JPS63270546A - Catalyst for conversion of hydrocarbon - Google Patents

Abstract

PURPOSE:To increase metal resistance and abrasion resistance of a catalyst for conversion of hydrocarbon by forming the catalyst by mixing crystalline aluminosilicate zeorite and matrix consisting of smectite type clay substance, etc., in a specified proportion. CONSTITUTION:The catalyst for conversion of hydrocarbon is produced by mixing alumina.magnesia.phosphia hydrogel slurry, and slurry of zeorite and clay substance, spray-drying the mixture with 200-350<= hot air and thereafter calcining it at 500-600 deg.C. The catalyst contains 3-40wt.% crystalline aluminosilicate zeorite and 60-97wt.% matrix consisting of alumina, magnesia, phosphia and smectite type clay substance. The matrix contains 5-80wt.% alumina, 1-40wt.% magnesia, 0.1-40wt.% phosphia and 10-90wt.% clay mineral.

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 0.5 ppm or more to obtain light oils such as gasoline and kerosene.

[Technical background of the invention and its problems 1] Conventional catalytic cracking decomposes petroleum hydrocarbons by contacting them with a catalyst to obtain a large amount of light components such as LPG and gasoline and a small amount of cracked light oil, etc. Furthermore, the coke deposited on the catalyst is removed by combustion with air, and the catalyst is recycled and reused.

At that time, the feedstock oil has conventionally been light gas oil (LGO) from the atmospheric distillation column, heavy gas oil (+-IGO>,
So-called distillate oil such as vacuum oil (VGO) from a vacuum distillation column is mainly used.

However, recently, with the global shift to heavier crude oil and changes in the demand structure 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 target oil.

However, heavy oil containing distillation residue contains much higher amounts of metals such as nickel, vanadium, iron, copper, and sodium than distillate oil, and these metals are not easily absorbed by catalysts. is known to significantly inhibit decomposition activity and selectivity. In other words, as metals accumulate on the catalyst, the decomposition rate decreases, making it practically impossible to achieve the desired decomposition rate, while the amount of hydrogen and coke generated increases significantly, making it difficult to operate the equipment. At the same time,
The yield of the desired liquid product is reduced.

Among the heavy metals contained in heavy oil, the main catalyst poisons are vanadium and nickel, but it has been revealed that there are considerable differences in the effects of these metals on catalysts. That is, nickel is said to hardly reduce catalytic activity, but increases coke and hydrogen yields, and vanadium mainly destroys zeolite and reduces activity.

Some catalysts that are resistant to the effects of such heavy metals have also been developed. For example, there is a method to improve vanadium resistance by increasing the zeolite content in the catalyst (Canadian Patent No. 1,089,390), but in this case, the octane number of the gasoline produced due to the high hydrogen transfer reaction activity of zeolite is The disadvantage is that it decreases. Catalysts using large pore size matrices (AmeriKong Patent 3,
944,482) has excellent vanadium resistance.

However, these catalysts are not resistant to the effects of nickelation. Catalysts containing aluminum phosphate in the matrix (U.S. Pat. No. 4,222,896@, U.S. Patent No. 4,
No. 228,036, No. 4,407.730, No. 4,4
07.732) has excellent metal resistance, but it has not yet been put into practical use because of its low catalyst strength and high cost. Catalysts with low catalytic strength have poor wear resistance, and when fluid catalytic cracking is performed using such catalysts, a large amount of catalyst is scattered outside the reactor, which not only requires a large amount of catalyst replenishment. , which is also unfavorable for the operation of the device.

[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, when cracking heavy oil containing 0.5 ppm or more of heavy metals such as nickel, vanadium, iron, etc., it can 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 having high properties and wear resistance.

[Constitution of the Invention] The present invention provides crystalline aluminosilicate gel olide with 3-
40wt%, a matrix consisting of alumina, magnesia, phosphere and smectite clay minerals
97 wt%, and the alumina content in the matrix is 5 to 80 wt%, and the magnesia content is 1 to 40 w.
t%, phosphere content is 0.1 to 40 wt%, and the clay mineral content is 10 to 90 wt%.

[Summary of the Invention] The alumina (AJ203) used in the present invention is preferably at least one selected from aluminum trihydrate selected from bi7lite, gibbsite, and norstrandite, or alumina via amorphous alumina hydrate. .

Examples of starting materials for producing alumina include aluminum chloride (AJCJ3, AJCl3.6H2).
0), aluminum nitrate [AJ (NO3)3/9
H20], aluminum I acid [A1.2(804)3
, AJ2 (804)3 ・18820F, sodium aluminate (Na AJO2), potassium aluminate) (
KAJ02), aluminum isopropoxide (A
J C0CH<H3)213 ), aluminum ethoxide [AJ (OC2H5)3 ], aluminum t-butoxide (AU [OC(CI-13)3]
3rd prize is mentioned.

Particularly preferred are aluminum salts, such as aluminum chloride (AJCJ3, AJCJ3 6H20),
Aluminum nitrate [Aj(NO3)3・9H20,
Aluminum sulfate [AJ2 (S04)3, AJ
2 (SO4)3.18H20], aluminum Mfg1 such as sodium aluminate (Na A102), and the like.

As a starting material for producing magnesia (M(IQ)) used in the present invention, for example, magnesium nitrate [Mg(NO3)2
・6H20], magnesium chloride (MgcJ2 ・
6H20), magnesium sulfate (MIJSO4/7
H20), etc.

The smectite clay mineral referred to in the present invention is crystalline3.
It is a phyllosilicate mineral with a layered structure, such as montmorillonite, bentonite, hectorite, nontronite, beidellite, saponite, sodalite, magnesium montmorillonite, iron montmorillonite, iron magnesia montmorillonite, aluminium beidellite, aluminum annontronite, aluminum At least one kind of clay mineral selected from niangsaponite and the like can be used.

In the present invention, montmorillonite and/or bentonite are particularly preferably used.

In the present invention, other clay minerals such as kaolin group, clay mica group, chlorite group, etc. are added to the smectite type clay mineral, specifically selected from kaolinite, detsucanite, nacrite, halloysite, clay ffff1, chlorite, etc. The content of at least one clay mineral of 90 wt% or less, preferably 60 wt% or less can be used.

The clay mineral used in the present invention has a surface area of 1 to 30 Td/
g, and those having an average particle diameter of 0.01 to 10 μ- are preferable.

Phosphoric acid or a phosphate salt is preferable as a starting material for producing the phosphere (P20s) used in this brief description. As phosphoric acid and phosphate salts, acids such as orthophosphoric acid, birophosphoric acid, polyphosphoric acid and metaphosphoric acid, and salts thereof such as ammonium salts and sodium salts are preferable.

The crystalline aluminosilicate zeolite used dispersed in the matrix in the present invention is a natural or synthetic crystalline aluminosilicate with a three-dimensional framework structure and a uniform pore size within the range of about 4 to 15 pores. It is a porous material. Natural zeolites include gmelinite, chabasite, dakiardofluorite, clinoptilolite, faujasite, kiftite, borofluorite, levinite, erionite, sodalite, cancrinite, ferrierite, Brewsterite, offretite,
Any of soda fluorite, mordenite, etc. may be used, but faujasite is most preferred.

Zeolites X, Y, and A are synthetic zeolites.

L, ZK-4, B, E, F, HJ, MlQlT.

Any of W, Z1 alpha, beta, ZSM type, omega etc. may be used, but Y type and X type zeolites or mixtures thereof are most preferred.

It is well known that when zeolite is used 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 zeolide can be reduced by the ion exchange method. Cations include calcium, magnesium,
Hydrogen or rare earth elements such as Ce, SC, Y, [a, AC, etc., and platinum, palladium, etc. are preferable, and when used as a catalytic cracking catalyst, hydrogen and rare earth elements or a mixture 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 80-150°C for a day and night, and then air-calcined at 400-650°C for 2-10 hours. Na2 in the zeolite thus obtained
The O content ω is 0.5 to 2.0 wt%, but by further ion exchange after air firing, the Na2O content m can be reduced to 1.
wt% or less.

The composition ratio of the catalyst of the present invention is such that the crystalline aluminosilicate zeolite content is 3 to 4 wt%, preferably 5 to 3 wt%.
It is 0wt%. The content of the matrix consisting of alumina, magnesia, phosphere and clay minerals is 60-9
7wt%, preferably 70-95wt%. If the content of the zeolite is less than 3 wt%, the catalytic activity is low, which is not preferable. In addition, the content of zeolite is 40
When the amount is more than % by weight, the catalyst activity is too high and over-decomposition occurs, resulting in a decrease in the yield of the desired product.

The alumina content in the matrix is 5 to 80 wt%
, preferably 10 to sowt%, the content of magnesia is 1 to 40 wt%, preferably 2 to 20 wt%, and the content of phosphere is 0.1 to 40 wt%, preferably 0.5 to 20 wt%. used.

If the alumina content in the matrix is less than 5 wt%, the wear resistance will be poor, and if it is more than 80 wt%, the metal resistance will be poor.

If the magnesia content in the matrix is less than 1 wt%, a catalyst with high metal resistance cannot be obtained.

Furthermore, when the phosphere content is less than 0.1 wt%, metal resistance is somewhat reduced. Also, if the magnesia content is more than 40 wt% or the phosphere content is 4
If the amount is more than 0 wt%, a catalyst with sufficient wear resistance cannot be obtained.

The content of clay mineral in the matrix is 10 to 90 wt.
%, preferably 40 to 80 wt%. If the clay content is less than 10 wt% or more than 90 wt%, a catalyst with sufficient wear resistance cannot be obtained.

As the clay mineral, at least one type of smectite clay mineral is preferably used, or clay minerals other than smectite type are preferably used in an amount of 90 wt% or less, preferably 60 wt%.
It is possible to use a clay mineral mixed with at least one smectite type clay mineral in a range of % or less.

The method for producing the catalyst of the present invention is not particularly limited, but examples include the following. First, a mixed aqueous solution of the starting materials, aluminum salt, magnesium salt, and phosphoric acid, is reacted with ammonia to form an alumina-magnesia-phosphere hydroglucose slurry.

The hydrogel slurry is then filtered and washed with sufficient pure water. The alumina in the cake thus obtained is
As a result of line diffraction, it was found to be an amorphous alumina hydrate.

Next, the alumina-magnesia-phosphere hydrogel slurry was mixed with each slurry of zeolite and clay mineral, and spray-dried with hot air at 200 to 350°C.
Obtained by firing at ~600°C.

The resulting catalyst is in a state in which zeolite is dispersed and supported in a matrix consisting of alumina, magnesia, phosphere, and clay minerals. Furthermore, alumina, magnesia, and phosphor are composite oxides of these.

In the present invention, a binder such as alumina sol or silica sol may be added to further increase the strength of the catalyst, and this is also included within the scope of the present invention.

The catalyst of the present invention has a surface area of 50 to 400 TIt/g, a pore volume of 0.1 to 1.2 cc/g, and an average particle size of 40 to 8
Preferably, the thickness is in the range of 0 μm.

[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.

Since the surface area of the clay mineral contained in the matrix of the catalyst of the present invention is very small compared to the alumina-magnesia-phosphere composite oxide, most of the heavy metals in heavy oil are carried on the alumina-magnesia-phosphere composite oxide. accumulate. Although the reason for the immobilization and inactivation of heavy metals deposited on the alumina-magnesia-phosphere composite oxide 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.

Vanadium pentoxide has a relatively low melting point of 674°C, so
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, 1. The vanadium pentoxide deposited on the alumina-magnesia-phosphere composite oxide is alumina,
It reacts with magnesia or phosphere to form a stable, high-melting-point composite oxide (for example, 3MoO.V20s) and is immobilized. Although the action of phospheres in the alumina-magnesia-phosphere composite oxide is not yet clear,
It is thought that the purpose is to promote the solid phase reaction as described above. In addition, although it is not clear why the catalyst strength increases by mixing the alumina/magnesia/phosphere composite oxide with clay minerals, it is possible to This is thought to be due to strong bonding with clay minerals.

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

Example 1 (A) Alumina-magnesia-phosphere hydrogel was prepared as follows.

Dissolve 186 g of aluminum nitrate, 320 g of magnesium nitrate, and 14 (l) of orthophosphoric acid in 1 J of pure water.

The above mixed solution is added dropwise to 4N ammonia water with vigorous stirring so that the final pH is 10. The resulting precipitate is filtered and washed with sufficient amount of pure water.

(B) 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 lanthanum chloride 415 (1) and 75 g of ammonium chloride, and add pure water to it so that the total volume is 5. While heating this to about 80℃, use a magnetic stirrer to
After stirring for an hour, it is filtered and washed with 5 J 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, it is baked at 500°C for 2 hours. la obtained in this way.

The a exchange rate of the H-Y type zeolite was 77%, and the residual N820M was 0.81 wt%.

Next, 28g of this zeolite and montmorillonite 1179
Catalyst A I got it.

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

That is, 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 catalyst A was determined according to ASTM ([)-
3907) Evaluated by MAT (Micro Activity Test). Additionally, in order to examine the nickel resistance of the catalyst, Mitchell added 1 wt% of nickel to the catalyst.
method (Ind, Eng, Chcm, Prod
.

Res, Dev,,19. 209 (1980))
It was carried in accordance with. 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. In addition, in order to make the performance of the catalyst obtained in this way the same as that of the equilibrium catalyst,
The catalyst was steamed at 770° C. for 6 hours before being subjected to MAT. MAT reaction conditions are WS2 V 1.6hr
-1, catalyst/oil conversion 3, reaction temperature was 482°C, and the raw material oil was an ASTM standard oil. The MAT results are shown in Table 1. Here, the decomposition rate in Table 1 is defined as follows.

Decomposition rate = [(raw oil - fraction with a boiling point of 216 ° C. or higher)/raw oil] x 100 (wt%) Example 2 Alumina-magnesia-phosphere hydrogel was prepared in the same manner as in Example 1 (A). , and in Example 1 (
The catalyst obtained by mixing zeolite 28 (l) of B), kaolin 399, and montmorillonite 78Q and treating the same as in Example 1 will be referred to as B.

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

Example 3 186 g of aluminum nitrate, 3217 magnesium nitrate, and 3.6 g of phosphoric acid are dissolved in 1] of pure water.

The above mixed solution is added dropwise to 4N ammonia water with vigorous stirring so that the final pH is 10. The resulting precipitate is filtered and washed with a sufficient amount of purified water to obtain an alumina-magnesia-phosphere hydrogel. To this, zeolite 23Q of Example 1 (B) and montmorillonite 98
The catalyst obtained by mixing G and treating in the same manner as in Example 1 is hereinafter referred to as C.

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

Comparative Example 1 An alumina-magnesia-phosphere hydrogel was prepared in the same manner as in (A) of Example 1, and 280 g of zeolite and 117 g of kaolin in (B) of Example 1 were mixed therein. A catalyst obtained by the same treatment as in Example 1 is designated as D.

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

Comparative Example 2 Alumina-magnesia-phosphere hydrogel was prepared in the same manner as in Example 1 (A), and added to it in Example 1 (A).
The catalyst obtained by mixing 7 g of zeolite B) and treating in the same manner as in Example 1 is referred to as E.

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

Comparative Example 3 186g of aluminum nitrate and 329g of magnesium nitrate are dissolved in 11g of pure water. The above mixed solution was added dropwise to 4N ammonia water with vigorous stirring until the final 1) H was 10. The resulting precipitate is filtered and washed with sufficient pure water to obtain an alumina-magnesia hydrogel. 21 g of the zeolite (B) of Example 1 and 91 CI of montmorillonite were mixed with this and treated in the same manner as in Example 1. The resulting catalyst was designated as F.

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

186 g of aluminum nitrate and 14 (J of phosphoric acid 1)
Dissolve in pure water. The above mixed solution is added dropwise to 4N ammonium water with vigorous stirring so that the final pH is 10. The resulting precipitate is filtered and washed with a sufficient amount of pure water to obtain an alumina phosphere hydrogel. The zeolite 24Q of Example 1 (8) and 102 g of montmorillonite were mixed with this and treated in the same manner as in Example 1. The resulting catalyst was designated as G.

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

From these results, it can be seen that catalysts A, B, and C have high metal resistance and high wear resistance. Touch [D, E
Both do not contain smectite clay minerals and have low wear resistance. A catalyst that does not contain phosphorus (catalyst F) has a somewhat higher dry gas and coke yield than catalyst A, and is inferior in metal resistance. A catalyst that does not contain magnesia (Catalyst G) has extremely poor metal resistance.

Claims (1)

[Claims] 1. Crystalline aluminosilicate zeolite of 3 to 40w
t%, a matrix consisting of alumina, magnesia, phosphere and smectite clay minerals from 60 to 97w.
t%, and the alumina content in the matrix is 5 to 80 wt%, the magnesia content is 1 to 40 wt%,
A hydrocarbon conversion catalyst characterized in that the phosphere content is 0.1 to 40 wt% and the clay mineral content is 10 to 90 wt%. 2. The hydrocarbon conversion catalyst according to claim 1, wherein the alumina is at least one selected from biaryte, gibbsite, norstrandite, and amorphous alumina hydrate. 3. The smectite clay mineral is montmorillonite,
Claim No. 1, which is at least one selected from bentonite, hectorite, beidellite, nontronite, saponite, sauconite, magnesium montmorillonite, iron montmorillonite, iron magnesia montmorillonite, aluminum beidellite, aluminum annontronite and aluminum saponite. The hydrocarbon conversion catalyst according to item 1. 4. The hydrocarbon conversion catalyst according to claim 1, wherein the smectite clay mineral is montmorillonite and/or bentonite.