CN109666506B - Method for catalytic cracking of hydrogenated oil - Google Patents
Method for catalytic cracking of hydrogenated oil Download PDFInfo
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- CN109666506B CN109666506B CN201710963527.8A CN201710963527A CN109666506B CN 109666506 B CN109666506 B CN 109666506B CN 201710963527 A CN201710963527 A CN 201710963527A CN 109666506 B CN109666506 B CN 109666506B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a catalytic cracking method of hydrogenated oil, which comprises the following steps: spraying non-hydrogenated oil into the riser reactor from a first nozzle at the lower part of the riser reactor to contact with a catalytic cracking catalyst from the bottom of the riser reactor and carrying out a first catalytic cracking reaction to obtain a first reaction product and a semi-spent catalyst; spraying the hydrogenated oil into the riser reactor from a second nozzle above the first nozzle, contacting a first reaction product and a semi-spent catalyst from the lower part of the second nozzle, and carrying out a second catalytic cracking reaction; wherein the weight ratio of the isobutane to the isobutene in the second reaction product is controlled to be between 0.5 and 1.2 by adjusting the feeding ratio of the non-hydrogenated produced oil and the hydrogenated produced oil. The method of the invention carries out layered feeding on the hydrogenated oil and the non-hydrogenated oil, can adjust the hydrogen transfer activity of the reaction system and improve the yield of the low-carbon olefin.
Description
Technical Field
The invention relates to a catalytic cracking method for hydrogenated oil.
Background
The low-carbon olefin such as ethylene, propylene and the like are important organic chemical raw materials, the annual equivalent consumption of the ethylene is estimated to reach 4800 ten thousand tons and the annual average growth rate is about 3.6 percent in China to 2020, and the annual equivalent consumption of the propylene is estimated to reach 4000 and the annual average growth rate is about 4.7 percent. The production of chemical raw materials such as low-carbon olefin, aromatic hydrocarbon and the like from heavy raw materials through oil refining devices such as catalytic cracking and the like is a reasonable technical path for solving the problem of insufficient chemical light oil, and the traditional catalytic hydrogenation and catalytic cracking combined process is generally used for improving the yield of fuel oil (gasoline and diesel oil) and improving the product distribution and product quality of catalytic cracking.
WO0031215 discloses a catalytic cracking process for the production of olefins, which uses vacuum gas oil as a feedstock, using a catalyst consisting of a matrix and a ZSM series of molecular sieves, wherein the matrix part comprises an inert matrix and a small amount of active matrix, and the molecular sieves use a large pore molecular sieve, the yield of lower olefins in the process can exceed 13 wt%, which is higher than that of conventional catalytic cracking processes.
US patent US4619757 discloses a process for the production of olefins from heavy distillates by two-stage hydroprocessing. The process comprises a hydrotreating process and a thermal cracking process, the hydrotreating process consisting of two stages, the first stage being primarily selective removal of polycyclic aromatic hydrocarbons and the second stage being primarily hydrodesulfurization and hydrodenitrogenation with a hydrotreating catalyst containing zeolite for treating feedstocks having a high polycyclic aromatic content such as vacuum gas oils, and the second stage being primarily hydrodesulfurization and hydrodenitrogenation and the hydrotreating catalyst not containing zeolite for treating feedstocks having a low polycyclic aromatic content such as atmospheric gas oils. The method has low hydrogen consumption, but low olefin yield.
WO0040677 discloses a combined process of hydrotreating and catalytic cracking. The process comprises at least two hydrotreaters and two catalytic crackers. Raw oil is firstly subjected to a first hydrotreatment device to obtain first hydrogenated tail oil; and the first hydrogenated tail oil enters a first catalytic cracking device to obtain naphtha, diesel oil and heavy oil, wherein the heavy oil enters a second hydrotreatment device for hydrogenation to obtain a second hydrogenated tail oil, and the second hydrogenated tail oil enters a second catalytic cracking device for cracking to obtain a corresponding product. The method has the advantages of complex flow, high investment and operation cost and low propylene yield.
Chinese patent CN1119397A discloses a residual oil hydrotreating-catalytic cracking combined process, in which residual oil and clarified oil enter a residual oil hydrotreating device together, and hydrogenation reaction is carried out in the presence of hydrogen and a hydrogenation catalyst; the hydrogenated residual oil obtained by the reaction enters a catalytic cracking device, the cracking reaction is carried out in the presence of a cracking catalyst, and the heavy cycle oil circulates in the catalytic cracking device; and separating the oil slurry obtained by the reaction by a separator to obtain clarified oil, and returning the clarified oil to the hydrogenation device. The method converts the catalytic cracking slurry oil into light oil products, improves the yield of gasoline and diesel oil, and reduces the yield of heavy oil, but the method has lower propylene yield.
The method refers to catalytic cracking of hydrogenated oil to produce more propylene, but does not provide an effective method for improving the yield and selectivity of low-carbon olefin of hydrogenated oil according to the hydrogen transfer reaction characteristics of hydrogenated oil.
Disclosure of Invention
The invention aims to provide a method for catalytically cracking hydrogenated oil, which can improve the yield of low-carbon olefins.
In order to achieve the above object, the present invention provides a method for catalytic cracking of hydrogenated oil, comprising: spraying non-hydrogenated oil into the riser reactor from a first nozzle at the lower part of the riser reactor to contact with a catalytic cracking catalyst from the bottom of the riser reactor and carrying out a first catalytic cracking reaction to obtain a first reaction product and a semi-spent catalyst; spraying hydrogenated oil into the riser reactor from a second nozzle above the first nozzle, contacting with a first reaction product and a semi-spent catalyst from the lower part of the second nozzle, and carrying out a second catalytic cracking reaction to obtain a second reaction product and a spent catalyst; wherein the second reaction product comprises at least isobutane and isobutene; the method further comprises the following steps: controlling the weight ratio of isobutane to isobutene in the second reaction product to be 0.5-1.2 by adjusting the feeding proportion of the non-hydrogenated produced oil and the hydrogenated produced oil; if the weight ratio of the isobutane to the isobutene is less than 0.5, reducing the feeding proportion of the non-hydrogenated generated oil; if the weight ratio of the isobutane to the isobutene is greater than 1.2, the feeding proportion of the non-hydrogenated product oil is increased.
Optionally, the weight ratio of isobutane to isobutene in the second reaction product is controlled to be 0.9-1.2 by adjusting the feeding ratio of the non-hydrogenated produced oil to the hydrogenated produced oil, and if the weight ratio of isobutane to isobutene is less than 0.9, the feeding ratio of the non-hydrogenated produced oil is reduced; if the weight ratio of the isobutane to the isobutene is greater than 1.2, the feeding proportion of the non-hydrogenated product oil is increased.
Optionally, the method further includes: controlling the weight ratio of isobutane to isobutene in the second reaction product to be 0.5-1.2 by adjusting the feeding proportion of the non-hydrogenated produced oil and the hydrogenated produced oil; wherein, if the weight ratio of the isobutane to the isobutene is less than 0.5, the feeding proportion of the non-hydrogenated product oil is reduced; if the weight ratio of the isobutane to the isobutene is greater than 1.2, the feeding proportion of the non-hydrogenated product oil is increased.
Optionally, the weight ratio of the non-hydrogenated product oil to the hydrogenated product oil is 0.05-2.
Optionally, the conditions of the first catalytic cracking reaction include: the temperature of the second nozzle is 550-680 ℃, the weight ratio of the catalytic cracking catalyst to the non-hydrogenation generated oil is 20-150, and the oil gas retention time is 0.05-2 seconds.
Optionally, the non-hydrogenated product oil is at least one selected from the group consisting of vacuum gas oil, atmospheric residue, vacuum residue and heavy oil.
Optionally, the conditions of the second catalytic cracking reaction include: the outlet temperature of the riser reactor is 460-620 ℃, the weight ratio of the catalytic cracking catalyst to the hydrogenation generated oil is 5-50, and the oil gas retention time is 0.5-4 seconds.
Optionally, the hydrogenated oil is at least one selected from the group consisting of hydrocracked tail oil, hydrorefined wax oil, hydrodesulfurized atmospheric residue, and hydrodesulfurized vacuum residue.
Optionally, the method further includes: and feeding the reaction material obtained by the second catalytic cracking reaction into a fluidized bed reactor for a third catalytic cracking reaction to obtain a second reaction product and a spent catalyst.
Optionally, the conditions of the third catalytic cracking reaction include: the temperature is 450 ℃ and 610 ℃, and the weight hourly space velocity is 0.5-30 h-1。
Optionally, the catalytic cracking catalyst comprises, on a dry basis and based on the weight of the catalytic cracking catalyst, from 1 to 60 wt% of a zeolite mixture, from 5 to 99 wt% of a refractory inorganic oxide, and from 0 to 70 wt% of a clay, wherein the zeolite mixture comprises, based on the total weight of the zeolite mixture, from 1 to 75 wt% of a modified beta zeolite and from 25 to 99 wt% of a zeolite having an MFI structure.
Optionally, the catalytic cracking catalyst comprises, on a dry basis and based on the weight of the catalytic cracking catalyst, from 10 to 50 wt% of the zeolite mixture, from 10 to 70 wt% of the refractory inorganic oxide, and from 0 to 60 wt% of the clay.
The method of the invention carries out layered feeding on the hydrogenated oil and the non-hydrogenated oil, can adjust the hydrogen transfer activity of the reaction system and improve the yield of the low-carbon olefin.
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 diagram of one embodiment of a catalytic cracking system used in the process of the present invention.
Description of the reference numerals
1 riser reactor 11 regenerant transfer line 12 flow control valve
13 first nozzle 14 second nozzle 15 steam nozzle
16 outlet distributor 2 fluidized bed reactor 3 stripper
31 spent agent delivery pipe 32 flow control valve 4 settler
5 regenerator
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 catalytic cracking method of hydrogenated oil, which comprises the following steps: spraying non-hydrogenated oil into the riser reactor from a first nozzle at the lower part of the riser reactor to contact with a catalytic cracking catalyst from the bottom of the riser reactor and carrying out a first catalytic cracking reaction to obtain a first reaction product and a semi-spent catalyst; spraying hydrogenated oil into the riser reactor from a second nozzle above the first nozzle, contacting with a first reaction product and a semi-spent catalyst from the lower part of the second nozzle, and carrying out a second catalytic cracking reaction to obtain a second reaction product and a spent catalyst; wherein the second reaction product comprises at least isobutane and isobutene; the method further comprises the following steps: controlling the weight ratio of isobutane to isobutene in the second reaction product to be 0.5-1.2 by adjusting the feeding proportion of the non-hydrogenated produced oil and the hydrogenated produced oil; if the weight ratio of the isobutane to the isobutene is less than 0.5, reducing the feeding proportion of the non-hydrogenated generated oil; if the weight ratio of the isobutane to the isobutene is greater than 1.2, the feeding proportion of the non-hydrogenated product oil is increased.
According to the invention, in order to adjust the hydrogen transfer activity of the reaction system, the weight ratio of isobutane to isobutene in the second reaction product is controlled to be 0.5-1.2, preferably 0.9-1.2 by adjusting the feeding ratio of non-hydrogenated produced oil and hydrogenated produced oil; wherein if the weight ratio of isobutane to isobutylene is less than 0.5, preferably less than 0.9, the feed ratio of the non-hydrogenated product oil is reduced; if the weight ratio of the isobutane to the isobutene is greater than 1.2, the feeding proportion of the non-hydrogenated product oil is increased.
According to the invention, the proportion of the non-hydrogenated product oil in the hydrogenated product oil is in inverse proportion to the coking rate of the non-hydrogenated product oil, namely the coking rate of the non-hydrogenated product oil is high, and the proportion of the non-hydrogenated product oil in the hydrogenated product oil is low. The proportion of the non-hydrogenated oil in the hydrogenated oil is in direct proportion to the hydrogen transfer activity of the reaction system, namely the hydrogen transfer activity of the reaction system is high, and the proportion of the non-hydrogenated oil in the hydrogenated oil is high. By adjusting the proportion of the non-hydrogenated oil and the hydrogenated oil, the hydrogen transfer activity of a reaction system in the reactor is controlled, and the yield and the selectivity of the low-carbon olefin of the hydrogenated oil can be effectively improved. The non-hydrogenated resultant oil may be present in a hydrogenated resultant oil weight ratio of 0.05 to 2.
Catalytic cracking reactions are well known to those skilled in the art in light of the present disclosure and are not described in detail herein. The conditions of the first catalytic cracking reaction may include: the temperature at the second nozzle is 550-680 ℃, preferably 590-660 ℃, the pressure (absolute pressure) is 0.15-0.4 MPa, preferably 0.18-0.35 MPa, the weight ratio of the catalytic cracking catalyst to the non-hydrogenation product oil is 20-150, and the oil gas residence time is 0.05-2 seconds, preferably 0.08-1.5 seconds. The conditions of the second catalytic cracking reaction may include: the outlet temperature of the riser reactor is 460-620 ℃, preferably 500-620 ℃, more preferably 520-600 ℃, the pressure (absolute pressure) is 0.15-0.4 MPa, preferably 0.18-0.35 MPa, the weight ratio of the catalytic cracking catalyst to the hydrogenation product oil is 5-50, and the oil gas residence time is 0.5-4 seconds, preferably 0.8-3.5 seconds.
According to the present invention, the non-hydrogenated resultant oil refers to a raw oil which has not been hydrotreated, and for example, the non-hydrogenated resultant oil may be at least one selected from the group consisting of a vacuum gas oil, an atmospheric residue, a vacuum residue and a heavy oil. The hydrogenated oil refers to a hydrotreated raw oil, and for example, the hydrogenated oil may be at least one selected from the group consisting of a hydrocracked tail oil, a hydrorefined wax oil, a hydrodesulfurized atmospheric residue (abbreviated as ARDS), and a hydrodesulfurized vacuum residue (abbreviated as VRDS).
According to the invention, the method may further comprise: and feeding the reaction material obtained by the second catalytic cracking reaction into a fluidized bed reactor for a third catalytic cracking reaction to obtain a second reaction product and a spent catalyst. The yield of low-carbon olefin such as propylene can be further improved by carrying out a third catalytic cracking reaction, wherein oil gas and a catalyst which leave a riser reactor are introduced into the fluidized bed reactor from the bottom of the fluidized bed reactor, a spent catalyst which leaves the fluidized bed reactor is also led out from the bottom of the fluidized bed reactor, a second reaction product which leaves the fluidized bed reactor is led out from the top of the fluidized bed reactor, the second reaction product after the reaction of the fluidized bed reactor is introduced into a settler, and the catalyst carried in the second reaction product is separated and then introduced into a fractionation system; introducing the reacted catalyst into a stripper, stripping the adsorbed hydrocarbon substances, and introducing into a regenerator for regeneration. The conditions of the third catalytic cracking reaction may include: temperature ofThe temperature is 450 ℃ and 610 ℃, the pressure (absolute pressure) is 0.15-0.4 MPa, and the weight hourly space velocity is 0.5-30 h-1。
Catalytic cracking catalysts according to the present invention are well known to those skilled in the art, for example, on a dry basis and based on the weight of the catalytic cracking catalyst, the catalytic cracking catalyst may contain 1 to 60% by weight of the zeolite mixture, 5 to 99% by weight of the refractory inorganic oxide and 0 to 70% by weight of the clay, preferably 10 to 50% by weight of the zeolite mixture, 10 to 70% by weight of the refractory inorganic oxide and 0 to 60% by weight of the clay, wherein the zeolite mixture may contain 1-75 wt% of the modified beta zeolite and 25-99 wt% of the zeolite having an MFI structure, preferably 10-70 wt% of the modified beta zeolite and 30-90 wt% of the zeolite having an MFI structure, based on the total weight of the zeolite mixture, and the modified beta zeolite may be a beta zeolite modified with phosphorus and a transition metal M. The modified beta zeolite can be prepared by various conventional methods, for example, phosphorus and a transition metal M can be introduced during the synthesis of the beta zeolite, or the phosphorus and the transition metal M can be introduced by steps of ammonium exchange, phosphorus modification, transition metal M modification, roasting treatment and the like after the synthesis of the beta zeolite. The transition metal M may be one or more selected from Fe, Co, Ni and Cu, preferably Fe and/or Cu. The zeolite having an MFI structure may be a high-silica zeolite having a Pentasil structure, for example, one or more selected from ZSM-5 and ZRP series zeolites. Preferably, the zeolite with MFI structure is one or more of a rare earth-containing ZRP zeolite (see CN1052290A, CN1058382A, US5232675), a phosphorus-containing ZRP zeolite (see CN11941 1194181A, US5951963), a phosphorus-and rare earth-containing ZRP zeolite (see CN1147420A), a phosphorus-and alkaline earth-metal-containing ZRP zeolite (see CN1211469A, CN1211470A, US6080698) and a phosphorus-and transition-metal-containing ZRP zeolite (see CN1465527A, CN 1611299A). The beta zeolite and the zeolite having an MFI structure may be commercially available or may be prepared by various methods known in the art, and will not be described herein. The heat-resistant inorganic oxide may be selected from SiO2And/or Al2O3. The clay may be various clays conventionally used in the art, such as kaolinClay and/or halloysite.
In order to reduce the oil and gas partial pressure in the reactor, a diluent can be injected into the reactor during the catalytic cracking reaction, and the diluent can be selected from water vapor, nitrogen and C1-C4One or more of the alkanes is preferably steam, and the weight ratio of the steam to the hydrogenation-forming oil is preferably (0.01-2): 1.
The invention also provides a catalytic cracking reaction device which can be used for the catalytic cracking method provided by the invention, and the catalytic cracking reaction device comprises a riser reactor and a fluidized bed reactor connected with the riser reactor in series, wherein the diameter ratio of the reaction tube of the fluidized bed reactor to the reaction tube of the riser reaction zone can be (2-6):1, and the riser reactor is provided with a second nozzle and a first nozzle in sequence from top to bottom. The riser reactor can be one or more of an equal-diameter riser, an equal-linear-speed riser and a variable-diameter riser, and is preferably an equal-diameter riser. The fluidized bed reactor can be one or more of a bulk fluidized bed reaction zone, a bubbling bed reaction zone or a turbulent bed reaction zone.
The invention is further illustrated by the following specific embodiments, but is not limited thereby.
As shown in fig. 1, the non-hydrogenated product oil enters the lower part of the riser reactor 1 through a first nozzle 13, contacts with the thermally regenerated catalyst from the regenerator 5, the regenerant delivery pipe 11 and the flow control valve 12 to perform a first catalytic cracking reaction, the first reaction product and the semi-spent catalyst are continuously lifted, contacts with the hydrogenated product oil introduced through a second nozzle 14 to perform a second catalytic cracking reaction, during which the reaction product can pass through a steam nozzle 15, and the obtained reaction material enters the fluidized bed reactor 3 through an outlet distributor 16 at the outlet of the riser reactor 1 to further perform a third catalytic cracking reaction; the spent catalyst reacted in the fluidized bed reactor 2 enters the stripper 3 through the bottom of the fluidized bed reactor, enters the regenerator 5 through a spent agent conveying pipe 31 and a flow control valve 32 for regeneration after stripping, a second reaction product reacted in the fluidized bed reactor 2 enters the settler 4 through the top of the fluidized bed reactor 2, and is separated by the cyclone separator to remove the catalyst carried in the second reaction product, and the second reaction product enters the fractionating device for fractionation. In addition, because the stripper 3 is in gas-solid communication with the fluidized bed reactor 2, the amount of the catalyst in the fluidized bed reactor 2 can be directly controlled by adjusting the flow control valve 32 for discharging the spent catalyst to the regenerator 5 through the stripper 3, and further the weight hourly space velocity of the reaction in the fluidized bed reactor can be controlled, thereby increasing the process flexibility of the catalytic cracking reaction. The catalyst regenerated by the regenerator 5 is introduced into the riser reactor 1 through the regenerant transfer line 11.
The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.
The catalysts used in the examples and comparative examples were aged at 800 ℃ for 12 hours with 100% steam.
Using a medium-sized test apparatus, the catalyst loading in the apparatus was 60 kg, the internal diameter of the riser reactor 1 was 18 mm and the height was 6 m, and the internal diameter of the fluidized bed reactor 3 was 64 mm and the height was 0.5 m.
Example 1
The catalyst used in this example consisted of: on a dry basis and based on the total weight of the catalyst, 20 wt% zeolite Y, 10 wt% ZRP-1 zeolite, 45 wt% kaolin clay and 25 wt% aluminum binder. The preparation method of the catalyst comprises the following steps: DASY zeolite (containing RE)2O32% by weight of a product of the medium petrochemical catalyst, Qilu division) and ZRP-1 (a product of the medium petrochemical catalyst, Qilu division) containing 1.1% by weight of RE2O31.2 weight percent P) is pulped by water to prepare slurry with the solid content of 30 weight percent, kaolin (produced by Suzhou China kaolin company), pseudo-boehmite (produced by Shandong aluminum industry company) and water are mixed and pulped to prepare slurry with the solid content of 30 weight percent, the two slurries are mixed and stirred for 30 minutes at the temperature of 50 ℃ to obtain catalyst slurry, and the catalyst slurry is sprayed and dried to obtain the catalyst.
In the present embodiment, the reaction flow is shown in fig. 1, after non-hydrogenated produced oil (properties are shown in table 1) enters a riser reaction zone 1 and contacts with a regenerated catalyst from a regenerator 5 to perform a first catalytic cracking reaction, a first reaction product and a semi-spent catalyst are continuously lifted, and the first reaction product and introduced hydrogenated produced oil (properties are shown in table 2) continuously contact with a second catalytic cracking reaction; introducing the reacted oil gas and catalyst to the bottom of the fluidized bed reactor 2, performing a third catalytic cracking reaction in the fluidized bed reactor 2, allowing the reacted second spent catalyst to leave the fluidized bed reactor from the bottom of the fluidized bed reactor 2 and enter a stripper, allowing the second reaction product to leave from the top of the fluidized bed reactor 2 and enter a settler, and separating out the carried catalyst and then entering a fractionation device; the reaction conditions and the reaction results are shown in Table 3. The ratio of non-hydrogenated product oil to hydrogenated product oil was 0.15.
Example 2
The procedure of this example is the same as example 1, except that the catalysts used are: on a dry basis and based on the total weight of the catalyst, the catalyst used contained 15 wt% of beta zeolite (product of Zhongpetrochemical catalyst, Zyguyu division), 15 wt% of ZSM-5 zeolite (silica to alumina ratio 40), 45 wt% of kaolin and 25 wt% of alumina binder, wherein the beta zeolite contained 1 wt% of iron and 1.5 wt% of phosphorus, calculated on elements; the reaction conditions and the reaction results are shown in Table 3.
Example 3
The procedure of this example is the same as example 1, except that the catalysts used are: on a dry basis and based on the total weight of the catalyst, the catalyst used contained 20 wt% of beta zeolite (product of Zhongpetrochemical catalyst, Zyguyu division), 10 wt% of ZSM-5 zeolite (silica to alumina ratio 40), 45 wt% of kaolin and 25 wt% of alumina binder, wherein the beta zeolite contained 1.5 wt% of iron and 1.0 wt% of phosphorus, calculated on elements; the reaction conditions and the reaction results are shown in Table 3.
Example 4
The flow chart of this example was the same as that of example 4, except that the ratio of the non-hydrogenated product oil to the hydrogenated product oil was 0.095. The reaction conditions and results are shown in Table 3.
Example 5
The flow chart of this example was the same as that of example 4 except that the ratio of the non-hydrogenated product oil to the hydrogenated product oil was 0.21. The reaction conditions and results are shown in Table 3.
Comparative example 1
After non-hydrogenated generated oil (properties are shown in table 1) enters a riser reactor 1 to be in contact reaction with a regenerated catalyst from a regenerator, oil gas and the catalyst after reaction are introduced to the bottom of a fluidized bed reactor 2 and react in the fluidized bed reactor 2, the catalyst after reaction leaves a fluidized bed reaction zone from the bottom of the fluidized bed reactor 2 and enters a stripper, the oil gas leaves from the top of the fluidized bed reaction zone 2 and enters a settler, and the carried catalyst is separated and enters a fractionation system; the catalyst was the same as in example 3. The reaction conditions and the reaction results are shown in Table 4.
Comparative example 2
The same as in comparative example 1, except that the feedstock was hydrogenated product oil (see Table 2). The reaction conditions and results are shown in Table 4.
Comparative example 3
The same as in example 1, except that the ratio of the non-hydrogenated product oil to the hydrogenated product oil was 0.04. The reaction conditions and results are shown in Table 4.
As can be seen from tables 3-4, the yield of light olefins was high using the process of the present invention.
TABLE 1
| Item | Non-hydrogenated product oil |
| Density (20 ℃ C.)/(g/cm)3) | 0.9008 |
| Dioptric light (70 degree) | 1.4883 |
| Kinematic viscosity/(mm)2Second) | |
| 80℃ | 39.95 |
| 100℃ | 22.31 |
| Freezing point/. degree.C | 44 |
| Carbon residue/weight% | 5.05 |
| Basic nitrogen/(mg/kg) | 786 |
| Four components/weight% | |
| Saturated hydrocarbons | 58.0 |
| Aromatic hydrocarbons | 24.3 |
| Glue | 17.7 |
| Asphaltenes | ＜0.1 |
| Elemental analysis/weight% | |
| C | 86.50 |
| H | 12.94 |
| S | 0.17 |
| N | 0.20 |
| Metal analysis/(microgram/gram) | |
| Ca | 7.5 |
| Cu | 0.5 |
| Fe | 12.1 |
| Na | 1.2 |
| Ni | 8.1 |
| V | 1.0 |
| Vacuum distillation range, deg.C | |
| Initial boiling point | 286 |
| 5% by weight | 364 |
| 10% by weight | 390 |
| 30% by weight | 456 |
| 50% by weight | 532 |
| 56.9% by weight | 546 |
TABLE 2
| Raw oil name | Hydrogenation to produce oil |
| Density (20 ℃ C.)/(g/cm)3) | 0.8333 |
| Kinematic viscosity (80 ℃ C.)/(mm)2Second) | 4.579 |
| Kinematic viscosity (100 ℃ C.)/(mm)2Second) | 3.332 |
| Freezing point/. |
32 |
| Aniline point/. degree.C | 108.6 |
| Carbon residue/%) | <0.05 |
| Refractive index, (nD70) | 1.4408 |
| Basic nitrogen/(microgram/gram) | 1.5 |
| Element composition/weight% | |
| C | 86.05 |
| H | 14.34 |
| N/(microgram/gram) | <1 |
| S/(microgram/gram) | 7.2 |
| Group composition/weight% | |
| Saturated hydrocarbons | 98.9 |
| Aromatic hydrocarbons | 0.8 |
| Glue | 0.3 |
| Asphaltenes | |
| Metal content/(microgram/gram) | |
| Ca | 0.7 |
| Cu | <0.1 |
| Fe | 0.3 |
| Na | 0.8 |
| Ni | <0.1 |
| V | <0.1 |
| Distillation range/. degree.C | |
| Initial boiling point | 192 |
| 5% by weight | 266 |
| 10% by weight | 316 |
| 30% by weight | 388 |
| 50% by weight | 413 |
| 70% by weight | 433 |
| 90% by weight | 468 |
| 95% by weight | 492 |
TABLE 3
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| First catalytic cracking reaction conditions | |||||
| Feed rate/(kg/h) | 0.78 | 0.78 | 0.78 | 0.52 | 1.04 |
| Reaction temperature/. degree.C | 638 | 638 | 638 | 645 | 630 |
| Oil gas residence time/second | 0.31 | 0.31 | 0.31 | 0.35 | 0.28 |
| Ratio of agent to oil | 77 | 77 | 77 | 115 | 58 |
| Second catalytic cracking reaction conditions | |||||
| Feed rate/(kg/h) | 5.22 | 5.22 | 5.22 | 5.48 | 4.96 |
| Reaction temperature/. degree.C | 582 | 582 | 582 | 580 | 584 |
| Oil gas residence time/second | 1.82 | 1.82 | 1.82 | 1.79 | 1.82 |
| Ratio of agent to oil | 11.5 | 11.5 | 11.5 | 10.9 | 12.1 |
| Third catalytic cracking reaction conditions | |||||
| Bed reaction temperature/. degree.C | 562 | 562 | 562 | 560 | 564 |
| Space velocity/hr of bed-1 | 4 | 4 | 4 | 4 | 4 |
| Total water injection (in total feed)/weight% | 25 | 25 | 25 | 25 | 25 |
| Material balance/weight% | |||||
| Dry gas | 8.52 | 8.35 | 8.44 | 8.43 | 8.44 |
| Liquefied gas | 52.06 | 53.86 | 53.97 | 54.5 | 53.48 |
| C5Gasoline (gasoline) | 26.09 | 25.14 | 25.97 | 25.94 | 25.95 |
| Diesel oil | 4.95 | 4.47 | 3.42 | 3.25 | 3.76 |
| Heavy oil | 1.78 | 1.65 | 1.65 | 1.63 | 1.69 |
| Coke | 6.6 | 6.53 | 6.55 | 6.25 | 6.68 |
| Total of | 100 | 100 | 100 | 100 | 100 |
| Gas yield/weight% | |||||
| Ethylene yield | 5.12 | 5.15 | 5.3 | 5.33 | 5.23 |
| Propylene yield | 24.01 | 24.95 | 24.92 | 24.62 | 22.63 |
| Butene yield | 15.98 | 16.45 | 17 | 16.78 | 16.83 |
| Ethylene + propylene + butene | 45.11 | 46.55 | 47.22 | 46.73 | 44.69 |
| Hydrogen transfer coefficient (isobutane/isobutene) | 1.10 | 1.09 | 1.01 | 1.17 | 1.16 |
TABLE 4
| Item | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| First catalytic cracking reaction conditions | |||
| Feed rate/(kg/h) | 6.00 | / | 0.23 |
| Reaction temperature/. degree.C | 580 | / | 638 |
| Oil gas residence time/second | 2.38 | / | 0.31 |
| Ratio of agent to oil | 10 | / | 260.9 |
| Second catalytic cracking reaction conditions | |||
| Feed rate/(kg/h) | / | 6.00 | 5.77 |
| Reaction temperature/. degree.C | / | 580 | 585 |
| Oil gas residence time/second | / | 2.15 | 1.83 |
| Ratio of agent to oil | / | 10 | 10.40 |
| Third catalytic cracking conditions | |||
| Reaction temperature/. degree.C | 561 | 564 | 565 |
| Heavy space timeSpeed/hour-1 | 4 | 4 | 4 |
| Total water injection (in total feed)/weight% | 25 | 25 | 25 |
| Material balance/weight% | |||
| Dry gas | 8.56 | 8.43 | 8.45 |
| Liquefied gas | 42.15 | 55.74 | 53.92 |
| C5Gasoline (gasoline) | 25.49 | 26.04 | 25.89 |
| Diesel oil | 10.92 | 2.07 | 3.02 |
| Heavy oil | 3.38 | 1.24 | 1.45 |
| Coke | 9.5 | 6.48 | 7.27 |
| Total of | 100 | 100 | 100 |
| Gas yield/weight% | |||
| Ethylene yield | 4.35 | 4.9 | 4.71 |
| Propylene yield | 16.25 | 20.42 | 19.57 |
| Butene yield | 10.32 | 11.76 | 13.17 |
| Ethylene + propylene + butene | 30.92 | 37.08 | 37.45 |
| Hydrogen transfer coefficient (isobutane/isobutene) | 1.29 | 3.04 | 2.76 |
Claims (11)
1. A process for the catalytic cracking of a hydroproduced oil, the process comprising:
spraying non-hydrogenated oil into the riser reactor from a first nozzle at the lower part of the riser reactor to contact with a catalytic cracking catalyst from the bottom of the riser reactor and carrying out a first catalytic cracking reaction to obtain a first reaction product and a semi-spent catalyst;
spraying hydrogenated oil into the riser reactor from a second nozzle above the first nozzle, contacting with a first reaction product and a semi-spent catalyst from the lower part of the second nozzle, and carrying out a second catalytic cracking reaction to obtain a second reaction product and a spent catalyst; wherein the second reaction product comprises at least isobutane and isobutene;
the method further comprises the following steps: controlling the weight ratio of isobutane to isobutene in the second reaction product to be 0.5-1.2 by adjusting the feeding proportion of the non-hydrogenated produced oil and the hydrogenated produced oil; if the weight ratio of the isobutane to the isobutene is less than 0.5, reducing the feeding proportion of the non-hydrogenated generated oil; if the weight ratio of the isobutane to the isobutene is greater than 1.2, the feeding proportion of the non-hydrogenated product oil is increased.
2. The method according to claim 1, wherein the weight ratio of isobutane to isobutene in the second reaction product is controlled to be between 0.9 and 1.2 by adjusting the feeding ratio of the non-hydrogenated product oil and the hydrogenated product oil, and if the weight ratio of isobutane to isobutene is less than 0.9, the feeding ratio of the non-hydrogenated product oil is reduced; if the weight ratio of the isobutane to the isobutene is greater than 1.2, the feeding proportion of the non-hydrogenated product oil is increased.
3. The process of claim 1, wherein the non-hydrogenated resultant oil is present in a hydrogenated resultant oil weight ratio of 0.05 to 2.
4. The method of claim 1, wherein the conditions of the first catalytic cracking reaction comprise: the temperature of the second nozzle is 550-680 ℃, the weight ratio of the catalytic cracking catalyst to the non-hydrogenation generated oil is 20-150, and the oil gas retention time is 0.05-2 seconds.
5. The method of claim 1, wherein the non-hydrogenated resultant oil is at least one selected from the group consisting of vacuum gas oil, atmospheric residue, vacuum residue, and heavy oil.
6. The method of claim 1, wherein the conditions of the second catalytic cracking reaction comprise: the outlet temperature of the riser reactor is 460-620 ℃, the weight ratio of the catalytic cracking catalyst to the hydrogenation generated oil is 5-50, and the oil gas retention time is 0.5-4 seconds.
7. The method of claim 1, wherein the hydrorefined oil is at least one selected from the group consisting of hydrocracked tail oil, hydrorefined wax oil, hydrodesulfurized atmospheric residue, and hydrodesulfurized vacuum residue.
8. The method of claim 1, further comprising: and (3) feeding the reaction material obtained by the second catalytic cracking reaction into the fluidized bed reactor for a third catalytic cracking reaction to obtain a second reaction product obtained after the reaction of the fluidized bed reactor and a spent catalyst obtained after the reaction of the fluidized bed reactor.
9. According to claim 8The method of (1), wherein the conditions of the third catalytic cracking reaction comprise: the temperature is 450 ℃ and 610 ℃, and the weight hourly space velocity is 0.5-30 h-1。
10. The process of claim 1 wherein the catalytic cracking catalyst comprises, on a dry basis and based on the weight of the catalytic cracking catalyst, from 1 to 60 wt% of a zeolite mixture comprising from 1 to 75 wt% of a modified beta zeolite and from 25 to 99 wt% of a zeolite having an MFI structure, from 5 to 99 wt% of a refractory inorganic oxide, and from 0 to 70 wt% of a clay, based on the total weight of the zeolite mixture.
11. The process of claim 10 wherein the catalytic cracking catalyst comprises 10 to 50 wt% of the zeolite mixture, 10 to 70 wt% of the refractory inorganic oxide, and 0 to 60 wt% of the clay on a dry basis and based on the weight of the catalytic cracking catalyst.
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| CN1232070A (en) * | 1999-04-23 | 1999-10-20 | 中国石油化工集团公司 | Catalytic conversion method for preparing propylene, isobutane and isoalkane-enriched gasoline |
| CN101362670A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method of propylene preparation |
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