CN109705913B - Method and system for producing high-octane gasoline and low-carbon olefins in high yield - Google Patents
Method and system for producing high-octane gasoline and low-carbon olefins in high yield Download PDFInfo
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Abstract
The invention relates to a method and a system for producing gasoline with high octane number and low-carbon olefin in a high yield, wherein the method comprises the following steps: sending the heavy raw material into a solvent extraction device for solvent extraction treatment, carrying out first hydrogenation treatment on the extract oil, and carrying out first fractionation on the obtained hydrogenation tail oil to obtain a hydrogenation tail oil light fraction and a hydrogenation tail oil heavy fraction; performing second fractionation on the light cycle oil, and performing second hydrotreating on the heavy fraction of the light cycle oil to obtain a second hydrogenation product; carrying out a first catalytic cracking reaction on a second hydrogenation product, and carrying out a second catalytic cracking reaction on raffinate oil and the hydrogenation tail oil heavy fraction to obtain a product for separation; and sending the light cycle oil product obtained by separation into the second fractionating device, and sending the obtained cycle oil product into the first hydrogenation device. The method and the system provided by the invention can reduce the sulfur content in the gasoline product, improve the octane number of the gasoline and produce more gasoline and low-carbon olefins such as ethylene, propylene and the like.
Description
Technical Field
The invention relates to a method and a system for producing gasoline with high octane number and low-carbon olefin in a high yield.
Background
The ethylene industry is the basis of the development of the chemical industry in China and is an important raw material for producing important chemical products such as polyethylene, ethylene oxide, dichloroethane and the like. The preparation of ethylene mainly uses naphtha as raw material, but faces the problem that the raw material resource is increasingly tense. The treatment capacity of the catalytic cracking process in China is nearly 100Mt/a, catalytic cracking products occupy an important position in the commodity market in China, and catalytic cracking gasoline accounts for nearly 80% of the finished gasoline pool, but the catalytic cracking gasoline has high sulfur and nitrogen content and high olefin content; the catalytic cracking light cycle oil has high sulfur and nitrogen content and low cetane number, and can only be used as a diesel oil blending component or fuel oil with poor quality. Therefore, the method has great economic benefit and practical significance for carrying out a series of pretreatment on the low-cost catalytic cracking raw material and producing clean high-value catalytic cracking products and simultaneously producing low-carbon olefins such as ethylene and the like.
Chinese patent CN 103773495 a discloses a catalytic conversion method for the production of high-yield clean high-octane gasoline. The method comprises the steps of sending wax oil and catalytic cracking cycle oil into a catalytic cracking device after hydrotreating, and obtaining dry gas, liquefied gas, catalytic cracking gasoline, LCO, recycle oil and oil slurry products through cracking reaction; the catalytic cracking light diesel oil adopts self-circulation, and the catalytic cracking circulating oil is circulated to the hydrotreatment device, and the method can greatly improve the yield and the quality of the catalytic cracking gasoline product.
Chinese patent CN 101724431a discloses a catalytic conversion method for preparing light fuel oil and propylene, which comprises subjecting catalytic cracking wax oil to hydrogenation treatment or/and solvent extraction to obtain hydrogenated catalytic wax oil or/and raffinate oil of catalytic wax oil as raw material of catalytic cracking reactor, wherein the catalytic cracking raw material treated by the method is very suitable for catalytic conversion, and realizes high-efficiency utilization of petroleum resources.
Chinese patent CN 104927915 a discloses a method for producing olefins and aromatics with naphtha as a raw material, which is to extract naphtha by solvent extraction to obtain extract oil and raffinate oil; the extract oil is sent to a steam cracking device through a pipeline, the extract oil is sent to a catalytic reforming device, and C3-C5 fractions obtained through reforming reaction are returned to a steam cracking area for cracking reaction. The method can effectively utilize naphtha to produce more low-carbon olefins and light aromatics.
From the above published documents, it can be found that: the pretreatment of the catalytic cracking raw material can effectively reduce the contents of sulfur and nitrogen in the catalytic cracking raw material, and simultaneously, the contents of colloid, asphaltene and heavy aromatic hydrocarbon are also effectively reduced. Based on the composition characteristics of the raw materials, the combination treatment by different processing technologies is a necessary condition for improving the atom utilization rate of the raw materials. However, the existing method can not realize the purpose of simultaneously producing low-carbon olefin and light aromatic hydrocarbon while producing high-octane clean catalytic cracking gasoline.
Disclosure of Invention
The invention aims to provide a method and a system for producing gasoline with high octane number and low-carbon olefins in a high yield.
In order to achieve the above object, the present invention provides a method for increasing the yield of high octane gasoline and low carbon olefins, comprising: sending the heavy raw material into a solvent extraction device for solvent extraction treatment to obtain extract oil and raffinate oil; sending the extract oil into a first hydrogenation device to contact with a first hydrogenation catalyst and carrying out first hydrogenation treatment to obtain hydrogenated naphtha, hydrogenated diesel oil and hydrogenated tail oil; sending the obtained hydrogenated tail oil into a first fractionation device for first fractionation to obtain a hydrogenated tail oil light fraction and a hydrogenated tail oil heavy fraction; feeding the light cycle oil into a second fractionating device for second fractionation to obtain a light cycle oil light fraction and a light cycle oil heavy fraction; sending the light cycle oil heavy fraction into a second hydrogenation device to contact with a second hydrogenation catalyst and carrying out second hydrogenation treatment to obtain a second hydrogenation product; feeding a second hydrogenation product into the lower part of a first reaction zone of the riser reactor from a first nozzle, feeding the light fraction of the light cycle oil into the middle part of the first reaction zone from a second nozzle, contacting with a catalytic cracking catalyst, and carrying out a first catalytic cracking reaction to obtain a first product and a semi-spent catalyst; the riser reactor is also provided with a second reaction zone positioned above the first reaction zone; feeding the obtained first product and the semi-spent catalyst into a second reaction zone, and carrying out a second catalytic cracking reaction on the first product and the semi-spent catalyst together with the raffinate oil and the hydrogenated tail oil heavy fraction which are sprayed into the second reaction zone from a third nozzle to obtain a second product and a spent catalyst; separating the second product to obtain dry gas, liquefied gas, a gasoline product, a light cycle oil product, a cycle oil product and oil slurry; sending the obtained light cycle oil product into the second fractionating device, and sending the obtained cycle oil product into the first hydrogenation device; and sending the hydrogenated naphtha, the hydrogenated diesel oil and the hydrogenated tail oil light fraction into a steam cracking device for steam cracking to obtain a steam cracking product.
Optionally, the heavy feedstock is at least one selected from vacuum wax oil, hydrogenated vacuum wax oil, coker wax oil, deasphalted oil, atmospheric residue, and vacuum residue.
Optionally, the conditions of the solvent extraction treatment include: the solvent extraction device is an extraction tower, an extraction solvent enters the extraction tower from the top of the extraction tower, a heavy raw material enters the extraction tower from the bottom of the extraction tower, the temperature of the extraction tower is 50-70 ℃, the extraction solvent is furfural, and the weight ratio of the extraction solvent to the heavy raw material is (1-2): 1.
optionally, the first hydrotreating conditions include: hydrogen partial pressure of 4-20 MPa, temperature of 330-450 deg.C, liquid hourly space velocity of 0.1-3.0 hr-1Hydrogen to oil volume ratio of 250-1800Nm3/m3。
Optionally, the first hydrogenation catalyst comprises a carrier and an active component, the carrier is at least one selected from alumina, silica and amorphous silica-alumina, and the active component is at least one selected from a group VIB metal and/or a group VIII non-noble metal.
Optionally, the temperature of the first fractionation is 200-300 ℃ and the temperature of the second fractionation is 220-270 ℃.
Optionally, the second hydrotreating conditions include: hydrogen partial pressure of 3-30 MPa, temperature of 310-450 deg.C, liquid hourly space velocity of 0.1-10.0 hr-1Hydrogen to oil volume ratio of 100-1500Nm3/m3。
Optionally, the second hydrogenation catalyst comprises a carrier and an active component, the carrier is at least one selected from alumina, silica and amorphous silica-alumina, and the active component is at least one selected from a group VIB metal and/or a group VIII non-noble metal.
Optionally, the conditions of the first catalytic cracking reaction include: the reaction temperature is 440-680 ℃, the absolute reaction pressure is 0.1-0.5 MPa, the weight ratio of the solvent to the oil is 1-50, the reaction time is 0.1-10 seconds, and the water-oil ratio is 0.01-100;
the conditions of the second catalytic cracking reaction include: the reaction temperature is 420-680 ℃, the absolute reaction pressure is 0.1-0.5 MPa, the weight ratio of the catalyst to the oil is 1-50, the reaction time is 0.1-10 seconds, and the water-oil ratio is 0.01-100.
Optionally, the catalytic cracking catalyst comprises a zeolite selected from the group consisting of rare earth-containing or non-rare earth-containing Y, HY, USY and Beta zeolites, an inorganic oxide and optionally a clay.
Optionally, the riser reactor is an equal-diameter riser reactor or a reducing riser reactor.
Optionally, the steam cracking temperature is 750-900 ℃.
Optionally, the residence time of the oil gas in the riser reactor between the first nozzle and the second nozzle is 0.1 to 5 seconds.
Optionally, at least part of the light cycle oil product and/or the produced light cycle oil is sent to the first hydrogenation device together for first hydrogenation treatment; the light cycle oil product and/or the produced light cycle oil accounts for 0-10 wt% of the total feed of the first hydrogenation device; and/or
And sending at least part of raffinate oil into the steam cracking device for steam cracking.
The invention also provides a system for producing gasoline with high octane number and low-carbon olefin in high yield, which comprises a solvent extraction device, a first hydrogenation device, a first fractionating device, a second hydrogenation device, a riser reactor, a settler, a regenerator, a catalytic cracking fractionating device and a steam cracking device; the solvent extraction device is provided with a heavy raw material inlet, an extract oil outlet and a raffinate oil outlet, the first hydrogenation device is provided with an inlet, a hydrogenated naphtha outlet, a hydrogenated diesel oil outlet and a hydrogenated tail oil outlet, the first fractionation device is provided with an inlet, a hydrogenated tail oil light fraction outlet and a hydrogenated tail oil heavy fraction outlet, the second fractionation device is provided with an inlet, a light cycle oil light fraction outlet and a light cycle oil heavy fraction outlet, the second hydrogenation device is provided with an inlet and a hydrogenated product outlet, the riser reactor is provided with a first reaction zone and a second reaction zone which are coaxial and are in fluid communication from bottom to top, the first reaction zone is provided with a catalyst inlet, a first nozzle at the lower part and a second nozzle at the middle part, the second reaction zone is provided with a top outlet and a third nozzle at the lower part, the settler is sleeved at the upper part of the second reaction zone, and the top outlet of the second reaction zone is positioned in the settler, the catalytic cracking fractionation device is provided with an inlet, a dry gas outlet, a liquefied gas outlet, a gasoline outlet, a light cycle oil outlet, a recycle oil outlet and an oil slurry outlet, and the steam cracking device is provided with an inlet and a product outlet; the extract oil outlet of the solvent extraction device, the recycle oil outlet of the catalytic cracking fractionation device and the light cycle oil outlet of the optional catalytic cracking fractionation device are communicated with the inlet of the first hydrogenation device, the hydrogenation tail oil outlet of the first hydrogenation device is communicated with the inlet of the first fractionation device, the light cycle oil outlet of the catalytic cracking fractionation device is communicated with the inlet of the second fractionation device, the light cycle oil heavy fraction outlet of the second fractionation device is communicated with the inlet of the second hydrogenation device, the hydrogenation product outlet of the second hydrogenation device is communicated with the first nozzle at the lower part of the first reaction zone, the light cycle oil light fraction outlet of the second fractionation device is communicated with the second nozzle at the middle part of the first reaction zone, the raffinate oil outlet of the solvent extraction device and the hydrogenation tail oil heavy fraction outlet of the first fractionation device are communicated with the third nozzle at the lower part of the second reaction zone, the top oil gas outlet of the settler is communicated with the inlet of the catalytic cracking fractionation device, the catalyst outlet of the settler is communicated with the catalyst inlet of the regenerator, the catalyst outlet of the regenerator is communicated with the catalyst inlet of the first reaction zone, and the hydrogenated naphtha outlet and the hydrogenated diesel oil outlet of the first hydrogenation device, the hydrogenated tail oil light fraction outlet of the first fractionation device and the raffinate oil outlet of the optional solvent extraction device are communicated with the inlet of the steam cracking device.
The method and the system have the advantages that:
1. the invention can produce low-sulfur high-cleanness catalytic cracking gasoline by taking heavy raw materials, recycle oil and the like as raw materials, can control the sulfur content in the catalytic cracking gasoline by controlling the hydrogenation depth, and simultaneously improves the octane number of the gasoline.
2. The invention adopts a plurality of nozzles to feed at different positions according to the composition characteristics of materials, and simultaneously adopts different unit operating parameters of different reaction zones of the riser reaction to control, thereby achieving the purpose of maximally producing clean high-octane gasoline.
3. The invention can effectively adjust the diesel-steam ratio of the catalytic cracking unit and improve the yield of light oil; and low-carbon olefin is produced.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. Non-critical streams are not shown in the figures, as required by the illustration, but do not limit the invention. In the drawings:
FIG. 1 includes a schematic flow diagram of one embodiment of the method of the present invention and also includes a schematic structural diagram of one embodiment of the system of the present invention.
Description of the reference numerals
1 pipeline 2 pipeline 3 pipeline
4 line 5 line 6 line
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28 line 29 solvent extraction unit 30 first hydrogenation unit
31 first fractionating unit 32 steam cracking unit 33 second fractionating unit
34 second hydrogenation unit 35 settler 36 second reaction zone
37 first reaction zone 38 regenerator 39 catalytic cracking fractionator
40 line 41 line 42 line
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for producing gasoline with high octane number and low-carbon olefin in a high yield, which comprises the following steps: sending the heavy raw material into a solvent extraction device for solvent extraction treatment to obtain extract oil and raffinate oil; sending the extract oil into a first hydrogenation device to contact with a first hydrogenation catalyst and carrying out first hydrogenation treatment to obtain hydrogenated naphtha, hydrogenated diesel oil and hydrogenated tail oil; sending the obtained hydrogenated tail oil into a first fractionation device for first fractionation to obtain a hydrogenated tail oil light fraction and a hydrogenated tail oil heavy fraction; feeding the light cycle oil into a second fractionating device for second fractionation to obtain a light cycle oil light fraction and a light cycle oil heavy fraction; sending the light cycle oil heavy fraction into a second hydrogenation device to contact with a second hydrogenation catalyst and carrying out second hydrogenation treatment to obtain a second hydrogenation product; feeding a second hydrogenation product into the lower part of a first reaction zone of the riser reactor from a first nozzle, feeding the light fraction of the light cycle oil into the middle part of the first reaction zone from a second nozzle, contacting with a catalytic cracking catalyst, and carrying out a first catalytic cracking reaction to obtain a first product and a semi-spent catalyst; the riser reactor is also provided with a second reaction zone positioned above the first reaction zone; feeding the obtained first product and the semi-spent catalyst into a second reaction zone, and carrying out a second catalytic cracking reaction on the first product and the semi-spent catalyst together with the raffinate oil and the hydrogenated tail oil heavy fraction which are sprayed into the second reaction zone from a third nozzle to obtain a second product and a spent catalyst; separating the second product to obtain dry gas, liquefied gas, a gasoline product, a light cycle oil product, a cycle oil product and oil slurry; sending the obtained light cycle oil product into the second fractionating device, and sending the obtained cycle oil product into the first hydrogenation device; and sending the hydrogenated naphtha, the hydrogenated diesel oil and the hydrogenated tail oil light fraction into a steam cracking device for steam cracking to obtain a steam cracking product.
According to the present invention, the heavy feedstock is well known to those skilled in the art, and for example, the heavy feedstock may be at least one selected from the group consisting of vacuum wax oil, hydrogenated vacuum wax oil, coker wax oil, deasphalted oil, atmospheric residue, and vacuum residue.
According to the invention, the solvent extraction is used for separating the heavy raw material to obtain the extract oil and the raffinate oil, so that the extract oil and the raffinate oil are respectively treated by proper processes, the extract oil enters the first hydrogenation device for hydrogenation treatment according to the composition and the property of the extract oil, and the raffinate oil enters the proper position of the riser reactor through the nozzle according to the composition and the property of the raffinate oil. The conditions of the solvent extraction treatment may include: the solvent extraction device is an extraction tower, an extraction solvent enters the extraction tower from the top of the extraction tower, a heavy raw material enters the extraction tower from the bottom of the extraction tower, extract oil rich in aromatic hydrocarbon and the extraction solvent flow out from the bottom of the extraction tower and are sent to a subsequent refining tank for treatment, the extraction solvent returns to the extraction tower, extract oil and the extraction solvent are obtained from the bottom of the refining tank, raffinate oil rich in alkane and a little extraction solvent flow out from the top of the extraction tower, raffinate oil and the extraction solvent are obtained after stripping and evaporation, the extraction solvent returns to the top of the extraction tower, the temperature of the extraction tower is 50-70 ℃, preferably 55-65 ℃, the extraction solvent is furfural, and the weight ratio of the extraction solvent to the heavy raw material is (1-2): 1.
according to the present invention, the first hydrotreating is used for saturating aromatic hydrocarbons in the extract oil, the recycle oil product and the light cycle oil product to facilitate cracking, and the conditions of the first hydrotreating may include: hydrogen partial pressure of 4-20 MPa, preferably 6-18 MPa, temperature of 330-450 deg.C, preferably 350-420 deg.C, liquid hourly space velocity of 0.1-3.0 hr-1Preferably 0.1 to 2.5 hours-1Hydrogen to oil volume ratio of 250-1800Nm3/m3Preferably 400-1700Nm3/m3. The first hydrogenation catalyst may include a support, which may be at least one selected from alumina, silica and amorphous silica-alumina, and an active component, which may be at least one selected from a group VIB metal and/or a group VIII non-noble metal.
According to the invention, a fractionation treatment is used to separate the distillates to facilitate subsequent treatments, the temperature of said first fractionation may be comprised between 200 and 300 ℃, preferably between 210 and 270 ℃, and the temperature of the second fractionation may be comprised between 220 and 270 ℃, preferably between 230 and 260 ℃.
According to the present invention, a second hydrotreatment is used for saturating the aromatics in the heavy fraction of the light cycle oil, and the conditions of the second hydrotreatment may include: hydrogen partial pressure of 3-30 MPa, preferably 4-20 MPa, temperature of 310-450 deg.C, preferably 320-420 deg.C, liquid hourly space velocity of 0.1-10.0 hr-1Preferably 0.5 to 5.0 hours-1Hydrogen to oil volume ratio of 100-1500Nm3/m3. The second hydrogenation catalyst may include a support, which may be at least one selected from alumina, silica and amorphous silica-alumina, and an active component, which may be at least one selected from a group VIB metal and/or a group VIII non-noble metal.
According to the present invention, different catalytic cracking conditions may be adopted according to the characteristics of different feeds, for example, the conditions of the first catalytic cracking reaction may include: the reaction temperature is 440-680 ℃, preferably 480-600 ℃, the absolute reaction pressure is 0.1-0.5 MPa, preferably 0.10-0.3 MPa, the weight ratio of the catalyst to the oil is 1-50, preferably 3-25, the reaction time is 0.1-10 seconds, namely the residence time of the oil gas in the riser reactor between the first nozzle and the third nozzle is 0.1-10 seconds, preferably 0.5-6 seconds, and the water-oil ratio is 0.01-100; the residence time of the oil gas in the riser reactor between the first nozzle and the second nozzle may be 0.1 to 5 seconds. The conditions of the second catalytic cracking reaction may include: the reaction temperature is 420-680 ℃, preferably 460-580 ℃, the absolute reaction pressure is 0.1-0.5 MPa, preferably 0.10-0.30 MPa, the weight ratio of the catalyst to the oil is 1-50, preferably 3-25, the reaction time is 0.1-5 seconds, and the water-oil ratio is 0.01-100, preferably 0.02-0.5. The catalytic cracking catalyst may comprise a zeolite, which may be one selected from rare earth-containing or non-rare earth-containing zeolites Y, HY, USY and Beta, an inorganic oxide, which may be silica and/or alumina, and optionally a clay, for example, in an amount of 5 to 50 wt% on a dry basis and based on the weight of the catalyst on a dry basis, 10 to 90 wt% inorganic oxide, and 5 to 70 wt% clay. The riser reactor can be an equal-diameter riser reactor or a reducing riser reactor, and the reactor and the regenerator can be in a high-low parallel type or a coaxial type.
According to the invention, steam cracking, which can be carried out at a temperature of 750-900 ℃, preferably 790-840 ℃, helps to improve the further conversion of light distillate into lower olefins.
According to the invention, in order to effectively utilize light cycle oil, at least part of the light cycle oil product and/or produced light cycle oil can be sent to the first hydrogenation device together for first hydrogenation treatment; the light cycle oil product and/or the produced light cycle oil accounts for 0-10 wt% of the total feed of the first hydrogenation device; and/or sending at least part of raffinate oil into the steam cracking device for steam cracking.
As shown in fig. 1, the present invention further provides a system for increasing the yield of high-octane gasoline and low-carbon olefins, which comprises a solvent extraction device 29, a first hydrogenation device 30, a first fractionation device 31, a second fractionation device 33, a second hydrogenation device 34, a riser reactor, a settler 35, a regenerator 38, a catalytic cracking fractionation device 39 and a steam cracking device 32; the solvent extraction device 29 is provided with a heavy raw material inlet, an extract oil outlet and a raffinate oil outlet, the first hydrogenation device 30 is provided with an inlet, a hydrogenation naphtha outlet, a hydrogenation diesel oil outlet and a hydrogenation tail oil outlet, the first fractionation device 31 is provided with an inlet, a hydrogenation tail oil light fraction outlet and a hydrogenation tail oil heavy fraction outlet, the second fractionation device 33 is provided with an inlet, a light cycle oil light fraction outlet and a light cycle oil heavy fraction outlet, the second hydrogenation device 34 is provided with an inlet and a hydrogenation product outlet, the riser reactor is provided with a first reaction zone 37 and a second reaction zone 36 which are coaxial and are communicated with each other in a fluid manner from bottom to top, the first reaction zone 37 is provided with a catalyst inlet, a first nozzle at the lower part and a second nozzle at the middle part, the second reaction zone 36 is provided with a top outlet and a third nozzle at the lower part, the settler 35 is sleeved on the upper part of the second reaction zone 36, and the top outlet of the second reaction zone 36 is positioned at the top In the settler 35, the settler 35 is provided with a top oil gas outlet and a lower catalyst outlet, the regenerator 38 is provided with a catalyst inlet and a catalyst outlet, the catalytic cracking fractionation device 39 is provided with an inlet, a dry gas outlet, a liquefied gas outlet, a gasoline outlet, a light cycle oil outlet, a recycle oil outlet and an oil slurry outlet, and the steam cracking device 32 is provided with an inlet and a product outlet; the extract oil outlet of the solvent extraction device 29, the recycle oil outlet of the catalytic cracking fractionation device 39 and the optional light cycle oil outlet of the catalytic cracking fractionation device 39 are communicated with the inlet of the first hydrogenation device 30, the hydrogenated tail oil outlet of the first hydrogenation device 30 is communicated with the inlet of the first fractionation device 31, the light cycle oil outlet of the catalytic cracking fractionation device 39 is communicated with the inlet of the second fractionation device 33, the light cycle oil heavy fraction outlet of the second fractionation device 33 is communicated with the inlet of the second hydrogenation device 34, the hydrogenated product outlet of the second hydrogenation device 34 is communicated with the first nozzle at the lower part of the first reaction zone 37, the light cycle oil light fraction outlet of the second fractionation device 33 is communicated with the second nozzle at the middle part of the first reaction zone 37, the raffinate oil outlet of the solvent extraction device 29 and the hydrogenated tail oil heavy fraction outlet of the first fractionation device 31 are communicated with the third nozzle at the lower part of the second reaction zone 36 The nozzles are communicated, the top oil gas outlet of the settler 35 is communicated with the inlet of the catalytic cracking fractionation device 39, the catalyst outlet of the settler 35 is communicated with the catalyst inlet of the regenerator 38, the catalyst outlet of the regenerator 38 is communicated with the catalyst inlet of the first reaction zone 37, and the hydrogenated naphtha outlet and the hydrogenated diesel oil outlet of the first hydrogenation device 30, the hydrogenated tail oil light fraction outlet of the first fractionation device 31 and the raffinate oil outlet of the optional solvent extraction device 29 are communicated with the inlet of the steam cracking device 32.
It should be noted that the devices in the system of the present invention are not limited to the above-mentioned inlets and outlets, and other inlets and outlets known to those skilled in the art may be provided, and the present invention will not be described in detail.
The following describes the present invention with reference to fig. 1.
The heavy raw material from the pipeline 1 is sent to a solvent extraction device 29, the heavy raw material is processed to obtain extract oil and raffinate oil, the extract oil from the pipeline 3, the recycle oil product from the pipeline 20 and the light cycle oil product from the pipeline 22 are sent to a first hydrogenation device 30 from a pipeline 4 in the presence of hydrogen for first hydrogenation treatment, the processed hydrogenated tail oil is sent to a first fractionating device 31 from a pipeline 6, two fractions of hydrogenated tail oil heavy fraction and hydrogenated tail oil light fraction are obtained by fraction cutting, the hydrogenated tail oil heavy fraction is sent to a second reaction zone of a riser reactor through a pipeline 13 and raffinate oil from a pipeline 27 through a pipeline 28 for second catalytic cracking reaction, the hydrogenated heavy oil light fraction from a pipeline 12, the hydrogenated naphtha from a pipeline 40, the hydrogenated naphtha from a pipeline 41 and optional hydrogenated raffinate oil from a pipeline 2 are sent to a steam cracking device 32 from a pipeline 7 and a pipeline 8, the resulting product is sent from line 9, line 10 and line 11. Feeding the light cycle oil product into a second fractionating device 33 for fraction cutting to obtain a light cycle oil light fraction and a light cycle oil heavy fraction; the light fraction of the light cycle oil is sent to the middle part of the first reaction area 37 of the riser reactor through a pipeline 24, the heavy fraction of the light cycle oil is sent to the second hydrogenation device 34 through a pipeline 25, after second hydrogenation treatment, the light fraction of the light cycle oil is sent to the lower part of the first reaction area 37 of the riser reaction, a first catalytic cracking reaction is carried out under the action of a catalytic cracking catalyst, and the light fraction of the light cycle oil, the liquefied gas, the gasoline product, the light cycle oil product, the recycle oil product and the oil slurry are obtained after treatment. The light cycle oil product is recycled in two streams, one stream (which is 0-20 wt% of the total recycle amount of the catalytically cracked light cycle oil) is recycled to the first hydrogenation unit 30 via line 19 and line 22, and the other stream is recycled to the second fractionation unit 33 via line 19 and line 23, or is mixed with optional external catalytically cracked light cycle oil from line 42 and then enters the second fractionation unit 33.
The following examples further illustrate the present invention, but the examples do not limit the present invention at all.
In the present invention, the gasoline octane number determination method (RON) is carried out by the GB/T5487-2015 method, and the gasoline octane number determination method (motor method, MON) is carried out by the GB/T503-2016 method. The sulfur content of the gasoline is measured by SH/T0689-2000.
Example 1
The embodiment adopts the method provided by the invention. As shown in fig. 1, the vacuum wax oil with properties shown in table 1 is sent to a solvent extraction device 29, and extracted oil and raffinate oil are obtained through extraction; the extract oil, the light cycle oil accounting for 5 wt% of the total cycle weight of the light cycle oil, the recycle oil and hydrogen are mixed and then sent to a first hydrogenation device 30 for first hydrogenation treatment, so that gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated tail oil are obtained. Feeding hydrogenated tail oil into a first fractionating device 31 for first fractionating to obtain hydrogenated tail oil light fraction and hydrogenated tail oil heavy fraction, feeding the mixture of the hydrogenated tail oil light fraction, hydrogenated naphtha and hydrogenated diesel oil into a steam cracking device 32, feeding light cycle oil accounting for 95 wt% of the total cycle weight of the light cycle oil into a second fractionating device 33 for second fractionating to obtain light cycle oil light fraction and light cycle oil heavy fraction, feeding the light cycle oil light fraction into the middle part of a first reaction zone 37 of a riser reactor, feeding the light cycle oil heavy fraction into the lower part of the first reaction zone 37 of the riser reactor after second hydrogenation treatment, carrying out first catalytic cracking reaction under the action of a catalytic cracking catalyst to obtain a semi-spent catalyst and a first reaction product, feeding the semi-spent catalyst and the first reaction product into a second reaction zone 36 to carry out second catalytic cracking reaction together with raffinate oil from a solvent extraction device 29 and the hydrogenated tail oil heavy fraction, separating the spent catalyst and the second reaction product, and treating to obtain dry gas, liquefied gas, a gasoline product, a light cycle oil product, a recycle oil product and oil slurry. The recycle oil product is recycled to the first hydrogenation unit 30; the light cycle oil product is recycled to the second fractionation unit 33.
The solvent extraction device is an extraction tower, the extraction solvent enters the extraction tower from the top of the extraction tower, the heavy raw material enters the extraction tower from the bottom of the extraction tower, the temperature of the extraction tower is 60 ℃, the extraction solvent is furfural, and the weight ratio of the extraction solvent to the heavy raw material is 1: 1; the cutting temperature of the light and heavy fractions of the light cycle oil fractionation device in the second fractionation device is controlled at 260 ℃; the cutting temperature of the first fractionation device is controlled at 230 ℃; the temperature of the steam cracking device is controlled at 810 ℃. In the embodiment, the commercial brand of the hydrotreating catalyst filled in the fixed bed reactor for carrying out the second hydrotreating on the heavy fraction is RN-23V, the commercial brand of the protective agent is RG-1, and the filling volume ratio of the hydrotreating catalyst to the protective agent is 95:5, which are all produced by China petrochemical catalyst division. In the embodiment, the first hydrotreatment of the extract oil is carried out in a double reactor, the first reactor is filled with a hydrogenation protective agent and a hydrodemetallization catalyst, the second reactor is filled with a hydrodesulfurization catalyst, and the ratio of the hydrogenation protective agent to the hydrodemetallization catalyst is 5:45:50, wherein the commercial brands of the hydrogenation protective agent, the hydrodemetallization catalyst and the hydrodesulfurization catalyst are RG-20B, RDM-33 and RMS-30 respectively. The commercial designation of the catalyst used in the catalytic cracker in the examples was CGP-1. The hydrotreater operating conditions are shown in table 2, the catalytic cracking operating conditions are shown in table 3, the steam cracking product distribution is 4, and the catalytic cracking product distribution is shown in table 5.
Comparative example 1
The operation parameters of the solvent extraction device, the first hydrogenation device and the first fractionation device in this example are the same as those of example 1, except that all the light cycle oil directly enters the lower part of the first reaction zone of the riser reactor without the second fractionation and the second hydrogenation. The hydrotreater operating conditions are shown in table 2, the catalytic cracking operating conditions are shown in table 3, the steam cracking product distribution is 4, and the catalytic cracking product distribution is shown in table 5.
As can be seen from tables 4-5, the method of the invention can reduce the sulfur content in the gasoline product, improve the octane number of the gasoline, and produce gasoline and low-carbon olefins such as ethylene, propylene and the like in a large amount.
Table 1 heavy feedstock properties
| Raw oil name | Pressure-reducing wax oil |
| Density (20 deg.C), kg/m3 | 932.1 |
| Distillation range, deg.C | |
| Initial boiling point | 256 |
| 50% by weight | 357 |
| 95% by weight | 585 |
| Mass Spectrometry Hydrocarbon composition, weight% | |
| Alkane hydrocarbons | 18.4 |
| Total cycloalkanes | 24.9 |
| Total aromatic hydrocarbons | 55.3 |
| Glue | 1.3 |
TABLE 2 hydrogenation unit operating conditions
| Item | First hydrogenation unit 30 | |
| Reaction conditions | ||
| Partial pressure of hydrogen, MPa | 6.5 | 15 |
| Volumetric space velocity, hour-1 | 1.2 | 0.9 |
| Reaction temperature of | 360 | 380 |
| Volume ratio of hydrogen to oil, Nm3/m3 | 1100 | 700 |
TABLE 3 catalytic cracking operating conditions
TABLE 4 steam cracking product distribution
| Example 1 | Comparative example 1 | |
| Yield of gaseous product,% by weight | ||
| Hydrogen gas | 0.43 | 0.45 |
| Carbon monoxide | 0.03 | 0.06 |
| Methane | 13.92 | 14.10 |
| Ethane (III) | 3.12 | 3.43 |
| Ethylene | 33.56 | 32.71 |
| Acetylene | 0.46 | 0.55 |
| Propane | 0.82 | 0.78 |
| Propylene (PA) | 18.15 | 17.35 |
| Propyne | 0.19 | 0.21 |
| Allene | 0.24 | 0.25 |
| Isobutane | 0.05 | 0.06 |
| N-butane | 0.13 | 0.13 |
| 1-butene | 4.35 | 4.15 |
| Butadiene | 6.50 | 5.73 |
| Acid gas | 0.04 | 0.05 |
| Yield of liquid product,% by weight | ||
| Pyrolysis gasoline | 14.27 | 15.67 |
| Light diesel oil | 1.34 | 1.60 |
| Fuel oil | 2.40 | 2.72 |
| Total of | 100.00 | 100.00 |
| Ethylene + propylene, wt.% | 51.71 | 50.06 |
TABLE 5 catalytic cracking product distribution
| Example 1 | Comparative example 1 | |
| Product distribution, weight% | ||
| Dry gas | 4.89 | 5.12 |
| Liquefied gas | 20.12 | 21.42 |
| Gasoline (gasoline) | 58.56 | 56.26 |
| Diesel oil | 0.00 | 0.00 |
| Oil slurry | 8.67 | 9.49 |
| Coke | 7.65 | 8.55 |
| Loss of power | 0.11 | 0.16 |
| Total up to | 100.00 | 100.00 |
| Ethylene + propylene, wt.% | 8.12 | 7.15 |
| Octane number of gasoline | ||
| MON | 93.1 | 92.7 |
| RON | 81.2 | 80.3 |
| Gasoline sulfur content, microgram/gram | 18 | 25 |
Claims (14)
1. A method for increasing the yield of high-octane gasoline and low-carbon olefins comprises the following steps:
sending the heavy raw material into a solvent extraction device for solvent extraction treatment to obtain extract oil and raffinate oil;
sending the extract oil into a first hydrogenation device to contact with a first hydrogenation catalyst and carrying out first hydrogenation treatment to obtain hydrogenated naphtha, hydrogenated diesel oil and hydrogenated tail oil;
sending the obtained hydrogenated tail oil into a first fractionation device for first fractionation to obtain a hydrogenated tail oil light fraction and a hydrogenated tail oil heavy fraction, wherein the temperature of the first fractionation is 200-300 ℃;
feeding the light cycle oil into a second fractionation device for second fractionation to obtain a light cycle oil light fraction and a light cycle oil heavy fraction, wherein the temperature of the second fractionation is 220-270 ℃;
sending the light cycle oil heavy fraction into a second hydrogenation device to contact with a second hydrogenation catalyst and carrying out second hydrogenation treatment to obtain a second hydrogenation product;
feeding a second hydrogenation product into the lower part of a first reaction zone of the riser reactor from a first nozzle, feeding the light fraction of the light cycle oil into the middle part of the first reaction zone from a second nozzle, contacting with a catalytic cracking catalyst, and carrying out a first catalytic cracking reaction to obtain a first product and a semi-spent catalyst; the riser reactor is also provided with a second reaction zone positioned above the first reaction zone;
feeding the obtained first product and the semi-spent catalyst into a second reaction zone, and carrying out a second catalytic cracking reaction on the first product and the semi-spent catalyst together with the raffinate oil and the hydrogenated tail oil heavy fraction which are sprayed into the second reaction zone from a third nozzle to obtain a second product and a spent catalyst;
separating the second product to obtain dry gas, liquefied gas, a gasoline product, a light cycle oil product, a cycle oil product and oil slurry;
sending the obtained light cycle oil product into the second fractionating device, and sending the obtained cycle oil product into the first hydrogenation device;
and sending the hydrogenated naphtha, the hydrogenated diesel oil and the hydrogenated tail oil light fraction into a steam cracking device for steam cracking to obtain a steam cracking product.
2. The process according to claim 1, wherein the heavy feedstock is at least one selected from the group consisting of vacuum wax oil, hydrogenated vacuum wax oil, coker wax oil, deasphalted oil, atmospheric residue, and vacuum residue.
3. The method of claim 1, wherein the conditions of the solvent extraction process comprise: the solvent extraction device is an extraction tower, an extraction solvent enters the extraction tower from the top of the extraction tower, a heavy raw material enters the extraction tower from the bottom of the extraction tower, the temperature of the extraction tower is 50-70 ℃, the extraction solvent is furfural, and the weight ratio of the extraction solvent to the heavy raw material is (1-2): 1.
4. the method of claim 1, wherein the first hydrotreating conditions comprise: hydrogen partial pressure of 4-20 MPa, temperature of 330-450 deg.C, liquid hourly space velocity of 0.1-3.0 hr-1Hydrogen to oil volume ratio of 250-1800Nm3/m3。
5. The process of claim 1, wherein the first hydrogenation catalyst comprises a support which is at least one selected from the group consisting of alumina, silica and amorphous silica-alumina and an active component which is at least one selected from the group consisting of a group VIB metal and/or a non-noble group VIII metal.
6. The method of claim 1, wherein the second hydrotreating conditions comprise: hydrogen partial pressure of 3-30 MPa, temperature of 310-450 deg.C, volume per liquidThe space velocity is 0.1-10.0 hours-1Hydrogen to oil volume ratio of 100-1500Nm3/m3。
7. The process of claim 1, wherein the second hydrogenation catalyst comprises a support which is at least one selected from alumina, silica and amorphous silica-alumina and an active component which is at least one selected from a group VIB metal and/or a non-noble group VIII metal.
8. The process of claim 1, wherein the conditions of the first catalytic cracking reaction comprise: the reaction temperature is 440-680 ℃, the absolute reaction pressure is 0.1-0.5 MPa, the weight ratio of the solvent to the oil is 1-50, the reaction time is 0.1-10 seconds, and the water-oil ratio is 0.01-100;
the conditions of the second catalytic cracking reaction include: the reaction temperature is 420-680 ℃, the absolute reaction pressure is 0.1-0.5 MPa, the weight ratio of the catalyst to the oil is 1-50, the reaction time is 0.1-10 seconds, and the water-oil ratio is 0.01-100.
9. The process of claim 1 wherein the catalytic cracking catalyst comprises a zeolite which is one selected from rare earth-containing or non-containing Y, HY, USY and Beta zeolites, an inorganic oxide and optionally a clay.
10. The method of claim 1 wherein the riser reactor is a constant diameter riser reactor or a variable diameter riser reactor.
11. The process of claim 1, wherein the temperature of the steam cracking is 750-900 ℃.
12. The method of claim 1 wherein the residence time of the oil and gas in the riser reactor between the first nozzle and the second nozzle is between 0.1 and 5 seconds.
13. The process of claim 1, wherein at least a portion of the light cycle oil product and/or produced light cycle oil is sent together to the first hydrotreater for first hydrotreatment; the light cycle oil product and/or the produced light cycle oil accounts for 0-10 wt% of the total feed of the first hydrogenation device; and/or
And sending at least part of raffinate oil into the steam cracking device for steam cracking.
14. A system suitable for the method for producing more high octane gasoline and lower olefins according to any one of claims 1 to 13, which comprises a solvent extraction device (29), a first hydrogenation device (30), a first fractionation device (31), a second fractionation device (33), a second hydrogenation device (34), a riser reactor, a settler (35), a regenerator (38), a catalytic cracking fractionation device (39) and a steam cracking device (32);
the device comprises a solvent extraction device (29), a first hydrogenation device (30), a second distillation device (33), a first hydrogenation device (34), a second hydrogenation device (36), a riser reactor, a first reaction zone (37) and a second reaction zone (36), wherein the solvent extraction device (29) is provided with a heavy raw material inlet, an extract oil outlet and a raffinate oil outlet, the first hydrogenation device (30) is provided with an inlet, a hydrogenated naphtha outlet, a hydrogenated diesel oil outlet and a hydrogenated tail oil outlet, the first distillation device (31) is provided with an inlet, a hydrogenated tail oil light fraction outlet and a hydrogenated tail oil heavy fraction outlet, the second distillation device (33) is provided with an inlet, a light cycle oil light fraction outlet and a light cycle oil heavy fraction outlet, the second hydrogenation device (34) is provided with an inlet and a hydrogenated product outlet, the riser reactor is provided with a first reaction zone (37) and a second reaction zone (36) which are coaxial and are in fluid communication from bottom to top, the first reaction zone (, the settler (35) is sleeved at the upper part of the second reaction zone (36), the top outlet of the second reaction zone (36) is positioned in the settler (35), the settler (35) is provided with a top oil gas outlet and a lower catalyst outlet, the regenerator (38) is provided with a catalyst inlet and a catalyst outlet, the catalytic cracking fractionation device (39) is provided with an inlet, a dry gas outlet, a liquefied gas outlet, a gasoline outlet, a light cycle oil outlet, a recycle oil outlet and an oil slurry outlet, and the steam cracking device (32) is provided with an inlet and a product outlet;
the extract oil outlet of the solvent extraction device (29), the recycle oil outlet of the catalytic cracking fractionation device (39) and the optional light cycle oil outlet of the catalytic cracking fractionation device (39) are communicated with the inlet of the first hydrogenation device (30), the hydrogenated tail oil outlet of the first hydrogenation device (30) is communicated with the inlet of the first fractionation device (31), the light cycle oil outlet of the catalytic cracking fractionation device (39) is communicated with the inlet of the second fractionation device (33), the light cycle oil heavy fraction outlet of the second fractionation device (33) is communicated with the inlet of the second hydrogenation device (34), the hydrogenated product outlet of the second hydrogenation device (34) is communicated with a first nozzle at the lower part of the first reaction zone (37), and the light cycle oil light fraction outlet of the second fractionation device (33) is communicated with a second nozzle at the middle part of the first reaction zone (37), the raffinate outlet of the solvent extraction device (29) and the heavy fraction outlet of the hydrogenated tail oil of the first fractionation device (31) are communicated with a third nozzle at the lower part of the second reaction zone (36), the top oil gas outlet of the settler (35) is communicated with the inlet of the catalytic cracking fractionation device (39), the catalyst outlet of the settler (35) is communicated with the catalyst inlet of the regenerator (38), the catalyst outlet of the regenerator (38) is communicated with the catalyst inlet of the first reaction zone (37), and the hydrogenated naphtha outlet and the hydrogenated diesel oil outlet of the first hydrogenation device (30), the light fraction outlet of the hydrogenated tail oil of the first fractionation device (31) and the raffinate outlet of the optional solvent extraction device (29) are communicated with the inlet of the steam cracking device (32).
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| CN112708461B (en) | 2019-10-24 | 2022-06-24 | 中国石油化工股份有限公司 | Method for increasing yield of propylene and low-sulfur fuel oil components |
| CN112745949B (en) * | 2019-10-31 | 2022-06-28 | 中国石油化工股份有限公司 | Method and system for combined processing of deoiled asphalt and aromatic-rich distillate oil |
| CN112745948B (en) * | 2019-10-31 | 2022-06-28 | 中国石油化工股份有限公司 | Method and system for processing heavy raw oil and aromatic-enriched distillate oil |
| CN114479928B (en) * | 2020-10-26 | 2023-07-21 | 中国石油化工股份有限公司 | Method and system for preparing low-carbon olefin |
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