JPH04132794A - Preparation of one or more light hydrocarbon oil distillate - Google Patents

Abstract

PURPOSE: To simply obtain a light hydrocarbon oil distillate by applying hydrocracking operation to a first hydrocarbon oil fraction and subsequently applying catalytic cracking operation to a second hydrocarbon oil fraction and separating the latter before applying hydrocracking operation to the residue and the former.

CONSTITUTION: Hydrocracking operation is applied to a first hydrocarbon oil fraction and catalytic cracking operation is applied to a second hydrocarbon oil fraction same to or different from the first hydrocarbon oil fraction and the obtained product is separated into a distillate and residue by distillation. Subsequently, the residue is subjected to hydrocracking operation along with the first hydrocarbon oil fraction and, from the obtained product and the product obtained by the above mentioned catalytic cracking operation, the objective light hydrocarbon oil distillate is isolated.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

[0001]

[Industrial application field]

The present invention is directed to hydrocarbon feedstock oil (FEEDS).
The present invention relates to a method for producing one or more light hydrocarbon oil distillates from tock). [0002]

[Conventional technology]

Atmospheric distillation of crude oil is carried out on a large scale in petroleum refineries to produce light hydrocarbon oil distillates such as gasoline fractions. Residual oil is obtained. The term "gasoline" used herein
means the fraction in the boiling range between the boiling point of n-hebutane and 220° C. at atmospheric pressure. In order to increase the yield of light hydrocarbon oil distillate obtained from crude oil, the following operations can be carried out: obtaining a heavy hydrocarbon oil distillate from said residue by vacuum distillation of said residue; The hydrocarbon oil distillate can be converted into one or more light hydrocarbon oil distillates by subjecting the hydrocarbon oil distillate to a hydrocracking or catalytic cracking operation in a relatively simple manner. can. [0003] Distillate having a boiling point of 180°C to 370°C at atmospheric pressure, ie, middle distillate
The operating method that can respond to the increasing demand for llates) is [
Oil, Gas, Journal J, February 16, 1987 issue, pages 55-66. It has now been discovered that unexpectedly high yields of gasoline fractions of light hydrocarbon distillates can be obtained when hydrocracking and catalytic cracking operations are carried out in combination according to certain methods. Ta. [0004]

[Structure of the invention]

Therefore, the present invention provides the following steps: (a) performing a hydrocracking operation on the first hydrocarbon oil fraction;
b) subjecting a second hydrocarbon oil fraction substantially the same as or different from said first hydrocarbon oil fraction to a catalytic cracking operation; and (c) producing the product obtained in said step (b). (d) adding to the residue obtained in step (c) said first
carrying out a hydrocracking operation in step (a) with the hydrocarbon oil fraction, and (e) carrying out a hydrocracking operation in step (a) and (b) as described above
), the process for producing one or more light hydrocarbon oil distillates, characterized in that one or more light hydrocarbon oil distillates are isolated from the product obtained in It is. [0005] Preferred embodiments of the invention will now be described in detail with reference to the accompanying drawings FIGS. 1 and 2. Identical parts are designated with the same reference numerals in these figures. In the apparatus shown in Figure 1, the heavy hydrocarbon oil distillate enters the hydrocracker (2) via pipe (1), where it is subjected to a hydrocracking reaction (step (a)). The product obtained in the hydrocracker (2) is taken out through the pipe (3),
After being left to stand, it is introduced into the distillation column (4). Distillation column (4
) the gas fraction produced in ) is taken off via pipe (5), the gasoline fraction is taken off through pipe (6), the kerosene fraction is taken off through pipe (7), the gas oil fraction is taken off through pipe (8),
The residue is removed via pipe (9). Hydrogen is fed to the hydrocracker (2) through a pipe (10). Substantially the same heavy hydrocarbon oil distillate (vacuum distillate) is introduced via pipe (11) into a catalytic cracker (12) where the distillate is subjected to a catalytic cracking reaction (step (b
)). The products obtained in the catalytic cracker (12) are removed from there through a pipe (13) and, after standing, are introduced into a distillation column (14). The gasoline fraction obtained in the distillation column (14) is removed therefrom via line (15), and the medium distillate fraction is removed via line (16). The coke-laden catalyst is removed from the catalytic cracker (12) through a pipe (17) for regeneration treatment and then returned to the catalytic cracker (12) through a quantity (not shown). The residue in the distillation column (14) is removed through line (18) and the gas fraction is removed through line 19. The residues in columns (4) and (14) are fed through pipes (18) and (1) to a hydrocracker, where they are subjected to a hydrocracking reaction (step (d)). The residues obtained in steps (a) and (b) are subjected to a hydrocracking reaction in step (d) according to the method described above. It is advantageous to work together with the distillate (vacuum distillate). [0006] The manufacturing apparatus shown in FIG. 2 will be explained. The heavy hydrocarbon distillate (distillate of vacuum distillation) is introduced into the hydrocracker (2) through the pipe (1a) and the pipe (1), and the potash is transferred to the catalytic cracker. (12), tube (1a)
and introduced through tube (11). In this process, the residue obtained from the distillation column (14) is subjected to a hydrocracking reaction in step (a) together with another acidic amount of heavy hydrocarbon oil distillate. On the other hand, the residue obtained in the distillation column (4) is subjected to step (b). By using hydrocrackers and catalytic crackers in the manner described above, gasoline is obtained in unexpectedly high yields. [0007] The hydrocarbon oil fraction to be converted by the method of the present invention is:
It may be any hydrocarbon oil distillate obtained from crude oil (vacuum distillation distillate). Preferably, said hydrocarbon oil distillate (distillate of vacuum distillation) is an oil (distillate of vacuum distillation) having a boiling point range of 220-700° C. under atmospheric pressure. Such oils may be a mixture of gas oils obtained by vacuum distillation (ie distillation under pressure below atmospheric pressure) and gas oils obtained by atmospheric distillation. The hydrocarbon oil fraction to be converted by the process of the invention contains at least one substance having a boiling point above 540°C.
It is preferable that the content is 0% by weight. According to another preferred embodiment of the process according to the invention, the first hydrocarbon oil fraction used therein is somewhat lighter than the second hydrocarbon oil fraction. Preferably, the first hydrocarbon oil fraction contains no more than 10 substances having a boiling point above 540°C.
% by weight, examples of which include relatively light hydrocarbon oil distillates obtained by vacuum distillation, whereas the second hydrocarbon oil fraction is preferably Examples include relatively heavy hydrocarbon oil distillates obtained by vacuum distillation. [0008] Preferably, the product obtained in step (a) is separated by distillation into one or more distillates and a residue;
The residue, together with a second hydrocarbon oil fraction, is then subjected to step (
In b) a catalytic cracking operation is carried out. In another preferred embodiment of the process according to the invention, the product obtained in step (a) is separated by distillation into one or more distillates and a residue, and the residue is subsequently subjected to step (a). The hydrocracking operation of a) is carried out together with the residue obtained in step (b) and the first hydrocarbon oil fraction. [0009] The hydrocracking operation of step (a) is carried out using a catalyst system. The catalyst system consists of one or more catalysts containing at least one metal selected from the group consisting of Ni, Mo and Co on a carrier (preferably alumina). Generally, the hydrocracking operation of step (a) is carried out in the presence of hydrogen at a temperature of 350-450°C and a pressure of 1O-500ON.
1-kg'. Highly preferred catalysts are cobalt and molybdenum on alumina and nickel and molybdenum on alumina. When carrying out the hydrocracking operation of step (a), a stacked-bed catalyst system is arranged, using the aforementioned catalyst as the upper catalyst bed and a metal-containing zeolite (e.g. Y) as the lower catalyst bed. is advantageous. A preferred catalyst for the lower catalyst bed is a catalyst comprising Ni and/or W on zeolite Y. [0010] According to the method of the present invention, a significant portion of the feedstock fed to the catalytic cracker is converted to a distillate type fraction. The catalytic cracking step is preferably carried out in the presence of a zeolite catalyst. Coke is deposited on the catalyst during the process. The coke can be removed from the catalyst by burning the catalyst in a catalyst regeneration step. The regenerated catalyst is returned to the catalytic cracker. The catalytic cracking process is carried out at a temperature of 400
It is advantageous to carry out at -900 DEG C. and a pressure of 1-10 bar. [0011] According to a preferred embodiment of the present invention, the catalytic cracking operation of step (b) comprises applying the second hydrocarbon oil fraction to a zeolite-based catalyst containing zeolite with a pore diameter of 0.3-0.7 nm;
This can be advantageously carried out by contacting at a temperature above 480° C. for a period of less than 10 seconds. By this method, lower olefins (c2-04) can be obtained simultaneously in high yields.
d). Ethylene and propylene are useful starting materials in a variety of chemical processes, while C4 olefins are the starting materials for alkylation and/or oligomerization reactions to produce high octane gasoline and/or medium distillates. Can be used advantageously as a substance. Isobutyne can advantageously be converted to methyl tert-butyl ether. [0012] Preferably, the minimum contact time is 0.1 seconds. Very good results are obtained when the second hydrocarbon oil fraction is brought into contact with the zeolite catalyst for 0.2-6 seconds. The temperature during the catalytic cracking reaction is relatively high. The conversion to olefins is higher when the operation is carried out in combination with the two conditions of high temperature use and short contact time. The preferred temperature range is 480-900°C, - layer preferably 55
It is 0-800°C. [0013] Examples of zeolite-based catalysts used in step (b) include pore diameters of 0.3-0.7 nm (preferably 0.5-0.7 nm).
Catalysts containing one or more zeolites (nm) are mentioned. Furthermore, the catalyst may contain a binder (bin).
It may advantageously contain refractory oxides as material. Examples of suitable refractory oxides include alumina, silica, silica-alumina, magnesia, titania,
Mention may be made of zirconia and mixtures thereof. Alumina is particularly preferred. Preferably, the weight ratio of refractory oxide to zeolite is from 10:90 to 90:10, preferably from 50:50 to 85:15. The zeolite-based catalyst may contain up to about 40% by weight of zeolite having a pore diameter greater than 7 nm. Preferred examples of the zeolite include faujasite-type zeolite, zeolite-beta, zeolite-omega, and
Particularly preferred are zeolites X and Y. Preferred zeolitic catalysts have pore diameters of substantially 0.3-
The catalyst is made of 0.7 nm zeolite. The term "zeolite" used herein is by no means limited to crystalline aluminum silicate. The term "zeolite" also refers to crystalline silica (silicalite) silicoaluminophosphate (SAPO) chromium silicate, gallium silicate, iron silicate, aluminum phosphate (AL
PO) Aluminosilicate, titanium (TAPO), iron aluminosilicate, etc. are also inclusive terms. [0014] Pore diameter 0 that can be used in step (b) of the method of the present invention
．． 3-0.7 nm zeolite example LtSAPO-1
-3! :5APO-11 (U.S. Patent No. 4,440°8
71 Specification) ALPO-11 (U.S. Patent No. 4,3
10,440) TAPO-11 (U.S. Pat. No. 4
, 500,651), TASO-45 (European Patent No. 229,295), boron silicate (US Pat. No. 4,254,297, etc.) and aluminum silicates such as erionite, ferrierite, Theta-type and ZSM-type zeolites (e.g. ZSM-5, ZS
M-11ZSM-12, ZSM-35, ZSM-23,
ZSM-38). Preferably, said zeolite is selected from the group consisting of crystalline metal silicates with ZSM-5 type structure, ferrierite, erionite and mixtures thereof. ZSM-5
Examples of suitable crystalline metal silicates having a type structure include aluminum, gallium, iron, scandium, rhodium and/or as described in GB 2.110559 and others.
Or silicates of similar metals. [0015] The weight ratio (catalyst/oilification: g/g) of the catalyst used in step (b) and the hydrocarbon mixture fraction to be converted can vary within a wide range, e.g. catalyst 150
kg/kg (hydrocarbon mixture fraction) or even higher. [0'016]

【Example】

EXAMPLES In order to specifically illustrate the present invention, examples are shown below. The boiling points described in the examples are the boiling points under atmospheric pressure. Example 1 The following operations were performed using the manufacturing apparatus shown in FIG. The feedstock fed through pipe (1) was a heavy flash distillate of Arabian crude oil, the properties of which were as follows. Initial boiling point 350℃400℃
, Distillation amount: 11% by weight, 500℃, Distillation amount: 65%, Distillation amount: 575℃, Distillation amount
92 end point
650°C The hydrocracking operation in step (a) is carried out at a temperature of 370°C.
°C, pressure 120 bar, 15 square meters per hour
32794 (10). The catalyst system used was of the stacked bed type, the upper bed catalyst comprising 2.8% by weight Ni and 12.8% by weight Mo (based on the total weight of the catalyst) on alumina as a support. and the catalyst in the lower bed is
8.2% by weight of W and N on zeolite Y as support
It contained 2.6% by weight of i (based on the total weight of the catalyst). The surface area of the catalyst in the upper bed is 171 m2/g, the pore volume is 046 ml/g, and the bulk density at consolidation (
That is, the bulk density) was 0.84 g/ml. The surface area of the catalyst in the lower bed is 492 m27 g, and the pore volume is 0.
The bulk density at the time of consolidation was 43 m1/g and 0.64 kg/l. [0017] The same raw material as above was fed through the pipe (11). The catalytic cracking operation in step (b) was performed at a temperature of 530°C, a pressure of 1 bar, and Voorhie severity.
The test was carried out under the condition of s 5everity) 4.5. The zeolite catalyst used was composed of zeolite Y. The surface area of the catalyst is 113m27g
, the pore volume is 0.29 m1/g, and the bulk density is 0.43 m
It was 1/g. The operation of the catalytic cracker (12) was such that the highest yield of gasoline was obtained and the total production of coke was 7% by weight. [0018] By feeding 90 parts by weight of the raw material through tube (1) and 10 parts by weight of the raw material through tube (11), the following various fractions were obtained as products. Gas fraction (tube 5) Gasoline fraction (tube 6) Kerosene fraction (tube 7) Gas oil fraction (tube 8) Residue fraction (tube 9) Gas fraction (tube 19) Gasoline fraction (tube 15) Medium distillate fraction (tube 16) 8.9 parts by weight 57.9 // 15, O // 12.5 // 31.6 // 2.4 // 4.1 // 1.8 SOO- Residue fraction (tube 18) 1. 1 [0019] Example 2 The following operations were performed in the manufacturing apparatus shown in FIG. The same raw materials as in Example 1 were used. The hydrocracking operation in step (a) was carried out in substantially the same manner as in Example 1. The same catalyst as in Example 1 was used in the catalytic cracking operation of step (b), and the operation was carried out at a temperature of 490° C., a pressure of 2 bar and a Ball Heath severity of 2.5. The operation of the catalytic cracker (12) was such that the highest yield of gasoline was obtained and the total production of coke was 4% by weight. [00201 100 parts by weight of raw material was fed through pipe 1a. The following amounts of various fractions were obtained as products: Heavy Flash Distillate Fraction (Tube 1) 90 parts by weight Heavy Flash Distillate Fraction (Tube 11) 1
0? Gas fraction (tube 5)
5.0//Gasoline fraction (6)
18.1 Kerosene fraction (tube 7)
11.5 Kugas oil fraction (tube 8)
15.34 Residue fraction (tube 9)
43.70 gas fraction (tube 19
) 11. l//gasoline (
Tube 15) 30.3//Medium Distillate Fraction (Tube 16) 8.1
Residue fraction (tube 18) 1
,9. .

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of manufacturing equipment used in a preferred embodiment of the invention.

FIG. 2 is a schematic diagram of a manufacturing apparatus used in another preferred embodiment of the present invention.

[Explanation of symbols]

Hydrocracker distillation column Catalytic cracking equipment distillation column

【Document name】

drawing [Figure 1]

[Figure 2]

Claims (10)

[Claims] 1. (a) subjecting a first hydrocarbon oil fraction to a hydrocracking operation; (b) a second hydrocarbon oil fraction that is substantially the same as or different from said first hydrocarbon oil fraction; (c) separating the product obtained in step (b) above into one or more distillates and a residue by distillation; (d) subjecting the oil fraction to a catalytic cracking operation; The residue obtained in step (c) is added with the first
carrying out a hydrocracking operation in step (a) together with the hydrocarbon oil fraction; and (e) producing one or more light hydrocarbon oils from the products obtained in steps (a) and (b) above. A process for producing one or more light hydrocarbon oil distillates, characterized in that the distillate is isolated. 2. Both the first hydrocarbon oil fraction and the second hydrocarbon oil fraction contain at least 10 substances having a boiling point above 540°C.
% by weight. 3. The first hydrocarbon oil fraction contains at most 10% by weight of substances having a boiling point above 540°C, and the second hydrocarbon oil fraction contains substances having a boiling point above 540°C. The method according to claim 1, wherein the content is at least 10% by weight. 4. The product obtained in step (a) is separated by distillation into one or more distillates and a residue, which residue is then combined with a second hydrocarbon oil fraction. The method according to any one of claims 1 to 3, wherein a catalytic cracking operation is carried out in step (b). 5. The product obtained in step (a) is separated by distillation into one or more distillates and a residue, the residue then containing the product obtained in step (b). 4. A process according to claim 1, wherein the residue and the first hydrocarbon oil fraction are subjected to a hydrocracking operation in step (a). 6. Step (a) is carried out at a temperature of 350-450°C and a pressure of 10-300°C.
6. A method according to any one of claims 1-5, carried out in a crowbar. 7. In step (a), a catalyst system is used, the catalyst system comprising at least one metal selected from the group consisting of Ni, Mo and Co on alumina as a support. 7. A method according to any one of claims 1-6. 8. A process according to claim 1, wherein step (b) is carried out at a temperature of 400-900° C. and a pressure of 1-10 bar. 9. The method according to claim 1, wherein a zeolitic catalyst is used in step (b). 10. A light hydrocarbon oil distillate produced by the method according to any one of claims 1-9.