CN114426873A - Method for producing carbon octa-arene from gasoline component - Google Patents
Method for producing carbon octa-arene from gasoline component Download PDFInfo
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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
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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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a system and a method for producing carbon octa-arene by using gasoline components, wherein the system comprises the following steps: an aromatization unit (M) for aromatizing and separating the gasoline component to obtain C3 ‑Component C4‑C5Component C6‑C7Component C8Component (A) and (C)9 +Preparing components; cracking and transalkylation unit (N) for C6‑C7Component (A) and (C)9 +The components are reacted and separated to obtain C3 ‑Component C4‑C5Component C6‑C7Component C8Component (A) and (C)9 +Preparing components; aromatic refining unit (O) for C8Refining the components to obtain high-purity C8Aromatic and non-aromatic components; cracking unit (P) for C3 ‑The components are subjected to olefin cracking. The invention can effectively convert gasoline hydrocarbon components (such as catalytic gasoline components) into carbon octa-arene to the maximum extent, and simultaneously produces a small amount of olefin as a byproduct to realize efficient conversion of gasoline into oilAnd (4) transforming.
Description
Technical Field
The invention relates to a method for producing carbon octa-arene by using a gasoline component.
Background
Aromatic hydrocarbon is a basic raw material of petrochemical industry, main products are BTX (benzene, toluene and xylene), wherein para-xylene isomer in the xylene is the most main aromatic hydrocarbon product, and the domestic supply gap reaches more than 1000 million tons per year. Therefore, the method for accelerating the production of aromatic hydrocarbon, especially improving the supply capacity of xylene, is of great importance to the development of the aromatic hydrocarbon industry in China. The industrial equipment uses naphtha as raw material, and adopts the catalytic reforming process to produce benzene, toluene, xylene and heavy aromatic hydrocarbon, then utilizes the isomerization and transalkylation unit to make toluene/benzene and C9+A is converted to xylene. In addition, the steam cracking device for producing low-carbon olefins in China also mainly takes naphtha as a raw material, so that the raw material for producing aromatic hydrocarbon and olefin is in short supply, and the cost of the aromatic hydrocarbon and olefin raw materials is high. Therefore, the search for lower-cost raw materials for producing aromatic hydrocarbons and olefins is a key factor for solving the bottleneck of the aromatic hydrocarbons and olefins in the future.
Along with the enlargement of the oil refining scale in China, the gasoline capacity is greatly improved, on the other hand, along with the large-scale application of new energy technology in China, the gasoline consumption market will show a descending trend in the future, and the contradiction that the gasoline supply is larger than the demand will be more and more prominent. In addition, with the upgrading of gasoline quality in China, the contents of aromatic hydrocarbon and olefin and the dry point in oil products are more strictly limited, the components of heavy hydrocarbon blended gasoline are further limited, and the widening of chemical conversion of gasoline components has potential market demands.
CN101208409 discloses a process for increasing the yield of benzene from hydrocarbon mixtures, which are subjected to dealkylation/transalkylation reactions to produce aromatic hydrocarbons and liquefied gases, and benzene is recovered by a solvent extraction process.
CN108485702 discloses a method for maximizing the production of aromatic hydrocarbons by using catalytically cracked gasoline, which recovers aromatic hydrocarbons and olefins through gasoline cutting, extractive distillation and aromatization processes.
Disclosure of Invention
The invention aims to mainly solve the problems that gasoline components are relatively excessive and aromatic hydrocarbon production raw materials are insufficient in China. The invention takes mixed hydrocarbon containing non-aromatic hydrocarbon and aromatic hydrocarbon as raw material, and the mixed hydrocarbon reacts with aromatization, cracking, alkyl transfer and aromatic hydrocarbon refining units to produce high-purity carbon octa-aromatic hydrocarbon and co-produce low-carbon olefin, thereby effectively widening the aromatic hydrocarbon production raw material and realizing oil conversion.
To achieve the foregoing object, according to a first aspect of the present invention, there is provided a system for producing a carbon octa-aromatic hydrocarbon from a gasoline component, the system comprising:
an aromatization unit for aromatizing and separating the gasoline component to obtain C3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
cracking and transalkylation unit for C6-C7Component (A) and (C)9 +The components are reacted and separated to obtain C3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
aromatic refining unit for C8Refining the components to obtain high-purity C8Aromatic and non-aromatic components;
cracking unit for C3 -The components are subjected to olefin cracking.
Preferably, C of the aromatization unit6-C7Component material outlet and C9 +The component material outlet is communicated with the feed inlet of the cracking and alkyl transfer unit;
the C8 component material outlet of the aromatization unit and the cracking and transalkylation unit is communicated with the feed inlet of the aromatic hydrocarbon refining unit;
c of aromatization unit and cracking and transalkylation unit3 -The component material outlet is communicated with a feed inlet of the cracking unit;
c of cracking and transalkylation unit4-C5Material out of componentThe port is communicated with a feed inlet of the aromatization unit;
the non-aromatic component material outlet of the aromatic hydrocarbon refining unit is communicated with the feed inlet of the aromatization unit and/or the feed inlet of the cracking unit.
According to a second aspect of the present invention, there is provided a process for producing a C-octaarene from a gasoline component, the process comprising: I) the gasoline component is subjected to aromatization unit reaction, and the reaction product is separated to obtain C3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
II) step I) C6-C7Component (A) and (C)9 +The components are cracked and further reacted with a transalkylation unit, and C is separated from the reaction product3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
III) removing C8 components in the step I) and/or C8 components in the step II) to an aromatic hydrocarbon refining unit, and separating high-purity C8 aromatic hydrocarbon and non-aromatic components;
IV) C in step I)3 -Component(s) and/or C in step II)3 -The components enter a cracking unit for cracking;
v) optionally, product C in step I)4-C5Component(s) and/or product C from step II)4-C5Returning the components to the step I) as raw materials; and/or, optionally, the non-aromatic components in step III) are returned to step I) and/or step IV) as starting materials.
Preferably, in step I), the gasoline component feed has a boiling range of 50 to 250 ℃, preferably a boiling range of 60 to 200 ℃.
Preferably, in the step I), the content of aromatic hydrocarbon in the gasoline component raw material is 10-100% by weight, and preferably 20-80%.
Preferably, in step I), the gasoline component feedstock is derived from catalytically cracked gasoline, hydrocracked gasoline, ethylene cracked gasoline, catalytically reformed gasoline, straight run gasoline, LPG or any mixture thereof.
Preferably, the operating conditions of the aromatization unit in step I) include: the aromatization unit catalyst is selected from one or more of Zn/ZSM-5, Mo/ZSM-5 and Mo-Zn/ZSM-5, the reaction temperature is 400-600 ℃, the reaction pressure is 0.2-3MPa, and the feed weight space velocity is 0.5-5h-1。
Preferably, the operating conditions of the cleavage and transalkylation unit in step II) include: the reaction temperature is 250-500 ℃, the reaction pressure is 1.5-6.5MPa, the hydrogen-hydrocarbon molar ratio is 1-10, and the feed weight space velocity is 0.5-5h-1。
Preferably, the aromatic hydrocarbon refining unit in the step III) is an aromatic hydrocarbon extraction separation unit or a non-aromatic selective cracking unit.
Preferably, the aromatic hydrocarbon extraction separation unit performs extraction separation by extractive distillation based on a sulfolane solvent.
Preferably, the operating conditions of the non-aromatic selective cracking unit include: the catalyst contains at least one of molecular sieves of ZSM-5, MCM-22, MOR and Beta, and can selectively contain metal components selected from VIB, VIIB and VIII groups; the reaction temperature is 300-600 ℃, the reaction pressure is 0.5-3.0MPa, the hydrogen-hydrocarbon molar ratio is 1-10, and the feed weight space velocity is 1-15h-1。
Preferably, the operating conditions of the cracking unit in step IV) include: the temperature of the cracking reaction is 600-1000 ℃.
According to the method, the content of aromatic hydrocarbon in the reaction product of the aromatization unit is increased by more than 10% compared with that of the raw material in terms of volume percentage, and in the optimized scheme, the content of aromatic hydrocarbon in the reaction product is increased by more than 20% compared with that of the raw material. The content of the carbon octa-arene in the reaction product of the cracking and alkyl transfer unit is improved by more than 15 percent compared with the raw material, and in the optimized scheme, the content of the carbon octa-arene in the reaction product is improved by more than 25 percent compared with the raw material. The aromatic hydrocarbon refining unit is an extraction separation or non-aromatic hydrocarbon cracking reaction unit, and the purity of the carbon octa-aromatic hydrocarbon in the product of the aromatic hydrocarbon refining unit is higher than 99.5 percent (by weight).
In the invention, the gasoline component is subjected to an aromatization unit to increase the yield of aromatic hydrocarbon products, and meanwhile, the byproduct low-carbon hydrocarbon is used as an olefin cracking raw material. C rich in aromatic hydrocarbon6 +The components are cracked againAnd a transalkylation unit converts benzene, toluene and C9+ aromatic hydrocarbon into carbon octa-aromatic hydrocarbon, and simultaneously, a byproduct of low-carbon hydrocarbon is used as an olefin cracking raw material. Finally, the high-purity carbon octaarene is obtained through a C8 arene refining unit. The method can effectively convert hydrocarbon components of gasoline (such as catalytic gasoline components) into the carbon octa-arene to the maximum extent, and simultaneously produces a small amount of olefin as a byproduct, thereby realizing high-efficiency oiling conversion.
Drawings
FIG. 1 is a schematic flow chart of a method according to example 1 of the present invention;
fig. 2 is a schematic flow chart of a method according to embodiment 2 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a system for producing carbon octa-arene by using gasoline components, which comprises the following components:
an aromatization unit M for aromatization reaction and separation of the gasoline component to obtain C3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
cracking and transalkylation unit N for C6-C7Component (A) and (C)9 +The components are reacted and separated to obtain C3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
aromatic refining unit O for C8Refining the components to obtain high-purity C8Aromatic and non-aromatic components;
cracking unit P for C3 -Component (C) to olefinAnd (6) cracking.
According to a preferred embodiment of the invention, C of the aromatization unit M6-C7Component material outlet and C9 +The component material outlet is communicated with the feed inlet of the cracking and transalkylation unit N.
According to a preferred embodiment of the invention, the outlet of the aromatization unit M and the feed of the C8 component of the cracking and transalkylation unit N is in communication with the inlet of the aromatics refining unit O.
According to a preferred embodiment of the invention, C of the aromatization unit M and of the cleavage and transalkylation unit N3 -The component material outlet is communicated with the feed inlet of the cracking unit P.
According to a preferred embodiment of the invention, C of the cleavage and transalkylation unit N4-C5The material outlet of the components is communicated with the feed inlet of the aromatization unit M.
According to a preferred embodiment of the invention, the non-aromatic fraction outlet of the aromatics refining unit O is in communication with the feed inlet of the aromatization unit M and/or the feed inlet of the cracking unit P.
According to a preferred embodiment of the present invention, each of the communicating pipes is independently provided with a valve for regulating the flow rate.
According to a preferred embodiment of the invention, the system comprises an automatic control unit for controlling the opening and closing or flow regulation of the respective valves according to the metered flow.
The system is used for treating gasoline components, so that high-purity carbon octa-arene can be maximally produced and low-carbon olefin can be co-produced.
The invention provides a method for producing carbon octa-arene by using a gasoline component, which comprises the following steps: I) the gasoline component is subjected to aromatization unit reaction, and the reaction product is separated to obtain C3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
II) step I) C6-C7Component (A) and (C)9 +The components are cracked and further reacted with a transalkylation unit, and the reaction product is separatedGo out C3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
III) removing C8 components in the step I) and/or C8 components in the step II) to an aromatic hydrocarbon refining unit, and separating high-purity C8 aromatic hydrocarbon and non-aromatic components;
IV) C in step I)3 -Component(s) and/or C in step II)3 -The components enter a cracking unit to be subjected to olefin cracking;
v) optionally, product C in step I)4-C5Component(s) and/or product C from step II)4-C5Returning the components to the step I) as raw materials; and/or, optionally, the non-aromatic components in step III) are returned to step I) and/or step IV) as starting materials.
In the present invention, C3 -Component C comprises3And the following components, C9 +Component C comprises9And the above components.
In the present invention, the high purity C8 aromatic hydrocarbon means that the purity of the aromatic hydrocarbon reaches or exceeds the purity requirement of a para-xylene adsorption separation or para-xylene crystallization separation unit on a C8 aromatic hydrocarbon raw material, for example, the purity is higher than 99%.
In the invention, the gasoline component is subjected to an aromatization unit to increase the yield of aromatic hydrocarbon products, and meanwhile, the byproduct low-carbon hydrocarbon is used as an olefin cracking raw material. C rich in aromatic hydrocarbon6 +The components are subjected to cracking and transalkylation units to convert benzene, toluene and C9+ aromatic hydrocarbon into carbon octa-aromatic hydrocarbon, and meanwhile, the byproduct low-carbon hydrocarbon is used as an olefin cracking raw material. Finally, the high-purity carbon octaarene is obtained through a C8 arene refining unit. The method can effectively convert hydrocarbon components of gasoline (such as catalytic gasoline components) into the carbon octa-arene to the maximum extent, and simultaneously produces a small amount of olefin as a byproduct, thereby realizing high-efficiency oiling conversion.
According to a preferred embodiment of the invention, the gasoline component feed in step I) has a boiling range of 50 to 250 ℃, preferably a boiling range of 60 to 200 ℃.
According to a preferred embodiment of the present invention, in step I), the gasoline component feedstock has an aromatic content of 10 to 100% by weight, preferably an aromatic content of 20 to 80% by weight, more preferably 22 to 44% by weight.
According to a preferred embodiment of the invention, in step I), the sulfur content of the aromatic-containing mixed hydrocarbon feedstock is from 2 to 3ppm by weight.
According to a preferred embodiment of the invention, in step I), the nitrogen content of the aromatic-containing mixed hydrocarbon feedstock is from 1 to 2ppm by weight.
According to a preferred embodiment of the invention, in step I), the olefin content in the mixed hydrocarbon feedstock containing aromatic hydrocarbons is from 20 to 35% by weight.
According to a preferred embodiment of the invention, in step I), the paraffinic hydrocarbon feedstock containing aromatic hydrocarbons comprises from 35 to 45% by weight of paraffinic hydrocarbons.
According to a preferred embodiment of the present invention, in step I), the gasoline component feedstock is derived from catalytically cracked gasoline, hydrocracked gasoline, ethylene cracked gasoline, catalytically reformed gasoline, straight run gasoline, LPG or any mixture thereof.
The above-mentioned preferred raw materials can be efficiently used by the treatment according to the method of the present invention.
In the present invention, the aromatization unit catalyst may be conventionally selected, for example, comprising at least one first component selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, and at least one second component selected from the group consisting of Zn, Ga, Pt, Mo, for example, one or more of Zn/ZSM-5, Mo/ZSM-5, and Mo-Zn/ZSM-5.
In the present invention, the catalyst of the non-aromatic selective cracking unit may be conventionally selected, for example, from at least one acidic molecular sieve having an eight-, ten-or twelve-membered ring structure, such as at least one molecular sieve of ZSM-5, MCM-22, MOR and Beta, and may optionally contain a metal component selected from groups VIB, VIIB and VIII.
According to the process of the present invention, the operating conditions of the aromatization unit in step I) can be selected in a wide range, and according to a preferred embodiment of the present invention, it is preferred that the operating conditions of the aromatization unit in step I) comprise: the aromatization unit catalyst is selected from one or more of Zn/ZSM-5, Mo/ZSM-5 and Mo-Zn/ZSM-5The reaction temperature is 400-600 ℃, the reaction pressure is 0.2-3MPa, and the feeding airspeed is 0.5-5h-1。
According to the process of the present invention, the operating conditions for the cleavage and transalkylation unit in step II) can be selected within a wide range, and for the present invention, it is preferred that the operating conditions for step II) include: the reaction temperature is 250-500 ℃, the reaction pressure is 1.5-6.5MPa, the hydrogen-hydrocarbon molar ratio is 1-10, and the feed weight space velocity is 0.5-5h-1。
According to the method, the aromatic hydrocarbon refining unit in the step III) is an aromatic hydrocarbon extraction and separation unit or a non-aromatic hydrocarbon selective cracking unit.
According to the method of the present invention, it is preferable that the aromatic hydrocarbon extraction separation unit performs extraction separation using extractive distillation based on a sulfolane solvent.
According to the process of the present invention, it is preferred that the operating conditions of the non-aromatic selective cracking unit comprise: the catalyst contains at least one of molecular sieves of ZSM-5, MCM-22, MOR and Beta, and can selectively contain metal components selected from VIB, VIIB and VIII groups; the reaction temperature is 300-600 ℃, the reaction pressure is 0.5-3.0MPa, the hydrogen-hydrocarbon molar ratio is 1-10, and the feed weight space velocity is 1-15h-1。
According to the process of the invention, it is preferred that the operating conditions of the cleavage unit in step IV) comprise: the temperature of the cracking reaction is 600-1000 ℃.
In the present invention, the operating conditions of the aromatic extraction unit are widely selectable, and the present invention has no special requirements for this, for example, C8 can be extracted and separated into high-purity C8 aromatic hydrocarbon and NA (non-aromatic hydrocarbon), as shown in fig. 2 of the present invention.
In the present invention, the transalkylation catalyst may be conventionally selected, and may for example be a catalyst comprising at least one first component selected from ZSM-5, ZSM-12, MOR, Beta, and at least one second component selected from Pt, Mo, Re.
According to a preferred embodiment of the present invention, the transalkylation catalyst comprises an acidic molecular sieve and an oxide promoter component immobilized with a hydrogenation metal and/or a hydrogenation metal oxide, wherein the hydrogenation metal is selected from one or more of VB, VIB and VIIB. In the invention, based on the hydrogen migration effect of the metal surface and the synergistic effect with the acid site of the molecular sieve, the loaded metal on the transalkylation catalyst is specifically distributed, the metal component loaded on the surface of the oxide auxiliary agent ensures that the acid site of the molecular sieve is not covered or neutralized by the metal, and the hydrogen migration effect of the hydrogenated metal surface and the acid site of the molecular sieve are coordinated to play a role in improving the conversion efficiency of heavy aromatics.
According to a preferred embodiment of the invention, the hydrogenation metal and/or hydrogenation metal oxide is/are supported on the oxide promoter by physical mixing and/or chemical bonding.
According to a preferred embodiment of the present invention, the transalkylation catalyst is prepared by: and (2) loading hydrogenation metal and/or hydrogenation metal oxide on the oxide auxiliary agent, and kneading and molding the oxide auxiliary agent and the acidic molecular sieve.
According to a preferred embodiment of the invention, the catalyst comprises P, more preferably P is supported on the oxide promoter component by physical mixing and/or chemical bonding, preferably in an amount of 0.01 to 5 wt.% calculated as oxide. The addition of P can increase the aromatics conversion of the catalyst.
According to a preferred embodiment of the present invention, the content of the acidic molecular sieve is 50 to 80 wt%, the content of the oxide promoter is 10 to 40 wt%, and the content of the hydrogenation metal and/or the hydrogenation metal oxide is 0.01 to 10 wt%, calculated as oxide, based on 100 wt% of the catalyst. The use of the foregoing preferred catalyst formulations can increase the aromatics conversion of the catalyst.
According to a preferred embodiment of the present invention, the hydrogenation metal is one or more of Mo, W and Re, preferably the hydrogenation metal is at least two of Mo, Re and W, and the mixing weight ratio of the two is 0.1-10: 1; more preferably a combination of the three, and the weight ratio of Mo, Re and W is 1: 0.1-0.4: 0.1-0.6. The use of the foregoing preferred catalyst formulation enables a significant increase in the conversion of heavy aromatics to the catalyst.
According to the present invention, the acidic molecular sieve can be selected from a wide range of acidic molecular sieves, and commonly used acidic molecular sieves can be used in the present invention, and according to a preferred embodiment of the present invention, the acidic molecular sieve is selected from acidic molecular sieves having eight-membered, ten-membered, or twelve-membered ring pore structure characteristics; preferably at least one selected from ZSM-5, SAPO-11, ZSM-11, Beta and Y molecular sieves.
According to the present invention, the kind of the oxide assistant is widely selectable, and a common oxide assistant may be used in the present invention, and for the present invention, one or more selected from the group consisting of alumina, silica, magnesia, titania and kaolin is preferable.
Catalysts meeting the aforementioned requirements of the present invention can be used in the present invention without particular requirements for the preparation process thereof, and according to a preferred embodiment of the present invention, there is provided a process for preparing the catalyst of the present invention, which comprises:
(1) dipping the hydrogenation metal source solution into an oxide assistant source, and carrying out heat treatment to obtain a solid;
(2) kneading the solid and an acidic molecular sieve source, and forming.
According to a preferred embodiment of the invention, the steps of heat-treating each comprise: firing or, drying and firing.
According to a preferred embodiment of the invention, the step of heat treating comprises the steps of drying and firing.
In the present invention, the optional range of the drying conditions is wide, and common drying conditions can be used in the present invention, and for the present invention, the preferable drying conditions include: the temperature is 50-200 ℃ and the time is 1-30 h.
In the present invention, the optional range of the roasting conditions is wide, and all the common roasting conditions can be used in the present invention, and for the present invention, the preferable roasting conditions include: heat-treating for 1-30 hours at 300-700 ℃ in an oxygen-containing atmosphere.
According to a preferred embodiment of the present invention, the oxygen-containing atmosphere is a mixed gas of air and water vapor, and the volume ratio of the air to the water vapor is 5-100: 1.
According to the invention, the source of hydrogenation metal can be selected from a wide range of species, for example a molybdenum-based hydrogenation metal-soluble compound, preferably a group VB, VIB and VIIB metal-containing soluble compound. And will not be described in detail herein.
In the present invention, the source of acidic molecular sieve may be selected from, for example, acidic molecular sieves having the structural characteristics of an eight-membered, ten-membered or twelve-membered ring pore.
In the present invention, the acidic molecular sieve is, for example, at least one selected from the group consisting of ZSM-5, SAPO-11, ZSM-11, Beta and Y molecular sieves.
In the present invention, the oxide assistant source may be selected from one or more of alumina, silica, magnesia, titania and kaolin, for example.
According to the invention, step (1) is preferably carried out in the presence of a phosphorus source, more preferably the phosphorus source is a soluble compound, and the type of the soluble compound has no special requirement and is not described herein again.
In the invention, the transalkylation catalyst is used for converting aromatic hydrocarbon and has the advantages of high reaction activity, low aromatic hydrocarbon loss and the like.
Before the cracking and transalkylation catalyst is used, the reduction is carried out according to the requirement, the reduction step has no special requirement, and the invention is not repeated.
The invention is further illustrated but is not limited by the following description of the examples.
In the following examples, the catalyst was prepared by a conventional method, unless otherwise specified.
Example 1
The present invention will now be described more fully with reference to fig. 1. After desulfurization and denitrification, the catalytically cracked gasoline enters an aromatization unit to carry out aromatization reaction (100 tons/hour), and C is separated from reaction products3 -As steam cracking feedstock, C4-C5Recycling the components to the aromatization unit, C6-C7And C9 +De-cracking and transalkylation unit, C8The components go to an aromatic refining unit. Separation of C from the product of cracking and transalkylation unit3 -As steam cracking feedstock, C4-C5Recycling the components to the aromatization unit, C6-C7And C9 +Recycling part or all of it back to the cracking and transalkylation unit, C8The components are sent to a non-aromatic hydrocarbon cracking unit for non-aromatic hydrocarbon cracking. Non-aromatic cracking unit product C3 -Light hydrocarbon as steam cracking raw material, C8Aromatic hydrocarbons are recovered as product, the remainder C6 +The components are partially or completely recycled to the aromatization unit to increase the yield of the aromatic hydrocarbon.
The aromatization unit contains a ZSM-5 molecular sieve catalyst loaded with 3 wt% of Zn as a catalyst, the reaction temperature is 480 ℃, the reaction pressure is 0.5MPa, and the feed weight space velocity is 1.5; the cracking and transalkylation unit catalyst is a mordenite catalyst loaded with 2 wt% of Mo (Mo is loaded on the mordenite by a one-step impregnation method), the reaction temperature is 360 ℃, the reaction pressure is 3.0MPa, the feeding weight space velocity is 4.0, and the hydrogen-hydrocarbon molar ratio is 3.0; the non-aromatic hydrocarbon cracking unit catalyst is ZSM-5 molecular sieve catalyst, the reaction temperature is 450 ℃, the reaction pressure is 3.0MPa, and the feeding weight space velocity is 1.0.
The raw material composition is shown in table 1, the unit reaction conditions are shown in table 2, and the integrated plant product yield is shown in table 3.
Example 2
The present invention will now be described more fully with reference to fig. 2. After desulfurization and denitrification, the catalytically cracked gasoline enters an aromatization unit to carry out aromatization reaction (100 tons/hour), and C is separated from reaction products3 -As steam cracking feedstock, C4-C5Recycling the components to the aromatization unit, C6-C7And C9 +De-cracking and transalkylation unit, C8The components go to an aromatic refining unit. Separation of C from the product of cracking and transalkylation unit3 -As steam cracking feedstock, C4-C5Recycling the components to the aromatization unit, C6-C7And C9 +Partially or fully recycled to the cleavage and transalkylation units. C8The component is removed to an aromatic extraction unit for further separating C8Aromatic and nonaromatic hydrocarbons, C8The aromatic hydrocarbon is extracted as a product, and the rest non-aromatic hydrocarbon components are partially or completely recycled to the aromatization unit to increase the yield of the aromatic hydrocarbon.
The aromatization unit contains a ZSM-5 molecular sieve catalyst loaded with 3 wt% of Ga as a catalyst, the reaction temperature is 520 ℃, the reaction pressure is 0.5MPa, and the feeding weight space velocity is 1.0; the cracking and transalkylation unit catalyst is a beta zeolite catalyst loaded with 0.5 wt% of Re (the Re is loaded on the beta zeolite by a one-step impregnation method), the reaction temperature is 380 ℃, the reaction pressure is 3.0MPa, the feeding weight space velocity is 3.0, and the hydrogen-hydrocarbon molar ratio is 4.0; the extraction unit is conventional liquid-liquid extraction or extractive distillation.
The raw material composition is shown in table 1, the unit reaction conditions are shown in table 2, and the integrated plant product yield is shown in table 3.
TABLE 1
TABLE 2
TABLE 3
Example 1 | Example 2 | |
Product(s) | Yield, t/h | Yield, t/h |
Ethylene | 22 | 12 |
Propylene (PA) | 10 | 8 |
C-octa-aromatic hydrocarbon | 52 | 68 |
C10 + | 2 | 1 |
Preparation of example 1
7.7g of alumina is dipped into certain amount of ammonium molybdate, dried for 10 hours at 120 ℃, and then roasted for 3 hours at 400 ℃ in the air atmosphere to obtain modified alumina, the modified alumina, 10 g of ZSM-5 and 10 g of Beta molecular sieve are mixed and formed, and the mixture is roasted for 2 hours at 550 ℃ to obtain the catalyst A with the molybdenum content of 8 percent (wt).
Preparation of example 2
7.7g of alumina is dipped into certain ammonium perrhenate, dried for 10 hours at 120 ℃, roasted for 3 hours at 400 ℃ in air atmosphere to obtain modified alumina, the modified alumina and 20 g of ZSM-5 molecular sieve are mixed and formed, and roasted for 2 hours at 550 ℃ to obtain the catalyst B with the rhenium content of 0.5 percent (wt).
Preparation of example 3
7.7g of alumina is dipped into a certain amount of ammonium tetramolybdate, dried at 120 ℃ for 10 hours, and then roasted at 400 ℃ for 3 hours in air atmosphere to obtain modified alumina, the metal modified alumina and 20 g of ZSM-5 are mixed and formed, and the mixture is roasted at 550 ℃ for 2 hours to obtain the catalyst C with the molybdenum content of 10% (wt).
Preparation of example 4
Prepared according to the method of example 1 except that certain amounts of alumina were taken to impregnate the ammonium molybdate and ammonium tungstate solutions, all under the same conditions, to provide catalyst D having a molybdenum content of 4 wt% and a tungsten content of 4 wt%.
Preparation of example 5
Prepared according to the method of example 1 except that certain amounts of alumina were impregnated with certain solutions of ammonium molybdate, ammonium tungstate and ammonium perrhenate, all conditions being the same, to give catalyst E having a molybdenum content of 5% (wt) and a tungsten content of 2.4% by weight and a rhenium content of 0.6% (wt).
Preparation of example 6
The preparation was carried out as described in example 1, except that 7.7g of alumina was impregnated with a certain amount of ammonium molybdate, dried at 120 ℃ for 10 hours, calcined at 400 ℃ for 3 hours in a mixed atmosphere of air and water vapor (volume ratio of air to water vapor 20: 1) to obtain modified alumina, mixed with molecular sieves and shaped, and calcined at 550 ℃ for 2 hours to obtain catalyst F having a molybdenum content of 8% (wt).
Preparation of example 7
The preparation was carried out as described in example 1, except that 7.7G of alumina was impregnated with a certain amount of ammonium molybdate, dried at 120 ℃ for 10 hours, calcined at 400 ℃ for 3 hours in a mixed atmosphere of air and water vapor (volume ratio of air to water vapor 5: 1) to obtain modified alumina, mixed with molecular sieve and shaped, and calcined at 550 ℃ for 2 hours to obtain catalyst G having a molybdenum content of 8% (wt).
Preparation of example 8
The preparation was carried out as described in example 1, except that 7.7g of alumina was impregnated with a certain amount of ammonium molybdate, dried at 120 ℃ to obtain modified alumina, mixed with molecular sieves and shaped, calcined at 550 ℃ for 2 hours to obtain catalyst H having a molybdenum content of 8% (wt).
Preparation of example 9
Prepared as described in example 1, except that a quantity of alumina is impregnated with a quantity of ammonium molybdate, ammonium phosphate solution, and the conditions are the same, to provide catalyst I having a molybdenum content of 7 wt% and a phosphorus content of 1 wt%.
Examples 3 to 11
Catalysts A to I were placed in a reactor before use, reduced by passing hydrogen at 450 ℃ for 3 hours, and then gasoline was treated in accordance with the method of example 1, except that step II) of example 1, the transalkylation catalyst, was replaced with catalysts A to I of the preparation examples, and the remaining operating conditions were unchanged, and the results are shown in Table 4.
TABLE 4
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A system for producing a carbon octa-aromatic hydrocarbon from a gasoline component, the system comprising:
an aromatization unit (M) for aromatizing and separating the gasoline component to obtain C3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
cracking and transalkylation unit (N) for C6-C7Component (A) and (C)9 +The components are reacted and separated to obtain C3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
aromatic refining unit (O) for C8Refining the components to obtain high-purity C8Aromatic and non-aromatic components;
cracking unit (P) for C3 -The components are cracked to prepare olefin.
2. The system of claim 1, wherein,
c of aromatization unit (M)6-C7Component material outlet and C9 +The component material outlet is communicated with the feed inlet of the cracking and transalkylation unit (N);
the C8 component material outlet of the aromatization unit (M) and the cracking and transalkylation unit (N) is communicated with the feed inlet of the aromatic hydrocarbon refining unit (O);
c of aromatization unit (M) and of cracking and transalkylation unit (N)3 -The component material outlet is communicated with the feed inlet of the cracking unit (P);
c of cracking and transalkylation unit (N)4-C5The material outlet of the component is communicated with the feed inlet of the aromatization unit (M);
the non-aromatic component material outlet of the aromatic hydrocarbon refining unit (O) is communicated with the feed inlet of the aromatization unit (M) and/or the feed inlet of the cracking unit (P).
3. A method for producing carbon octa-aromatic hydrocarbon from gasoline component is characterized by comprising the following steps:
I) the gasoline component is subjected to aromatization unit reaction, and the reaction product is separated to obtain C3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
II) step I) C6-C7Component (A) and (C)9 +The components are cracked and further reacted with a transalkylation unit, and C is separated from the reaction product3 -Component C4-C5Component C6-C7Component C8Component (A) and (C)9 +Preparing components;
III) removing C8 components in the step I) and/or C8 components in the step II) to an aromatic hydrocarbon refining unit, and separating high-purity C8 aromatic hydrocarbon and non-aromatic components;
IV) C in step I)3 -Component(s) and/or C in step II)3 -The components enter a cracking unit for cracking;
v) optionally, product C in step I)4-C5Component(s) and/or product C from step II)4-C5Returning the components to the step I) as raw materials; and/or, optionally, the non-aromatic components in step III) are returned to step I) and/or step IV) as starting materials.
4. The method of claim 3, wherein,
the boiling range of the gasoline component raw material in the step I) is 50-250 ℃, and the preferred boiling range is 60-200 ℃; and/or
In the step I), the gasoline component raw material has an aromatic hydrocarbon content of 10-100% by weight, preferably 20-80% by weight; and/or
In step I), the gasoline component raw material is selected from catalytic cracking gasoline, hydrocracking gasoline, ethylene cracking gasoline, catalytic reforming gasoline, straight-run gasoline, LPG or any mixture thereof.
5. The method of claim 3 or 4,
the operating conditions of the aromatization unit in step I) include: the aromatization unit catalyst is selected from one or more of Zn/ZSM-5, Mo/ZSM-5 and Mo-Zn/ZSM-5, the reaction temperature is 400-600 ℃, the reaction pressure is 0.2-3MPa, and the feed weight space velocity is 0.5-5h-1(ii) a And/or
The operating conditions of the cleavage and transalkylation unit in step II) include: the reaction temperature is 250-500 ℃, the reaction pressure is 1.5-6.5MPa, the hydrogen-hydrocarbon molar ratio is 1-10, and the feed weight space velocity is 0.5-5h-1(ii) a And/or
In the step III), the aromatic hydrocarbon refining unit is an aromatic hydrocarbon extraction and separation unit or a non-aromatic hydrocarbon selective cracking unit, preferably:
the aromatic extraction separation unit adopts extractive distillation based on a sulfolane solvent for extraction separation;
the operating conditions of the non-aromatic selective cracking unit include: the catalyst contains at least one of molecular sieves of ZSM-5, MCM-22, MOR and Beta, and can selectively contain metal components selected from VIB, VIIB and VIII groups; the reaction temperature is 300-600 ℃, the reaction pressure is 0.5-3.0MPa, the hydrogen-hydrocarbon molar ratio is 1-10, and the feed weight space velocity is 1-15h-1;
The operating conditions of the cracking unit in step IV) include: the temperature of the cracking reaction is 600-1000 ℃.
6. The process of any of claims 3-5, wherein the transalkylation catalyst in step II) comprises an acidic molecular sieve and an oxide promoter component immobilized with a hydrogenation metal and/or a hydrogenation metal oxide, wherein the hydrogenation metal is selected from one or more of VB, VIB and VIIB;
based on 100 wt% of the catalyst, calculated by oxide, the content of the acidic molecular sieve is 50-80 wt%, the content of the oxide auxiliary agent is 10-40 wt%, and the content of the hydrogenation metal and/or the hydrogenation metal oxide is 0.01-10 wt%.
7. The method of claim 6, wherein,
the hydrogenation metal is a combination of Mo, W and Re, and the weight ratio of Mo, Re and W is 1: 0.1-0.4: 0.1-0.6; and/or
The acidic molecular sieve is selected from at least one of ZSM-5, SAPO-11, ZSM-11, Beta and Y molecular sieves; and/or
The oxide auxiliary agent is selected from one or more of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide and kaolin.
8. The process according to claim 6 or 7, wherein the transalkylation catalyst of step II) is prepared by a process comprising:
(1) dipping the hydrogenation metal source solution into an oxide assistant source, and carrying out heat treatment to obtain a solid;
(2) kneading the solid and an acidic molecular sieve source, and forming.
9. The method of claim 8, wherein,
in the step (1), the heat treatment step includes: baking or, drying and baking; preferably, the first and second electrodes are formed of a metal,
the drying conditions include: the temperature is 50-200 ℃, and the time is 1-30 h; and/or
The roasting conditions include: heat-treating for 1-30 hours at 300-700 ℃ in an oxygen-containing atmosphere.
10. The method according to claim 9, wherein the oxygen-containing atmosphere is a mixed gas of air and water vapor at a volume ratio of 5-100: 1.
11. The process according to any one of claims 8 to 10, wherein step (1) is carried out in the presence of a phosphorus source, which is a soluble compound.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1155416A (en) * | 1965-08-16 | 1969-06-18 | Yawata Chem Ind Co Ltd | Process for the production of High-Pure Aromatic Hydrocarbons from Cracked Gasoline |
CN101734986A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | Method for hydrogenation pyrolysis of prolific benzene and xylene by using pyrolysis gasoline |
CN104557368A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | System for preparing ethylene, ethylene and arene from kinds of raw materials by coupling and transformation and method for system |
CN107916131A (en) * | 2016-10-11 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of method that isomerization gasoline and aromatic hydrocarbons are produced by alkane |
-
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1155416A (en) * | 1965-08-16 | 1969-06-18 | Yawata Chem Ind Co Ltd | Process for the production of High-Pure Aromatic Hydrocarbons from Cracked Gasoline |
CN101734986A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | Method for hydrogenation pyrolysis of prolific benzene and xylene by using pyrolysis gasoline |
CN104557368A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | System for preparing ethylene, ethylene and arene from kinds of raw materials by coupling and transformation and method for system |
CN107916131A (en) * | 2016-10-11 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of method that isomerization gasoline and aromatic hydrocarbons are produced by alkane |
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