CN110628462B - Hydrocracking and catalytic cracking combined process and device - Google Patents

Hydrocracking and catalytic cracking combined process and device Download PDF

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CN110628462B
CN110628462B CN201910971938.0A CN201910971938A CN110628462B CN 110628462 B CN110628462 B CN 110628462B CN 201910971938 A CN201910971938 A CN 201910971938A CN 110628462 B CN110628462 B CN 110628462B
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catalytic cracking
reactor
hydrocracking
riser
treatment
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CN110628462A (en
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孙世源
孟凡东
闫鸿飞
张亚西
武立宪
李秋芝
张瑞风
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China Petroleum and Chemical Corp
Sinopec Engineering Group Co Ltd
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China Petroleum and Chemical Corp
Sinopec Engineering Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1077—Vacuum residues

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to the technical field of petroleum refining, in particular to a hydrocracking and catalytic cracking combined process and a hydrocracking and catalytic cracking combined device. An integrated hydrocracking and catalytic cracking process comprising the steps of: a) after hydrocracking treatment of a residual oil raw material, collecting heavy oil for catalytic cracking treatment, and collecting diesel oil fraction or gasoline fraction; b) carrying out catalytic cracking treatment on the diesel oil fraction or the gasoline fraction again, and collecting a product; the diesel oil fraction is subjected to hydrofining pretreatment before being subjected to catalytic cracking treatment again; wherein the initial boiling point of the heavy oil is 160-350 ℃. The device comprises a hydrocracking reactor, a catalytic cracking reactor and a fractionation unit; the hydrocracking reactor is connected with the catalytic cracking reactor, and the catalytic cracking reactor is connected with the fractionation unit. The invention can optimize the combined process of hydrocracking and catalytic cracking according to market change, flexibly produce more liquefied gas or gasoline with high added value and improve economic benefit.

Description

Hydrocracking and catalytic cracking combined process and device
Technical Field
The invention relates to the technical field of petroleum refining, in particular to a hydrocracking and catalytic cracking combined process and a hydrocracking and catalytic cracking combined device.
Background
At present, the industrialized residual oil processing technology and combined technology are many, and generally, the selection of the residual oil processing technology should be comprehensively considered according to the residual oil properties, the product requirements, the product price, the economic and environmental requirements and the like. Along with the aggravation of the worldwide trend of crude oil heaviness and deterioration and the continuous increase of imported inferior crude oil, the difficulty of deep processing of heavy oil is more and more, how to economically and reasonably utilize precious petroleum resources, convert the heavy components of the crude oil into clean fuel oil and chemical raw materials which are urgently needed by the market, and improve the utilization rate of the crude oil is a serious challenge for oil refineries.
The residual oil hydrogenation process removes impurities such as sulfur, nitrogen, heavy metals and the like in residual oil through hydrogenation reaction, cracks macromolecular components, is a key technology for realizing clean and efficient conversion of residual oil, and gradually becomes one of the main residual oil processing technical means of refineries. In the residual oil hydrogenation technology, the hydrocracking technology tends to be mature, the utilization rate of the catalyst is high, the residual oil hydrogenation conversion rate is high, the application field is continuously expanded, and the method is a preferred technology for processing high carbon residue and high metal vacuum residual oil in the future.
However, the hydrogenation apparatus has a large investment at one time, a high operation cost, and poor economy, and reducing the process cost has become an important issue for all petroleum companies in the world. The residue hydrogenation-catalytic cracking combined process takes hydrogenated distillate oil as a catalytic cracking raw material, compensates by the higher product yield and quality of catalytic cracking and the lower operation cost, reduces the overall cost, and is a direction for the development of residue lightening technology.
The existing hydrocracking and catalytic cracking combined process mainly focuses on the aspects of saving equipment investment, reducing operation cost and the like, and researches on optimizing the hydrocracking-catalytic cracking combined process and improving the yield of high value-added products are not carried out. The hydrocracking raw material is more inferior, the property difference of the hydrocracking tail oil is larger than that of the conventional catalytic cracking raw material oil and the fixed bed hydrotreating tail oil, and the hydrocracking tail oil is processed by the conventional catalytic cracking technical means, so that the economic benefit of the hydrocracking-catalytic cracking combined process cannot be optimized.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a hydrocracking and catalytic cracking combined process to solve the technical problems of low yield of products with high added values and low economic benefit in the prior art.
The second purpose of the invention is to provide a hydrocracking and catalytic cracking combined device which has simple structure, relatively low operation cost and good economic benefit.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the combined hydrocracking and catalytic cracking process includes the following steps:
a) after hydrocracking treatment of a residual oil raw material, collecting heavy oil for catalytic cracking treatment, and collecting diesel oil fraction or gasoline fraction;
b) carrying out catalytic cracking treatment on the diesel oil fraction or the gasoline fraction again, and collecting a product; the diesel oil fraction is subjected to hydrofining pretreatment before being subjected to catalytic cracking treatment again;
wherein the initial boiling point of the heavy oil is 160-350 ℃.
The invention utilizes the hydrocracking and catalytic cracking combined process to process the inferior residual oil, optimizes the combined process of hydrocracking and catalytic cracking, can flexibly produce more liquefied gas or gasoline with high added value according to actual requirements, and obtains the maximum economic benefit.
The raw material subjected to catalytic cracking treatment in the invention can include or not include diesel oil fraction, taking the diesel oil fraction as an example, after the raw material is subjected to catalytic cracking treatment, the yield of catalytic diesel oil is higher compared with the raw material not including the diesel oil fraction, the diesel oil subjected to hydrofining is high in yield, the hydrofined diesel oil is subjected to catalytic cracking again, the processing amount of the catalytic cracking treatment again is obviously improved, the yield of the produced gasoline is higher, and therefore, the gasoline with high added value is produced in a large amount. Taking the fraction without diesel oil as an example, after the raw material is subjected to catalytic cracking treatment, compared with the raw material comprising the diesel oil fraction, the catalytic gasoline has high catalytic gasoline yield and gasoline olefin content, the catalytic gasoline is subjected to secondary catalytic cracking, so that the processing amount of the secondary catalytic cracking treatment is obviously improved, the yield of the produced liquefied gas is higher, and the liquefied gas with high added value is produced more.
In one or more embodiments of the invention, in the step a), heavy oil with an initial boiling point of 160-240 ℃ is collected for catalytic cracking treatment, and diesel oil fraction is collected.
In one or more embodiments of the invention, in the step a), heavy oil with a primary boiling point of 300-350 ℃ is collected for catalytic cracking treatment, and a gasoline fraction is collected.
The combined process of the invention can be selected and adjusted according to actual requirements, as follows.
When the gasoline demand is more vigorous, the combined process comprises the following steps:
a) after hydrocracking treatment of the residual oil raw material, collecting heavy oil for catalytic cracking treatment, and separating and collecting diesel oil fraction;
b) after the diesel fraction is subjected to hydrofining pretreatment, carrying out catalytic cracking treatment again, and collecting a product;
wherein the initial boiling point of the heavy oil is 160-240 ℃.
In one or more preferred embodiments, the diesel fraction in the product is separated and the operation in step b) is repeated. The diesel oil fraction in the product is subjected to hydrofining pretreatment again and then catalytic cracking treatment again, so that the gasoline quantity can be further improved, the diesel oil mixing amount can be reduced, and the diesel-gasoline ratio can be reduced.
When the demand of liquefied gas and other chemical products is more vigorous, the combined process comprises the following steps:
a) after hydrocracking treatment of a residual oil raw material, collecting heavy oil for catalytic cracking treatment, and separating and collecting gasoline fraction;
b) carrying out catalytic cracking treatment on the gasoline fraction again, and collecting a product;
wherein the initial boiling point of the heavy oil is 300-350 ℃.
In one or more preferred embodiments, the gasoline fraction of the product is separated and the operation in step b) is repeated.
The gasoline fraction separated from the product is subjected to catalytic cracking treatment again, so that the liquefied gas amount can be further increased, and high-octane gasoline, vehicle diesel and the like can be produced.
In one or more embodiments of the present invention, in step a), the conditions of the catalytic cracking process comprise: 450-600 ℃, preferably 480-550 ℃.
In one or more embodiments of the invention, the conditions of the second catalytic cracking treatment in step b) include: 430 to 650 ℃, preferably 500 to 600 ℃.
In one or more embodiments, the catalytic cracking processes in steps a) and b) may be performed in a main-riser catalytic cracking reactor and a secondary-riser catalytic cracking reactor, respectively.
The catalyst for catalytic cracking treatment may be a conventional catalyst for catalytic cracking treatment. In one or more embodiments of the invention, the catalytic cracking treated catalyst includes a silica-alumina catalyst, a silica-magnesium catalyst, an acid treated clay, and a molecular sieve catalyst, preferably a molecular sieve catalyst, such as X-type, Y-type, ZSM-5, M-type, layered column, and the like.
The catalytic cracking treated catalyst may be regenerated. The medium used for regeneration is air. The regeneration conditions include: 600-800 ℃, preferably 650-750 ℃, and the weight ratio of the oil to the solvent is 2-30, preferably 4-10; the contact time of the medium and the catalyst is 0.1-15.0 seconds, preferably 0.5-5.0 seconds; the pressure is 0.1-0.5 MPa.
In one or more embodiments of the present invention, the resid feedstock is a vacuum resid. Preferably, the content of H in the vacuum residue is 9.5-10.5%, and the content of carbon residue is 20-25%. The vacuum residue has low H content, high carbon residue, poor quality of the vacuum residue and low added value. The combined process of the invention can be used for processing the residual oil with poor quality, and products with high added values are produced, thereby having remarkable economic benefit.
In one or more embodiments of the present invention, the hydrocracking conditions include: the reaction pressure is 6-20 MPa, the reaction temperature is 350-480 ℃, and the liquid hourly space velocity is 0.1-5.0 h-1The volume ratio of hydrogen to oil (under standard conditions) is 300-1000. Preferably, the hydrocracking conditions include: the reaction pressure is 15-20 MPa, the reaction temperature is 420-470 ℃, and the liquid hourly space velocity is 0.5-2.0 h-1(ii) a The volume ratio of hydrogen to oil (under standard conditions) is 400-1000.
In practice, the catalyst employed for hydrocracking may be a conventional hydrocracking treatment catalyst. As in the various embodiments, the active metal in the hydrocracking treatment catalyst may be one or more of nickel, cobalt, molybdenum or tungsten. In one or more embodiments, the hydrocracking treatment catalyst may include, in weight percent: 1 to 10 percent of nickel or cobalt (calculated by oxide), 2 to 30 percent of molybdenum or tungsten (calculated by oxide), and the carrier is selected from one or more of alumina, silica, alumina-silica or titanium oxide. After the hydrocracking treatment catalyst is formed, the bulk density is 0.4-0.9 g/cm3The diameter is 0.08-1.2 mm, and the specific surface area is 100-300 m2/g。
The residual oil raw material is mixed with hydrogen after being pressurized and enters a hydrocracking reactor, and the mixture is contacted with a hydrocracking treatment catalyst, so that part of impurities such as metal, sulfur, nitrogen and the like in the residual oil raw material can be removed, the carbon residue value of the raw material is reduced, and the feeding requirement of downstream catalytic cracking treatment is met to a certain extent.
In a preferred embodiment of the present invention, the conditions of the hydrofinishing pretreatment include: the reaction temperature is 320-390 ℃, the hydrogen partial pressure is 5.0-10.0 MPa, and the volume space velocity is 0.5-1.5 h-1The volume ratio of hydrogen to oil is 300-800: 1. In one or more embodiments, the hydrofinishing pretreatment can employ a fixed bed hydrogenation process.
The catalyst for the hydrofining pretreatment can adopt a conventional hydrofining catalyst. In a preferred embodiment of the present invention, the active metal in the hydrofinishing catalyst comprises one or more of nickel, cobalt, molybdenum or tungsten. Wherein the mass of the active metal is 12-30%.
In a preferred embodiment of the invention, the diesel fraction and the gasoline fraction are collected by means of fractional distillation.
And separating and collecting the product by fractional distillation. According to actual requirements, dry gas, liquefied gas, gasoline, diesel oil and/or oil slurry and the like in the product are separated and collected.
The invention also provides a hydrocracking and catalytic cracking integrated device, which comprises a hydrocracking reactor, a catalytic cracking reactor and a fractionating unit;
the hydrocracking reactor is connected with the catalytic cracking reactor, and the catalytic cracking reactor is connected with the fractionation unit.
The device has simple structure, can change the processing technology according to the actual requirement, and does not need to repeatedly reform the unit of the device.
In one or more embodiments of the present invention, at least two catalytic cracking reactors are included. For example, the catalytic cracking reactor is a dual riser catalytic cracking reactor, including a main riser catalytic cracking reactor and a secondary riser catalytic cracking reactor.
The fractionation unit may be a fractionation column. When the fractionating unit comprises a fractionating tower, the catalytic cracking reactor is a double-riser catalytic cracking reactor, the hydrocracking reactor is connected to the main riser catalytic cracking reactor, the main riser catalytic cracking reactor is connected to the fractionating tower, the fractionating tower is connected to the auxiliary riser catalytic cracking reactor, and the auxiliary riser catalytic cracking reactor is connected to the fractionating tower.
In one or more embodiments of the invention, the fractionation unit includes at least two fractionation columns, a main fractionation column and a sub-fractionation column.
In one or more embodiments of the present invention, the hydrocracking reactor is connected to the main riser catalytic cracking reactor, the main riser catalytic cracking reactor is connected to the main fractionation column, the main fractionation column is connected to the secondary riser catalytic cracking reactor, and the secondary riser catalytic cracking reactor is connected to the secondary fractionation column.
In one or more embodiments of the invention, the discharge port of the secondary riser catalytic cracking reactor is connected to the feed port of the secondary fractionating tower, and the discharge port of the secondary fractionating tower is connected to the feed port of the secondary riser catalytic cracking reactor.
In one or more embodiments of the present invention, further comprising a separator coupled to the hydrocracking reactor and the catalytic cracking reactor.
The separator separates the products after reaction in the hydrocracking reactor, and the heavy oil is sent into the catalytic cracking reactor for catalytic cracking reaction.
The invention also provides another hydrocracking and catalytic cracking integrated device, which also comprises a hydrofining reactor;
the fractionating unit is connected to the hydrofining reactor, and the hydrofining reactor is connected to the catalytic cracking reactor.
The device has simple structure, can change the processing technology according to the actual requirement, and does not need to repeatedly reform the unit of the device.
When the fractionating unit comprises a fractionating tower, the catalytic cracking reactor is a double-riser catalytic cracking reactor, the hydrocracking reactor is connected to the main riser catalytic cracking reactor, the main riser catalytic cracking reactor is connected to the fractionating tower, the fractionating tower is connected to the hydrofining reactor, the hydrofining reactor is connected to the auxiliary riser catalytic cracking reactor, and the auxiliary riser catalytic cracking reactor is connected to the fractionating tower.
In one or more embodiments of the invention, the main fractionation column is connected to the hydrofinishing reactor, which is connected to the secondary riser catalytic cracking reactor.
In one or more embodiments of the invention, the secondary fractionation column is connected to the hydrofinishing reactor.
The secondary fractionating tower is connected with the hydrofining reactor, and can send the diesel fraction obtained by fractionation into the hydrofining reactor for hydrofining pretreatment.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method utilizes a hydrocracking and catalytic cracking combined process to process the inferior residual oil, flexibly produces more liquefied gas or gasoline with high added value by optimizing the combined process of hydrocracking and catalytic cracking according to market change at lower processing cost, and improves economic benefit;
(2) the process of the invention can avoid the device reconstruction, and avoids the cost increase caused by the large device reconstruction for adapting the process;
(3) the device has simple structure, can perform connection mode conversion and the like on the basis of the conventional device, does not need large transformation, and has low cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of a hydrocracking and catalytic cracking integrated unit according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a hydrocracking and catalytic cracking integrated unit according to another embodiment of the present invention.
Reference numerals:
1-residuum feedstock line; 2-a hydrocracking reactor; 3-a first heavy oil line;
4-a main riser catalytic cracking reactor; 5-a first effluent line; 6-main fractionation column;
7-a first gas line; 8-a first gasoline line; 9-a first diesel line;
10-a first slurry line; 11-a hydrofining reactor; 12-a first distillate line;
13-auxiliary riser catalytic cracking reactor; 14-a second effluent line; 15-a secondary fractionation column;
16-a second gas line; 17-a second gasoline line; 18-a second diesel line;
19-a second slurry line; 20-a separator; 21-a light ends line;
22-second heavy oil line.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The invention provides a hydrocracking and catalytic cracking integrated device, which comprises: a hydrocracking reactor, a catalytic cracking reactor and a fractionating unit; the hydrocracking reactor is connected with the catalytic cracking reactor, and the catalytic cracking reactor is connected with the fractionation unit.
Optionally, the apparatus comprises at least two catalytic cracking reactors. For example, the catalytic cracking reactor is a dual riser catalytic cracking reactor, including a main riser catalytic cracking reactor and a secondary riser catalytic cracking reactor.
Optionally, the fractionation unit is a fractionation column. When the fractionating unit comprises a separation tower, the catalytic cracking reactor is a double-riser catalytic cracking reactor, the hydrocracking reactor is connected to the main riser catalytic cracking reactor, the main riser catalytic cracking reactor is connected to the fractionating tower, the fractionating tower is connected to the auxiliary riser catalytic cracking reactor, and the auxiliary riser catalytic cracking reactor is connected to the fractionating tower.
Optionally, the fractionation unit comprises at least two fractionation columns, namely a main fractionation column and a sub-fractionation column.
Further, the hydrocracking reactor is connected to the main riser catalytic cracking reactor, the main riser catalytic cracking reactor is connected to the main fractionating tower, the main fractionating tower is connected to the auxiliary riser catalytic cracking reactor, and the auxiliary riser catalytic cracking reactor is connected to the auxiliary fractionating tower.
Furthermore, a discharge hole of the auxiliary riser catalytic cracking reactor is connected to a feed hole of the auxiliary fractionating tower, and a discharge hole of the auxiliary fractionating tower is connected to a feed hole of the auxiliary riser catalytic cracking reactor.
Optionally, the apparatus further comprises a separator connected to the hydrocracking reactor and the catalytic cracking reactor. The separator separates the products after reaction in the hydrocracking reactor, and the heavy oil is sent into the catalytic cracking reactor for catalytic cracking reaction.
The invention also provides another hydrocracking and catalytic cracking integrated device, which also comprises a hydrofining reactor;
the fractionating unit is connected to the hydrofining reactor, and the hydrofining reactor is connected to the catalytic cracking reactor.
When the fractionating unit comprises a fractionating tower, the catalytic cracking reactor is a double-riser catalytic cracking reactor, the hydrocracking reactor is connected to the main riser catalytic cracking reactor, the main riser catalytic cracking reactor is connected to the fractionating tower, the fractionating tower is connected to the hydrofining reactor, the hydrofining reactor is connected to the auxiliary riser catalytic cracking reactor, and the auxiliary riser catalytic cracking reactor is connected to the fractionating tower.
Optionally, the main fractionation column is connected to the hydrofining reactor, and the hydrofining reactor is connected to the secondary riser catalytic cracking reactor.
Further, the secondary fractionation column is connected to the hydrofining reactor. The secondary fractionating tower is connected with the hydrofining reactor, and can send the diesel fraction obtained by fractionation into the hydrofining reactor for hydrofining pretreatment.
Fig. 1 is a schematic structural diagram of a hydrocracking and catalytic cracking integrated apparatus according to an embodiment of the present invention. The hydrocracking and catalytic cracking integrated unit provided by the embodiment comprises a hydrocracking reactor 2, a main riser catalytic cracking reactor 4, a main fractionating tower 6, a secondary riser catalytic cracking reactor 13 and a secondary fractionating tower 15.
Further, the hydrocracking reactor 2 is connected to the main riser catalytic cracking reactor 4, the main riser catalytic cracking reactor 4 is connected to the main fractionating tower 6 through a first effluent line 5, the main fractionating tower 6 is connected to the secondary riser catalytic cracking reactor 13 through a first gasoline line 8, and the secondary riser catalytic cracking reactor 13 is connected to the secondary fractionating tower 15 through a second effluent line 14.
Further, the secondary fractionation tower 15 is connected to the feed inlet of the secondary riser catalytic cracking reactor 13 through a second gasoline line 17.
Optionally, the apparatus further comprises a separator 20. The hydrocracking reactor 2 is connected to the separator 20 through a first heavy oil line 3, and the separator 20 is connected to the main riser catalytic cracking reactor 4 through a second heavy oil line 22. The separator 20 separates the products after the reaction in the hydrocracking reactor 2, and feeds the heavy oil into the main riser catalytic cracking reactor 4 for catalytic cracking reaction.
Further, the main fractionation tower 6 is further provided and connected with a first gas pipeline 7, a first gasoline pipeline 8 and a first slurry oil pipeline 10, which are respectively used for collecting, transporting and separating the obtained gas, gasoline, slurry oil and the like, and can be sent to a downstream system and the like.
Further, the secondary fractionating tower 15 is further provided and connected with a second gas line 16, a second gasoline line 17 and a second slurry oil line 19, which are respectively used for collecting, transporting and separating the obtained gas, gasoline, slurry oil and the like, and can be sent to a downstream system and the like.
Fig. 2 is a schematic structural diagram of a hydrocracking and catalytic cracking integrated unit according to another embodiment of the present invention. The hydrocracking and catalytic cracking integrated apparatus provided in this embodiment includes a hydrocracking reactor 2, a main riser catalytic cracking reactor 4, a main fractionating tower 6, a hydrofining reactor 11, a sub-riser catalytic cracking reactor 13, and a sub-fractionating tower 15.
Further, the hydrocracking reactor 2 is connected to the main riser catalytic cracking reactor 4, the main riser catalytic cracking reactor 4 is connected to the main fractionating tower 6 through a first effluent pipeline 5, the main fractionating tower 6 is connected to the hydrofining reactor 11 through a first diesel pipeline 9, the hydrofining reactor 11 is connected to the secondary riser catalytic cracking reactor 13 through a first distillate pipeline 12, and the secondary riser catalytic cracking reactor 13 is connected to the secondary fractionating tower 15 through a second effluent pipeline 14.
Optionally, the apparatus further comprises a separator 20. The hydrocracking reactor 2 is connected to the separator 20 through a first heavy oil line 3, and the separator 20 is connected to the main riser catalytic cracking reactor 4 through a second heavy oil line 22. The separator 20 separates the products after the reaction in the hydrocracking reactor 2, and feeds the heavy oil into the main riser catalytic cracking reactor 4 for catalytic cracking reaction.
Further, the secondary fractionation column 15 is connected to the feed port of the hydrofinishing reactor 11 through a second diesel line 18.
Example 1
This example provides a hydrocracking and catalytic cracking integrated process, which is referred to as using the hydrocracking and catalytic cracking integrated apparatus shown in fig. 1, and includes the following steps:
1) after the pressure of the residual oil raw material is increased, the residual oil raw material is mixed with hydrogen and enters a hydrocracking reactor 2 through a residual oil raw material pipeline 1, and the residual oil raw material is contacted with a hydrocracking treatment catalyst to remove partial metal, sulfur, nitrogen and other impurities in the residual oil raw material and reduce the carbon residue value of the raw material; the product in the hydrocracking reactor 2 enters a separator 20, the separator 20 separates light fraction and heavy oil, the heavy oil enters the bottom of the main riser catalytic cracking reactor 4 through a second heavy oil pipeline 22 to perform catalytic cracking reaction, and the light fraction is sent to a downstream system through a light fraction pipeline 21; after the catalytic cracking reaction of the main riser catalytic cracking reactor 4, the product enters a main fractionating tower 6 through a first effluent pipeline 5 for fractionation; the gas, the diesel oil fraction and the slurry oil which are separated by fractionation of the main fractionating tower 6 are respectively collected and sent to a downstream system through a first gas pipeline 7, a first diesel oil pipeline 9 and a first slurry oil pipeline 10, and the gasoline fraction which is separated by fractionation is sent to a secondary riser catalytic cracking reactor 13 through a first gasoline pipeline 8; wherein, the hydrocracking catalyst can be KF-1302, and other hydrocracking catalysts can also be adopted; the catalyst for catalytic cracking treatment can be DFC-1, and other catalytic cracking catalysts can also be adopted;
2) after the gasoline fraction is subjected to catalytic cracking reaction again at the bottom of the auxiliary riser catalytic cracking reactor 13, the product enters an auxiliary fractionating tower 15 through a second effluent pipeline; the gas, the diesel oil fraction and the oil slurry separated by the secondary fractionating tower 15 are respectively collected and sent to a downstream system through a second gas line 16, a second diesel oil line 18 and a second oil slurry line 19;
3) the gasoline fraction separated by the fractionation of the secondary fractionating tower is sent to the secondary riser catalytic cracking reactor 13 through a second gasoline pipeline 17, and the operation in the step 2) is repeated.
Wherein, the properties of the heavy oil (i.e. the reaction raw material fed into the main riser catalytic cracking reactor 4) separated and collected after the residual oil raw material in the step 1) is subjected to the hydrocracking reaction are shown in Table 1, the hydrogenation reaction temperature is 420 ℃, the system pressure is 15MPa, and the liquid hourly volume space velocity is 1.5h-1The volume ratio of hydrogen to oil (under standard conditions) is 800; the reaction conditions in the main riser catalytic cracking reactor 4 and the sub-riser catalytic cracking reactor 13 are shown in table 2; the distribution of the final product collected after the whole procedure is run is shown in table 3; the properties of the gasoline in the final product are shown in table 4.
TABLE 1 heavy oil Properties collected by separation after hydrocracking
Figure BDA0002232371500000131
Figure BDA0002232371500000141
TABLE 2 main operating conditions of catalytic cracking reaction
Figure BDA0002232371500000142
TABLE 3 distribution of the final product
Figure BDA0002232371500000143
TABLE 4 gasoline Properties in the final product
Figure BDA0002232371500000151
Example 2
This example provides a hydrocracking and catalytic cracking integrated process, which is referred to as using the hydrocracking and catalytic cracking integrated apparatus shown in fig. 2, and includes the following steps:
1) after the pressure of the residual oil raw material is increased, the residual oil raw material is mixed with hydrogen and enters a hydrocracking reactor 2 through a residual oil raw material pipeline 1, and the residual oil raw material is contacted with a hydrocracking treatment catalyst to remove partial metal, sulfur, nitrogen and other impurities in the residual oil raw material and reduce the carbon residue value of the raw material; the product in the hydrocracking reactor 2 enters a separator 20, the separator 20 separates light fraction and heavy oil, the heavy oil enters the bottom of the main riser catalytic cracking reactor 4 through a second heavy oil pipeline 22 to perform catalytic cracking reaction, and after the catalytic cracking reaction of the main riser catalytic cracking reactor 4, the product enters a main fractionating tower 6 through a first effluent pipeline 5 to be fractionated; the method comprises the following steps that gas, gasoline and slurry oil which are fractionated and separated by a main fractionating tower 6 are collected and sent to a downstream system through a first gas pipeline 7, a first gasoline pipeline 8 and a first slurry oil pipeline 10 respectively, diesel oil fractions which are fractionated and separated are sent to a hydrofining reactor 11 through a first diesel oil pipeline 9 for hydrofining, double-ring and tri-ring aromatic hydrocarbons in the diesel oil fractions are saturated and converted into saturated hydrocarbons and monocyclic aromatic hydrocarbons, the saturated hydrocarbons are easy to crack, part of cracked diesel oil fractions can enter a gasoline component, the side chains of the monocyclic aromatic hydrocarbons with the side chains are easy to break, the side chains after cracking can partially enter the gasoline component, and the remaining monocyclic aromatic hydrocarbons with shorter side chains just enter the gasoline fraction, wherein the part is a high-octane number gasoline component; after being subjected to hydrofining treatment by a hydrofining reactor 11, a product enters an auxiliary riser catalytic cracking reactor 13 through a first distillate pipeline 12; wherein, the hydrocracking catalyst can be KF-1302, and other hydrocracking catalysts can also be adopted; the catalyst for catalytic cracking treatment can be DFC-1, and other catalytic cracking catalysts can also be adopted; the hydrofining catalyst can be RS-1000, and other hydrofining catalysts can also be adopted;
2) after the hydrorefined product is subjected to catalytic cracking reaction again at the bottom of the auxiliary riser catalytic cracking reactor 13, the product enters an auxiliary fractionating tower 15 through a second effluent pipeline; the gas, the gasoline and the slurry oil separated by the fractionation of the secondary fractionating tower 15 are respectively collected and sent to a downstream system through a second gas line 16, a second gasoline line 17 and a second slurry oil line 19;
3) the diesel fraction separated by the fractionation of the secondary fractionating tower is sent to the secondary riser catalytic cracking reactor 13 through a second diesel pipeline 18, and the operation in the step 2) is repeated.
Wherein, the hydrorefining reactor 11 may adopt a fixed bed hydrogenation reactor.
Wherein, the properties of the heavy oil (i.e. the reaction raw material fed into the main riser catalytic cracking reactor 4) generated after the residual oil raw material in the step 1) is subjected to hydrocracking reaction are shown in Table 5, the hydrogenation reaction temperature is 420 ℃, the system pressure is 15MPa, and the liquid hourly volume space velocity is 1.5h-1The volume ratio of hydrogen to oil (under standard conditions) is 800; the reaction conditions in the main riser catalytic cracking reactor 4 and the sub-riser catalytic cracking reactor 13 are shown in table 6; the distribution of the final product collected after the whole procedure is run is shown in table 7; the properties of the gasoline in the final product are shown in Table 8.
TABLE 5 heavy oil Properties collected by separation after hydrocracking
Figure BDA0002232371500000161
Figure BDA0002232371500000171
TABLE 6 main operating conditions of catalytic cracking reaction
Figure BDA0002232371500000172
TABLE 7 final product distribution
Figure BDA0002232371500000173
Figure BDA0002232371500000181
TABLE 8 gasoline Properties in the Final product
Figure BDA0002232371500000182
Comparative example 1
Comparative example 1 the same residual oil raw material as in example 1 was used in the same hydrocracking treatment by using a conventional hydrocracking-catalytic cracking combined process, and the light diesel oil component in the obtained product was used for blending vehicle diesel oil, and the rest components were fed into a catalytic cracking reactor for cracking reaction, and passed through once, and the products were gas, gasoline, diesel oil and slurry oil. The main operating conditions and product distribution of the catalytic cracking are shown in tables 9 and 10, respectively, and the gasoline properties in the final product obtained are shown in table 11.
TABLE 9 main operating conditions for catalytic cracking reaction
Figure BDA0002232371500000183
TABLE 10 final product distribution
Figure BDA0002232371500000184
Figure BDA0002232371500000191
TABLE 11 Properties of gasoline in the final product
Figure BDA0002232371500000192
Comparative example 2
Comparative example 2 the same residue oil raw material as in example 2 was used in the conventional hydrocracking-catalytic cracking combined process, and after the same hydrocracking treatment, the product was fed into a catalytic cracking reactor for cracking reaction, and passed through in a single pass, and the product was gas, gasoline, diesel oil and slurry oil. The main operating conditions and product distribution of the catalytic cracking are shown in tables 12 and 13, respectively, and the gasoline properties in the final product obtained are shown in table 14.
TABLE 12 main operating conditions for catalytic cracking reactions
Figure BDA0002232371500000193
Figure BDA0002232371500000201
TABLE 13 final product distribution
Figure BDA0002232371500000202
TABLE 14 gasoline Properties in the Final product
Figure BDA0002232371500000203
Compared with the conventional process, the combined hydrocracking and catalytic cracking process disclosed by the invention has the advantages that the yield of liquefied gas is improved by 9.11%, the olefin content of gasoline is reduced from 43.5 v% to 16.0 v%, the olefin content of gasoline is reduced by 27.5 v%, the property of gasoline is obviously improved, and the gasoline can be used as a qualified blending component of vehicle gasoline.
Compared with the conventional process, the hydrocracking and catalytic cracking combined process disclosed by the invention has the advantages that the yield of diesel oil is reduced to 0 from 26.64%, the yield of gasoline is improved by 19.22%, the olefin content of gasoline is reduced by 5%, and the octane number of gasoline is improved by 2 units by comparing example 2 with comparative example 2.
The hydrocracking and catalytic cracking combined process can flexibly and more produce the motor gasoline or liquefied gas with high added value on the premise of not greatly modifying a device, obviously reduces the yield of diesel oil or obviously improves the property of the gasoline, and has obvious economic benefit.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (14)

1. The hydrocracking and catalytic cracking combined process is characterized by comprising the following steps of:
a) after hydrocracking treatment of a residual oil raw material, collecting heavy oil for catalytic cracking treatment, and collecting diesel oil fraction or gasoline fraction;
b) carrying out catalytic cracking treatment on the diesel oil fraction or the gasoline fraction again, and collecting a product; the diesel oil fraction is subjected to hydrofining pretreatment before being subjected to catalytic cracking treatment again;
wherein the initial boiling point of the heavy oil is 160-350 ℃;
in the step a), heavy oil with an initial boiling point of 160-240 ℃ is collected for catalytic cracking treatment, and diesel oil fraction is collected;
in the step a), collecting heavy oil with an initial boiling point of 300-350 ℃ for catalytic cracking treatment, and collecting gasoline fraction;
the device for implementing the hydrocracking and catalytic cracking combined process comprises a hydrocracking reactor, a catalytic cracking reactor and a fractionation unit;
the hydrocracking reactor is connected with the catalytic cracking reactor, and the catalytic cracking reactor is connected with the fractionation unit;
the apparatus further comprises a hydrofinishing reactor; the fractionating unit is connected to the hydrofining reactor, and the hydrofining reactor is connected to the catalytic cracking reactor;
the apparatus further comprises a separator connected to the hydrocracking reactor and the catalytic cracking reactor;
the apparatus comprises at least two catalytic cracking reactors;
the catalytic cracking reactor is a double-riser catalytic cracking reactor and comprises a main riser catalytic cracking reactor and an auxiliary riser catalytic cracking reactor;
the hydrocracking reactor is connected with the main riser catalytic cracking reactor, the main riser catalytic cracking reactor is connected with the fractionation unit, the fractionation unit is connected with the auxiliary riser catalytic cracking reactor, and the auxiliary riser catalytic cracking reactor is connected with the fractionation unit;
the fractionating unit is connected with the auxiliary riser catalytic cracking reactor through the hydrofining reactor.
2. The integrated hydrocracking and catalytic cracking process according to claim 1, wherein a diesel fraction or a gasoline fraction is separated from the product and the operation in step b) is repeated.
3. The integrated hydrocracking and catalytic cracking process according to claim 1, wherein in step a), the catalytic cracking treatment conditions comprise: 450 to 600 ℃.
4. The combined hydrocracking and catalytic cracking process according to claim 1, wherein in the step a), the catalytic cracking treatment is carried out at 480-550 ℃.
5. The integrated hydrocracking and catalytic cracking process according to claim 1, wherein the conditions for the re-catalytic cracking treatment in step b) comprise: 430 to 650 ℃.
6. The combined hydrocracking and catalytic cracking process according to claim 1, wherein in the step b), the condition of the re-catalytic cracking treatment is 500-600 ℃.
7. The integrated hydrocracking and catalytic cracking process of claim 1, wherein the residuum feedstock is a vacuum residuum.
8. The integrated hydrocracking and catalytic cracking process of claim 7, wherein the vacuum residue has a H content of 9.5-10.5% and a residual carbon content of 20-25%.
9. The integrated hydrocracking and catalytic cracking process of claim 1, wherein the hydrofinishing pretreatment conditions comprise: the reaction temperature is 320-390 ℃, the hydrogen partial pressure is 5.0-10.0 MPa, and the volume space velocity is 0.5-1.5 h-1The volume ratio of hydrogen to oil is 300-800: 1.
10. The integrated hydrocracking and catalytic cracking process of claim 1, wherein the fractionation unit comprises a main fractionation column and a sub-fractionation column.
11. The integrated hydrocracking and catalytic cracking process of claim 10, wherein the main riser catalytic cracking reactor is connected to the main fractionator, the main fractionator is connected to the secondary riser catalytic cracking reactor, and the secondary riser catalytic cracking reactor is connected to the secondary fractionator.
12. The integrated hydrocracking and catalytic cracking process of claim 10, wherein the discharge port of the secondary riser catalytic cracking reactor is connected to the feed port of the secondary fractionating tower, and the discharge port of the secondary fractionating tower is connected to the feed port of the secondary riser catalytic cracking reactor.
13. The integrated hydrocracking and catalytic cracking process of claim 10, wherein the main fractionator is connected to the hydrofinishing reactor, and the hydrofinishing reactor is connected to the secondary riser catalytic cracking reactor.
14. The integrated hydrocracking and catalytic cracking process of claim 10, wherein the secondary fractionator is connected to the hydrofinishing reactor.
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