CN110655952B - Method and system for producing light olefins and aromatic hydrocarbons in high yield - Google Patents
Method and system for producing light olefins and aromatic hydrocarbons in high yield Download PDFInfo
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- CN110655952B CN110655952B CN201810689048.6A CN201810689048A CN110655952B CN 110655952 B CN110655952 B CN 110655952B CN 201810689048 A CN201810689048 A CN 201810689048A CN 110655952 B CN110655952 B CN 110655952B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Abstract
The invention relates to a method and a system for producing light olefins and aromatic hydrocarbons in a high yield, wherein the method comprises the following steps: separating the diesel raw material into a light diesel fraction and a heavy diesel fraction; carrying out hydrofining treatment on the obtained heavy diesel oil fraction to obtain a hydrofined product; carrying out a first catalytic cracking reaction on the obtained hydrofined product; carrying out a second catalytic cracking reaction on the obtained first catalytic cracking product and the semi-spent catalyst; carrying out a third catalytic cracking reaction on the obtained light diesel oil fraction to obtain a third catalytic cracking product and a second spent catalyst; and separating the obtained second catalytic cracking product and the third catalytic cracking product to obtain a low-carbon olefin product, a light naphtha product, a heavy naphtha product, a circulating oil product and an oil slurry product. The process and system of the present invention can increase the yield of propylene, butenes, and aromatics.
Description
Technical Field
The invention relates to a method and a system for producing light olefins and aromatic hydrocarbons in a high yield.
Background
Ethylene, propylene and light aromatic hydrocarbons (benzene, toluene and xylene, abbreviated as BTX) are basic chemical raw materials, and the conventional petrochemical industry is based on the production of ethylene by steam cracking. In our country, the main raw material of steam cracking is naphtha, while crude oil in our country is generally heavier, the yield of light oil is lower, and the raw material for steam cracking production is obviously insufficient, so that the traditional steam cracking process is restricted by the raw material supply in our country, and meanwhile, in recent years, the wide application of a steam cracking device using shale gas as the raw material in north america continuously squeezes the economy of the process using naphtha as the raw material for ethylene cracking. 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.
At present, one of the main devices for producing propylene in oil refining chemical enterprises is a catalytic cracking device. The main raw materials of the catalytic cracking device comprise naphtha, diesel oil, wax oil and residual oil, wherein the yield of propylene in the catalytic cracking unit can reach 20 percent or even more than 30 percent after the residual oil raw material is subjected to hydrotreating. However, catalytic crackers that use diesel as the feedstock have a low propylene yield. Therefore, by selecting a proper process route, the yield of propylene produced by catalytic cracking of diesel oil and the production of light aromatic hydrocarbon are improved greatly.
Chinese patent CN106590741A discloses a catalytic conversion method for high yield of low carbon olefins and light aromatics, in which gasoline component rich in aromatics and initial catalytic cracking product are further catalytically cracked to finally obtain liquefied gas rich in low carbon olefins, gasoline fraction rich in light aromatics, diesel oil fraction and slurry oil. The raw oil can be at least one of C4 distillate oil, gasoline, diesel oil, crude oil, wax oil, coal liquefied oil and oil sand oil, the method can further catalytically crack the gasoline component rich in aromatic hydrocarbon, and the obtained gasoline component rich in aromatic hydrocarbon is subjected to aromatic hydrocarbon extraction, but the raw material is not optimized, and the source of the gasoline component is limited, so the improvement range of the yield of light aromatic hydrocarbon is limited.
Chinese patent CN101063047A discloses a method for hydrotreating-catalytic cracking heavy raw material for improving propylene yield, heavy distillate oil and optional light cycle oil from a catalytic cracking unit can be reacted together in one reaction zone, or can be reacted in two hydrogenation reaction zones filled with different hydrogenation catalysts, respectively, after cooling, separating and fractionating the reaction effluent, the obtained heavy liquid phase fraction is sent to the catalytic cracking unit, and the catalytic cracking reaction product is separated by a separator to obtain the final product. According to the method provided by the patent, the property of the wax oil raw material of the catalytic cracking unit is improved through a hydrotreating method, but the diesel oil raw material is not cut, so that the hydrogenation consumption is increased in the hydrogenation process, the yield of light aromatic hydrocarbon is reduced, the light naphtha fraction is not recycled, and the yield of low-carbon olefin is further reduced.
Chinese patent CN101139529A discloses a coking diesel oil-steam cracking combined process method, which takes heavy hydrogenation coking diesel oil as a raw material, and the heavy hydrogenation coking diesel oil is subjected to fixed bed hydrotreating to generate oil for fraction cutting, wherein the cutting point is 260-320 ℃, and the hydrogenation heavy components directly enter a cracking furnace, so that the yield of the low-carbon olefins ethylene, propylene and butadiene is about 27%.
Disclosure of Invention
The invention aims to provide a method and a system for producing light olefins and aromatic hydrocarbons in a high yield, and the method and the system can improve the yield of propylene, butylene and aromatic hydrocarbons.
In order to achieve the above object, the present invention provides a method for increasing the yield of lower olefins and aromatic hydrocarbons, the method comprising:
separating the diesel raw material into a light diesel fraction and a heavy diesel fraction, wherein the cut points of the light diesel fraction and the heavy diesel fraction are in the range of 220 ℃ and 240 ℃;
introducing the obtained heavy diesel oil fraction into a hydrofining reactor to contact with a hydrofining catalyst and carrying out hydrofining treatment to obtain a hydrofining product;
introducing the obtained hydrofined product into a first catalytic cracking reactor to contact with a first catalytic cracking catalyst and carry out a first catalytic cracking reaction to obtain a first catalytic cracking product and a semi-spent catalyst;
introducing the obtained first catalytic cracking product and the semi-spent catalyst into a second catalytic cracking reactor to carry out a second catalytic cracking reaction to obtain a second catalytic cracking product and a first spent catalyst;
introducing the obtained light diesel oil fraction into a third catalytic cracking reactor to contact with a second catalytic cracking catalyst and carry out a third catalytic cracking reaction to obtain a third catalytic cracking product and a second spent catalyst;
separating the obtained second catalytic cracking product and the third catalytic cracking product to obtain a low-carbon olefin product, a light naphtha product, a heavy naphtha product, a circulating oil product and an oil slurry product;
and feeding the obtained first spent catalyst and the second spent catalyst into a regenerator for regeneration, wherein the obtained regenerated catalyst is used as the first catalytic cracking catalyst and the second catalytic cracking catalyst.
Optionally, the method further comprises at least one of the following steps:
(1) introducing the obtained light naphtha product into the third catalytic cracking reactor to carry out the third catalytic cracking reaction;
(2) introducing the obtained cycle oil product into the hydrofining reactor to carry out hydrofining treatment;
(3) and introducing at least part of second spent catalyst obtained by the third catalytic cracking reaction into the second catalytic cracking reactor to carry out the second catalytic cracking reaction.
Optionally, the cetane number of the diesel fuel raw material is less than 25, and the distillation range is in the range of 170-400 ℃.
Optionally, the diesel feedstock comprises catalytic cracking diesel, with or without coker diesel.
Optionally, the hydrorefining catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the carrier is at least one selected from alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia, and the active metal component is at least one selected from group VIB metal elements and VIII and at least one selected from group VIII metal elements; based on the total weight of the hydrofining catalyst, the content of at least one metal element selected from VIB group is 1-30 wt% calculated by oxide, and the content of at least one metal element selected from VIII group is 3-35 wt% calculated by oxide;
the conditions of the hydrofining treatment comprise: the hydrogen partial pressure is 3-12MPa, the reaction temperature is 260 ℃ to 450 ℃, and the volume ratio of hydrogen to oil is 400 Nm to 1600Nm3/m3The liquid hourly space velocity is 0.3-4.0h-1。
Optionally, in the hydrofining treatment, the polycyclic aromatic hydrocarbon saturation rate of the heavy diesel oil fraction is not less than 85 wt%, the total aromatic hydrocarbon saturation rate of the heavy diesel oil fraction is 12-35 wt%, and the distillation range of the hydrofining product is within the range of 200-400 ℃.
Optionally, the conditions of the first catalytic cracking reaction include: the reaction temperature is 500-650 ℃, the reaction time is 0.5-8s, the reaction pressure is 0.10-1.0MPa, and the weight ratio of the first catalytic cracking catalyst to the hydrorefining product is (2-100): 1, the weight ratio of the atomized steam to the hydrofining product is (0.05-0.5): 1;
the reaction temperature of the second catalytic cracking reaction is 10-100 ℃ higher than that of the first catalytic cracking reaction, and the weight hourly space velocity of the second catalytic cracking reaction is 1-35h-1；
The conditions of the third catalytic cracking reaction include: the reaction temperature is 600-750 ℃, the reaction time is 0.5-10s, the reaction pressure is 0.1-1.0MPa, and the weight ratio of the second catalytic cracking catalyst to the light diesel fraction is (4-100): 1.
optionally, the reaction temperature of the third catalytic cracking reaction is 30-100 ℃ higher than the reaction temperature of the second catalytic cracking reaction.
Optionally, the first catalytic cracking catalyst and the second catalytic cracking catalyst each independently comprise a zeolite, an inorganic oxide binder, and optionally a clay;
based on the total weight of the catalyst, the content of the zeolite is 10-50 wt%, the content of the inorganic oxide is 5-90 wt%, and the content of the clay is 0-70 wt%;
the zeolite is at least one selected from the group consisting of rare earth-containing or non-rare earth-containing Y-type or HY-type zeolite, rare earth-containing or non-rare earth-containing ultrastable Y-type zeolite, and zeolite having MFI structure.
Optionally, the distillation range of the light naphtha product is within 65-135 ℃, the distillation range of the heavy naphtha product is within 130-175 ℃, and the distillation range of the cycle oil product is within 175-450 ℃.
Optionally, the first catalytic cracking reactor and the third catalytic cracking reactor are both riser reactors, and the second catalytic cracking reactor is a fluidized bed reactor.
The invention also provides a system for producing the light olefins and the aromatic hydrocarbons in a high yield, which comprises a fractionation device, a hydrofining reactor, a first catalytic cracking reactor, a second catalytic cracking reactor, a third catalytic cracking reactor, a regenerator, a second oil agent separation device and a product separation device;
the fractionating device is provided with a diesel raw material inlet, a light diesel fraction outlet and a heavy diesel fraction outlet, the hydrofining reactor is provided with a hydrogen inlet, a raw oil inlet and a hydrofining product outlet, the first catalytic cracking reactor, the second catalytic cracking reactor and the third catalytic cracking reactor are respectively and independently provided with a material inlet and a material outlet, the second oil agent separating device is provided with a material inlet, an oil gas outlet and a catalyst outlet, the regenerator is provided with a catalyst inlet and a catalyst outlet, and the product separating device is provided with an oil gas inlet, a low-carbon olefin outlet, a light naphtha outlet, a heavy naphtha outlet, a circulating oil outlet and an oil slurry outlet;
a heavy diesel oil fraction outlet of the fractionating device is communicated with a raw oil inlet of the hydrofining reactor, a hydrofining product outlet of the hydrofining reactor is communicated with a material inlet of the first catalytic cracking reactor, a material outlet of the first catalytic cracking reactor is communicated with a material inlet of the second catalytic cracking reactor, a material outlet of the second catalytic cracking reactor is communicated with a material inlet of the second oil separating device, a light diesel oil fraction outlet of the fractionating device is communicated with a material inlet of the third catalytic cracking reactor, and a material outlet of the third catalytic cracking reactor is communicated with a material inlet of the second oil separating device; and a catalyst outlet of the second oil agent separation device is communicated with a catalyst inlet of the regenerator, a catalyst outlet of the regenerator is respectively communicated with material inlets of the first catalytic cracking reactor and the third catalytic cracking reactor, and an oil-gas outlet of the second oil agent separation device is communicated with an oil-gas inlet of the product separation device.
Optionally, the system further includes a first oil separation device, the first oil separation device is provided with a material inlet, a catalyst outlet and an oil-gas outlet, the material outlet of the third catalytic cracking reactor is communicated with the material inlet of the first oil separation device, the catalyst outlet of the first oil separation device is communicated with the material inlet of the second catalytic cracking reactor, and the oil-gas outlet of the first oil separation device is communicated with the material inlet of the second oil separation device; and/or
A light naphtha outlet of the product separation device is communicated with a material inlet of the third catalytic cracking reactor; and/or
And a circulating oil outlet of the product separation device is communicated with a raw oil inlet of the hydrofining reactor.
Optionally, the first catalytic cracking reactor and the third catalytic cracking reactor are both riser reactors, and the second catalytic cracking reactor is a fluidized bed reactor.
According to the method and the system, high-value products such as propylene, ethylene, aromatic hydrocarbon and the like with high yield can be obtained by cutting the diesel raw material, then carrying out hydrofining on the heavy diesel fraction, and carrying out catalytic cracking treatment on the light diesel fraction and the hydrofined product in different reactors.
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. 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.
FIG. 2 is a schematic flow diagram of the process of comparative example 1 of the present invention.
Description of the reference numerals
1 pipeline 2 diesel fractionating tower 3 pipeline
4 line 5 hydrofining reactor 6 recycle hydrogen compressor
7 line 8 line 9 line
10 separator 11 line 12 first catalytic cracking reactor
13 second catalytic cracking reactor 14 regenerator 15 third catalytic cracking reactor
16 first oil agent separation device 17 second oil agent separation device 18 product separation device
19 line 20 line 21 line
22 line 23 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 light olefins and aromatics in a high yield, which comprises the following steps:
separating the diesel raw material into a light diesel fraction and a heavy diesel fraction, wherein the cut point of the light diesel fraction and the heavy diesel fraction is in the range of 220-240 ℃, preferably 225-235 ℃, and further preferably 228-235 ℃;
introducing the obtained heavy diesel oil fraction into a hydrofining reactor to contact with a hydrofining catalyst and carrying out hydrofining treatment to obtain a hydrofining product;
introducing the obtained hydrofined product into a first catalytic cracking reactor to contact with a first catalytic cracking catalyst and carry out a first catalytic cracking reaction to obtain a first catalytic cracking product and a semi-spent catalyst;
introducing the obtained first catalytic cracking product and the semi-spent catalyst into a second catalytic cracking reactor to carry out a second catalytic cracking reaction to obtain a second catalytic cracking product and a first spent catalyst;
introducing the obtained light diesel oil fraction into a third catalytic cracking reactor to contact with a second catalytic cracking catalyst and carry out a third catalytic cracking reaction to obtain a third catalytic cracking product and a second spent catalyst;
separating the obtained second catalytic cracking product and the third catalytic cracking product to obtain a low-carbon olefin product, a light naphtha product, a heavy naphtha product, a circulating oil product and an oil slurry product; the lower olefins may include ethylene and propylene;
and feeding the obtained first spent catalyst and the second spent catalyst into a regenerator for regeneration, wherein the obtained regenerated catalyst is used as the first catalytic cracking catalyst and the second catalytic cracking catalyst.
According to the invention, the method may further comprise at least one of the following steps: (1) introducing the obtained light naphtha product into the third catalytic cracking reactor to carry out the third catalytic cracking reaction; (2) introducing the obtained cycle oil product into the hydrofining reactor to carry out hydrofining treatment; (3) and introducing at least part of second spent catalyst obtained by the third catalytic cracking reaction into the second catalytic cracking reactor to carry out the second catalytic cracking reaction. The steps (1) to (2) can improve the utilization rate of the raw materials and the yield of the low-carbon olefin, and the step (3) can improve the utilization rate of the second spent catalyst which is obtained by the third catalytic cracking reaction and has low coke formation.
Diesel feedstocks, which may or may not include coker gas oil, may have a cetane number of less than 25, and a distillation range of about 170-. In the hydrofining treatment, at least part of polycyclic aromatic hydrocarbon in the heavy diesel oil fraction can be saturated to improve the cracking performance and generate more olefin and aromatic hydrocarbon, wherein in the hydrofining treatment, the polycyclic aromatic hydrocarbon saturation rate of the heavy diesel oil fraction can be not less than 85 weight percent, preferably not less than 90 weight percent and preferably not more than 95 weight percent, the total aromatic hydrocarbon saturation rate of the heavy diesel oil fraction can be 12-35 weight percent and preferably 15-32 weight percent, and the distillation range of the hydrofining product is preferably within the range of 200-; wherein the content of the first and second substances,
the polycyclic aromatic hydrocarbon saturation ratio of the heavy diesel oil fraction is calculated by adopting the following formula:
a2m ═ (A2 f-A2 p)/A2f × 100% by weight;
in the formula: a2m is polycyclic aromatic hydrocarbon saturation rate of heavy diesel oil fraction, weight percent;
a2f is the weight fraction of polycyclic aromatic hydrocarbon in the heavy diesel oil fraction;
a2p is the weight percentage of polycyclic aromatic hydrocarbon in the hydrofining product of heavy diesel oil fraction.
The total aromatics saturation of the heavy diesel fraction is calculated using the following formula:
ata ═ (Aaf-Aap)/Aaf × 100% by weight;
in the formula: ata is the total aromatic saturation rate of the heavy diesel oil fraction, weight percent;
aaf is the weight fraction of all aromatics in the heavy diesel fraction;
aap is the weight fraction of all aromatics in the heavy diesel distillate hydrofinishing product, wt%.
The separation of the diesel feedstock according to the invention is well known to the person skilled in the art and can be, for example, a fractionation, which leads to a catalytic cracking of the light diesel fraction without hydrogenation, thus reducing the hydrogen consumption while producing more olefins and aromatics.
According to the present invention, the hydrofinishing catalyst may comprise a carrier which may be at least one selected from the group consisting of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia, and an active metal component supported on the carrier, the active metal component being at least one selected from the group VIB metal elements and at least one selected from the group VIII metal elements, the group VIB metal element preferably being molybdenum and/or tungsten, the VIII group metal element is preferably cobalt and/or nickel; based on the total weight of the hydrofining catalyst, the content of at least one metal element selected from VIB group is 1-30 wt% calculated by oxide, and the content of at least one metal element selected from VIII group is 3-35 wt% calculated by oxide; the hydrofinishing catalyst may be in the form of extrudates or spheres and may have a bulk density of from 0.4 to 1.3g/cm3The average particle diameter (spherical diameter or bar diameter) of the catalyst may be 0.08-1.2mm, and the specific surface area may be 100-300m2/g。
According to the invention, the conditions of the hydrofinishing treatment may include: the hydrogen partial pressure is 3-12MPa, preferably 6-12MPa, the reaction temperature is 260-450 ℃, preferably 280-400 ℃, and the volume ratio of hydrogen to oil is 400-1600Nm3/m3Preferably 500-1000Nm3/m3The liquid hourly space velocity is 0.3-4.0h-1Preferably 0.5 to 2.0h-1。
Catalytic cracking reactions are well known to those skilled in the art in light of the present disclosure and are not described in detail herein. The invention sets different reactors and different reaction conditions for different raw materials to optimize the cracking performance of each raw material. The conditions of the first catalytic cracking reaction may include: the reaction temperature is 500-650 ℃, preferably 540-600 ℃, the reaction time is 0.5-8s, preferably 1-5s, and the reaction pressure isThe absolute pressure is 0.10-1.0MPa, and the weight ratio of the first catalytic cracking catalyst to the hydrofining product is (2-100): 1, preferably (5-50): 1, the weight ratio of the atomized steam to the hydrofining product is (0.05-0.5): 1, preferably (0.1-0.25): 1; the reaction temperature of the second catalytic cracking reaction is 10-100 ℃, preferably 20-60 ℃ higher than that of the first catalytic cracking reaction, and the weight hourly space velocity of the second catalytic cracking reaction is 1-35h-1Preferably 2 to 33h-1(ii) a The conditions of the third catalytic cracking reaction include: the reaction temperature is 600-750 ℃, preferably 600-700 ℃, the reaction time is 0.5-10s, preferably 2-8s, the reaction pressure (absolute pressure) is 0.1-1.0MPa, and the weight ratio of the second catalytic cracking catalyst to the light diesel oil fraction is (4-100): 1, preferably (5-80): 1. further preferably, the reaction temperature of the third catalytic cracking reaction is higher than that of the second catalytic cracking reaction, preferably 30-100 ℃ higher, and more preferably 40-80 ℃ higher, so that the yield of the low-carbon olefin and the aromatic hydrocarbon is improved.
According to the present invention, it is preferred that the reaction raw materials fed into each reactor are preheated to a temperature not higher than the reaction temperature, for example, the hydrofinishing product fed into the first catalytic cracking reactor is preheated to 250-450 ℃, and the light diesel fraction, raffinate and light naphtha products fed into the third catalytic cracking reactor are preheated to 100-250 ℃.
In the invention, the oil agent mixture obtained by the third catalytic cracking reactor and the second catalytic cracking reactor can be mixed and then subjected to oil agent separation, or can be separated respectively, preferably, after the oil agent mixture obtained by the third catalytic cracking reactor is subjected to oil agent crude separation in the first oil agent separation device, the obtained second spent catalyst is sent into the second catalytic cracking reactor for reaction, and the obtained third reaction product carrying the catalyst is separated from the oil agent obtained by the second catalytic cracking reactor.
According to the present invention, the first catalytic cracking catalyst and the second catalytic cracking catalyst may be the same or different, preferably the same, and may each independently comprise a zeolite, an inorganic oxide binder, and optionally a clay; the zeolite may be present in an amount of 10 to 50 wt%, the inorganic oxide may be present in an amount of 5 to 90 wt%, and the clay may be present in an amount of 0 to 70 wt%, based on the total weight of the catalyst (clay content of 0 wt% indicates no clay); the zeolite is at least one selected from Y-type or HY-type zeolite with or without rare earth, ultrastable Y-type zeolite with or without rare earth, and zeolite with MFI structure, the inorganic oxide binder may be alumina and/or silica, and the clay may be kaolin, halloysite, etc.
The manner in which the catalytic cracking product is separated in accordance with the present invention is well known to those skilled in the art, the light naphtha product may have a boiling range of 65-135 deg.C, the heavy naphtha product may have a boiling range of 130-175 deg.C, and the cycle oil product may have a boiling range of 175-450 deg.C.
According to the present invention, the catalytic cracking reactor is well known to those skilled in the art, the first catalytic cracking reactor, the second catalytic cracking reactor and the third catalytic cracking reactor may each independently include at least one of a riser reactor, a fluidized bed reactor and a downer reactor, each reactor may be of a constant diameter or a variable diameter, and preferably, the first catalytic cracking reactor and the third catalytic cracking reactor are both riser reactors, and the second catalytic cracking reactor is a fluidized bed reactor.
As shown in fig. 1, the present invention further provides a system for producing a large amount of light olefins and aromatics, which includes a fractionation device 2, a hydrofining reactor 5, a first catalytic cracking reactor 12, a second catalytic cracking reactor 13, a third catalytic cracking reactor 15, a regenerator 14, a second oil separation device 17, and a product separation device 18; the fractionating device 2 is provided with a diesel raw material inlet, a light diesel fraction outlet and a heavy diesel fraction outlet, the hydrofining reactor 5 is provided with a hydrogen inlet, a raw material oil inlet and a hydrofining product outlet, the first catalytic cracking reactor 12, the second catalytic cracking reactor 13 and the third catalytic cracking reactor 15 are respectively and independently provided with a material inlet and a material outlet, the second oil agent separating device 17 is provided with a material inlet, an oil gas outlet and a catalyst outlet, the regenerator 14 is provided with a catalyst inlet and a catalyst outlet, and the product separating device 18 is provided with an oil gas inlet, a low-carbon olefin outlet, a light naphtha outlet, a heavy naphtha outlet, a circulating oil outlet and an oil slurry outlet; a heavy diesel fraction outlet of the fractionating device 2 is communicated with a raw oil inlet of the hydrofining reactor 5, a hydrofining product outlet of the hydrofining reactor 5 is communicated with a material inlet of the first catalytic cracking reactor 12, a material outlet of the first catalytic cracking reactor 12 is communicated with a material inlet of the second catalytic cracking reactor 13, a material outlet of the second catalytic cracking reactor 13 is communicated with a material inlet of the second oil separating device 17, a light diesel fraction outlet of the fractionating device 2 is communicated with a material inlet of the third catalytic cracking reactor 15, and a material outlet of the third catalytic cracking reactor 15 is communicated with a material inlet of the second oil separating device 17; the catalyst outlet of the second oil agent separation device 17 is communicated with the catalyst inlet of the regenerator 14, the catalyst outlet of the regenerator 14 is respectively communicated with the material inlets of the first catalytic cracking reactor 12 and the third catalytic cracking reactor 15, and the oil gas outlet of the second oil agent separation device 17 is communicated with the oil gas inlet of the product separation device 18.
According to the invention, the system can further comprise a first oil agent separation device 16, the first oil agent separation device 16 is provided with a material inlet, a catalyst outlet and an oil gas outlet, the material outlet of the third catalytic cracking reactor 15 can be communicated with the material inlet of the first oil agent separation device 16, the catalyst outlet of the first oil agent separation device 16 can be communicated with the material inlet of the second catalytic cracking reactor 13, and the oil gas outlet of the first oil agent separation device 16 can be communicated with the material inlet of the second oil agent separation device 17; and/or the light naphtha outlet of the product separation device 18 may be in communication with the feed inlet of the third catalytic cracking reactor 15; and/or the cycle oil outlet of the product separation device 18 may communicate with the raw oil inlet of the hydrofinishing reactor 5. The first oil agent separation device is arranged, so that the utilization rate of the second spent catalyst with low coke formation obtained by the third catalytic cracking reaction can be improved, the utilization rate of raw materials can be improved by recycling the circulating oil product and the light naphtha product, and the yield of low-carbon olefin and aromatic hydrocarbon is improved.
According to the present invention, the catalytic cracking reactor is well known to those skilled in the art, the first catalytic cracking reactor, the second catalytic cracking reactor and the third catalytic cracking reactor may each independently include at least one of a riser reactor, a fluidized bed reactor and a downer reactor, each reactor may be of a constant diameter or a variable diameter, and preferably, the first catalytic cracking reactor and the third catalytic cracking reactor are both riser reactors, and the second catalytic cracking reactor is a fluidized bed reactor.
According to a preferred embodiment, the process of the invention is carried out using the scheme shown in FIG. 1, in particular:
introducing a diesel raw material into a diesel fractionating tower 2 through a pipeline 1 to be separated into light diesel fraction and heavy diesel fraction, and introducing the heavy diesel fraction into a hydrofining reactor 5 through a pipeline 4 to be hydrofined to obtain a hydrofining reaction effluent.
Introducing the effluent of the hydrorefining reaction into a separator 10 through a pipeline 9 for separation, treating hydrogen-rich gas in a gas-phase product at the top of the separator obtained by separation by a recycle hydrogen compressor 6, mixing the hydrogen-rich gas with supplementary fresh hydrogen from a pipeline 7 to obtain mixed hydrogen, and recycling the mixed hydrogen into the hydrorefining reactor 5 through a pipeline 8. The liquid phase product obtained by the separation of the separator 10 is taken as a hydrofining product and is introduced into the bottom of a first catalytic cracking reactor 12 through a pipeline 11 to contact with a part of regenerated catalyst from a regenerator 14 and carry out a first catalytic cracking reaction; the first catalytic cracking product and the spent catalyst obtained from the outlet of the first catalytic cracking reactor 12 enter a second catalytic cracking reactor 13 coaxially arranged from bottom to top for a second catalytic cracking reaction. The light diesel oil fraction separated by the diesel oil fractionating tower 2 enters a third catalytic cracking reactor 15 through a pipeline 3 to contact with the other part of regenerated catalyst from the regenerator 14 and carry out a third catalytic cracking reaction; and then introducing a third reaction product and a second spent catalyst obtained at the outlet of the third catalytic cracking reactor 15 into the first oil agent separation device 16 for separation, and introducing the second spent catalyst obtained by separation into the second catalytic cracking reactor 13 for a second catalytic cracking reaction. And introducing a second catalytic cracking product and a first spent catalyst obtained at the outlet of the second catalytic cracking reactor and a third catalytic cracking product from the third catalytic cracking reactor 15 into a second oil agent separation device 17 for separation to obtain oil gas and spent catalyst respectively, introducing the spent catalyst obtained by separation into a regenerator 14 for regeneration, introducing the oil gas obtained by separation into a further product separation device 18 for separation to obtain low-carbon olefin, light naphtha, heavy naphtha, circulating oil and catalytic cracking slurry oil, and leading out the low-carbon olefin, the light naphtha, the heavy naphtha, the circulating oil and the catalytic cracking slurry oil through a pipeline 23, a pipeline 19, a pipeline 20, a pipeline 24 and a pipeline 21 respectively. The cycle oil is recycled to the hydrofinishing reactor 5. The light naphtha from line 19 is introduced into the third catalytic cracking reactor 15 for a third catalytic cracking reaction. The first catalytic cracking reactor and the third catalytic cracking reactor are both riser reactors, the third catalytic cracking reactor is a fluidized bed reactor, the first catalytic cracking reactor and the second catalytic cracking reactor are coaxially arranged, and the second catalytic cracking reactor is arranged above the third catalytic cracking reactor.
In the present invention, the ethylene, propylene, and the like are represented by lower olefins in the above preferred embodiment.
The present invention will be described in detail below by way of examples.
The various starting materials used are commercially available below unless otherwise specified.
The reactions of the following examples were carried out in catalytic cracking pilot plants and fixed bed diesel hydrogenation pilot plants. The first catalytic cracking reactor and the third catalytic cracking reactor are riser reactors, the third catalytic cracking reactor is a fluidized bed reactor, the first catalytic cracking reactor and the second catalytic cracking reactor are coaxially arranged, the second catalytic cracking reactor is arranged above the third catalytic cracking reactor, the inner diameter of the first catalytic cracking reactor is 24mm, the height of the first catalytic cracking reactor is 6m, the inner diameter of the second catalytic cracking reactor is 40mm, the height of the second catalytic cracking reactor is 2m, the inner diameter of the third catalytic cracking reactor is 24mm, and the height of the third catalytic cracking reactor is 8 m.
The same hydrofining catalysts as used in the examples and comparative examples were used, and alumina-supported nickel-tungsten catalysts each in the form of a strip, wherein the hydrofining catalysts contained 24.5 wt% of WO based on the total amount of the hydrofining catalysts34.50 wt% of NiO, and the balance of carrier.
The catalytic cracking catalysts used in the examples and comparative examples were the same as those used in MMC-2, which was produced by the Qilu division of China petrochemical Co., Ltd., and the properties of the catalysts are shown in Table 2.
The yield of a product in the catalytic cracking product distribution is equal to the weight of a product obtained by the product separation unit 18/weight of the diesel fuel feedstock x 100%.
Example 1
The embodiment is carried out by using the process flow chart shown in fig. 1, and the specific steps are as follows:
the diesel raw material D is introduced into a diesel fractionating tower 2 and is separated into a light diesel fraction E with the distillation range of less than 230 ℃ and a heavy diesel fraction F with the distillation range of more than 230 ℃ according to the cutting point of 230 ℃, and the properties of the diesel raw material D, the light diesel fraction E and the heavy diesel fraction F are shown in a table 1. And introducing the heavy diesel oil fraction into a hydrofining reactor 5 for hydrofining treatment to obtain a hydrofining reaction effluent.
Introducing the effluent of the hydrorefining reaction into a separator 10 for separation, treating the hydrogen-rich gas in the gas-phase product at the top of the separator 10 obtained by separation by a recycle hydrogen compressor 6, and mixing the hydrogen-rich gas with supplementary fresh hydrogen to obtain mixed hydrogen, wherein the mixed hydrogen is used for being recycled to the hydrorefining reactor 5. Introducing the liquid phase product obtained by the separation of the separator into the first catalytic cracking reactor 12 as a hydrofining product, and introducing a part of regenerated catalyst from the regenerator 14 into the first catalytic cracking reactor to participate in a first catalytic cracking reaction; the first catalytic cracking product obtained from the outlet of the first catalytic cracking reactor and the semi-spent catalyst enter the second catalytic cracking reactor 13 together upwards for the second catalytic cracking reaction.
And introducing the light diesel fraction E into a third catalytic cracking reactor 15 to contact with the regenerated catalyst from the regenerator 14 for a third catalytic cracking reaction, and introducing the second spent catalyst into the second catalytic cracking reactor to participate in the second catalytic cracking reaction after separating the second spent catalyst from the third catalytic cracking reactor through a first oil agent separating device 16 and the third catalytic cracking product.
Introducing a mixture of a second catalytic cracking product and a first catalyst to be generated obtained at the outlet of the second catalytic cracking reactor and a third catalytic cracking product from the third catalytic cracking reactor into a second oil agent separation device 17 for separation to respectively obtain reaction oil gas and a catalyst to be generated, introducing the catalyst to be generated obtained by separation into a regenerator for regeneration, introducing the reaction oil gas obtained by separation into a product separation device 18 for further separation to obtain low-carbon olefin, light naphtha (with the distillation range of 65-135 ℃), heavy naphtha (with the distillation range of 130-175 ℃), circulating oil (with the distillation range of 175-400 ℃) and catalytic cracking oil slurry. Recycling the cycle oil to the hydrofinishing reactor.
The reaction conditions and product distribution of the hydrofinishing reactor in this example are shown in Table 3 and the reaction conditions of the catalytic cracking reactor are shown in Table 4. The product profile obtained by the process of this example is shown in table 4.
Comparative example 1
Comparative example a conventional fixed bed hydrogenation of diesel oil and a conventional catalytic cracking combined process were used, and the process flow diagram of comparative example 1 is shown in fig. 2, unlike example 1, comparative example 1 was not provided with a third catalytic cracking reactor. Specifically, the method comprises the following steps:
the diesel raw material D is introduced into a diesel fractionating tower 2 and is separated into a light diesel fraction E with the distillation range of less than 230 ℃ and a heavy diesel fraction F with the distillation range of more than 230 ℃ according to the cutting point of 230 ℃, and the properties of the diesel raw material D, the light diesel fraction E and the heavy diesel fraction F are shown in a table 1. And introducing the heavy diesel oil fraction into a hydrofining reactor 5 for hydrofining treatment to obtain a hydrofining reaction effluent.
Introducing the effluent of the hydrorefining reaction into a separator 10 for separation, treating the hydrogen-rich gas in the gas-phase product at the top of the separator 10 obtained by separation by a recycle hydrogen compressor 6, and mixing the hydrogen-rich gas with supplementary fresh hydrogen to obtain mixed hydrogen, wherein the mixed hydrogen is used for being recycled to the hydrorefining reactor 5. Introducing the liquid phase product obtained by separation in the separator as a hydrofining product and a light diesel fraction F into the first catalytic cracking reactor 12, and introducing a part of regenerated catalyst from the regenerator 14 into the first catalytic cracking reactor to participate in a first catalytic cracking reaction; the first catalytic cracking product and the semi-spent catalyst obtained from the outlet of the first catalytic cracking reactor are fed upwards into the second catalytic cracking reactor 13 together to perform a second catalytic cracking reaction with the supplemented regenerated catalyst.
Introducing a mixture of a second catalytic cracking product and a spent catalyst obtained at the outlet of the second catalytic cracking reactor into a second oil agent separation device 17 for separation to respectively obtain reaction oil gas and a spent catalyst, introducing the spent catalyst obtained by separation into a regenerator for regeneration, and introducing the reaction oil gas obtained by separation into a product separation device 18 for further separation to obtain low-carbon olefin, light naphtha (the distillation range is 65-135 ℃), heavy naphtha (the distillation range is 130 ℃ -. Recycling the cycle oil to the hydrofinishing reactor.
The reaction conditions and product distribution of the hydrofinishing reactor in this comparative example are shown in Table 3, and the reaction conditions of the catalytic cracking reactor are shown in Table 4. The product distribution obtained by the process of this comparative example is shown in table 4.
As can be seen from the results in table 4, the ethylene, propylene and aromatic yields in example 1 are improved by 2.7 percentage points, 1.0 percentage point and 2.7 percentage points, respectively, compared to comparative example 1.
Example 2
Example 2 was carried out using the same process flow as example 1, except that the reaction conditions and product distribution of the hydrofinishing reactor of example 2 are shown in table 3 and the reaction conditions of the catalytic cracking reactor are shown in table 4. The product profile obtained by the process of example 2 is shown in table 4.
Comparative example 2
Comparative example 2 was conducted using the same process flow as comparative example 1, except that the reaction conditions and product distribution of the hydrofinishing reactor of comparative example 2 are shown in table 3 and the reaction conditions of the catalytic cracking reactor are shown in table 4. The product distribution obtained with the process of comparative example 2 is shown in table 4.
As can be seen from the results in table 4, the yields of ethylene and propylene, and aromatic hydrocarbons in example 2 are improved by 1.9 percentage points, 0.8 percentage points, and 4.3 percentage points, respectively, as compared to comparative example 2.
Example 3
This example was carried out in a similar manner to example 1, except that the reaction temperature in the third catalytic cracking reactor of the catalytic cracking reaction zone of this example was 50 ℃ higher than the reaction temperature in the second catalytic cracking reactor, specifically, the reaction conditions and the product distribution of the hydrofinishing reactor of this example are shown in table 3, and the reaction conditions of the catalytic cracking reactor are shown in table 4. The product profile obtained by the process of this example is shown in table 4.
Comparative example 3
The same as example 1 except that: the light diesel fraction is subjected to hydrofining treatment and then subjected to a third catalytic cracking reaction, the hydrofining treatment conditions of the light diesel fraction are the same as those of the heavy diesel fraction, the conditions of the third catalytic cracking reaction are the same as those of example 1, and the conditions and specific reaction results of the catalytic cracking reactor are shown in table 5.
As can be seen from the results of table 5, the ethylene and propylene yields of example 1 were unchanged from those of comparative example 3; the yield of the aromatic hydrocarbon is improved by 4.0 percent.
Comparative example 4
The same as example 1 except that: only the hydrorefined product is subjected to the first catalytic cracking reaction without the second catalytic cracking reaction, the obtained first catalytic cracking product is directly sent to a product separation device for separation, the specific reaction conditions are the same as those in example 1, and the conditions and specific reaction results of the catalytic cracking reactor are shown in table 5.
As can be seen from the results in table 5, the ethylene and propylene yields in example 1 are improved by 1.7 percentage points and 1.7 percentage points, respectively, as compared to comparative example 4; the yield of the aromatic hydrocarbon is improved by 3.4 percentage points.
Comparative example 5
The same as example 1 except that: the cut points of the light diesel oil fraction and the heavy diesel oil fraction were 260 ℃, the specific reaction conditions were the same as in example 1, and the conditions and specific reaction results of the catalytic cracking reactor are shown in table 5.
As can be seen from the results in table 5, the ethylene and propylene yields in example 1 are improved by 0.3 percentage points and 2.3 percentage points, respectively, as compared to comparative example 5; the yield of the aromatic hydrocarbon is improved by 4.5 percentage points.
It can be seen from the results of the examples and comparative examples of the present invention that the method of the present invention organically combines the fixed bed hydrogenation process with the catalytic cracking process according to the property characteristics of the inferior diesel, especially different fractions of the catalytic diesel product, and can significantly improve the yield of high value products such as propylene, ethylene, etc. in the combined process.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the content of the present invention as long as it does not depart from the gist of the present invention.
TABLE 1 raw oils
| Raw oil | Diesel feedstock D | Light diesel oil E | Heavy diesel oil F |
| Density (20 ℃ C.), (g/cm)3) | 0.9357 | 0.8786 | 0.9960 |
| Sulfur content (μ g/g) | 2500 | 1300 | 3200 |
| Nitrogen content (μ g/g) | 350 | 128 | 536 |
| Total aromatic hydrocarbons, wt.% | 81.1 | 70.9 | 82.7 |
| Monocyclic aromatic content,% by weight | 25.6 | 60.4 | 12.2 |
| Polycyclic aromatic hydrocarbons content, wt.% | 53.9 | 10.2 | 71.1 |
| Distillation range (ASTM D-86), deg.C | |||
| Initial boiling point | 175 | 175 | 231 |
| 50% by volume | 253 | 219 | 279 |
| End point of distillation | 331 | 231 | 331 |
| |
19 | / | / |
TABLE 2 catalytic cracking catalyst Properties
| Catalyst and process for preparing same | MMC-2 |
| Chemical composition, weight% | |
| RE2O3(weight ratio of rare earth oxide to catalyst) | 0.56 |
| Active metal element composition, weight% (relative to the total amount of active metal oxide) | |
| Fe2O3 | 5.8 |
| CeO2 | 5.2 |
| La2O3 | 5.1 |
| Nd2O3 | 3.4 |
| Y2O3 | 12.2 |
| Al2O3 | 54.0 |
| Physical Properties | |
| Specific area, m2/g | 120 |
| Pore volume, cm3/g | 0.17 |
| Apparent density, g/cm3 | 0.91 |
| Sieving, weight percent | |
| 0-20μm | 0.8 |
| 0-40μm | 10.4 |
| 0-80μm | 70.8 |
| 0-110μm | 88.5 |
| 0-149μm | 97.8 |
| >149μm | 2.2 |
| Average particle diameter, μm | 64.3 |
TABLE 3 reaction conditions of the hydrofinishing reactor
TABLE 4 reaction conditions and product distribution in the catalytic cracking reaction zone
The lower olefins include ethylene and propylene.
The aromatic hydrocarbon yield is the sum of aromatic hydrocarbon yields in light naphtha and heavy naphtha
TABLE 5
The lower olefins include ethylene and propylene.
The aromatic hydrocarbon yield is the sum of aromatic hydrocarbon yields in light naphtha and heavy naphtha
Claims (14)
1. A method for producing a high yield of light olefins and aromatic hydrocarbons, the method comprising:
separating the diesel raw material into a light diesel fraction and a heavy diesel fraction, wherein the cut points of the light diesel fraction and the heavy diesel fraction are in the range of 220 ℃ and 240 ℃;
introducing the obtained heavy diesel oil fraction into a hydrofining reactor to contact with a hydrofining catalyst and carrying out hydrofining treatment to obtain a hydrofining product;
introducing the obtained hydrofined product into a first catalytic cracking reactor to contact with a first catalytic cracking catalyst and carry out a first catalytic cracking reaction to obtain a first catalytic cracking product and a semi-spent catalyst;
introducing the obtained first catalytic cracking product and the semi-spent catalyst into a second catalytic cracking reactor to carry out a second catalytic cracking reaction to obtain a second catalytic cracking product and a first spent catalyst;
introducing the obtained light diesel oil fraction into a third catalytic cracking reactor to contact with a second catalytic cracking catalyst and carry out a third catalytic cracking reaction to obtain a third catalytic cracking product and a second spent catalyst;
separating the obtained second catalytic cracking product and the third catalytic cracking product to obtain a low-carbon olefin product, a light naphtha product, a heavy naphtha product, a circulating oil product and an oil slurry product;
and feeding the obtained first spent catalyst and the second spent catalyst into a regenerator for regeneration, wherein the obtained regenerated catalyst is used as the first catalytic cracking catalyst and the second catalytic cracking catalyst.
2. The method of claim 1, further comprising at least one of:
(1) introducing the obtained light naphtha product into the third catalytic cracking reactor to carry out the third catalytic cracking reaction;
(2) introducing the obtained cycle oil product into the hydrofining reactor to carry out hydrofining treatment;
(3) and introducing at least part of second spent catalyst obtained by the third catalytic cracking reaction into the second catalytic cracking reactor to carry out the second catalytic cracking reaction.
3. The process as claimed in claim 1, wherein the diesel feedstock has a cetane number of less than 25 and a distillation range in the range of 170-400 ℃.
4. The process of claim 1, wherein the diesel feedstock comprises catalytically cracked diesel, with or without coker diesel.
5. The process according to claim 1, wherein the hydrofinishing catalyst comprises a carrier which is at least one member selected from the group consisting of alumina, silica, alumina-silica, titania, magnesia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia, and an active metal component which is at least one member selected from the group consisting of group VIB metal elements VIII and at least one member selected from the group consisting of group VIII metal elements and which is supported on the carrier; based on the total weight of the hydrofining catalyst, the content of at least one metal element selected from VIB group is 1-30 wt% calculated by oxide, and the content of at least one metal element selected from VIII group is 3-35 wt% calculated by oxide;
the conditions of the hydrofining treatment comprise: the hydrogen partial pressure is 3-12MPa, the reaction temperature is 260 ℃ to 450 ℃, and the volume ratio of hydrogen to oil is 400 Nm to 1600Nm3/m3The liquid hourly space velocity is 0.3-4.0h-1。
6. The method as claimed in claim 1, wherein in the hydrofining treatment, the polycyclic aromatic hydrocarbon saturation rate of the heavy diesel fraction is not less than 85 wt%, the total aromatic hydrocarbon saturation rate of the heavy diesel fraction is 12-35 wt%, and the distillation range of the hydrofining product is within the range of 200-400 ℃.
7. The method of claim 1, wherein the conditions of the first catalytic cracking reaction comprise: the reaction temperature is 500-650 ℃, the reaction time is 0.5-8s, the reaction pressure is 0.10-1.0MPa, and the weight ratio of the first catalytic cracking catalyst to the hydrorefining product is (2-100): 1, the weight ratio of the atomized steam to the hydrofining product is (0.05-0.5): 1;
the reaction temperature of the second catalytic cracking reaction is 10-100 ℃ higher than that of the first catalytic cracking reaction, and the weight hourly space velocity of the second catalytic cracking reaction is 1-35h-1；
The conditions of the third catalytic cracking reaction include: the reaction temperature is 600-750 ℃, the reaction time is 0.5-10s, the reaction pressure is 0.1-1.0MPa, and the weight ratio of the second catalytic cracking catalyst to the light diesel fraction is (4-100): 1.
8. the method of claim 7, wherein the reaction temperature of the third catalytic cracking reaction is 30-100 ℃ higher than the reaction temperature of the second catalytic cracking reaction.
9. The process of claim 1, wherein the first and second catalytic cracking catalysts each independently comprise a zeolite, an inorganic oxide binder, and optionally a clay;
based on the total weight of the catalyst, the content of the zeolite is 10-50 wt%, the content of the inorganic oxide is 5-90 wt%, and the content of the clay is 0-70 wt%;
the zeolite is at least one selected from the group consisting of rare earth-containing or non-rare earth-containing Y-type or HY-type zeolite, rare earth-containing or non-rare earth-containing ultrastable Y-type zeolite, and zeolite having MFI structure.
10. The process as claimed in claim 1, wherein the distillation range of the light naphtha product is within 65-135 ℃, the distillation range of the heavy naphtha product is within 130-175 ℃, and the distillation range of the cycle oil product is within 175-450 ℃.
11. The method of claim 1, wherein the first catalytic cracking reactor and the third catalytic cracking reactor are both riser reactors and the second catalytic cracking reactor is a fluidized bed reactor.
12. A system for producing light olefins and aromatics in a large quantity comprises a fractionation device (2), a hydrofining reactor (5), a first catalytic cracking reactor (12), a second catalytic cracking reactor (13), a third catalytic cracking reactor (15), a regenerator (14), a second oil agent separation device (17) and a product separation device (18);
the fractionating device (2) is provided with a diesel raw material inlet, a light diesel fraction outlet and a heavy diesel fraction outlet, the hydrofining reactor (5) is provided with a hydrogen inlet, a raw oil inlet and a hydrofining product outlet, the first catalytic cracking reactor (12), the second catalytic cracking reactor (13) and the third catalytic cracking reactor (15) are respectively and independently provided with a material inlet and a material outlet, the second oil agent separation device (17) is provided with a material inlet, an oil gas outlet and a catalyst outlet, the regenerator (14) is provided with a catalyst inlet and a catalyst outlet, and the product separation device (18) is provided with an oil gas inlet, a low-carbon olefin outlet, a light naphtha outlet, a heavy naphtha outlet, a circulating oil outlet and an oil slurry outlet;
a heavy diesel fraction outlet of the fractionating device (2) is communicated with a raw oil inlet of the hydrofining reactor (5), a hydrofining product outlet of the hydrofining reactor (5) is communicated with a material inlet of the first catalytic cracking reactor (12), a material outlet of the first catalytic cracking reactor (12) is communicated with a material inlet of the second catalytic cracking reactor (13), a material outlet of the second catalytic cracking reactor (13) is communicated with a material inlet of the second oil separating device (17), a light diesel fraction outlet of the fractionating device (2) is communicated with a material inlet of the third catalytic cracking reactor (15), and a material outlet of the third catalytic cracking reactor (15) is communicated with a material inlet of the second oil separating device (17); the catalyst outlet of the second oil agent separation device (17) is communicated with the catalyst inlet of the regenerator (14), the catalyst outlet of the regenerator (14) is respectively communicated with the material inlets of the first catalytic cracking reactor (12) and the third catalytic cracking reactor (15), and the oil gas outlet of the second oil agent separation device (17) is communicated with the oil gas inlet of the product separation device (18).
13. The system according to claim 12, wherein the system further comprises a first oil agent separation device (16), the first oil agent separation device (16) is provided with a material inlet, a catalyst outlet and an oil gas outlet, the material outlet of the third catalytic cracking reactor (15) is communicated with the material inlet of the first oil agent separation device (16), the catalyst outlet of the first oil agent separation device (16) is communicated with the material inlet of the second catalytic cracking reactor (13), and the oil gas outlet of the first oil agent separation device (16) is communicated with the material inlet of the second oil agent separation device (17); and/or
The light naphtha outlet of the product separation device (18) is communicated with the material inlet of the third catalytic cracking reactor (15); and/or
And a circulating oil outlet of the product separation device (18) is communicated with a raw oil inlet of the hydrofining reactor (5).
14. The system of claim 12, wherein the first catalytic cracking reactor and the third catalytic cracking reactor are both riser reactors and the second catalytic cracking reactor is a fluidized bed reactor.
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| CN107779226A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | The method of low-carbon olefines high-output and the system for low-carbon olefines high-output |
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| CN107779226A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | The method of low-carbon olefines high-output and the system for low-carbon olefines high-output |
| CN107974286A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons |
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