Title of invention: Additive for fluid catalytic cracking catalyst and method for producing the same
Technical field
[0001]
　INDUSTRIAL APPLICABILITY The present invention is used with a fluid catalytic cracking catalyst (hereinafter also referred to as “FCC catalyst”) in fluid catalytic cracking (hereinafter also referred to as “FCC”) to increase the octane number of gasoline and increase the production of lower olefins. Additive and a method for producing the same.
Background technology
[0002]
　In a fluid catalytic cracking unit (hereinafter also referred to as "FCC unit") of an oil refinery, the main purpose is to catalytically crack a raw hydrocarbon oil to produce a gasoline fraction, and it is desired that gasoline has a high octane number. It is rare. Also, depending on the refinery, it is required to catalytically crack the raw material hydrocarbon oil with an FCC unit to produce a gasoline fraction, and at the same time to increase the production amount of lower olefins, particularly propylene and butene, which are petrochemical raw materials. There are cases.
[0003]
　In order to meet this demand, various methods have been proposed for carrying out FCC by adding a composition (also referred to as an additive catalyst) containing a pentasil-type zeolite such as ZSM-5 type zeolite to the catalyst used for FCC. ..
[0004]
　As such an additive, for example, Patent Document 1 discloses a composition comprising a pentasil-type zeolite and an inorganic oxide matrix, which has many macropores having a pore diameter of about 100 nm. Patent Document 2 discloses a composition that is a particle composed of a pentasil-type zeolite, a porous inorganic oxide, and phosphorus pentoxide, in which the content of phosphorus pentoxide in the surface portion is higher than that in the central portion of the particle. Has been done. Patent Document 3 discloses an FCC catalyst additive containing a binder containing zeolite such as ZSM-5, phosphate, clay, and silica as an additive capable of increasing the production amount of propylene and the like. Further, Patent Document 4 discloses an FCC catalyst additive containing a modified ZSM-5 type zeolite having predetermined characteristics, a filler, and a binder.
[0005]
　Further, Patent Document 5 discloses a catalyst containing a large amount of zeolite and containing phosphorus and alumina and excellent in abrasion resistance. This catalyst can be used by adding it to the catalyst in the FCC method. In addition, US Pat. No. 6,096,639 discloses an FCC catalyst containing zeolite, kaolin, phosphorus compounds, a high density of non-reactive components and optionally reactive alumina, which catalyst is added to the cracking process using large pore molecular sieve components. It is also suitable as an agent.
Prior art documents
Patent literature
[0006]
Patent Document 1: Japanese Patent Laid-Open No. 2005-270851
Patent Document 2: Japanese Patent Laid-Open No. 2007-244964
Patent Document 3: Special Table 2014-527459
Patent Document 4: International Publication No. 2017/82345
Patent Document 5: Special Table
Japanese Patent Laid-Open No. 2002-537976 Patent Document 6: Japanese Patent Laid-Open No. 2007-534485
Summary of the invention
Problems to be Solved by the Invention
[0007]
　When the raw hydrocarbon oil to be catalytically cracked is a heavy hydrocarbon oil such as atmospheric distillation residual oil or vacuum distillation residual oil, the raw hydrocarbon oil contains a large amount of heavy metals such as vanadium and nickel. .. Vanadium promotes dealumination from zeolite, destroys its crystal structure, and reduces activity. In addition, nickel produces a large amount of coke because of its high dehydrogenation activity, and this coke poisons the active sites of the FCC catalyst and also generates heat during regeneration of the FCC catalyst to promote the deterioration of the zeolite.
[0008]
　Conventional FCC catalyst additives have room for further improvement from the viewpoint of obtaining lower olefins such as propylene in a high yield even when the feedstock hydrocarbon oil to be catalytically cracked contains a large amount of heavy metals. ..
[0009]
　In view of such problems, the present invention is an additive for FCC catalysts used together with FCC catalysts in FCC, and has a high yield even when the feedstock hydrocarbon oil contains a large amount of heavy metals such as vanadium and nickel. It is an object of the present invention to provide an additive (additive catalyst) for an FCC catalyst that can obtain a lower olefin such as propylene at a constant rate, and a method for producing the additive.
Means for solving the problem
[0010]
　The gist of the present invention is as follows.
　[1]
　A fluid catalytic cracking catalyst additive containing a pentasil-type zeolite and an inorganic oxide matrix,
　wherein the amount of the pentasil-type zeolite is 10 to 60% by mass, and
　phosphorus is converted into the mass of P 2 O 5. 5 to 20% by mass, and the
　inorganic oxide matrix contains the alumina component in an amount of 2 to 20% by mass of aluminum converted to Al 2 O 3 (however, the amount of the additive is 100% by mass). The following
　formula (1):
　　　0.02≦P(−25 ppm)/P(−30 ppm)≦0.40
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　(1)
[In the formula, P(−25 ppm) and P(−30 ppm) Are the peak area ratios of -25 ppm and -30 ppm in 31 P-NMR measurement , respectively . ] The additive for fluid catalytic cracking catalysts which
is satisfied
.
[0011]
　[2] A
　pentasil-type zeolite,
　a binder raw material containing phosphorus,
　at least one alumina component selected from the group consisting of gibbsite and a calcined product of gibbsite, and
　an extender comprising an inorganic oxide (excluding the alumina component), And a
　dispersion medium
,
　wherein the amount of the pentasil-type zeolite is 10 to 60% by mass, and
　the amount of the binder raw material containing phosphorus is 5 to 5% by weight when converted to the mass of P 2 O 5. 20% by mass, and the amount of the
　alumina component is such that the amount of aluminum converted to the mass of Al 2 O 3 is 2 to 20% by mass
(however, the solid content of the slurry is Of 100% by weight) is spray-dried to obtain a
　powder , the powder is heated at a temperature rising rate of 150° C. or higher/hour, and then heat treated at 500 to 750° C. for
fluid catalytic cracking catalyst additive. Manufacturing method.
Effect of the invention
[0012]
　According to the FCC catalyst additive of the present invention, a lower olefin such as propylene can be obtained in a high yield even when the feedstock hydrocarbon oil contains a large amount of heavy metals such as vanadium and nickel. Further, according to the production method of the present invention, an additive for an FCC catalyst capable of obtaining a lower olefin such as propylene in a high yield even when the feedstock hydrocarbon oil contains a large amount of heavy metals such as vanadium and nickel. It can be manufactured.
MODE FOR CARRYING OUT THE INVENTION
[0013]
　Hereinafter, the present invention will be described in more detail.
　　　　　　　　　　　 [FCC Catalyst Additive]
　The FCC catalyst additive according to the present invention
　is a fluid catalytic cracking catalyst additive containing a pentasil-type zeolite and an inorganic oxide matrix, and
　the amount of the pentasil-type zeolite is 10 to 60 mass. %,
　phosphorus is contained in an amount of 5 to 20% by weight in terms of P 2 O 5 , and the
　inorganic oxide matrix contains an alumina component in an amount of 2 to 20% by weight in terms of Al 2 O 3 ( However, the content of the additive is 100% by mass), and the following
　formula (1):
　　　0.02≦P(−25 ppm)/P(−30 ppm)≦0.40
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　(1)
[In the formula, P(-25 ppm) and P(-30 ppm) are the peak area ratio of -25 ppm and the peak area ratio of -30 ppm in 31 P-NMR measurement , respectively . ]
Is satisfied
.
[0014]
　The pentasil-type zeolite is dispersed in the inorganic oxide matrix.
　Examples of the pentasil-type zeolite include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, and ZSM-48. ZSM-5 is particularly preferable because it has a solid acid with high acid strength and exhibits high shape selectivity, and thus has a great effect of increasing the octane number of gasoline and the yield of lower olefins.
[0015]
　The amount of the pentasil-type zeolite in the FCC catalyst additive of the present invention is 10% by mass or more, preferably 30% by mass or more, from the viewpoint of increasing the yield of lower olefins such as propylene. It is 60% by mass or less, preferably 50% by mass or less, from the viewpoint of not lowering the production amount of lower olefins and from the viewpoint of maintaining physical properties (for example, moldability or abrasion resistance) in a practically usable range.
[0016]
　The ratio of silicon to aluminum contained in the pentasil-type zeolite is preferably 25 to 100 when converted into the mass ratio of SiO 2 and Al 2 O 3 (mass of SiO 2 /mass of Al 2 O 3 ). .
[0017]
　When the mass ratio is 25 or more, the acid density on the pentasil-type zeolite is not too high, so that overcracking of the raw hydrocarbon oil can be prevented and the yield of the target lower olefin can be increased. Further, when the mass ratio is 100 or less, the acid density on the pentasil-type zeolite is appropriate, so that the decomposition activity of the raw material hydrocarbon oil is excellent.
[0018]
　The primary particle size of the pentasil-type zeolite is preferably 0.3 to 5 μm.
　The primary particle diameter is a median diameter (D50) measured by the method adopted in Examples described later.
[0019]
　The primary particle size of the pentasil-type zeolite is from the viewpoint of preventing the hydrothermal resistance of the additive for FCC catalyst from being lowered and lowering the yield of lower olefin, and the pentasil-type zeolite particles in the additive for FCC catalyst. From the viewpoint of preventing the ABD from decreasing and the attrition from deteriorating by increasing the number of voids between them, it is preferably 0.3 μm or more.
[0020]
　In addition, the primary particle size of the pentasil-type zeolite is preferably from the viewpoint of preventing a decrease in the catalytic activity due to a decrease in the dispersibility of the reaction field due to the solid acid or pores of the zeolite in the particles of the FCC catalyst additive. It is 5 μm or less.
[0021]
　The inorganic oxide matrix contains a binder that binds each component in the FCC catalyst additive, and the binder is made of an oxide containing phosphorus, preferably an oxide containing phosphorus and aluminum.
[0022]
　The amount of phosphorus in the FCC catalyst additive is 5% by mass or more, preferably 7% by mass or more, when converted into the amount of diphosphorus pentoxide (P 2 O 5 ). The amount of phosphorus can be measured by ICP emission spectroscopy under the conditions adopted in the examples described below. When the amount of phosphorus is in this range, the additive for FCC catalyst has excellent wear resistance because the binder has a large force to bind the pentasil-type zeolite, the alumina component and the extender such as kaolin, and further the pentasil-type zeolite. Since the hydrothermal stability of is maintained, the yield of lower olefins such as propylene can be increased in the catalytic cracking of hydrocarbon oils. The amount of phosphorus is 20% by mass or less, preferably 15% by mass or less, based on the above-mentioned criteria. When the amount of phosphorus is in this range, the pore volume of the FCC catalyst additive is not too small, the reactant diffuses in the pores, and the yield of lower olefins such as propylene in catalytic cracking of hydrocarbon oil is increased. Can be increased.
[0023]
　The inorganic oxide matrix contains an alumina component. This alumina component is preferably obtained by subjecting at least one alumina component selected from the group consisting of gibbsite (a type of aluminum hydroxide) and a calcined product of gibbsite to the heat treatment described below.
[0024]
　In the FCC catalyst additive of the present invention, the amount of aluminum in which the alumina component is converted into Al 2 O 3 in the inorganic oxide matrix is 2 to 20% by mass, preferably 2.5 to 15% by mass. It is included in the amount (however, the amount of the FCC catalyst additive is 100% by mass). When the amount of the alumina component is in the above range, it is possible to sufficiently suppress the decrease in propylene yield due to the poisoning of metals (heavy metals such as vanadium and nickel contained in the raw hydrocarbon oil) during FCC, which is practically usable. A wide range of catalyst physical properties (for example, moldability or abrasion resistance) can be maintained.
[0025]
　The inorganic oxide matrix may contain, as a binder, any binder other than the above-described oxide containing phosphorus and aluminum. Optional binders include inorganic oxides such as silica, silica-magnesia, titania, zirconia, silica-zirconia and calcium silicate.
　The amount of the optional binder contained in the FCC catalyst additive of the present invention is preferably 5 to 25% by mass, more preferably 10 to 15% by mass.
[0026]
　Further, the inorganic oxide matrix contains a filler made of an inorganic oxide that is usually blended with an additive for FCC catalyst. Examples of the extender include clay minerals such as kaolin, bentonite, and halloysite, and kaolin is particularly preferable. The extender may be a heat-treated product of these clay minerals.
[0027]
　The amount of the extender contained in the FCC catalyst additive of the present invention is the amount obtained by subtracting the total amount of the pentasil-type zeolite, the binder, and the alumina component from the amount of the FCC catalyst additive.
[0028]
　The FCC catalyst additive of the present invention satisfies the following formula (1):
　　　0.02≦P(−25 ppm)/P(−30 ppm)≦0.40
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　(1)
.
　In the formula (1), P(−25 ppm) and P(−30 ppm) are the −25 ppm peak area ratio and −30 ppm peak area ratio in 31 P-NMR measurement , respectively , and the details are as follows. ..
[0029]
　The FCC catalyst additive was uniformly filled in a 3.2 mm diameter NMR solid sample tube, and the sample tube was set in an NMR apparatus (magnetic field strength: 14.1 T ( 1 H resonance frequency: 600 MHz)). , Rotate at 20 kHz with a magic angle (54.7°) to the external magnetic field. As a secondary standard for chemical shift, the peak of NH 4 H 2 PO 4 is set to 1 ppm. Using the single pulse method, the flip angle of the pulse is set to 90° and the pulse repetition time is set to 11.5 seconds.
[0030]
　The obtained spectrum is analyzed as follows. First, spectrum baseline correction is performed. Next, five peaks having chemical shifts of about -6 ppm, -18 ppm, -25 ppm, -30 ppm, and -37 ppm are separated into Voigt's function. The area intensity of all the functions was calculated, and the area intensity of the peak with a chemical shift of about -25 ppm (P(-25 ppm)) and the area intensity of the peak with a chemical shift of about -30 ppm (P(-30 ppm)) were calculated. Calculate the ratio.
[0031]
　The peak with a chemical shift of about -25 ppm is attributed to berlinite formed by the reaction of gibbsite or a calcined product of gibbsite with a binder raw material containing a phosphorus component, and the peak with a chemical shift of about -30 ppm is amorphous aluminum phosphate. Belong to.
[0032]
　The above formula (1) is an index showing the reactivity of the binder raw material containing the alumina component and the phosphorus component when the additive for FCC catalyst is produced by the production method described later. It means that the component is more reactive with the binder raw material containing the phosphorus component.
[0033]
　The value of P(−25 ppm)/P(−30 ppm) is 0.02 to 0.40, preferably 0.02 to 0.35, more preferably 0.02 to 0.30, and further preferably 0. It is from 02 to 0.25, and particularly preferably from 0.02 to 0.20. If the P(-25 ppm)/P(-30 ppm) is less than 0.02, the FCC catalyst additive may have poor resistance to heavy metals.
[0034]
　The value of P(−25 ppm)/P(−30 ppm) is set to a value of alumina particles having a large particle diameter by increasing the temperature rising rate during firing in the method for producing an additive for FCC catalyst described later, for example. It can be reduced by using or by using an alumina component having a high sodium content.
[0035]
　When the amount of phosphorus and the amount of alumina component are in the above ranges and the above formula (1) is satisfied, aluminum in the alumina component in the inorganic oxide matrix exerts an excellent effect as a metal scavenger, As a result, it is considered that the lower olefins such as propylene can be obtained in a high yield even when the feedstock hydrocarbon oil in FCC contains a large amount of heavy metals such as vanadium and nickel.
[0036]
　The pore volume of the FCC catalyst additive of the present invention in the range of pore diameter 2 to 50 nm measured by the BJH method is preferably 0.03 ml/g or more, and the upper limit thereof is, for example, 0.08 ml/g. It may be g.
[0037]
　When the pore volume is within the above range, lower olefins such as propylene can be obtained in high yield even when the feedstock hydrocarbon oil in FCC contains a large amount of heavy metals such as vanadium and nickel.
[0038]
　The additive for FCC catalyst of the present invention preferably satisfies the following formula (A):
　　　Al(9ppm)/Al(T)≧0.10 (A)
.
　In the formula (A), Al(9 ppm) and Al(T) are the sum of the peak area ratio of about 9 ppm in 27 Al-NMR measurement and the total peak area in the range of -30 ppm to 80 ppm , respectively , and the details are as follows. It is as follows.
[0039]
　The FCC catalyst additive was uniformly filled in a 3.2 mm diameter NMR solid sample tube, and the sample tube was set in an NMR apparatus (magnetic field strength: 14.1 T ( 1 H resonance frequency: 600 MHz)). , Rotate at 20 kHz with a magic angle (54.7°) to the external magnetic field. As a chemical shift standard, the peak of the 1 mol/L Al(NO 3 ) 3 aqueous solution is set to 0 ppm. Using the single pulse method, the flip angle of the pulse is set to 10° and the pulse repetition time is set to 0.1 second.
[0040]
　The obtained spectrum is analyzed as follows. First, spectrum baseline correction is performed. Next, seven peaks having chemical shifts of about −9 ppm, about 0 ppm, about 9 ppm, about 27 ppm, about 40 ppm, about 55 ppm, and about 60 ppm are separated into Voigt's function. The area intensities of all the functions are calculated, and the ratio of the area intensity of the peak with a chemical shift of about 9 ppm (Al(9 ppm)) to the sum of the area intensities of all the functions (Al(T)) is calculated.
[0041]
　The peak with a chemical shift of about 9 ppm is assigned to hexacoordinated Al. This peak is derived from, for example, an alumina component such as gibbsite added in the production method described later, and the more the alumina component is added, the more phosphorus is contained in the catalyst contained in the production method described later. The smaller the reaction between the binder raw material and the alumina component, the larger the peak area and the higher the value of the formula (A).
[0042]
　The FCC catalyst additive according to the present invention usually has a fine spherical particle shape. Since the additive for FCC catalyst is used as a mixture with the FCC catalyst containing faujasite-type zeolite for the purpose of gasoline production used in the FCC unit, the particle size of the additive for FCC catalyst is , Preferably at or above the level of conventional FCC catalysts.
[0043]
　The average particle size of the fine spherical particles measured by the laser diffraction/scattering method under the conditions adopted in the examples described later is preferably 40 to 140 μm, more preferably 60 to 120 μm.
[0044]
　　　　　　　　　 [Method for producing FCC catalyst additive]
　The method for producing an FCC catalyst additive according to the present invention 　comprises 　at least one selected from the group consisting of a
　pentasil-type zeolite,
a binder raw material containing phosphorus,
gibbsite and a calcined product of gibbsite. A slurry containing an alumina component,
　an extender composed of an inorganic oxide (excluding the alumina component), and a
　dispersion medium
,
　wherein the amount of the pentasil-type zeolite is 10 to 60 mass% and the
　phosphorus is contained. The amount of the binder raw material is such that the amount of phosphorus converted to the mass of P 2 O 5 is 5 to 20% by mass, and the amount of the
　alumina component is the amount of aluminum converted to the mass of Al 2 O 3. 2 to 20% by weight and comprising an amount
slurry (provided that the solid slurry content (i.e.,. as 100% by mass amount of dispersing components other than medium)) to afford a powder by spray-drying,
　the powder was heated at a heating rate of 0.99 ° C. or higher / time, and then heat treated at 500 ~ 750 ° C.
is characterized by.
[0045]
　Specific embodiments and preferable embodiments of the pentasil-type zeolite are as described above.
　The amount of the pentasil-type zeolite is 10% by mass or more, preferably 30% by mass or more from the viewpoint of obtaining an FCC catalyst additive having a high yield of a lower olefin such as propylene. From the viewpoint of obtaining an FCC catalyst additive that does not reduce the amount of lower olefins produced, the amount is 60% by mass or less, preferably 50% by mass or less (however, the total amount of components other than the dispersion medium of the slurry is 100% by mass). Yes.).
[0046]
　The binder raw material containing phosphorus is preferably a compound that generates phosphate ions (PO 4 3− ) when heated (for example, 500 to 750° C.) . The binder material containing phosphorus is preferably a compound containing phosphorus, aluminum and oxygen, and examples of such a compound include aluminum dihydrogen phosphate (Al(H 2 PO 4 ) 3 ), aluminum hydrogen phosphate (Al 2 (HPO 4 ) 3 ) and aluminum phosphate (AlPO 4 ) are preferable, and aluminum dihydrogen phosphate (Al(H 2 PO 4 ) 3 ) is preferable from the viewpoint of curing bondability or high reactivity with zeolite . These compounds may be used alone or in combination of two or more. The phosphorus-containing binder raw material preferably contains aluminum dihydrogen phosphate as a main component (a component accounting for 70% by mass or more).
[0047]
　An aqueous solution thereof may be used as the binder raw material containing phosphorus. As the aqueous solution, if it is a commercial product, an aluminum dihydrogen phosphate (Al(H 2 PO 4 ) 3 ) aqueous solution (brand name: 50 L, 100 L, acidphos 120M, manufactured by Taki Chemical Co., Ltd.) and the like can be mentioned.
[0048]
　In the binder raw material containing phosphorus, the amount of phosphorus becomes 5 to 20% by mass, preferably 6 to 15% by mass in terms of diphosphorus pentoxide (P 2 O 5 ) (however, the dispersion medium of the slurry is The total amount of the components other than 100% by mass is used). When the amount of phosphorus is in the above range, when it is 5% by mass or more, it is excellent in wear resistance and is an additive for FCC catalyst capable of obtaining a lower olefin such as propylene in a high yield in catalytic cracking of hydrocarbon oil. Can be manufactured.
[0049]
　The slurry may contain any binder other than the binder raw material, and its specific embodiment is as described above.
　The addition of at least one alumina component selected from the group consisting of gibbsite and calcined products of gibbsite provides the FCC catalyst obtained as compared to the case where alumina in another form, for example, boehmite which is alumina monohydrate is added. The additives for use have high hydrothermal resistance and metal resistance, and have a high yield of lower olefins even when a large amount of vanadium, nickel, etc. are deposited. The reason is that the alumina component such as a gibbsite type has a low reactivity with a phosphorus source, and further, mesopores derived from the alumina component can be generated in the catalyst, and a reaction field for trapping heavy metals such as vanadium and nickel is provided. It is presumed that this is because more can be added.
[0050]
　As the calcined product of gibbsite, calcined product containing χ-alumina, gibbsite is heated at a temperature rising rate of 150° C. (preferably 180° C.)/hour or more, and heated at 500 to 750° C. (preferably 550 to 700° C.). It is preferably heat-treated for 0.2 to 5.0 hours (more preferably 0.5 to 2.0 hours).
[0051]
　The alumina component is such that the amount of aluminum converted to Al 2 O 3 is 2 to 20% by mass, preferably 2.5 to 15% by mass (however, the total amount of the components other than the dispersion medium of the slurry is 100% by mass). Mass%). When the amount of the alumina component is within the above range, a decrease in the yield of lower olefins such as propylene due to metal poisoning during FCC can be sufficiently suppressed, and the catalyst physical properties within a practically usable range (for example, moldability). Or wear resistance) can be maintained.
[0052]
　The average particle diameter of the alumina component measured by the method adopted in Examples described later is preferably 2 to 50 μm, more preferably 5 to 30 μm. When the average particle size is in the above range, the particles of the alumina component can be sufficiently diffused in the FCC catalyst additive, and further, the side reaction between the alumina component and the binder raw material containing phosphorus can be suppressed, and vanadium, nickel, etc. A large number of reaction fields for trapping metal components can be formed. On the other hand, if the content exceeds this range excessively, the properties required for practical use (for example, moldability or wear resistance) may be impaired
.
[0053]
　As the gibbsite, if it is a commercially available product, "C-303", "C-301N", "CL-303" (manufactured by Sumitomo Chemical Co., Ltd.), "B-316" (brand name, manufactured by Almorix Co., Ltd. ), etc. Examples of the calcined product of gibbsite include “AP-22” manufactured by POLOCEL, which is a commercially available product.
[0054]
　Specific and preferred embodiments of the filler made of an inorganic oxide are as described above.
　The amount of the filler is an amount obtained by subtracting the total amount of the binder raw material containing the pentasil-type zeolite, the phosphorus and aluminum, and the arbitrary binder raw material from the total amount of components other than the dispersion medium of the slurry.
　Water is preferable as the dispersion medium.
[0055]
　In the production method of the present invention, first, the pentasil-type zeolite, a binder raw material containing the phosphorus, the gibbsite type aluminum hydroxide, the extender, and the dispersion medium, and if necessary, the binder raw material is mixed. To prepare a slurry. A conventionally known method can be applied to the preparation of the slurry. The solid content concentration of the slurry is preferably about 25 to 50% by mass from the viewpoint of spray drying operation.
[0056]
　Next, the slurry is spray-dried to obtain a powder, and the powder is heated at a heating rate of 150° C./hour or more, preferably 180° C./hour or more. If the temperature rising rate is lower than the lower limit value, the reaction between the alumina component and the binder raw material containing phosphorus will proceed excessively, and the heavy metal poisoning of the FCC catalyst additive will cause the collection of lower olefins such as propylene. The rate may decrease. The upper limit of the heating rate depends on the heating apparatus, but may be 800° C./hour, for example.
[0057]
　Then, heat treatment is performed at a temperature of 500 to 750° C., preferably 550 to 700° C., preferably for 0.2 to 5.0 hours, more preferably for 0.5 to 2.0 hours, whereby the FCC catalyst additive is removed. can get.
[0058]
　The conditions of spray drying are as follows, for example.
　　　Spray inlet temperature: 200 to 450° C.
　　　Outlet temperature: 110 to 350° C. The
　powder obtained by spray drying is allowed to cool to room temperature (for example, 0 to 40° C.) and then classified to have an average particle diameter of, for example, 40 to 40° C. It may be adjusted to 140 μm, preferably 60 to 120 μm and then subjected to heat treatment.
[0059]
　By heat treating the spray-dried powder under the above conditions, the reaction between the added alumina component and the binder raw material containing phosphorus can be suppressed, and the obtained FCC catalyst additive has vanadium or nickel on the surface of the alumina component. It is presumed that a large number of reaction fields trapping heavy metals such as, for example, are formed, and high metal resistance is exhibited.
[0060]
　The heat treatment is preferably performed in a steam atmosphere from the viewpoints of further diffusing the binder raw material containing phosphorus, accelerating the modification of the zeolite acid sites, and suppressing clogging of the zeolite pores with polyphosphoric acid.
[0061]
　　　　　　　　　 [Method of Using Additive for FCC Catalyst]
　The additive for FCC catalyst according to the present invention (also referred to as “additive catalyst”) contains a faujasite-type zeolite in fluid catalytic cracking of hydrocarbon oil in an FCC apparatus. It is used as a mixture with the FCC catalyst.
[0062]
　As the FCC catalyst containing the faujasite type zeolite, a normal FCC catalyst used in an FCC device can be used. Examples of such FCC catalysts include commercially available FCC catalysts such as DCT, ACZ, CVZ (all are trademarks or registered trademarks of products manufactured by JGC Catalysts & Chemicals Co., Ltd.).
[0063]
　When the total amount of the FCC catalyst additive and the FCC catalyst is 100% by mass, the amount of the FCC catalyst additive is such that propylene and the like are produced in a high yield even when the feedstock hydrocarbon oil in the FCC contains a large amount of heavy metals. From the viewpoint of obtaining a lower olefin, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, and from the viewpoint of the cracking activity of the raw hydrocarbon oil, it is generally used at 30% by mass or less. However, it may be added up to 60 mass% in a new process for increasing the production of light olefins.
[0064]
　In a fluid catalytic cracking process of a hydrocarbon oil in which the FCC catalyst additive according to the present invention is used, a normal FCC catalyst is used except that the FCC catalyst additive according to the present invention is used as the FCC catalyst additive. Fluidized catalytic cracking conditions of hydrocarbon oil in the device can be adopted.
Example
[0065]
　Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
　[Example 1]
　ZSM-5 type zeolite produced according to Example 1 of JP 2011-213525 A was suspended in pure water and pulverized with a bead mill until the average particle size became 2.5 µm, and ZSM- A slurry having a type 5 zeolite concentration of 25% by mass (hereinafter, also referred to as "ZSM-5 crushed slurry") was prepared. 2,400 g of this ZSM-5 crushed slurry (amount in which the mass of ZSM-5 type zeolite is 40% by mass (600 g) based on the mass (1,500 g) of the target product (additive for catalyst; the same applies below)) Then, a 15% ammonium aqueous solution was added until the pH of the ZSM-5 ground slurry reached 9.0. Kaolin 651.0 g (the mass after dehydration is 36.5 mass% (547.5 g) based on the mass of the target product) is mixed, and gibbsite (gibbsite-type aluminum hydroxide) (Sumitomo Chemical ( Co., Ltd. "C-303", median diameter 5.3 μm) 225.2 g (aluminum mass converted to Al 2 O 3 mass is 10.0 mass% (150 g) based on the mass of the target product) (Amount) was mixed, and the slurry was subjected to dispersion treatment with a homogenizer. In the obtained slurry, aluminum dihydrogen phosphate containing aluminum ( 8.5% by mass in terms of Al 2 O 3) and phosphorus by 33.5% by mass in terms of P 2 O 5 (Al(H 2The mass of phosphorus obtained by converting the aqueous solution containing PO 4 ) 3 ) (“100 L” manufactured by Taki Chemical Co., Ltd.) into 482.1 g ( the mass of P 2 O 5 ) is 10.8 mass based on the mass of the target product. % (162 g)), and further, 527.3 g of pure water was added so that the concentration of the slurry was about 35% by mass (converted to the concentration of the target substance), and the concentration was about A 35% by mass slurry (hereinafter also referred to as “mixed slurry”) was obtained. This mixed slurry is spray-dried (spray inlet temperature: 250 to 260° C., outlet temperature: 150° C.), and the obtained particles are allowed to cool to about 25° C. and then classified with a sieve having a mesh size of 212 μm. Fine spherical particles having an average particle diameter of 84 μm were prepared. Using a small rotary furnace, 150 g of the fine spherical particles are placed in a firing container (volume: 6.2 L), heated to 600° C. at a heating rate of 300° C./hour, and fired at 600° C. for 30 minutes, An additive A for FCC catalyst was obtained. In order to make the inside of the container a 100% steam atmosphere, water was added at a rate of 1.0 g/min until the temperature inside the baking container reached 150°C and the holding at 600°C was completed. Table 1 shows the physical properties and the like of the additive A for FCC catalyst.
[0066]
　[Example 2]
　The amounts of kaolin, gibbsite type aluminum hydroxide, and aluminum dihydrogen phosphate aqueous solution were each 740.2 g (the mass after dehydration was 41.5 g based on the mass of the target product (1,500 g)). the mass% amount), 112.6 g (Al 2 O 3 weight of aluminum in terms of the mass of the amount of 5 mass% on the mass of desired product as a reference), and 446.4G (P 2 O 5 of The same operation as in Example 1 was carried out except that the mass of phosphorus converted to mass was changed to 10.0 mass% based on the mass of the target product) to obtain FCC catalyst additive B. .. Table 1 shows the physical properties and the like of the additive B for FCC catalyst.
[0067]
　[Example 3]
　The same operation as in Example 1 was performed except that the type of gibbsite type aluminum hydroxide was changed to "C-301N" (median diameter 2.5 μm) manufactured by Sumitomo Chemical Co., Ltd. Additive C was obtained. Table 1 shows the physical properties and the like of the additive C for FCC catalyst.
[0068]
　[Example 4]
　The same operation as in Example 1 was performed except that the type of gibbsite type aluminum hydroxide was changed to "B-316" (median diameter: 17.4 µm) manufactured by Almorix Co., Ltd. Additive D was obtained. Table 1 shows the physical properties and the like of the FCC catalyst additive D.
[0069]
　[Example 5]
　Except that the type of gibbsite type aluminum hydroxide was changed to "CL-303" manufactured by Sumitomo Chemical Co., Ltd. (median diameter 5.6 μm, Na 2 O content 0.19% by weight). The same operation as in Example 1 was performed to obtain an additive E for FCC catalyst. Table 1 shows the physical properties and the like of the additive E for FCC catalyst.
[0070]
　[Example 6]
　The same operation as in Example 1 was performed except that the type of aluminum hydroxide was changed to a calcined product of gibbsite (the crystal phase was χ-alumina) ("AP-22" manufactured by POROCEL), and the FCC catalyst was used. The additive F for use was obtained. Table 1 shows the physical properties of the FCC catalyst additive F.
[0071]
　[Example 7]
　The amount of ZSM-5 crushed slurry was adjusted to 1,800 g (the amount of the ZSM-5 type zeolite was 30.0% by mass (450 g) based on the mass of the target product (1,500 g)). Changed, the amount of kaolin and aluminum dihydrogen phosphate aqueous solution was 891.7 g each (the amount after dehydration was 50.0% by mass based on the mass of the target product (1,500 g)), 358 0.2 g ( the mass of phosphorus converted to the mass of P 2 O 5 is 8.0 mass% based on the mass of the target), and the amount of pure water added for adjusting the concentration of the mixed slurry. The same operation as in Example 1 was carried out except that the amount was changed to 1010.6 g to obtain an additive G for FCC catalyst. Table 1 shows the physical properties and the like of the additive G for FCC catalyst.
[0072]
　[Example 8]
　The amount of ZSM-5 pulverized slurry was changed to 3,000 g (the amount by which the mass of ZSM-5 type zeolite was 50% by mass (750 g) based on the mass of the target product (1,500 g)). And the amounts of kaolin and aluminum dihydrogen phosphate aqueous solution were 413.8 g (the amount after dehydration was 23.2% by mass based on the mass of the target product (1,500 g)) and 604, respectively. FCC was performed in the same manner as in Example 1 except that the amount of phosphorus converted to the mass of P 2 O 5 was 13.5% by mass based on the mass of the target product. A catalyst additive H was obtained. Table 1 shows the physical properties and the like of the additive H for FCC catalyst.
[0073]
　[Example 9]
　The amounts of kaolin and gibbsite type aluminum hydroxide were each 561.8 g (the amount after dehydration was 31.5% by mass based on the mass of the target product (1,500 g)), and The same operation as in Example 1 was performed except that the amount was changed to 337.8 g ( the amount of aluminum converted to the amount of Al 2 O 3 was 15.0% by mass based on the mass of the target). An additive I for FCC catalyst was obtained. Table 1 shows the physical properties and the like of the additive I for FCC catalyst.
[0074]
　[Comparative Example 1]
　The same operation as in Example 1 was carried out except that the temperature rising rate was changed to 100°C/hour to obtain an additive J for FCC catalyst. Table 1 shows the physical properties and the like of the additive J for FCC catalyst.
[0075]
　[Comparative Example 2]
　Without using gibbsite type aluminum hydroxide, the amounts of kaolin and aluminum dihydrogen phosphate aqueous solution were each 847.2 g (the mass after dehydration was based on the mass of the target product (1,500 g)). As the amount of 47.5% by mass) and 446.4 g (the amount of phosphorus converted to the mass of P 2 O 5 becomes 10.0% by mass based on the mass of the target). Except for this, the same operation as in Example 1 was performed to obtain an additive K for FCC catalyst. Table 1 shows the physical properties and the like of the additive K for FCC catalyst.
[0076]
　[Comparative Example 3]
　instead of the gibbsite type aluminum hydroxide, 83.0 wt% of boehmite type aluminum hydroxide (Sasol Ltd., "CATAPAL 200") 90.4 g (Al 2 O 3 weight of aluminum in terms of the mass of , 5 mass% based on the mass of the target product (1,500 g), and the amounts of kaolin and the monoaluminum phosphate aqueous solution are 758.0 g (42 mass% based on the mass of the target product), respectively. 0.5% by mass) and 446.4 g (amount of 12.5% ​​by mass based on the mass of the target), the same operation as in Example 1 was carried out, and the addition for FCC catalyst was performed. Item L was obtained. Table 1 shows the physical properties and the like of the additive L for FCC catalyst.
[0077]
　[Comparative Example 4]
　An additive K for FCC catalyst was prepared in accordance with the description of the preparation method of Sample B in Example 1 of JP-B-2002-537976. Specifically, 800 g (dry basis) ZSM-5, 830 g (dry basis) kaolin, 130 g (Al 2 O 3 conversion, dry basis) CATAPAL B (manufactured by Sasol), 390 g of 85% H 3 PO 4. The aqueous solution and pure water were mixed to obtain a mixed slurry having a solid content concentration of 45%. The mixed slurry was sufficiently stirred and spray-dried under the same conditions as in Example 1 to prepare fine spherical particles. The obtained fine spherical particles were allowed to stand, heated to 530° C. at a heating rate of 300° C./hour, and calcined at 530° C. for 2 hours to obtain an additive M for FCC catalyst. Table 1 shows the physical properties and the like of the additive M for FCC catalyst.
[0078]
　[Measurement Method or Evaluation Method]
　The measurement method and evaluation test method in Examples and the like are as follows.
　(Measurement Method of Content of
　Each Element ) For mass analysis of each element, chemical analysis was performed with an atomic absorption spectrophotometer for Na and an inductively coupled plasma spectroscopic analyzer other than Na. Specifically, the zeolite (ZSM-5) or the catalyst was added with sulfuric acid and hydrofluoric acid and heated to dryness, the dried solid was dissolved in concentrated hydrochloric acid, and diluted with water to a concentration of 10 to 100 mass ppm. The solution was prepared and analyzed with an atomic absorption spectrophotometer (Z-2310) manufactured by Hitachi High-Tech Science Co., Ltd. and an inductively coupled plasma spectroscopic analyzer (ICPS-8100) manufactured by Shimadzu Corporation. The wavelength is Na:589.6 nm, Al:396.2 nm, Si:251.6 nm,P:178.3 nm.
[0079]
　( 27 Al-MAS NMR measurement and 31 P-MAS NMR measurement) An
　FCC catalyst additive was uniformly filled in a sample tube for NMR solid having a diameter of 3.2 mm, and an NMR apparatus (VNMR-600 manufactured by Agilent, magnetic field) was used. The intensity was set to 14.1 T ( 1 H resonance frequency: 600 MHz)) and rotated at a high speed of 20 kHz at a magic angle (54.7°) with respect to an external magnetic field.
[0080]
　 In 27 Al measurement, the peak of the 1 mol/L Al(NO 3 ) 3 aqueous solution was set to 0 ppm as a chemical shift standard . Using the single pulse method, the pulse flip angle was set to 10° and the pulse repetition time was set to 0.1 s.
[0081]
　 In 31 P measurement, the peak of NH 4 H 2 PO 4 was used as the secondary standard for chemical shift , and was set to 1 ppm. Using the single pulse method, the flip angle of the pulse was set to 90° and the pulse repetition time was set to 11.5 s.
[0082]
　The obtained spectrum was analyzed using Origin. First, the baseline of the spectrum was corrected. Next, each peak was separated into Voigt's function. 27 Al-MAS NMR separated seven peaks with chemical shifts of about -9 ppm, about 0 ppm, about 9 ppm, about 27 ppm, about 40 ppm, about 55 ppm, and about 60 ppm as a function. The area intensity of all the functions was calculated, and the area ratio of each peak was calculated|required by calculating each peak ratio with respect to the total area. Among them, the area ratio of about 9 ppm attributed to the hexacoordinated Al derived from the added aluminum hydroxide or boehmite alumina was calculated.
[0083]
　 In 31 P-MAS NMR, five peaks having chemical shifts of about −6 ppm, −18 ppm, −25 ppm, −30 ppm, and −37 ppm were separated into a function, and the area ratio of each peak was obtained by the same method. The ratio of the area ratio of -25 ppm attributed to berlinite produced by the reaction of aluminum hydroxide and phosphorus component to the area ratio of -30 ppm attributed to amorphous aluminum phosphate etc. was calculated.
[0084]
　(Average particle size of zeolite and aluminum hydroxide) The particle size
　distribution of the sample was measured with a laser diffraction/scattering particle size distribution analyzer (LA-950V2) manufactured by Horiba Ltd. Specifically, the sample is put in a solvent (water) so that the light transmittance is in the range of 70 to 95%, the circulation rate: 5.0 L/min, ultrasonic irradiation: 1 minute, and the number of repetitions: 15 times. It was measured under the conditions. The median diameter (D50) was adopted as the average particle diameter. The measurement was carried out with a refractive index of 1.46 for zeolite and 1.66 for aluminum hydroxide.
[0085]
　(Average particle size of FCC catalyst additive) The particle size
　distribution of the sample was measured with a laser diffraction/scattering particle size distribution analyzer (LA-300) manufactured by Horiba Ltd. Specifically, the sample is put in a solvent (water) so that the light transmittance is in the range of 70 to 95%, the circulation rate is 2.8 L/min, the ultrasonic wave irradiation is 3 minutes, and the number of repetitions is 30 times. It was measured under the conditions. The median diameter (D50) was adopted as the average particle diameter.
[0086]
　(Specific surface area and pore volume of FCC catalyst additive)
　Specific surface area (SA) and pore volume of pores having a pore diameter of 50 nm or less are measured by BELSORP-mini Ver2.5 manufactured by Microtrac Bell Co., Ltd. .6. Specifically, the catalyst was pretreated at 500° C. for 1 hour, and nitrogen was used as an adsorption gas. The specific surface area (SA) of the FCC catalyst additive is measured by the BET method, the volume of micropores having a pore diameter of 2 nm or less of the FCC catalyst additive is measured by the MP method, and the volume of mesopores having a pore diameter of 2 to 50 nm is measured by the BJH method. Calculated.
[0087]
　(Ammonia Adsorption Amount) The
　ammonia adsorption amount was measured by the thermal desorption (TPD) method using BELCAT Version 2.5.5 of Microtrac Bell Co., Ltd. Specifically, the FCC catalyst additive was pseudo-equilibrium treated (Ni/V=2000ppm/4000ppm, 810°C-12 hours 100% steaming) for activity evaluation, and pretreated at 500°C for 1 hour. I was there. 0.2 g of the pretreated sample was heat-treated in a TPD device at 500° C. for 1 hour under flowing helium, and then cooled to 100° C. Ammonia was adsorbed at 100° C. for 30 minutes, and degassed for 30 minutes under the same temperature and helium flow. Thereafter, the amount of desorbed ammonia when the temperature was raised from 100° C. to 500° C. at 10° C./min was detected by TCD, and the amount of adsorbed ammonia was calculated from the desorbed amount.
[0088]
　(Catalyst performance) Using the
　ACE-MAT (Advanced Cracking Evaluation-Micro Activity Test), the additive evaluations A to J for FCC catalysts produced in Examples and the like were subjected to a catalyst evaluation test under the same feed oil and reaction conditions. It was Before performing the catalyst evaluation test, each catalyst was loaded with Ni/V=2000 ppm/4000 ppm by the Mitchell method and pretreated in a steam atmosphere at 100° C. for 12 hours at 810° C.
[0089]
　The additive for FCC catalyst pretreated to the FCC equilibrium catalyst was blended so that the amount of the additive for FCC catalyst in the mixed catalyst was a constant amount of 2.4% by weight to prepare a mixed catalyst, and ACE-MAT The mixed catalyst was evaluated (measurement of propylene yield (mass %)) with an activity tester.
　The reaction conditions were as follows.
Reaction temperature: 510° C.
Raw material oil: Desulfurized vacuum gas oil (DSVGO) 100% by mass oil
WHSV: 8 h −1
Catalyst/oil ratio: 5% by mass/mass% The
　evaluation results are shown in Table 1.
[0090]
[table 1]

The scope of the claims
[Claim 1]
　An additive for a fluid catalytic cracking catalyst containing a pentasil-type zeolite and an inorganic oxide matrix,
　wherein the amount of the pentasil-type zeolite is 10 to 60% by mass, and the
　phosphorus is 5 to 5 in terms of the mass of P 2 O 5. An amount of 20% by mass,
　wherein the inorganic oxide matrix contains 2 to 20% by mass of aluminum component converted to Al 2 O 3 (provided that the amount of the additive is 100% by mass). The following
　formula (1):
　　0.02≦P(−25 ppm)/P(−30 ppm)≦0.40
　　　　　　　　　　　　　　　　　　　　　　　　　　　(1)
[wherein P(−25 ppm) and P(−30 ppm) are respectively The peak area ratio is -25 ppm and the peak area ratio is -30 ppm in 31 P-NMR measurement. ] The additive for fluid catalytic cracking catalysts which
is satisfied
.
[Claim 2]
　Pentasil-type zeolite,
　a binder raw material containing phosphorus,
　at least one alumina component selected from the group consisting of gibbsite and a calcined product of gibbsite,
　an extender comprising an inorganic oxide (excluding the alumina component), and a
　dispersion medium.
In which
　the amount of the pentasil-type zeolite is 10 to 60% by mass, and
　the amount of the binder raw material containing phosphorus is 5 to 20% by mass based on the mass of P 2 O 5. And the amount of the
　alumina component is such that the amount of aluminum converted to the mass of Al 2 O 3 is 2 to 20% by mass
(however, the solid content of the slurry is 100% by mass). % to.) to afford a powder by spray drying,
　the powder was heated at a heating rate of 0.99 ° C. or higher / time, and then heat treated at 500 ~ 750 ° C.
method of manufacturing fluid catalytic cracking catalyst additive ..