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

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

 

TECHNICAL AREA

The present invention relates to a catalyst for catalytic cracking in a fluidized bed (hereinafter referred to as "FCC") of heavy fuel oil and the way the FCC oil using such a catalyst. More specifically the present invention relates to a very durable FCC catalyst, which not only passivates contained in the oil poison the catalyst metals, such as Nickel and vanadium, reduces the quantity of generated hydrogen or coke, has excellent craterous activity and the ability of processing residues from oil pickup and can give gas and the fraction of light cycle gas oil with high yields without lowering the octane number, but also can save these performance characteristics at a high level for a long period of time, and refers to the way the FCC, 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 oil feedstock, and at the same time, there is a growing trend of heavier crude oil.

Heavy oil feedstock contains a huge number of metals such as Nickel, vanadium and the like, and these metals are almost completely the d deposited on the catalyst.

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

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

When used oil feedstock containing a large amount of heavy oil residues (e.g. residues after distillation light ends or distillation under vacuum), is crucial, not only the influence of metals, but also contained in the oil residues sulfur compounds cause the problem, consisting in the fact that an increasing number of SOxin flue gases from the column regeneration of the catalyst, and the fraction of petroleum products, particularly gasoline, has a high concentration of sulfur.

In addition, the increase of the processing amount of oil residue leads to an increase replenished amount of the catalyst and the mod is my problem, associated with the increase in the cost of the catalyst and the burden on the environment due to the increased amount of waste catalysts.

Still for passivation of toxic metals such as vanadium and similar, which are deposited on the catalyst, different methods have been proposed that implement the alkaline catalyst connection or similar as passivator metal, in order thereby to improve the stability of the catalyst to the effects of metals. Examples include a method in which a water-soluble compound of alkaline-earth metal or similar is subjected to ion exchange with the zeolite or a matrix of an inorganic oxide, and a method in which water-insoluble oxide (e.g., dolomite, thick, anionic clay or similar) embedded in a matrix of inorganic oxide (JP-A-62-57652, JP-A-63-182031, JP-A-3-293039 etc).

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

In the above-described catalyst obtained by the introduction of compounds of alkaline-earth metal in the crystalline aluminosilicate zeolite by ion exchange, there are problems which, for example, that the gasoline product obtained in the reaction of catalytic cracking, has a low octane number (RON).

In addition, when used anionic clay or similar, clay natural origin is rare and, therefore, significantly increases the cost of the catalyst, while synthetic products-clay are also not cheap and lead to increased cost of the catalyst.

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

In particular, compounds of magnesium are leached in a stage of washing the catalyst with an aqueous solution of ammonia, an aqueous solution of ammonium sulfate or similar (removal of alkali metal such as sodium or potassium from the catalyst). Therefore, it is difficult to rinse containing magnesium catalyst, and its implementation in the catalysts is problematic is.

On the other hand, an additional advantage of the above-described compositions of the catalysts, with the effect of the capture of vanadium, is that they have the ability to associate SOx(see U.S. patent 4889615 etc). The ability is effective to reduce the content of SOxin the exhaust from the column regeneration and reduce the sulphur content in the oil.

Heavy oil, in particular, have a high content of sulfur and sulfur compounds deposited on the catalyst with coke and turn into SOxin the column regeneration installation FCC. SOxreacts with alkali metal oxide and thus is captured by the catalyst. Captured thus sulfur can be separated and disposed of, after its conversion to hydrogen sulfide by reaction in an upward flow. It is known that the composition of the catalysts thus reduce the number of SOxin gases of combustion and reduce the sulfur content in the product oil.

However, when the surface of the catalyst accumulates Nickel, often there are cases when the above passivator metal does not pestiviruses effect on the Nickel. Accordingly, there has been proposed a method of filing a special antimony compounds (organic compounds antimony and so on) in crude oil, in order thereby to asseverate Nickel, OSA is built on the catalyst surface (JP-A-63-63688, JP-A-1-213399 etc).

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

Description of the INVENTION

With the above-described various points of view of the objective of the present invention consists in the proposal of the FCC catalyst is very durable type (with a service life of at least two times greater than the service life of standard catalysts), where passivator metal may be introduced without reducing the catalytic activity, and which not only effectively passivates poison the catalyst metals contained in part recycled oil feedstock of heavy hydrocarbons, reducing the resulting amount of hydrogen or coke, has excellent craterous activity and the ability to process oil residues and can with high yield to give the gasoline and the fraction of light cycle gas oil without reducing the octane number but it can also save these performance characteristics at a high level for a long period of time.

The applicants of the present invention conducted intensive studies in order to achieve this goal. In the result, it was found that when as passivator m is metal carbonate is used, selected from crystalline carbonates of metals, including ferrous metal, and crystalline carbonates of metals, including divalent metal and a trivalent metal, then (a) poison the catalyst metals contained in the oil raw materials, such as Nickel, vanadium and similar, can be effectively passivated, (b) the catalyst can be prepared regardless of the form of a matrix of inorganic oxide as a binder, and a catalyst can be used as a catalyst FCC on a common basis, which does not require for its work, the presence of other catalytic materials (hereinafter in this description of "solid catalyst"), or additive catalyst used in combination with other catalysts, and (C) gasoline and a fraction of light cycle gas oil can be obtained with high yields, at the same time maintaining a low selectivity to hydrogen and coke and without reducing the octane number, and these performance characteristics can be maintained at a high level for a long period of time. Thus was accomplished the present invention.

The FCC catalyst of the present invention, which was obtained based on the discovery that (1) includes a compound that is a compound of the divalent metal, or the connection is of divalent and trivalent metals, showing the x-ray carbonate of the divalent metal.

The catalyst compound may be (2) dispersed in a matrix of inorganic oxide or may be (3) dispersed together with a crystalline aluminosilicate zeolite in a matrix of inorganic oxide.

The way the FCC according to the present invention includes the use of a standard catalyst And obtained a uniform (homogeneous) dispersing a crystalline aluminosilicate zeolite in a matrix of inorganic oxide in the form of a mixture, at least one of the catalysts described above in (1), which is described above in (2), and D, which are described above in (3); catalyst D in the form of a mixture, at least one of the catalysts b and C; or a single catalyst D.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 shows the x-ray MC-1 (Mn-Al-CO3).

Figure 2 shows the x-ray, MS-2 (Ca-Al-CO3).

Figure 3 shows the x-ray, MS-3 (Sr-Al-CO3).

Figure 4 shows the x-ray, MS-4 (Ba-Al-CO3).

Figure 5 shows the x-ray, MS-7 (Sa-CO3).

6 shows the x-ray, MS-8 (Sa-CO3the shells of scallops).

Fig.7 shows the x-ray MC-9 (CA-CO3shell oysters).

Fig shows the radiograph of hydrotalcite.

The BEST MODE of carrying out the INVENTION

Above the th in (1) the catalyst according to the present invention does not have kekirawa activity when used alone. This FCC catalyst of the so-called additive type, which is added to the FCC catalyst and FCC catalyst, such as described above, the standard catalyst a, which has kekirawa activity.

Above in (2) the catalyst is a catalyst in which the active ingredient of the catalyst dispersed in a matrix of inorganic oxide, and which has an improved mechanical strength. The catalyst also has no kekirawa activity when used alone. Like the catalyst In the catalyst is a catalyst FCC so-called additive type, which is added to the FCC catalyst and FCC catalyst, such as described above, the standard catalyst A.

Above in (3) catalyst D is a catalyst in which the active ingredient of the catalyst dispersed in a matrix of inorganic oxide together with a crystalline aluminosilicate zeolite, which has kekirawa activity. Catalyst D has kekirawa activity, even when used alone, and can be used as a catalyst FCC so-called integral type.

The catalyst of the present invention, including the compound of the divalent metal, or a combination of divalent and trivalent m is the metal, showing the x-ray carbonate of the divalent metal (hereinafter referred to as "compound of bivalent and trivalent metals") and having one peak, which can be attributed to the anionic clay or similar, is the catalyst In the present invention.

As the divalent and trivalent metals, you can use any divalent and trivalent metal. However, preferably the divalent metal is at least one metal selected from the group consisting of Mg2+, Mn2+, CA2+, Sr2+BA2+Sn2+and Zn2+and more preferably is at least one metal selected from the group consisting of Mn2+, CA2+, Sr2+BA2+and Sn2+. Trivalent metal preferably represents at least one metal selected from the group consisting of Al3+, Fe3+, Cr3+With3+La3+, Mn3+, Ti3+, Ga3+, Sb3+and Bi3+and more preferably is at least one metal selected from the group consisting of Al3+and Mn3+. In particular, Al3+is the most preferred because it gives more surface area.

The above compound of the divalent metal and the compound of bivalent and trejbal nnogo metals can be the connection of any desired combination, at least one of the above metals.

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

As compounds of divalent and trivalent metals are particularly effective for passivation poisoning the catalyst metals and the removal of SOxis a combination of at least one element selected from Mn2+, CA2+, Sr2+BA2+and Sn2+with Al3+because the catalyst effectively absorb the oxides of Nickel, vanadium oxides and sulfur oxides. In this case, at least two divalent metal can be mixed in any proportion and at least two trivalent metal can be mixed in any proportion. However, the proportion of the divalent metal to the trivalent metals, in which they must mix is such that the molar ratio of divalent metal/trivalent metal is preferably from 0.5 to 10, more preferably from 2 to 5.

When a matrix of inorganic oxide in the catalysts C and D is aluminum oxide, the connection of the two is Alentova metal, from among the metal compounds is preferably a compound containing CA2+, Sr2+or VA2+because the catalyst has a high ability to asseverate poison the catalyst metals.

When the catalyst is used In connection divalent metal or a compound of bivalent and trivalent metals, a suitable form of connection is a granular form having an average particle diameter equal to the diameter of the particles of the standard catalyst a or catalyst C or D that you want to use him in combination, i.e. from 50 to 90 μm, bulk density of 0.3 to 1.2 g/ml and the absorbance of oil 0.1 cm3/g or more.

On the other hand, when the compound is mixed with a matrix of inorganic oxide, a crystalline aluminosilicate zeolite, etc. and used as a component of the catalyst or D suitable form is granular form having a mean 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 the diameter of its particles exceeds 60 μm, the resulting catalyst C or D is undesirable as FCC catalyst from the point of view of bulk density, the strength of the catalyst, etc. because such a particle diameter equal to the average diameter of particles of the catalyst or D. It is when its particle diameter is less than 0,0001 μm, handling difficult.

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

When a matrix of inorganic oxide in the catalysts C and D use the aluminum oxide, the preferred carbonates are calcium carbonate, strontium carbonate and barium carbonate, in which the divalent metals are CA2+, Sr2+and Ba2+from the point of view of not only the ability to asseverate poison the catalyst metals, but also the durability of the catalyst attrition. In particular, calcium carbonate is the most preferred because it has a lower true density compared with strontium carbonate and barium carbonate, prevents increased bulk density of the resulting catalyst and makes it easy preparation of the catalyst, in addition, calcium carbonate is safe, easy to apply and it is readily available.

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

The carbonate of the bivalent metal is the llah get adding an aqueous solution of a water-soluble salt of the divalent metal to the aqueous solution of carbonate of alkaline metal and adjusting its pH of the aqueous alkali solution to obtain a suspension of crystalline carbonate.

When using at least two divalent metal in combination, aqueous solutions of water-soluble salts of 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, after 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 salt can be an inorganic salt or organic salt. Examples of counterions in salt include F-, Cl-, Br-I-, NO3-, CO32-, SO42-, PO43-, ClO4-IN32-CH3Soo-, oxalic acid, salicylic acid and similar. Preferred are the Xia cheap Cl -, NO3-, SO42-and CO32-.

There are times when acid ions are introduced into the gel during aging the suspension, depending on the type of such counterions, and embedded ions of the acid is difficult to completely remove. Residual ions acids may have a deleterious effect on the catalyst. Salt with NO3-are the most preferred because the counterion is able to evaporate when processed by calcination and therefore does not cause such complications.

As for the aqueous solution of alkali carbonate to which you want to add an aqueous solution of any of these water-soluble salts, preferred are carbonates, in which alkali ions (protivootecnami) are NH4, Na and K, since, as a rule, they are inexpensive and readily available. However, when aged easy to use without washing or similar processing, there are cases when ions are introduced into the gel during aging, depending on the type of alkali and adversely affect the catalyst, as in the case of salts of divalent metals and trivalent metals described above. NH4salts are preferred because the counterion is able to evaporate when processed by calcination and therefore does not cause tako what about the complications.

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

Usually longer periods of aging are favorable for obtaining crystals of a larger size (particle diameter)and shorter periods of aging can be used to obtain crystals of smaller size. In addition, the higher the aging temperature, the higher the crystallinity.

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

After aging of the crystal suspension of crystalline carbonate can be subjected to without any processing drying and ordering of the diameter of particles to be used as a catalyst, or can be used without any processing as a component of the catalyst or D. However, it is preferable to use a suspension after washing with an aqueous solution of am is IACA or aqueous solution of ammonium salt and water to remove metal impurities and other impurities, which could adversely affect the catalyst.

When the suspension is used as a component of the catalyst or D, you can regulate it to have a smaller diameter particles compared to particles of FCC catalyst, subjecting the slurry was spray-drying or drying and subsequent grinding or similar procedure. However, from the viewpoint of reducing the time required for the preparation of catalyst C or D, preferably pre-order particle diameter to the above size and suspension.

Crystalline carbonate of the divalent metal or divalent and trivalent metals significantly changes its basicity during heat treatment, and the basicity has a significant impact on the ability to asseverate metals.

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

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

Examples of ores include calcite, IP the Andean spar, aragonite, limestone, marble, chalk, strontianite, witherite, rhodochrosite and similar.

As a natural shells and animal bones can be used any shells and animal bones. Examples include shell abalone, Corbicula, clam Tapes Philippinarum, bivalves, oysters, scallops, snails Turbo and similar, and the bones of cattle, pigs, horses, sheep, chickens, fish and similar. They are readily available and cheap. In addition, when using the shell, they give the effect is to increase the strength of the catalyst attrition.

Natural carbonates can be used individually or you can choose at least two of them and use them in the form of their mixtures in appropriate proportions.

Shells and bones contain organic matter, water and similar. Therefore, it is preferable to use shells or bones after they are washed, calcined and then crushed. The annealing can be performed under any conditions for removing organic substances, water, etc., Appropriate annealing is carried out at a temperature of from 300 to 900°C for about from 10 minutes to 5 hours, preferably at a temperature from 500 to 800°C for about from 30 minutes to 5 hours.

Shells or bones, which were calcined under such circumstances, could the t to be relatively easily crushed. They can directly grind at the mill. Alternative initially, they can be crushed water jet or the like, and then grind in a mill for wet grinding, or first crush on a hammer mill or similar device, and then grind in a mill for dry grinding. Thus, calcined shells or bones order to have the above average particle diameter.

It is desirable that catalysts b and C, which are catalysts of additive type, has the same material properties as used them in combination a standard catalyst And, or used them in combination catalyst D, which is a solid catalyst type. When the catalysts differ from each other in strength, the particle diameter or bulk density, then there are times when heterogeneous catalysts are mixed with each other and unable to show sufficient characteristics catalytic performance.

Material properties of catalysts a to D cannot be determined unconditionally because they vary depending on the type of installation FCC and working conditions. However, from the viewpoint of obtaining satisfactory fluidity in the installation of the FCC, as a rule, the catalysts preferably have an average particle diameter of from 50 to 90 mcm, bulk density of 0.3 to 1.2 g/ml and the absorbance of oil 0.1 cm3/g or more, as described above.

The catalyst of the present invention includes a matrix of inorganic oxide dispersed therein a compound of the divalent metal or a compound of bivalent and trivalent metals and has no FCC activity. That is, it is a catalyst additive type, which is added to the FCC catalyst and the used catalyst FCC with FCC-activity, such as the standard catalyst A, catalyst D, etc.

In the catalyst With the amount of coupling metal is preferably from 1 to 90 wt.% and more preferably from 30 to 70 wt.% in the calculation of dry weight. When its amount is less than 1 wt.%, the ability to asseverate metals and the ability to absorb SOxis low. If its quantity increases so that it is more than 90 wt.%, it is not only essentially receive no increase of effect, but relatively a reduced amount of inorganic oxide also reduces the bonding strength of the particles, which is a property of the inorganic oxide.

Examples of inorganic oxide in the catalyst include known inorganic oxides used in conventional cracking catalysts, such as silicon dioxide, silicon dioxide-oxidine, aluminum oxide, silicon dioxide-magnesium oxide, aluminum oxide-magnesium oxide, phosphorus-alumina, silica-Zirconia, silica-magnesium oxide-aluminum oxide and similar. With inorganic oxide can be mixed clay, such as kaolin, halloysite, montmorillonite or similar.

Particularly preferred examples of the catalyst is a catalyst comprising a combination of aluminum oxide as the inorganic oxide and calcium carbonate as compounds of divalent metal because it has a high ability to asseverate catalyst poisons.

The catalyst can be obtained by adding the compound of the metal to the inorganic oxide, followed by uniform dispersion, spray drying the resulting slurry mixture in the usual way, washing the resulting particles, if necessary, and again drying or drying/calcination.

In this activity, metal compounds of a certain type because of their alkaline nature may be difficult to uniformly mix with inorganic oxide or other optional ingredients present catalyst. In this case, it is preferable to lower the basicity of the compounds of metals by coating them with phosphoric acid, coated aluminum oxide or the like.

Catalysis is tor D according to the present invention includes a compound of the divalent metal or a compound of bivalent and trivalent metals, crystalline aluminosilicate zeolite and a matrix of inorganic oxide, in which the dispersed compound of the metal and the zeolite. The catalyst has the effect of passivation of metals, which is the connection property of the metal, and additionally has a FCC-activity crystalline aluminosilicate zeolite. Therefore, the catalyst D is a solid catalyst of a type that may be used as a catalyst FCC.

The catalyst D, the number of connection metal 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 SOxis insufficient. When its amount exceeds 20 wt.%, the relative content of the crystalline aluminosilicate zeolite and inorganic oxide is reduced, and the activity of FCC and selectivity for gasoline decreases. The result is to produce catalytic cracking of crude oil in the desired manner is not only difficult, but also there are problems, which, for example, in reducing the strength of the catalyst.

The amount of crystalline aluminosilicate zeolite catalyst D is preferably from 10 to 50 wt.% and more preferably from 20 to 40 wt.% the calculation of dry weight.

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

Examples of inorganic oxides in the catalyst D include the same inorganic oxide as the oxide used in the catalyst C. In the inorganic oxide can be introduced clay, such as is used in the catalyst C.

Examples of crystalline aluminosilicate zeolites include zeolite X, zeolite Y, zeolite β, mordenite, zeolite ZSM, natural zeolites and similar. Similarly to conventional FCC catalysts zeolites can be used in the form, subjected to ion exchange 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 the temperature of the crystalline aluminosilicate zeolite (hereinafter referred to as the HS zeolite"), which is obtained by firing the stabilized zeolite Y having a molar ratio of SiO2/Al2O3from 5 to 15, the parameter of the unit cell from 24,50 Å to less than 24,70 Å and the content of alkaline metal (based on oxide) of from 0.02 wt.% to less than 1 wt.% at a temperature of from 600 to 1200°C for from 5 to 300 min in air or in nitrogen atmosphere in order to reduce the crystallinity of the stabilized zeolite Y by 20% or less.

The zeolite has a molar ratio of SiO2/Al2O3the volume ranges from 5 to 15, and the molar ratio of aluminum present in the structure of the zeolite, the entire aluminum is from 0.3 to 0.6. Zeolites have the unit cell parameters of the less than 24,45 Å and the content of alkaline metal (based on oxide) of from 0.02 wt.% to less than 1 wt.% and has a distribution of pores having characteristic peaks near 50 Å and 180 Åwhere the volume of pores with a size of at least 100 Å ranges from 10 to 40% of the total pore volume. The zeolite has an x-ray, which is the main x-ray zeolite Y (Cm. the Japan patent No. 2544317.)

Catalyst D can be obtained by adding the zeolite and the metal connection to the inorganic oxide, followed by uniform dispersion, to thereby prepare a slurry mixture, and treating the suspension in the same way as PR is the receiving of the catalyst, which is described above.

This production may be difficult to uniformly mix the compound of the metal due to its alkaline nature with an inorganic oxide or crystalline aluminosilicate zeolite, or other optional included ingredients of the catalyst. In this case, the alkaline nature of the connection metal can be reduced by covering it with phosphoric acid, coating the aluminum oxide and the like, at the time of receipt of catalyst C.

The standard catalyst a, which can be used in combination with at least one of these catalysts B-D, includes a matrix containing an inorganic oxide and a crystalline aluminosilicate zeolite, uniformly dispersed in the matrix. Can be any of a variety of commonly used catalysts cracking.

Examples of inorganic oxide and a crystalline aluminosilicate zeolite include compounds that are the same as in 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 containing inorganic oxide and clay, is about 10 to 50 wt.% and preferably from about 20 to 40 wt.%. However, in the us oasam the invention must take into account the proportion of the mixed catalyst, C or D, as the catalyst, C or D is used in combination with standard catalyst A.

Specifically is appropriate to adjust the amount of crystalline aluminosilicate zeolite, at least up to 10 wt.%, preferably from 10 to 50 wt.% and more preferably from 20 to 40 wt.% of the total number of catalysts a, b, C or D.

When the amount of zeolite is less than 10 wt.%, you cannot achieve the desired level of activity FCC. Even when its quantity increases so that it is 50 wt.% or more, the effect of mixing with the zeolite no longer increases. Therefore, such large amounts of zeolite are not cheap.

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

Above the desired standard catalyst And can be obtained by adding crystalline aluminosilicate zeolite to the inorganic oxide, followed by uniform dispersion, spray drying the resulting slurry mixture in the usual way, washing the resulting particles, if necessary, and again drying or calcination of the particles after drying.

The way the FCC of the present invention is performed using at least one of the above catalyst and additive type and isopycnal catalyst D one-piece type in combination with a standard catalyst And or using catalyst D integral type, in combination, at least one of the catalyst and additive type, or using a single catalyst D integral type.

When at least one of the catalysts B-D is used in combination with a standard catalyst And the proportion of the used catalysts determine, taking into account the following.

When the standard catalyst And is used in combination with catalyst D, can be selected any of their proportions in accordance with the desired ability passivation of metals and the desired absorption capacity SOx.

When one or both catalyst a and D are used in combination with one or both of the catalysts b and C, is appropriate to the relationship one or both of the catalysts a and D)/(one or both of the catalysts b and C) were of 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 terms of weight. When one or both of the catalyst and additive types make up more than half of the total amount of catalyst, the activity of the FCC and selectivity for gasoline are reduced, making it difficult catalytic cracking of crude oil in the desired manner.

In the way the FCC of the present invention catalysts A-D can be used as independent of bulk catalysts in certain higher proportions or used in the form of particles p is iegotovlenna in advance of a mixture of catalysts in the above proportions. FCC you can spend, resulting in contact of the heavy liquid oil as the oil feedstock with the catalyst particles under the conditions of the FCC.

Examples of heavy hydrocarbon oils are, for example, gas oils, vacuum distillation, distillation residues of light fractions, vacuum distillation residues, mixtures of these balances, etc.

The FCC catalyst of the present invention is effective even when the quality of crude oil used heavy liquid petroleum products with reduced content of compounds of Nickel and / or vanadium and sulfur compounds. However, the catalyst is extremely useful when it is used for catalytic cracking of low-grade heavy liquid oil containing poison the catalyst metals and sulfur compounds in large quantities (for example, having a sulfur content of 0.2 wt.% or more and the metal content of 50 ppm (calculated on the amount of metal) or more). Therefore, the way the FCC of the present invention can provide a remarkable effect when the oil raw materials use of such low-grade heavy liquid petroleum product.

In the implementation in practice of the method of the FCC of the present invention take into account the number of impurities of metals and sulfur compounds contained in crude oil. When their number is significant, there may be used a mixture of a hundred the standard catalyst a or catalyst D solid type catalyst or additive of the type to contain the increased proportion of catalyst or additive type. Thus, the decrease of activity FCC, which may be due to the relatively reduced number of standard catalyst a or catalyst D one-piece type, can be compensated for by increasing the number of crystalline aluminosilicate zeolite dispersed in a standard catalyst a or catalyst D integral type.

The FCC conditions used in the present invention can be commonly used terms FCC. Typical examples of FCC conditions represent the following conditions:

The reaction temperature: 460-540°

Average hourly feed rate: 4-20 h-1

The ratio of catalyst/oil: 4-12

In the methods FCC FCC catalysts which have been deactivated by coke deposition, usually recovered by burning off the carbon and re-use in the reactions FCC. In the FCC catalyst and the way the FCC according to the present invention, the standard catalyst A, the catalyst solid type D, and the catalyst additive of the type b and C, which were depleted, you can also regenerate existing regenerators under normal conditions of regeneration and reuse.

Regeneration is carried out at a temperature of from 600 to 750°C. the Catalysts B-D of the present invention show excellent efficiency is t capture SO x, which is formed during the regeneration.

Catalysts B-D of the present invention Passepartout poison the catalyst metals contained in the oil raw materials, such as Nickel and vanadium, lead to the formation of smaller amounts of hydrogen and coke, have excellent kekirawa activity and ability to recycle the remains of the pickup oil and can give gas and the fraction of light cycle gas oil with high yields. In addition, the catalysts can save operational characteristics at a high level for a long period of time and, therefore, have improved the service life of the catalyst. In addition, since the catalysts absorb SOxin large quantities, they are effective from the standpoint of reducing the number of SOxcontained in the exhaust installation FCC.

EXAMPLES

The preparation of the catalyst:

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

Example 1

The 3-liter (hereinafter liter referred to as "l", and the milliliter referred to as "ml") glass beaker containing 1000 ml of distilled water, dissolve 271,9 g of the pentahydrate manganese sulfate, followed by stirring with a magnetic stirrer in techenie min to obtain solution A. The solution has a pH of 4.54.

A 3-liter glass beaker containing 1000 ml of distilled water, dissolve 125 g octadecahydrate of aluminum sulfate, followed by stirring with a magnetic stirrer for 15 min to obtain solution C. Solution has a pH of 1.63.

The solution is mixed with a solution In a 5-liter glass beaker, heated to 80°and mix With a magnetic stirrer to obtain solution C.

A 5-liter glass beaker containing 1000 ml of distilled water, dissolve 113,8 g of sodium carbonate, followed by heating up to 80°and mixing ultraliberalism for 15 min to obtain a solution D. Solution has a pH D 11,47.

As mixing the solution D ultraliberalism to gradually feed pump add solution C. during this operation also add aqueous ammonia to maintain the pH of the mixture solutions at the value of 9.

The mixture of the solutions are subjected to aging, stirring at 80°C for 3 h to obtain the compound of the metal.

After aging the solution is filtered through a Buechner funnel. To separate suspensions (connection metal) add 2 l of distilled water, heated to 80°C. the resulting mixture is stirred and filtered. Operation is repeated, that is to carry out the flushing twice.

Separated by filtration, the suspension is dried at 100°C for about 24 h to obtain the compound of the metal.

The compound of the metal, which was dried, ground in a mill to a particle diameter of 15 μm or less.

The compound of the metal is called MS-1 (Mn-Al-CO3).

Define APS (average particle diameter) and SA (surface area) MS-1 and install the metal content using a spectrometer with inductively coupled plasma. The results are shown in table 1. Before the study spectroscopy with inductively coupled plasma samples are fired at 1100°C for 2 h as pre-processing.

Next to crystal structure analysis using x-ray diffractometer. The results are shown in figure 1.

In figure 1 the results of the analysis by x-ray diffractometer is shown in the upper part, the data for the maximums shown in the middle part and the data of the Mn-Al-CO3from JCPDS-PDF (Joint Committee on Power Diffraction Standards - Power Diffraction; data Bank, collecting x-ray data powdered samples) shown in the lower part.

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

Example 2

Prepare crystalline metal compounds as in example 1, except that the divalent metal replacement is ut CA 2+, Sr2+, Ba2+or Sn2+using the chloride or nitrate of the metal in solution As in example 1 in a quantity equimolar to the sulphate of manganese.

Crystalline metal compounds prepared using CA2+, Sr2+, Ba2+or Sn2+as divalent metals, hereinafter referred to as MS-2 (Ca-Al-CO3), MS-3 (Sr-Al-CO3), MS-4 (Ba-Al-CO3and MS-5 (Sn-Al-CO3respectively.

Explore the APS and SA MS-2, MS-3, MS-4 and MS-5 and install the metal content using a spectrometer with inductively coupled plasma. The results are shown in table 1.

In addition, for the analysis of crystal structure from MC-2 through MC-4 using x-ray diffractometer. The results are shown in Fig.2-4. Figure 2-4 the data in the upper, middle and lower parts have the same values as in figure 1. Figure 2-4 clearly show that each of the samples from MC-2 through MC-4 has a crystalline structure of the carbonate of the divalent metal.

Example 3

The crystalline compound of the metal is prepared in the same manner as in example 1, except that the trivalent metal will replace another metal, using sulfate or nitrate trivalent metal in the solution as in example 1 in a quantity equimolar to the aluminum sulfate.

The crystalline compound of the metal is prepared using as trehu entogo metal Mn 3+call MS-6 (Mn-Mn-CO3).

Define APS and SA for MS-6 and install the metal content using a spectrometer with inductively coupled plasma. The results are shown in table 1.

Example 4

Reagent calcium carbonate first grade, produced by Kanto Chemical Co., Inc., hereinafter referred to as MS-7 (caso3); and the powders obtained from the shells of clams and oysters, with annealing at 700°C for 2 h and then crushed into a powder, known as MS-8 (caso3and MS-9 (caso3respectively.

Define APS and SA for the MC-7, MC-8 and MC-9 and install the metal content spectrometer with inductively coupled plasma. The results are shown in table 1.

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

Table 1

Dry weight (wt.%)
HydrotalciteMS-1MS-2MS-3MS-4
Al2O337,418,5834,6324,5315,61
MgO60----
Mn2About3-77,32---
CaO--expenses 63.81--
Sr2O3---73,91-
HLW----84,03
SnO2-----
Na2O--1,561,560,36
To2O -----
APS (micron)0,523,61,31,1
SA (m2/g)150104272432
Table 1 (continued)

Dry weight (wt.%)
MS-5MS-6MS-7MS-8MS-9
Al2O3there is a 10.03--0,40,3
MgO---0,110,1
Mn2About3-its 98.45-0,040,06
CaO--99,596,11 92,45
Sr2O3---0,1-
HLW-----
SnO289,89----
Na2O0,08--0,30,35
To2O---0,060,07
APS (micron)1.61,51,72,73,5
SA (m2/g)531225,96,9

2. Preparation of catalysts

Example 5

To 400 g of the Hydrosol of silicon dioxide containing 10 wt.% SiO2add 64 g of zeolite HS and 86 g of kaolin clay per su is th mass, to obtain a slurry mixture.

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

The standard catalyst And is called the base 1. It is used mainly as a reference for comparison with catalyst D integral type.

On the other hand, the standard catalyst And get on an industrial scale in the amount of approximately 100 tons in one operation. The catalyst is called the base 2. It is used mainly as a benchmark for the evaluation of catalysts b and C of the additive type.

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

Example 6

To 400 g of the Hydrosol of silicon dioxide containing 10 wt.% SiO2add 64 g of zeolite HS, 86 g of kaolin clay per dry weight and 10 g prepared in examples 1 and 2 compounds of metals having a particle diameter of 15 μm or less to get through a suspension of the mixture.

The slurry mixture is subjected to spray drying in order to obtain the particles having the average particle diameter 68±5 μm. The particles are washed and then dried to obtain the solid catalyst type, containing the associated metal connection.

The solid catalysts of the type that uses MS-1, MS-2, MS-5, MS-7 and hydrotalcite KW-2200 manufactured by Kyowa Chemical Co., Ltd. as a metal link, denoted as catalysts of D1, D2, D3, D4 and X, respectively.

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

In addition, using a spectrometer with inductively coupled plasma install the metal content. In the result set that the catalysts contain metal compounds in an amount of about 5 wt.% calculated on dry basis.

Hydrotalcite KW-2200 manufactured by Kyowa Chemical Co., Ltd., dried at 100°C. After that, hydrotalcite examined by radiography and establish the structure of hydrotalcite. The results are shown in Fig.

Table 2
Name catalystBasis 1XD1
The catalyst composition:
Passivator metal-hydrotalciteMC-1
Binderdioxidedioxidedioxide
Zeolitesilicon

zeolite HS
silicon

CE is lit HS
silicon

zeolite HS
Matrixkaolinkaolinkaolin
Catalysts:
APS (micron)687170
SA (m2/g)223,9185,5212,2
ABD (g/ml)0,780,710,71
PV (ml/g)0,160,140,16
Table 2 (continued)
Name catalystD2D3D4
The catalyst composition:
Passivator metalMS-2MS-5MS-7
Binder

Zeolite
silicon dioxide

zeolite HS
silicon dioxide

zeolite HS
silicon dioxide

zeolite HS
Matrixkaolinkaolinkaolin
Catalysts:
APS (micron)707068
SA (m2 to 178.4193133
ABD (g/ml)0,730,750,69
PV (ml/g)0,160,150,16

Example 7

To 600 g of the Hydrosol of silicon dioxide containing 10 wt.% SiO2add 40 g per dry weight prepared in examples 1-4 compounds of metals having a particle diameter of 15 μm or less, to thereby obtain a slurry mixture.

The slurry mixture is subjected to spray drying in order to obtain particles having an average particle diameter 68±5 microns.

The particles are washed and then dried to obtain the catalyst additive of the type with associated metal connection.

Catalysts With additive type, which uses a metal link MS-1 and hydrotalcite KW-2200 manufactured by Kyowa Chemical Co., Ltd., called catalysts Cl and Y, respectively.

Define APS, SA, ABD and PV catalysts Cl and Y. the Results are shown in table 3.

In addition, using a spectrometer with inductively coupled plasma install the metal content. In the result set that the catalysts contain metal compounds in an amount of about 40 wt.% calculated on dry basis.

Example 8

To 3 kg of a suspension of hydrogel of alumina containing 10 wt.% Al2O3add 200 g per dry weight prepared in examples 1-4 compounds of metals having a particle diameter of 15 μm or less. The suspension is subjected to spray drying in order to obtain particles with an average diameter 68±5 μm. Thus obtained catalyst additive of the type with associated metal connection.

The catalyst additive of the type obtained using the MC-1, MC-2, MC-3, MC-4, MC-5, MC-6, MC-7, MC-8 and MC-9 as a metal link, denoted as catalysts C2, C3, C4, C5, C6, C7, C8, C9 and C10, respectively.

Define APS, SA, ABD and PV catalysts C2, C3, C4, C5, C6, C7, C8, C9 and C10. Catalysts C3, C8, C9 and C10 additionally examined to assess the strength of the catalyst to abrasion [initial small fraction (referred to as "IF"), and the average loss from abrasion (referred to as "AL")]. The results are shown in table 4.

Next, using a spectrometer with an induction coupled plasma install the metal content. In the result set that the catalyst contains metal compounds in an amount of about 40 wt.% by dry weight.

In addition, 3 kg of a suspension of hydrogel of alumina containing 10 wt.% Al2O3, is subjected to spray drying, so that the result is to obtain particles, having an average diameter 68±5 μm. The resulting catalyst is designated as catalyst Z.

Define APS, SA, ABD and PV catalyst Z. the Results are shown in table 4.

Table 3
Name catalystPillar 2YC1
The supplements:
Passivator metal-hydrotalciteMS-1
Binder-dioxidedioxide
siliconSilicon
Zeolite---
Matrix---
Properties of the catalyst;
APS (micron)656767
SA (m2/g)189,283,297,6
ABD (g/ml)0,720,640,67
PV (ml/g)0,150,220,245
The proportion of additives:
Pillar 2 (wt.%)1009090
Additive type01010
(wt.%)
Table 4
Name catalystThe base 2ZC2C3
The supplements:
Passivator metal--MS-1MS-2
Type binding-oxideoxideoxide
aluminumaluminumaluminum
Zeolite----
Matrix----
Properties
catalyst:
APS (micron)65696864
SA (m2/g)189,2/td> 259205184
ABD (g/ml)0,720,540,50, 67
PV (ml/g)0,150,6520,7150,322
IF---17,87
AL---20,61
The proportion of additives:
Pillar 2 (wt.%)100909090
Additive type0101010
(wt.%)
Table 4 (continued)
Name catalystC4C5C6C7
The supplements:
Passivator metalMS-3MS-4MS-5MS-6
Type bindingoxideoxideoxideoxide
aluminumaluminumaluminum
Zeolite----
Matrix----
Properties
catalyst:
APS (micron)65686567
SA (m2/g)201174186145
ABD (g/ml)0,670,780,840,7
PV (ml/g)0,2710,2940,280,23
IF----
AL----
The proportion of additives:
Pillar 2 (wt.%)90909090
Additive type10101010
(wt.%)

Table 4 (continued)
Name catalystC8C9C10
The supplements:
Passivator metalMS-7MS-8MS-9
Type bindingoxideoxideoxide
aluminumaluminumaluminum
Zeolite---
Matrix---
Catalysts:
APS (micron)736968
SA (m2/g)133176,7192.5 kg
ABD (g/ml)0,780,810,83
PV (ml/g)0,2010,207of € 0.195
IF12,66,637,01
AL17,653,142,87
Proportion to the where it is refuelled:
Pillar 2 (wt.%)909090
Additive type101010
(wt.%)

3. Analytical instruments, testing conditions, etc.

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

ICP (composition analysis):

"IRIS Advantage"manufactured by Thermo Jarrell Ash.

APS (average particle diameter):

"Electromagnetic vibration filter type M-2"manufactured by Tsutsui Rikagaku Kiki K.K.

SA (surface area):

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

ABD (apparent bulk density):

"Measuring bulk density", manufactured by Tokyo Kuramochi Called Kikai Seisakusho (JIS Z 2504).

PV (pore volume):

"MICROMERITICS AUTOPORE II 9220", manufactured by Shimadzu Corp.

IF (source small fraction)*:

[(particle fine fraction through 0-12 h (dry mass, g))/(number of sample)]×100

AL (the average loss from abrasion)*:

[(particle fine fraction through 12-42 h (dry mass, g))/(number of sample)]×100

* Original fine fraction and the average loss from abrasion define test of strength the catalyst attrition, conducted in the following manner and with the help of calculation.

Treated with 50 g of catalyst (sample)by heating at 500°C for 5 h, add thereto 5 g of water and the catalyst flows through the tube to the catalyst at a rate of flow 0.102 m/s the Number of particles of the fine fraction (dry weight g), which is present in the pipe to catalyst, measured at the time when it took 12 hours after initiation of the flow (0-12 h) and at a time when this was a 42 h (12-42 h). Calculate the original fine fraction and the average loss from abrasion using data from the above expressions.

X-ray* diffractometer:

"RINT 2500V", manufactured by Rigaku Corp.

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

The tube voltage: 50 kV

Tube current: 300 mA

Scan mode: continuous

Scanning speed: 2°/min

Step scan of 0.02°

Range scan (2θ): 5-90°

Forming a gap: 1°

The receiving slit: 0.3 mm

4. Test activity MAT

Evaluation conditions:

Obtained in examples 5-8 catalysts subjected to the following imitating balance processing. Then evaluate the activity of FCC catalysts and the ability to asseverate metals, applying the device tests macroactivity the fixed layer according to ASTM (3907) and using liquid petroleum products, having shown in table 5 properties under the following test conditions.

Conditions simulating equilibrium processing:

Each fresh catalyst is heated from room temperature to 500°C for 30 min and then maintained at 500°C for 5 h with the purpose of ignition.

After that, each catalyst was impregnated with a solution of cyclohexane containing Nickel naphthenate and vanadium naphthenate in these quantities (1000 and 2000 ppm by weight).

The catalyst was dried at 100°C, then heated from room temperature to 500°C for 30 min and then maintained at 500°C for 5 h to him again ignited.

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

After the steam treatment assess FCC activity of each catalyst.

When assessing the ability of each catalyst to asseverate metals the amount of Nickel and vanadium on the catalyst is set to 0 and 0 ppm by weight, 1000 and 2000 ppm by weight, 2000 and 4000 ppm by mass or 3000 and 6000 ppm by mass.

Table 5

Test n is theproduct: gas oil vacuum distillation
Sample
12
Density 15°g/cm30,89590,8819
Vacuum distillation
Initial boiling point319294
5% °362352
10% °383367
20% °406390
30% °421402
40% °433415
50% °446424
60% °460436
70% °481451
80% °509471
90% °566506
95% °531
97% °544
The end of the boil, °605548
The total amount of distillate, %93,598,5
The amount of residue, %6,51,5
Loss, % 00
Pour point, °3335
Dynamic viscosity of 50°mm2/s34,5418,67
The content of nitrogen (method
chemiluminescence) wt.%0,050,02
Sulfur content (x-ray)
wt.%0,150,01
The refractive index 70 nD1,481,47
Density of 70°g/cm30,860,84
Molecular weight
(calculated viscosity)475402
Asphaltenes (UOP) wt.%.0,38
Method n-d-m (70° (C)% aromatics15,212,8
% naphthenes14,618,8
% paraffinsto 70.268,4
Aniline point (method U-shaped Tube) °95,494,5
Dynamic viscosity of 75°mm2/s14,568,77
Dean is dynamic viscosity 100° With mm2/sto 7.674,99
Nitrogenous base, wt.%0,0014
Bromine number g Br2/100 g1,90
The hydrogen content, wt.%13,03
The content of the coke residue, wt.%1,250,06

Test conditions: stationary layer

The reaction temperature: 500°

The mass ratio of the catalyst/liquid petroleum:

2,5; 3,0; 3,5

The test period: 75

5. Evaluation of the performance characteristics of the catalyst

Example 9

The catalysts of D1, D2, D3 and D4 integral type, containing MC-1, MC-2, MS-5 and MS-7, respectively, is subjected to imitate equilibrium process and then test the activity MAT, using sample 2. The results are shown in table 21.

Example 10

The catalyst X is subjected to imitate equilibrium process and then test the activity MAT, using sample 2. The results are also shown in table 21.

Conversion (wt.%):
Table 21
Name catalystBasis 1XD1
The name passivator metal-HydrotalciteMS-1
The catalyst/oil333
The number of inserted metal:
Ni/V (h/m)
0/073,1358,5673,49
1000/200067,7056,3468,83
2000/400055,5049,5360,25
3000/600030,6436,1654,43
Selectivity (wt.%):
The number of inserted metal: Ni/V=2000/4000 (ppm)
Conversion (wt.%):60,0060,0060,00
The output of each ingredient
(wt.%)
H20,200,360,16
S1-21,432,021,31
Liquefied petroleum gas11,4312,4912,05
Gasoline 43,3940,3943,79
Light cycle oil24,3820,5125,71
Heavy cycle oil15.62 wide19,4914,29
Cox3,054,742,69
Road octane number88,4988,4188,40
Table 21 (continued)
Name catalystD2D3D4
The name passivator metalMS-2MS-5MS-7
Conversion (wt.%):
The catalyst/oil333
The number of inserted metal:
Ni/V (h/m)
0/072,6272,7172,19
1000/200067,9768,7067,72
2000/400057,4858,9055,95
3000/600046,4351,2841,68
Selectivity (wt.%):
The number of inserted metal: Ni/V=2000/4000 (ppm)
Conversion (wt.%):60,0060,0060,00
The output of each ingredient
(wt.%)
H20,190,170,21
S1-21,411,311,56
Liquefied petroleum gas11,9212,3612, 99
Gasoline43,5943,1842,03
Light cycle oil24,6025,2322.98mm
Heavy cycle oil15,4014,7717,02
Cox2,892,983,21
Road octane number88,5388,3888,46

Example 11

Catalyst C1 additive type containing MS-1, physically mixed in an amount of 10 wt.% with the catalyst of the base 2. The resulting catalyst is subjected to imitate equilibrium process and then test the activity MAT, ISOE is isua sample 2. The results are shown in table 31.

Example 12

Catalyst Y additive type, containing hydrotalcite KW-2200, physically mixed in the amount of 10% of the mass with catalyst type base 2. The resulting catalyst is subjected to imitate equilibrium process and then test the activity MAT, using sample 2. The results are also shown in table 31.

Selectivity (wt.%):
Table 31
Name catalystPillar 2YC1
The name passivator metal-HydrotalciteMS-1
Conversion (wt.%):
The catalyst/oil333
The number of inserted metal:
Ni/V (h/m)
0/070,9366,7170,19
1000/200063,2156,2964,89
2000/400051,6548,1858,70
3000/600027,3635,5251,98
The number of inserted metal: Ni/V=2000/4000 (ppm)
Conversion (wt.%):60,060,060,0
The output of each ingredient
(wt.%)
H20,200,290,15
S1-21,281,301,23
Liquefied petroleum gas12,0612,0812,56
Gasoline43,4743,3643,59
Light cycle oil24,7624,6726,57
Heavy cycle oil15,2415,3313,43
Cox2,992,972,47
Road octane number88,4388,3588,65

Example 13

The catalysts C2, C3, C4, C5, C6, C7, C8, C9 and C10 additive type containing MC-1, MC-2, MC-3, MC-4, MC-5, MC-6, MC-7, MC-8 and MC-9, respectively, are physically mixed in the amount of 10% of the mass with catalyst type base 2. The resulting catalyst is subjected to imitate equilibrium process and then test the activity MAT, using sample 1. The results are shown in table 41.

Example 14

Catalyst Z additive type physically mixed in the amount of 10% of the mass with catalyst type base 2. The resulting catalyst is subjected to imitate equilibrium process and then test the activity MAT, using sample 1. The results are also shown in table 41.

53,43
Table 41 (1)
Name catalystPillar 2ZC2C3
The name passivator metal--MS-1MS-2
Conversion (wt.%):
The catalyst/oil3333
The number of inserted metal:
Ni/V (h/m)
0/067,7167,2968,0767,21
1000/200059,9662,4866,6265,68
2000/400048,7762,3864,08
3000/600023,5135,4561,0361,99
Selectivity (wt.%):
The number of inserted metal: Ni/V=1000/2000 (ppm)
Conversion (wt.%):60,0060,0060,0060,00
The output of each ingredient
(wt.%)
H20,350,430,200,15
S1-20,840,960,830,76
Liquefied petroleum gas12,50to 11.6112,27of 12.26
Gasoline43,8143,5044,7844,97
Light cycle oil27,9729,3429,7829,63
Heavy cycle oila 12.0310,6610,2210,37
Cox2,503,501, 92to 1.86
The road is Stanovoi number 89,3789,4189,0689,58
Selectivity (wt.%):
The number of inserted metal: Ni/V=3000/6000 (ppm)
Conversion (wt.%):60,0060,0060,0060,00
The output of each ingredient
(wt.%)
H2--0,330,36
S1-2--0,910,91
Liquefied petroleum gas--12,93br12.62
Gasoline--43,3843,77
Light cycle oil--27,7926,68
Heavy cycle oil--12,2113,32
Cox--2,452,34
Road octane number--89,5289,81

Table 41 (2)
Name catalystC4C5C6C7
The name passivator metalMS-3MS-4MS-5MS-6
Conversion (wt.%):
The catalyst/oil3333
The amount of the metal;
Ni/V (h/m)
0/067,3367,8067,3667,45
1000/200065,9766,1464,8163,49
2000/400063,8963,8357,6558,40
3000/600062,4361,8143,1850,22
Selectivity (wt.%):
The number of inserted metal: Ni/V=1000/2000 (ppm)
Conversion (wt.%):60,0060,00 60,0060,00
The output of each ingredient
(wt.%)
H20,160,150,220,26
S1-20,790,850,810,71
Liquefied petroleum gasto 12.2812,0812,7111,96
Gasoline44,8744,8644,0244,93
Light cycle oil29,9129,6928,9129,51
Heavy cycle oilto 10.0910,3111,0910,49
Cox1,90to 2.062,242,14
Road octane number89,3389,3089,2189,17
Selectivity (wt.%):
The number of inserted metal: Ni/V=3000/6000 (ppm)
Conversion (wt.%):60,0060,0060,0060,00
Access to the each ingredient
(wt.%)
H20,320,30--
S1-20,870,92--
Liquefied petroleum gas12,82of 12.73--
Gasoline43,6443,67--
Light cycle oil26,8226,96--
Heavy cycle oilof 13.1813,04--
Cox2,352,38--
Road octane number89,6789,62--

Table 41 (3)
Name catalystC8C9C10
The name passivator metalMS-7MS-8MS-9
Conversion (wt.%):
The catalyst/oil333
The number of inserted metal:
Ni/V (h/m)
0/067,5568,3267,75
1000/200065,7466,0965,92
2000/400063,9863,9264,21
3000/600061,5462,0761,84
Selectivity (wt.%):
The number of inserted metal: Ni/V=1000/2000 (ppm)
Conversion (wt.%):60,0060,0060,00
The output of each ingredient
(wt.%)
H20,140,140,15
S1-20,780,770,79
Liquefied petroleum gasof 12.3312,3212,29
Gasoline44,8944, 9644,90
Easy the cycle oil 29,8129,9229,87
Heavy cycle oilof 10.2110,1310,28
Cox1,841,761,72
Road octane number89,4389,4189,38
Selectivity (wt.%):
The number of inserted metal: Ni/V=3000/6000 (ppm)
Conversion (wt.%):60,0060,0060,00
The output of each ingredient
(wt.%)
H20,290,300,31
S1-20,900,910,92
Liquefied petroleum gas12,5812,6912,49
Gasoline43,6643,8743,91
Light cycle oil28,0927,9727,92
Heavy cycle oil12,3012,2112,12
Cox2,182,052,33
Road octane number89,7589,6789,52

6. Test assessment activity bench scale.

To test assessing the activity of the catalysts used with the installation of bench scale, comprising a reactor with a fluidized bed with circulation, equipped reaction vessel and the catalyst regenerator.

To test the catalysts (base 2, C3, C8 and C9), subject to the following procedure simulate equilibrium with circulation.

As crude oil is used desulfuromonas gas oil vacuum distillation is shown in table 6. Use the following test conditions.

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

The reaction temperature: 500°

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

The number of circulating catalyst: 60 g/min

Imitation equilibrium with circulation:

Using the method and apparatus described in JP-A-11-179192 (application for Japan patent No. 352940/1997). Fresh catalyst or a mixed catalyst consisting of a fresh catalyst and the catalyst, which introduced the metal, heated to 775°and calcined/steamed in an atmosphere of 50% air and 50% PA is a (stage heating/annealing/steam treatment).

After that, the mixed catalyst is cooled to room temperature and the gaseous nitrogen is sprayed with a solution of metal, so that it sticks to the catalyst. The catalyst was dried at 250°and solvent vapours are separated from removing gaseous nitrogen (stage desorption). Operation repeat for 6 h per day for 10 days.

Standard conditions:

Spend processing under the same conditions as described above in simulating circulation equilibrium, except that the average of the entered amount of Nickel and vanadium adjust to 2500 and 5000 ppm by weight, respectively, and the average period of steaming change up to 20 hours

Duplication of conditions over the lifetime of the catalyst:

Spend processing under the same conditions as in the standard conditions, except that the average of the entered amount of Nickel and vanadium adjust to 5000 and 10000 ppm by weight, respectively, and the average period of steaming change to 40 hours

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

Table 6

Test oil: g is soil vacuum distillation
Sample 3
Density 15°g/cm30,9094
Vacuum distillation
Initial boiling point330
5% °366
10% °382
20% °406
30% °424
40% °443
50% °465
60% °488
70% °518
80% °553
Final boiling point, °575
The total amount of distillate, %85,0
The amount of residue, %15,0
Loss, %0
Pour point, °20
Dynamic viscosity of 50°mm2/s56,22
The nitrogen content (chemiluminescence method)0,089
wt.%.
Sulfur content (x-ray method) wt.%0,20
The refractive index 70 nD1,487
Density of 70°g/cm30,8709
Molecular weight (calculated from viscosity)498
Asphaltenes (UOP) wt.%0,66
Method n-d-m (70°C)% aromatics16,6
% naphthenes16,0
% paraffins67,4
Aniline point (method U-shaped tube) °95,1
Dynamic viscosity of 75°mm2/c-
Dynamic viscosity of 100°mm2/c10,250
Nitrogenous base, wt.%0,0181
Bromine number g Br2/100 gof 5.4
The hydrogen content, wt.%12,61
The content of the coke residue, wt.%2,23

10,79
Table 7
Name catalystPillar 2C2C8C9
The name passivator metal-MS-2MS-7MS-8
Conversion (wt.%):
The catalyst/oil8888
The average number entered
metal:
Ni/V (h/m)
2500/500060,8067,4367,5267,21
5000/1000040,1066,5065,8265,56
Selectivity (wt.%):
The average number of inserted metal: Ni/V=2500/5000 (ppm)
The average period of steaming: 20 PM
Conversion (wt.%):60,0060,0060,0060,00
The output of each ingredient
(wt.%)
H20,230,140,130,13
S1-20,890,870,880,87
Liquefied petroleum gasof 10.9310,9510,82
Gasoline41,2442,3542,3542,41
Light cycle oil21,3722.98mm23,2122,93
Heavy cycle oil19,0817,3217,3817,68
Cox6,265,395,235,19
Road octane number88,8088,7988,7888,79
Selectivity (wt.%):
The average number of inserted metal: Ni/V=5000/10000 (ppm)
The average period of steaming: 40 PM
Conversion (wt.%):60,0060,0060,0060,00
The output of each ingredient
(wt.%)
H20,310,250,230,22
S1-20,731,000,910,92
Liquefied petroleum gas17,7011,34 10,9011,12
Gasoline35,8641,6542,2142,34
Light cycle oil17,2523,3823,1223,46
Heavy cycle oil20,2516,2616,6216,12
Coxof 7.906,126,01of 5.82
Road octane number88,8089,5089,3489,45

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

Definition

In table 8, the analysis used the same instruments and equations for the calculations, which are described in sec3 (p.38-39).

Obtaining catalyst

The catalysts were obtained by the following method.

To 3 kg of a suspension of hydrogel of alumina containing 10 wt.% Al2SO3added caso3as indicated in table 8. The suspension was spray dried. Thus was obtained a catalyst additive of the type with fixed therein, caso3.

The specific number of caso3mentioned below. In addition, they depend on the content of caso3" in the catalysts.

Caso3(g)
Catalyst R (20%)75
Catalyst Q and Z (40%)200
Catalyst V (90%)2700

Caso3had the average particle diameter (APS) of 0.97 or 45 microns.

In the Table AND the BASE 1 and BASE 2 was obtained in the following way.

To 400 g of the Hydrosol of silicon dioxide containing 10 wt.% SiO2added 64 g of zeolite HS and 86 g of kaolin clay, calculated on dry substance, mixture in suspension.

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

The standard Catalyst And is specified as the BASIS of 1.

On the other hand, the Standard Catalyst And received on a commercial scale in an amount of about 100 t per cycle.

This catalyst is indicated as the BASIS 2.

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

Other

In table 8 the method of Mitchell, which is the pseudoequilibrium method is a method described with on p.40 p.41 (line 4) of the present description.

Pseudoequilibrium method specified in table 8, was carried out in the following conditions is:

Conditions are simulated equilibrium processing:

Each fresh catalyst was heated for 30 min from room temperature to 500°and kept at 500°C for 5 h for his firing.

Then, each catalyst was impregnated cyclohexanebis a solution containing Nickel naphthenate and vanadium naphthenate in certain quantities (1000 and 2000 ppm based on the weight).

The catalyst was dried at 100°C, then heated for 30 min from room temperature to 500°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°in an atmosphere of air. After the temperature reached 800°With, the atmosphere was replaced with 100% steam for processing of catalyst within 6 hours

In table 8 specifically States that the term "pseudo" has the same meaning as the term "mimic", as indicated on p.40 of the present description.

Next, we discuss the results presented in table 8.

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

Catalysts Q, R and V show the results obtained for the 40 wt.% Caso3that could fit into the stated limits, and for 20 and 90 wt.% Caso3that in both cases is outside the stated limits.

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

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

Now as for the catalyst V, the content of calcium carbonate in it is 90 wt.%, what is claimed exceeds the upper limit. The catalyst shows the worst abrasion resistance, which is not sufficient for practical use.

With regard to indicators of resistance to abrasion, lower values mean better durability, thus, in General, the catalysts having higher than 30, have a tendency to spray, and it is believed that their practical use is difficult because of such reasons as the destruction of equipment, etc. Therefore, the catalysts proposed in the present invention, having a measure of resistance to abrasion 20 or below are preferred for practical use.

Additional data show that the preferred content of calcium carbonate is 30 to 70%, and that when the content goes beyond the defined range, the resulting product is not useful from a practical point of view metrosexualism agent additive type due to significantly lower metalloservisa ability or resistance to abrasion.

Relative to the average particle diameter of calcium carbonate: dimensional constraints: from 0.001 to 30 μm

Presents additional data show the results for catalysts using metallizovanogo agent additive type, in which the average particle diameter of caso3is 45 μm, which is higher than the stated upper limit. The results show that the abrasion resistance is markedly reduced from the value of 20 or lower, which is the limit for practical use.

Also it should be noted that the catalysts having a particle size of less than the specified lower limit of 0.001 μm, it is difficult to produce.

Data resistance to abrasion for caso3with an average particle diameter of from 1.7 to 3.5 μm is presented in the Examples. These data show that the abrasion resistance is useful from a practical point of view within 20 or below.

Summarizing the above, the average particle diameter of the calcium carbonate used in the present invention, is preferably from 0.001 to 30 μm. Particles of calcium carbonate having a particle size of below mentioned item is Edilov, it is difficult to obtain. On the other hand, the calcium carbonate in the form of particles with a size greater than a specified upper limit does not demonstrate the improved resistance to abrasion.

The following are additional notes on table 8 to the best of its understanding.

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

With regard to the proportion of catalyst and oil, this ratio is 3 hours of catalyst per 100 g oil.

It should be stated that for catalysts V, and Z provides no data regarding the exit. As can be seen from table 8, the values of both indicators is the initial content of fine particles (IF) and AL - extremely high. Therefore, the catalysts V, and Z could be used for catalytic cracking in a fluidized bed of heavy oil.

Table 8
← the content of caso3
← particle diameter of caso3
Name catalystQRVZ
Addie is active composition
Deactivator metal (wt.%)Caso3(40)Caso3(20)Caso3(90)Caso3(40)
The type of binder (wt.%)Alumina (60)Alumina (80)Alumina (10)Alumina (60)
Zeolite (wt.%)
Matrix (wt.%)
Physical properties of deactivator metal
APS (micron)0,970,970,9745
SA (m2/g)58169638
ABD (ml/kg)0,830,720,320,78
PV (ml/g)0,2900,2070,4030,187
The original content of fine particles (IF)3,23,035,639,8
AL3,33,034,835,6
The content of additives
Pillar 2 (wt.%) (Same9090
the composition of the catalyst as the BASICS 1)
Additive type (wt.%)1010
Characteristics conditions: the same as in the Examples presented in the description
inventions
Pseudoequilibrium methodMethod MitchellMethod Mitchell
The steam processing800° × 6 hours800° × 6 hours
Original oil MATDS-VGO(86')DS-VGO(86')
Conversion (wt%) with a ratio
The catalyst/oil33
The amount of metal: Ni/V (h/m)
0/068,0266,90
1000/200065,9061,53
2000/400064,0757,25ÈA;
3000/600061,8343,24
Selectivity (% mass) when the number of metal: Ni/V=1000/2000 (ppm)
Conversion (% mass)60,0060,00
The output of each ingredient (% mass)
H20,120,28
Ci-20,800,84
LPG12,3411,72
GASO44,9544,15
LCO29,8429,43
HCO+10,1610,57
Cox1,793,01
RON89,4689,41
Selectivity (% mass) when the number of metal: Ni/V=3000/6000 (ppm)
Conversion (% mA is (C) 60,00
The output of each ingredient (% mass)
H20,25
Ci-20,91
LPG12,97
GASO43,73
LCO27,98
HCO+12,02
Cox2,4
RON89,81

Although the invention has been described in detail and with reference to specific variations in its implementation, the person skilled in the art it will be clear that it can be made various changes and modifications without departure from the essence and scope.

This application is based on patent application of Japan No. 2000-257669, filed August 28, 2000, and the application for pentaphone No. 2001-246232, filed August 14, 2001, and that such content is included here by reference.

APPLICABILITY IN INDUSTRY.

As described above, the catalyst according to the present invention has a lower selectivity for hydrogen and coke and can give gas and the fraction of light cycle gas oil with high yield without lowering the octane number. In addition, the catalyst can save these performance characteristics at a high level for a long period of time. The FCC catalyst can be considerably improved service life before the poisoning metals (at least 3 times more durable than standard catalyst A). (When processed oil feedstock containing metals in a quantity at least 3 times greater than the amount of metals in the oil, which serves as the raw material in modern processes, the catalyst according to the present invention can have the same performance as used in the present catalysts, i.e. the standard catalyst A).

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

1. The catalyst for catalytic cracking of heavy petroleum products in the fluidized bed composed of a mixture including

(1) produce the p in the form of particles, the resulting homogeneous dispersion of the crystalline aluminosilicate zeolite in an inorganic oxide matrix, and

(2) the catalyst additive of the type in the form of particles, decontaminating metals, poison the catalyst contained in the crude oil, in which the calcium carbonate with an average particle diameter of from 0.001 to 30 μm dispersed in an inorganic oxide matrix, whereby a specified number of calcium carbonate ranges from 30 to 70% (based on dry substance;

moreover, the ratio of catalyst/catalyst additive type is of 99.9/0.1 to 50/50.

2. The catalyst according to claim 1, where the specified catalyst additive has a mean particle diameter of from 50 to 90 μm, bulk density of 0.3 to 1.2 g/ml and the absorbance of oil from 0.1 cm3/g or more.

3. The catalyst according to claim 1, where the calcium carbonate has an average particle diameter of 0.1 to 10 microns.



 

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