CN110857401B - Processing method and system of coking gasoline - Google Patents
Processing method and system of coking gasoline Download PDFInfo
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- CN110857401B CN110857401B CN201810975602.7A CN201810975602A CN110857401B CN 110857401 B CN110857401 B CN 110857401B CN 201810975602 A CN201810975602 A CN 201810975602A CN 110857401 B CN110857401 B CN 110857401B
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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 processing method and a system of coker gasoline, 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 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 and the residual oil into a catalytic cracking reactor to contact with a catalytic cracking catalyst for catalytic cracking reaction to obtain a reaction product and a spent catalyst; separating the obtained reaction product from the spent catalyst, feeding the obtained spent catalyst into a regenerator for coke burning regeneration, and returning at least part of the obtained regenerated catalyst to the catalytic cracking reactor for use as the catalytic cracking catalyst. 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 processing method and a system of coker gasoline.
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 processing method and a system for coker gasoline, which are used for processing the coker gasoline and have high yields of ethylene and propylene.
In order to achieve the above object, the present invention provides a process for processing coker gasoline, 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 and the residual oil into a catalytic cracking reactor to contact with a catalytic cracking catalyst for catalytic cracking reaction to obtain a reaction product and a spent catalyst, wherein the desorbed oil feed port is positioned at the upstream of the residual oil feed port according to the flow direction of a reaction material in the catalytic cracking reactor;
separating the obtained reaction product from the spent catalyst, feeding the obtained spent catalyst into a regenerator for coke burning regeneration, and returning at least part of the obtained regenerated catalyst to the catalytic cracking reactor for use as the 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 catalytic cracking reactor is a riser reactor.
Optionally, the ratio of the distance between the desorption oil feed port and the residual oil suction feed port to the total height of the riser reactor is 2-20%.
Optionally, the conditions of the 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).
Optionally, the conditions of the catalytic cracking reaction include: the reaction temperature is 580-720 ℃, the reaction time is 2-6 seconds, and the weight ratio of the catalyst to the oil is 10-50.
Optionally, the conditions of the catalytic cracking reaction include: the reaction temperature is 600-680 ℃, the reaction time is 2-4 seconds, and the weight ratio of the catalyst to the oil is 20-40.
Optionally, the method further includes: preheating desorption oil and residual absorption oil, and introducing the preheated desorption oil and the preheated residual absorption oil into a catalytic cracking reactor, wherein the temperatures of the preheated desorption oil and the preheated residual absorption oil are respectively 350-450 ℃.
Optionally, the catalytic cracking catalyst comprises, 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.
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: feeding the regenerated catalyst from the regenerator into a degassing tank for degassing, then feeding the regenerated catalyst into a catalytic cracking reactor for use as the 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 catalytic cracking 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 outlet and a desorption oil outlet, the catalytic cracking reactor is provided with a desorption oil feed inlet, an oil absorption feed inlet, a catalyst inlet and an oil agent outlet, the desorption oil feed inlet is arranged at the upstream of the oil absorption feed inlet according to the flow direction of reaction materials in the catalytic cracking reactor, 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 residual oil export of absorption desorption reactor with the absorption residual oil feed inlet fluid intercommunication of catalytic cracking reactor, the desorption oil export of absorption desorption reactor with the desorption oil feed inlet fluid intercommunication of catalytic cracking reactor, the finish outlet of catalytic cracking reactor with finish splitter's finish entry fluid intercommunication, the catalyst entry of catalytic cracking reactor with the catalyst export fluid intercommunication of regenerator, the catalyst entry of regenerator with finish splitter's catalyst export 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;
the catalytic cracking reactor is a riser reactor, and the proportion of the distance between the desorption oil feed port and the residual oil suction feed port in the total height of the riser reactor is 2-20%.
Optionally, the system further comprises a degassing tank through which the catalyst inlet of the catalytic cracking 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 catalytic cracking 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 carry out cracking reaction by preferentially contacting the normal alkane component with the regenerated catalyst, so that a small amount of carbon deposit on the regenerated catalyst can reasonably adjust the property of the catalyst, reduce the number of strong acid centers on the catalyst, provide proper catalyst acidity for non-normal alkanes with higher reaction activity, particularly alkenes, and improve the yield and selectivity of ethylene and propylene.
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 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 regenerative chute
13 regenerative slide valve 14 line 15 line
16 line 17 line 18 line
19 line 20 large oil and gas line 21 line
22 air distributor 23 line 24 cyclone
25 flue gas pipeline 26 adsorption and desorption reactor 27 pipeline
28 line 29 line 30 line
31 heating furnace
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 processing method of coker gasoline, 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 preheated desorption oil and the preheated raffinate oil into a catalytic cracking reactor to contact with a catalytic cracking catalyst for catalytic cracking reaction to obtain a reaction product and a spent catalyst, wherein a desorption oil feed port is arranged at the upstream of a raffinate oil feed port according to the flow direction of reaction materials in the catalytic cracking reactor;
separating the obtained reaction product from the spent catalyst, feeding the obtained spent catalyst into a regenerator for coke burning regeneration, and returning at least part of the obtained regenerated catalyst to the catalytic cracking reactor for use as the 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%, nitrogen content can be 0-100 microgram/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 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, and when carried out in a fixed bed reactor, zeolite is preferably used as the n-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。
According to the present invention, catalytic cracking is well known to those skilled in the art, the catalytic cracking reactor can be various reactors, for example, it can be selected from a riser reactor and/or a fluidized bed reactor, preferably a riser reactor, desorption oil and raffinate oil enter the riser reactor from different feed inlets, the feed ratio of each feed inlet can be the same or different, the number of feed inlets can be two or more, preferably two, and the distance between the desorption oil feed inlet and raffinate oil feed inlet can account for 2% -20% of the total height of the riser reactor. The riser reactor can be an equal-diameter riser reactor or a variable-diameter riser reactor, preferably an equal-diameter riser reactor, the variable-diameter riser reactor is, for example, an equal linear velocity riser reactor, the riser reactor can include a pre-lifting section and at least one reaction zone from bottom to top, and the number of the reaction zones can be 2-8, preferably 2-3, in order to enable the raw oil to fully react and meet the quality requirements of different target products.
Catalytic cracking reactions according to the present invention are well known to those skilled in the art, and in particular for the purposes of the present invention, the conditions of the catalytic cracking reaction may include: the reaction temperature (outlet temperature, the same below) is 560-: 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 for the catalytic cracking reaction preferably include: the reaction temperature is 580-720 ℃, the reaction time is 2-6 seconds, and the weight ratio of the catalyst to the oil is 10-50. More preferably, the conditions for the catalytic cracking reaction include: the reaction temperature is 600-680 ℃, the reaction time is 2-4 seconds, and the weight ratio of the catalyst to the oil is 20-40.
According to the invention, the method may further comprise: the desorption oil and the residual oil are preheated and then introduced into a catalytic cracking 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.
Catalytic cracking catalysts are 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 catalytic cracking catalyst may comprise from 1 to 60 wt% zeolite, from 5 to 99 wt% inorganic oxide, and from 0 to 70 wt% 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 MFI structure, such as ZSM-series zeolite and/or ZRP zeolite, or the medium pore zeolite may be treated with a nonmetal element such as phosphorus and/or a transition metal element such as iron, cobalt, nickelModifications, more detailed description of the ZRP are found in U.S. Pat. No. 5,232,675, the ZSM series of zeolites is selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and mixtures of one or more of the other zeolites of similar structure, and more detailed description of the ZSM-5 is found in U.S. Pat. No. 3,702,886. 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: the regenerated catalyst from the regenerator is sent to a degassing tank for degassing and then sent to a catalytic cracking reactor to be used as the catalytic cracking catalyst, oxygen-containing gas obtained by degassing in the degassing tank is returned to the regenerator, and impurities such as oxygen are removed from the regenerated catalyst in the degassing tank by 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 catalytic cracking 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 outlet and a desorption oil outlet, the catalytic cracking reactor is provided with a desorption oil feed inlet, an oil absorption feed inlet, a catalyst inlet and an oil agent outlet, the desorption oil feed inlet is arranged at the upstream of the oil absorption feed inlet according to the flow direction of reaction materials in the catalytic cracking reactor, 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 residual oil export of absorption desorption reactor with the absorption residual oil feed inlet fluid intercommunication of catalytic cracking reactor, the desorption oil export of absorption desorption reactor with the desorption oil feed inlet fluid intercommunication of catalytic cracking reactor, the finish outlet of catalytic cracking reactor with finish splitter's finish entry fluid intercommunication, the catalyst entry of catalytic cracking reactor with the catalyst export fluid intercommunication of regenerator, the catalyst entry of regenerator with finish splitter's catalyst export fluid intercommunication.
In the invention, 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 catalytic cracking reactor can be a riser reactor, and the proportion of the distance between the desorption oil feed port and the residual oil suction feed port in the total height of the riser reactor can be 2-20%.
According to the invention, the system can further comprise a degassing tank, the catalyst inlet of the catalytic cracking 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 catalytic cracking 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 raw material enters the top of the adsorption and desorption reactor 26 through a pipeline 27, and after adsorption and separation by a molecular sieve adsorbent, the absorption residual oil enters a heating furnace 31 through a pipeline 30; nitrogen is injected into the bottom of the adsorption and desorption reactor 26 through a line 28 to desorb the adsorbed normal paraffins from the molecular sieve, and the resulting desorbed oil is introduced into a heating furnace 31 through a line 29.
The pre-lifting medium enters from the bottom of the riser reactor 1 through a pipeline 14, the regenerated catalyst from a regenerated inclined pipe 12 enters the bottom of the riser reactor 1 after being regulated by a regeneration slide valve 13, and moves upwards and quickly along the riser under the lifting action of the pre-lifting medium, the preheated desorption oil is injected into the bottom of the riser reactor 1 through a pipeline 16 together with the atomized steam from a pipeline 15 and is mixed with the existing material flow of the riser reactor, and the raw oil undergoes a cracking reaction on the hot catalyst and moves upwards and quickly. Preheated raffinate is injected into the middle lower part of the riser reactor 1 through a pipeline 18 and atomized steam from a pipeline 17, is mixed with the existing material flow of the riser reactor, and undergoes cracking reaction on a catalyst and moves upwards in an accelerated manner. 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 stripped by contact 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 inclined tube 8 and a spent slide valve 9, 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 stripped 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 1
The test is carried out on a medium-sized device of a riser reactor, preheated coker gasoline raw material enters the bottom of a riser to carry out catalyst cracking reaction, a reaction product and a 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 according to the distillation range in a separation system, 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 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 the coker gasoline feedstock (the sum of the yields of the products except for pyrolysis gasoline) was only 44.29 wt%, the yields of ethylene and propylene were 4.58 wt% and 14.50 wt%, respectively, and the normal paraffin content in the pyrolysis gasoline was still 29.23 wt%.
Example 1
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: the temperature is 300 ℃, and the weight hourly space velocity of the coking gasoline raw material is 1.0 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 ℃.
The catalytic cracking reaction is carried out on a medium-sized device of a riser reactor, preheated desorption oil enters the bottom of the riser reactor to carry out the cracking reaction, preheated absorption residual oil enters the middle lower part of the riser reactor to be mixed with existing material flow in the riser reactor and reacts on a small amount of carbon-deposited catalyst, the proportion of the distance between a desorption oil feed inlet and an absorption residual oil feed inlet to the total height of the riser reactor is 10 percent, and the weight ratio of the desorption oil to the absorption residual oil in unit time is 1: 3. the reaction product, steam and 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 non-hydrocarbon gas impurities 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%.
Comparative example 2
The same as example 1 except that: the feed inlets for the absorbed residual oil and desorbed oil were changed in weight ratio to the feed per unit time, i.e., the absorbed residual oil was fed from the bottom of the riser reactor, and the desorbed oil was fed from the lower part of the riser reactor, the distance between the absorbed residual oil feed inlet and the desorbed oil feed inlet accounted for 10% of the total height of the riser reactor, the other steps and conditions were the same as those in example 1, and the operating conditions and product distribution are shown in table 2.
It can be seen from the comparison of the examples and the comparative examples that the process and the system of the present invention greatly increase the conversion rate of coker gasoline, greatly reduce the content of normal paraffins in pyrolysis gasoline, and have 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 1 | Example 1 | Comparative example 2 | |
| Adsorption separation reaction and desorption treatment | |||
| Adsorption temperature of low DEG C | / | 300 | 300 |
| Weight hourly space velocity of raw materials, hours-1 | / | 1.0 | 1.0 |
| Desorption temperature,. degree.C | / | 360 | 360 |
| Weight hourly space velocity, hour of desorbed gas-1 | / | 150 | 150 |
| Catalytic cracking reaction | |||
| Riser outlet temperature,. deg.C | 635 | 635 | 635 |
| Reaction time in |
2 | 2 | 2 |
| Water to oil weight ratio | 0.3 | 0.3 | 0.3 |
| Weight ratio of solvent to |
25 | 25 | 25 |
| Product distribution, weight% | |||
| Hydrogen + methane | 2.45 | 3.88 | 3.3 |
| Ethylene | 4.58 | 11.21 | 10.53 |
| Ethane (III) | 1.51 | 2.87 | 2.91 |
| Liquefied gas | 32.64 | 45.9 | 43.9 |
| Pyrolysis gasoline | 55.71 | 29.14 | 30.83 |
| Cracking diesel oil | 1.23 | 3.24 | 3.78 |
| Coke | 1.88 | 3.76 | 4.75 |
| Total up to | 100 | 100 | 100 |
| Propylene (PA) | 14.5 | 23.28 | 16.68 |
| Conversion, wt.% | 44.29 | 70.86 | 69.17 |
| Composition by weight of cracked gasoline hydrocarbon | |||
| N-alkanes | 29.23 | 14.62 | 16.08 |
| Isoalkanes | 18.98 | 14.12 | 12.86 |
| Olefins | 10.8 | 9.56 | 8.7 |
| Cycloalkanes | 6.66 | 3.92 | 3.57 |
| Aromatic hydrocarbons | 34.33 | 57.78 | 58.79 |
Claims (17)
1. A process for processing coker gasoline, 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 and the residual oil into a catalytic cracking reactor to contact with a catalytic cracking catalyst for catalytic cracking reaction to obtain a reaction product and a spent catalyst, wherein the desorbed oil feed port is positioned at the upstream of the residual oil feed port according to the flow direction of a reaction material in the catalytic cracking reactor;
separating the obtained reaction product from the spent catalyst, feeding the obtained spent catalyst into a regenerator for coke burning regeneration, and returning at least part of the obtained regenerated catalyst to the catalytic cracking reactor to be used as the 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 adsorptive separation reaction is a condition packageComprises the following steps: 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 catalytic cracking reactor is a riser reactor.
6. The process of claim 5, wherein the separation distance between the desorption oil feed port and the raffinate oil feed port accounts for 2-20% of the total height of the riser reactor.
7. The method of claim 1, wherein the conditions of the 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).
8. The method of claim 1, wherein the conditions of the catalytic cracking reaction comprise: the reaction temperature is 580-720 ℃, the reaction time is 2-6 seconds, and the weight ratio of the catalyst to the oil is 10-50.
9. The method of claim 1, wherein the conditions of the catalytic cracking reaction comprise: the reaction temperature is 600-680 ℃, the reaction time is 2-4 seconds, and the weight ratio of the catalyst to the oil is 20-40.
10. The method of claim 1, further comprising: preheating desorption oil and residual absorption oil, and introducing the preheated desorption oil and the preheated residual absorption oil into a catalytic cracking reactor, wherein the temperatures of the preheated desorption oil and the preheated residual absorption oil are respectively 350-450 ℃.
11. The process of claim 1 wherein the catalytic cracking catalyst comprises, 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.
12. The process of claim 11 wherein 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.
13. The process of claim 11 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 silica Y;
the inorganic oxide is silicon dioxide and/or aluminum oxide;
the clay is kaolin and/or halloysite.
14. The method of claim 1, further comprising: feeding the regenerated catalyst from the regenerator into a degassing tank for degassing, then feeding the regenerated catalyst into a catalytic cracking reactor for use as the catalytic cracking catalyst, and returning oxygen-containing gas obtained by degassing in the degassing tank to the regenerator.
15. A processing system of coking gasoline comprises an adsorption and desorption reactor, a catalytic cracking reactor, an oil agent 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 outlet and a desorption oil outlet, the catalytic cracking reactor is provided with a desorption oil feed inlet, an oil absorption feed inlet, a catalyst inlet and an oil agent outlet, the desorption oil feed inlet is arranged at the upstream of the oil absorption feed inlet according to the flow direction of reaction materials in the catalytic cracking reactor, 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 residual oil export of absorption desorption reactor with the absorption residual oil feed inlet fluid intercommunication of catalytic cracking reactor, the desorption oil export of absorption desorption reactor with the desorption oil feed inlet fluid intercommunication of catalytic cracking reactor, the finish outlet of catalytic cracking reactor with finish splitter's finish entry fluid intercommunication, the catalyst entry of catalytic cracking reactor with the catalyst export fluid intercommunication of regenerator, the catalyst entry of regenerator with finish splitter's catalyst export fluid intercommunication.
16. The system of claim 15, wherein the adsorption-desorption reactor is a fixed bed reactor, a moving bed reactor, a simulated moving bed reactor, or an expanded bed reactor;
the catalytic cracking reactor is a riser reactor, and the proportion of the distance between the desorption oil feed port and the residual oil suction feed port in the total height of the riser reactor is 2-20%.
17. The system of claim 15, wherein the system further comprises a degassing tank through which a catalyst inlet of the catalytic cracking reactor is in fluid communication with a 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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| 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 |
| CN102344831A (en) * | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Petroleum hydrocarbon catalytic conversion method |
| 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 |
| CN103146427A (en) * | 2011-12-06 | 2013-06-12 | 中国石油化工股份有限公司 | Modification method of coker gasoline |
| CN105400546A (en) * | 2014-09-12 | 2016-03-16 | 中石化洛阳工程有限公司 | Catalytic cracking method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102344831A (en) * | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Petroleum hydrocarbon catalytic conversion method |
| 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 |
| CN103146427A (en) * | 2011-12-06 | 2013-06-12 | 中国石油化工股份有限公司 | Modification method of coker gasoline |
| CN105400546A (en) * | 2014-09-12 | 2016-03-16 | 中石化洛阳工程有限公司 | Catalytic cracking method |
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