CN115197747A - Method and system for producing more low-carbon olefins - Google Patents
Method and system for producing more low-carbon olefins Download PDFInfo
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- CN115197747A CN115197747A CN202110396618.4A CN202110396618A CN115197747A CN 115197747 A CN115197747 A CN 115197747A CN 202110396618 A CN202110396618 A CN 202110396618A CN 115197747 A CN115197747 A CN 115197747A
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Images
Classifications
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/049—The hydrotreatment being a hydrocracking
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Abstract
The invention relates to the field of petroleum processing, and discloses a method and a system for producing a large amount of low-carbon olefins. The method comprises the following steps: introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone for hydrotreating reaction I, separating a residual oil hydrotreating reaction effluent, introducing catalytic cracking oil slurry and partial hydrogenation slag reduction into a solvent deasphalting zone for solvent deasphalting and separation, introducing first hydrogenated heavy oil and deasphalted oil into a fixed bed wax oil hydrotreating reaction zone for hydrotreating reaction II, separating a wax oil hydrotreating reaction effluent, introducing second hydrogenated heavy oil and the rest hydrogenation slag reduction into a catalytic cracking reaction zone for catalytic cracking reaction, and separating the catalytic cracking reaction effluent to obtain low-carbon olefin. The invention can obviously improve the hydrogenation depth of the residual oil raw material and finally realize the obvious improvement of the yield of the low-carbon olefin high-value product in the combined process.
Description
Technical Field
The invention relates to the field of hydrocarbon oil processing, in particular to a method and a system for producing more low-carbon olefins.
Background
The low-carbon olefin represented by ethylene and propylene is a basic raw material in chemical industry, can be used for producing various organic chemical products, and plays an important role in national economy. In the traditional petrochemical industry, naphtha is mainly used as a raw material to prepare ethylene through steam cracking. However, in recent years, as petroleum prices have been rising and shale gas exploitation technology has been maturing, steam cracking apparatuses using shale gas as a raw material are widely used in north america, and the economics of ethylene cracking processes using naphtha as a raw material have been driven.
Compared with the ethylene product market, the impact of the shale gas revolution on propylene is small, and the gap of the market on propylene is still large. Therefore, in the period of low price of crude oil, the process technology for producing more propylene is developed, and the method has wide application prospect in the future.
Currently, about 60% to 65% of the propylene in the world is produced by steam cracking processes, about 30% of the propylene is produced by catalytic cracking processes (including catalytic cracking processes), and the remainder is produced by processes such as propane dehydrogenation. The main raw materials of the catalytic cracking unit comprise wax oil and residual oil, and have certain advantages in raw material cost.
However, the yield of propylene in the catalytic cracking unit is not high, for example, the yield of propylene in the catalytic cracking unit can reach 20% or even more than 30% by using the intermediate-based hydrogenated wax oil as the raw material, and for example, the yield of propylene in the catalytic cracking unit is usually not more than 20% by using the intermediate-based hydrogenated residual oil as the raw material. In addition, if a residue hydrogenation unit that simply uses hydrogenated residue as a catalytic cracking feedstock needs to operate at a higher reaction severity, the operation cycle or the economy of the residue hydrogenation unit may be affected.
It is necessary to select a proper process route to improve the yield of the catalytic cracking propylene of the residual oil raw material and reduce the operation severity of a catalytic cracking raw material pretreatment device.
CN101045884A discloses a method for producing clean diesel and low-carbon olefins from residual oil and heavy distillate oil, in the method, the residual oil and optional catalytic cracking slurry oil enter a solvent deasphalting unit, the obtained deasphalted oil and optional heavy distillate oil enter a hydrogenation unit, a hydrocracking reaction is carried out in the presence of hydrogen, and the reaction product is separated to obtain light and heavy naphtha fractions, a diesel fraction and hydrogenated tail oil; and (3) the hydrogenated tail oil enters a catalytic cracking unit to carry out catalytic cracking reaction, products are separated to obtain low-carbon olefin, gasoline fraction, diesel oil fraction and slurry oil, all the catalytic cracking diesel oil fraction is recycled to the catalytic cracking reactor, and all or part of the catalytic cracking slurry oil returns to the solvent deasphalting unit. The method organically combines the residual oil solvent deasphalting, the hydrocracking and the catalytic cracking, improves the utilization rate of heavy oil, and produces a part of low-carbon olefin, but the residual oil raw material in the method is not completely used as the raw material for the catalytic cracking, and the yield of the low-carbon olefin is not maximized.
CN101063047A discloses a heavy raw material hydrotreating-catalytic cracking method for improving propylene yield, heavy distillate oil and optional light cycle oil from a catalytic cracking unit can be jointly reacted in one reaction zone, or can be reacted in two hydrogenation reaction zones filled with different hydrogenation catalysts, after cooling, separating and fractionating the reaction effluent, the obtained heavy liquid phase fraction is sent to a catalytic cracking unit, and the catalytic cracking reaction product is separated to obtain the final product. The method provided by the invention is suitable for treating wax oil raw materials, and has the defects of short running period, low impurity removal rate and the like when treating heavy residual oil raw materials.
CN101747935A provides a method for producing low-carbon olefins and monocyclic aromatics from heavy hydrocarbons, in which a wax oil raw material and light and heavy cycle oils of a catalytic cracking device are subjected to hydrogenation reaction in a first reaction zone, a reaction effluent and residual oil are mixed and then enter a second reaction zone for hydrogenation reaction, and a separated hydrogenated heavy fraction enters a catalytic cracking reaction zone for reaction to obtain the required products of low-carbon olefins, monocyclic aromatics and the like. The method widens the source of catalytic cracking raw materials by introducing the residual oil in front of the second reaction zone, increases the processing amount of low-value residual oil, and solves the problem of thermal balance of a catalytic cracking unit.
Disclosure of Invention
The invention aims to overcome the defect of low yield of low-carbon olefin products such as ethylene, propylene and the like in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a method for increasing the production of lower olefins, the method comprising:
(1) In the presence of hydrogen, introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone for hydrotreating reaction I, and separating a residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I is carried out to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated residue reduction;
(2) In the presence of a solvent, introducing the catalytic cracking oil slurry and a part of the hydrogenation slag reduction into a solvent deasphalting area for solvent deasphalting and separation to obtain deasphalted oil and deoiled asphalt;
(3) In the presence of hydrogen, introducing the first hydrogenated heavy oil and the deasphalted oil into a fixed bed wax oil hydrotreating reaction zone for hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after the hydrotreating reaction II is performed to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
(4) Introducing the second hydrogenated heavy oil and the rest part of the hydrogenation slag reduction into a catalytic cracking reaction zone for catalytic cracking reaction, and separating catalytic cracking reaction effluent obtained after the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
(5) And (3) performing at least one operation of an extraction device, a fixed bed wax oil hydrotreating reaction zone and a fixed bed residual oil hydrotreating reaction zone on the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil independently, and circulating the catalytic cracking slurry oil to the solvent deasphalting zone.
In a second aspect, the present invention provides a system for producing more light olefins, the system comprising:
the fixed bed residual oil hydrotreating reaction unit is used for carrying out hydrotreating reaction I on a residual oil raw material to obtain a residual oil hydrotreating reaction effluent;
the first separation unit is used for separating the residual oil hydrotreating reaction effluent to obtain a first gas effluent, a first hydrogenated naphtha, a first hydrogenated heavy oil and hydrogenated slag reduction;
the solvent deasphalting unit is used for performing solvent deasphalting and separation on the catalytic cracking oil slurry and a part of the hydrogenation slag reduction to obtain deoiled asphalt and deasphalted oil;
the fixed bed wax oil hydrotreating reaction unit is used for carrying out hydrotreating reaction II on the first hydrogenated heavy oil and the deasphalted oil to obtain wax oil hydrotreating reaction effluent;
the second separation unit is used for separating the wax oil hydrotreating reaction effluent to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
the catalytic cracking reaction unit is used for carrying out catalytic cracking reaction on the second hydrogenated heavy oil and the rest part of the hydrogenated slag-reducing oil to obtain a catalytic cracking reaction effluent;
a third separation unit for separating the effluent of the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil, and the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are respectively and independently subjected to at least one operation of an extraction device, a circulation back to the fixed bed wax oil hydrotreating reaction zone and a circulation back to the fixed bed residual oil hydrotreating reaction zone, and the catalytic cracking slurry oil is circulated to the solvent deasphalting unit through a pipeline.
The inventor finds that the hydrogenation depth of the residual oil raw material can be obviously improved by organically combining the fixed bed residual oil hydrotreating process, the fixed bed wax oil hydrotreating process, the catalytic cracking process and the solvent deasphalting process, so that the yield of low-carbon olefin products such as propylene, ethylene and the like in the combined process is obviously improved.
Drawings
FIG. 1 is a process flow diagram of a preferred embodiment of the process of the present invention.
Description of the reference numerals
1. Residual oil raw material 2, fixed bed residual oil hydrotreating reaction unit
3. Residual oil hydrotreating reaction effluent 4 and first separation unit
5. First gas effluent 6, first hydrogenated naphtha
7. First hydrogenated heavy oil 8, hydrogenation slag reduction
9. Solvent deasphalting unit 10, deasphalted oil
11. Deoiled asphalt 12 and fixed bed wax oil hydrotreating reaction unit
13. Wax oil hydrotreating reaction effluent 14, second separation unit
15. Second gaseous effluent 16, second hydrogenated naphtha
17. Second hydrogenation heavy oil 18, catalytic cracking reaction unit
19. Catalytic cracking reaction effluent 20, third separation unit
21. Light olefin 22, catalytic cracking naphtha
23. Catalytic cracking light cycle oil 24 and catalytic cracking heavy cycle oil
25. Catalytic cracking slurry oil
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
In the present invention, the pressures are gauge pressures unless otherwise specified.
In the present invention, the particle size of the residue hydrotreating catalyst means the maximum straight-line distance between two different points on the particle cross section, unless otherwise specified. The particle size of the wax oil hydroprocessing catalyst has a similar definition.
In the present invention, the lower olefins include, but are not limited to, ethylene and propylene unless otherwise specified.
In the invention, under the condition of not correspondingly describing, the liquid hourly volume space velocity is the residual oil volume space velocity, namely, the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are not calculated when the volume space velocity is calculated.
As described above, the first aspect of the present invention provides a method for producing a large amount of light olefins, the method comprising:
(1) In the presence of hydrogen, introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone for hydrotreating reaction I, and separating a residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I is carried out to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated residue reduction;
(2) In the presence of a solvent, introducing the catalytic cracking oil slurry and a part of the hydrogenation slag reduction into a solvent deasphalting area for solvent deasphalting and separation to obtain deasphalted oil and deoiled asphalt;
(3) In the presence of hydrogen, introducing the first hydrogenated heavy oil and the deasphalted oil into a fixed bed wax oil hydrotreating reaction zone for hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after the hydrotreating reaction II is performed to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
(4) Introducing the second hydrogenated heavy oil and the rest part of the hydrogenation slag reduction into a catalytic cracking reaction zone for catalytic cracking reaction, and separating catalytic cracking reaction effluent obtained after the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
(5) The catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are respectively and independently subjected to at least one operation of an extraction device, a circulation back to the fixed bed wax oil hydrotreating reaction zone and a circulation back to the fixed bed residual oil hydrotreating reaction zone; and recycling the catalytic cracking slurry oil to the solvent deasphalting area.
The present invention does not require any special treatment for the catalytically cracked naphtha, the catalytically cracked light cycle oil, the catalytically cracked heavy cycle oil, and the catalytically cracked slurry oil, and those skilled in the art can perform the operations known in the art, for example, the catalytically cracked naphtha in the present invention is extracted from the catalytically cracked naphtha extraction apparatus or is hydrotreated to remove sulfides, and then is extracted to obtain monocyclic aromatic hydrocarbons, and the catalytically cracked slurry oil in the present invention can be introduced into the solvent deasphalting zone directly or after being filtered.
The inventor finds that after the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are circulated to the fixed bed wax oil hydrotreating reaction zone and/or the fixed bed residual oil hydrotreating reaction zone for hydrotreating, low-carbon olefins and monocyclic aromatic hydrocarbons can be cracked and generated in the subsequent catalytic cracking reaction zone, so that the yield of low-carbon olefin products is greatly improved.
It is noted that the catalytically cracked slurry oil and at least a portion of the hydrodeoxygenation sludge can also be introduced into the delayed coking reaction zone, either separately or after mixing, depending on the process requirements. In step (3) of the present invention, the first hydrogenated heavy oil and the deasphalted oil can be introduced into the fixed bed wax oil hydrotreating reaction zone separately or after being mixed according to the process requirements. In step (4) of the present invention, the second hydrogenated heavy oil and the remaining part of the hydrogenated slag-reduction can also be introduced into the catalytic cracking reaction zone separately or after being mixed according to the process requirements.
Preferably, in step (1), the residue feedstock is selected from at least one of atmospheric residue, vacuum residue.
Preferably, in step (1), the reaction conditions of the fixed bed residue hydrotreating reaction zone include: the reaction temperature is 300-460 ℃, the hydrogen partial pressure is 6-25MPa, and the liquid hourly space velocity is 0.10-1.0h -1 Of hydrogenThe oil volume ratio is 100-1500.
More preferably, in step (1), the reaction conditions of the fixed bed residue hydrotreating reaction zone include: the reaction temperature is 350-440 ℃, the hydrogen partial pressure is 12-20MPa, and the liquid hourly space velocity is 0.15-0.4h -1 The volume ratio of hydrogen to oil is 300-1000.
Preferably, in the step (1), the fixed bed residue hydrotreating reaction zone is filled with a residue hydrotreating catalyst having an average particle diameter of 0.5 to 50mm and a bulk density of 0.3 to 1.2g/cm 3 The average pore diameter is 6-30nm, the specific surface area is 50-400m 2 /g。
Preferably, in step (1), the residue hydrotreating catalyst is selected from at least one of a protecting catalyst I, a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodecarbonization catalyst.
Preferably, the fixed bed residue oil hydrotreating reaction zone is sequentially filled with the protection catalyst I, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydrodecarbon residue catalyst along the material flow direction.
More preferably, the loading volume ratio of the protective catalyst I, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydrodecarbonization catalyst is 1:4-8:1-5:2-6.
According to a particularly preferred embodiment, in step (1), the residue hydrotreating catalyst contains a carrier selected from at least one of alumina, silica and titania, and an active metal element selected from a group vib metal element and/or a group viii metal element supported on the carrier.
Preferably, in the residuum hydroprocessing catalyst, the active metal element is selected from at least one of a nickel-tungsten combination, a nickel-tungsten-cobalt combination, a nickel-molybdenum combination, and a cobalt-molybdenum combination.
Preferably, in the residue hydrotreating catalyst, the carrier further contains at least one element of boron, germanium, zirconium, phosphorus, chlorine, and fluorine.
Preferably, the active metal element is present in the residue hydroprocessing catalyst in an amount of 1 to 30wt%, preferably 1 to 25wt%, calculated as oxide, based on the total weight of the residue hydroprocessing catalyst.
In the present invention, the residual oil hydrotreating catalyst may be selected from commercial catalysts conventional in the art or prepared by a conventional method of the prior art, and illustratively, the residual oil hydrotreating catalyst may be an RG series, RDM series, RMS series, RCS series, and RSN series commercial catalysts developed by the institute of petrochemical engineering science, china.
Preferably, in the step (1), the separation conditions of the residue hydrotreating reaction effluent are controlled such that the first hydrogenated naphtha has a first boiling point of 50 to 70 ℃, the first hydrogenated naphtha and the first hydrogenated heavy oil have a cut point of 160 to 180 ℃, and the first hydrogenated heavy oil has a final cut point of 500 to 580 ℃.
Preferably, in step (2), the solvent is C 3 -C 7 Alkane and/or C 3 -C 7 At least one of olefins.
More preferably, in step (2), the solvent is C 4 -C 6 Alkane and/or C 4 -C 6 At least one of olefins.
Preferably, in step (2), the operating conditions of the solvent deasphalting zone comprise: the temperature is 50-260 ℃, the pressure is 1-7MPa, and the volume ratio of the solvent to the hydrogenation slag reduction is 2-12.
More preferably, in step (2), the operating conditions of said solvent deasphalting zone comprise: the temperature is 60-240 ℃, the pressure is 2-6MPa, and the volume ratio of the solvent to the hydrogenation slag reduction is 3-10:1.
preferably, in step (2), the deasphalted oil constitutes from 10 to 80% by weight of the total amount of feedstock introduced into the solvent deasphalting zone.
More preferably, in step (2), the deasphalted oil represents from 30 to 70% by weight of the total amount of feedstock introduced into the solvent deasphalting zone.
Preferably, in step (3), the reaction conditions in the fixed bed wax oil hydrotreating reaction zone and/or the catalyst gradation in the fixed bed wax oil hydrotreating reaction zone are controlled so that the hydrogen content of the reaction effluent of the wax oil hydrotreating reaction is not less than 13.2% by weight, preferably not less than 13.5% by weight. The inventor finds that the yield of the low-carbon olefin product can be higher by adopting the specific implementation mode of the preferable case.
Preferably, in the step (3), the reaction conditions of the fixed bed wax oil hydrotreating reaction zone include: hydrogen partial pressure is 6-25MPa, reaction temperature is 300-460 ℃, liquid hourly space velocity is 0.1-5.0h -1 The volume ratio of hydrogen to oil is 200-2000.
More preferably, in step (3), the reaction conditions of the fixed bed wax oil hydrotreating reaction zone include: hydrogen partial pressure is 10-20MPa, reaction temperature is 350-440 ℃, and liquid hourly space velocity is 0.5-2.0h -1 The volume ratio of hydrogen to oil is 400-1200.
Preferably, in the step (3), the fixed bed wax oil hydrotreating reaction zone is filled with a wax oil hydrotreating catalyst, and the bulk density of the wax oil hydrotreating catalyst is 0.4-1.3g/cm 3 Average particle diameter of 0.5-50mm and specific surface area of 50-400m 2 /g。
According to a particularly preferred embodiment, in step (3), the wax oil hydrotreating catalyst is selected from at least one of the group consisting of the protecting catalyst II, the wax oil hydrofinishing catalyst.
Preferably, the fixed bed wax oil hydrotreating reaction zone is sequentially filled with the protective catalyst II and the wax oil hydrofining catalyst along the material flow direction.
More preferably, the loading volume ratio of the protective catalyst II to the wax oil hydrofining catalyst is 1:9-99.
Preferably, in the step (3), the wax oil hydrotreating catalyst contains a carrier selected from at least one of alumina, a combination of alumina and silica, and titania, and an active metal element supported on the carrier selected from at least one of nickel, cobalt, molybdenum, and tungsten.
More preferably, in the wax oil hydrotreating catalyst, the total content of nickel and cobalt in terms of oxide is 0 to 30wt%, the total content of molybdenum and tungsten in terms of oxide is 0 to 35 wt%, and the sum of the contents of nickel, cobalt, molybdenum and tungsten in terms of oxide is greater than 0, based on the total weight of the wax oil hydrotreating catalyst.
Preferably, in the step (3), the separation conditions of the wax oil hydrotreating reaction effluent are controlled such that the initial boiling point of the second hydrogenated naphtha is 50 to 70 ℃, the cutting points of the second hydrogenated naphtha and the second hydrogenated heavy oil are 160 to 180 ℃, and the final boiling point of the second hydrogenated heavy oil is 500 to 580 ℃.
Preferably, in step (4), the catalytic cracking reaction zone is filled with a catalytic cracking catalyst, and the catalytic cracking catalyst contains zeolite, inorganic oxide, and optionally clay, wherein the inorganic oxide is at least one selected from silica, alumina, zirconia, titania and amorphous silica-alumina, and based on the total weight of the catalytic cracking catalyst, the content of zeolite is 10-50 wt%, the content of inorganic oxide is 5-90 wt%, and the content of clay is 0-70 wt%.
Preferably, in the catalytic cracking catalyst, the zeolite is at least one selected from the group consisting of Y-type zeolite with or without rare earth element, HY-type zeolite with or without rare earth element, ultrastable Y-type zeolite with or without rare earth element, and zeolite having MFI structure.
The present invention is not particularly limited in the apparatus of the catalytic cracking reaction zone and the separation zone, and the catalytic cracking reaction zone and the separation zone may use a conventional catalytic cracking system, and exemplarily may include a reactor, a regenerator and a fractionation system and an absorption stabilization system, in the form of a combined reactor composed of a riser and a dense-phase fluidized bed.
According to a particularly preferred embodiment, in step (4), the reaction conditions of the catalytic cracking reaction zone are: the weight ratio of the atomizing steam to the residual oil raw material is 0.05-0.5:1, the weight ratio of agent oil is 6-20:1, the temperature is 500-68 DEG C0 ℃, the weight hourly space velocity of 1-6h -1 The reaction pressure is 0.05-1MPa.
In the present invention, the weight ratio of the solvent to the oil is the weight ratio of the sum of the catalytic cracking catalyst and the total weight of the feedstock introduced into the catalytic cracking reaction zone, unless otherwise specified. Wherein the raw material of the catalytic cracking reaction zone comprises the second hydrogenated wax oil and the rest part of the hydrogenated slag reduction.
Preferably, in the step (4), the separation conditions of the catalytic cracking reaction effluent are controlled, so that the initial boiling point of the catalytic cracking light cycle oil is 150-180 ℃, the cutting points of the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are 340-360 ℃, and the final boiling point of the catalytic cracking heavy cycle oil is 500-580 ℃.
Preferably, in step (4), the hydrogenated slag reduction introduced into the catalytic cracking reaction zone is 5 to 95 wt%, preferably 20 to 80 wt%, based on the total weight of the hydrogenated slag reduction.
Preferably, the method further comprises: and separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha.
The present invention has no particular requirements for the subsequent treatment of the light naphtha and the heavy naphtha, and the person skilled in the art can use the operation known in the art to carry out the subsequent treatment, for example, the light naphtha of the present invention can be introduced into the catalytic cracking reaction zone to carry out the catalytic cracking reaction, and the heavy naphtha is led out of the device to be used as the raw material for extracting the aromatic hydrocarbon.
Preferably, the separation conditions of the first and/or second hydrogenated naphtha are controlled such that the light naphtha has a first boiling point in the range of 50 to 70 ℃, the light and heavy naphthas have a cut point in the range of 120 to 140 ℃ and the heavy naphtha has a final cut point in the range of 170 to 190 ℃.
As previously mentioned, a second aspect of the present invention provides a system for the high yield of lower olefins, the system comprising:
the fixed bed residual oil hydrotreating reaction unit is used for carrying out hydrotreating reaction I on a residual oil raw material to obtain a residual oil hydrotreating reaction effluent;
the first separation unit is used for separating the residual oil hydrotreating reaction effluent to obtain a first gas effluent, a first hydrogenated naphtha, a first hydrogenated heavy oil and hydrogenated slag reduction;
the solvent deasphalting unit is used for performing solvent deasphalting and separation on the catalytic cracking oil slurry and a part of the hydrogenation slag reduction to obtain deoiled asphalt and deasphalted oil;
the fixed bed wax oil hydrotreating reaction unit is used for carrying out hydrotreating reaction II on the first hydrogenated heavy oil and the deasphalted oil to obtain wax oil hydrotreating reaction effluent;
the second separation unit is used for separating the wax oil hydrotreating reaction effluent to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
the catalytic cracking reaction unit is used for carrying out catalytic cracking reaction on the second hydrogenated heavy oil and the rest part of the hydrogenated slag-reducing oil to obtain a catalytic cracking reaction effluent;
a third separation unit, configured to separate the catalytic cracking reaction effluent to obtain a low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil, and catalytic cracking slurry oil, where the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are each independently subjected to at least one operation of an extraction device, a circulation back to the fixed bed wax oil hydrotreating reaction zone, and a circulation back to the fixed bed residue hydrotreating reaction zone; and recycling the catalytic cracking slurry oil to the solvent deasphalting unit through a pipeline.
Preferably, the fixed bed residue hydroprocessing reaction unit comprises at least 1 fixed bed reactor.
According to a particularly preferred embodiment, the fixed bed residue hydroprocessing reaction unit comprises 3 to 6 fixed bed reactors.
Preferably, the fixed bed wax oil hydrotreating reaction unit includes at least 1 fixed bed reactor.
According to a particularly preferred embodiment, the fixed bed wax oil hydroprocessing reaction unit comprises 1-3 fixed bed reactors.
Preferably, the system further comprises: and the fourth separation unit is used for separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha.
The following provides a process flow of a preferred embodiment of the method for producing more light olefins according to the present invention with reference to fig. 1:
(1) In the presence of hydrogen, introducing a residual oil raw material 1 into a fixed bed residual oil hydrotreating reaction unit 2 for hydrotreating reaction I, and introducing a residual oil hydrotreating reaction effluent 3 obtained after the hydrotreating reaction I into a first separation unit 4 for separation to obtain a first gas effluent 5, a first hydrogenated naphtha 6, first hydrogenated heavy oil 7 and hydrogenated slag reduction 8;
(2) In the presence of a solvent, introducing the catalytic cracking slurry oil 25 and a part of the hydrogenation residue reduction 8 into a solvent deasphalting unit 9 for solvent deasphalting and separation to obtain deasphalted oil 10 and deoiled asphalt 11;
(3) In the presence of hydrogen, introducing the first hydrogenated heavy oil 7 and the deasphalted oil 10 into a fixed bed wax oil hydrotreating reaction unit 12 for hydrotreating reaction II, and introducing a wax oil hydrotreating reaction effluent 13 obtained after the hydrotreating reaction II into a second separation unit 14 for separation to obtain a second gas effluent 15, a second hydrogenated naphtha 16 and a second hydrogenated heavy oil 17;
(4) Introducing the second hydrogenated heavy oil 17 and the rest part of the hydrogenated slag reduction 8 into a catalytic cracking reaction unit 18 for catalytic cracking reaction, and introducing a catalytic cracking reaction effluent 19 obtained after the catalytic cracking reaction into a third separation unit 20 for separation to obtain low-carbon olefin 21, catalytic cracking naphtha 22, catalytic cracking light cycle oil 23, catalytic cracking heavy cycle oil 24 and catalytic cracking slurry oil 25;
(5) And (3) performing at least one operation of leading-out equipment, circulating the catalytic cracking light cycle oil 23 and the catalytic cracking heavy cycle oil 24 back to the fixed bed wax oil hydrotreating reaction unit 12 and the fixed bed residual oil hydrotreating reaction unit 2 independently, and circulating the catalytic cracking slurry oil 25 back to the solvent deasphalting unit 9.
The method of the invention also has the following specific advantages:
1. the invention adopts 100 percent of residual oil raw materials (normal slag and/or slag reduction) to produce high-quality catalytic cracking raw materials, and can reduce the cost of raw materials for producing low-carbon olefin to the maximum extent.
2. The invention realizes deep hydrogenation on wax oil fraction contained in residual oil raw material, first hydrogenated heavy oil cracked in residual oil hydrotreating reaction, deasphalted oil, catalytic cracking light cycle oil and catalytic cracking heavy cycle oil, thereby providing higher-quality raw material for catalytic cracking.
3. The residual oil hydrotreating reaction zone can be operated under the conventional residual oil hydrogenation process condition, does not need to be operated under high severity for producing catalytic cracking raw materials, and is favorable for long-period operation of a residual oil hydrogenation device.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used unless otherwise specified are commercially available.
In the following examples, without corresponding indications:
the hydrotreating reaction I is carried out in a medium-sized device for hydrotreating residual oil in a fixed bed;
the hydrotreating reaction II is carried out in a medium-sized fixed bed wax oil hydrotreating device;
the catalytic cracking reaction is carried out in a catalytic cracking medium-sized apparatus.
The resid feed is a middle east resid, the properties of which are shown in table 1.
In a fixed bed residual oil hydrotreating reaction zone, a catalyst A, a catalyst B, a catalyst C and a catalyst D are sequentially filled along the material flow direction, wherein the filling volume ratio of the catalyst A to the catalyst B to the catalyst C to the catalyst D is 5:40:25:30;
in the solvent deasphalting zone, the solvent is pentane;
in a fixed bed wax oil hydrotreating reaction zone, a catalyst A and a catalyst E are sequentially filled along the material flow direction, and the filling volume ratio of the catalyst A to the catalyst E is 5:95;
the catalysts A-E are all produced by ChangLing catalyst factories, china petrochemical catalyst division, and the properties thereof are shown in Table 2;
wherein, the catalyst A is a protective catalyst, the catalyst B is a hydrodemetallization catalyst, the catalyst C is a hydrodesulfurization catalyst, the catalyst D is a hydrodecarbonization catalyst, and the catalyst E is a wax oil hydrotreating catalyst.
The catalytic cracking catalyst is MMC-2, which is produced by Qilu division of China petrochemical Co., ltd, and the properties of the catalyst MMC-2 are shown in Table 3.
The dry gas and the liquefied gas are rectified to obtain low-carbon olefins such as ethylene, propylene and the like.
In the following examples, the feed and product flow rates to each reaction zone are calculated (without hydrogen) based on 100g/h of fresh residuum feed without corresponding indication.
Table 1: residual oil feedstock properties
| Properties of | |
| Density (20 ℃ C.), g/cm 3 | 0.9747 |
| Hydrogen content, wt.% | 11.16 |
| Carbon residueContent by weight% | 10.34 |
| Sulfur content, wt.% | 3.56 |
| Nitrogen content, wt.% | 0.24 |
| (Nickel + vanadium) content, μ g/g | 60.6 |
Table 2: composition and physicochemical properties of residual oil hydrotreating catalyst and wax oil hydrotreating catalyst
| Item | Catalyst A | Catalyst B | Catalyst C | Catalyst D | Catalyst E |
| MO 3 To weight percent | 3.0 | 8.4 | 13.0 | 16.2 | 2.3 |
| NiO, wt.% | 0.8 | 1.5 | 3.5 | 4.5 | 2.4 |
| WO 3 To weight percent | - | - | - | - | 26.0 |
| Pore volume, mL/g | 0.80 | 0.66 | 0.64 | 0.64 | 0.28 |
| Specific surface area, m 2 /g | 100 | 157 | 210 | 186 | 150 |
| Bulk density, g/cm 3 | 0.45 | 0.47 | 0.62 | 0.64 | 0.82 |
| Particle size, mm | 3.5 | 1.1 | 1.1 | 1.1 | 1.1 |
Table 3: catalytic cracking catalyst Properties
Example 1
The embodiment provides a method for producing more light olefins, which comprises the following steps:
(1) In the presence of hydrogen, introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone filled with a residual oil hydrotreating catalyst to carry out hydrotreating reaction I, and separating a residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I is carried out to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated slag reduction; wherein the cut point of the first hydrogenated naphtha and the first hydrogenated heavy oil is 175 ℃;
(2) Introducing the catalytic cracking slurry oil and 50 wt% of the hydrogenation slag reduction into a solvent deasphalting area containing a solvent for solvent deasphalting and separation to obtain deasphalted oil and deoiled asphalt;
(3) In the presence of hydrogen, introducing the first hydrogenated heavy oil and the deasphalted oil into a fixed bed wax oil hydrotreating reaction zone filled with a wax oil hydrotreating catalyst to perform a hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after the hydrotreating reaction II is performed to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil; wherein the cut point of the second hydrogenated naphtha and the second hydrogenated heavy oil is 175 ℃;
(4) Introducing the second hydrogenated heavy oil and 50 wt% of the hydrogenation residue as raw materials for catalytic cracking into a catalytic cracking reaction zone filled with a catalytic cracking catalyst for catalytic cracking reaction, and separating catalytic cracking reaction effluent obtained after the catalytic cracking reaction to obtain dry gas, liquefied gas, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil; the cutting point of the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil is 350 ℃, the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are led out of the device in a circulating mode, and the catalytic cracking slurry oil is circulated back to the solvent deasphalting area.
The reaction conditions and the product distribution of the fixed bed residue oil hydrotreating reaction zone are shown in table 4, the process conditions and the product distribution of the solvent deasphalting zone are shown in table 5, the reaction conditions and the product distribution of the fixed bed wax oil hydrotreating reaction zone are shown in table 6, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and the product distribution of the catalytic cracking reaction zone are shown in table 8;
from the data in tables 4-8, it can be seen that 5.2g of ethylene and 18.6g of propylene are obtained per 100g of the residua feedstock in this example.
Comparative example 1
This comparative example is similar to the method of example 1, except that a fixed bed residue hydrotreating-solvent deasphalting-catalytic cracking process is used to produce lower olefins, i.e., the residue feedstock is reacted in a fixed bed residue hydrotreating reaction zone and a first gas effluent, a first hydrogenated naphtha, a first hydrogenated heavy oil and a hydrogenation residue reduction are separated, then the catalytic cracking slurry oil and 50 wt% of the hydrogenation residue reduction are introduced into a solvent deasphalting zone for solvent deasphalting and separation to obtain deasphalted oil and deasphalted asphalt, and finally the first hydrogenated heavy oil, the deasphalted oil and 50 wt% of the hydrogenation residue reduction are introduced into a catalytic cracking reaction zone for catalytic cracking reaction.
The reaction conditions and product distribution in the fixed bed residue hydrotreating reaction zone are shown in table 4, the process conditions and product distribution in the solvent deasphalting zone are shown in table 5, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and product distribution in the catalytic cracking reaction zone are shown in table 8.
As can be seen from the data in tables 4-8, 4.5g of ethylene and 16.6g of propylene were obtained per 100g of the resid feed in this comparative example.
Example 2
This example is similar to the operation of example 1, except that the hydrodeoxygenation slag introduced into the catalytic cracking reaction zone accounts for 30wt% of the total weight of the hydrodeoxygenation slag, and the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are mixed and introduced into the fixed bed wax oil hydrotreating reaction zone.
The reaction conditions and product distribution of the fixed bed residue oil hydrotreating reaction zone are shown in table 4, the process conditions and product distribution of the solvent deasphalting zone are shown in table 5, the reaction conditions and product distribution of the fixed bed wax oil hydrotreating reaction zone are shown in table 6, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 8.
From the data in tables 4-8, it can be seen that 5.8g of ethylene and 21.2g of propylene are obtained per 100g of the residua feedstock in this example.
Example 3
This example is similar to the process of example 1, except that the hydrodeoxygenation slag introduced into the catalytic cracking reaction zone comprises 60 wt% of the total weight of the hydrodeoxygenation slag, and the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are mixed and introduced into the fixed bed residue hydrotreating reaction zone.
The reaction conditions and product distribution in the fixed bed residue oil hydrotreating reaction zone are shown in table 4, the process conditions and product distribution in the solvent deasphalting zone are shown in table 5, the reaction conditions and product distribution in the fixed bed wax oil hydrotreating reaction zone are shown in table 6, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and product distribution in the catalytic cracking reaction zone are shown in table 8.
As can be seen from the data in tables 4-8, 5.7g of ethylene and 20.5g of propylene were obtained per 100g of the resid feed in this example.
Example 4
This example is similar to the process of example 1, except that the first and second hydroprocessed naphthas are combined and separated into a light naphtha and a heavy naphtha, and the light naphtha is also introduced into the catalytic cracking reaction zone for catalytic cracking.
The reaction conditions and product distribution in the fixed bed residue oil hydrotreating reaction zone are shown in table 4, the process conditions and product distribution in the solvent deasphalting zone are shown in table 5, the reaction conditions and product distribution in the fixed bed wax oil hydrotreating reaction zone are shown in table 6, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and product distribution in the catalytic cracking reaction zone are shown in table 8.
As can be seen from the data in tables 4-8, 5.4g of ethylene and 18.8g of propylene were obtained per 100g of the resid feed in this example.
Example 5
This example is similar in operation to example 1, except that in step (3), the effluent hydrogen content in the fixed bed wax oil hydrogenation reaction zone is 13.07 wt.%.
The reaction conditions and product distribution of the fixed bed residue oil hydrotreating reaction zone are shown in table 4, the process conditions and product distribution of the solvent stripping zone are shown in table 5, the reaction conditions and product distribution of the fixed bed wax oil hydrotreating reaction zone are shown in table 6, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 8.
As can be seen from the data in tables 4-8, 4.6g of ethylene and 16.7g of propylene were obtained per 100g of the resid feed in this example.
Table 4: reaction conditions and product distribution in fixed bed residue hydrotreating reaction zone
Table 5: process conditions and product distribution in solvent deasphalting zone
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | |
| Feed rate of feed in g/h | ||||||
| Slag reduction by hydrogenation | 20.8 | 29.1 | 16.8 | 20.8 | 20.8 | 19.9 |
| Catalytic cracking slurry oil | 2.6 | 2.3 | 2.3 | 2.6 | 2.6 | 3.2 |
| Is totaled | 23.4 | 31.4 | 19.1 | 23.4 | 23.4 | 23.1 |
| Process conditions | ||||||
| Solvent(s) | Pentane (pentane) | Pentane (pentane) | Pentane (pentane) | Pentane (pentane) | Pentane (pentane) | Pentane (pentane) |
| Temperature, C | 150 | 150 | 150 | 150 | 150 | 150 |
| Pressure, MPa | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Volume ratio of solvent to hydrogenation slag reduction | 5:1 | 5:1 | 5:1 | 5:1 | 5:1 | 5:1 |
| Product flow, g/h | ||||||
| Deasphalted oil | 11.8 | 15.9 | 9.6 | 11.8 | 11.8 | 11.5 |
| Deoiled asphalt | 11.6 | 15.5 | 9.5 | 11.6 | 11.6 | 11.6 |
| Total up to | 23.4 | 31.4 | 19.1 | 23.4 | 23.4 | 23.1 |
Table 6: reaction conditions and product distribution in fixed bed wax oil hydrotreating reaction zone
Table 7: nature of feedstock in catalytic cracking reaction zone
| Properties of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Density (20 ℃ C.), g/cm 3 | 0.8924 | 0.8806 | 0.8942 | 0.8914 | 0.9121 | 0.9200 |
| Hydrogen content, wt.% | 13.08 | 13.35 | 13.05 | 13.08 | 12.64 | 12.46 |
| Carbon residue, by weight% | 3.13 | 1.81 | 3.42 | 3.11 | 3.11 | 3.02 |
| Sulfur content, wt.% | 0.20 | 0.11 | 0.21 | 0.20 | 0.20 | 0.17 |
| Nitrogen content, wt.% | 0.065 | 0.031 | 0.059 | 0.065 | 0.055 | 0.050 |
| (Nickel + vanadium) content, μ g/g | 3.8 | 2.1 | 3.5 | 3.8 | 3.9 | 3.3 |
Table 8: reaction conditions and product distribution in a catalytic cracking reaction zone
As can be seen from the results of tables 4 to 8: the invention organically combines the fixed bed residual oil hydrotreating process, the fixed bed wax oil hydrotreating process, the catalytic cracking process and the solvent deasphalting process, and can obviously improve the hydrogenation depth of the residual oil raw material, thereby obviously improving the yield of low-carbon olefin products such as propylene, ethylene and the like in the combined process.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (24)
1. A method for producing more light olefins is characterized by comprising the following steps:
(1) In the presence of hydrogen, introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone for hydrotreating reaction I, and separating a residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I is performed to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated slag reduction;
(2) In the presence of a solvent, introducing the catalytic cracking oil slurry and a part of the hydrogenation slag reduction into a solvent deasphalting area for solvent deasphalting and separation to obtain deasphalted oil and deoiled asphalt;
(3) In the presence of hydrogen, introducing the first hydrogenated heavy oil and the deasphalted oil into a fixed bed wax oil hydrotreating reaction zone for hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after the hydrotreating reaction II is performed to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
(4) Introducing the second hydrogenated heavy oil and the rest part of the hydrogenation slag reduction into a catalytic cracking reaction zone for catalytic cracking reaction, and separating catalytic cracking reaction effluent obtained after the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
(5) And (3) performing at least one operation of an extraction device, a fixed bed wax oil hydrotreating reaction zone and a fixed bed residual oil hydrotreating reaction zone on the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil independently, and circulating the catalytic cracking slurry oil to the solvent deasphalting zone.
2. The process of claim 1, wherein in step (1), the residuum feedstock is selected from at least one of an atmospheric resid, a vacuum resid.
3. The process of claim 1 or 2, wherein in step (1), the reaction conditions of the fixed bed residue hydroprocessing reaction zone comprise: the reaction temperature is 300-460 ℃, the hydrogen partial pressure is 6-25MPa, and the liquid hourly space velocity is 0.10-1.0h -1 The volume ratio of hydrogen to oil is 100-1500;
preferably, in step (1), the reaction conditions of the fixed bed residue hydrotreating reaction zone include: the reaction temperature is 350-440 ℃, the hydrogen partial pressure is 12-20MPa, and the liquid hourly space velocity is 0.15-0.4h -1 The volume ratio of hydrogen to oil is 300-1000.
4. The method as claimed in any one of claims 1 to 3, wherein, in the step (1), the fixed bed residue hydrotreating reaction zone is packed with a residue hydrotreating catalyst having an average particle diameter of0.5-50mm, and bulk density of 0.3-1.2g/cm 3 The average pore diameter is 6-30nm, and the specific surface area is 50-400m 2 /g。
5. The process of claim 4, wherein, in step (1), the residue hydrotreating catalyst is selected from at least one of a protected catalyst I, a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodecarbon residue catalyst;
preferably, in step (1), the residue hydrotreating catalyst contains a carrier and an active metal element supported on the carrier, wherein the carrier is selected from at least one of alumina, silica and titania, and the active metal element is selected from a group vib metal element and/or a group viii metal element.
6. The process of claim 5, wherein in step (1), in the residuum hydroprocessing catalyst, the active metal element is selected from at least one of a nickel-tungsten combination, a nickel-tungsten-cobalt combination, a nickel-molybdenum combination, a cobalt-molybdenum combination;
preferably, in the residue hydrotreating catalyst, the carrier further contains at least one element of boron, germanium, zirconium, phosphorus, chlorine and fluorine;
preferably, the content of the active metal element in the residual oil hydrotreating catalyst is 1 to 30wt%, preferably 1 to 25wt%, in terms of oxide, based on the total weight of the residual oil hydrotreating catalyst.
7. The process as claimed in any one of claims 1 to 6, wherein, in the step (1), the separation conditions of the residue hydrotreating reaction effluent are controlled so that the initial boiling point of the first hydrogenated naphtha is 50 to 70 ℃, the cut points of the first hydrogenated naphtha and the first hydrogenated heavy oil are 160 to 180 ℃, and the end point of the first hydrogenated heavy oil is 500 to 580 ℃.
8. The method according to any one of claims 1-7, wherein in step (hi)In step (2), the solvent is C 3 -C 7 Alkane and/or C 3 -C 7 At least one of an olefin;
preferably, in step (2), the solvent is C 4 -C 6 Alkane and/or C 4 -C 6 At least one of olefins.
9. The process of any one of claims 1-8, wherein in step (2), the operating conditions of the solvent deasphalting zone comprise: the temperature is 50-260 ℃, the pressure is 1-7MPa, and the volume ratio of the solvent to the hydrogenation slag reduction is 2-12;
preferably, in step (2), the operating conditions of said solvent deasphalting zone comprise: the temperature is 60-240 ℃, the pressure is 2-6MPa, and the volume ratio of the solvent to the hydrogenation slag reduction is 3-10:1.
10. the process of any one of claims 1-9, wherein in step (2), the deasphalted oil comprises 10-80 wt% of the total amount of feedstock introduced to the solvent deasphalting zone;
preferably, in step (2), the deasphalted oil constitutes from 30 to 70% by weight of the total amount of feedstock introduced into the solvent deasphalting zone.
11. The process according to any one of claims 1 to 10, wherein in step (3), the reaction conditions in the fixed bed wax oil hydrotreating reaction zone and/or the catalyst gradation in the fixed bed wax oil hydrotreating reaction zone are controlled so that the hydrogen content of the effluent of the wax oil hydrotreating reaction is not less than 13.2% by weight, preferably not less than 13.5% by weight.
12. The process of any one of claims 1 to 11, wherein in step (3), the reaction conditions of the fixed bed wax oil hydroprocessing reaction zone comprise: hydrogen partial pressure is 6-25MPa, reaction temperature is 300-460 ℃, liquid hourly space velocity is 0.1-5.0h -1 The volume ratio of hydrogen to oil is 200-2000;
preferably, in the step (3), the reaction conditions of the fixed bed wax oil hydrotreating reaction zone include: hydrogen partial pressure is 10-20MPa, reaction temperature is 350-440 ℃, and liquid hourly space velocity is 0.5-2.0h -1 The volume ratio of hydrogen to oil is 400-1200.
13. The process according to any one of claims 1 to 12, wherein in step (3), the fixed bed wax oil hydrotreating reaction zone is packed with a wax oil hydrotreating catalyst having a bulk density of 0.4 to 1.3g/cm 3 Average particle diameter of 0.5-50mm, specific surface area of 50-400m 2 /g。
14. The process according to claim 13, wherein in step (3), the wax oil hydrotreating catalyst is selected from at least one of a protecting catalyst II, a wax oil hydrofinishing catalyst;
preferably, in the step (3), the wax oil hydrotreating catalyst contains a carrier selected from at least one of alumina, a combination of alumina and silica, and titania, and an active metal element supported on the carrier selected from at least one of nickel, cobalt, molybdenum, and tungsten;
preferably, in the wax oil hydrotreating catalyst, the total content of nickel and cobalt in terms of oxide is 0 to 30wt%, the total content of molybdenum and tungsten in terms of oxide is 0 to 35 wt%, and the sum of the contents of nickel, cobalt, molybdenum and tungsten in terms of oxide is more than 0, based on the total weight of the wax oil hydrotreating catalyst.
15. The method as claimed in any one of claims 1 to 14, wherein, in the step (3), the separation conditions of the wax oil hydrotreating reaction effluent are controlled such that the initial boiling point of the second hydrogenated naphtha is 50 to 70 ℃, the cut points of the second hydrogenated naphtha and the second hydrogenated heavy oil are 160 to 180 ℃, and the final boiling point of the second hydrogenated heavy oil is 500 to 580 ℃.
16. The method according to any one of claims 1 to 15, wherein in step (4), the catalytic cracking reaction zone is filled with a catalytic cracking catalyst, the catalytic cracking catalyst comprises zeolite, inorganic oxide and optionally clay, the inorganic oxide is selected from at least one of silica, alumina, zirconia, titania and amorphous silica-alumina, and the content of the zeolite is 10 to 50 wt%, the content of the inorganic oxide is 5 to 90 wt% and the content of the clay is 0 to 70 wt% based on the total weight of the catalytic cracking catalyst;
preferably, in the catalytic cracking catalyst, the zeolite is at least one selected from the group consisting of Y-type zeolite with or without rare earth element, HY-type zeolite with or without rare earth element, ultrastable Y-type zeolite with or without rare earth element, zeolite having MFI structure.
17. The method as claimed in claim 16, wherein, in step (4), the reaction conditions of the catalytic cracking reaction zone are: the weight ratio of the atomizing steam to the residual oil raw material is 0.05-0.5:1, the weight ratio of agent oil is 6-20:1, the temperature is 500-680 ℃, and the weight hourly space velocity is 1-6h -1 The reaction pressure is 0.05-1MPa.
18. The process according to any one of claims 1 to 17, wherein in step (4), the separation conditions of the catalytic cracking reaction effluent are controlled so that the initial boiling point of the catalytic cracking light cycle oil is 150 to 180 ℃, the cut point of the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil is 340 to 360 ℃, and the final boiling point of the catalytic cracking heavy cycle oil is 500 to 580 ℃.
19. The process of any one of claims 1 to 18, wherein in step (4), the hydrogenated bagasse introduced into the catalytic cracking reaction zone comprises 5 to 95 wt%, preferably 20 to 80 wt%, of the total weight of the hydrogenated bagasse.
20. The method of any one of claims 1-19, wherein the method further comprises: separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha;
preferably, the separation conditions of the first and/or second hydrogenated naphtha are controlled such that the light naphtha has a first boiling point in the range of 50 to 70 ℃, the light and heavy naphthas have a cut point in the range of 120 to 140 ℃ and the heavy naphtha has a final cut point in the range of 170 to 190 ℃.
21. A system for producing a higher amount of lower olefins, the system comprising:
the fixed bed residual oil hydrotreating reaction unit is used for carrying out hydrotreating reaction I on a residual oil raw material to obtain a residual oil hydrotreating reaction effluent;
the first separation unit is used for separating the residual oil hydrotreating reaction effluent to obtain a first gas effluent, a first hydrogenated naphtha, a first hydrogenated heavy oil and hydrogenated slag reduction;
the solvent deasphalting unit is used for performing solvent deasphalting and separation on the catalytic cracking oil slurry and a part of the hydrogenation slag reduction to obtain deoiled asphalt and deasphalted oil;
the fixed bed wax oil hydrotreating reaction unit is used for carrying out hydrotreating reaction II on the first hydrogenated heavy oil and the deasphalted oil to obtain wax oil hydrotreating reaction effluent;
the second separation unit is used for separating the wax oil hydrotreating reaction effluent to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
the catalytic cracking reaction unit is used for carrying out catalytic cracking reaction on the second hydrogenated heavy oil and the rest part of the hydrogenated slag-reducing oil to obtain a catalytic cracking reaction effluent;
a third separation unit for separating the effluent of the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil, and the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are respectively and independently subjected to at least one operation of an extraction device, a circulation back to the fixed bed wax oil hydrotreating reaction zone and a circulation back to the fixed bed residual oil hydrotreating reaction zone, and the catalytic cracking slurry oil is circulated to the solvent deasphalting unit through a pipeline.
22. The system of claim 21, wherein the fixed bed residue hydroprocessing reaction unit comprises at least 1 fixed bed reactor;
preferably, the fixed bed residue hydroprocessing reaction unit comprises 3 to 6 fixed bed reactors.
23. The system of claim 21 or 22, wherein the fixed bed wax oil hydroprocessing reaction unit comprises at least 1 fixed bed reactor;
preferably, the fixed bed wax oil hydrotreating reaction unit includes 1-3 fixed bed reactors.
24. The system of any one of claims 21-23, wherein the system further comprises:
and the fourth separation unit is used for separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha.
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| CN101045884A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil |
| US20100314287A1 (en) * | 2006-12-27 | 2010-12-16 | Chuanfeng Niu | combined process for hydrotreating and catalytic cracking of residue |
| CN106701188A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Heavy oil product treatment processing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101045884A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil |
| US20100314287A1 (en) * | 2006-12-27 | 2010-12-16 | Chuanfeng Niu | combined process for hydrotreating and catalytic cracking of residue |
| CN106701188A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Heavy oil product treatment processing method |
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