CN110540866B - Processing method of crude oil whole fraction - Google Patents
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- CN110540866B CN110540866B CN201810523356.1A CN201810523356A CN110540866B CN 110540866 B CN110540866 B CN 110540866B CN 201810523356 A CN201810523356 A CN 201810523356A CN 110540866 B CN110540866 B CN 110540866B
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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
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Abstract
The invention relates to a processing method of crude oil whole fraction, which comprises the following steps: (1) separating the whole fraction of the crude oil to obtain light distillate oil, medium distillate oil and heavy distillate oil; (2) introducing the obtained heavy distillate oil into a first riser reactor from a heavy distillate oil feeding nozzle, introducing the obtained medium distillate oil into the first riser reactor from a medium distillate oil feeding nozzle, and contacting with a first catalytic cracking catalyst from the bottom of the first riser reactor to perform a first catalytic cracking reaction; (3) mixing the obtained light distillate oil with catalytic cracking gasoline, introducing the mixture into a second riser reactor, contacting with a second catalytic cracking catalyst, and carrying out a second catalytic cracking reaction; (4) and introducing the obtained second reaction product and the semi-spent catalyst into the fluidized bed reactor for a third catalytic cracking reaction to obtain a third reaction product and a second spent catalyst. The method has high yield of the low-carbon olefin.
Description
Technical Field
The invention relates to a processing method of crude oil whole fraction.
Background
From the production conditions of gasoline and diesel oil in China in recent years, the yield of gasoline and diesel oil in China, particularly the gasoline yield, keeps continuously increasing, but the apparent consumption of gasoline falls back from 2016, and the apparent consumption of diesel oil is continuously reduced. In 2016, the gasoline export of China is increased by 64.4 percent in the same proportion, and the diesel oil export is increased by 115 percent in the same proportion. The surplus of the production capacity and the increased competition of the finished oil market are the main problems in the domestic oil refining industry. On the other hand, the domestic shortage of olefin, aromatic hydrocarbon and other chemical raw materials is still large, and the transformation from fuel type to chemical type in oil refining enterprises is a great trend.
Catalytic cracking is used as an important crude oil secondary processing technology, and has irreplaceable status in the aspects of producing light oil products and low-carbon olefins by using the characteristics of wide raw material adaptability, high heavy oil conversion rate, flexible product scheme and the like. In view of the current development and development trend of catalytic cracking technology for producing chemical raw materials in recent years, research is mainly carried out on four aspects of improving reaction severity, using a catalyst or an auxiliary agent containing a shape-selective molecular sieve, using a novel reactor structure, recycling a fraction rich in a propylene precursor and the like.
Chinese patent CN101531923A discloses a catalytic conversion method for preparing propylene and high octane gasoline, which considers oil slurry, diesel oil, gasoline, and hydrocarbons with 4-8 carbon atoms as raw materials which are difficult to crack, and vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residual oil, atmospheric residual oil, and hydrogenated heavy oil as raw materials which are easy to crack. The method contacts the raw material difficult to crack with the thermal regeneration catalytic cracking catalyst, and the reaction temperature is 600-750 ℃, the weight hourly space velocity is 100-800h-1The cracking reaction is carried out under the condition of (1), the reactant flow is mixed with the raw oil easy to crack, and the cracking reaction is carried out under the conditions of the reaction temperature of 450-620 ℃ and the weight hourly space velocity of 0.1-100. The method can improve the yield and selectivity of propylene.
Chinese patent CN102899078A discloses a catalytic cracking method for producing propylene, which is based on a combined reactor composed of double risers and a fluidized bed, and comprises introducing heavy raw oil and a first catalyst into a first riser reactor for reaction, and separating the oil and then feeding the oil into a separation system. Introducing the cracked heavy oil into a second riser reactor to contact and react with the catalyst introduced into the second riser reactor, introducing light hydrocarbon into the second riser reactor to contact with a mixture formed by the contact and reaction of the cracked heavy oil and a second strand of cracking catalyst, wherein the light hydrocarbon comprises C4 hydrocarbon or gasoline fraction obtained by a product separation system. And then introducing the oil gas reacted by the second riser reactor and a catalyst into the fluidized bed reactor for reaction. Through the optimization of the process scheme, the proper catalyst is prepared, the selective conversion is carried out on different feeds, and the yield of propylene and butylene is higher.
Chinese patent CN103666551A discloses a catalytic processing method and device for high-temperature Fischer-Tropsch synthetic oil, which fully considers the distillation range distribution and divides the Fischer-Tropsch synthetic oil into three fractions, namely gaseous hydrocarbon, high-temperature condensate and low-temperature condensate, the method comprises the steps of enabling the gaseous hydrocarbon and the high-temperature condensate to enter a first riser reactor for catalytic conversion, enabling low condensate and recycle cracking light gasoline fraction to enter a combined bed reactor for conversion, enabling a catalyst introduced into a second riser reactor to be a regenerated catalyst from a regenerator and a spent catalyst from a stripper or a mixture of the regenerated catalyst and the spent catalyst, and constructing a processing route for the high-temperature Fischer-Tropsch synthetic oil, wherein the yield of processed propylene is high.
Chinese patent CN102533322A discloses a method for producing propylene by Fischer-Tropsch synthetic oil catalytic cracking, in which a material flow rich in small molecular olefins and a Fischer-Tropsch synthetic oil raw material are mixed and injected into a reactor, and not only a heavy Fischer-Tropsch synthetic fraction but also a light Fischer-Tropsch synthetic oil fraction can be processed. Under the same reaction conditions, when the method is used for processing the Fischer-Tropsch synthetic oil, the yield of the propylene is improved by 6.74 percent.
The method does a great deal of work in the aspect of process design of catalytic cracking for producing more low-carbon olefins, achieves a certain effect, and has certain consideration on processing of the Fischer-Tropsch synthetic oil whole fraction raw material, but the crude oil whole fraction and the Fischer-Tropsch synthetic oil are obviously different in hydrocarbon composition and catalytic cracking properties, so that further research is needed on how to process the crude oil whole fraction and how to optimally produce the low-carbon olefins.
Disclosure of Invention
The invention aims to provide a crude oil whole fraction processing method which is high in low-carbon olefin yield.
In order to achieve the above object, the present invention provides a method for processing a whole fraction of crude oil, comprising:
(1) separating the whole fraction of the crude oil to obtain light distillate oil, medium distillate oil and heavy distillate oil; wherein the crude oil whole fraction is at least one selected from mineral oil, coal liquefaction oil, synthetic oil, oil sand oil, shale oil, compact oil and animal and vegetable oil; the initial boiling point of the light distillate is in the range of 15-100 ℃, the cut points of the light distillate and the medium distillate are in the range of 140-300 ℃, and the cut points of the medium distillate and the heavy distillate are in the range of 450-500 ℃;
(2) introducing the obtained heavy distillate oil into a first riser reactor from a heavy distillate oil feeding nozzle, introducing the obtained medium distillate oil into the first riser reactor from the medium distillate oil feeding nozzle, and contacting with a first catalytic cracking catalyst from the bottom of the first riser reactor to perform a first catalytic cracking reaction to obtain a first reaction product and a first catalyst to be generated; wherein the middle distillate feed nozzle is positioned above the heavy distillate feed nozzle;
(3) mixing the obtained light distillate oil with catalytic cracking gasoline, introducing the mixture into a second riser reactor, contacting with a second catalytic cracking catalyst, and carrying out a second catalytic cracking reaction to obtain a second reaction product and a semi-spent catalyst; wherein the distillation range of the catalytic cracking gasoline is between 30 and 240 ℃;
(4) introducing the obtained second reaction product and the semi-spent catalyst into a fluidized bed reactor for a third catalytic cracking reaction to obtain a third reaction product and a second spent catalyst;
(5) feeding the obtained first spent catalyst and the second spent catalyst into a regenerator for regeneration, wherein the obtained regenerated catalyst is used as the first catalytic cracking catalyst and the second catalytic cracking catalyst;
(6) and separating the first reaction product and the third reaction product to obtain a gas product, a gasoline product, a diesel oil product and a heavy oil product.
Optionally, the distillation range of the catalytically cracked gasoline in the step (3) is between 30 and 120 ℃.
Optionally, the method further includes: introducing at least a portion of the gasoline product obtained in step (6) into said second riser reactor as said catalytically cracked gasoline.
Optionally, the crude oil whole fraction has a UOP K value greater than 12.2.
Optionally, the initial cut point of the light distillate is 25-35 ℃, the cut points of the light distillate and the medium distillate are in the range of 160-280 ℃, and the cut points of the medium distillate and the heavy distillate are in the range of 480-500 ℃.
Optionally, the weight ratio of the heavy distillate oil to the whole fraction of the crude oil is not higher than 30 wt%, and/or
The 5 volume percent distillation point of the medium fraction oil is in the range of 180-300 ℃.
Optionally, the method further includes: if the 5 volume percent distillation point of the medium distillate oil is T1 ℃, the outlet temperature of the first riser reactor is T2 ℃, and the outlet temperature of the fluidized bed reactor is T3 ℃, the outlet temperature of the first riser reactor is adjusted to be T2-T/10 x a ℃ and the outlet temperature of the fluidized bed reactor is adjusted to be T3-T/10 x b ℃ every time the 5 volume percent distillation point T of the medium distillate oil is increased, wherein a is any value from 0.5 to 4, and b is any value from 0.5 to 3.
Optionally, the medium distillate is introduced 0.3-2 seconds after the heavy distillate is introduced into the first riser reactor.
Optionally, the conditions of the first catalytic cracking reaction include: the reaction temperature is 480-560 ℃, the oil gas retention time is 0.5-5 seconds, and the ratio of the weight of the first catalytic cracking catalyst to the total weight of the medium distillate oil and the heavy distillate oil is 4-10.
Optionally, the conditions of the second catalytic cracking reaction include: the reaction temperature is 600-670 ℃, the oil gas retention time is 0.5-5 seconds, the ratio of the weight of the second catalytic cracking catalyst to the total weight of the light distillate oil and the catalytic cracking gasoline is 6-20, and the weight ratio of the light distillate oil to the catalytic cracking gasoline is 1: (0.1-1).
Optionally, the conditions of the third catalytic cracking reaction include: the reaction temperature is 580-650 ℃, and the weight hourly space velocity is 3-15 h-1。
Optionally, the first catalytic cracking catalyst and the second catalytic cracking catalyst each independently comprise a carrier and an active component, and the active component is at least one selected from the group consisting of Y or HY type zeolite with or without rare earth, ultrastable Y type zeolite with or without rare earth, ZSM-5 series zeolite, high silica zeolite with pentasil structure and beta zeolite.
Compared with the prior art, the method provided by the invention fully considers the cracking characteristics of different fractions of crude oil, and can remarkably improve the yield of low-carbon olefin in the catalytic cracking process and improve the economic benefit of a catalytic cracking device through zone reaction control and heat coupling.
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 is a schematic flow diagram of one embodiment of the process of the present invention.
Description of the reference numerals
1 first riser reactor 11 transfer pipe 12 flow control valve
13 heavy distillate oil feed nozzle 14 medium distillate oil feed nozzle 15 gas-solid rapid separation device
2 second riser reactor 21 transfer pipe 22 flow control valve
23 feed nozzle 24 outlet distributor
3 baffle of fluidized bed reactor 31
4-settler 41 primary cyclone 42 secondary cyclone
5 stripper 51 baffle 52 duct
53 flow control valve
6 regenerator
7 gap
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a processing method of crude oil whole fraction, which comprises the following steps:
(1) separating the whole fraction of the crude oil to obtain light distillate oil, medium distillate oil and heavy distillate oil; wherein the crude oil whole fraction is at least one selected from mineral oil, coal liquefaction oil, synthetic oil, oil sand oil, shale oil, compact oil and animal and vegetable oil; the initial boiling point of the light distillate is in the range of 15-100 ℃, the cut points of the light distillate and the medium distillate are in the range of 140-300 ℃, and the cut points of the medium distillate and the heavy distillate are in the range of 450-500 ℃;
(2) introducing the obtained heavy distillate oil into a first riser reactor from a heavy distillate oil feeding nozzle, introducing the obtained medium distillate oil into the first riser reactor from the medium distillate oil feeding nozzle, and contacting with a first catalytic cracking catalyst from the bottom of the first riser reactor to perform a first catalytic cracking reaction to obtain a first reaction product and a first catalyst to be generated; wherein the middle distillate feed nozzle is positioned above the heavy distillate feed nozzle;
(3) mixing the obtained light distillate oil with catalytic cracking gasoline, introducing the mixture into a second riser reactor, contacting with a second catalytic cracking catalyst, and carrying out a second catalytic cracking reaction to obtain a second reaction product and a semi-spent catalyst; wherein the distillation range of the catalytic cracking gasoline is between 30 and 240 ℃;
(4) introducing the obtained second reaction product and the semi-spent catalyst into a fluidized bed reactor for a third catalytic cracking reaction to obtain a third reaction product and a second spent catalyst;
(5) feeding the obtained first spent catalyst and the second spent catalyst into a regenerator for regeneration, wherein the obtained regenerated catalyst is used as the first catalytic cracking catalyst and the second catalytic cracking catalyst;
(6) and separating the first reaction product and the third reaction product to obtain a gas product, a gasoline product, a diesel oil product and a heavy oil product.
The crude oil whole fraction refers to the extracted oil product which is only cut simply, and the processes such as atmospheric and vacuum distillation, hydrotreating, catalytic cracking and the like are not performed. The UOP K value of the whole fraction of the crude oil is preferably greater than 12.2, which is well known to those skilled in the art and may be referred to as the crude oil figure of merit or watson K value, as a function of the average boiling point and relative density of the oil.
According to the invention, the catalytically cracked gasoline comes from a catalytic cracking unit, the distillation range of the catalytically cracked gasoline in the step (3) is preferably between 30 and 120 ℃, and in order to further improve the yield of the low-carbon olefins, the method can further comprise the following steps: introducing at least a portion of the gasoline product obtained in step (6) into said second riser reactor as said catalytically cracked gasoline.
In the present invention, the initial cut point of the light fraction is preferably in the range of 25-80 ℃, the cut points of the light fraction and the medium fraction are preferably in the range of 160-280 ℃, and the cut points of the medium fraction and the heavy fraction are preferably in the range of 480-500 ℃.
In the present invention, the weight ratio of the heavy fraction to the whole crude oil fraction is preferably not higher than 30 wt%, and/or the 5 vol% cut point of the middle fraction is preferably in the range of 180-300 ℃, and the 5 vol% cut point of the middle fraction is determined by the ASTM D86 standard method. The reaction temperature of the first riser reactor and the reaction temperature of the fluidized bed reactor are greatly related to the 5 vol% distillate point of the middle distillate oil. The 5 vol% of the distillate point of the medium fraction is raised and a part of the crackable components are transferred from the reaction in the first riser with the aim of producing propylene and propylene precursors to the light fraction and to the production of propylene at high severity in the second riser reactor and the fluidized bed reactor. The 5 volume percent distillation point of the medium distillate oil is increased, the reaction severity of the first lifting pipe is reduced, and the coke forming amount is reduced. The reaction severity of the fluidized bed is correspondingly reduced because of the increased amount of the scissile components. However, the 5 vol% cut point of the middle distillate cannot be too high, which would result in a large amount of dry gas and coke formation in the high severity fluidized bed reactor.
In one embodiment, the method further comprises: if the 5 volume percent distillation point of the medium distillate oil is T1 ℃, the outlet temperature of the first riser reactor is T2 ℃, and the outlet temperature of the fluidized bed reactor is T3 ℃, the outlet temperature of the first riser reactor is adjusted to be T2-T/10 x a ℃ (i.e. T/10 x a reduction) when the 5 volume percent distillation point T ℃ of the medium distillate oil is increased, and the outlet temperature of the fluidized bed reactor is adjusted to be T3-T/10 x b ℃ (i.e. T/10 x b reduction), wherein a is any value from 0.5 to 4, and b is any value from 0.5 to 3. For example, if the 5 vol% cut point of the middle distillate increases by 40 ℃, the outlet temperature of the first riser reactor decreases by 2 to 16 ℃ and the outlet temperature of the fluidized bed reactor decreases by 2 to 12 ℃.
According to the invention, the first riser reactor takes heavy distillate oil and medium distillate oil as raw materials, adopts proper reaction conditions, and maximally produces propylene and propylene precursors. Because the heavy distillate contains a large amount of coke precursors and has less crackable components than other fractions, the coke generated in the catalytic cracking process of the heavy distillate is a main source of heat of the whole reaction-regeneration system. The first riser reactor adopts a layered feeding form of feeding advanced heavy distillate oil and then medium distillate oil, so that the cracking reaction of the crackable components can be maximally reserved, and the condensation coking reaction of the crackable components can be inhibited.
According to the present invention, catalytic cracking reactions are well known to those skilled in the art, and the present invention is not described in detail, and the conditions of the first catalytic cracking reaction may include: the reaction temperature (outlet temperature) is 480-. The conditions of the second catalytic cracking reaction may include: the reaction temperature (outlet temperature) is 600-670 ℃, the oil gas retention time is 0.5-5 seconds, the ratio of the weight of the second catalytic cracking catalyst to the total weight of the light distillate oil and the catalytic cracking gasoline is 6-20, and the weight ratio of the light distillate oil to the catalytic cracking gasoline is 1: (0.1-1). The conditions of the third catalytic cracking reaction comprise: the reaction temperature (outlet temperature) is 580-650 ℃, and the weight hourly space velocity is 3-15 h-1。
The catalytic cracking catalyst according to the present invention is well known to those skilled in the art, for example, the first catalytic cracking catalyst and the second catalytic cracking catalyst may each independently comprise a support and an active component, the active component being at least one selected from the group consisting of Y or HY type zeolite with or without rare earth, ultrastable Y type zeolite with or without rare earth, ZSM-5 series zeolite, high silica zeolite having a pentasil structure and beta zeolite, and those skilled in the art may also adopt catalysts of other compositions.
The following further describes embodiments of the present invention with reference to the accompanying drawings.
As shown in fig. 1, the regenerated catalyst is transferred to the first riser reactor 1 through a transfer pipe 11. The amount of catalyst delivered by the regenerated catalyst to the first riser reactor 1 is regulated by means of a flow control valve 12. The heavy distillate oil is sprayed into the first riser reactor 1 through the heavy distillate oil feeding nozzle 13, contacts with the regenerated catalyst and carries out a first catalytic cracking reaction. The medium distillate oil is sprayed into the first riser reactor 1 through the medium distillate oil feeding nozzle 14, and is in contact reaction with a mixture formed by the contact reaction of the heavy distillate oil and the regenerated catalyst to form a first oil agent mixture. The first oil mixture is separated by a gas-solid rapid separation device 15, the separated first catalyst to be generated enters a stripper 5, and the separated first reaction product is introduced into a fractionation device. The mixture of light distillate oil and catalytic cracking gasoline is sprayed into a second riser reactor 2 through a feeding nozzle 23, and contacts with a heat regeneration catalyst which comes from a conveying pipe 21 and has flow controlled by a flow control valve 22 to carry out a second catalytic cracking reaction, the obtained second reaction product and a semi-spent catalyst are not separated, and enter a fluidized bed reactor 3 through an outlet distributor 24 and a baffle 31, after a third catalytic cracking reaction is carried out in the fluidized bed reactor 3, the second spent catalyst enters a settler 4 through an outlet of the fluidized bed reactor 3, the second spent catalyst is separated from the third reaction product in the settler 4, the second spent catalyst enters a stripper 5 through a gap 7 and is subjected to oil separation through a baffle 51, and reaction oil gas enters a fractionating device after further separating catalyst fine powder carried in the reaction oil gas through a primary cyclone separator 41 and a secondary cyclone separator 42, further separating to obtain gas, gasoline, diesel oil and heavy oil. Gas oil gas is introduced into the settler 4 through the interspace 7. The spent catalyst is stripped in a stripper 5 to obtain adsorbed hydrocarbon products, the hydrocarbon products are sent to a regenerator 6 for regeneration through a conveying pipe 52 and a flow control valve 53, and the regenerated hot catalyst returns to the two riser reactors through a pipeline 21 and a pipeline 11 respectively for reuse.
The process according to the invention is further illustrated by the following examples, without the invention being restricted thereby.
The catalytic cracking catalysts used in the examples and comparative examples were industrially produced by the Qilu Branch of catalyst, of petrochemical Co., Ltd., China, under the trade name of MMC-2. The catalyst contains ultrastable Y-type zeolite and ZSP zeolite with average pore diameter less than 0.7 nm, and is hydrothermally aged for 14 hr at 800 deg.C before use, and its main physicochemical properties are shown in Table 1. The properties of the whole crude oil fractions used in the examples and comparative examples are shown in Table 2.
Example 1
Separating the whole fraction of the crude oil into heavy distillate oil, medium distillate oil and light distillate oil, wherein the initial boiling point of the light distillate oil is 67.2 ℃, the cutting point of the light distillate oil and the medium distillate oil is 220 ℃, the cutting point of the medium distillate oil and the heavy distillate oil is 480 ℃, the weight ratio of the heavy distillate oil to the whole fraction of the crude oil is 25 wt%, and the 5 vol% of the distillation point of the medium distillate oil is 240 ℃.
The test was carried out in a medium riser catalytic cracking unit. As shown in fig. 1, in the mesoscale apparatus, the first riser reactor 1 has an inner diameter of 16 mm and a length of 3800 mm, the second riser reactor 2 has an inner diameter of 16 mm and a length of 3200 mm, the outlet of the second riser reactor 2 is connected to a dense-phase fluidized bed reactor 3, and the fluidized bed reactor 3 has an inner diameter of 64 mm and a height of 600 mm. The high-temperature regenerated catalyst with the temperature of 700 ℃ is respectively introduced into the bottoms of the first riser reactor 1 and the second riser reactor 2 through a regenerator 6 by a regeneration inclined pipe and flows upwards under the action of pre-lifting steam. After being mixed with atomized water vapor, heavy distillate oil enters a first riser reactor 1 through a heavy distillate oil feeding nozzle 13 to contact with a hot regenerated catalyst for a first catalytic cracking reaction, after being mixed with atomized water vapor, medium distillate oil enters the first riser reactor 1 through a medium distillate oil feeding nozzle 14 above the heavy distillate oil feeding nozzle 13 to contact with an upward oil gas and catalyst mixture for the first catalytic cracking reaction, the mixture of a first reaction product and a first catalyst to be regenerated continuously moves upward along the first riser reactor 1 to pass through a quick separation device at an outlet for gas-solid separation, and reaction oil gas is introduced into a settler and then introduced into a product separation system for separation. The light distillate oil and catalytic cracking gasoline (distillation range of 30-120 ℃) are mixed according to the weight ratio of 1: 0.3, under the condition of atomized steam medium, the mixture enters the lower part of a second riser reactor 2 through a feed nozzle 23 to contact with a hot regenerant to carry out a second catalytic cracking reaction, the mixture of a second reaction product and a semi-spent catalyst enters a fluidized bed reactor 3 through an outlet of the second riser reactor 2 along the second riser reactor 2 to continuously participate in a third catalytic cracking reaction, the obtained third reaction product and the second spent catalyst are introduced into a settler 4 to carry out oil separation, reaction oil gas is introduced into a product separation system to be separated into gas and liquid products, and the obtained catalytic cracking gasoline returns to the second riser reactor 2 to be recycled. The first spent catalyst containing coke from the first riser reactor 1 and the second spent catalyst containing coke from the fluidized bed reactor 3 enter a stripper 5, and the stripping steam is used for stripping hydrocarbon products adsorbed on the spent catalyst and then enters a settler through the fluidized bed reactor for gas-solid separation. The spent agent after steam stripping enters a regenerator through a spent agent inclined pipe, contacts with air and is burned and regenerated at high temperature of 700 ℃. The regenerated catalyst returns to the riser reactor through the regenerated inclined tube for recycling. The medium-sized devices use electrical heating to maintain the temperature of the reaction-regeneration system.
The main operating conditions and results are listed in table 3.
Example 2
Example 2 is essentially the same as example 1 except that the 5 vol% cut point of the middle distillate is 280 c, i.e. the cut point of the light and middle distillates is adjusted to 260 c, the outlet temperature of the first riser reactor 1 is reduced by 10 c and the outlet temperature of the fluidized bed reactor is reduced by 5 c.
The main operating conditions and results are listed in table 3.
Example 3
Example 3 is essentially the same as example 1 except that the 5 vol% cut point of the middle distillate is 280 c, i.e. the cut points of the light and middle distillates are adjusted to 260 c.
The main operating conditions and results are listed in table 3.
Example 4
Example 4 is essentially the same as example 1 except that the medium distillate is injected into the first riser reactor 1 at a different height above the heavy distillate feed nozzle.
The main operating conditions and results are listed in table 3.
Comparative example 1
Comparative example 1 is essentially the same as example 1 except that both the medium distillate and the heavy distillate enter the first riser reactor 1 through a heavy distillate feed nozzle.
The main operating conditions and results are listed in table 3.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that the whole crude oil fraction is not cut, but the flow rates and positions of the whole crude oil fractions introduced into the first riser reactor 1 and the second riser reactor 2 are the same as those of example 1, and the catalytically cracked gasoline is mixed with the whole crude oil fraction introduced into the second riser reactor 2 and introduced into the second riser reactor 2.
The main operating conditions and results are listed in table 3.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that the catalytically cracked gasoline is not injected into the second riser reactor 2, i.e., the second riser reactor 2 is injected with only the light distillate.
The main operating conditions and results are listed in table 3.
As can be seen from the data in Table 3, the method provided by the invention can obviously improve the yield of low-carbon olefins such as propylene and the like, and can improve the economic benefit of a catalytic cracking unit.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the content of the present invention as long as it does not depart from the gist of the present invention.
TABLE 1
| Catalyst and process for preparing same | Equilibrium catalyst |
| Physical Properties | |
| Specific surface area/m2G-1 | 143 |
| Pore volume/cm-3G-1 | 0.186 |
| Apparent density g.cm-3 | 0.85 |
| Chemical composition/weight% | |
| Al2O3 | 54.8 |
| SiO2 | 39.9 |
| RE2O3 | 0.44 |
| Particle size distribution/weight% | |
| 0-20 micron | 1.6 |
| 0-40 micron | 15.0 |
| 0-80 micron | 58.1 |
| 0-110 micron | 76.6 |
| 0-149 mu m | 92.5 |
| Microreflective activity/weight% | 63 |
TABLE 2
| Item | Crude oil whole fraction |
| Density (20 deg.C)/g.cm-3 | 0.813 4 |
| Freezing point/. degree.C | 40 |
| Carbon residue/weight% | 1.21 |
| Element composition/weight% | |
| C | 85.79 |
| H | 14.15 |
| Crude oil composition/weight% | |
| Glue | 2.8 |
| Asphaltenes | 0.1 |
| Distillation range/. degree.C | |
| HK | 67.2 |
| 5% by volume | 108.1 |
| 10% by volume | 154.7 |
| 30% by volume | 216.6 |
| 50% by volume | 322.1 |
| 70% by volume | 461.9 |
| 90% by volume | 584.7 |
| UOP K value | 12.6 |
TABLE 3
Claims (11)
1. A method of processing a whole fraction of crude oil, the method comprising:
(1) separating the whole fraction of the crude oil to obtain light distillate oil, medium distillate oil and heavy distillate oil; the initial boiling point of the light distillate is in the range of 15-100 ℃, the cut points of the light distillate and the medium distillate are in the range of 140-300 ℃, and the cut points of the medium distillate and the heavy distillate are in the range of 450-500 ℃;
(2) introducing the obtained heavy distillate oil into a first riser reactor from a heavy distillate oil feeding nozzle, introducing the obtained medium distillate oil into the first riser reactor from the medium distillate oil feeding nozzle, and contacting with a first catalytic cracking catalyst from the bottom of the first riser reactor to perform a first catalytic cracking reaction to obtain a first reaction product and a first catalyst to be generated; wherein the middle distillate feed nozzle is positioned above the heavy distillate feed nozzle;
(3) mixing the obtained light distillate oil with catalytic cracking gasoline, introducing the mixture into a second riser reactor, contacting with a second catalytic cracking catalyst, and carrying out a second catalytic cracking reaction to obtain a second reaction product and a semi-spent catalyst; wherein the distillation range of the catalytic cracking gasoline is between 30 and 240 ℃;
(4) introducing the obtained second reaction product and the semi-spent catalyst into a fluidized bed reactor for a third catalytic cracking reaction to obtain a third reaction product and a second spent catalyst;
(5) feeding the obtained first spent catalyst and the second spent catalyst into a regenerator for regeneration, wherein the obtained regenerated catalyst is used as the first catalytic cracking catalyst and the second catalytic cracking catalyst;
(6) separating the first reaction product and the third reaction product to obtain a gas product, a gasoline product, a diesel oil product and a heavy oil product;
wherein, the 5 volume percent distillation point of the medium distillate is in the range of 180-300 ℃, and if the 5 volume percent distillation point of the medium distillate is T1 ℃, the outlet temperature of the first riser reactor is T2 ℃, and the outlet temperature of the fluidized bed reactor is T3 ℃, the outlet temperature of the first riser reactor is adjusted to be T2-T/10 x a ℃ and the outlet temperature of the fluidized bed reactor is adjusted to be T3-T/10 x b ℃ every time the 5 volume percent distillation point T of the medium distillate is increased, wherein, a is any value from 0.5 to 4, and b is any value from 0.5 to 3.
2. The process according to claim 1, wherein the catalytic cracked gasoline of step (3) has a distillation range between 30-120 ℃.
3. The method of claim 1 or 2, further comprising: introducing at least a portion of the gasoline product obtained in step (6) into said second riser reactor as said catalytically cracked gasoline.
4. The method of claim 1 wherein the crude oil whole fraction has a UOP K value greater than 12.2.
5. The process as claimed in claim 1, wherein the initial cut of the light fraction is in the range of 25-80 ℃, the cut of the light fraction and the medium fraction is in the range of 160-280 ℃, and the cut of the medium fraction and the heavy fraction is in the range of 480-500 ℃.
6. The process according to claim 1 or 5, wherein the weight ratio of heavy distillate oil to whole crude oil fraction is not higher than 30% by weight.
7. The process of claim 1, wherein the middle distillate is introduced 0.3 to 2 seconds after the heavy distillate is introduced into the first riser reactor.
8. The process of claim 1, wherein the conditions of the first catalytic cracking reaction comprise: the reaction temperature is 480-560 ℃, the oil gas retention time is 0.5-5 seconds, and the ratio of the weight of the first catalytic cracking catalyst to the total weight of the medium distillate oil and the heavy distillate oil is 4-10.
9. The process of claim 1, wherein the conditions of the second catalytic cracking reaction comprise: the reaction temperature is 600-670 ℃, the oil gas retention time is 0.5-5 seconds, the ratio of the weight of the second catalytic cracking catalyst to the total weight of the light distillate oil and the catalytic cracking gasoline is 6-20, and the weight ratio of the light distillate oil to the catalytic cracking gasoline is 1: (0.1-1).
10. The process of claim 1, wherein the conditions of the third catalytic cracking reaction comprise: the reaction temperature is 580-650 ℃, and the weight hourly space velocity is 3-15 h-1。
11. The process according to claim 1, wherein the first and second catalytic cracking catalysts each independently comprise a support and an active component which is at least one selected from the group consisting of Y or HY type zeolite with or without rare earth, ultrastable Y type zeolite with or without rare earth, ZSM-5 series zeolite, high silica zeolite with pentasil structure and beta zeolite.
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| CN103045300A (en) * | 2011-10-14 | 2013-04-17 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
| CN104560149A (en) * | 2013-10-16 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocarbon catalytic conversion method of productive butene |
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| CN103045300A (en) * | 2011-10-14 | 2013-04-17 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
| CN104560149A (en) * | 2013-10-16 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocarbon catalytic conversion method of productive butene |
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