wt% of the alumina is alumina via pseudoboehmite, ■ The total pore volume of the catalyst is 0. 25 to 1.0 cc/g, the pore volume of 600 Å or less is 0.2 to 0.7 cc/g, and the pore volume of 600 Å or less is 70% or more of the total pore volume. The purpose of the present invention is to provide a hydrocarbon conversion catalyst.

[Summary of the Invention] Alumina<Al2O2) used in the present invention is alumina made by a conventional method such as thermal decomposition of alumina hydrate. In the present invention, 10 to yowt% of the alumina,
Preferably, it is necessary to contain 20 to 50 wt% of alumina (hereinafter referred to as alumina (2)) via pseudo-boehmite (boehmite gel).

In the present invention, at least one type of alumina selected from crystalline alumina hydrate and amorphous alumina hydrate is preferably used as the alumina other than pseudoboehmite-mediated alumina (hereinafter referred to as alumina (1)). It will be done.

If the amount of alumina (2) via pseudo-boehmite is less than 10 wt%, the wear resistance of the catalyst will decrease, and if it is more than 70 wt%, the metal resistance of the catalyst will deteriorate.

The aluminum trihydrate can be obtained by a conventional method using an alkali aluminate or an aluminum salt as a starting material. Examples of the aluminum trihydrate include bayerite, gibbsite, and nordstrandite. These can be used alone or as a mixture of two or more.

The pseudoboehmite (boehmite gel) described above is mH-like alumina hydrate, and can be obtained by a conventional method using an alkali aluminate and an aluminum salt as starting materials. For example, it can be obtained by reacting an aqueous solution of an aluminum salt and an aqueous solution of an alkali aluminate in steps 1) 85 to 11.

If necessary, add this to I) 89-11.5 at 20-100℃.
It may be aged for minutes to 20 hours. Examples of the aluminum salts include aluminum sulfate, aluminum nitrate,
Examples include aluminum chloride, and aluminum sulfate is particularly preferred. Examples of alkali aluminates include sodium aluminate and potassium aluminate.

The magnesia (M!70) used in the present invention is a magnesium salt, such as magnesium nitrate (Ma(NO3)).
2 ・6H20), magnesium chloride <MQCJ2
・6H20), magnesium sulfate (M(l SO2
- 7H20) etc. prepared by a conventional method can be used.

The phosphere (P205) referred to in the present invention can be prepared from a phosphorus-containing compound such as phosphoric acid or a phosphate salt by a conventional method. Preferred examples of phosphoric acid and phosphate salts include orthophosphoric acid, birophosphoric acid, polyphosphoric acid, metaphosphoric acid, etc., and salts thereof such as ammonium salts and sodium salts.

In the present invention, the content ratio of alumina, magnesia and phosphere in the matrix is 40 to 9.
0wt%, preferably 68-90wt%, magnesia 2-50wt%, preferably 8-3wt%, phosphere 0.1-30wt%, preferably 0.5-2wt%
is appropriate.

If the alumina content in the matrix is less than 40 wt%, the wear resistance will be poor, and if it is more than 90 wt%, the metal resistance will be poor. Furthermore, if the magnesia content is less than 2 wt%, a catalyst with high metal resistance cannot be obtained, and if it is more than 50 wt%, a catalyst with sufficient wear resistance cannot be obtained. Also, phosphy? When the content is less than 0.1 wt%, a catalyst with high metal resistance cannot be obtained, and when it is more than 30 wt%, wear resistance becomes poor.

The crystalline aluminosilicate zeolite used dispersed in the catalyst of the present invention is a natural or synthetic crystalline aluminosilicate with a three-dimensional framework structure and approximately 4 to 1
It is a porous material with a uniform pore size within the range of 5. Natural zeolites include gmelinite, shabasite, dakialdofutuite, clinoptilolite, faujasite, kiftuite, borofluorite, levinite, erionite, sodalite, cancrinite, ferrierite,
Brewster fluorite, offretite, soda fluorite,
Any of mordenite and the like may be used, but faujasite is most preferred. Synthetic zeolites include zeolite X, Y, A, L, ZK-4, BLE, F, HJ, M, Q
, T, WSZ, alpha, beta, ZSM type, omega, etc., but Y type and X type zeolites or mixtures thereof are most preferred.

It is well known that when using zeolite as a highly active catalytic cracking catalyst, it is desirable to reduce the Na2O content in the zeolite as much as possible. Zeolite with a high Na2O content not only has low activity but also poor heat resistance, resulting in a short catalyst life. N in zeolite
The a ion can be exchanged with other cations, and the Na2O content in the zeolite can be reduced by ion exchange method. Cations include calcium, magnesium,
Hydrogen, or Ce%Sc SY, La.

Rare earth elements such as AC, as well as platinum and palladium, are preferred, and when used as a catalytic cracking catalyst, hydrogen and rare earth elements or mixtures thereof are particularly suitable.

The method for producing the zeolite is not particularly limited, and it can be produced, for example, by the following method.

Mix Na-Y type zeolite, rare earth element chloride, and ammonium chloride, and heat the mixture at 60 to 100°C for 2 hours.
Stir for ~10 hours to perform ion exchange.

The above ion exchange operation is repeated 2 to 5 times as necessary. Next, the filtered zeolite is dried at 30-150°C for a day and night, and then air-calcined at 400-650°C for 2-10 hours. Na2 in the zeolite thus obtained
"O content" is 0.5 to 2. Owt% THEAL is further ion-exchanged after air firing to reduce the Na2O content to 1.
wt% or less.

Alumina (1) and (2) contained in the catalyst of the present invention
The content layer of the matrix consisting of magnesia and phosphere is 60 to 97 wt%, preferably 10 to 97 wt%.
It is 95%. The content of crystalline aluminosilicate zeolite is 3 to 40 wt%, preferably 5 to 30 wt%
%. If the zeolite content layer is less than 3 wt%, the catalytic activity will be low, which is not preferable. Moreover, when the content of zeolite is more than 40 wt%, the catalyst activity is too high, causing excessive decomposition, resulting in a decrease in the yield of the desired product.

An example of the method for preparing the catalyst of the present invention will be described below.

First, an alumina (1)/magnesia/phosphiahydride O gel slurry is produced by reacting an aqueous solution containing an aluminum salt, a magnesium salt, and phosphorus with an aqueous solution of a basic compound at a pH of 8.5 or higher. Examples of the basic compounds include ammonia (NH3), sodium hydroxide (NaOH), potassium hydroxide (KO) (>
etc. The reaction between an aqueous solution containing an aluminum salt, a magnesium salt, and phosphorus and an aqueous solution of a basic compound is performed at pH
Although there are no particular limitations as long as the pH is 8.5 or higher, preferably 9.0 to 11.0, a method of dropping an aqueous solution containing an aluminum salt, a magnesium salt, and phosphorus into an aqueous solution of a basic compound is preferred. If the pH during production of the alumina (1)/magnesia/phosphere hydrogel is lower than 8.5, precipitation of magnesia will not occur sufficiently, which is not preferable.

Next, the alumina (1)/magnesia/phosphere hydrogel slurry and pseudo-boehmite drogel slurry are mixed. The mixing method may be simply mechanical kneading for 5 minutes to 10 hours, but at this time it is preferable to heat at 50 to 100°C. Alternatively, an aqueous solution containing an aluminum salt, a magnesium salt, and phosphorus may be added to a hydrogel slurry of pseudoboehmite, and an aqueous solution of a basic compound may be further added thereto to produce an alumina (1)/magnesia/phosphere hydrogel.

Next, after dispersing the crystalline aluminosilicate zeolite in a hydrogel slurry obtained by mixing the alumina (1)/magnesia/phosphere hydrogel slurry and the pseudoboehmite hydrogel slurry,
Spray dry with hot air at 50°C, and then dry at 400-700°C.
It is preferably obtained by firing at 500 to 600°C. As a result, the alumina (1) and (2)/magnesia/phosphere hydrogels become alumina/magnesia/phosphere composite oxides. In this case, a binder such as alumina sol or silica sol may be added to increase the strength of the catalyst.

In the present invention, the pore structure of the catalyst is also an important factor, and in order for the catalyst of the present invention to have sufficient performance,
The total pore volume of the catalyst is 0.25-1.0007 g, preferably 0.35-0. ToolQ, pore volume of 600 Å or less is 0.2 to 0.7 cc/g, preferably 0.25 to 0
．． 50C/Q, and the pore volume of 6008 or less is required to be 10% or more, preferably 80% or more of the total pore volume. The total pore volume is 1. Occ/g over 600
Pore volume below 0.7cc/t; more than J or 6
If the pore volume of 00 Å or less is smaller than 70% of the total pore volume, the abrasion resistance of the catalyst decreases, which is not preferable. In addition, if the total pore volume is less than 0.2500/Q or if the pore volume of 6 GOA or less is less than 0.2 cc/a, it is not preferable because the diffusion of the feedstock oil into the catalyst becomes poor and the catalyst activity decreases. .

[Effects and operations of the invention] By using the catalyst of the present invention for catalytic cracking of heavy oil, heavy metals such as nickel and vanadium contained in the heavy oil are immobilized on the catalyst of the present invention, and are also immobilized. activated. As a result, the increase in hydrogen and coke yield and the decrease in activity due to metals accumulated on the catalyst are suppressed, and the gas compressor, which is one of the distillation equipment for cracked products, and the air that supplies air for coke combustion on the catalyst are suppressed. Not only is the blower load reduced, but the selectivity and yield of the preferred liquid product is increased. Further, since the catalyst of the present invention has excellent abrasion resistance, loss of the catalyst is small and a stable fluid state can be maintained in the reaction apparatus.

Although the reason for the immobilization and inactivation of the heavy metals deposited on the catalyst of the present invention is not fully clear, the following reasons may be considered. The nickel deposited on the alumina-magnesia-phosphere composite oxide in the reaction tower becomes nickel oxide in the regeneration tower, but the ionic radius of nickel at this time is almost equal to the ionic radius of magnesium, so the nickel oxide is Easily penetrates or replaces solid solution in magnesia-phosphere composite oxide. The solid-dissolved nickel oxide is stable and will not be reduced again in the reaction tower, so that the dehydrogenation activity of nickel is lost and the production of hydrogen and coke is suppressed. Vanadium is similarly oxidized to vanadium pentoxide in the regeneration tower. Since vanadium pentoxide has a relatively low melting point of 674°C, it is said that it moves over the catalyst in the regeneration tower and reacts with the zeolite, destroying the crystal structure of the zeolite and reducing the catalyst activity. However, the vanadium pentoxide deposited on the alumina/magnesia/phosphere composite oxide reacts with alumina, magnesia, or phosphere to form a stable, high-melting-point composite oxide (e.g. 3M (IQ/V20s)).
is formed and immobilized. Although the action of phospheres is not yet clear, it is thought to promote the solid phase reaction as described above.

In addition, the abrasion resistance of the catalyst can be improved by making at least 70 wt% of the alumina in the catalyst into alumina (2) via pseudo-boehmite. Therefore, when the gel containing pseudo-boehmite is dried and fired, its fibers become entangled to form strong catalyst particles.

[Embodiments of the invention] Next, examples of the present invention will be described.

LLL top (A) Alumina (1) and (2)・Magnesia・
The phosphere hydrogel was prepared as follows.

151 J of sodium aluminate and o, scc of gluconic acid are dissolved in 150 CC of pure water and heated to 50°C. Separately, 16 g of aluminum sulfate was dissolved in 150 cc of pure water and heated to 50°C. Add the aluminum sulfate solution to the above sodium aluminate solution while stirring vigorously,
Form an alumina hydrogel. The pH at this time was 9.
It is 5. This hydrogel is aged at 50° C. for 1 hour to obtain pseudo-boehmite. Then into ammonia water 489 aluminum chloride, 20g magnesium chloride and 0.7
Drop 200 cc of phosphoric acid mixed aqueous solution of
)・Generate magnesia phosphere hydrogel.

The pH at this time is 9.5.

Next, this alumina (1)/magnesia/phosphere hydrogel and the pseudo-boehmite hydrogel were mixed,
Aging for 4 hours at a temperature of 5°C. After aging, the gel is filtered and washed with a sufficient amount of pure water. The above alumina (1) was a mixture of aluminum trihydrate and amorphous alumina hydrate.

(8) La, HY type zeolite was prepared from Na-Y type zeolite as follows.

100g of Na-Y type zeolite in a 5-inch beaker,
Add 415 g of lanthanum chloride and 15 g of ammonium chloride, and add pure water to make a total volume of 5 g. While heating this to about 80℃, use a magnetic stirrer to
After stirring for an hour, it is filtered and washed with 5 liters of pure water. After repeating the above operation three times, it was dried in an oven at 110°C for a day and night, and then air-baked at 540°C for 3 hours. Finally, the above ion exchange operation is performed one more time, and after washing and drying, the product is baked at 500° C. for 2 hours. La obtained in this way
, the 1a exchange rate of H-Y type zeolite is 77%,
The amount of residual N820 was 0.81 wt%.

Next, with the zeolite (8) 4,4a and (A):
Catalyst A was obtained by kneading all the colors of the hydrogel prepared by II, spray drying, and air-calcining at 600° C. for 2 hours.

The properties of this catalyst A are shown in Table 1.

A wear resistance test of this catalyst was carried out as follows.

A predetermined amount of catalyst is fluidized for 30 hours at a constant air flow rate.

At this time, a part of the catalyst was pulverized and scattered out of the system, and the proportion of this pulverized catalyst was taken as the wear resistance index.

Next, the activity and selectivity of the catalytic IA was determined by ASTM (D-3).
907) Evaluated by MAT (Microactivity Test). In addition, in order to examine the nickel resistance of the catalyst, 1 wt% of nickel was added to the catalyst.
methods (Ind, Eng, Cheap, Pro
d.

Res, Dev, , 19. 209 (1980)
). That is, after the catalyst was impregnated in a toluene solution of nickel naphthinate, the solvent was evaporated, and then this was air-calcined at 550° C. for 3 hours. Furthermore, in order to make the performance of the catalyst thus obtained the same as that of the equilibrium catalyst, the catalyst was steamed at 170° C. for 6 hours before being subjected to MAT. MAT reaction conditions are WHS V 1.6
hr −1, catalyst/oil conversion 3, reaction temperature 482°C,
The raw material oil is an ASTM standard oil. The MA■ results are shown in Table 1. Here, the decomposition rate in Table 1 is defined as follows.

Decomposition rate = [(Feedstock oil - fraction with boiling point of 216°C or higher)/Feedstock oil] x 100 (wt%) Tomo 11L 6g of sodium aluminate and 0.20C gluconic acid 6g
Dissolve in 0 cc of pure water and heat to 50°C. Separately, 6.4 g of aluminum sulfate was dissolved in 60 cc of pure water and heated to 50°C. Thereafter, both solutions are mixed in the same manner as in Example 1 (A) to obtain pseudo-boehmite. 77 (l of aluminum chloride, 20 g of magnesium chloride and 0.7 g of phosphoric acid mixed aqueous solution 300C) into ammonia.
C was added dropwise to form an alumina (1)/magnesia/phosphere hydrogel. The pH at this time is 9.5. Next, this hydrogel and the pseudo-boehmite hydrogel are mixed and aged at a temperature of 85° C. for 4 hours. After aging, the gel is filtered and washed with a sufficient amount of pure water. The total amount of the alumina (1) and (2) magnesia phosphere hydrogel thus obtained and 4.4 g of the zeolite prepared in <8) of Example 1 were kneaded, and then treated in the same manner as in Example 1. The catalyst obtained is designated as B.

The wear resistance and catalytic performance of this catalyst were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Dissolve 96G of aluminum chloride, 20(J) of magnesium chloride and 0.7g of phosphoric acid in 400CC of pure water. Add ammonia water to the above mixed solution and dissolve alumina (1).
- Obtain magnesia phosphere hydrogel. The pH at this time is 9.5. This hydrogel is then aged for 4 hours at a temperature of 85°C. After aging, the gel is filtered and washed with a sufficient amount of pure water.

The total amount of alumina (1)/magnesia/phosphere hydrogel thus obtained was mixed with 464 g of zeolite prepared in (B) of Example 1, and the resulting catalyst was then treated in the same manner as in Example 1. Let it be C.

The wear resistance and catalytic performance of this catalyst were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

1N2 The same amount of pseudoboehmite as in Example 1 was prepared in the same manner as in Example 1 (A). Next, 200 cc of a mixed aqueous solution of 489 aluminum chloride and 20 g of magnesium chloride is dropped into the ammonia to form an alumina (1)/magnesia hydrogel. The pH at this time is 9.5. Next, this hydrogel and the pseudo-boehmite human 0 gel are mixed and aged at a temperature of 85° C. for 4 hours. After aging, the gel is filtered and washed with a sufficient amount of pure water. The total amount of alumina (1) and (2)/magnesia hydrogel thus obtained was mixed with 4.3 g of zeolite prepared in (B) of Example 1, and then treated in the same manner as in Example 1. The catalyst is designated as D.

The wear resistance and catalytic performance of this catalyst were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

L rice f1 30g of sodium aluminate and 1cc of gluconic acid 3
Dissolve in 00 cc of pure water and heat to 50°C. Separately, 32Q aluminum sulfate was dissolved in 300 cc of pure water and heated to 50°C. Thereafter, both solutions are mixed in the same manner as in Example 1 (A) to obtain pseudo-boehmite. Then into ammonia 209 of magnesium chloride and 0.1
100 cc of a phosphoric acid mixed aqueous solution of 100 g was added dropwise to form a magnesia phosphere hydrogel. The pH at this time is 9.5. Next, this hydrogel and the boehmite hydrogel are mixed and aged at 85° C. for 4 hours. After aging, the gel is filtered and washed with a sufficient amount of pure water. The alumina (2)/magnesia/phosphere hydrogel thus obtained and 4.4 g of the zeolite prepared in (8) of Example 1
The catalyst obtained by kneading and treating in the same manner as in Example 1 is hereinafter referred to as E.

The wear resistance and catalytic performance of this catalyst were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Table 1 [Alumina (2)/(Alumina (1) + Alumina (2)
) ] x 100 From these results, it can be seen that catalysts A and B have excellent metal resistance and are catalysts with high wear resistance. A catalyst that does not contain alumina (2) via pseudo-boehmite (catalyst C) has high metal resistance but low wear resistance. On the other hand, a catalyst containing only alumina (2) via pseudo-boehmite (catalyst E) has high wear resistance but poor metal resistance. Further, a catalyst that does not contain phosphorus (catalyst D) has poor metal resistance.

Claims (1)

[Scope of Claims] A catalyst containing a matrix consisting of 1.3 to 40 wt% of crystalline aluminosilicate zeolite and 60 to 97 wt% of alumina, magnesia, and phosphere, (1) the alumina content in the matrix is 40-9
0 wt%, magnesia content is 2 to 50 wt%, phosphere content is 0.1 to 30 wt%, (2) 10 to 70 wt% of the alumina is alumina via pseudoboehmite, (3) All pores of the catalyst Volume is 0.25~1.0cc/
g, pore volume of 600 Å or less is 0.2 to 0.7 cc/g
, and the pore volume of 600 Å or less is 70% of the total pore volume.
A hydrocarbon conversion catalyst characterized by the following.