JPS59149985A - Fluidized catalytic cracking method of heavy oil - Google Patents

Abstract

PURPOSE:To suppress the generation of dry gas and coke without lowering the yield of a light distillate fraction, by subjecting heavy oil containing an Ni and V-containing distillation residue to fluidized catalytic cracking in the presence of a specific catalyst. CONSTITUTION:Heavy oil containing a distillation residue containing Ni and V in a total amount of 0.5ppm or more is subjected to fluidized catalytic cracking in the presence of a catalyst prepared by containing matrix of which the magnesia content is 2-5wt%. By this method, hydrogen increased by the metal accumulated on the catalyst and the yield of coke are suppressed and the loads of a gas compressor which is a member of the distillation equipment of a cracking product and an air blower for supplying air for burning the coke on the catalyst are reduced while the yield of a pref. liquid product is increased and the yield of a light distillate fraction reaches 50% or more.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for fluid catalytic cracking of heavy oil, and more specifically, to catalytic cracking of heavy oil containing distillation residue containing heavy metals such as nickel, vanadium, and iron. In particular, it relates to a method for suppressing the formation of dry gas and coke without impairing the yield of light fractions.

In normal fluid catalytic cracking, petroleum hydrocarbons are cracked by contacting them with a catalyst to obtain a large amount of light components such as LPG and gasoline and a small amount of cracked light oil, and then the coke deposited on the catalyst is burned off with air. The catalyst is recycled and reused. Furthermore, conventionally, so-called distillate oils such as light gas oil (LGO) from atmospheric distillation columns, heavy gas oil (HGO), and vacuum gas oil (CVGO') from vacuum distillation columns have been mainly used as feedstock oils. do not have.

However, as crude oil has recently become heavier worldwide and the demand structure has changed in Japan, there has been a tendency for heavy oils to be in excess from both the supply and demand perspective. It has become necessary to target heavy oil as well.

However, heavy oil containing distillation residue contains much higher amounts of metals such as nickel, vanadium, iron, copper, and sodium than distillate oil, and these metals act as catalysts. is known to significantly inhibit the activity and selectivity of decomposition by depositing on the surface. In other words, as metals accumulate on the catalyst, the decomposition rate decreases, making it practically impossible to achieve the desired decomposition rate, while the amount of hydrogen and coke generated increases significantly, making it difficult to operate the equipment. At the same time,
The problem is that the yield of the desired liquid product is reduced.

The present invention provides a method for fluid catalytic cracking of heavy oil that solves these problems. In particular, when cracking heavy oil, it is possible to combine hydrogen and hydrogen without reducing the yield of gasoline and middle distillates. The present invention provides a method for suppressing the production amount.

That is, in the present invention, heavy oil containing distillation residue containing nickel and vanadium in a total amount of 0.5 ppm or more is added to an alumina-magnesia matrix having a magnesia content of 2 to 50 wt% in an amount of 3 to 40 wt4 (total catalyst amount). A heavy oil that is subjected to fluid catalytic cracking in the presence of a catalyst containing zeolite of provides a fluid catalytic cracking method.

Catalysts commercially available for fluid catalytic cracking of heavy oil are generally made of a combination of Y-type zeolite and an amorphous silica/alumina matrix, similar to ordinary fluid catalytic cracking catalysts made from distillate oil. In such heavy oil cracking catalysts, metal resistance is improved by reducing the matrix surface area. However, for reasons that are not clear, the catalyst used in the present invention has high metal resistance regardless of the size of the matrix surface area because it contains alumina-magnesia 1 trix as a component of the catalyst.

The present invention will be explained in more detail below.

The heavy oil referred to in the present invention may be derived from one type of crude oil, or may be derived from a mixture of two or more types of oil,
For example, heavy oil that is a mixture of southern, Middle Eastern, African, North and South American, Mexican, North Sea, and Alaskan crude oils may be used.

In addition, the heavy oil referred to here substantially contains asphaltene or resin (usually contains 0.5 wt% or more), and the combined amount of nickel and vanadium is 0.5 ppm.
Refers to hydrocarbon mineral oils containing the above, including residual components separated by distillation during the petroleum silk manufacturing process.
Specifically, atmospheric distillation residue oil, vacuum distillation residue oil, solvent deasphalted oil, solvent deasphalted asphalt, and any of these and distillate oil with a normal boiling point of 200°C or higher from atmospheric distillation or vacuum distillation.For example, LGOC Boiling point range 200-300℃), 1
1GOC300-500℃) and/or VGO (30
An example is a mixed oil having a temperature of 0 to 570°C. The content of residual oil in the mixed oil is 1 tut- or more.

Examples of heavy TI oils include shale oil, tar sand oil, and coal liquefied oil.

The catalyst used in the present invention consists of a non-iron oxide part called a matrix and a crystalline aluminosilicate part called a zeolite.

The matrix is a synthetic product mainly composed of alumina (A1203)/magnesia CMaO) or a processed product of naturally occurring clay minerals, and has a magnesia content of 2 to 50 wt%, preferably 4 to 30 wt%. are used. When the magnesia content in the matrix is less than 2 wt%, the characteristic effects seen in the present invention are unlikely to appear. In addition, the magnesia content is 50
If it is more than wt%, it is not preferable because sufficient catalytic activity cannot be obtained. The manufacturing method of the matrix is not particularly limited. For example, it can also be made by the following method. A mixed aqueous solution of an aluminum salt and a magnesium salt is reacted with ammonia to form an alumina/magnesia hydrogel slurry. Any salt may be used at this time, such as chloride, nitrate, and sulfate. Next, after aging the above hydrogel slurry, it was rinsed with twice as much pure water and dried at, for example, 110C for a day and night.
Air bake at ~600°C for 4-10 hours. The specific surface area of the matrix thus obtained is 50 to 300n? /ff
The pore volume is 0.1 to 1.2 cc/r, and the average A'...pore size is 10 to 200λ.

The zeolites used in the present invention are natural or synthetic crystalline aluminosilicates and are porous materials with a three-dimensional framework structure and uniform pore sizes ranging from about 4 to about 15X. Natural zeolites include gmelinite, shatsukusite, dakialdofutuite, clinoptilolite, faujasite, kihusite, borofluorite, levinite, erionite, sodalite, cankrinite,
Any of ferrierite, Brewster's fluorite, offretite, soda fluorite, mordenite, etc. may be used, and faujasite is most preferred. Examples of synthetic zeolites include zeolites Y, Y, A, L, ZK-4, E, and E.

F, HJ, M, Q, T, W, Z, alpha, beta,
Any of the Z-8M type, omega, etc. zeolites may be used, and in the present invention, Y type and X type zeolites or a mixture thereof are the best.

The Ha ions in the zeolite can be exchanged with other cations, and those exchanged with hydrogen or rare earth metals are preferred.

The catalyst used in the present invention includes the zeolite and alumina.
A magnesia matrix is mixed therein, and the zeolite content at this time is 3 to 40 wt%, preferably 5 to 30 wt%. Zeolite content is 3w
When the amount is less than tqb, the catalyst activity is low and it is not preferable.

Moreover, when the content of zeolite is more than 40 wt%, the catalyst activity is too high and over-decomposition occurs, resulting in a poor yield of the desired product. The method of mixing the zeolite and the matrix is not particularly limited, and for example, a method of mixing a gel or sol of the matrix with a zeolite slurry and drying the mixture using a tin spray method, as in the case of a normal FCC catalyst, may be used.

In this case, a binder such as alumina sol or silica sol may be added.

When the above catalyst is used for fluid catalytic cracking of heavy oil, the increased hydrogen and coke yield is suppressed by the metals accumulated on the catalyst, although the reason is not fully clear, and the distillation equipment for the cracked products is This not only reduces the load on the gas compressor and air blower that supplies air for coke combustion over the catalyst, but also increases the yield of the desired liquid product.

The specific method of using the catalyst is to periodically replenish the new catalyst of Ryu's invention necessary to maintain the amount of metal accumulation on the catalyst within a certain range in the fluid catalytic cracker, and to reduce losses during operation. This is to remove the catalyst in use from the equipment in an amount that corresponds to the amount of replenishment. The amount of replenishment depends on the amount of heavy oil to be processed, the metal content in the heavy oil and the metal accumulation capacity of the catalyst. The catalyst has a high tl capacity for metal accumulation and requires little replenishment, making it possible to provide an economical heavy oil cracking method. The catalyst according to the present invention is an economically excellent catalyst because the amount of hydrogen and coke produced is suppressed within the normally permissible range up to a metal accumulation of 210 t%, and only a small amount of replenishment is required.

Equipment used to carry out the catalytic cracking of the present invention,
That is, the fluid catalytic cracking apparatus having a reaction zone, a separation zone, a stripping zone, a catalyst regeneration zone, and a distillation zone is not particularly limited, but is preferably suitable for substantially cracking heavy oil.

For example, the reaction zone should preferably be equipped with a riser reaction zone to shorten the contact time between oil and catalyst to reduce the amount of coke produced, and the regeneration zone should be equipped with equipment that can withstand high temperatures up to about 750°C or heat removal equipment. What you have is good. Further, the operating conditions of the apparatus are not particularly limited, but an example is a reaction temperature of 450 to 550'C.

Pressure 0.5-3 K9/cJ G 1 Catalyst regeneration degree 55
0 to 750°C, catalyst/oil field 3 to 20 wt/wt, contact time 0.5 to 5 sec, CFR ((new feedstock oil + circulating oil)/new feedstock oil) 1.0 to 2.0 vol/q
It's a no-ol.

The light distillate as referred to in the present invention is a fraction having a boiling point range of 35 to 350°C, and is a fraction used for gasoline and middle distillates (kerosene, gas oil). The yield of the light fraction is 50
It is more than 70 inches, and even more than 70 inches. The yield of the light fraction is calculated using the following formula, based on the substances at 350° C. or higher in the raw oil.

The dry gas in the present invention refers to hydrogen and hydrocarbons having 1 to 2 carbon atoms (methane, ethane, ethylene).

The dry gas yield (sc, fl bbl ) is generally 400 or less, preferably 250 or less.

The method of the invention will be more clearly understood through the examples given below. Note that the present invention is not limited to these.

Examples 1 to 3 and Comparative Examples 1 to 3 In order to compare the nickel resistance of the catalysts, 6 kg of each of six types of new catalysts (A-F) with different compositions were air-calcined at 600°C for 3 hours and then impregnated with nickel naphthinate. Let's do it, 110
After supporting 000 pp of Ni, steaming was performed at 770° C. for 6 hours (to make the same conditions as the equilibrium catalyst).

4Kt of each steaming treatment catalyst was charged into a circulating flow bench apparatus, reaction temperature was 490C, and regeneration tower temperature was 6301C.
, normal pressure, catalyst/oil field, 7.0, raw material supply rate To(hn
A catalytic cracking reaction of Sumatralite atmospheric distillation residue oil was carried out under conditions of 1/hr. Table 1 shows the physical properties and reaction results of the new catalyst.

The hydrogen/methane ratio is often used as an indicator of metal poisoning.
The higher the ratio, the greater the effect of metal poisoning. Catalyst A, B, C
, D have matrix compositions of Al2O3・MQO
! 9 catalysts, in which the MQO in the matrix
Catalyst #, A, B, and C with a content of 2 wt% or more have a small hydrogen/methane ratio compared to a catalyst with a MgO content of 2 wt % or more and a dry gas (hydrogen, methane, ethylene, ethane). It can be seen that both the yield and the coke yield are extremely low, indicating that the catalyst has high nickel resistance. Also, SiO
Both catalysts E and F, which have a matrix of composition 2.Al2O3 or SiO2.MgO, have high dry gas yields and coke yields, and can be said to be catalysts that are not resistant to nickel.

-568 procedural correction officer May 12, 1981 Mr. Kazuo Wakasugi, Commissioner of the Patent Office 1.Display of the incident 1981 Patent Application No. 22902 2. Name of the invention Heavy oil stream 1TiI + catalytic cracking method 3. Person who makes corrections Relationship to the case Patent applicant Name: Heavy oil countermeasure technology research gathering Detailed description of the invention in the specification 6. Contents of amendment

Claims (2)

[Claims] (1) Total amount of nickel and vanadium: 0.5pp
Heavy oil containing distillation residue containing m or more is subjected to fluid catalytic cracking in the presence of a catalyst containing 3 to 40 wt% of zeolite in an alumina/magnesia matrix with a magnesia content of 2 to 50 wt% in the matrix. A fluid catalytic cracking method for heavy oil, characterized in that the yield of the eaves fraction is 50% or more, and the production of dry gas is extremely small. (2) A patent claim in which the heavy oil is an atmospheric distillation residue oil, a vacuum distillation residue oil, a solvent deasphalted oil, a solvent deasphalted asphalt, or a mixture of any of these and distillate oil from atmospheric distillation or vacuum distillation. The method described in paragraph (1).