JPH0114275B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for catalytically cracking hydrocarbon oil in the presence of a catalyst containing at least one crystalline zeolite, and to a catalyst thereof. JP 54/122692 discloses contacting a hydrocarbon oil in the presence of a catalyst containing at least one crystalline zeolite and contaminated with a small amount of at least one heavy metal and further containing 0.01 to 2.5% by weight of boron. It concerns the method of decomposition. Zeolite-containing cracking catalysts are used on a large scale in industrial cracking equipment for producing motor fuels or their components. Crystalline zeolite-containing catalysts differ from conventional amorphous cracking catalysts consisting of alumina and silica by their higher activity and selectivity. However, zeolites have the disadvantage of being susceptible to contamination with heavy metals such as cobalt, molybdenum, tungsten, copper and especially vanadium, nickel and iron. In particular, the latter three metals are present in certain crude oil fractions to be catalytically cracked. While methods for removing heavy metals of this type from crude oil or fractions thereof are known, it is further desirable to seek a means of eliminating the need to perform this removal prior to optional conversion of the hydrocarbon oil. During the catalytic cracking of hydrocarbon oils, the polluting effect of heavy metals manifests itself in a gradual decrease in the activity and selectivity of the catalyst and an increase in the formation of coke, an undesirable by-product. Deterioration of the desired properties is accompanied by a gradual increase in the heavy metal content of the cracking catalyst. According to JP-A-54/122692, the undesirable effects of heavy metals on cracking catalysts can be reduced by incorporating small amounts of boron into the catalyst. It has now been found that this undesirable effect can be gradually reduced surprisingly effectively if the catalyst also contains tin in addition to boron. Therefore, the present invention provides at least one crystalline zeolite of the group consisting of vanadium, nickel and iron and a small amount of at least one heavy metal from 0.01 to
The present invention relates to a method for catalytic cracking of hydrocarbon oils, in which cracking is carried out in the presence of a catalyst containing 2.5% by weight of boron and 0.01 to 2.5% by weight of tin. Preferably the catalyst contains 0.1-1.5% by weight of boron and 0.1-1.5% by weight of boron.
1.5% by weight of tin, where weight percentages are based on the weight of fresh catalyst. contaminated heavy metals,
In particular, the amounts of vanadium, nickel and iron are usually in the range from 0.1 to 2.0% by weight, calculated as the total amount of metals based on the weight of fresh catalyst. The catalytic decomposition process is preferably carried out at temperatures ranging from 400°C to 650°C and pressures ranging from reduced pressure to several hundred bar. Fixed bed, moving bed, fluidized catalyst, suspended or ascending operations can be applied. No hydrogen is added and the specific conditions depend on the nature of the feed and desired product. The feedstock for the cracking operation is a hydrocarbon oil derived from petroleum, shale oil and/or tar sands and has an initial boiling point higher than the final boiling point of gasoline. Suitable feedstocks are, for example, gas oils, fuel oils, deasphalted oils, waxes and residual oils. The method uses a catalyst hybridized with naturally occurring or synthetic crystalline aluminosilicates, ie zeolites. The zeolite component of the catalyst is preferably ion-exchanged with non-toxic metal ions, such as rare earth metal ions, which improve the activity of the catalyst. Boron and tin can be incorporated into the catalyst before and during the cracking reaction by known methods such as ion exchange, dry mixing, impregnation or precipitation. This incorporation is very preferably carried out by using a volatile boron compound and a volatile tin compound or a solution of an organic or inorganic boron compound and an organic or inorganic tin compound in water or an organic solvent for the regeneration of the catalyst. or to the hydrocarbon feed or circulating oil, or to the steam used for stripping the catalyst before regeneration. During catalyst regeneration, boron and tin or boron compounds and tin compounds are almost always converted to boron oxide and tin oxide. The treatment agent that can be used in the method of the invention consists of a boron compound and a tin compound. These may be organic or inorganic. Examples of suitable tin compounds are tin chloride (), tin chloride (), tin naphthenate, tin nitrate (and), tetraethyltin, tetrabutyltin, tetraphenyltin, dodecyltin, dibutyltin dilaurate, tetraoctyltin, tin citrate, Includes tin tartrate and mixtures of these compounds. Examples of suitable boron compounds are orthoboric acid, tetraboric acid, boron pentasulfide, boron trichloride, ammonium diborate, calcium borate,
Diborane, magnesium borate, methyl borate, butyl borate, tricyclohexylborate, 2,6-
Includes ditertiary-butylphenyl dibutylborate, cyclohexylboronic acid, monoethyldodecyl acid boronate, and mixtures of these compounds. Processing agents containing significant proportions of sodium, such as sodium tetraborate, or other known cracking catalyst poisons are less desirable. The normal operation of the cracking process is not affected by the presence of boron and tin in the catalyst and therefore typical values for cracking and regeneration temperatures, hydrocarbon feed rate, feed/circulation oil ratio and other parameters are selected. It is possible to do so. EXAMPLES A series of cracking experiments were conducted in the presence of a cracking catalyst containing phasiasite Y under the following conditions. Pressure 1 bar Reaction temperature 485°C Regeneration temperature 600°C Feed Kuwait distillate space velocity 6.4 Kg/Kgh The specific selectivity of conversion (S _R ) during the cracking operation is determined by the formula S _R = P _B /P _C determined, where P _B is the product fraction C ₅ −221° C. expressed as a percentage of the feed.
and P _C is the total weight of coke expressed as a percentage of feed. Amounts of iron naphthenate (0.5% by weight Fe), vanadium naphthenate (0.2% by weight V) and nickel naphthenate (0.1% by weight Ni) were added to the catalyst by impregnation. The elements boron and tin were added to the cracking catalyst by impregnation using butyl borate and dibutyltin dilaurate, respectively. The test results are shown in the table, which also includes for comparison the results of catalytic cracking tests with only boron or only tin added to the cracking catalyst or without any of these metals.

【table】

[Table] Additional relationships The main part of the constitution of the original invention stated in claim 1 of Patent No. 1448300 (Japanese Patent Publication No. 62-55897) is that “at least one crystalline zeolite” , a small amount of at least one heavy metal from the group consisting of vanadium, nickel and iron, and 0.01 to 2.5% by weight of boron. , the present invention is an invention in which the main parts of the essential parts of the structure of the original invention are the main parts of the essential parts of the structure, and it achieves the same purpose as the original invention, and is patentable. It meets the requirements for an additional patent as stipulated in Article 31, Item 1 of the Act.

Claims (1)

[Claims] 1. At least one crystalline zeolite, a small amount of at least one heavy metal from the group consisting of vanadium, nickel and iron, 0.01-2.5% by weight of boron and 0.01-2.5% by weight of tin. A method for catalytic cracking of hydrocarbon oil, characterized by cracking in the presence of a catalyst contained therein. 2. The method of claim 1, wherein the catalyst contains 0.1-1.5% by weight of boron and 0.1-1.5% by weight of tin. 3. The method according to claim 1 or 2, wherein the catalyst contains vanadium, nickel and iron as heavy metals. 4. A method according to claim 3, wherein the heavy metals are present in a total amount in the range 0.1-2.0% by weight. 5 characterized in that it contains at least one crystalline zeolite, a small amount of at least one heavy metal of the group consisting of vanadium, nickel and iron, 0.01-2.5% by weight of boron and 0.01-2.5% by weight of tin. A catalyst for catalytic cracking of hydrocarbon oil. 6. The catalyst according to claim 5, wherein the catalyst contains 0.1 to 1.5% by weight of boron and 0.1 to 1.5% by weight of tin.