JP4717587B2 - Method for producing high octane gasoline base material - Google Patents

Description

  The present invention relates to a gasoline base material obtained by fluid catalytic cracking (FCC) of heavy hydrocarbon oil. More specifically, the present invention relates to a catalytically cracked gasoline obtained from a product oil of a cracking reaction in fluid catalytic cracking (FCC). Hereinafter, the present invention relates to a method for producing a high-octane gasoline substrate by increasing the octane number of a fraction (sometimes referred to as “FCC gasoline”).

  In recent years, increasing awareness of the global environment and countermeasures against global warming have come to be emphasized. Among them, automobile exhaust has a great impact on the environment, and cleanliness is expected. It is generally known that the purification of automobile exhaust gas is affected by the performance of the automobile and the fuel composition of gasoline. In particular, the oil refining industry is required to provide high-quality gasoline.

Gasoline is generally produced by mixing a plurality of gasoline bases obtained in a crude oil refining process. In particular, FCC gasoline obtained by catalytic cracking reaction of heavy hydrocarbon oil has a large blending amount in gasoline and has a great influence on quality improvement of gasoline.
Catalytic cracking of heavy hydrocarbon oil is a reaction that converts low-grade heavy oil obtained in the oil refining process into light hydrocarbon oil by catalytic cracking. FCC gasoline has a gas oil fraction ( A distillate in the boiling range that can be used as a gasoline base, generally as a 95% distillation temperature, as a liquid mixture with Light Cycle Oil (LCO) and heavy fraction (Heavy Cycle Oil: HCO). A fraction up to 200 ° C. is used as FCC gasoline.

  Japanese Industrial Standards (JIS) K2202 stipulates No. 1 automobile gasoline with a research octane number of 96.0 or more and No. 2 automobile gasoline of 89.0 or more. In the case of blending gasoline, generally, so-called light FCC gasoline in which a fraction having a 95% distillation temperature of 90 ° C. or lower is selectively separated by distillation is used. However, although light FCC gasoline has a high octane number, it has a drawback of low yield.

  Further, there is a conventional method for improving the octane number of FCC gasoline by changing the catalyst used in the FCC apparatus. For example, a method has been proposed in which high-silica zeolite having a high acid property such as ZSM-5 is added to a catalyst to increase the light olefin content in FCC gasoline and to improve the octane number of FCC gasoline (for example, Patent Document 1). reference). However, in this method, the production amount of light gas components generated by the reaction increases, so that the yield of relative FCC gasoline decreases, or the operation of the FCC apparatus is restricted due to the increase in the production amount of light gas components. Have problems such as receiving. In addition, a catalytic cracking method for converting heavy oil into a light olefin component and a high-octane FCC gasoline has been proposed (see, for example, Patent Document 2). In this method, the amount of olefin that increases the octane number increases, but the amount of coke that accumulates on the catalyst increases, and there is a problem that the operation of the FCC apparatus is similarly restricted.

  In this way, FCC gasoline is economically produced because it is obtained by cracking low-grade heavy hydrocarbon oil compared to other gasoline bases such as catalytic reforming gasoline bases and alkylate gasoline bases. On the other hand, since the octane number is lower than that of catalytic reformed gasoline base and alkylate gasoline base, there is a method that can improve the octane number of FCC gasoline and economically produce a high octane gasoline base. It was a common problem for those skilled in the art.

JP 60-208395 A Japanese Patent Laid-Open No. 10-195454

  In view of the above-mentioned conventional points, an object of the present invention is to provide a method capable of economically producing a high-octane gasoline base material by increasing the octane number of FCC gasoline obtained by catalytic cracking of heavy hydrocarbon oil. To do.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have found that the distribution of hydrocarbon compounds contained in FCC gasoline is unevenly distributed in the low-boiling range with hydrocarbon compounds exhibiting a high octane number. As a result of further researches, the rare earth content in the catalytic cracking catalyst used (hereinafter sometimes referred to as “FCC catalyst”) is controlled to be constant, and the catalyst with the rare earth content controlled is used. As a result of the catalytic cracking, it was found that the octane number in the low boiling point region can be further increased, and the present invention has been completed. That is, this invention provides the manufacturing method of the high octane number gasoline base material which has the characteristics shown below.

1. Catalytic cracking of heavy hydrocarbon oil using a catalytic cracking catalyst with a rare earth metal / crystalline aluminosilicate mass ratio of 0.003 to 0.01 , and distillation of the resulting oil yields a 95% distillation temperature. A method for producing a high-octane gasoline base material, characterized in that a fraction having a temperature of 90 to 150 ° C. is obtained.
2. 2. The high octane gasoline substrate according to 1 above, wherein the catalytic cracking catalyst used has a crystalline aluminosilicate content of 20 to 50% by mass, a binder of 5 to 40% by mass and a clay mineral of 10 to 75% by mass. Manufacturing method.
3. 3. The method for producing a high octane gasoline substrate according to 1 or 2 above, wherein the molar ratio of Al in the framework of the crystalline aluminosilicate to the total Al is 0.3 to 1.0.

The FCC gasoline obtained according to the present invention has a high octane number and becomes a high quality gasoline base material.
In general, the base material of FCC gasoline obtained by cracking low-grade heavy hydrocarbon oil is brought about by improving the octane number of FCC gasoline because of its high blending amount in product gasoline shipped to the market. The benefits of product gasoline are very large.
As described above, according to the present invention, it is possible to economically and efficiently produce a gasoline base having a high octane number, and the product gasoline prepared using this gasoline base is excellent in performance and practically used. It is extremely effective.

<Catalytic decomposition process>
Here, the process of catalytically cracking heavy hydrocarbon oil to produce FCC gasoline from heavy hydrocarbon oil is a method in which a flowing catalyst and heavy hydrocarbon oil are brought into contact with each other at a high temperature, and gasoline is contacted. This refers to the process of obtaining fractions and middle fractions. This process includes, for example, HYDRROCARBON PROCESSING / NOVEMBER 2000, pages 107-110, ABB Lummus Global Inc., Kellogg Brown & Roots, Inc., Shell Global Solutions International BV, Stone & Webster Inc., a Shaw Group Co./ There are FCC (Fluid Catalytic Cracking) processes proposed by various process manufacturers such as Institut Francais du Petorole. And UOP LLC.

<Catalytic decomposition operation and conditions>
In order to obtain a high octane gasoline base material in the present invention, a hydrocarbon oil (hydrocarbon mixture) boiling above the boiling point of gasoline is converted into a so-called solid acidity such as zeolite, silica alumina, or alumina by the above FCC process. What is necessary is just to make it contact at high temperature with the FCC catalyst which is the catalytic cracking catalyst shown.
The FCC process on a commercial scale is usually performed by continuously circulating an FCC catalyst exhibiting solid acidity in an FCC apparatus consisting of two types of containers, a vertically installed cracking reactor and a catalyst regenerator. . That is, the hot regenerated catalyst coming out of the catalyst regenerator is mixed with the heavy hydrocarbon oil to be decomposed, and guided upward in the cracking reactor. As a result, the catalyst deactivated by the coke deposited on the catalyst is separated from the decomposition product, and after stripping, it is transferred to a catalyst regenerator. The deactivated catalyst transferred to the catalyst regenerator is regenerated by removing the coke on the catalyst by air combustion, and is circulated again in the cracking reactor. On the other hand, the decomposition product is separated by distillation into one or more heavy fractions such as dry gas, LPG, gasoline fraction, LCO and HCO, or slurry oil. Of course, part or all of the heavy fraction such as LCO, HCO and slurry oil separated from the cracked product can be recycled in the cracking reactor to further promote the cracking reaction.

As operating conditions of the cracking reactor in the FCC apparatus at this time, the reaction temperature is about 400 ° C. to 600 ° C., preferably about 450 ° C. to 550 ° C., the reaction pressure is normal pressure to 5 kg / cm ² , preferably normal pressure to It is appropriate that the mass ratio of 3 kg / cm ² and catalyst / raw hydrocarbon oil is about 2 to 20, preferably about 4 to 15.
If reaction temperature is 400 degreeC or more, the decomposition reaction of hydrocarbon oil will advance suitably and a decomposition product can be obtained suitably. Moreover, if it is 600 degrees C or less, since the amount of light gas production | generations, such as dry gas produced | generated by decomposition | disassembly, and LPG, can be reduced and the yield of the gasoline fraction of a target object increases relatively, it is economical. If the reaction pressure is 5 kg / cm ² or less, the progress of the decomposition reaction in which the number of moles is increased is hardly inhibited. Further, if the mass ratio of the catalyst / raw hydrocarbon oil is 2 or more, the catalyst concentration in the cracking reactor can be kept moderate, and the decomposition of the raw hydrocarbon oil suitably proceeds. On the other hand, if it is 20 or more, the effect of increasing the catalyst concentration is saturated, and an effect commensurate with increasing the catalyst concentration cannot be obtained, which is disadvantageous.

<Target high octane gasoline base material>
FCC gasoline obtained by catalytic cracking of heavy hydrocarbon oil is a fraction of hydrocarbons mixed with normal paraffins, isoparaffins, olefins, naphthenes and aromatics, and has a high octane number It also contains low octane hydrocarbons.
By using an FCC catalyst in which the mass ratio of rare earth metal / crystalline aluminosilicate used in the present invention is controlled to be constant, the content of light olefins having a high octane number can be selectively increased, and the resulting gasoline fraction The FCC gasoline, which is the desired high octane gasoline base material, is distilled by performing distillation so that the 95% distillation temperature of is 90 to 150 ° C, preferably 100 to 150 ° C, more preferably 110 to 150 ° C. Can be manufactured.

<Heavy hydrocarbon oil as raw material>
The raw material heavy hydrocarbon oil used in the present invention may be a hydrocarbon mixture that boils above the boiling point of gasoline, a light oil fraction obtained by atmospheric or vacuum distillation of crude oil, or an atmospheric distillation residue oil. Of course, coke light oil, solvent defoaming oil, solvent deasphalting asphalt, tar sand oil, shale oil oil, and coal liquefied oil are also included. Furthermore, the above-mentioned heavy hydrocarbon oils are well-known hydrotreating, that is, hydrotreating Ni-Mo catalyst, Co-Mo catalyst, Ni-Co-Mo catalyst, Ni-W catalyst, etc. It goes without saying that hydrotreated oil hydrodesulfurized under high temperature and high pressure in the presence of a catalyst can also be used as a raw heavy hydrocarbon oil.

<Catalytic cracking catalyst>
In the present invention, a catalytic cracking catalyst (FCC catalyst) having a mass ratio of rare earth metal / crystalline aluminosilicate of 0.03 or less is used. In general, the FCC catalyst used in the present invention can be obtained by mixing the crystalline aluminosilicate, the binder, and the clay mineral to form an aqueous slurry, which is spray-dried.

(Crystalline aluminosilicate)
As the crystalline aluminosilicate for the catalytic cracking catalyst, it is preferable to use stabilized Y zeolite. Stabilized Y zeolite is generally synthesized using Y zeolite as a starting material. Stabilized Y zeolite exhibits resistance to deterioration of crystallinity as compared to Y zeolite. In general, Y zeolite is subjected to steam treatment at high temperature several times, and if necessary, It can be obtained by treating with a mineral acid such as hydrochloric acid, a base such as sodium hydroxide, a salt such as calcium fluoride, or a chelating agent such as ethylenediaminetetraacetic acid. The stabilized Y zeolite obtained by the above method can be used in an ion exchanged form with a cation selected from hydrogen, ammonium or a polyvalent metal. Further, a heat shock crystalline aluminosilicate zeolite (see Japanese Patent No. 2544317) having more excellent stability can also be used.

As stabilized Y zeolite, (a) bulk SiO ₂ / Al ₂ O ₃ molar ratio by chemical composition analysis is 4-15, preferably 5-10, and (b) unit cell size is 24.35-24.65２４. , Preferably 24.40 to 24.60%, and (c) the molar ratio of Al in the zeolite framework to the total Al is 0.3 to 1.0, preferably 0.4 to 1.0. preferable. This stabilized Y zeolite has basically the same crystal structure as natural faujasite and has the following composition formula (I) as an oxide.
(0.02 to 1.0) R _{2 / m} O · Al ₂ O ₃ · (5 to 11) SiO ₂ · (5 to 8) H ₂ O ... Composition formula (I):
R: Na, K, other alkali metal ions, alkaline earth metal ions m: R valence

The unit cell size in the zeolite can be measured by an X-ray diffractometer (XRD), and the number of moles of Al in the zeolite framework relative to the total Al is determined by the chemical composition analysis of the SiO ₂ / Al ₂ O ₃ ratio and the unit cell. It is a value calculated from the dimensions using the following mathematical formulas (A) to (C). Note that the mathematical formula (A) K. Beyer et al. , J .; Chem. Soc. , Faraday Trans. 1, (81), 2899 (1985). Is adopted.
N _Al = (a ₀ -2.425) /0.000868 ...... Formula (A)
a ₀ : unit cell size / nm
N _Al : Number of Al atoms per unit cell
2.425: Unit cell dimensions when all Al atoms in the unit cell skeleton are desorbed from the skeleton
0.000868: Calculated value obtained by experiment, slope when a ₀ and N _Al are arranged by a linear equation (a ₀ = 0.000868 N _Al +2.425)
(Si / Al) calculation formula = (192−N _Al ) / N _Al ...... Formula (B)
192: Number of atoms of (Si + Al) per unit cell size of Y zeolite Al in zeolite framework / total Al = (Si / Al) chemical composition analysis value / (Si / Al) calculation formula (C)

The SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite indicates the acid strength of the catalyst, and the larger the molar ratio, the stronger the acid strength of the catalyst. When the SiO ₂ / Al ₂ O ₃ molar ratio is 4 or more, the acid strength necessary for the catalytic cracking of heavy hydrocarbon oil can be obtained, and as a result, the cracking reaction preferably proceeds. If the SiO ₂ / Al ₂ O ₃ molar ratio is 15 or less, the acid strength of the catalyst becomes strong, the necessary number of acids can be secured, and the decomposition activity of the heavy hydrocarbon oil can be easily secured.

  The unit cell size of the zeolite indicates the size of the unit unit constituting the zeolite, but if it is 24.35 mm or more, the number of Al necessary for the decomposition of the heavy oil is appropriate, and as a result Proceed suitably. If it is 24.65% or less, it is easy to prevent the zeolite crystals from being deteriorated, and it is possible to avoid a significant decrease in the decomposition activity of the catalyst.

If the amount of Al constituting the zeolite crystal is too small, as a result, the Al ₂ O ₃ particles dropped from the skeleton of the zeolite will increase, and there is a possibility that the catalytic decomposition reaction will not proceed because the strong acid point is not expressed. The above phenomenon can be avoided if the molar ratio of Al in the zeolite framework to the total Al is 0.3 or more. Moreover, when the molar ratio of Al in the zeolite framework to the total Al is close to 1, it means that most of the Al in the zeolite is taken into the zeolite unit cell, and the Al in the zeolite is effective for the expression of strong acid sites. It is preferable because it contributes to

(Binder)
A silica binder, an alumina binder, etc. can be used as a binder. These binders are present between particles such as crystalline aluminosilicates and clay minerals, improve the moldability when the catalyst is made fine, make it spherical, and the fluidity and resistance of the resulting catalyst fine particles. It is used for wear.

Several types of silica binders are known. If colloidal silica is taken as an example, there are silica sols such as sodium type, lithium type, and acid type. Any of these types can be used. Considering production on a commercial scale, silica hydrosol obtained by reacting a dilute water glass aqueous solution and a sulfuric acid aqueous solution can also be used.
The alumina binder uses particles obtained by decomposing dibsite, vialite, boehmite, bentonite, crystalline alumina, etc. in an acid solution, boehmite gel, particles in which amorphous alumina gel is dispersed in an aqueous solution, or alumina sol. be able to.
In addition, as long as it does not deviate from the effect acquired by this catalyst, a silica binder and an alumina binder can also be mixed and used as needed.

(Clay mineral)
As the clay mineral, montmorillonite, kaolinite, halloysite, bentonite, attapulgite, bauxite and other clay minerals can be used, and silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, It can also be used in combination with oxide fine particles of known inorganic oxides used in ordinary decomposition catalysts such as silica-zirconia and silica-magnesia-alumina.

(Catalyst composition and preparation)
The catalyst of the present invention comprising the components as described above can be prepared by various techniques, and examples thereof include the following procedures. First, a crystalline aluminosilicate, a binder, and a clay mineral are mixed in a mixing vessel to obtain a uniform aqueous slurry.
At this time, the mixing ratio of the crystalline aluminosilicate, the binder, and the clay mineral is 20 to 50% by mass of the crystalline aluminosilicate, preferably 25 to 45% by mass, and 5 to 5% of the binder on the basis of the catalyst drying. It is preferable to set the range of 40% by mass, preferably 10 to 35% by mass, and clay mineral 10 to 75% by mass, preferably 15 to 70% by mass.

  If the crystalline aluminosilicate is 20% by mass or more, the desired decomposition activity can be obtained. If the crystalline aluminosilicate is 50% by mass or less, the amount of clay mineral and binder is relatively reduced. The following undesirable phenomenon can be avoided. That is, if the amount of clay mineral or the like is too small, not only the catalyst strength is lowered, but also the bulk density of the catalyst is reduced, which produces undesirable results in the operation of the apparatus.

  In addition, if the amount of the binder is 5% by mass or more, the strength of the catalyst can be maintained, so that it is possible to avoid undesirable phenomena such as scattering of the catalyst and mixing in the produced oil. An improvement in catalyst performance commensurate with the amount used is recognized, which is economically advantageous.

  Further, if the clay mineral is 10% by mass or more, the catalyst strength and the bulk density of the catalyst are small, and it can be avoided that the operation of the apparatus is hindered. It can be avoided that the amount of crystalline aluminosilicate and the binder is reduced and the desired decomposition activity cannot be obtained, and that the catalyst is difficult to prepare due to the insufficient amount of the binder.

  About 5-60 mass% is preferable, and, as for the ratio of the solid content in the aqueous slurry formed by mixing each said component, More preferably, it is 10-50 mass%. If the ratio of the solid content is within this range, the amount of water to be evaporated becomes an appropriate amount, so that there is no trouble in the spray drying process, etc., and the viscosity of the slurry becomes too high, making it difficult to transport the slurry. There is no.

  Next, the aqueous slurry is usually spray-dried to obtain microspheres (catalyst or catalyst precursor). This spray drying is preferably performed by a spray drying apparatus at a gas inlet temperature of about 200 to 400 ° C. and a gas outlet temperature of about 100 to 200 ° C. Microspheres obtained by spray drying generally have a particle size of about 20 to 150 μm and a water content of about 10 to 30% by weight.

  Furthermore, the spray-dried microspheres can be fired at 200 ° C. or higher to be fired microspheres, and the gas outlet temperature is kept at 200 ° C. or higher when spray drying aqueous slurry with a spray dryer. In the case where a facility capable of performing the above is provided, it is also possible to include a fine particle firing step in the spray drying step.

(Washing and ion exchange)
The microspheres obtained as described above are ion-exchanged by a known method, if necessary, and subsequently washed with water to remove excess alkali metals and soluble impurities brought from various raw materials, Then dry. In addition, when an excess alkali metal, a soluble impurity, etc. do not exist in a microsphere, you may dry as it is, without performing ion exchange etc.

Specifically, the ion exchange is performed using an aqueous solution of an ammonium salt or a rare earth salt such as an aqueous ammonium sulfate solution or an aqueous lanthanum nitrate solution, and the alkali metal remaining in the microsphere can be reduced by this ion exchange.
Moreover, the amount of soluble impurities can be reduced by washing with water following ion exchange.
It is preferable to reduce the alkali metal and soluble impurities to about 1.0% by mass or less, preferably about 0.5% by mass or less, respectively, based on the dry catalyst, in order to increase the catalytic activity. Moreover, these washing | cleaning and ion exchange processes can also be performed in reverse order, as long as the effect of this invention is acquired.
After ion exchange and washing, the microspheres are generally dried at a temperature of about 100 to 500 ° C. to a moisture content of about 1 to 25% by mass and then optionally calcined to obtain the catalyst used in the present invention. It is done.

(Rare earth metal)
The rare earth metal in the ion exchange can contain one or more of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium, etc., preferably lanthanum, cerium It is. When the rare earth metal is contained, the decay of the zeolite crystals can be suppressed, and the durability of the catalyst can be enhanced.
The amount of rare earth metal contained in the catalyst used in the present invention is 0.03 or less, preferably 0.02 or less, based on the dry basis and the mass ratio of rare earth metal / crystalline aluminosilicate. If it exceeds 0.03, the desired high octane fraction cannot be obtained. If it is 0.03 or less, acceleration of the hydrogen transfer reaction when the amount of rare earth metal relative to the crystalline aluminosilicate is too large can be suppressed, and as a result, the content of light olefins increasing the octane number of FCC gasoline is increased. Therefore, the intended high octane gasoline base material of the present invention can be obtained.

In addition to the ion exchange of the calcined microspheres containing the crystalline aluminosilicate with the rare earth metal, the rare earth metal is contained in the catalyst, and the rare earth metal is supported on the crystalline aluminosilicate, so-called metal modified type. It can also be contained in the form of crystalline aluminosilicate.
In short, the rare earth metal can be contained in the crystalline aluminosilicate by a conventionally known method. For example, in either case of ion exchange or support, crystals of rare earth metals such as lanthanum and cerium, aqueous solutions containing one or more compounds such as nitrates, sulfates, acetates, etc. are in a dry state. It is possible to carry out by ion-exchange or impregnation of a functional aluminosilicate and heating as necessary.

Similarly to the non-modified crystalline aluminosilicate, a slurry of the metal-modified crystalline aluminosilicate is prepared together with a binder and a clay mineral, and then spray-dried to form microspheres. Then, after carrying out a calcination treatment to obtain calcined microspheres, known washing can be performed as necessary, and finally a catalyst for catalytic cracking of heavy oil can be obtained. That is, in the catalyst used in the present invention, as long as the rare earth metal / crystalline aluminosilicate mass ratio is in the range of 0.03 or less, the rare earth metal content may be any form.
Further, the catalyst used in the present invention may contain a metal other than rare earths as long as the desired effect of the present invention can be obtained.

<Production gasoline preparation>
The high octane gasoline base material obtained in the present invention can be suitably prepared by mixing one or more of other known gasoline base materials.
Other known gasoline base materials include light naphtha obtained by atmospheric distillation of crude oil, preferably desulfurized light naphtha obtained by desulfurizing it, and catalytic reformed gasoline obtained by catalytic reforming after desulfurization of heavy naphtha. Debenzene-catalyzed reformed gasoline, debenzene light-catalyzed reformed gasoline, debenzene heavy-catalyzed reformed gasoline, and a mixture thereof, cracked gasoline obtained by hydrocracking, etc., By adding lower olefins to hydrocarbons such as light cracked gasoline, heavy cracked gasoline, and their mixtures, isomerized gasoline obtained by isomerizing light naphtha, isobutane, etc. The resulting alkylate, butane obtained by distillation during the atmospheric distillation of crude oil, during the production of reformed gasoline, or during the production of cracked gasoline, C4 fraction mainly composed of tens, raffinate, methanol, ethanol, propanol, butanol, alcohols such as t-butyl alcohol (TBA), methyl-t-butyl ether (MTBE) and ethyl-t-butyl ether (ETBE) , T-amyl methyl ether (TAME), ethers such as t-amyl ethyl ether (TAEE), etc., and usually used gasoline base materials can be arbitrarily used, and are not particularly limited.

<Gasoline additive>
In addition, various additives can be appropriately blended as necessary in the product gasoline prepared by mixing the high octane gasoline base obtained in the present invention and other known gasoline bases. Such additives include phenolic and amine antioxidants, metal deactivators such as thioamide compounds, surface ignition inhibitors such as organophosphorus compounds, succinimides, polyalkylamines, polyetheramines. , Detergent dispersants such as polyisobutyleneamine, friction modifiers (FM) such as long chain alkylamines, amides, imides and derivatives thereof, anti-icing agents such as polyhydric alcohols and ethers thereof, alkali metals and alkaline earths of organic acids Metal salts, auxiliary agents such as sulfates of higher alcohols, anionic surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, rust inhibitors such as alkenyl succinates, and azo dyes Known fuel additives such as colorants can be used. These can be added singly or in combination. The addition amount of these fuel additives is arbitrary, but usually the total addition amount is preferably 0.1% by mass or less.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, these are illustrations and this invention is not restrict | limited at all by the following examples.

Example 1
<Preparation of catalyst A>
The faujasite type zeolite having the physical properties shown in Table 1 as the crystalline aluminosilicate, the water glass (JIS No. 3 water glass SiO ₂ concentration 28.9 mass%) aqueous solution as the silica sol of the binder, and kaolinite as the clay mineral, Each was used.

A mixed solution of 138 g of water glass and pure water was added dropwise to dilute sulfuric acid to prepare an aqueous silica sol solution (SiO ₂ concentration 10.2 mass%). On the other hand, distilled water was added to 76 g (dry basis) of faujasite type zeolite having the physical properties shown in Table 1 to prepare a zeolite slurry. To the above silica sol aqueous solution, 84 g of kaolinite (dry basis) was added and mixed, and further the above zeolite slurry was added and further mixed for 5 minutes. The obtained aqueous slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C., and the obtained microspheres were used as a catalyst precursor. The catalyst precursor was ion-exchanged twice with 3 L (liter) of a 5% by mass ammonium sulfate aqueous solution, and further washed with 3 L of distilled water. Next, the washed microspheres were ion-exchanged with 1.0 L of a 0.002 mol / L lanthanum nitrate aqueous solution for 15 minutes, and then washed with 3 L of distilled water. Then, it dried at 110 degreeC overnight in the dryer, and the catalyst A was obtained.

  The amount of lanthanum metal contained in catalyst A was measured with an ICP emission analyzer (IRIS Advantage) manufactured by Nippon Jarrell Ash Co., Ltd., and the mass ratio of rare earth / crystalline aluminosilicate of catalyst A was 0. .01.

<Fluid catalytic cracking using catalyst A>
About the obtained catalyst A, using a bench scale plant which is a fluidized bed catalytic cracking apparatus having a reaction vessel and a catalyst regenerator, desulfurization containing 90% by mass of heavy oil boiling at 353 ° C. or higher as a raw material oil Using a mixture of vacuum gas oil and atmospheric distillation residue, a catalytic cracking reaction was performed under the test conditions shown in Table 2.
Prior to the test, the catalyst was dried at 500 ° C. for 5 hours in order to approximate the actual use state, that is, equilibrated, and then nickel and vanadium were 1000 ppm by mass and 2000 ppm by mass, respectively. Then, a cyclohexane solution containing nickel naphthenate and vanadium naphthenate was absorbed, dried and calcined at 500 ° C. for 5 hours, and then each catalyst was treated at 785 ° C. in 100% steam atmosphere for 6 hours. .

  The obtained cracked product oil was analyzed by gas chromatography using an AC Simdis Analyzer manufactured by Agilent Technologies, and the gasoline yield when the 95% distillation temperature of gasoline was 145 ° C. was calculated. Further, the octane number of the obtained gasoline was measured by a gas chromatographic method for research octane number (GC-RON) using a PONA analyzer manufactured by Hured Packard. These results are shown in Table 3 together with the catalyst composition.

Examples 2-4
Except that the 95% distillation temperature of gasoline in cracked product oil is 92 ° C, 102 ° C, and 112 ° C, an experiment of catalytic cracking reaction was conducted in the same manner as in Example 1, and the gasoline yield and GC-RON Was calculated. These results are shown in Table 3 together with the catalyst composition.

Example 5
<Preparation of catalyst B>
A faujasite type zeolite having the physical properties shown in Table 1 was used as the crystalline aluminosilicate, alumina sol (trade name: AP-3, manufactured by Catalyst Kasei Co., Ltd.) was used as the binder for the binder, and kaolinite was used as the clay mineral.

105 g of pure water was added to 42.8 g of alumina sol to prepare an aqueous solution of alumina sol (Al ₂ O ₃ concentration 20.3% by mass). Meanwhile, distilled water was added to 64 g (dry basis) of faujasite type zeolite having the physical properties shown in Table 1 to prepare a zeolite slurry. To the above-mentioned alumina sol aqueous solution, 106 g of kaolinite (dry basis) and the above zeolite slurry were added and further mixed for 5 minutes. The obtained aqueous slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C. to obtain microspheres. The microspheres were calcined at 240 ° C. for 30 minutes in a muffle furnace to form calcined microspheres, ion-exchanged twice with 3 L of a 5% by mass ammonium sulfate aqueous solution, and further washed with 3 L of distilled water. Then, it dried at 110 degreeC overnight in the dryer, and the catalyst B was obtained.

  The amount of lanthanum metal contained in catalyst B was measured with an ICP emission analyzer (IRIS Advantage) manufactured by Nippon Jarrell Ash Co., Ltd., and the mass ratio of rare earth / crystalline aluminosilicate in catalyst B was 0. 0.003.

<Fluid catalytic cracking using catalyst B>
The catalyst B obtained above was subjected to a catalytic cracking reaction using a bench scale plant in the same manner as in Example 1, and the gasoline yield and GC− when the 95% distillation temperature of the gasoline was 145 ° C. RON was calculated. These results are shown in Table 3 together with the catalyst composition.

Comparative Example 1
<Preparation of catalyst C>
The faujasite type zeolite having the physical properties shown in Table 1 as the crystalline aluminosilicate, the water glass (JIS No. 3 water glass SiO ₂ concentration 28.9 mass%) aqueous solution as the silica sol of the binder, and kaolinite as the clay mineral, Each was used.

A mixed solution of 138 g of water glass and pure water was added dropwise to dilute sulfuric acid to prepare an aqueous silica sol solution (SiO ₂ concentration 10.2 mass%). Meanwhile, distilled water was added to 64 g (dry basis) of faujasite type zeolite having the physical properties shown in Table 1 to prepare a zeolite slurry. To the above silica sol aqueous solution, 96 g of kaolinite (dry basis) was added and mixed, and the above zeolite slurry was further added and further mixed for 5 minutes. The obtained aqueous slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C., and the obtained microspheres were used as a catalyst precursor. The catalyst precursor was ion-exchanged twice with 3 L of a 5% by mass aqueous ammonium sulfate solution, and further washed with 3 L of distilled water. Next, the washed microspheres were ion-exchanged with 1.0 L of 0.01 mol / L lanthanum nitrate aqueous solution for 15 minutes, and then washed with 3 L of distilled water. Then, it dried at 110 degreeC overnight in the dryer, and the catalyst C was obtained.

  The amount of lanthanum metal contained in the catalyst C was measured with an ICP emission analyzer (IRIS Advantage) manufactured by Nippon Jarrel Ash Co., Ltd., and the mass ratio of rare earth / crystalline aluminosilicate in the catalyst C was 0. .04.

<Fluid catalytic cracking using catalyst C>
The catalyst C obtained above was subjected to a catalytic cracking reaction using a bench scale plant in the same manner as in Example 1, and the gasoline yield and GC− when the 95% distillation temperature of gasoline was 145 ° C. RON was calculated. These results are shown in Table 3 together with the catalyst composition.

Comparative Example 2
Except for setting the 95% distillation temperature of gasoline in cracked product oil to 80 ° C., the catalytic cracking reaction was conducted in the same manner as in Comparative Example 1, and the gasoline yield and GC-RON were calculated. These results are shown in Table 3 together with the catalyst composition.

Comparative Example 3
Except that the 95% distillation temperature of gasoline in the cracked product oil was 160 ° C., the catalytic cracking reaction was conducted in the same manner as in Example 1, and the gasoline yield and GC-RON were calculated. These results are shown in Table 3 together with the catalyst composition.

  Further, Table 4 shows the properties of the high-octane gasoline base material obtained in Example 1 and the gasoline base material obtained in Comparative Example 1.

  In Table 4, GC-MON is a motor octane number determined by gas chromatography. RVP indicates the reed vapor pressure (RVP) of gasoline and is a value measured according to JIS K2258. Further, T50 represents a 50% distillation temperature, E70 represents a 70 ° C. distillation amount, and these distillation properties are values measured in accordance with JIS K 2254.

As can be seen from Table 3, in Comparative Examples 1 and 3 that do not follow the present invention, although the yield of FCC gasoline is high, the octane number is low and a high octane gasoline base cannot be produced.
Moreover, in the comparative example 2, although the octane number of FCC gasoline is high, the yield of FCC gasoline is extremely low, and it is also disadvantageous in consideration of economy.
However, in Examples 1 to 5 according to the present invention, the octane number of FCC gasoline is high, and a high octane number gasoline base material can be produced in a high yield.
Moreover, as is clear from Table 4, the high octane gasoline base material produced according to the present invention is a gasoline base material having a high octane number and a low T50. When a gasoline composition is prepared using this base material, since the octane number is high, it is possible to increase the content of low-grade, low-octane desulfurized light naphtha and at the same time to lower T50. It turns out that it is excellent as a material.

Claims (3)

Catalytic cracking of heavy hydrocarbon oil using a catalytic cracking catalyst with a rare earth metal / crystalline aluminosilicate mass ratio of 0.003 to 0.01 , and distillation of the resulting oil yields a 95% distillation temperature. A method for producing a high-octane gasoline base material, characterized in that a fraction having a temperature of 90 to 150 ° C. is obtained.   The high octane gasoline group according to claim 1, wherein the catalytic cracking catalyst used has a crystalline aluminosilicate in a proportion of 20 to 50% by mass, a binder in a proportion of 5 to 40% by mass, and a clay mineral in a proportion of 10 to 75% by mass. A method of manufacturing the material. The method for producing a high-octane gasoline substrate according to claim 1 or 2, wherein a molar ratio of Al in the skeleton of the crystalline aluminosilicate to total Al is 0.3 to 1.0.