RU2283177C2 - Catalyst for fluidized-bed catalytic cracking of heavy hydrocarbons and fluidized-bed catalytic cracking process - Google Patents

Abstract

FIELD: petroleum processing.

SUBSTANCE: catalyst represents a mixture comprising: particulate catalyst prepared by homogenously dispersing crystalline aluminosilicate zeolite in inorganic oxide matrix and particulate additive-type catalyst deactivating metals impairing catalyst and contained in oil feedstock, un which catalyst calcium carbonate with average particle diameter 0.001 to 30 μm is dispersed in inorganic matrix through which amount of said calcium carbonate achieved 30 to 70% based on dry material. Ratio of catalyst to additive-type catalyst ranges between 99.9:1 and 50:50. Catalyst shows excellent cracking power and is able to process petroleum distillation residues.

EFFECT: increased catalytic activity and prolonged lifetime.

3 cl, 8 dwg, 11 tbl, 14 ex

Description

TECHNICAL AREA

The present invention relates to a catalyst for catalytic cracking in a fluidized bed (hereinafter referred to as "FCC") of heavy petroleum products and a method for FCC oil using such a catalyst. More specifically, the present invention relates to a very durable FCC catalyst, which not only passivates the metals poisoning the catalyst contained in the oil, for example nickel and vanadium, reduces the amount of hydrogen or coke generated, has excellent cracking activity and the ability to process oil residue and can produce gasoline and fraction of light recycle gas oil with high yields without lowering the octane number, but can also maintain these performance characteristics at a high level not for a long period of time, and relates to an FCC method using this catalyst.

BACKGROUND OF THE INVENTION

Recently, in the catalytic cracking of liquid petroleum products, there is a need to improve the quality of less expensive low-grade heavy crude oil and at the same time there is an ever-increasing tendency to increase the weight of crude oil.

Heavy petroleum feeds contain a huge amount of metals such as nickel, vanadium and the like, and these metals are almost completely deposited on the catalyst.

In particular, it is known that when vanadium precipitates and accumulates on the catalyst, it destroys the crystalline structure of crystalline aluminosilicate zeolite, which is the active ingredient of the catalyst, and therefore a significant decrease in catalytic activity occurs, and the amount of hydrogen and coke generated increases.

On the other hand, it is known that nickel causes catalytic dehydrogenation during deposition and accumulation on the surface of the catalyst and therefore increases the amount of hydrogen and coke generated, resulting in nickel causing problems such as, for example, a rise in temperature in the regeneration column.

When petroleum feedstocks containing a large amount of heavy petroleum residues (for example, residues after distillation of light fractions or distillation under vacuum) are used, not only the influence of metals becomes significant, but also sulfur compounds contained in the petroleum residues cause a problem in that the amount is increased SO _x in the flue gases from the catalyst regeneration column, and the fraction of the oil product, in particular gasoline, has an increased sulfur concentration.

In addition, an increase in the processed amount of oil residue leads to an increase in the replenished amount of the catalyst and causes problems associated with an increase in the cost of the catalyst and the environmental load due to an increase in the amount of catalyst waste.

So far, various methods have been proposed for the passivation of poisonous metals such as vanadium and the like, which are deposited on the catalyst, which incorporate an alkaline compound or the like as a metal passivator in the catalyst, thereby improving the resistance of the catalyst to metals. Examples include a method in which a water-soluble alkaline earth metal compound or the like is ion exchanged with a zeolite or inorganic oxide matrix, and a method in which a water-insoluble oxide (e.g. dolomite, sepiolite, anionic clay or the like) is embedded in a matrix of inorganic oxide (JP-A-62-57652, JP-A-63-182031, JP-A-3-293039, etc.).

Although alkaline earth metal compounds have the effect of passivation of toxic metals, they do not have cracking ability when used alone. Therefore, they are used as a metal passivator after incorporation into the inorganic oxide matrix having cracking ability, as described above. However, since alkaline earth metal migrates (especially a magnesium compound or the like) in the form of a low-melting compound during catalytic cracking reactions and its alkaline nature destroys the crystalline structure of crystalline aluminosilicate zeolite, the thermal stability of the catalyst decreases.

The catalyst described above, obtained by incorporating an alkaline earth metal compound into crystalline aluminosilicate zeolite by ion exchange, has problems, for example, in that the gasoline product resulting from the catalytic cracking reaction has a reduced octane number (RON).

In addition, in the case where anionic clay or the like is used, clay of natural origin is rare and therefore significantly increases the cost of the catalyst, while synthetic clay products are also not cheap and lead to an increased cost of the catalyst.

In addition, when the alkaline earth metal compound is dispersed as a metal passivator in the inorganic oxide matrix, the pH of the catalyst suspension varies significantly due to the alkaline nature of the compound, so that the catalyst is difficult to produce.

In particular, magnesium compounds are washed out in the washing step of the catalyst with an aqueous solution of ammonia, an aqueous solution of ammonium sulfate or the like (removal of an alkali metal such as sodium or potassium from the catalyst). Therefore, it is difficult to wash the magnesium-containing catalyst, and its incorporation into the catalysts is problematic.

On the other hand, an additional advantage of the above described catalyst compositions having a vanadium capture effect is that they have the ability to bind SO _x (see US Pat. No. 4,889,615, etc.). The ability is effective to reduce the content of SO _x in the exhaust gas from the regeneration column and to reduce the sulfur content in the oil product.

Heavy oil products, in particular, have a high sulfur content, and sulfur compounds are deposited on the catalyst together with coke and converted to SO _x in the regeneration column of the FCC unit. SO _x reacts with an alkali metal oxide and is thus captured by the catalyst. Sulfur trapped in this way can be separated and disposed of after it has been converted to hydrogen sulfide by upstream reactions. It is known that catalyst compositions thus reduce the amount of SO _x in the combustion gases and lower the sulfur content in the oil product.

However, when nickel accumulates on the surface of the catalyst, there are often cases where the metal passivator described above does not have a passivating effect on nickel. Accordingly, a technique was proposed for supplying a specific antimony compound (an organic antimony compound, etc.) to petroleum feedstocks to thereby passivate nickel deposited on the catalyst surface (JP-A-63-63688, JP-A-1-213399, etc. .d.).

However, the antimony compound accumulates in the form of precipitated metal antimony (a low-melting compound having a melting point of 500 to 700 ° C) on a control valve and similar devices in the FCC unit.

DESCRIPTION OF THE INVENTION

From the various points of view described above, an object of the present invention is to provide an FCC catalyst of a very durable type (having a service life of at least two times that of standard catalysts), where a metal passivator can be introduced without compromising catalytic activity, and which does not it only effectively passivates the catalyst poisoning metals contained in heavy hydrocarbons included in the refined petroleum feedstock, reduces the amount of hydrogen or coke generated It has excellent cracking activity and the ability to process oil residues and can yield gasoline and a fraction of light recycle gas oil in high yield without lowering the octane number, but can also maintain these performance characteristics for a long time.

The applicants of the present invention have conducted intensive research in order to achieve this goal. As a result, it was found that when a specific carbonate selected from crystalline metal carbonates including a divalent metal and crystalline metal carbonates including a divalent metal and a trivalent metal is used as a metal passivator, then (a) the metals poisoning the catalyst contained in the petroleum feed such as nickel, vanadium and the like, can be effectively passivated, (b) the catalyst can be prepared regardless of the type of matrix of the inorganic oxide as a binder, and the catalyst can be used as an FCC catalyst on one common basis that does not require the presence of other catalytic materials (hereinafter “solid catalyst”) or an additive catalyst which is used in combination with other catalysts and (c) gasoline and the light recycle gas oil fraction can be obtained in high yields, while at the same time maintaining reduced selectivity for hydrogen and coke and without reducing the octane number, and these performance characteristics can be supported live at a high level for a long period of time. Thus, the present invention has been completed.

The FCC catalyst of the present invention, which was obtained based on this finding, (1) includes a compound that is a divalent metal compound, or a divalent and trivalent metal compound, showing a radiograph of a divalent metal carbonate.

In the catalyst, the compound may be (2) dispersed in an inorganic oxide matrix or may (3) be dispersed together with crystalline aluminosilicate zeolite in an inorganic oxide matrix.

The FCC method of the present invention involves the use of a standard catalyst A obtained by uniformly (uniformly) dispersing crystalline aluminosilicate zeolite in an inorganic oxide matrix as a mixture with at least one of the catalysts B described above in (1), C, which described above in (2), and D, which is described above in (3); catalyst D in the form of a mixture of at least one of catalysts B and C; or one catalyst D.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows the x-ray of MS-1 (Mn-Al-CO ₃ ).

Figure 2 shows an X-ray diffraction pattern of MS-2 (Ca-Al-CO ₃ ).

Figure 3 shows the roentgenogram of MS-3 (Sr-Al-CO ₃ ).

Figure 4 shows the x-ray of MS-4 (Ba-Al-CO ₃ ).

Figure 5 shows the x-ray of MS-7 (Ca-CO ₃ ).

6 shows an X-ray diffraction pattern of MS-8 (Ca-CO ₃ scallop shells).

Fig.7 shows the x-ray of MS-9 (Ca-CO ₃ oyster shells).

Fig. 8 shows a radiograph of hydrotalcite.

BEST MODE FOR CARRYING OUT THE INVENTION

The catalyst B of the present invention described in (1) does not exhibit cracking activity when one is used. This is a so-called additive type FCC catalyst that is added to the FCC catalyst and used with an FCC catalyst, such as the standard catalyst A described above, which has cracking activity.

Catalyst C described in (2) above is a catalyst in which the active ingredient of catalyst B is dispersed in an inorganic oxide matrix and which has improved mechanical strength. Catalyst C also does not have cracking activity when one is used. Like Catalyst B, Catalyst C is a so-called additive type FCC catalyst that is added to the FCC catalyst and used with an FCC catalyst such as the standard catalyst A described above.

Catalyst D described in (3) above is a catalyst in which the active ingredient of catalyst B is dispersed in an inorganic oxide matrix together with crystalline aluminosilicate zeolite that has cracking activity. Catalyst D has cracking activity, even when one is used, and can be used as the so-called solid type FCC catalyst.

The catalyst of the present invention, comprising a divalent metal compound, or a divalent and trivalent metal compound, showing a radiograph of a bivalent metal carbonate (hereinafter referred to as a “divalent and trivalent metal compound”) and having one peak that can be attributed to anionic clay or the like, is catalyst B of the present invention.

As divalent and trivalent metals, any divalent and trivalent metal can be used. However, preferably the divalent metal is at least one metal selected from the group consisting of Mg ²⁺ , Mn ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sn ²⁺ and Zn ²⁺ , and more preferably is at least one metal selected from the group consisting of Mn ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ and Sn ²⁺ . The trivalent metal is preferably at least one metal selected from the group consisting of Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , La ³⁺ , Mn ³⁺ , Ti ³⁺ , Ga ³⁺ , Sb ³⁺ and Bi ³⁺ , and more preferably is at least one metal selected from the group consisting of Al ³⁺ and Mn ³⁺ . In particular, Al ³⁺ is most preferred since it gives a large surface area.

The above-described divalent metal compound and the divalent and trivalent metal compound may be a compound of any desired combination of at least one of the above metals.

Namely, the divalent metal compound may be a compound having one of these divalent metals as the only divalent metal, or it may be a mixed compound having a combination of two or more of these metals. In this case, the metals can be mixed in any proportion.

As a compound of divalent and trivalent metals, a combination of at least one element selected from Mn ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ and Sn ²⁺ c is especially effective for passivation of catalyst poisoning metals and removal of SO _x Al ³⁺ , since the catalyst effectively absorbs nickel oxides, vanadium oxides and sulfur oxides. In this case, at least two divalent metals can be mixed in any proportion and at least two trivalent metals can be mixed in any proportion. However, the proportion of divalent metals to trivalent metals in which they must be mixed is such that the molar ratio of the divalent metal / trivalent metal is preferably from 0.5 to 10, more preferably from 2 to 5.

When aluminum oxide is used as the matrix of inorganic oxide in catalysts C and D, the divalent metal compound among the metal compounds is preferably a compound containing Ca ²⁺ , Sr ²⁺ or Ba ²⁺ , since the catalyst has a high ability to passivate the catalyst poisoning metals.

When a bivalent metal compound or a divalent and trivalent metal compound is used as catalyst B, a suitable form of the compound is a free-flowing form having an average particle diameter equal to the particle diameter of standard catalyst A or catalyst C or D that must be used in combination with it, i.e. e. from 50 to 90 microns, bulk density from 0.3 to 1.2 g / ml and oil absorption of 0.1 cm ³ / g or more.

On the other hand, when the compound is mixed with an inorganic oxide matrix, crystalline aluminosilicate zeolite, etc. and used as a component of the catalyst C or D, its suitable form is a free-flowing form having an average particle diameter of from 0.0001 to 60 μm, preferably from 0.001 to 30 μm and most preferably from 0.1 to 10 μm. When its particle diameter exceeds 60 μm, the resulting catalyst C or D is undesirable as an FCC catalyst in terms of bulk density, catalyst strength, etc., since this particle diameter is equal to the average particle diameter of the catalyst C or D. When it the particle diameter is less than 0.0001 microns, it is difficult to handle.

Examples of the divalent metal compound and examples of the divalent and trivalent metal compounds include oxides, carbonates, sulfates, halides, phosphates and the like. Among these compounds, carbonates are preferred. Carbonates can be synthetic or natural, and commercial products can be used as they are.

When alumina is used as the inorganic oxide matrix in catalysts C and D, calcium carbonate, strontium carbonate and barium carbonate are preferred carbonates, in which Ca ²⁺ , Sr ²⁺ and Ba ²⁺ are divalent metals, from the point of view of not only passivate the catalyst poisoning metals, but also the abrasion resistance of the catalyst. In particular, calcium carbonate is most preferable because it has a lower true density compared to strontium carbonate and barium carbonate, prevents the increased bulk density of the resulting catalyst and makes the preparation of the catalyst easy, and calcium carbonate is safe and easy to handle. and it is easily accessible.

Synthetic carbonates can be obtained, for example, as follows.

Divalent metal carbonate is obtained by adding an aqueous solution of a water-soluble divalent metal salt to an aqueous solution of an alkali metal carbonate and adjusting its pH with an aqueous alkali solution to obtain a suspension of crystalline carbonate.

When at least two divalent metals are used in combination, aqueous solutions of the water-soluble salts of the at least two divalent metals are pre-mixed together and the mixture is treated in the same manner as described above to thereby obtain a suspension.

Carbonates of divalent and trivalent metals are obtained by pre-mixing an aqueous solution of a water-soluble salt of at least one divalent metal with an aqueous solution of a water-soluble salt of at least one trivalent metal and treating the mixture in the same manner as described above to thereby obtain a suspension .

The above water-soluble salts may be inorganic salts or organic salts. Examples of counterions in salts include F ^- , Cl ^- , Br ^- , I ^- , NO ₃ ^- , CO ₃ ^2- , SO ₄ ^2- , PO ₄ ^3- , ClO ₄ ^- , BO ₃ ^2- , CH ₃ COO ^- , oxalic acid, salicylic acid and the like. Preferred are inexpensive Cl ^- , NO ₃ ^- , SO ₄ ^2- and CO ₃ ^2- .

There are cases when acid ions are introduced into the gel during the aging of the suspension, depending on the type of such counterions, and the embedded acid ions are difficult to completely remove. Residual acid ions can have a deleterious effect on the resulting catalyst. Salts with NO ₃ ^- are most preferred, since the counterion is able to volatilize during processing by calcination and therefore does not cause such a complication.

As for the aqueous alkaline carbonate solution, to which it is necessary to add an aqueous solution of any of these water-soluble salts, carbonates are preferred in which the alkaline ions (counter-cations) are NH ₄ , Na and K, since they are generally inexpensive and readily available. However, when an aged suspension is used without washing or similar treatment, there are cases when ions are incorporated into the gel during aging depending on the type of alkali and adversely affect the resulting catalyst, as in the case of divalent metal salts of trivalent metals described above. NH ₄ salts are preferred because the counterion is capable of volatilizing during calcination and therefore does not cause such a complication.

The crystals of the crystalline carbonate suspension thus obtained are aged. Preferably, aging is carried out at a pH of from 6 to 14 and a temperature of from 0 to 100 ° C. Aging can be carried out for any period of time.

Generally, longer aging periods are favorable for producing larger crystals (particle diameter), and shorter aging periods can be used to produce smaller crystals. In addition, the higher the aging temperature, the higher the crystallinity.

To obtain crystalline particles having the particle diameter shown above, it is preferable that aging be carried out for 0.5 to 36 hours at a temperature of 50 to 90 ° C. and a pH of 8 to 11. Any carbonate thus obtained under such aging conditions is suitable for use as catalyst B of the present invention or as a component of catalyst C or D.

After aging of the crystals, the suspension of crystalline carbonate can be dried without any treatment and particle diameter ordering to be used as catalyst B, or it can be used without any treatment as a component of catalyst C or D. However, it is preferable to use the suspension after washing with an aqueous solution ammonia or an aqueous solution of ammonium salt and water to remove metal impurities and other impurities that may adversely affect the catalyst.

When the suspension is used as a component of catalyst C or D, control can be made so that it has a smaller particle diameter compared to FCC catalyst particles by spray-drying or drying the suspension, followed by grinding or a similar procedure. However, from the viewpoint of reducing the time period required to prepare the catalyst C or D, it is preferable to pre-arrange the particle diameter to the above size and use a suspension.

The crystalline carbonate of a divalent metal or divalent and trivalent metals significantly changes its basicity during heat treatment, and basicity has a significant effect on the ability to passivate metals.

Used in the present invention, the crystalline carbonate of a divalent metal or divalent and trivalent metals can be dried and calcined at a temperature of from 20 to 900 ° C. However, from the point of view of increasing the ability to passivate metals, the treatment is preferably carried out at a temperature of from 300 to 800 ° C, more preferably from 500 to 700 ° C.

Examples of natural carbonates include animal ores, shells, and bones.

Examples of ores include calcite, Icelandic spar, aragonite, limestone, marble, chalk, strontianite, witerite, rhodochrosite and the like.

As natural shells and bones of animals, any shells and bones of animals can be used. Examples include abalone shells, corbicula, mollusk Tapes Philippinarum, bivalves, oysters, scallops, Turbo snails and the like, and bones of cattle, pigs, horses, sheep, chickens, fish and the like. They are readily available and cheap. In addition, when shells are used, they give an effect of increasing the abrasion resistance of the catalyst.

Natural carbonates can be used individually or, accordingly, at least two of them can be selected and used in the form of a mixture thereof in an appropriate proportion.

Shells and bones contain organic matter, water, and the like. Therefore, it is preferable to use shells or bones after they are washed, calcined and then ground. Calcination can be carried out under any conditions that ensure the removal of organic substances, water, etc. The corresponding calcination is carried out at a temperature of from 300 to 900 ° C for about 10 minutes to 5 hours, preferably at a temperature of from 500 to 800 ° C for about 30 minutes to 5 hours.

Shells or bones that have been calcined under such conditions can be relatively easily ground. They can be directly chopped in a mill. Alternatively, they can first be crushed with a water jet or the like, and then crushed in a wet mill, or first crushed in a hammer mill or the like, and then crushed in a dry mill. Thus, the calcined shells or bones are ordered to have the average particle diameter described above.

It is desirable that catalysts B and C, which are additive type catalysts, have the same material properties as the standard catalyst A used with them in combination, or as the catalyst D used with them in combination, which is an integral type catalyst. When the catalysts differ in strength, particle diameter or bulk density, there are times when the catalysts are not uniformly mixed with each other and are unable to show sufficient catalytic performance.

The material properties of the catalysts A to D cannot be determined unconditionally, since they differ depending on the type of FCC unit and the operating conditions for it. However, from the point of view of obtaining satisfactory fluidity in an FCC apparatus, typically, the catalysts preferably have an average particle diameter of from 50 to 90 μm, a bulk density of from 0.3 to 1.2 g / ml and an oil absorption of 0.1 cm ³ / g or more as described above.

Catalyst C of the present invention includes an inorganic oxide matrix and a divalent metal compound dispersed therein or a divalent and trivalent metal compound and does not have FCC activity. That is, it is an additive type catalyst that is added to the FCC catalyst and used with an FCC catalyst having FCC activity, for example, standard catalyst A, catalyst D, etc.

In catalyst C, the amount of the metal compound is preferably from 1 to 90% by weight, and more preferably from 30 to 70% by weight, based on dry weight. When its amount is less than 1 wt.%, The ability to passivate metals and the ability to absorb SO _x is low. If its amount is increased so that it is more than 90 wt.%, Then not only do not substantially increase the effect, but a relatively reduced amount of inorganic oxide also leads to a decrease in particle bonding strength, which is a property of the inorganic oxide.

Examples of the inorganic oxide in catalyst C include known inorganic oxides used in conventional cracking catalysts, such as silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica zirconia, silica-magnesium oxide-alumina and the like. Clay such as kaolin, halloysite, montmorillonite or the like can be mixed with the inorganic oxide.

A particularly preferred example of catalyst C is a catalyst comprising a combination of alumina as an inorganic oxide and calcium carbonate as a divalent metal compound, since it has a high ability to passivate catalytic poisons.

Catalyst C can be prepared by adding a metal compound to an inorganic oxide, followed by uniform dispersion, spray drying the resulting mixture in a conventional manner, washing the resulting particles, if necessary, and then drying or drying / calcining them again.

In this operation, metal compounds of a certain type, due to their alkaline nature, can be difficult to uniformly mix with inorganic oxide or other optionally present catalyst ingredients. In this case, it is preferable to lower the basicity of the metal compounds by coating them with phosphoric acid, alumina coating or the like.

Catalyst D of the present invention includes a divalent metal compound or a divalent and trivalent metal compound, a crystalline aluminosilicate zeolite, and an inorganic oxide matrix in which the metal compound and zeolite are dispersed. The catalyst has a metal passivation effect, which is a property of a metal compound, and further has the FCC activity of crystalline aluminosilicate zeolite. Therefore, catalyst D is an integral type catalyst that can be used alone as an FCC catalyst.

In the catalyst D, the amount of the metal compound is preferably from 0.01 to 20 wt.%, More preferably from 0.1 to 10 wt.% And, most preferably from 0.5 to 5 wt.% By dry weight.

When its amount is less than 0.01 wt.%, The effect of passivation of metals and the capture of SO _x is insufficient. When its amount exceeds 20 wt.%, The relative content of crystalline aluminosilicate zeolite or inorganic oxide decreases, and FCC activity and gasoline selectivity decrease. As a result, it is not only difficult to produce catalytic cracking of petroleum feedstocks in a desirable manner, but also problems arise, such as, for example, reducing the strength of the catalyst.

The amount of crystalline aluminosilicate zeolite in the catalyst D is preferably from 10 to 50 wt.% And more preferably from 20 to 40 wt.% Calculated on the dry weight.

When its amount is less than 10 wt.%, The FCC activity and selectivity for gasoline decreases, which makes it difficult to catalytic cracking of crude oil in a desirable manner. When its amount exceeds 50 wt.%, The relative content of the metal compound or matrix of the inorganic oxide decreases and the desired metal passivation effect is not achieved or the desired catalyst strength cannot be obtained.

Examples of inorganic oxides in catalyst D include the same inorganic oxides as the oxides used in catalyst C. Clays such as those used in catalyst C can be introduced into the inorganic oxide.

Examples of crystalline aluminosilicate zeolites include zeolites X, zeolites Y, zeolites β, mordenite, ZSM zeolites, natural zeolites and the like. Similar to conventional FCC catalysts, zeolites can be used in an ion-exchanged form with a cation selected from hydrogen, ammonium and polyvalent metals.

Especially preferred are zeolites Y, and USY zeolites, which have excellent hydrothermal stability, are most preferred.

The most preferred zeolite is subjected to "thermal shock", i.e. a sharp increase in temperature crystalline aluminosilicate zeolite (hereinafter referred to as "HS zeolite"), which is obtained by firing stabilized zeolite Y, having a molar ratio of SiO ₂ / Al ₂ O ₃ from 5 to 15, the unit cell parameter from 24.50 Å to less than 24 , 70 Å and the alkali metal content (in terms of oxide) from 0.02 wt.% To less than 1 wt.% At a temperature of from 600 to 1200 ° C for 5 to 300 minutes in air or in nitrogen atmosphere, so that lead to a decrease in crystallinity of stabilized zeolite Y by 20% or less.

In zeolite, the molar ratio of SiO ₂ / Al ₂ O ₃ in the volume is from 5 to 15, and the molar ratio of aluminum present in the zeolite structure to the entire aluminum is from 0.3 to 0.6. Zeolite has a unit cell parameter of less than 24.45 Å and an alkali metal content (in terms of oxide) of 0.02 wt.% To less than 1 wt.% And has a pore distribution having characteristic peaks near 50 Å and 180 Å, where the pore volume with a size of at least 100 Å is from 10 to 40% of the total pore volume. The zeolite has a radiograph, which is the main radiograph of zeolites Y (See Japan Patent No. 2544317.)

Catalyst D can be prepared by adding zeolite and a metal compound to an inorganic oxide, followed by uniform dispersion to thereby prepare a suspension of the mixture, and treating the suspension in the same manner as in the preparation of catalyst C as described above.

In this production, it may be difficult to uniformly mix the metal compound due to its alkaline nature with inorganic oxide or crystalline aluminosilicate zeolite, or other optionally included catalyst ingredients. In this case, the alkaline nature of the metal compound can be reduced by coating it with phosphoric acid, coating with aluminum oxide, etc., as in the preparation of catalyst C.

Standard catalyst A, which can be used in combination with at least one of the B-D catalysts described above, comprises a matrix comprising an inorganic oxide and crystalline aluminosilicate zeolite uniformly dispersed in the matrix. Any variety of commonly used cracking catalysts may be used.

Examples of inorganic oxide and crystalline aluminosilicate zeolite include compounds that are the same as those of catalysts C and D of the present invention, which are described above.

In commonly used FCC catalysts, the amount of crystalline aluminosilicate zeolite dispersed in a matrix comprising an inorganic oxide or comprising an inorganic oxide and clay is from about 10 to 50 wt.% And preferably from about 20 to 40 wt.%. However, in the present invention, it is necessary to take into account the proportion of mixed catalyst B, C or D, since catalyst B, C or D is used in combination with standard catalyst A.

It is particularly suitable to control the amount of crystalline aluminosilicate zeolite to at least 10 wt.%, Preferably from 10 to 50 wt.% And more preferably from 20 to 40 wt.% Of the total amount of catalysts A, B, C or D.

When the amount of zeolite is less than 10 wt.%, The desired FCC activity cannot be achieved. Even when its amount is increased so that it is 50 wt.% Or more, the effect of mixing with zeolite is no longer enhanced. Therefore, such large amounts of zeolite are not economical.

To obtain the desired proportion of zeolite, it is advantageous to pre-adjust the amount of zeolite in the FCC catalyst.

The aforementioned desired standard catalyst A can be obtained by adding crystalline aluminosilicate zeolite to an inorganic oxide, followed by uniform dispersion, spray drying the resulting mixture in a conventional manner, washing the resulting particles, if necessary, and again drying or calcining the particles after drying .

The FCC method of the present invention is carried out using at least one of the additive type B and C catalysts described above and the whole type catalyst D described above in combination with the standard catalyst A or using the whole type catalyst D in combination with at least one from addition type catalysts B and C, or using one integral type D catalyst.

When at least one of the B-D catalysts is used in combination with standard catalyst A, the proportions of the catalysts used are determined taking into account the following.

When standard catalyst A is used in combination with catalyst D, any proportions thereof can be selected according to the desired metal passivation ability and the desired SO _x absorption capacity.

When one or both of catalysts A and D are used in combination with one or both of catalysts B and C, it is suitable that the ratio (one or both of catalysts A and D) / (one or both of catalysts B and C) be from 99, 9 / 0.1 to 50/50, preferably from 99.5 / 0.5 to 80/20, and more preferably from 99/1 to 90/10 in a weight ratio. When one or both additive type catalysts B and C comprise more than half the total amount of catalyst, the FCC activity and gasoline selectivity are reduced, which makes it difficult to catalyze cracking the crude oil in a desirable manner.

In the FCC method of the present invention, the A-D catalysts can be used as independent bulk catalysts in the proportions defined above, or used as particles of a pre-prepared mixture of catalysts in the proportions described above. FCC can be carried out by contacting a heavy liquid oil product as a crude oil with catalyst particles under FCC conditions.

Examples of heavy liquid petroleum products are, for example, vacuum distillation gas oil, light distillation residues, vacuum distillation residues, mixtures of these residues, and the like.

The FCC catalyst of the present invention is effective even when heavy liquid petroleum products with a reduced content of nickel or vanadium compounds and sulfur compounds are used as petroleum feed. However, the catalyst is extremely useful when it is used for catalytic cracking of low-grade heavy liquid petroleum products containing large amounts of poisonous metals and sulfur compounds (for example, having a sulfur content of 0.2 wt.% Or more and a metal content of 50 ppm (calculated on the amount of metal) or more). Therefore, the FCC method of the present invention can have a remarkable effect when such a low grade heavy liquid oil is used as a petroleum feed.

When practicing the FCC method of the present invention, the amount of metal impurities and sulfur compounds contained in the petroleum feed is taken into account. When their amount is significant, a mixture of a standard catalyst A or an integral type D catalyst with an additive type catalyst B or C can be used so that an increased proportion of the additive type catalyst B or C is contained. Thus, the decrease in FCC activity that may occur due to the relatively reduced amount of standard catalyst A or whole type D catalyst can be compensated by an increase in the amount of crystalline aluminosilicate zeolite dispersed in standard catalyst A or whole type D catalyst.

The FCC conditions used in the present invention may constitute commonly used FCC conditions. Typical examples of FCC conditions are the following conditions:

Reaction temperature: 460-540 ° C

Hourly average feed rate: 4-20 h ^-1

Catalyst / Oil Ratio: 4-12

In FCC methods, FCC catalysts that have been deactivated by coke deposition are typically regenerated by burning carbon and reused in FCC reactions. In the FCC catalyst and the FCC method of the present invention, standard catalyst A, whole type D catalyst, and additive type B and C catalysts that have been depleted can also be regenerated by existing regenerators under normal regeneration conditions and reused.

Regeneration is carried out at a temperature of from 600 to 750 ° C. The BD catalysts of the present invention exhibit an excellent SO _x trapping effect that is generated during this regeneration.

The BD catalysts of the present invention passivate the catalyst poisoning metals contained in petroleum feedstocks, such as nickel and vanadium, produce less hydrogen and coke, have excellent cracking activity and the ability to process oil stripping residues, and can produce gasoline and a light recycle gas fraction with high exits. In addition, the catalysts can maintain their performance at a high level over a long period of time and therefore have an improved catalyst life. In addition, since the catalysts absorb SO _x in large quantities, they are effective in reducing the amount of SO _x contained in the exhaust gas of the FCC unit.

EXAMPLES

Catalyst Preparation:

1. Preparation of crystalline metal compounds, including divalent metal or including divalent and trivalent metals

Example 1

In a 3-liter (hereinafter, liter is referred to as “l”, and milliliter is referred to as “ml”) glass beaker containing 1000 ml of distilled water, 271.9 g of manganese sulfate pentahydrate is dissolved, followed by stirring with a magnetic stirrer for 15 minutes obtaining a solution A. Solution A has a pH of 4.54.

In a 3-liter glass beaker containing 1000 ml of distilled water, 125 g of aluminum sulfate octadecahydrate is dissolved, followed by stirring with a magnetic stirrer for 15 minutes to obtain solution B. Solution B has a pH of 1.63.

Solution A is mixed with solution B in a 5 liter glass beaker, heated to 80 ° C. and stirred with a magnetic stirrer to obtain a solution C.

113.8 g of sodium carbonate are dissolved in a 5-liter glass beaker containing 1000 ml of distilled water, followed by heating to 80 ° C and stirring with an ultradisperser for 15 minutes to obtain a solution D. Solution D has a pH of 11.47.

As solution D is mixed with an ultradispersant, solution C is gradually added to it with a feed pump. During this operation, an aqueous ammonia solution is also added to maintain the pH of the solution mixture at a value of 9.

The mixture of solutions is aged by stirring at 80 ° C. for 3 hours to obtain a metal compound.

After aging, the solution is filtered through a Buchner funnel. To the separated suspension (metal compound), 2 L of distilled water heated to 80 ° C. is added. The resulting mixture was stirred and filtered. The operation is repeated to flush twice.

The suspension separated by filtration was dried at 100 ° C for about 24 hours to obtain a metal compound.

The metal compound that has been dried is ground in a mill to a particle diameter of 15 μm or less.

The metal compound is referred to as MS-1 (Mn-Al-CO ₃ ).

APS (average particle diameter) and SA (specific surface area) MS-1 were determined and the metal content was determined using an inductively coupled plasma spectrometer. The results are shown in table 1. Before the study by inductively coupled plasma spectroscopy, the samples were fired at 1100 ° C for 2 hours as a preliminary treatment.

Further, an X-ray diffractometer is used to analyze the crystal structure. The results are shown in FIG.

In Fig. 1, the results of an analysis by an X-ray diffractometer are shown in the upper part, data on the maxima are shown in the middle part, and Mn-Al-CO ₃ data from JCPDS-PDF (Joint Committee on Power Diffraction Standards - Power Diffraction; x-ray data bank powder samples) are shown at the bottom.

Figure 1 clearly shows that MS-1 has a crystalline structure of a divalent metal carbonate.

Example 2

Crystalline metal compounds are prepared in the same manner as in Example 1, except that the divalent metal is replaced with Ca ²⁺ , Sr ²⁺ , Ba ²⁺ or Sn ²⁺ using metal chloride or nitrate in solution A in Example 1 in an amount , equimolar manganese sulfate.

Crystalline metal compounds prepared using Ca ²⁺ , Sr ²⁺ , Ba ²⁺ or Sn ²⁺ as divalent metals are hereinafter referred to as MS-2 (Ca-Al-CO ₃ ), MS-3 (Sr-Al-CO ₃ ), MS-4 (Ba-Al-CO ₃ ) and MS-5 (Sn-Al-CO ₃ ), respectively.

APS and SA MS-2, MS-3, MS-4 and MS-5 are examined and the metal content is determined using an inductively coupled plasma spectrometer. The results are shown in table 1.

In addition, an X-ray diffractometer is used to analyze the crystal structure from MS-2 to MS-4. The results are shown in FIGS. 2-4. In Fig.2-4, the data in the upper, middle and lower parts have the same values as in Fig.1. Figure 2-4 clearly show that each of the samples from MS-2 to MS-4 has a crystalline structure of a divalent metal carbonate.

Example 3

A crystalline metal compound is prepared in the same manner as in Example 1, except that the trivalent metal is replaced with another metal using trivalent metal sulfate or nitrate in solution B in Example 1 in an amount equimolar aluminum sulfate.

A crystalline metal compound prepared using Mn ³⁺ as the trivalent metal is referred to as MS-6 (Mn-Mn-CO ₃ ).

APS and SA are determined for MS-6 and the metal content is determined using an inductively coupled plasma spectrometer. The results are shown in table 1.

Example 4

The first grade calcium carbonate reagent manufactured by Kanto Chemical Co., Inc. is hereinafter referred to as MS-7 (CaCO ₃ ); and powders obtained from scallop and oyster shells, calcined at 700 ° C for 2 hours and then pulverized, are designated as MS-8 (CaCO ₃ ) and MS-9 (CaCO ₃ ), respectively.

APS and SA are determined for MS-7, MS-8 and MS-9 and the metal content is determined by an inductively coupled plasma spectrometer. The results are shown in table 1.

In addition, an X-ray diffractometer is used to analyze the crystal structure of samples from MS-7 to MS-9. The results are shown in FIGS. 5-7. 5-7, the data in the upper, middle and lower parts have the same meaning as in figure 1. 5-7 clearly show that each of the samples from MS-7 to MS-9 has a crystalline structure of a divalent metal carbonate.

Table 1
Dry weight (wt.%) Hydrotalcite MS-1 MS-2 MS-3 MS-4 Al ₂ O ₃ 37,4 18.58 34.63 24.53 15.61 MgO 60 - - - - Mn ₂ About ₃ - 77.32 - - - CaO - - 63.81 - - Sr ₂ O ₃ - - - 73.91 - Wow - - - - 84.03 Sno ₂ - - - - - Na ₂ O - - 1,56 1,56 0.36 K ₂ O - - - - - APS (μm) 0.5 2 3.6 1.3 1,1 SA (m ² / g) 150 104 27 24 32 Table 1 (continued)
Dry weight (wt.%) MS-5 MS-6 MS-7 MS-8 MS-9 Al ₂ O ₃ 10.03 - - 0.4 0.3 MgO - - - 0.11 0.1 Mn ₂ About ₃ - 98.45 - 0.04 0.06 CaO - - 99.5 96.11 92.45 Sr ₂ O ₃ - - - 0.1 - Wow - - - - - Sno ₂ 89.89 - - - - Na ₂ O 0.08 - - 0.3 0.35 K ₂ O - - - 0.06 0,07 APS (μm) 1.6 1,5 1.7 2.7 3,5 SA (m ² / g) 53 12 2 5.9 6.9

2. Preparation of catalysts

Example 5

To 400 g of a silica hydrosol containing 10 wt.% SiO ₂ , 64 g of HS zeolite and 86 g of kaolin clay calculated on a dry weight basis are added to obtain a suspension of the mixture.

The suspension of the mixture is spray dried in order to obtain particles having an average particle diameter of 68 ± 5 μm. The particles are washed and then dried again to obtain standard catalyst A.

Standard catalyst A is called base 1. It is used mainly as a reference for comparison with whole type D catalyst.

On the other hand, standard catalyst A is produced on an industrial scale in an amount of about 100 tons in a single operation. The catalyst is called base 2. It is used mainly as a reference for evaluating additive type B and C catalysts.

APS, SA, ABD (apparent bulk density) and PV (pore volume) of standard catalysts A (base 1 and 2) were determined. The results are shown in tables 2 and 3.

Example 6

To 400 g of a silica hydrosol containing 10 wt.% SiO ₂ , add 64 g of HS zeolite, 86 g of kaolin clay calculated on dry weight and 10 g of a metal compound prepared in examples 1 and 2, having a particle diameter of 15 μm or less, to thereby obtain a suspension of the mixture.

The suspension of the mixture is spray dried in order to obtain particles having an average particle diameter of 68 ± 5 μm. The particles are washed and then dried again to obtain an integral type D catalyst containing a metal compound associated with it.

One-piece catalysts using MS-1, MS-2, MS-5, MS-7 and KW-2200 hydrotalcite manufactured by Kyowa Chemical Co., Ltd. as a metal compound, are designated as catalysts D1, D2, D3, D4 and X, respectively.

APS, SA, ABD and PV of catalysts D1, D2, D3 and D4 are determined. The results are shown in table 2.

In addition, the metal content is determined using an inductively coupled plasma spectrometer. As a result, it is established that the catalysts contain metal compounds in an amount of about 5 wt.% Based on the dry weight.

KW-2200 hydrotalcite manufactured by Kyowa Chemical Co., Ltd. is dried at 100 ° C. After this, hydrotalcite is examined by X-ray diffraction and the hydrotalcite structure is established. The results are shown in FIG.

table 2 Catalyst name Foundation 1 X D1 The composition of the catalyst: Metal passivator - hydrotalcite MC-1 Binder dioxide dioxide dioxide Zeolite silicon
zeolite HS silicon
zeolite HS silicon
zeolite HS Matrix kaolin kaolin kaolin Catalyst Properties: APS (μm) 68 71 70 SA (m ² / g) 223.9 185.5 212.2 ABD (g / ml) 0.78 0.71 0.71 PV (ml / g) 0.16 0.14 0.16 Table 2 (continued) Catalyst name D2 D3 D4 The composition of the catalyst: Metal passivator MS-2 MS-5 MS-7 Binder
Zeolite silica
zeolite HS silica
zeolite HS silica
zeolite HS Matrix kaolin kaolin kaolin Catalyst Properties: APS (μm) 70 70 68 SA (m ² / g) 178.4 193 133 ABD (g / ml) 0.73 0.75 0.69 PV (ml / g) 0.16 0.15 0.16

Example 7

To 600 g of a silica hydrosol containing 10 wt.% SiO ₂ , 40 g, based on the dry weight of the metal compound prepared in Examples 1-4, having a particle diameter of 15 μm or less, is added to thereby obtain a suspension of the mixture.

The suspension of the mixture is spray dried in order to obtain particles having an average particle diameter of 68 ± 5 μm.

The particles are washed and then dried to give an additive type catalyst C containing a metal compound associated with it.

Additive type catalysts C utilizing MC-1 and KW-2200 hydrotalcite as a metal compound manufactured by Kyowa Chemical Co., Ltd. are referred to as Cl and Y catalysts, respectively.

APS, SA, ABD and PV of the Cl and Y catalysts are determined. The results are shown in Table 3.

In addition, the metal content is determined using an inductively coupled plasma spectrometer. As a result, it is established that the catalysts contain metal compounds in an amount of about 40 wt.% Based on the dry weight.

Table 3 Catalyst name Foundation 2 Y C1 The composition of the additive: Metal passivator - hydrotalcite MS-1 Binder - dioxide dioxide silicon Silicon Zeolite - - - Matrix - - - Catalyst properties; APS (μm) 65 67 67 SA (m ² / g) 189.2 83,2 97.6 ABD (g / ml) 0.72 0.64 0.67 PV (ml / g) 0.15 0.22 0.245 The proportion of additives: Base 2 (wt.%) one hundred 90 90 Additive type 0 10 10 (mass%)

Example 8

To 3 kg of a suspension of an alumina hydrogel containing 10 wt.% Al ₂ O ₃ , add 200 g calculated on the dry weight of the metal compound prepared in examples 1-4, having a particle diameter of 15 μm or less. The suspension is spray dried to obtain particles having an average diameter of 68 ± 5 μm. In this way, an additive type catalyst C is obtained containing a metal compound associated with it.

Additive type catalysts prepared using MS-1, MS-2, MS-3, MS-4, MS-5, MS-6, MS-7, MS-8 and MS-9 as a metal compound are designated as catalysts C2, C3, C4, C5, C6, C7, C8, C9 and C10, respectively.

APS, SA, ABD and PV of catalysts C2, C3, C4, C5, C6, C7, C8, C9 and C10 are determined. Catalysts C3, C8, C9 and C10 are further examined to evaluate the abrasion resistance of the catalyst [initial fine fraction (referred to as “IF”) and the average attrition loss (referred to as “AL”)]. The results are shown in table 4.

Next, using a spectrometer with inductively coupled plasma, the metal content is determined. As a result, it is established that the catalyst contains metal compounds in an amount of about 40% by weight on a dry weight basis.

In addition, 3 kg of a suspension of an alumina hydrogel containing 10 wt.% Al ₂ O ₃ is spray dried to obtain particles having an average diameter of 68 ± 5 μm. The catalyst thus obtained is designated as catalyst Z.

Determine APS, SA, ABD and PV of catalyst Z. The results are shown in table 4.

Table 4 Catalyst name Base 2 Z C2 C3 The composition of the additive: Metal passivator - - MS-1 MS-2 Type of binder - oxide oxide oxide aluminum aluminum aluminum Zeolite - - - - Matrix - - - - Properties catalyst: APS (μm) 65 69 68 64 SA (m ² / g) 189.2 259 205 184 ABD (g / ml) 0.72 0.54 0.5 0, 67 PV (ml / g) 0.15 0.652 0.715 0.322 IF - - - 17.87 AL - - - 20.61 The proportion of additives: Base 2 (wt.%) one hundred 90 90 90 Additive type 0 10 10 10 (mass%) Table 4 (continued) Catalyst name C4 C5 C6 C7 The composition of the additive: Metal passivator MS-3 MS-4 MS-5 MS-6 Type of binder oxide oxide oxide oxide aluminum aluminum aluminum aluminum Zeolite - - - - Matrix - - - - Properties catalyst: APS (μm) 65 68 65 67 SA (m ² / g) 201 174 186 145 ABD (g / ml) 0.67 0.78 0.84 0.7 PV (ml / g) 0.271 0.294 0.28 0.23 IF - - - - AL - - - - The proportion of additives: Base 2 (wt.%) 90 90 90 90 Additive type 10 10 10 10 (mass%)

Table 4 (continued) Catalyst name C8 C9 C10 The composition of the additive: Metal passivator MS-7 MS-8 MS-9 Type of binder oxide oxide oxide aluminum aluminum aluminum Zeolite - - - Matrix - - - Catalyst Properties: APS (μm) 73 69 68 SA (m ² / g) 133 176.7 192.5 ABD (g / ml) 0.78 0.81 0.83 PV (ml / g) 0.201 0,207 0.195 IF 12.6 6.63 7.01 AL 17.65 3.14 2.87 The proportion of additives: Base 2 (wt.%) 90 90 90 Additive type 10 10 10 (mass%)

3. Analytical instruments, analysis conditions, etc.

Instruments and equations for calculation or similar procedures used in the analyzes described above are as follows.

ICP (composition analysis):

"IRIS Advantage" manufactured by Thermo Jarrell Ash.

APS (average particle diameter):

“Electromagnetic vibrating microfilter type M-2”, manufactured by Tsutsui Rikagaku Kiki K.K.

SA (specific surface area):

BELSORP 28 (high precision, fully automatic gas absorber) manufactured by Bel Japan Inc.

ABD (apparent bulk density):

"Bulk density meter" manufactured by Tokyo Kuramochi Kagaku Kikai Seisakusho (JIS Z 2504).

PV (pore volume):

"MICROMERITICS AUTOPORE II 9220" manufactured by Shimadzu Corp.

IF (initial fine fraction) *:

[(fine particles after 0-12 h (dry weight g)) / (amount of sample)] × 100

AL (average abrasion loss) *:

[(fine particles after 12-42 hours (dry weight g)) / (amount of sample)] × 100

* The initial fine fraction and the average loss from abrasion is determined by testing the abrasion resistance of the catalyst, carried out as follows and by calculation.

50 g of the catalyst (sample) are treated by heating at 500 ° C for 5 hours, 5 g of water are added to them and the catalyst flows through the catalyst tube at a flow rate of 0.102 m / s. The amount of fine particles (dry weight g) present in the catalyst tube is measured at the moment when 12 hours have passed after the initiation of the leak (0-12 hours) and at the moment when 42 hours have passed (12-42 hours). The initial fine fraction and the average attrition loss are calculated using the data from the above expressions.

X-ray * diffractometer:

"RINT 2500V" manufactured by Rigaku Corp.

* X-ray diffraction analysis is carried out under the following conditions, using a sample prepared by drying each catalyst at 100 ° C for 24 hours:

Tube Voltage: 50 kV

Tube Current: 300 mA

Scan Mode: Continuous

Scan Speed: 2 ° / min

Scan Step: 0.02 °

Scanning Range (2θ): 5-90 °

Forming Slit: 1 °

Receiving gap: 0.3 mm

4. MAT activity test

Evaluation Conditions:

Obtained in examples 5-8, the catalysts are subjected to the following imitation balance treatment. After that, the activity of the FCC catalysts and the ability to passivate metals are evaluated using the ASTM (3907) fixed-bed microactivity testing device and using liquid petroleum products having the properties shown in Table 5 under the following test conditions.

Equilibrium processing conditions:

Each fresh catalyst was warmed from room temperature to 500 ° C for 30 minutes and kept at 500 ° C for 5 hours to calcine.

After that, each catalyst is impregnated with a cyclohexane solution containing nickel naphthenate and vanadium naphthenate in given amounts (1000 and 2000 ppm by weight).

The catalyst was dried at 100 ° C, then it was heated from room temperature to 500 ° C for 30 minutes and then kept at 500 ° C for 5 hours to calcine it again.

Then, each catalyst in a fluidized state is heated from room temperature to 800 ° C for 90 minutes in air. After the temperature reaches 800 ° C, the atmosphere is replaced with an atmosphere of 100% steam in order to treat the catalyst with it for 6 hours.

After this steam treatment, the FCC activity of each catalyst was evaluated.

When evaluating the ability of each catalyst to passivate metals, the amount of nickel and vanadium on the catalysts is set to 0 and 0 ppm by mass, 1000 and 2000 ppm by mass, 2000 and 4000 ppm by mass, or 3000 and 6000 ppm by mass .

Table 5
Test oil: vacuum distillation gas oil Sample one 2 Density 15 ° C g / cm ³ 0.8959 0.8819 Vacuum distillation Boiling point 319 294 5% ° C 362 352 10% ° C 383 367 20% ° C 406 390 30% ° C 421 402 40% ° C 433 415 50% ° C 446 424 60% ° C 460 436 70% ° C 481 451 80% ° C 509 471 90% ° C 566 506 95% ° C 531 97% ° C 544 The end of the boil, ° C 605 548 The total amount of distillate,% 93.5 98.5 The amount of residue,% 6.5 1,5 Loss% 0 0 Pour point, ° C 33 35 Dynamic viscosity 50 ° C mm ² / s 34.54 18.67 Nitrogen content (method chemiluminescence) wt.% 0.05 0.02 Sulfur content (X-ray method) wt.% 0.15 0.01 Refractive Index 70 nD 1.48 1.47 Density 70 ° C g / cm ³ 0.86 0.84 Molecular mass (calculated by viscosity) 475 402 Asphaltenes (UOP) wt.%. 0.38 Method n-d-m (70 ° C)% aromatics 15,2 12.8 % naphthenes 14.6 18.8 % paraffins 70,2 68,4 Aniline point (U-tube method) ° C 95.4 94.5 Dynamic viscosity 75 ° C mm ² / s 14.56 8.77 Dynamic viscosity 100 ° C mm ² / s 7.67 4.99 Nitrogen base, wt.% 0.0014 Bromine number g Br _2/100 g 1.90 The hydrogen content, wt.% 13.03 The content of coke residue, wt.% 1.25 0.06

Test conditions: fixed bed

Reaction temperature: 500 ° C

The mass ratio of the catalyst / liquid petroleum product:

2.5; 3.0; 3,5

Test period: 75 s

5. Evaluation of the performance of the catalyst

Example 9

The whole-type catalysts D1, D2, D3, and D4 containing MC-1, MC-2, MC-5, and MC-7, respectively, are subjected to equilibrium treatment and then tested for MAT activity using sample 2. The results are shown in Table 21.

Example 10

Catalyst X was subjected to an equilibrium simulator and then tested for MAT activity using sample 2. The results are also shown in table 21.

Table 21 Catalyst name Foundation 1 X D1 Metal Passivator Name - Hydrotalcite MS-1 Conversion (wt.%): Catalyst / oil 3 3 3 The amount of metal introduced: Ni / V (ppm) 0/0 73.13 58.56 73.49 1000/2000 67.70 56.34 68.83 2000/4000 55.50 49.53 60.25 3000/6000 30.64 36.16 54.43 Selectivity (wt.%): The amount of metal introduced: Ni / V = 2000/4000 (ppm) Conversion (wt.%): 60.00 60.00 60.00 The output of each ingredient (mass%) H ₂ 0.20 0.36 0.16 C1-2 1.43 2.02 1.31 Liquefied petroleum gas 11.43 12.49 12.05 Petrol 43.39 40.39 43.79 Light recycle gas oil 24.38 20.51 25.71 Heavy cycle gas oil 15.62 19.49 14.29 Coke 3.05 4.74 2.69 Road Octane 88.49 88.41 88.40 Table 21 (continued) Catalyst name D2 D3 D4 Metal Passivator Name MS-2 MS-5 MS-7 Conversion (wt.%): Catalyst / oil 3 3 3 The amount of metal introduced: Ni / V (ppm) 0/0 72.62 72.71 72.19 1000/2000 67.97 68.70 67.72 2000/4000 57.48 58.90 55.95 3000/6000 46.43 51.28 41.68 Selectivity (wt.%): The amount of metal introduced: Ni / V = 2000/4000 (ppm) Conversion (wt.%): 60.00 60.00 60.00 The output of each ingredient (mass%) H ₂ 0.19 0.17 0.21 C1-2 1.41 1.31 1,56 Liquefied petroleum gas 11.92 12.36 12, 99 Petrol 43.59 43.18 42.03 Light recycle gas oil 24.60 25.23 22.98 Heavy cycle gas oil 15.40 14.77 17.02 Coke 2.89 2.98 3.21 Road Octane 88.53 88.38 88.46

Example 11

Additive type catalyst C1 containing MS-1 is physically mixed in an amount of 10 wt.% With catalyst — base 2. The resulting catalyst is subjected to equilibrium treatment and then tested for MAT activity using sample 2. The results are shown in table 31.

Example 12

Additive type catalyst Y containing hydrotalcite KW-2200 is physically mixed in an amount of 10% by weight with a base type 2 catalyst. The resulting catalyst is subjected to an equilibrium simulation and then tested for MAT activity using sample 2. The results are also shown in table 31.

Table 31 Catalyst name Foundation 2 Y C1 Metal Passivator Name - Hydrotalcite MS-1 Conversion (wt.%): Catalyst / oil 3 3 3 The amount of metal introduced: Ni / V (ppm) 0/0 70.93 66.71 70.19 1000/2000 63.21 56.29 64.89 2000/4000 51.65 48.18 58.70 3000/6000 27.36 35.52 51.98 Selectivity (wt.%): The amount of metal introduced: Ni / V = 2000/4000 (ppm) Conversion (wt.%): 60.0 60.0 60.0 The output of each ingredient (mass%) H ₂ 0.20 0.29 0.15 C1-2 1.28 1.30 1.23 Liquefied petroleum gas 12.06 12.08 12.56 Petrol 43,47 43.36 43.59 Light recycle gas oil 24.76 24.67 26.57 Heavy cycle gas oil 15.24 15.33 13.43 Coke 2.99 2.97 2.47 Road Octane 88.43 88.35 88.65

Example 13

Catalysts C2, C3, C4, C5, C6, C7, C8, C9 and C10 additive type containing MS-1, MS-2, MS-3, MS-4, MS-5, MS-6, MS-7, MS-8 and MS-9, respectively, are physically mixed in an amount of 10% by weight with a base type 2 catalyst. The resulting catalysts are subjected to equilibrium simulations and then tested for MAT activity using sample 1. The results are shown in table 41.

Example 14

Additive type Z catalyst was physically mixed in an amount of 10% by weight with a base type 2 catalyst. The resulting catalyst was subjected to an equilibrium simulation and then tested for MAT activity using sample 1. The results are also shown in table 41.

Table 41 (1) Catalyst name Foundation 2 Z C2 C3 Metal Passivator Name - - MS-1 MS-2 Conversion (wt.%): Catalyst / oil 3 3 3 3 The amount of metal introduced: Ni / V (ppm) 0/0 67.71 67.29 68.07 67.21 1000/2000 59.96 62.48 66.62 65.68 2000/4000 48.77 53.43 62.38 64.08 3000/6000 23.51 35.45 61.03 61,99 Selectivity (wt.%): The amount of metal introduced: Ni / V = 1000/2000 (ppm) Conversion (wt.%): 60.00 60.00 60.00 60.00 The output of each ingredient (mass%) H ₂ 0.35 0.43 0.20 0.15 C1-2 0.84 0.96 0.83 0.76 Liquefied petroleum gas 12.50 11.61 12.27 12.26 Petrol 43.81 43.50 44.78 44.97 Light recycle gas oil 27.97 29.34 29.78 29.63 Heavy cycle gas oil 12.03 10.66 10.22 10.37 Coke 2,50 3,50 1, 92 1.86 Road Octane 89.37 89.41 89.06 89.58 Selectivity (wt.%): The amount of metal introduced: Ni / V = 3000/6000 (ppm) Conversion (wt.%): 60.00 60.00 60.00 60.00 The output of each ingredient (mass%) H ₂ - - 0.33 0.36 C1-2 - - 0.91 0.91 Liquefied petroleum gas - - 12.93 12.62 Petrol - - 43.38 43.77 Light recycle gas oil - - 27.79 26.68 Heavy cycle gas oil - - 12.21 13.32 Coke - - 2.45 2,34 Road Octane - - 89.52 89.81

Table 41 (2) Catalyst name C4 C5 C6 C7 Metal Passivator Name MS-3 MS-4 MS-5 MS-6 Conversion (wt.%): Catalyst / oil 3 3 3 3 The amount of metal introduced; Ni / V (ppm) 0/0 67.33 67.80 67.36 67.45 1000/2000 65.97 66.14 64.81 63.49 2000/4000 63.89 63.83 57.65 58.40 3000/6000 62,43 61.81 43.18 50.22 Selectivity (wt.%): The amount of metal introduced: Ni / V = 1000/2000 (ppm) Conversion (wt.%): 60.00 60.00 60.00 60.00 The output of each ingredient (mass%) H ₂ 0.16 0.15 0.22 0.26 C1-2 0.79 0.85 0.81 0.71 Liquefied petroleum gas 12.28 12.08 12.71 11.96 Petrol 44.87 44.86 44.02 44.93 Light recycle gas oil 29.91 29.69 28.91 29.51 Heavy cycle gas oil 10.09 10.31 11.09 10.49 Coke 1.90 2.06 2.24 2.14 Road Octane 89.33 89.30 89.21 89.17 Selectivity (wt.%): The amount of metal introduced: Ni / V = 3000/6000 (ppm) Conversion (wt.%): 60.00 60.00 60.00 60.00 The output of each ingredient (mass%) H ₂ 0.32 0.30 - - C1-2 0.87 0.92 - - Liquefied petroleum gas 12.82 12.73 - - Petrol 43.64 43.67 - - Light recycle gas oil 26.82 26.96 - - Heavy cycle gas oil 13.18 13.04 - - Coke 2,35 2,38 - - Road Octane 89.67 89.62 - -

Table 41 (3) Catalyst name C8 C9 C10 Metal Passivator Name MS-7 MS-8 MS-9 Conversion (wt.%): Catalyst / oil 3 3 3 The amount of metal introduced: Ni / V (ppm) 0/0 67.55 68.32 67.75 1000/2000 65.74 66.09 65.92 2000/4000 63.98 63.92 64.21 3000/6000 61.54 62.07 61.84 Selectivity (wt.%): The amount of metal introduced: Ni / V = 1000/2000 (ppm) Conversion (wt.%): 60.00 60.00 60.00 The output of each ingredient (mass%) H ₂ 0.14 0.14 0.15 C1-2 0.78 0.77 0.79 Liquefied petroleum gas 12.33 12.32 12.29 Petrol 44.89 44, 96 44.90 Light recycle gas oil 29.81 29.92 29.87 Heavy cycle gas oil 10.21 10.13 10.28 Coke 1.84 1.76 1.72 Road Octane 89.43 89.41 89.38 Selectivity (wt.%): The amount of metal introduced: Ni / V = 3000/6000 (ppm) Conversion (wt.%): 60.00 60.00 60.00 The output of each ingredient (mass%) H ₂ 0.29 0.30 0.31 C1-2 0.90 0.91 0.92 Liquefied petroleum gas 12.58 12.69 12.49 Petrol 43.66 43.87 43.91 Light recycle gas oil 28.09 27.97 27.92 Heavy cycle gas oil 12.30 12.21 12.12 Coke 2.18 2.05 2,33 Road Octane 89.75 89.67 89.52

6. Test benchmark activity.

For the test of evaluating the activity of the catalysts, a bench-scale installation is used, including a circulation fluidized bed reactor equipped with a reaction vessel and a catalyst regenerator.

Prior to the test, the catalysts (base 2, C3, C8 and C9) are subjected to the following procedure to simulate equilibrium by circulation.

As the crude oil, desulphurized vacuum distillation gas oil is used, as shown in Table 6. The following test conditions are used.

The test is carried out with a catalyst / liquid oil ratio (mass ratio) of 6, 8, 10 and 12, and the results are compared to evaluate the activity.

Reaction temperature: 500 ° C

The mass ratio of the catalyst / liquid oil: 6, 8, 10, 12

The amount of circulating catalyst: 60 g / min.

Imitation of balance through circulation:

Use the method and device described in JP-A-11-179192 (Japanese Patent Application No. 352940/1997). A fresh catalyst or a mixed catalyst consisting of a fresh catalyst and a catalyst into which metal is introduced is heated to 775 ° C and calcined / treated with steam in an atmosphere of 50% air and 50% steam (heating / calcination / steam treatment step).

After this, the mixed catalyst is cooled to room temperature and a metal solution is sprayed with nitrogen gas so that it adheres to the catalyst. The catalyst was dried at 250 ° C and the solvent vapor was removed to remove nitrogen gas (desorption step). The operation is repeated for 6 hours a day for 10 days.

Standard conditions:

Processing is carried out under the same conditions as in the circulating equilibrium described above, except that the average amount of nickel and vanadium introduced is adjusted to 2500 and 5000 ppm by weight, respectively, and the average period of steam treatment is changed to 20 hours.

Duplication of conditions for the service life of the catalyst:

Processing is carried out under the same conditions as under standard conditions, except that the average amount of nickel and vanadium introduced is adjusted to 5,000 and 10,000 ppm by weight, respectively, and the average steam treatment period is changed to 40 hours.

When processing carried out under standard conditions, and processing when duplicating the conditions for the life of the catalyst, the metal sources used are naphthenic acid compounds diluted with toluene, as in the Mitchell method.

Table 6
Test Oil Products: Vacuum Distillation Gas Oil Sample 3 Density 15 ° C g / cm ³ 0.9094 Vacuum distillation Boiling point 330 5% ° C 366 10% ° C 382 20% ° C 406 30% ° C 424 40% ° C 443 50% ° C 465 60% ° C 488 70% ° C 518 80% ° C 553 End boiling point, ° С 575 The total amount of distillate,% 85.0 The amount of residue,% 15.0 Loss% 0 Pour point, ° C twenty Dynamic viscosity 50 ° C mm ² / s 56.22 Nitrogen content (chemiluminescence method) 0,089 wt.%. Sulfur content (X-ray method) wt.% 0.20 Refractive Index 70 nD 1,487 Density 70 ° C g / cm ³ 0.8709 Molecular mass (calculated by viscosity) 498 Asphaltenes (UOP) wt.% 0.66 N-d-m method (70 ° C)% aromatics 16.6 % naphthenes 16,0 % paraffins 67.4 Aniline point (U-tube method) ° С 95.1 Dynamic viscosity 75 ° C mm ² / s - Dynamic viscosity 100 ° C mm ² / s 10,250 Nitrogen base, wt.% 0.0181 Bromine number g Br _2/100 g 5,4 The hydrogen content, wt.% 12.61 The content of coke residue, wt.% 2.23

Table 7 Catalyst name Foundation 2 C2 C8 C9 Metal Passivator Name - MS-2 MS-7 MS-8 Conversion (wt.%): Catalyst / oil 8 8 8 8 Average amount entered metal: Ni / V (ppm) 2500/5000 60.80 67.43 67.52 67.21 5000/10000 40.10 66.50 65.82 65.56 Selectivity (wt.%): Average amount of metal introduced: Ni / V = 2500/5000 (ppm) Average steaming period: 20 hours Conversion (wt.%): 60.00 60.00 60.00 60.00 The output of each ingredient (mass%) H ₂ 0.23 0.14 0.13 0.13 C1-2 0.89 0.87 0.88 0.87 Liquefied petroleum gas 10.93 10.95 10.82 10.79 Petrol 41.24 42.35 42.35 42.41 Light recycle gas oil 21.37 22.98 23.21 22.93 Heavy cycle gas oil 19.08 17.32 17.38 17.68 Coke 6.26 5.39 5.23 5.19 Road Octane 88.80 88.79 88.78 88.79 Selectivity (wt.%): Average amount of metal introduced: Ni / V = 5000/10000 (ppm) Average steaming period: 40 hours Conversion (wt.%): 60.00 60.00 60.00 60.00 The output of each ingredient (mass%) H ₂ 0.31 0.25 0.23 0.22 C1-2 0.73 1.00 0.91 0.92 Liquefied petroleum gas 17.70 11.34 10.90 11.12 Petrol 35.86 41.65 42.21 42.34 Light recycle gas oil 17.25 23.38 23.12 23.46 Heavy cycle gas oil 20.25 16.26 16.62 16.12 Coke 7.90 6.12 6.01 5.82 Road Octane 88.80 89.50 89.34 89.45

7. The effect of the average particle diameter and the content of calcium carbonate on the properties of the catalyst according to the invention

Definitions

In table 8, when conducting analyzes, the same instruments and equations were used for the calculations that are described in Section 3 (p. 38-39).

Catalyst Preparation

Catalysts were prepared in the following manner.

To 3 kg of a suspension of hydrogel of alumina containing 10 wt.% Al ₂ SO ₃ was added CaCO ₃ , as indicated in table 8. The suspension was spray dried. Thus, an additive type catalyst was obtained containing CaCO ₃ fixed therein.

Specific amounts of CaCO ₃ are indicated below. In addition, they depend on the "content of CaCO ₃ " in the catalysts.

CaCO ₃ (g) Catalyst R (20%) 75 Catalyst Q and Z (40%) 200 Catalyst V (90%) 2700

CaCO ₃ had an average particle diameter (APS) of 0.97 or 45 μm.

In Table A, BASE 1 and BASE 2 were obtained in the following manner.

To 400 g of a silica hydrosol containing 10 wt.% SiO ₂ was added 64 g of HS zeolite and 86 g of kaolin clay, calculated on the dry matter, to obtain a mixture in the form of a suspension.

The suspension was spray dried to give particles having an average particle diameter of 68 ± 5 μm. The particles were washed and then dried again to obtain Standard Catalyst A.

Standard Catalyst A is listed as BASE 1.

On the other hand, Standard Catalyst A was produced on a commercial scale in an amount of about 100 tons per cycle.

This catalyst is listed as BASE 2.

Investigated APS, SA, ABD (apparent bulk density) and PV (pore volume) of Standard Catalyst A (BASES 1 and 2). The results are presented in the description in table 2.

Other

In table 8, the Mitchell method, which is a pseudo-equilibrium method, is the method described from page 40 to page 41 (line 4) of the present description.

The pseudo-equilibrium method specified in table 8 was carried out under the following conditions:

Conditions for simulated equilibrium treatment:

Each fresh catalyst was heated for 30 min from room temperature to 500 ° С and kept at 500 ° С for 5 h for its roasting.

Then, each catalyst was impregnated with a cyclohexane solution containing nickel naphthenate and vanadium naphthenate in certain amounts (1000 and 2000 ppm based on weight).

The catalyst was dried at 100 ° C, then heated for 30 min from room temperature to 500 ° C and kept at 500 ° C for 5 h for re-firing.

Then, each catalyst in a fluidized state was heated for 90 min from room temperature to 800 ° C in an atmosphere of air. After the temperature reached 800 ° C, the atmosphere was replaced with 100% steam to treat it with a catalyst for 6 hours.

Table 8 specifically indicates that the term "pseudo" has the same meaning as the term "mimicking", indicated on page 40 of the present description.

The following are the results presented in table 8.

Regarding the content of calcium carbonate: 30-70% calculated on the dry matter

Catalysts Q, R and V show the results obtained for 40 wt.% CaCO ₃ , which is well within the stated limits, and for 20 and 90 wt.% CaCO ₃ , which in both cases is outside the stated limits.

As for catalyst Q, the content of calcium carbonate in it is 40 wt.% (Within the stated range), this catalyst has excellent abrasion resistance (IF and AL) and the ability to capture metals.

In contrast, the catalyst R, in which the calcium carbonate content is 20 wt.%, Which is lower than the stated lower limit, demonstrates the worst ability to capture metals (i.e. worse activity).

Now with regard to catalyst V, the calcium carbonate content in it is 90 wt.%, Which exceeds the upper declared limit. Catalyst V exhibits worse abrasion resistance, which is not sufficient for practical use.

As regards the abrasion resistance indices, lower values mean better abrasion resistance, thus, in general, catalysts having indices higher than 30 tend to spray, and it is believed that their practical use is hindered due to reasons such as destruction of equipment, etc. . Therefore, the catalysts proposed in the present invention, having an index of abrasion resistance of 20 or lower, are preferred for practical use.

The additional data presented show that the preferred content of calcium carbonate is from 30 to 70%, and that when the content is outside the specified range, the resulting product is not practical from the point of view of metal additive agent of the additive type due to the markedly lower metal-picking ability or resistance to abrasion.

Relative to the average particle diameter of calcium carbonate: dimensional restrictions: from 0.001 to 30 microns

The additional data presented shows the results for catalysts using a metal-type additive agent of an additive type in which the average particle diameter of CaCO ₃ is 45 μm, which is above the stated upper limit. The results show that abrasion resistance is markedly reduced from a value of 20 or lower, which is the limit for practical use.

It should also be noted separately that catalysts having a particle size less than the indicated lower limit of 0.001 μm are difficult to manufacture.

The abrasion resistance data for CaCO ₃ with an average particle diameter of 1.7 to 3.5 μm are presented in the Examples. These data show that abrasion resistance is in a practical range of 20 or less.

Summarizing the above, the average particle diameter of the calcium carbonate used in the present invention is preferably from 0.001 to 30 microns. Particles of calcium carbonate having a particle size below these limits are difficult to obtain. On the other hand, particulate calcium carbonate larger than the specified upper limit does not exhibit improved abrasion resistance.

The following are additional notes on table 8 for a better understanding.

As shown on the first page of table 8, the left column, the fourth group of the described substances, 10 wt.% "Additive type" was added to 90 wt.% BASIS 2. BASIC 1 was practically not used here.

As for the ratio of catalyst to oil, this ratio is 3 parts of catalyst per 100 parts of oil.

It should be noted that for catalysts V and Z no yield data are provided. As can be seen from table 8, the values of both indicators - the initial content of fine particles (IF) and AL - are extremely high. Therefore, catalysts V and Z could not be used for catalytic cracking in a fluidized bed of heavy petroleum products.

Table 8 ← CaCO ₃ content → ← CaCO ₃ particle diameter → Catalyst name Q R V Z Additive composition Metal deactivator (wt.%) CaCO ₃ (40) CaCO ₃ (20) CaCO ₃ (90) CaCO ₃ (40) Type of binder (wt.%) Alumina (60) Alumina (80) Alumina (10) Alumina (60) Zeolite (wt.%) Matrix (wt.%) Physical properties of a metal deactivator APS (μm) 0.97 0.97 0.97 45 SA (m ² / g) 58 169 6 38 ABD (ml / kg) 0.83 0.72 0.32 0.78 PV (ml / g) 0.290 0,207 0.403 0.187 The initial content of fine particles (IF) 3.2 3.0 35.6 39.8 AL 3.3 3.0 34.8 35.6 Additive content BASE 2 (wt.%) (The same 90 90 catalyst composition as in BASIC 1) Additive type (wt.%) 10 10 Characterization of conditions: the same as in the Examples presented in the description inventions Pseudo-equilibrium method Mitchell method Mitchell method Steaming 800 ° C × 6 hours 800 ° C × 6 hours MAT Oil Source DS-VGO (86 ') DS-VGO (86 ') Conversion (% mass) in the ratio Catalyst / Oil Product 3 3 Metal amount: Ni / V (ppm) 0/0 68.02 66.90 1000/2000 65.90 61.53 2000/4000 64.07 57.25 3000/6000 61.83 43.24 Selectivity (% mass) with the amount of metal: Ni / V = 1000/2000 (ppm) In the conversion (% mass) 60.00 60.00 The output of each ingredient (% mass) H ₂ 0.12 0.28 Ci-2 0.80 0.84 LPG 12.34 11.72 Gaso 44.95 44.15 LCO 29.84 29.43 HCO + 10.16 10.57 Coke 1.79 3.01 Ron 89.46 89.41 Selectivity (% mass) when the amount of metal: Ni / V = 3000/6000 (ppm) In the conversion (% mass) 60.00 The output of each ingredient (% mass) H ₂ 0.25 Ci-2 0.91 LPG 12.97 Gaso 43.73 LCO 27.98 HCO + 12.02 coke 2,4 Ron 89.81

Although the invention has been described in detail and with reference to specific options for its implementation, the specialist in this field will be clear that various changes and modifications can be made in it without departing from its essence and scope.

This application is based on Japanese Patent Application No. 2000-257669, filed August 28, 2000, and Japanese Patent Application No. 2001-246232, filed August 14, 2001, and their contents are hereby incorporated by reference.

INDUSTRIAL APPLICABILITY

As described above, the catalyst of the present invention has a reduced selectivity for hydrogen and coke and can produce gasoline and a fraction of light recycle gas oil in high yield, without lowering the octane number. In addition, the catalyst can maintain these performance characteristics at a high level for a long period of time. The FCC catalyst can have a significantly improved service life before metal poisoning (at least 3 times longer than standard catalyst A). (When refining petroleum feedstocks containing metals in an amount of at least 3 times greater than the amount of metals in the oil serving as feedstock in modern processes, the catalyst of the present invention may have the same performance as the currently used catalysts i.e. standard catalyst A).

According to the method of the present invention using this catalyst, low grade heavy oil products can be subjected to FCC at low cost.

Claims (3)

1. The catalyst for the catalytic cracking of heavy petroleum products in a fluidized bed, which is a mixture comprising (1) a particulate catalyst obtained by uniformly dispersing crystalline aluminosilicate zeolite in an inorganic oxide matrix, and (2) a particulate additive type catalyst that deactivates metals that poison the catalyst and are contained in petroleum feeds in which calcium carbonate with an average particle diameter of 0.001 to 30 μm is dispersed in an inorganic oxide matrix, whereby the amount of said calcium carbonate is from 30 to 70% calculated on the dry matter; moreover, the ratio of the catalyst / additive type catalyst is from 99.9 / 0.1 to 50/50. 2. The catalyst according to claim 1, where the specified additive type catalyst has an average particle diameter of from 50 to 90 microns, bulk density of from 0.3 to 1.2 g / ml and oil absorption of 0.1 cm ³ / g or more. 3. The catalyst according to claim 1, where the calcium carbonate has an average particle diameter of from 0.1 to 10 microns.

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