Method and system for producing gasoline and propylene
阅读说明：本技术 一种生产汽油和丙烯的方法和系统 (Method and system for producing gasoline and propylene ) 是由 张博函 白旭辉 许友好 王新 左严芬 于 2019-03-22 设计创作，主要内容包括：本发明涉及一种生产汽油和丙烯的方法和系统,该方法包括：将C<Sub>4</Sub>烯烃进行叠合反应,得到含有C<Sub>12</Sub>烯烃的叠合产物；将原料油进行第一催化转化反应；将所得第一反应产物至少分离出含C<Sub>4</Sub>烯烃的馏分段和催化蜡油；分离出含C<Sub>4</Sub>烯烃的馏分段优选地循环进行叠合反应,得到含有C<Sub>12</Sub>烯烃的叠合产物；将所得含有C<Sub>12</Sub>烯烃的叠合产物分离出C<Sub>12</Sub>烯烃,将所得至少部分C<Sub>12</Sub>烯烃和/或其他来源至少部分C<Sub>12</Sub>烯烃进行催化转化反应；可选地将所得催化蜡油送入第一加氢处理反应器中与第一加氢处理催化剂接触并进行第一加氢处理,得到加氢催化蜡油,优选地将至少部分加氢催化蜡油送入所述第一催化转化反应器中和/或送入第二催化转化反应器中。本发明具有高丙烯和汽油产率。(The present invention relates to a process and system for producing gasoline and propylene, the process comprising: c is to be 4 Olefin is subjected to a polymerization reaction to obtain a catalyst containing C 12 A product of the polymerization of olefins; carrying out a first catalytic conversion reaction on raw oil; separating at least C from the first reaction product 4 Olefin fractionation and catalytic wax oil; separating out C-containing 4 The olefin cut is preferably recycled to the polymerization to give a C-containing product 12 A product of the polymerization of olefins; the obtained compound containing C 12 C is separated from the olefin polymerization product 12 Olefins, at least part of the resulting C 12 Olefins and/or other sources at least partially C 12 Carrying out catalytic conversion reaction on the olefin; optionally will beAnd (3) feeding the obtained catalytic wax oil into a first hydrotreating reactor to contact with a first hydrotreating catalyst and carrying out first hydrotreating to obtain hydrogenated catalytic wax oil, and preferably feeding at least part of the hydrogenated catalytic wax oil into the first catalytic conversion reactor and/or into a second catalytic conversion reactor. The invention has high propylene and gasoline yield.)
1. A process for producing gasoline and propylene, the process comprising:
c is to be4Olefin is sent into a polymerization reactor to contact with a polymerization catalyst and carry out polymerization reaction to obtain a catalyst containing C12A product of the polymerization of olefins;
sending raw oil into a first catalytic conversion reactor to contact with a catalytic conversion catalyst and carrying out a first catalytic conversion reaction to obtain a first reaction product and a first catalyst to be generated;
regenerating the first catalyst to be regenerated, and returning the regenerated catalyst to the first catalytic conversion reactor;
separating at least C from the first reaction product4A fraction of olefins and a catalytic wax oil, the resulting C-containing4The fraction containing olefins is preferably recycled to the polymerization reactor and contacted with the polymerization catalyst and subjected to polymerization reaction to obtain a product containing C12A product of the polymerization of olefins;
the obtained compound containing C12C is separated from the olefin polymerization product12Olefins, at least part of the resulting C12Olefins and/or other sources at least partially C12The olefin is sent into the first catalytic conversion reactor and/or sent into the second catalytic conversion reactor; said C is12The olefin is contacted with a second catalytic conversion catalyst in a second catalytic conversion reactor and subjected to a second catalytic conversion reaction to obtain a second catalystA reaction product and a second spent catalyst; regenerating the obtained second spent catalyst, and returning the obtained regenerated catalyst to the second catalytic conversion reactor; optionally separating the resulting second reaction product together with the first reaction product;
optionally, feeding the obtained catalytic wax oil into a first hydrotreating reactor to contact with a first hydrotreating catalyst and perform first hydrotreating to obtain hydrogenated catalytic wax oil;
preferably, at least part of the hydrocatalytic wax oil is fed to the first catalytic conversion reactor and/or to a second catalytic conversion reactor.
2. The method of claim 1, wherein the conditions of the polymerization reaction include: the temperature is 50-500 ℃, the pressure is 0.5-5.0 MPa, and the weight hourly space velocity is 0.1-100 hours-1；
The polymerization catalyst is selected from one or more of phosphoric acid catalyst, acidic resin, silicon-aluminum solid acid catalyst and molecular sieve solid acid catalyst;
wherein the phosphoric acid catalyst is one or more of a catalyst formed by loading phosphoric acid on diatomite, a catalyst formed by loading phosphoric acid on activated carbon, a catalyst formed by quartz sand soaked by phosphoric acid, a catalyst formed by loading phosphoric acid on silica gel and a catalyst formed by loading copper pyrophosphate on silica gel;
the silicon-aluminum solid acid catalyst is formed by loading metal ions on alumina and/or an amorphous silicon-aluminum carrier, and the loaded metal ions are selected from VIII group metals and/or IVA group metals;
based on the weight of the molecular sieve solid acid catalyst, the molecular sieve solid acid catalyst comprises 10-100 wt% of zeolite and 0-90 wt% of matrix, wherein the zeolite is selected from one or more of Y-type zeolite, ZSM-5 zeolite and beta zeolite.
3. The method of claim 1, wherein C4Olefins and/or C12Sources of olefins include, but are not limited to: the catalytic converter and other catalystsThe conversion unit and other products contain C4Olefins and/or C12A unit for olefins;
based on the weight of the superimposed product, C in the superimposed product12The content of olefin is more than 20 wt%;
said C is4Fraction C of olefins4The content of olefin is 40-100 wt%;
to contain C4Said fraction containing C based on the weight of the olefin fraction4In the olefin distillation section, the sulfur content is not more than 20 micrograms/gram, the alkaline nitride content is not more than 0.6 micrograms/gram, the water content is 600-1800 micrograms/gram, and the diene content is not more than 200 micrograms/gram;
c fed to the first catalytic conversion reactor and/or to the second catalytic conversion reactor12The olefin is present in an amount of 0.1 to 100 wt%, preferably 0.5 to 95 wt%, most preferably 1 to 80 wt%, based on the weight of the feed oil.
4. The method of claim 1, further comprising: contacting the raw oil with a second hydrotreating catalyst in a second hydrotreating reactor, and carrying out second hydrotreating, and then sending an obtained hydrogenation product into the first catalytic conversion reactor;
the properties of the raw oil meet at least one of the following indexes:
density 900-3Preferably 930-960 kg/m3Carbon residue of 4 to 15 wt.%, preferably 6 to 12 wt.%, metal content of 15 to 600ppm, preferably 15 to 100ppm, acid value of 0.5 to 20 mg KOH/g, preferably 0.5 to 10 mg KOH/g;
the second hydrotreating conditions include: the hydrogen partial pressure is 3.0-20.0 MPa, the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 100-2000 standard cubic meter/cubic meter, and the volume space velocity is 0.1-3.0 hours-l；
The second hydrotreating catalyst comprises a carrier and an active metal, wherein the carrier is selected from one or more of alumina, silicon dioxide and amorphous silicon-aluminum, and the active metal is selected from a VIB group metal and/or a VIII group metal.
5. The method of claim 1, wherein the first hydrotreating conditions comprise: hydrogen partial pressure of 3.0-20.0 MPa, reaction temperature of 300--1The volume ratio of hydrogen to oil is 100-1500 standard cubic meters/cubic meter; the first hydrotreating catalyst comprises a carrier and an active metal, wherein the carrier is selected from one or more of alumina, silicon dioxide and amorphous silicon-aluminum, and the active metal is selected from a VIB group metal and/or a VIII group metal.
6. The method of claim 1, further comprising: separating diesel oil from the obtained first reaction product, and sending at least part of the obtained diesel oil and the catalytic wax oil into a first hydrotreatment reactor together for carrying out the first hydrotreatment, wherein the diesel oil subjected to the first hydrotreatment accounts for 0-50 wt% of the catalytic wax oil.
7. The process of claim 1, wherein the first catalytic conversion reactor and the second catalytic conversion reactor are each independently selected from the group consisting of a constant diameter riser, a constant linear velocity riser, a variable diameter riser, a fluidized bed, a combined constant diameter riser and fluidized bed reactor, an upflow conveyor line, and a downflow conveyor line, or a combination thereof in series.
8. The method of claim 7, wherein the variable diameter riser comprises a first reaction zone and a second reaction zone in terms of reactant flow direction;
one or more chilling medium inlets are arranged at the bottom of the second reaction zone, and/or a heat remover is arranged in the second reaction zone, and the height of the heat remover accounts for 50-90% of the height of the second reaction zone.
9. The method of claim 1, wherein the first and second catalytic conversion catalysts are each independently an amorphous silica-alumina catalyst and/or a zeolite catalyst, wherein the zeolite in the zeolite catalyst is selected from one or more of Y-type zeolite, HY-type zeolite, ultrastable Y-type zeolite, ZSM-5 series zeolite, heulandite having a pentasil structure, and ferrierite.
10. The method of claim 1, further comprising: separating oil slurry from the first reaction product and/or the second reaction product, and returning at least part of the oil slurry to the first catalytic conversion reactor and/or the second catalytic conversion reactor.
11. The method of claim 1, wherein the feedstock oil comprises a petroleum hydrocarbon and/or other mineral oil, wherein the petroleum hydrocarbon is selected from one or more of atmospheric gas oil, vacuum gas oil, atmospheric residue, vacuum residue, hydrogenated residue, coker gas oil, and deasphalted oil; the other mineral oil is selected from one or more of coal and natural gas derived liquid oil, oil sand oil, dense oil and shale oil.
12. The method according to claim 1, wherein the raw oil, hydrocatalytic wax oil and the C are mixed12At least one feed of olefins is fed to the first catalytic conversion reactor at the same feed point and/or at two or more feed points.
13. The method according to claim 7, wherein the first catalytic conversion reactor is a variable-diameter riser and comprises a first reaction zone and a second reaction zone according to the flow direction of the reaction materials, and the raw oil, the hydrocatalytic wax oil and the C are mixed12Feeding an olefin to a first reaction zone;
the conditions of the first catalytic conversion reaction include:
a first reaction zone: the reaction temperature is 450-620 ℃, preferably 500-600 ℃, the reaction time is 0.5-2.0 seconds, preferably 0.8-1.5 seconds, the weight ratio of the catalyst to the raw oil is 3-15: 1, preferably 4-12: 1, and the weight ratio of the water vapor to the raw oil is 0.03-0.3: 1, preferably 0.05-0.15: 1;
a second reaction zone: the reaction temperature is 460-550 ℃, preferably 480-530 ℃, the reaction time is 2-30 seconds, preferably 3-15 seconds, the weight ratio of the catalyst to the raw oil is 4-18: 1, preferably 4.5-15: 1, and the weight ratio of the water vapor to the raw oil is 0.03-0.3: 1, preferably 0.05-0.15: 1.
14. The method of claim 1, wherein the conditions of the second catalytic conversion reaction include: the reaction temperature is 450 ℃ and 620 ℃, the reaction time is 0.5-20.0 seconds, the weight ratio of the catalyst to the oil is 1-25, and the weight ratio of the water to the oil is 0.03-0.3.
15. A system for producing gasoline and propylene, the system comprising a first catalytic conversion reactor, a regenerator, a finish oil separation unit, a product separation unit, a folding reactor, a rectifying tower and optionally a second catalytic conversion reactor;
the first catalytic conversion reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet, the regenerator is provided with a catalyst inlet and a catalyst outlet, the oil agent separation device is provided with an oil agent inlet, an oil gas outlet and a catalyst outlet, and the product separation device is at least provided with an oil gas inlet and C-containing oil gas4The distillation section outlet of the olefin, the polymerization reactor comprises a raw material inlet and a polymerization product outlet, and the rectifying tower is provided with an oil gas inlet and a C12The second catalytic conversion reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet;
the catalyst inlet of the first catalytic conversion reactor is communicated with the catalyst outlet of the regenerator, the oil agent outlet of the first catalytic conversion reactor is communicated with the oil agent inlet of the oil agent separating device, the catalyst outlet of the oil agent separating device is communicated with the catalyst inlet of the regenerator, the oil gas outlet of the oil agent separating device is communicated with the oil gas inlet of the product separating device, and the C-containing oil of the product separating device is communicated with the oil gas inlet of the product separating device4The outlet of the fraction section of the olefin is communicated with the raw material inlet of the polymerization reactor, and the outlet of the polymerization product of the polymerization reactor is communicated with the raw material inlet of the polymerization reactorThe oil gas inlet of the fractionating tower is communicated with the oil gas inlet of the fractionating tower C12An olefin outlet is in communication with the feed inlet of the first catalytic conversion reactor, optionally in communication with the feed inlet of a second catalytic conversion reactor;
preferably, the system further comprises a first hydrotreating reactor, the product separation device is further provided with a catalytic wax oil outlet, the raw material inlet of the first hydrotreating reactor is communicated with the catalytic wax oil outlet of the product separation device, and the product outlet of the first hydrotreating reactor is communicated with the raw material inlet of the first catalytic conversion reactor, and optionally communicated with the raw material inlet of the second catalytic conversion reactor.
16. The system of claim 15, further comprising a second hydroprocessing reactor provided with a feedstock inlet and a product outlet, the product outlet of the second hydroprocessing reactor being in communication with the feedstock inlet of the first catalytic conversion reactor;
the product separation device is also provided with a diesel oil outlet, and the diesel oil outlet of the product separation device is communicated with the raw material inlet of the first hydrotreating reactor.
Technical Field
The invention relates to a method and a system for producing gasoline and propylene.
Background
Propylene is one of important chemical raw materials, is an important raw material for producing polypropylene, various important organic chemical raw materials, synthetic resins and synthetic rubber, and can also be used for preparing acrylonitrile, isopropanol, phenol, acetone, butanol, octanol, acrylic acid and esters thereof, and preparing propylene oxide, propylene glycol, epichlorohydrin, synthetic glycerol and other chemicals. Propylene is mainly produced by a steam cracking device and a catalytic cracking device, the steam cracking has limited potential for increasing the yield of propylene by taking light oil as a raw material, and in recent years, the route is increasingly limited by a plurality of restriction factors such as shortage of light raw oil, insufficient production capacity, over-high cost and the like. The catalytic cracking process is a main secondary processing process of heavy oil, propylene which is a byproduct of catalytic cracking is also one of important sources for producing propylene, and the yield of the propylene is about one third of the total yield of the propylene. The catalytic cracking can regulate the yield of propylene by selecting different process modes. Therefore, the method has the advantages of wide raw material adaptability, flexible operation and the like, and the catalytic cracking improvement technology for increasing the yield of propylene is rapidly developed in recent years.
Chinese patent CN 107286972A discloses a catalytic cracking method for producing more propylene. The patent realizes the quick termination of an independent high-temperature cracking reaction zone and a fluidized bed by arranging the first reactor and the second reactor, relieves the contradiction between the yield increase of propylene and the reduction of dry gas, and reduces the yield of the dry gas and coke while increasing the yield of the propylene.
U.S. patent No. USP 7261807 discloses a catalytic cracking process that increases propylene yield. The process sends at least part of gasoline product into the second lift pipe to carry out cracking reaction again, and the adopted catalyst composition contains large-hole USY zeolite, ZSM-5 and other medium-hole zeolite and inorganic binder component with cracking performance. Wherein the inorganic binder component contains phosphorus, and the P/Al ratio is 0.1-10. The technological process can greatly increase the yield of low-carbon olefine, especially the yield of propylene.
Chinese patent CN 1299403A discloses a method for selectively producing C from heavy light raw materials2～C4A two-stage catalytic cracking process for light olefins. Heavy raw materials are converted into lower boiling point products in the presence of a conventional large-pore zeolite catalytic cracking catalyst in a first reaction section consisting of a catalytic cracking unit; and (3) sending the naphtha fraction in the generated lower boiling point product into a second reaction section, and contacting the naphtha fraction with a zeolite catalyst containing about 10-50% of zeolite with the average pore diameter of less than about 0.7 nm at the temperature of 500-600 ℃ to generate a cracked product, wherein the yield of propylene is up to 16.8%.
Disclosure of Invention
The object of the present invention is to provide a process and a system for producing gasoline and propylene, which has high propylene and gasoline yields.
In order to achieve the above object, the present invention provides a method for producing gasoline and propylene, comprising:
c is to be4Olefin is sent into a polymerization reactor to contact with a polymerization catalyst and carry out polymerization reaction to obtain a catalyst containing C12A product of the polymerization of olefins;
sending raw oil into a first catalytic conversion reactor to contact with a catalytic conversion catalyst and carrying out a first catalytic conversion reaction to obtain a first reaction product and a first catalyst to be generated;
regenerating the first catalyst to be regenerated, and returning the regenerated catalyst to the first catalytic conversion reactor;
separating at least C from the first reaction product4A fraction of olefins and a catalytic wax oil, the resulting C-containing4The fraction containing olefins is preferably recycled to the polymerization reactor and contacted with the polymerization catalyst and subjected to polymerization reaction to obtain a product containing C12A product of the polymerization of olefins;
the obtained compound containing C12C is separated from the olefin polymerization product12Olefins, at least part of the resulting C12Olefins and/or other sources at least partially C12The olefin is sent into the first catalytic conversion reactor and/or sent into the second catalytic conversion reactor; said C is12The olefin is contacted with a second catalytic conversion catalyst in a second catalytic conversion reactor and carries out a second catalytic conversion reaction to obtain a second reaction product and a second spent catalyst; regenerating the obtained second spent catalyst, and returning the obtained regenerated catalyst to the second catalytic conversion reactor; optionally separating the resulting second reaction product together with the first reaction product;
optionally, feeding the obtained catalytic wax oil into a first hydrotreating reactor to contact with a first hydrotreating catalyst and perform first hydrotreating to obtain hydrogenated catalytic wax oil;
preferably, at least part of the hydrocatalytic wax oil is fed to the first catalytic conversion reactor and/or to a second catalytic conversion reactor.
C4Olefins and/or C12Sources of olefins include, but are not limited to: the present catalytic converter, other catalytic converters, and other products contain C4Olefins and/or C12A unit for olefins;
optionally, the conditions of the polymerization reaction include: the temperature is 50-500 ℃, the pressure is 0.5-5.0 MPa, and the weight hourly space velocity is 0.1-100 hours-1；
The polymerization catalyst is selected from one or more of phosphoric acid catalyst, acidic resin, silicon-aluminum solid acid catalyst and molecular sieve solid acid catalyst;
wherein the phosphoric acid catalyst is one or more of a catalyst formed by loading phosphoric acid on diatomite, a catalyst formed by loading phosphoric acid on activated carbon, a catalyst formed by quartz sand soaked by phosphoric acid, a catalyst formed by loading phosphoric acid on silica gel and a catalyst formed by loading copper pyrophosphate on silica gel;
the silicon-aluminum solid acid catalyst is formed by loading metal ions on alumina and/or an amorphous silicon-aluminum carrier, and the loaded metal ions are selected from VIII group metals and/or IVA group metals;
based on the weight of the molecular sieve solid acid catalyst, the molecular sieve solid acid catalyst comprises 10-100 wt% of zeolite and 0-90 wt% of matrix, wherein the zeolite is selected from one or more of Y-type zeolite, ZSM-5 zeolite and beta zeolite.
Optionally, C in the superimposed product is based on the weight of the superimposed product12The content of olefin is more than 20 wt%;
said C is4Fraction C of olefins4The content of olefin is 40-100 wt%;
to contain C4Said fraction containing C based on the weight of the olefin fraction4In the olefin distillation section, the sulfur content is not more than 20 micrograms/gram, the alkaline nitride content is not more than 0.6 micrograms/gram, the water content is 600-1800 micrograms/gram, and the diene content is not more than 200 micrograms/gram;
c fed to the first catalytic conversion reactor and/or to the second catalytic conversion reactor12The olefin is present in an amount of 0.1 to 100 wt%, preferably 0.5 to 95 wt%, most preferably 1 to 80 wt%, based on the weight of the feed oil.
Optionally, the method further includes: contacting the raw oil with a second hydrotreating catalyst in a second hydrotreating reactor, and carrying out second hydrotreating, and then sending an obtained hydrogenation product into the first catalytic conversion reactor;
the properties of the raw oil meet at least one of the following indexes:
density 900-3Preferably 930-960 kg/m3Carbon residue of 4 to 15 wt.%, preferably 6 to 12 wt.%, metal content of 15 to 600ppm,preferably 15 to 100ppm, and an acid number of 0.5 to 20 mg KOH/g, preferably 0.5 to 10 mg KOH/g;
the second hydrotreating conditions include: the hydrogen partial pressure is 3.0-20.0 MPa, the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 100-2000 standard cubic meter/cubic meter, and the volume space velocity is 0.1-3.0 hours-l；
The second hydrotreating catalyst comprises a carrier and an active metal, wherein the carrier is selected from one or more of alumina, silicon dioxide and amorphous silicon-aluminum, and the active metal is selected from a VIB group metal and/or a VIII group metal.
Optionally, the first hydrotreating conditions include: hydrogen partial pressure of 3.0-20.0 MPa, reaction temperature of 300--1The volume ratio of hydrogen to oil is 100-1500 standard cubic meters/cubic meter; the first hydrotreating catalyst comprises a carrier and an active metal, wherein the carrier is selected from one or more of alumina, silicon dioxide and amorphous silicon-aluminum, and the active metal is selected from a VIB group metal and/or a VIII group metal.
Optionally, the method further includes: separating diesel oil from the obtained first reaction product, and sending at least part of the obtained diesel oil and the catalytic wax oil into a first hydrotreatment reactor together for carrying out the first hydrotreatment, wherein the diesel oil subjected to the first hydrotreatment accounts for 0-50 wt% of the catalytic wax oil.
Optionally, the first catalytic conversion reactor and the second catalytic conversion reactor are independently selected from one or two of a combined reactor consisting of a constant-diameter riser, a constant-linear-speed riser, a variable-diameter riser, a fluidized bed, a constant-diameter riser and a fluidized bed, an ascending conveyor line and a descending conveyor line, which are connected in series.
Optionally, the reducing riser comprises a first reaction zone and a second reaction zone according to the flow direction of the reaction materials;
one or more chilling medium inlets are arranged at the bottom of the second reaction zone, and/or a heat remover is arranged in the second reaction zone, and the height of the heat remover accounts for 50-90% of the height of the second reaction zone.
Optionally, the first catalytic conversion catalyst and the second catalytic conversion catalyst are each independently an amorphous silica-alumina catalyst and/or a zeolite catalyst, and the zeolite in the zeolite catalyst is selected from one or more of Y-type zeolite, HY-type zeolite, ultrastable Y-type zeolite, ZSM-5 series zeolite, high-silica zeolite having a pentasil structure, and ferrierite.
Optionally, the method further includes: separating oil slurry from the first reaction product and/or the second reaction product, and returning at least part of the oil slurry to the first catalytic conversion reactor and/or the second catalytic conversion reactor.
Optionally, the raw oil comprises petroleum hydrocarbon and/or other mineral oil, wherein the petroleum hydrocarbon is selected from one or more of atmospheric gas oil, vacuum gas oil, atmospheric residue, vacuum residue, hydrogenated residue, coker gas oil and deasphalted oil; the other mineral oil is selected from one or more of coal and natural gas derived liquid oil, oil sand oil, dense oil and shale oil.
Optionally, mixing the raw oil, hydrocatalytic wax oil and C12At least one feed of olefins is fed to the first catalytic conversion reactor at the same feed point and/or at two or more feed points.
Optionally, the first catalytic conversion reactor is a variable-diameter riser and comprises a first reaction zone and a second reaction zone according to the flow direction of the reaction materials, and the raw oil, the hydrocatalytic wax oil and the C are mixed12Feeding an olefin to a first reaction zone;
the conditions of the first catalytic conversion reaction include:
a first reaction zone: the reaction temperature is 450-620 ℃, preferably 500-600 ℃, the reaction time is 0.5-2.0 seconds, preferably 0.8-1.5 seconds, the weight ratio of the catalyst to the raw oil is 3-15: 1, preferably 4-12: 1, and the weight ratio of the water vapor to the raw oil is 0.03-0.3: 1, preferably 0.05-0.15: 1;
a second reaction zone: the reaction temperature is 460-550 ℃, preferably 480-530 ℃, the reaction time is 2-30 seconds, preferably 3-15 seconds, the weight ratio of the catalyst to the raw oil is 4-18: 1, preferably 4.5-15: 1, and the weight ratio of the water vapor to the raw oil is 0.03-0.3: 1, preferably 0.05-0.15: 1.
Optionally, the conditions of the second catalytic conversion reaction include: the reaction temperature is 450 ℃ and 620 ℃, the reaction time is 0.5-20.0 seconds, the weight ratio of the catalyst to the oil is 1-25, and the weight ratio of the water to the oil is 0.03-0.3.
The invention also provides a system for producing gasoline and propylene, which comprises a first catalytic conversion reactor, a regenerator, an oil agent separation device, a product separation device, a superposition reactor, a rectifying tower and an optional second catalytic conversion reactor;
the first catalytic conversion reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet, the regenerator is provided with a catalyst inlet and a catalyst outlet, the oil agent separation device is provided with an oil agent inlet, an oil gas outlet and a catalyst outlet, and the product separation device is at least provided with an oil gas inlet and C-containing oil gas4The distillation section outlet of the olefin, the polymerization reactor comprises a raw material inlet and a polymerization product outlet, and the rectifying tower is provided with an oil gas inlet and a C12The second catalytic conversion reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet;
the catalyst inlet of the first catalytic conversion reactor is communicated with the catalyst outlet of the regenerator, the oil agent outlet of the first catalytic conversion reactor is communicated with the oil agent inlet of the oil agent separating device, the catalyst outlet of the oil agent separating device is communicated with the catalyst inlet of the regenerator, the oil gas outlet of the oil agent separating device is communicated with the oil gas inlet of the product separating device, and the C-containing oil of the product separating device is communicated with the oil gas inlet of the product separating device4The outlet of the fraction section of the olefin is communicated with the raw material inlet of the polymerization reactor, the outlet of the polymerization product of the polymerization reactor is communicated with the oil gas inlet of the fractionating tower, and the C of the fractionating tower12An olefin outlet is in communication with the feed inlet of the first catalytic conversion reactor, optionally in communication with the feed inlet of a second catalytic conversion reactor;
preferably, the system further comprises a first hydrotreating reactor, the product separation device is further provided with a catalytic wax oil outlet, the raw material inlet of the first hydrotreating reactor is communicated with the catalytic wax oil outlet of the product separation device, and the product outlet of the first hydrotreating reactor is communicated with the raw material inlet of the first catalytic conversion reactor, and optionally communicated with the raw material inlet of the second catalytic conversion reactor.
Optionally, the system further includes a second hydrotreating reactor, the second hydrotreating reactor is provided with a raw oil inlet and a product outlet, and the product outlet of the second hydrotreating reactor is communicated with the raw material inlet of the first catalytic conversion reactor;
the product separation device is also provided with a diesel oil outlet, and the diesel oil outlet of the product separation device is communicated with the raw material inlet of the first hydrotreating reactor.
Compared with the prior art, the invention has the following advantages:
(1) the invention can optimize the product distribution, which is concretely characterized in that the yield of coke and dry gas can be reduced, and the yield of light oil can be improved;
(2) the invention will C4C obtained after olefin polymerization12Olefins and/or other sources C12The propylene yield can be improved by feeding the olefin into the catalytic conversion reactor;
(3) and part of diesel oil is mixed with the catalytic wax oil, so that the viscosity of the catalytic wax oil raw material can be reduced, and the hydrogenation effect can be improved.
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 detailed description of the first embodiment, serve to explain the invention without limiting the scope of the invention. In the drawings:
fig. 1 comprises a schematic flow diagram of a first embodiment of the method of the present invention, and also comprises a schematic structural diagram of a first embodiment of the system of the present invention.
Fig. 2 comprises a schematic flow diagram of a second embodiment of the method of the present invention, and also comprises a schematic structural diagram of a second embodiment of the system of the present invention.
FIG. 3 comprises a schematic flow diagram of a third embodiment of the method of the present invention, and also comprises a schematic structural diagram of a third embodiment of the system of the present invention.
Fig. 4 includes a schematic flow chart of a fourth embodiment of the method of the present invention, and also includes a schematic structural diagram of the fourth embodiment of the system of the present invention.
Fig. 5 includes a schematic flow chart of a fifth embodiment of the method of the present invention, and also includes a schematic structural diagram of the fifth embodiment of the system of the present invention.
Description of the reference numerals
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I first catalytic conversion reactor II second catalytic conversion reactor
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention provides a process for producing gasoline and propylene, the process comprising:
c is to be4Olefin is sent into a polymerization reactor to contact with a polymerization catalyst and carry out polymerization reaction to obtain a catalyst containing C12A product of the polymerization of olefins;
sending raw oil into a first catalytic conversion reactor to contact with a catalytic conversion catalyst and carrying out a first catalytic conversion reaction to obtain a first reaction product and a first catalyst to be generated;
regenerating the first catalyst to be regenerated, and returning the regenerated catalyst to the first catalytic conversion reactor;
separating at least C from the first reaction product4A fraction of olefins and a catalytic wax oil, the resulting C-containing4The olefin cut is preferably recycled to the feed stackContacting with a polymerization catalyst in a polymerization reactor and carrying out polymerization reaction to obtain a catalyst containing C12A product of the polymerization of olefins;
the obtained compound containing C12C is separated from the olefin polymerization product12Olefins, at least part of the resulting C12Olefins and/or other sources at least partially C12The olefin is sent into the first catalytic conversion reactor and/or sent into the second catalytic conversion reactor; said C is12The olefin is contacted with a second catalytic conversion catalyst in a second catalytic conversion reactor and carries out a second catalytic conversion reaction to obtain a second reaction product and a second spent catalyst; regenerating the obtained second spent catalyst, and returning the obtained regenerated catalyst to the second catalytic conversion reactor; optionally separating the resulting second reaction product together with the first reaction product;
optionally, feeding the obtained catalytic wax oil into a first hydrotreating reactor to contact with a first hydrotreating catalyst and perform first hydrotreating to obtain hydrogenated catalytic wax oil;
preferably, at least part of the hydrocatalytic wax oil is fed to the first catalytic conversion reactor and/or to a second catalytic conversion reactor.
The present inventors have unexpectedly found that the reaction product contains C4Olefins and/or other sources C4The fraction of olefin is separated out for polymerization reaction, and C in the polymerization product is12Olefins and/or other sources C12Olefin is sent into the catalytic conversion reactor for further catalytic conversion reaction, so that the yield of propylene can be obviously improved.
The polymerization reaction is well known to the person skilled in the art and is used for the polymerization of C according to the invention4Reaction of olefins to C12An olefin. The conditions of the polymerization reaction may include: at 50-500 deg.C, preferably 60-400 deg.C, pressure of 0.5-5.0 MPa, and weight hourly space velocity of 0.1-100 hr-1(ii) a The polymerization catalyst may be selected from one or more of phosphoric acid catalysts, acidic resins, silicoaluminophosphate solid acid catalysts, and molecular sieve solid acid catalysts. Wherein the phosphoric acid catalyst can be a catalyst formed by supporting phosphoric acid on diatomiteOne or more of a catalyst formed by loading phosphoric acid on activated carbon, a catalyst formed by soaking quartz sand in phosphoric acid, a catalyst formed by loading phosphoric acid on silica gel and a catalyst formed by loading copper pyrophosphate on silica gel; the silicon-aluminum solid acid catalyst can be a catalyst formed by loading metal ions on alumina and/or an amorphous silicon-aluminum carrier, wherein the loaded metal ions are selected from VIII group metals and/or IVA group metals; the molecular sieve solid acid catalyst may include 10-100 wt% zeolite and 0-90 wt% matrix, based on the weight of the molecular sieve solid acid catalyst, and the zeolite may be selected from one or more of Y-type zeolite, ZSM-5 zeolite, and beta zeolite.
The present invention controls reaction conditions and selects catalysts to maximize production of C12Olefins as object, C4Olefins and/or C12Sources of olefins include, but are not limited to: the present catalytic converter, other catalytic converters, and other products contain C4Olefins and/or C12A unit for olefins; for example, from a refinery, a chemical plant, the refinery unit is selected from at least one of a catalytic conversion unit selected from at least one of various catalytic cracking units, a catalytic conversion unit for producing isoparaffin, a catalytic cracking unit (for example, DCC unit), and a catalytic thermal cracking unit, and/or a thermal conversion unit selected from at least one of various thermal cracking units, and various coking units (for example, delayed coking unit); the chemical plant unit is selected from a steam cracking unit or/and an olefin polymerization unit. Those skilled in the art can obtain C according to production needs and practical situations4Olefins and/or C12Olefins, the present invention is not described in detail. For example, C in the superimposed product is based on the weight of the superimposed product12The content of olefin is more than 20 wt%; in addition, by optimizing the C content4Fraction C of olefins4The olefin content, as well as the impurities, can further promote the polymerization, for example, the C-containing4Fraction C of olefins4The content of olefin is 40-100 wt%; to contain C4Said fraction containing C based on the weight of the olefin fraction4In the olefin distillation section, the sulfur content is not more than 20 micrograms/gram, the alkaline nitride content is not more than 0.6 micrograms/gram, the water content is 600-1800 micrograms/gram, and the diene content is not more than 200 micrograms/gram; c fed to the first catalytic conversion reactor and/or to the second catalytic conversion reactor12The olefin accounts for 0.1-80 wt%, preferably 1-70 wt% of the raw oil.
To further increase C4Utilization of olefins, the method may further comprise: will separate out C12The olefin polymerization product is returned to the polymerization reactor for polymerization reaction, and C can be separated12Further separating C from the olefin polymerization product4Olefin, C4The olefin is returned to the polymerization reaction.
According to the present invention, there is provided a process for producing gasoline and propylene from a feedstock oil having properties satisfying at least one of the following criteria: density 900-3Preferably 930-960 kg/m3Carbon residue of 4 to 15 wt.%, preferably 6 to 12 wt.%, metal content of 15 to 600ppm, preferably 15 to 100ppm, acid value of 0.5 to 20 mg KOH/g, preferably 0.5 to 10 mg KOH/g; the method may further comprise: contacting raw oil with a second hydrotreating catalyst in a second hydrotreating reactor, and carrying out second hydrotreating, and then sending the obtained hydrogenation product into the first catalytic conversion reactor, wherein the yield of the hydrogenation product is controlled to be 85-95 wt% and the initial boiling point of the hydrogenation product is 330-350 ℃ on the basis of the raw oil; the second hydrotreating conditions include: the hydrogen partial pressure is 3.0-20.0 MPa, the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 100-2000 standard cubic meter/cubic meter, and the volume space velocity is 0.1-3.0 hours-l(ii) a The second hydrotreating catalyst comprises a carrier and an active metal, wherein the carrier is selected from one or more of alumina, silicon dioxide and amorphous silicon-aluminum, and the active metal is selected from a VIB group metal and/or a VIII group metal. The second hydrotreating catalyst can be filled in the second hydrotreating reactor according to a certain grading, and the catalyst grading refers to a hydrogenation protective agent, a hydrodemetallization catalyst, a hydrodesulfurization catalyst and hydrodenitrification and carbon residue removalThe catalyst is loaded in the whole hydrogenation catalyst bed layer according to the physical properties and chemical properties such as catalyst size, aperture and activity. Preferably, the hydrodemetallization catalyst in the catalyst grading represents more than 30 wt.% of the total catalyst weight. Preferably, the catalyst grading is such that the guard/demetallization catalyst is present in an amount of from 20 to 70 wt%, preferably from 30 to 50 wt%, based on the weight of the total catalyst; the desulfurization catalyst is 20 to 70 wt%, preferably 40 to 60 wt%; the denitrification/decarbonation catalyst is 0 to 60 wt%, preferably 10 to 40 wt%. The second hydrotreating catalyst is a hydrotreating catalyst and/or a modified catalyst as is conventional in the art. The quality of raw oil can be improved through the second hydrotreatment, and the yield of catalytically converted gasoline and propylene can be improved.
The catalytic wax oil can be separated from the obtained first reaction product and/or second reaction product, and the obtained catalytic wax oil is sent into a first hydrotreating reactor to contact with a first hydrotreating catalyst and is subjected to first hydrotreating to obtain the hydrogenated catalytic wax oil; wherein the first hydrotreating conditions may include: the hydrogen partial pressure is 3.0-20.0 MPa, the preferable pressure is 4-16 MPa, the reaction temperature is 300-450 ℃, the preferable temperature is 320-420 ℃, and the volume space velocity is 0.1-10.0 h-1Preferably 0.1 to 5.0 hours-1Hydrogen to oil volume ratio of 100-1500 standard cubic meters per cubic meter (Nm)3/m3) (ii) a The first hydrotreating catalyst comprises a carrier and an active metal, wherein the carrier is selected from one or more of alumina, silicon dioxide and amorphous silicon-aluminum, and the active metal is selected from a VIB group metal and/or a VIII group metal. The catalytic wax oil is a heavy fraction at the bottom of a catalytic conversion distillation tower and belongs to catalytic conversion slurry oil fractionated by a conventional catalytic conversion distillation tower, the cut point of the catalytic wax oil can be not lower than 250 ℃, preferably not lower than 300 ℃, more preferably not lower than 330 ℃, for example, the cut point can be 250-700 ℃, preferably 280-470 ℃, and the density can be 0.89-1.2 g/cm3The hydrogen content may be not less than 10.5% by weight, preferably not less than 10.8% by weight, and the solid particle content may be 0.1 to 10 g/l. In addition, the product obtained by the hydrotreating reaction can be subjected to gas-liquid reactionAnd separating to remove light hydrocarbon and hydrogen, and then obtaining the hydrogenation catalytic wax oil. In the hydrogenated catalytic wax oil after the hydrogenation treatment, polycyclic aromatic hydrocarbon is saturated to generate aromatic hydrocarbon below two rings, the catalytic conversion performance is obviously improved, and the aromatic hydrocarbon is led back to a catalytic conversion reactor and/or other catalytic conversion devices for further reaction, so that more high-quality fuel oil can be obtained.
Further, the method may further include: separating diesel oil from the obtained first reaction product, and feeding the obtained diesel oil and the catalytic wax oil into a first hydrotreatment reactor together for carrying out the first hydrotreatment, wherein the diesel oil subjected to the first hydrotreatment accounts for 0-50 wt% of the catalytic wax oil, and preferably accounts for 1-30 wt%. By hydrogenating the diesel oil and the catalytic wax oil together, the viscosity of the catalytic wax oil raw material can be reduced, and the hydrogenation effect can be improved.
Catalytic conversion reactors according to the present invention are well known to those skilled in the art, for example, the first catalytic conversion reactor and the second catalytic conversion reactor are each independently selected from the group consisting of a constant diameter riser, a constant linear velocity riser, a variable diameter riser, a fluidized bed and a combined reactor of a constant diameter riser and a fluidized bed, one or two of an ascending conveyor line and a descending conveyor line in series, preferably a variable diameter riser reactor or a combined reactor of a constant diameter riser and a fluidized bed. The fluidized bed reactor can be one or two of a series combination of an equal linear speed fluidized bed, an equal diameter fluidized bed, an ascending conveyor line and a descending conveyor line. The riser can be a conventional equal-diameter riser or can be a riser with variable diameters in various forms. Wherein the gas velocity of the fluidized bed can be 0.1-2 m/s, and the gas velocity of the riser can be 2-30 m/s (excluding catalyst). The best mode of the invention is to operate in a reducing riser reactor, and the structure of the reducing riser reactor can be as follows: the pre-lifting section, the first reaction zone, the second reaction zone which is radially enlarged than the first reaction zone and the outlet zone which is radially reduced than the second reaction zone are sequentially arranged along the vertical direction from bottom to top and are coaxial with each other, the tail end of the outlet zone is connected with the settler through a horizontal pipe, the total height of the settler is 10-60 meters, the cracking reaction is carried out in the first reaction zone, the hydrogen transfer and isomerization reaction are carried out in the second reaction zone, the diameter of the pre-lifting section is the same as that of a conventional equal-diameter riser reactor, generally is 0.02-5 meters, and the height of the pre-lifting section accounts for 5-10 percent of the total height of the reactor. The first reaction zone is similar in structure to a conventional constant diameter riser reactor, and may have the same diameter as the pre-lift section or a slightly larger diameter than the pre-lift section, the ratio of the diameter of the first reaction zone to the diameter of the pre-lift section being 1.0-2.0:1, and the height of the first reaction zone being 10-30% of the total height of the reactor. After the raw oil and the catalyst are mixed in the zone, the cracking reaction mainly occurs under the conditions of higher reaction temperature, higher weight ratio of the raw oil and the catalyst and shorter retention time (generally 0.5-3.0 seconds). The diameter of the second reaction zone is larger than that of the first reaction zone, the ratio of the diameter of the second reaction zone to that of the first reaction zone is 1.5-5.0:1, the height of the second reaction zone accounts for 30% -60% of the total height of the reactor, and the second reaction zone has the function of reducing the flow rate of oil gas and catalyst and the reaction temperature. The method for reducing the reaction temperature of the zone can inject cold shock medium from the joint of the zone and the first reaction zone, and/or can reduce the reaction temperature of the zone by arranging a heat extractor in the zone and taking away part of heat, thereby achieving the purposes of inhibiting secondary cracking reaction and increasing isomerization reaction and hydrogen transfer reaction. The chilling medium is one or a mixture of more than one of chilling agent, cooled regenerated catalyst and cooled semi-regenerated catalyst in any proportion. Wherein the chilling agent is one or a mixture of more than one of liquefied gas, crude gasoline, stable gasoline, diesel oil, heavy diesel oil or water in any proportion; the cooled regenerated catalyst and the cooled semi-regenerated catalyst are obtained by cooling the spent catalyst after two-stage regeneration and one-stage regeneration respectively, the carbon content of the regenerated catalyst is less than 0.1 wt%, preferably less than 0.05 wt%, and the carbon content of the semi-regenerated catalyst is 0.1-0.9 wt%, preferably 0.15-0.7 wt%. If a heat remover is provided, its height is 50-90% of the height of the second reaction zone. The residence time of the stream in the reaction zone may be relatively long, ranging from 2 to 30 seconds. See ZL99105903.4 for a more detailed description of the reactor.
According to the invention, catalytic conversion catalysts are well known to the person skilled in the art, for example, the first catalytic conversion catalystThe catalyst and the second catalytic conversion catalyst can be amorphous silicon-aluminum catalyst and/or zeolite catalyst respectively, the zeolite in the zeolite catalyst can be one or more selected from Y-type zeolite, HY-type zeolite, ultrastable Y-type zeolite, ZSM-5 series zeolite, high-silicon zeolite with five-membered ring structure and ferrierite, and the zeolite can contain rare earth and/or phosphorus or can not contain rare earth and phosphorus. The catalysts fed to the different reaction zones of the catalytic conversion reactor may be of the same type or of different types. The different types of catalysts may be catalysts of different particle sizes and/or catalysts of different apparent bulk densities. The catalyst with different particles and/or the catalyst with high and low apparent bulk density can enter different reaction zones respectively, for example, the catalyst with large particles of ultrastable Y-type zeolite enters a first reaction zone to increase cracking reaction, the catalyst with small particles of rare earth Y-type zeolite enters a second reaction zone to increase hydrogen transfer reaction, the catalyst with different particle sizes is stripped in the same stripper and regenerated in the same regenerator, then the catalyst with large particles and the catalyst with small particles are separated, and the catalyst with small particles is cooled and enters the second reaction zone. The catalysts with different particle sizes are divided between 30 and 40 microns, and the catalysts with different apparent bulk densities are 0.6 to 0.7 g/cm3The division between them.
According to the invention, the method may further comprise: separating oil slurry from the first reaction product and/or the second reaction product, and returning at least part of the oil slurry to the first catalytic conversion reactor and/or the second catalytic conversion reactor. By recycling the slurry oil, the yields of gasoline and propylene can be increased.
In the present invention, the raw oil is well known to those skilled in the art, and for example, the raw oil may include petroleum hydrocarbon and/or other mineral oil, wherein the petroleum hydrocarbon may be selected from one or more of atmospheric gas oil, vacuum gas oil, atmospheric residue, vacuum residue, hydrogenated residue, coker gas oil, and deasphalted oil; the other mineral oil is selected from one or more of coal and natural gas derived liquid oil, oil sand oil, dense oil and shale oil.
According toInvention, C12The olefin and the hydrocatalytic wax oil can be fed into the first catalytic conversion reactor at any position, for example, the raw material oil, hydrocatalytic wax oil and the C can be fed into the first catalytic conversion reactor12At least one feed of olefins is fed to the first catalytic conversion reactor at the same feed point and/or at two or more feed points.
According to the invention, the first catalytic conversion reactor can be a variable-diameter riser and can comprise a first reaction zone and a second reaction zone according to the flow direction of reaction materials, and the raw oil, the hydrocatalytic wax oil and the C are mixed12Feeding an olefin to a first reaction zone; the conditions of the first catalytic conversion reaction may include: the conditions of the first catalytic conversion reaction include: a first reaction zone: the reaction temperature is 450-620 ℃, preferably 500-600 ℃, the reaction time is 0.5-2.0 seconds, preferably 0.8-1.5 seconds, the weight ratio of the catalyst to the raw oil is 3-15: 1, preferably 4-12: 1, and the weight ratio of the water vapor to the raw oil is 0.03-0.3: 1, preferably 0.05-0.15: 1; a second reaction zone: the reaction temperature is 460-550 ℃, preferably 480-530 ℃, the reaction time is 2-30 seconds, preferably 3-15 seconds, the weight ratio of the catalyst to the raw oil is 4-18: 1, preferably 4.5-15: 1, and the weight ratio of the water vapor to the raw oil is 0.03-0.3: 1, preferably 0.05-0.15: 1. The second catalytic conversion reaction may be under the same conditions as the first catalytic conversion reaction, or may be under different conditions, for example, the conditions may include: the reaction temperature is 450 ℃ and 620 ℃, the reaction time is 0.5-20.0 seconds, preferably 2-20 seconds, the weight ratio of the catalyst to the oil is 1-25, and the weight ratio of the water to the oil is 0.03-0.3.
According to the invention, the reaction product, in addition to the above-mentioned fractionation stages, can also be freed of dry gas, propane, propene and C5+ gasoline, etc. Containing C4The separation of olefins in the distillation section is well known to the person skilled in the art, preferably by extractive distillation in acetonitrile as solvent, it being possible for C to be separated off first by fractional distillation4Fractionating the fraction and then further fractionating C4Separation of alkanes in the fractionation section to obtain C-containing fractions4The fraction of olefins. Since diolefins are liable to poison the catalyst, too high a level of sulphur, especially mercaptans and hydrogen sulphide, leads to polymerization catalysisReduced activity and enhanced gum formation in gasoline blends containing C4The fraction section of the olefin can be treated by pretreatment units such as selective hydrogenation for removing diene, ethanolamine for desulfurization, alkali washing and water washing, alkali and nitrogen compound removal and the like, and then the superposition reaction is carried out, wherein the treatment modes are well known by the technical personnel in the field, and the details are not repeated.
The invention also provides a system for producing gasoline and propylene, which comprises a first catalytic conversion reactor, a regenerator, an oil agent separation device, a product separation device, a superposition reactor, a rectifying tower and an optional second catalytic conversion reactor; the first catalytic conversion reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet, the regenerator is provided with a catalyst inlet and a catalyst outlet, the oil agent separation device is provided with an oil agent inlet, an oil gas outlet and a catalyst outlet, and the product separation device is at least provided with an oil gas inlet and C-containing oil gas4The distillation section outlet of the olefin, the polymerization reactor comprises a raw material inlet and a polymerization product outlet, and the rectifying tower is provided with an oil gas inlet and a C12The second catalytic conversion reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet; the catalyst inlet of the first catalytic conversion reactor is communicated with the catalyst outlet of the regenerator, the oil agent outlet of the first catalytic conversion reactor is communicated with the oil agent inlet of the oil agent separating device, the catalyst outlet of the oil agent separating device is communicated with the catalyst inlet of the regenerator, the oil gas outlet of the oil agent separating device is communicated with the oil gas inlet of the product separating device, and the C-containing oil of the product separating device is communicated with the oil gas inlet of the product separating device4The outlet of the fraction section of the olefin is communicated with the raw material inlet of the polymerization reactor, the outlet of the polymerization product of the polymerization reactor is communicated with the oil gas inlet of the fractionating tower, and the C of the fractionating tower12An olefin outlet is in communication with the feed inlet of the first catalytic conversion reactor, optionally in communication with the feed inlet of a second catalytic conversion reactor; preferably, the system further comprises a first hydrotreating reactor, the product separation device is further provided with a catalytic wax oil outlet, and the raw material of the first hydrotreating reactorThe material inlet is communicated with the catalytic wax oil outlet of the product separation device, the product outlet of the first hydrotreating reactor is communicated with the raw material inlet of the first catalytic conversion reactor, and is optionally communicated with the raw material inlet of the second catalytic conversion reactor. The reactors and apparatus of the system of the present invention are well known to those skilled in the art and will not be described in detail herein.
The present inventors have unexpectedly found that the reaction product contains C4The fraction of olefin is separated out for polymerization reaction, and C in the polymerization product is12Olefins and/or other sources C12The olefin is sent into the catalytic conversion reactor for catalytic conversion reaction, so that the yield of the propylene can be obviously improved, the diesel oil and the catalytic wax oil can be recycled after being hydrogenated through the first hydrotreating reactor, and the yield of the gasoline and the propylene is improved.
In one embodiment, the system further comprises a second hydrotreating reactor provided with a feedstock inlet and a product outlet, the product outlet of the second hydrotreating reactor being in communication with the feedstock inlet of the first catalytic conversion reactor; the product separation device is also provided with a diesel oil outlet, and the diesel oil outlet of the product separation device is communicated with the raw material inlet of the first hydrotreating reactor. The quality of the raw oil can be improved through the second hydrotreatment reactor, and the yield of the catalytic conversion gasoline and the propylene can be improved.
The invention will be further explained with reference to the drawings, but the invention is not limited thereto.
A first embodiment will be described with reference to fig. 1.
In FIG. 1, preheated raw oil from a
A second embodiment will be described with reference to fig. 2.
In FIG. 2, preheated feed oil from line 46 and hydrogen from line 53 are mixed and fed into second hydrotreatment reactor 47, the hydrogenation product is fed into hydrogenation separation device 49 through line 48, the hydrogen separated by hydrogenation separation device 49 is fed into recycle hydrogen treatment device 30 through line 51, and then fed into recycle compressor 32 through line 31, the pressurized hydrogen is returned to second hydrotreatment reactor 47 through line 52, and the mixture of new hydrogen from line 35 and line 34 can be recycled and mixed with the feed and fed back to second hydrotreatment reactor 47 through line 53; the gas, gasoline and diesel oil separated by the hydrogenation separation device 49 are discharged out of the device through a pipeline 59, a pipeline 60 and a pipeline 61 respectively; the hydrogenation product obtained by separation of the hydrogenation separation device 49 is mixed with atomized steam from the pipeline 3 through the pipeline 50 and then sent to the first reaction zone 9 of the first catalytic conversion reactor I, the regenerated catalyst from the pipeline 16 is pre-lifted through the pre-lifting steam from the pipeline 1, oil gas and catalyst are conveyed upwards to selectively react with the oil slurry atomized through the pipeline 3 from the pipeline 5, the oil gas and the catalyst are conveyed upwards to the second reaction zone 8 of the first catalytic conversion reactor I for continuous reaction, the obtained first reaction product and the first catalyst to be generated are subjected to oil gas and catalyst separation in the settler 7, the separated catalyst to be generated with carbon is subjected to oil gas stripping through the steam from the pipeline 11 through the stripping section 10, the oil gas carried by the oil gas enters the regenerator 13 through the pipeline 12 for burning, and the regenerated flue gas is sent out of the regenerator through the pipeline 15. The air from
A third embodiment will be described with reference to fig. 3.
In FIG. 3, preheated feed oil from
A fourth embodiment will be described with reference to fig. 4.
In FIG. 4, preheated feed oil from
A fifth embodiment will be described with reference to fig. 5.
In FIG. 5, preheated feed oil from
The following examples further illustrate the invention but are not intended to limit the invention thereto.