CN110857400B - Method and system for processing coker gasoline by using double lifting pipes - Google Patents
Method and system for processing coker gasoline by using double lifting pipes Download PDFInfo
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- CN110857400B CN110857400B CN201810975592.7A CN201810975592A CN110857400B CN 110857400 B CN110857400 B CN 110857400B CN 201810975592 A CN201810975592 A CN 201810975592A CN 110857400 B CN110857400 B CN 110857400B
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- 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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
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Abstract
The invention relates to a method and a system for processing coker gasoline by using double lifting pipes, wherein the method comprises the following steps: introducing a coking gasoline raw material into an adsorption and desorption reactor to contact with an n-alkane adsorbent and perform adsorption separation reaction; carrying out desorption treatment on the obtained adsorbent adsorbing the normal alkane by adopting desorption gas; introducing the desorbed oil into a first riser reactor to contact with a first catalytic cracking catalyst and perform a first catalytic cracking reaction; and introducing the residual oil into the second riser reactor to contact with a second catalytic cracking catalyst and perform a second catalytic cracking reaction. The method and the system of the invention are used for processing the coker gasoline and have high ethylene and propylene yields.
Description
Technical Field
The invention relates to a method and a system for processing coker gasoline by using double lifting pipes.
Background
Ethylene and propylene are important petrochemical industry base stocks. Currently, about 98% of the world's ethylene comes from tubular furnace steam cracking technology, with 46% naphtha and 34% ethane in the ethylene production feed. About 62% of the propylene comes from the co-production of ethylene by steam cracking. The steam cracking technology is perfected day by day, and is a process of consuming a large amount of energy, and is limited by the use of high-temperature materials, and the potential of further improvement is very small.
Coking is an important thermal processing process in petroleum refining, and the coking gasoline generated in the coking process is low-quality gasoline which is rich in olefin, has high contents of impurities such as sulfur, nitrogen compounds, diene and the like, has the characteristics of bad odor, poor stability, low octane number and the like, and the service performance of the coking gasoline needs to be improved through secondary processing.
U.S. Pat. No. 5,5685972 discloses a method for improving the octane number of gasoline by first carrying out hydrodesulfurization treatment on coker gasoline and then carrying out aromatization modification on coker gasoline by using a metal modified ZSM-5 molecular sieve catalyst.
Chinese patent CN1715372A discloses a method for reforming coker gasoline, in which hydrogenated coker distillate is cut to obtain reformed raw oil with a suitable distillation range, and then the coker gasoline is reformed under the reaction condition of catalytic reforming to produce high-octane gasoline blending component.
Chinese patent CN 1160746 discloses a catalytic conversion method for increasing gasoline octane number. Injecting low-quality gasoline such as straight-run gasoline and coking gasoline into the lower part of a riser reactor, and preferentially contacting and reacting with a regenerated catalyst; the reaction temperature is 600 ℃ and 700 ℃, and the weight hourly space velocity is 1-180h-1The ratio of agent to oil is 6-180. The method can improve the octane number of the low-quality gasoline and reduce the olefin content of the gasoline to a certain extent.
Chinese patent CN1069054 adopts a double-riser reactor to perform reaction, low-quality gasoline including catalytic cracking crude gasoline and coker gasoline is injected into the riser reactor, and catalytic modification of the low-quality gasoline is realized by utilizing reaction conditions of high temperature and large catalyst-to-oil ratio, so that the yield of liquefied gas and the octane number of the gasoline are improved.
Chinese patent CN201110420264 provides a method for modifying coker gasoline, the coker gasoline is subjected to selective cracking reaction under the action of selective cracking catalyst, the reaction product is subjected to gas-liquid separation, the separated liquid product is subjected to aromatization reaction, the liquid product of aromatization reaction is subjected to hydrodesulfurization, and all the reaction products are fractionated to obtain hydrofined aromatization oil of low-carbon olefin products.
Among the above methods, the hydrofining method can reduce the content of impurities and olefins in the coker gasoline, improve the stability, and can still cause great influence on the octane number of a refinery gasoline pool due to low octane number of the hydrofining method as a gasoline blending component. The coking gasoline can directly enter a catalytic cracking device for cracking, and has the problems that the inactivation of a cracking catalyst is accelerated by high nitrogen content, the product distribution is influenced, the alkane cracking reaction activity in the gasoline is low, and a large amount of unreacted alkane enters a gasoline product to influence the octane number of the gasoline. When the coking gasoline is used as a reforming raw material, the octane number and the reforming hydrogen production rate of the reforming gasoline are influenced by overlarge blending proportion due to low aromatic hydrocarbon potential, and the blending proportion is generally below 30 percent. In recent years, under the conditions that the environmental protection requirement is increasingly strict, the quality of gasoline products is continuously upgraded and the demand of chemical raw materials is vigorous, how to reduce the content of impurities and olefin of the coker gasoline as much as possible and greatly improve the octane number of the coker gasoline or convert the coker gasoline into the chemical raw materials such as ethylene, propylene and the like to the maximum is an urgent task.
Disclosure of Invention
The invention aims to provide a method and a system for processing coker gasoline by adopting double lifting pipes, and the method and the system for processing coker gasoline have high ethylene and propylene yield.
In order to achieve the above object, the present invention provides a process for coker gasoline processing using dual risers, the process comprising:
introducing a coking gasoline raw material into an adsorption and desorption reactor to contact with an n-alkane adsorbent and carry out adsorption separation reaction to obtain the adsorbent adsorbed with n-alkane and absorption residual oil;
carrying out desorption treatment on the obtained adsorbent with adsorbed normal alkane by adopting desorption gas to obtain desorbed adsorbent and desorbed oil;
introducing the desorbed oil into a first riser reactor to contact with a first catalytic cracking catalyst and perform a first catalytic cracking reaction to obtain a first reaction product and a first catalyst to be generated;
introducing the residual oil into a second riser reactor to contact with a second catalytic cracking catalyst and perform a second catalytic cracking reaction to obtain a second reaction product and a second spent catalyst;
separating the obtained first reaction product from the first catalyst to be regenerated, separating the obtained second reaction product from the second catalyst to be regenerated, sending the obtained first catalyst to be regenerated and the obtained second catalyst to be regenerated into a regenerator for scorching, and returning at least part of the obtained regenerated catalyst to the first riser reactor and the second riser reactor to be used as the first catalytic cracking catalyst and the second catalytic cracking catalyst.
Optionally, the coking gasoline raw material contains 6-30 wt% of normal paraffin, 20-40 wt% of olefin and 100-1000 microgram/g of nitrogen;
the nitrogen content in the raffinate oil is 60-600 micrograms/gram;
the n-alkane content in the desorption oil is 90-98 wt%, and the nitrogen content is 0-100 micrograms/gram.
Optionally, the adsorption and desorption reactor is a fixed bed reactor, a moving bed reactor, a simulated moving bed reactor or an expanded bed reactor.
Optionally, the n-alkane adsorbent is one or more selected from activated carbon, activated carbon fibers, carbonized resin silica gel, natural zeolite, synthetic zeolite and activated alumina.
Optionally, the conditions of the adsorption separation reaction include: the temperature is 250-380 ℃, and the weight hourly space velocity of the coking gasoline raw material is 0.1-20 hours-1；
The conditions of the desorption treatment include: the temperature is 300-450 ℃, the desorption gas is nitrogen or hydrogen, and the weight hourly space velocity of the desorption gas is 100-200 hours-1。
Optionally, the conditions of the first catalytic cracking reaction include: the reaction temperature is 560 ℃ and 750 ℃, the reaction time is 1-10 seconds, the weight ratio of the catalyst to the oil is 1-100, and the weight ratio of the water to the oil is (0.01-1): 1, the feeding weight ratio of the desorption oil to the absorption residual oil in unit time is 1: (2.5-4.0);
the conditions of the second catalytic cracking reaction include: the reaction temperature is 560 ℃ and 750 ℃, the reaction time is 1-10 seconds, the weight ratio of the catalyst to the oil is 1-100, and the weight ratio of the water to the oil is (0.01-1): 1.
optionally, the method further includes: preheating desorption oil and residual absorption oil, and then respectively introducing the preheated desorption oil and the preheated residual absorption oil into a first riser reactor and a second riser reactor, wherein the temperatures of the preheated desorption oil and the preheated residual absorption oil are respectively 350-450 ℃.
Optionally, the first catalytic cracking catalyst and the second catalytic cracking catalyst each independently comprise, on a dry basis and based on the total weight of the catalyst, from 1 to 60 weight percent zeolite, from 5 to 99 weight percent inorganic oxide, and from 0 to 70 weight percent clay;
the zeolite comprises 50 to 100 wt% of a medium pore zeolite and 0 to 50 wt% of a large pore zeolite, on a dry basis and based on the total weight of the zeolite.
Optionally, the zeolite comprises 70 to 100 wt% of a medium pore zeolite and 0 to 30 wt% of a large pore zeolite, on a dry basis and based on the total weight of the zeolite.
Optionally, the medium pore zeolite is a ZSM series zeolite and/or a ZRP zeolite, and the large pore zeolite is one or more selected from rare earth Y, rare earth hydrogen Y, ultrastable Y and high silica Y;
the inorganic oxide is silicon dioxide and/or aluminum oxide;
the clay is kaolin and/or halloysite.
Optionally, the method further includes: delivering the regenerated catalyst from the regenerator into a degassing tank for degassing, delivering the degassed regenerated catalyst into the first riser reactor and/or the second riser reactor for use as a first catalytic cracking catalyst and/or a second catalytic cracking catalyst, and returning oxygen-containing gas obtained by degassing in the degassing tank to the regenerator.
The invention also provides a processing system of the coker gasoline, which comprises an adsorption and desorption reactor, a first riser reactor, a second riser reactor, oil agent separation equipment and a regenerator;
the adsorption and desorption reactor is provided with a coking gasoline raw material inlet, a desorption gas inlet, an oil absorption residual oil outlet and a desorption oil outlet, the first riser reactor is provided with a desorption oil feed inlet, a catalyst inlet and an oil agent outlet, the second riser reactor is provided with an oil absorption residual oil feed inlet, a catalyst inlet and an oil agent outlet, the oil agent separation equipment is provided with an oil agent inlet, a catalyst outlet and an oil gas outlet, and the regenerator is provided with a catalyst inlet and a catalyst outlet;
the absorption desorption reactor inhale the residual oil export with the residual oil feed inlet fluid intercommunication that inhales of second riser reactor, the desorption oil export of absorption desorption reactor with the desorption oil feed inlet fluid intercommunication of first riser reactor, the finish outlet of first riser reactor and second riser reactor with finish oil splitter's finish oil entry fluid intercommunication, the catalyst entry of first riser reactor and second riser reactor with the catalyst outlet fluid intercommunication of regenerator, the catalyst entry of regenerator with finish oil splitter's catalyst outlet fluid intercommunication.
Optionally, the adsorption and desorption reactor is a fixed bed reactor, a moving bed reactor, a simulated moving bed reactor or an expanded bed reactor.
Optionally, the system further comprises a degassing tank through which the catalyst inlet of the first riser reactor and/or the second riser reactor is in fluid communication with the catalyst outlet of the regenerator; and/or
The system also comprises a preheating device for preheating the desorption oil and/or the residual absorption oil.
The normal alkane component with lower reaction activity (namely desorption oil) and the non-normal alkane component with higher reaction activity (namely absorption residual oil) in the coking gasoline are separated, and the normal alkane component enters the reactor independently to be in contact reaction with the regenerated catalyst, so that the competitive reaction of the non-normal alkane component on the active center of the catalyst is reduced, the catalytic cracking reaction performance of the normal alkane component is improved, and the yield of ethylene and propylene in the catalytic cracking process of the coking gasoline is improved.
The invention can partially remove nitrogen compounds in the coking gasoline in the adsorption separation process, and reduces the toxic action of the adsorption of the nitrogen compounds on the catalytic cracking catalyst on the active center of the catalyst.
The invention not only solves the problem of reasonable and efficient utilization of the coking gasoline, but also solves the problem of shortage of petrochemical raw materials, and improves the economic benefit and the social benefit of the petrochemical industry.
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.
Description of the reference numerals
1 first riser reactor 2 regenerator 3 settler
4 stripping section 5 degassing tank 6 cyclone separator
7 gas collection chamber 8 spent inclined tube 9 spent slide valve
10 line 11 line 12 regeneration pipe chute
13 regenerative spool valve 14 line 15 line
16 line 17 line 18 line
19 line 20 large oil-gas line 21 line
22 air distributor 23 line 24 cyclone
25 flue gas duct 27 line 28 line
29 pipeline 30 pipeline 31 adsorption and desorption reactor
32 furnace 33 line 34 second riser reactor
Detailed Description
The following describes in detail specific embodiments of the present invention. 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 processing coker gasoline by using double lifting pipes, which comprises the following steps:
introducing a coking gasoline raw material into an adsorption and desorption reactor to contact with an n-alkane adsorbent and carry out adsorption separation reaction to obtain the adsorbent adsorbed with n-alkane and absorption residual oil;
carrying out desorption treatment on the obtained adsorbent with adsorbed normal alkane by adopting desorption gas to obtain desorbed adsorbent and desorbed oil;
introducing the desorbed oil into a first riser reactor to contact with a first catalytic cracking catalyst and perform a first catalytic cracking reaction to obtain a first reaction product and a first catalyst to be generated;
introducing the residual oil into a second riser reactor to contact with a second catalytic cracking catalyst and perform a second catalytic cracking reaction to obtain a second reaction product and a second spent catalyst;
separating the obtained first reaction product from the first catalyst to be regenerated, separating the obtained second reaction product from the second catalyst to be regenerated, sending the obtained first catalyst to be regenerated and the obtained second catalyst to be regenerated into a regenerator for scorching, and returning at least part of the obtained regenerated catalyst to the first riser reactor and the second riser reactor to be used as the first catalytic cracking catalyst and the second catalytic cracking catalyst.
According to the present invention, Coker gasoline (english name: Coker naptha), also known as Coker Naphtha, is a gasoline fraction produced by a delayed coking process. The normal paraffin content in the coking gasoline raw material can be 6-30 wt%, the olefin content can be 20-40 wt%, and the nitrogen content can be 100-1000 microgram/g.
According to the invention, the adsorption separation reaction and the desorption treatment can remove part of nitrogen in the coker gasoline and can also enable the desorption oil to be rich in normal paraffin, for example, the nitrogen content in the raffinate oil can be 60-600 micrograms/gram; the n-alkane content in the desorption oil can be 90-98 wt%, the nitrogen content can be 0-100 micrograms/gram, and the adsorption and desorption reactor can be a fixed bed reactor, a moving bed reactor, a simulated moving bed reactor or an expanded bed reactor, and is preferably a fixed bed reactor. The n-alkane adsorbent may be selected from the group consisting of activated carbon, and activated carbonOne or more of charcoal, activated carbon fiber, carbonized resin silica gel, natural zeolite, synthetic zeolite and activated alumina, and when carried out in a fixed bed reactor, zeolite is preferably used as the normal alkane adsorbent. The conditions of the adsorptive separation reaction may include: the temperature is 250-380 ℃, and the weight hourly space velocity (the weight ratio of the coking gasoline raw material feed to the adsorbent in the reactor in unit time) of the coking gasoline raw material is 0.1-20 hours-1(ii) a The conditions of the desorption treatment may include: the temperature is 300-450 ℃, the desorption gas is nitrogen or hydrogen, the desorption gas can be used as carrier gas for conveying desorption oil and is sent into the catalytic cracking reactor for reaction, the weight hourly space velocity (the weight ratio of the desorption gas feed to the adsorbent in the reactor in unit time) of the desorption gas is 100-200 h-1。
Riser reactors according to the invention are well known to those skilled in the art, and in particular for the purposes of the present invention, can be selected from constant diameter riser reactors and/or constant linear velocity riser reactors, preferably using constant diameter risers. More preferably, the riser reactor comprises a pre-lifting section and at least one reaction zone from bottom to top in sequence, and in order to enable the raw oil to react sufficiently and meet the quality requirements of different target products, the number of the reaction zones can be 2-8, and preferably 2-3.
Catalytic cracking is well known to those skilled in the art in accordance with the present invention, and in particular for the purposes of the present invention, the conditions of the first catalytic cracking reaction may include: the reaction temperature is 560 ℃ and 750 ℃, the reaction time is 1-10 seconds, the reaction pressure is 0.05-1 MPa, the weight ratio of the catalyst to the oil is 1-100, and the weight ratio of the water to the oil is (0.01-1): 1, the feeding weight ratio of the desorption oil to the absorption residual oil in unit time is 1: (2.5-4.0); the conditions of the second catalytic cracking reaction may include: the reaction temperature is 560 ℃ and 750 ℃, the reaction pressure is 0.05-1 MPa, the reaction time is 1-10 seconds, the weight ratio of the catalyst to the oil is 1-100, and the weight ratio of the water to the oil is (0.01-1): 1.
according to the invention, the method may further comprise: the desorption oil and the residual oil are preheated and then respectively introduced into the first riser reactor and the second riser reactor, the temperature of the preheated desorption oil and the preheated residual oil is respectively and independently 350-450 ℃, preferably 380-420 ℃, and the desorption oil and the residual oil are both in a gas state, so that the contact efficiency of the oil agent is improved, and a heat source can be provided for the reaction.
According to the present invention, catalytic cracking catalysts are well known to those skilled in the art, and in particular for the purposes of the present invention, the first catalytic cracking catalyst and the second catalytic cracking catalyst may each independently comprise from 1 to 60 wt% of a zeolite, from 5 to 99 wt% of an inorganic oxide, and from 0 to 70 wt% of a clay, on a dry basis and based on the total weight of the catalyst; the zeolite may comprise as an active component a medium pore zeolite and/or a large pore zeolite, which may comprise, on a dry basis and based on the total weight of the zeolite, from 50 to 100% by weight of medium pore zeolite and from 0 to 50% by weight of large pore zeolite, preferably from 70 to 100% by weight of medium pore zeolite and from 0 to 30% by weight of large pore zeolite. The medium and large pore zeolites are defined as conventional in the art, i.e., the medium pore zeolite has an average pore size of 0.5 to 0.6nm and the large pore zeolite has an average pore size of 0.7 to 1.0 nm. The medium pore zeolite may be a zeolite having an MFI structure, such as a ZSM-series zeolite and/or a ZRP zeolite, which may also be modified with a nonmetallic element such as phosphorus and/or a transition metal element such as iron, cobalt, nickel, as described in more detail in U.S. Pat. No. 5,232,675, and the ZSM-series zeolite is selected from one or more mixtures of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other zeolites of similar structure, as described in more detail in US3,702,886. The large-pore zeolite can be one or more selected from Rare Earth Y (REY), Rare Earth Hydrogen Y (REHY), ultrastable Y and high silicon Y; the inorganic oxide may be silicon dioxide (SiO) as a binder2) And/or aluminum oxide (Al)2O3) (ii) a The clay as a matrix (carrier) may be kaolin and/or halloysite.
According to the present invention, the spent catalyst and the reaction product are generally separated to obtain the spent catalyst and the reaction product, then the obtained reaction product is subjected to a subsequent separation system to separate fractions such as dry gas, liquefied gas, pyrolysis gasoline and pyrolysis diesel oil, then the dry gas and the liquefied gas are further separated by a gas separation device to obtain ethylene, propylene and the like, and the method for separating ethylene, propylene and the like from the reaction product is similar to the conventional technical method in the art, and the present invention is not limited thereto, and is not described in detail herein.
According to the present invention, the regeneration of the spent catalyst is well known to those skilled in the art, all or at least part of the catalytic cracking catalyst can be from the regenerated catalyst, during the regeneration process, an oxygen-containing gas is generally introduced from the bottom of the regenerator, the oxygen-containing gas can be, for example, air, and then the spent catalyst is contacted with oxygen for coke burning regeneration, the gas-solid separation is performed on the upper part of the regenerator on the flue gas generated after the catalyst is burned and regenerated, and the flue gas enters the subsequent energy recovery system. The method of the present invention preferably further comprises: delivering the regenerated catalyst from the regenerator into a degassing tank for degassing, delivering the degassed regenerated catalyst into the first riser reactor and/or the second riser reactor for use as a first catalytic cracking catalyst and/or a second catalytic cracking catalyst, and returning oxygen-containing gas obtained by degassing in the degassing tank to the regenerator. The regenerated catalyst in the degassing tank is subjected to removal of impurities such as oxygen by a stripping gas such as water vapor. The conditions for regeneration may include: the regeneration temperature is 550-750 ℃, preferably 600-730 ℃, and more preferably 650-700 ℃; the gas superficial linear velocity is 0.5 to 3 m/s, preferably 0.8 to 2.5 m/s, more preferably 1 to 2 m/s, and the average residence time of the spent catalyst is 0.6 to 3 minutes, preferably 0.8 to 2.5 minutes, more preferably 1 to 2 minutes.
The invention also provides a processing system of the coker gasoline, which comprises an adsorption and desorption reactor, a first riser reactor, a second riser reactor, oil agent separation equipment and a regenerator;
the adsorption and desorption reactor is provided with a coking gasoline raw material inlet, a desorption gas inlet, an oil absorption residual oil outlet and a desorption oil outlet, the first riser reactor is provided with a desorption oil feed inlet, a catalyst inlet and an oil agent outlet, the second riser reactor is provided with an oil absorption residual oil feed inlet, a catalyst inlet and an oil agent outlet, the oil agent separation equipment is provided with an oil agent inlet, a catalyst outlet and an oil gas outlet, and the regenerator is provided with a catalyst inlet and a catalyst outlet;
the absorption desorption reactor inhale the residual oil export with the residual oil feed inlet fluid intercommunication that inhales of second riser reactor, the desorption oil export of absorption desorption reactor with the desorption oil feed inlet fluid intercommunication of first riser reactor, the finish outlet of first riser reactor and second riser reactor with finish oil splitter's finish oil entry fluid intercommunication, the catalyst entry of first riser reactor and second riser reactor with the catalyst outlet fluid intercommunication of regenerator, the catalyst entry of regenerator with finish oil splitter's catalyst outlet fluid intercommunication.
In the present invention, the adsorption and desorption reactor may be a fixed bed reactor, a moving bed reactor, a simulated moving bed reactor or an expanded bed reactor, and is preferably a fixed bed reactor.
According to the invention, the system can further comprise a degassing tank, the catalyst inlet of the first riser reactor and/or the second riser reactor is in fluid communication with the catalyst outlet of the regenerator through the degassing tank, the degassing tank can be provided with a catalyst inlet, a catalyst outlet, a stripping gas inlet and a stripping gas outlet, the catalyst inlet is communicated with the catalyst outlet of the regenerator, the catalyst outlet is communicated with the catalyst inlet of the reactor, the stripping gas inlet is used for introducing stripping gas such as water vapor, and the stripping gas outlet is communicated with the regenerator and is used for feeding oxygen-containing stripped gas into the regenerator; and/or the system can also comprise a preheating device for preheating the desorption oil and/or the residual absorption oil, wherein the preheating device can be a heating furnace and the like.
The invention will be further illustrated by means of specific embodiments in the following description with reference to the drawings, without being restricted thereto.
As shown in fig. 1, the coker gasoline enters the top of an adsorption-desorption reactor 31 through a pipeline 27, and after adsorption and separation by an adsorbent, the absorption residual oil enters a heating furnace 32 through a pipeline 30 for preheating; nitrogen is injected into the bottom of the adsorption and desorption reactor through a pipeline 28 to cause the molecular sieve to desorb the adsorbed normal paraffin components, and the generated desorption oil enters a heating furnace 32 through a pipeline 29 to be preheated.
The pre-lifting medium enters from the bottom of the second riser reactor 1 through a pipeline 14, the regenerated catalyst from the regenerated inclined pipe 12 enters the bottom of the first riser reactor 1 after being regulated by a regeneration slide valve 13, and moves upwards and quickly along the first riser reactor under the lifting action of the pre-lifting medium, the preheated raffinate oil is injected into the bottom of the first riser reactor 1 through a pipeline 18 together with the atomized steam from a pipeline 17, and is mixed with the existing material flow of the first riser reactor, and the raffinate oil is subjected to catalytic cracking reaction on the hot catalyst and moves upwards and quickly. The regenerated catalyst from line 33 enters the bottom of the second riser reactor 34 and moves upward and accelerated along the second riser reactor under the lifting action of the pre-lifting medium, the preheated desorption oil is injected into the lower part of the second riser reactor 34 through line 16 together with the atomized steam from line 15, and is mixed with the existing material flow of the second riser reactor, and the desorption oil undergoes catalytic cracking reaction on the catalyst and moves upward and accelerated. The generated reaction product and the inactivated spent catalyst enter a cyclone separator 6 in a settler 3 to realize the separation of the spent catalyst and the reaction product, the reaction product enters an air collection chamber 7, and the fine powder of the catalyst returns to the settler. Spent catalyst in the settler flows to the stripping section 4 where it is contacted with steam from line 19. The reaction product stripped from the spent catalyst enters the gas collection chamber 7 after passing through the cyclone separator. The stripped spent catalyst enters the regenerator 2 after being regulated by a spent slide valve 9 through a spent inclined pipe 8, air from a pipeline 21 enters the regenerator 2 after being distributed by an air distributor 22, coke on the spent catalyst in a dense bed layer at the bottom of the regenerator 2 is burned off to regenerate the inactivated spent catalyst, and flue gas enters a subsequent energy recovery system through an upper flue gas pipeline 25 of a cyclone separator 24. Wherein the pre-lifting medium may be dry gas, water vapor or a mixture thereof.
The regenerated catalyst enters a degassing tank 5 through a pipeline 10 communicated with a catalyst outlet of a regenerator 2, and is contacted with a stripping medium from a pipeline 23 at the bottom of the degassing tank 5 to remove flue gas (namely oxygen-containing gas) carried by the regenerated catalyst, the degassed regenerated catalyst circulates to the bottom of a riser reactor 1 through a regeneration inclined tube 12, the catalyst circulation amount can be controlled through a regeneration slide valve 13, the flue gas returns to the regenerator 2 through a pipeline 11, and reaction product oil gas in a gas collection chamber 7 enters a subsequent separation system through a large oil gas pipeline 20.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The feedstocks used in the examples and comparative examples were coker gasoline having the properties shown in Table 1.
The catalytic cracking catalyst used in the examples and comparative examples was sold under the trade name MMC-2.
Comparative example
The method comprises the steps of performing a test on a medium-sized device of a riser reactor, feeding preheated coker gasoline into the bottom of the riser reactor for catalytic cracking reaction, feeding a reaction product and a spent catalyst into a closed cyclone separator from an outlet of the reactor, rapidly separating the reaction product from the spent catalyst, and cutting the reaction product in a separation system according to a distillation range, thereby obtaining fractions such as ethylene, propylene, cracked gasoline and the like.
The spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped spent catalyst enters a regenerator and is in contact with air for regeneration; the regenerated catalyst enters a degassing tank to remove oxygen-containing gas adsorbed and carried by the regenerated catalyst; the degassed regenerated catalyst returns to the riser reactor for recycling; the operating conditions and the product distribution are listed in table 2.
As can be seen from the results in table 2, the conversion of coker gasoline was only 44.29 wt%, the yields of ethylene and propylene were 4.58 wt% and 14.5 wt%, respectively, and the normal paraffin content in the pyrolysis gasoline was still 29.23 wt%.
Examples
The test is carried out according to the flow of fig. 1, the raw oil is a coker gasoline raw material, the adsorption separation reaction is carried out on a fixed bed adsorption and desorption reactor, the normal alkane adsorbent is a 5A molecular sieve, and the adsorption separation reaction conditions are as follows: temperature 300 ℃, weight hourly space velocity of coker gasoline feedstock1.0 hour-1(ii) a Desorption treatment conditions: the desorption gas is nitrogen, and the weight hourly space velocity of the desorption gas is 150 hours-1And the temperature is 360 ℃. The nitrogen content in the raffinate oil is 350 microgram/g, the normal alkane content in the desorbed oil is 95 weight percent, and the nitrogen content is 10 microgram/g. The desorbed oil and the residual oil generated by the adsorption separation of the coker gasoline enter a heating furnace and are heated to 420 ℃.
Catalytic cracking reaction is carried out on the medium-sized device of riser reactor, and the desorption oil of preheating gets into first riser reactor bottom and carries out first catalytic cracking reaction, and the residual oil that inhales that preheats gets into second riser reactor bottom and carries out second catalytic cracking reaction, and desorption oil and the unit interval of inhaling the residual oil feed weight ratio are 1: 3, the reaction product and the spent catalyst enter a closed cyclone separator from the outlet of the reactor, the reaction product and the spent catalyst are quickly separated, and the reaction product is cut in a separation system according to the distillation range, so that fractions such as ethylene, propylene, pyrolysis gasoline and the like are obtained; the spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped catalyst enters a regenerator and is in contact with air for regeneration; the regenerated catalyst enters a degassing tank to remove oxygen-containing gas adsorbed and carried by the regenerated catalyst; the degassed regenerated catalyst returns to the riser reactor for recycling; the operating conditions and the product distribution are listed in table 2.
As can be seen from the results in table 2, the conversion of coker gasoline was 70.86 wt%, the yields of ethylene and propylene were 11.21 wt% and 23.28 wt%, respectively, and the normal paraffin content in the pyrolysis gasoline was reduced to 14.62 wt%.
It can be seen from the results of the examples that the method of the present invention greatly improves the conversion rate of the coker gasoline, greatly reduces the content of normal paraffin in the pyrolysis gasoline, and has the obvious advantage of high yields of ethylene and propylene.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may 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
| Properties of crude oil | |
| Density (20 deg.C), g/cm3 | 0.7373 |
| Vapour pressure, kilopascal | 50.0 |
| Nitrogen content, microgram/gram | 400 |
| Group composition, weight% | |
| N-alkanes | 28.2 |
| Isoalkanes | 18.1 |
| Olefins | 35.8 |
| Cycloalkanes | 7.9 |
| Aromatic hydrocarbons | 10.0 |
| Distillation range, deg.C | |
| Initial boiling point | 44 |
| 10% by volume | 65 |
| 30% by volume | 90 |
| 50% by volume | 122 |
| 70% by volume | 153 |
| 90% by volume | 184 |
| 95% by volume | 195 |
| End point of distillation | 208 |
TABLE 2
| Comparative example | Examples | |
| Adsorption separation reaction and desorption treatment | ||
| Adsorption temperature of low DEG C | / | 300 |
| Weight hourly space velocity of raw materials, hours-1 | / | 1.0 |
| Desorption temperature,. degree.C | / | 360 |
| Weight hourly space velocity, hour of desorbed gas-1 | / | 150 |
| Catalytic cracking unit | ||
| Outlet temperature of the first riser, deg.C | 635 | 635 |
| First riser reaction time, second | 2 | 1.8 |
| Water-oil weight ratio of the first lift pipe | 0.3 | 0.2 |
| First riser |
25 | 25 |
| Outlet temperature of the second riser, deg.C | / | 635 |
| Second riser reaction time, second | / | 1.8 |
| Water-oil weight ratio of second lift pipe | / | 0.2 |
| Second riser oil weight ratio | / | 25 |
| Product distribution, weight% | ||
| Hydrogen + methane | 2.45 | 3.88 |
| Ethylene | 4.58 | 11.21 |
| Ethane (III) | 1.51 | 2.87 |
| LPG | 32.64 | 45.9 |
| Pyrolysis gasoline | 55.71 | 29.14 |
| Cracking diesel oil | 1.23 | 3.24 |
| Coke | 1.88 | 3.76 |
| Total up to | 100 | 100 |
| Propylene (PA) | 14.5 | 23.28 |
| Conversion, wt.% | 44.29 | 70.86 |
| Composition by weight of cracked gasoline hydrocarbon | ||
| N-alkanes | 29.23 | 14.62 |
| Isoalkanes | 18.98 | 14.12 |
| Olefins | 10.8 | 9.56 |
| Cycloalkanes | 6.66 | 3.92 |
| Aromatic hydrocarbons | 34.33 | 57.78 |
Claims (13)
1. A method for coker gasoline processing using dual risers, the method comprising:
introducing a coking gasoline raw material into an adsorption and desorption reactor to contact with an n-alkane adsorbent and carry out adsorption separation reaction to obtain the adsorbent adsorbed with n-alkane and absorption residual oil;
carrying out desorption treatment on the obtained adsorbent with adsorbed normal alkane by adopting desorption gas to obtain desorbed adsorbent and desorbed oil;
introducing the desorbed oil into a first riser reactor to contact with a first catalytic cracking catalyst and perform a first catalytic cracking reaction to obtain a first reaction product and a first catalyst to be generated;
introducing the residual oil into a second riser reactor to contact with a second catalytic cracking catalyst and perform a second catalytic cracking reaction to obtain a second reaction product and a second spent catalyst;
separating the obtained first reaction product from the first catalyst to be regenerated, separating the obtained second reaction product from the second catalyst to be regenerated, sending the obtained first catalyst to be regenerated and the obtained second catalyst to be regenerated into a regenerator for scorching, and returning at least part of the obtained regenerated catalyst to the first riser reactor and the second riser reactor to be used as the first catalytic cracking catalyst and the second catalytic cracking catalyst;
the coking gasoline raw material contains 6-30 wt% of normal paraffin, 20-40 wt% of olefin and 1000 microgram/g of 100-one nitrogen;
the nitrogen content in the raffinate oil is 60-600 micrograms/gram;
the n-alkane content in the desorption oil is 90-98 wt%, and the nitrogen content is 0-100 micrograms/gram.
2. The process of claim 1, wherein the adsorption-desorption reactor is a fixed bed reactor, a moving bed reactor, a simulated moving bed reactor, or an expanded bed reactor.
3. The method according to claim 1, wherein the n-alkane adsorbent is one or more selected from the group consisting of activated carbon, activated carbon fiber, carbonized resin silica gel, natural zeolite, synthetic zeolite, and activated alumina.
4. The method of claim 1, wherein the conditions of the adsorptive separation reaction comprise: the temperature is 250-380 ℃, and the weight hourly space velocity of the coking gasoline raw material is 0.1-20 hours-1；
The conditions of the desorption treatment include: the temperature is 300-450 ℃, the desorption gas is nitrogen or hydrogen, and the weight hourly space velocity of the desorption gas is 100-200 hours-1。
5. The method of claim 1, wherein the conditions of the first catalytic cracking reaction comprise: the reaction temperature is 560 ℃ and 750 ℃, the reaction time is 1-10 seconds, the weight ratio of the catalyst to the oil is 1-100, and the weight ratio of the water to the oil is (0.01-1): 1, the feeding weight ratio of the desorption oil to the absorption residual oil in unit time is 1: (2.5-4.0);
the conditions of the second catalytic cracking reaction include: the reaction temperature is 560 ℃ and 750 ℃, the reaction time is 1-10 seconds, the weight ratio of the catalyst to the oil is 1-100, and the weight ratio of the water to the oil is (0.01-1): 1.
6. the method of claim 1, further comprising: preheating desorption oil and residual absorption oil, and then respectively introducing the preheated desorption oil and the preheated residual absorption oil into a first riser reactor and a second riser reactor, wherein the temperatures of the preheated desorption oil and the preheated residual absorption oil are respectively 350-450 ℃.
7. The process of claim 1, wherein the first and second catalytic cracking catalysts each independently comprise, on a dry basis and based on the total weight of the catalyst, from 1 to 60 wt% zeolite, from 5 to 99 wt% inorganic oxide, and from 0 to 70 wt% clay;
the zeolite comprises 50 to 100 wt% of a medium pore zeolite and 0 to 50 wt% of a large pore zeolite, on a dry basis and based on the total weight of the zeolite.
8. The process of claim 7 wherein the zeolite comprises from 70 to 100 wt% of a medium pore zeolite and from 0 to 30 wt% of a large pore zeolite, on a dry basis and based on the total weight of the zeolite.
9. The process of claim 7 wherein the medium pore zeolite is a ZSM-series zeolite and/or a ZRP zeolite and the large pore zeolite is one or more selected from rare earth Y, rare earth hydrogen Y, ultrastable Y and high silicon Y;
the inorganic oxide is silicon dioxide and/or aluminum oxide;
the clay is kaolin and/or halloysite.
10. The method of claim 1, further comprising: delivering the regenerated catalyst from the regenerator into a degassing tank for degassing, delivering the degassed regenerated catalyst into the first riser reactor and/or the second riser reactor for use as a first catalytic cracking catalyst and/or a second catalytic cracking catalyst, and returning oxygen-containing gas obtained by degassing in the degassing tank to the regenerator.
11. A system suitable for the method for processing coker gasoline by using double risers as claimed in any one of claims 1 to 10, the system comprising an adsorption and desorption reactor, a first riser reactor, a second riser reactor, an oil separation device and a regenerator;
the adsorption and desorption reactor is provided with a coking gasoline raw material inlet, a desorption gas inlet, an oil absorption residual oil outlet and a desorption oil outlet, the first riser reactor is provided with a desorption oil feed inlet, a catalyst inlet and an oil agent outlet, the second riser reactor is provided with an oil absorption residual oil feed inlet, a catalyst inlet and an oil agent outlet, the oil agent separation equipment is provided with an oil agent inlet, a catalyst outlet and an oil gas outlet, and the regenerator is provided with a catalyst inlet and a catalyst outlet;
the absorption desorption reactor inhale the residual oil export with the residual oil feed inlet fluid intercommunication that inhales of second riser reactor, the desorption oil export of absorption desorption reactor with the desorption oil feed inlet fluid intercommunication of first riser reactor, the finish outlet of first riser reactor and second riser reactor with finish oil splitter's finish oil entry fluid intercommunication, the catalyst entry of first riser reactor and second riser reactor with the catalyst outlet fluid intercommunication of regenerator, the catalyst entry of regenerator with finish oil splitter's catalyst outlet fluid intercommunication.
12. The system of claim 11, wherein the adsorption-desorption reactor is a fixed bed reactor, a moving bed reactor, a simulated moving bed reactor, or an expanded bed reactor.
13. The system according to claim 11, wherein the system further comprises a degassing tank through which the catalyst inlet of the first riser reactor and/or the second riser reactor is in fluid communication with the catalyst outlet of the regenerator; and/or
The system also comprises a preheating device for preheating the desorption oil and/or the residual absorption oil.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1160746A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司 | Gasoline octane number-raising catalytic conversion method |
| CN101935544A (en) * | 2009-06-30 | 2011-01-05 | 中国石油化工股份有限公司石油化工科学研究院 | Method for processing catalytically cracked gasoline |
| WO2012171426A1 (en) * | 2011-06-15 | 2012-12-20 | Shi Baozhen | Method and device for catalytic cracking |
| CN102899078A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Catalytic cracking method for producing propylene |
-
2018
- 2018-08-24 CN CN201810975592.7A patent/CN110857400B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1160746A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司 | Gasoline octane number-raising catalytic conversion method |
| CN101935544A (en) * | 2009-06-30 | 2011-01-05 | 中国石油化工股份有限公司石油化工科学研究院 | Method for processing catalytically cracked gasoline |
| WO2012171426A1 (en) * | 2011-06-15 | 2012-12-20 | Shi Baozhen | Method and device for catalytic cracking |
| CN102899078A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Catalytic cracking method for producing propylene |
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