CN112225632A - Method for synthesizing aromatic hydrocarbon component in aviation kerosene by using low-carbon aromatic hydrocarbon - Google Patents

Method for synthesizing aromatic hydrocarbon component in aviation kerosene by using low-carbon aromatic hydrocarbon Download PDF

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CN112225632A
CN112225632A CN202011059498.0A CN202011059498A CN112225632A CN 112225632 A CN112225632 A CN 112225632A CN 202011059498 A CN202011059498 A CN 202011059498A CN 112225632 A CN112225632 A CN 112225632A
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molecular sieve
low
aromatic hydrocarbon
sieve catalyst
carbon
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CN112225632B (en
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定明月
郭帅
邬玉珊
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Shenzhen Research Institute of Wuhan University
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Shenzhen Research Institute of Wuhan University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/073—Ethylbenzene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/085—Isopropylbenzene
    • 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
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C10G2300/1092—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • 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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Abstract

The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps: carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst; wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium. According to the method, the solid molecular sieve catalyst is used for carrying out gas-phase heterogeneous reaction in the fixed bed, so that reactants and products can be continuously discharged, the problem of difficult separation does not exist, the obtained alkylated product is mainly C8-C15 aromatic hydrocarbon meeting the requirement of aviation kerosene, the reactants continuously pass through the catalyst under a proper reaction condition, and the products are discharged after being condensed by a cold trap, so that the effective separation of the products and the catalyst is realized. Under the best state, the selectivity of C8-C15 aromatic hydrocarbon in the product reaches more than 90 percent, and the conversion rate of the alkylating agent olefin mixture is about 100 percent.

Description

Method for synthesizing aromatic hydrocarbon component in aviation kerosene by using low-carbon aromatic hydrocarbon
Technical Field
The invention relates to the technical field of fuel energy, in particular to a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon.
Background
With the rapid development of the aviation industry and the civil aviation industry, the usage amount of aviation fuel all over the world is increased sharply. The aviation fuel is prepared by refining petroleum and the like in industry, and meanwhile, the aviation industry faces a phenomenon of non-renewable energy shortage in the process of preparing fuel oil and a series of problems of environmental pollution, waste reutilization, carbon emission policy and the like in the synthesis and use processes. In recent years, the worldwide concern about depletion of fossil energy and environmental pollution causes urgent need for developing various new aviation fuel synthesis methods to ensure sustainable use of energy, reduce the degree of environmental pollution, and provide theoretical support and technical guidance for aviation industry and future development trend of energy industry. Aviation kerosene belongs to a category of aviation fuels, and is the most widely used jet fuel for large passenger planes at present, aromatic hydrocarbon accounts for 8-25% of aviation kerosene, and the carbon number distribution of aromatic hydrocarbon molecules is concentrated in C8-C15.
Low-carbon aromatic hydrocarbon byproducts are generated in the petroleum refining and steam cracking processes, lignin in biomass can also generate low-carbon aromatic hydrocarbon after deep pyrolysis, and the low-carbon aromatic hydrocarbon is converted into aromatic hydrocarbon components meeting the aviation kerosene requirement through C-C coupling, so that people gradually pay attention in recent years. The technology can provide a reutilization way of the petrochemical industry by-products, and reduce environmental pollution. Meanwhile, the lignin has huge content in plants, the lignin regeneration speed is high every year all over the world, and the aviation fuel can be controllably synthesized by utilizing the product obtained after the deep pyrolysis of the lignin, so that the energy guarantee can be provided for the development of aviation industry, and the carbon emission in the process of using the fuel can be reduced.
However, in the petrochemical industry, the alkylation reaction of low-carbon aromatic hydrocarbon is mainly used to synthesize single products, such as toluene, p-xylene, ethylbenzene, etc., and the polyalkylation and transalkylation of low-carbon aromatic hydrocarbon are rarely used to synthesize the mixture of macromolecular aromatic hydrocarbon.
Disclosure of Invention
In view of the above, the invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons, so as to overcome the technical defects in the prior art.
In a first aspect, the invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a gallium-loaded ZSM-5 molecular sieve catalyst.
Optionally, in the method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons, the preparation method of the modified ZSM-5 molecular sieve catalyst is as follows:
dissolving aluminum isopropoxide in desalted water, and uniformly stirring to obtain a first solution;
mixing a tetrapropyl ammonium hydroxide solution and a tetraethyl orthosilicate solution, and uniformly stirring to obtain a second solution;
and dropwise adding the first solution into the second solution, uniformly stirring, placing in a reaction kettle for hydrothermal reaction, and separating, washing and drying after the reaction is finished to obtain the modified ZSM-5 molecular sieve catalyst.
Optionally, in the method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons, the preparation method of the gallium-loaded ZSM-5 molecular sieve catalyst is as follows:
mixing the modified ZSM-5 molecular sieve catalyst with gallium salt, dispersing the mixture into water, heating the mixture, and evaporating the mixture to dryness;
and calcining the evaporated substances, and reducing in a hydrogen atmosphere to obtain the gallium-loaded ZSM-5 molecular sieve catalyst.
Optionally, in the method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons, the gas-phase heterogeneous reaction conditions are as follows: the molar ratio of the low-carbon aromatic hydrocarbon to the low-carbon olefin is 0.5: 1-31, the temperature is 200-400 ℃, the pressure is 1-4 MPa, and the space velocity is 0.2-2 h-1。
Optionally, in the method for synthesizing the aromatic hydrocarbon component in the aviation kerosene by using the low-carbon aromatic hydrocarbons, the low-carbon aromatic hydrocarbons include aromatic hydrocarbons of C6-C7, and the low-carbon olefins include olefins of C2-C3.
Optionally, in the method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons, the particle size of the modified ZSM-5 molecular sieve catalyst is 500-1000 nm.
Optionally, in the method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, the first solution is dropwise added into the second solution, the mixture is uniformly stirred and then placed in a reaction kettle for hydrothermal reaction, and after the reaction is finished, the mixture is separated, washed and dried and then calcined at 520-550 ℃ for 5-10 hours to obtain the modified ZSM-5 molecular sieve catalyst; wherein the temperature of the hydrothermal reaction is 150-180 ℃ and the time is 60-80 h.
Optionally, the method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon further comprises, before passing the low-carbon aromatic hydrocarbon and the low-carbon olefin through a fixed bed reactor filled with a molecular sieve catalyst: and introducing nitrogen into the fixed bed reactor filled with the molecular sieve catalyst until the pressure is 1-1.2 MPa, and heating to 320-360 ℃.
Optionally, in the method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, the modified ZSM-5 molecular sieve catalyst is mixed with gallium salt and then dispersed into water, heated to 50-60 ℃, evaporated to dryness and then dried at 100-110 ℃; and calcining the dried substance at 530-550 ℃ for 4-8 h, and reducing at 480-510 ℃ in a hydrogen atmosphere to obtain the gallium-loaded ZSM-5 molecular sieve catalyst.
Optionally, in the method for synthesizing the aromatic hydrocarbon component in the aviation kerosene by using the low-carbon aromatic hydrocarbon, the molar ratio of tetraethyl orthosilicate, aluminum isopropoxide and tetrapropylammonium hydroxide is 1 (0.002-0.3) to (0.1-1).
Compared with the prior art, the method for synthesizing the aromatic hydrocarbon component in the aviation kerosene by using the low-carbon aromatic hydrocarbon has the following beneficial effects:
(1) the method for synthesizing the aromatic hydrocarbon component in the aviation kerosene by using the low-carbon aromatic hydrocarbon uses the solid molecular sieve catalyst to carry out gas-phase heterogeneous reaction in the fixed bed, so that reactants and products can be continuously discharged, and the problem of difficult separation does not exist. By using the method, the obtained alkylation product is mainly C8-C15 aromatic hydrocarbon meeting the requirements of aviation kerosene, reactants continuously pass through the catalyst under a proper reaction condition, and the product is condensed by a cold trap and then discharged, so that the effective separation of the product and the catalyst is realized. Under the best state, the selectivity of C8-C15 aromatic hydrocarbon in the product reaches more than 90 percent, the conversion rate of an alkylating agent olefin mixture is about 100 percent, gas phase byproducts account for little gas-liquid total mass and are lower than 2 weight percent, and the selectivity of C8-C15 aromatic hydrocarbon in the alkylation product can reach more than 95 percent;
(2) the method for synthesizing the aromatic hydrocarbon component in the aviation kerosene by using the low-carbon aromatic hydrocarbon adopts the continuous gas-phase heterogeneous reaction, does not have the operation of separating the catalyst from the liquid product, has simple operation in the synthesis process of the aviation kerosene aromatic hydrocarbon component, is easy to control, and can almost completely convert the low-carbon olefin serving as the alkylating agent with high price; the catalyst adopted by the method has simple preparation process, low cost and good stability, can be produced, transported and stored in large scale, can be regenerated in situ when used, and avoids complicated operation; the method has good capability of regulating and controlling the low-carbon aromatic hydrocarbon polyalkylation reaction, and has industrial application prospect.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
It should be noted that in the embodiments of the present application, the low-carbon aromatic hydrocarbon is C6 or C7 type low-carbon aromatic hydrocarbon, and specifically, the embodiments of the present application use a model compound benzene; the low-carbon olefin is C2 and C3 low-carbon olefins, can be a pure substance or a mixture of multiple substances, can be derived from petrochemical industry products or biomass pyrolysis products, and specifically, in the embodiment of the application, the low-carbon olefin is a mixed gas of 15% by volume of ethylene, 10% by volume of propylene and 75% by volume of nitrogen, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
dissolving aluminum isopropoxide in desalted water, performing ultrasonic dispersion for 0.5h, and then stirring in a water bath at 85 ℃ for 3h to obtain a first solution; aluminum isopropoxide provides the source of aluminum;
mixing a tetrapropyl ammonium hydroxide solution and a tetraethyl orthosilicate solution, and stirring the mixture in a water bath at the temperature of 35 ℃ for 3 hours to obtain a second solution; wherein tetrapropylammonium hydroxide is used as a template agent, and tetraethoxysilane is used as a silicon source;
and (3) dropwise adding the first solution into the second solution, stirring the solution in a water bath at the temperature of 35 ℃ for 2 hours, keeping the solution at the temperature of 80 ℃ for 2 hours, removing ethanol generated by hydrolysis, adding water to the original liquid level, uniformly stirring and mixing the solution at the temperature of 35 ℃, adding the solution into a crystallization reaction kettle with a polytetrafluoroethylene lining, heating the solution at the temperature of 170 ℃ for 72 hours, separating the crystallized mixture, washing the solution to be neutral, drying the solution at the temperature of 100 ℃ overnight, and roasting the solution at the temperature of 540 ℃ for 6 hours to remove a template agent to obtain the modified ZSM-5 molecular sieve catalyst.
Specifically, the molar ratio of tetraethyl orthosilicate, aluminum isopropoxide and tetrapropylammonium hydroxide is 1:0.066: 0.27.
Specifically, 1g of modified ZSM-5 molecular sieve catalyst was packed in a fixed bedIntroducing nitrogen to the pressure of 1.0MPa, raising the temperature to 350 ℃ in the protection of nitrogen flow, then introducing benzene and low-carbon olefin (namely mixed gas of ethylene, propylene and nitrogen), and simultaneously adjusting the benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, the space velocity is 0.47h-1。
The molecular sieve in the embodiment of the application is a common solid catalyst used in alkylation reaction, has the characteristics of convenient synthesis, transportation and storage, no harm to reaction equipment and easy industrial amplification, and is favored by researchers. In the process of preparing aromatic hydrocarbon, the solid molecular sieve catalyst is used for carrying out gas-phase heterogeneous reaction in a fixed bed, so that reactants and products can be continuously discharged, and the problem of difficult separation is avoided. By using the method, the obtained alkylation product is mainly C8-C15 aromatic hydrocarbon meeting the requirements of aviation kerosene, reactants continuously pass through the catalyst under a proper reaction condition, and the product is condensed by a cold trap and then discharged, so that the effective separation of the product and the catalyst is realized. Under the best state, the selectivity of C8-C15 aromatic hydrocarbon in the product reaches more than 90 percent, the conversion rate of an alkylating agent olefin mixture is about 100 percent, gas phase byproducts account for less than 2wt percent of the total mass of gas and liquid, the selectivity of C8-C15 aromatic hydrocarbon in the alkylated product can reach more than 95 percent, the modified ZSM-5 molecular sieve catalyst can be reused after coking and deactivation and in-situ regeneration for several hours under the oxygen atmosphere at 550 ℃, and the gallium-loaded ZSM-5 molecular sieve catalyst can be reused after in-situ hydrogen reduction after being roasted according to the same procedure to remove coking substances.
The embodiment of the application adopts continuous gas-phase heterogeneous reaction, the operation of separating the catalyst from the liquid product does not exist, the operation of the synthetic process of the aviation kerosene aromatic hydrocarbon component is simple, the alkylating agent low-carbon olefin which is easy to control and high in price can be almost completely converted; the catalyst adopted by the method has simple preparation process, low cost and good stability, can be produced, transported and stored in large scale, can be regenerated in situ when used, and avoids complicated operation; the method has good capability of regulating and controlling the low-carbon aromatic hydrocarbon polyalkylation reaction, and has industrial application prospect.
Example 2
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
In the embodiment of the present application, the low-carbon aromatic hydrocarbon is benzene which is a model compound; the low-carbon olefin is a mixed gas of 15% of ethylene, 10% of propylene and 75% of nitrogen in volume fraction, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
dissolving aluminum isopropoxide in desalted water, performing ultrasonic dispersion for 0.5h, and then stirring in a water bath at 85 ℃ for 3h to obtain a first solution; aluminum isopropoxide provides the source of aluminum;
mixing a tetrapropyl ammonium hydroxide solution and a tetraethyl orthosilicate solution, and stirring the mixture in a water bath at the temperature of 35 ℃ for 3 hours to obtain a second solution; wherein tetrapropylammonium hydroxide is used as a template agent, and tetraethoxysilane is used as a silicon source;
and (3) dropwise adding the first solution into the second solution, stirring the solution in a water bath at the temperature of 35 ℃ for 2 hours, keeping the solution at the temperature of 80 ℃ for 2 hours, removing ethanol generated by hydrolysis, adding water to the original liquid level, uniformly stirring and mixing the solution at the temperature of 35 ℃, adding the solution into a crystallization reaction kettle with a polytetrafluoroethylene lining, heating the solution at the temperature of 170 ℃ for 72 hours, separating the crystallized mixture, washing the solution to be neutral, drying the solution at the temperature of 100 ℃ overnight, and roasting the solution at the temperature of 540 ℃ for 6 hours to remove a template agent to obtain the modified ZSM-5 molecular sieve catalyst.
Specifically, the molar ratio of tetraethyl orthosilicate, aluminum isopropoxide and tetrapropylammonium hydroxide is 1: 0.02: 0.27.
specifically, 1g of modified ZSM-5 molecular sieve catalyst was loaded into a fixed bed, nitrogen was introduced to a pressure of 1.0MPa, the temperature was raised to 350 ℃ under the protection of nitrogen flow, and then benzene and low-carbon olefins (i.e., ethylene and propylene) were introducedAnd nitrogen), while adjusting benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, the space velocity is 0.47h-1。
Example 3
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
In the embodiment of the present application, the low-carbon aromatic hydrocarbon is benzene which is a model compound; the low-carbon olefin is a mixed gas of 15% of ethylene, 10% of propylene and 75% of nitrogen in volume fraction, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
dissolving aluminum isopropoxide in desalted water, performing ultrasonic dispersion for 0.5h, and then stirring in a water bath at 85 ℃ for 3h to obtain a first solution; aluminum isopropoxide provides the source of aluminum;
mixing a tetrapropyl ammonium hydroxide solution and a tetraethyl orthosilicate solution, and stirring the mixture in a water bath at the temperature of 35 ℃ for 3 hours to obtain a second solution; wherein tetrapropylammonium hydroxide is used as a template agent, and tetraethoxysilane is used as a silicon source;
and (2) dropwise adding the first solution into the second solution, stirring for 2 hours in a water bath at 35 ℃, keeping the temperature at 80 ℃ for 1.5 hours, removing ethanol generated by hydrolysis, adding water to the original liquid level, stirring and mixing uniformly at 35 ℃, adding the mixture into a crystallization reaction kettle with a polytetrafluoroethylene lining, heating for 72 hours at 170 ℃, separating the crystallized mixture, washing to be neutral, drying at 100 ℃ overnight, and roasting at 540 ℃ for 6 hours to remove a template agent to obtain the modified ZSM-5 molecular sieve catalyst.
Specifically, the mole ratio of tetraethyl orthosilicate, aluminum isopropoxide and tetrapropylammonium hydroxide is 1: 0.014: 0.27.
specifically, 1g of modified ZSM-5 molecular sieve catalyst was loaded into a fixed bed, nitrogen was introduced to a pressure of 1.0MPa, and the pressure was raised to 350 ℃ under the protection of nitrogen flow, and then benzene and lower olefins (i.e., a mixed gas of ethylene, propylene, and nitrogen) were introduced while adjusting the benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, the space velocity is 0.47h-1。
Example 4
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
In the embodiment of the present application, the low-carbon aromatic hydrocarbon is benzene which is a model compound; the low-carbon olefin is a mixed gas of 15% of ethylene, 10% of propylene and 75% of nitrogen in volume fraction, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
dissolving aluminum isopropoxide in desalted water, performing ultrasonic dispersion for 0.5h, and then stirring in a water bath at 85 ℃ for 3h to obtain a first solution; aluminum isopropoxide provides the source of aluminum;
mixing a tetrapropyl ammonium hydroxide solution and a tetraethyl orthosilicate solution, and stirring the mixture in a water bath at the temperature of 35 ℃ for 3 hours to obtain a second solution; wherein tetrapropylammonium hydroxide is used as a template agent, and tetraethoxysilane is used as a silicon source;
and (3) dropwise adding the first solution into the second solution, stirring for 2 hours in a water bath at 35 ℃, keeping the temperature for 1 hour at 80 ℃, removing ethanol generated by hydrolysis, adding water to the original liquid level, uniformly stirring and mixing at 35 ℃, adding into a crystallization reaction kettle with a polytetrafluoroethylene lining, heating for 72 hours at 170 ℃, separating the crystallized mixture, washing to be neutral, drying at 100 ℃ overnight, and roasting at 540 ℃ for 6 hours to remove the template agent to obtain the modified ZSM-5 molecular sieve catalyst.
Specifically, the mole ratio of tetraethyl orthosilicate, aluminum isopropoxide and tetrapropylammonium hydroxide is 1: 0.006: 0.27.
specifically, 1g of modified ZSM-5 molecular sieve catalyst was loaded into a fixed bed, nitrogen was introduced to a pressure of 1.0MPa, and the pressure was raised to 350 ℃ under the protection of nitrogen flow, and then benzene and lower olefins (i.e., a mixed gas of ethylene, propylene, and nitrogen) were introduced while adjusting the benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, the space velocity is 0.47h-1。
Example 5
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
In the embodiment of the present application, the low-carbon aromatic hydrocarbon is benzene which is a model compound; the low-carbon olefin is a mixed gas of 15% of ethylene, 10% of propylene and 75% of nitrogen in volume fraction, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
dissolving aluminum isopropoxide in desalted water, performing ultrasonic dispersion for 0.5h, and then stirring in a water bath at 85 ℃ for 3h to obtain a first solution; aluminum isopropoxide provides the source of aluminum;
mixing a tetrapropyl ammonium hydroxide solution and a tetraethyl orthosilicate solution, and stirring the mixture in a water bath at the temperature of 35 ℃ for 3 hours to obtain a second solution; wherein tetrapropylammonium hydroxide is used as a template agent, and tetraethoxysilane is used as a silicon source;
and (2) dropwise adding the first solution into the second solution, stirring for 2 hours in a water bath at 35 ℃, keeping the temperature at 80 ℃ for 0.5 hour, removing ethanol generated by hydrolysis, adding water to the original liquid level, stirring and mixing uniformly at 35 ℃, adding into a crystallization reaction kettle with a polytetrafluoroethylene lining, heating at 170 ℃ for 72 hours, separating the crystallized mixture, washing to be neutral, drying at 100 ℃ overnight, and roasting at 540 ℃ for 6 hours to remove a template agent to obtain the modified ZSM-5 molecular sieve catalyst.
Specifically, the mole ratio of tetraethyl orthosilicate, aluminum isopropoxide and tetrapropylammonium hydroxide is 1: 0.004: 0.27.
specifically, 1g of modified ZSM-5 molecular sieve catalyst was loaded into a fixed bed, nitrogen was introduced to a pressure of 1.0MPa, and the pressure was raised to 350 ℃ under the protection of nitrogen flow, and then benzene and lower olefins (i.e., a mixed gas of ethylene, propylene, and nitrogen) were introduced while adjusting the benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, the space velocity is 0.47h-1。
Example 6
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
In the embodiment of the present application, the low-carbon aromatic hydrocarbon is benzene which is a model compound; the low-carbon olefin is a mixed gas of 15% of ethylene, 10% of propylene and 75% of nitrogen in volume fraction, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
dissolving aluminum isopropoxide in desalted water, performing ultrasonic dispersion for 0.5h, and then stirring in a water bath at 85 ℃ for 3h to obtain a first solution; aluminum isopropoxide provides the source of aluminum;
mixing a tetrapropyl ammonium hydroxide solution and a tetraethyl orthosilicate solution, and stirring the mixture in a water bath at the temperature of 35 ℃ for 3 hours to obtain a second solution; wherein tetrapropylammonium hydroxide is used as a template agent, and tetraethoxysilane is used as a silicon source;
and (3) dropwise adding the first solution into the second solution, stirring the solution in a water bath at the temperature of 35 ℃ for 2 hours, keeping the solution at the temperature of 80 ℃ for 2 hours, removing ethanol generated by hydrolysis, adding water to the original liquid level, uniformly stirring and mixing the solution at the temperature of 35 ℃, adding the solution into a crystallization reaction kettle with a polytetrafluoroethylene lining, heating the solution at the temperature of 170 ℃ for 72 hours, separating the crystallized mixture, washing the solution to be neutral, drying the solution at the temperature of 100 ℃ overnight, and roasting the solution at the temperature of 540 ℃ for 6 hours to remove a template agent to obtain the modified ZSM-5 molecular sieve catalyst. The particle size of the modified ZSM-5 molecular sieve catalyst is 150 nm.
Specifically, the mole ratio of tetraethyl orthosilicate, aluminum isopropoxide and tetrapropylammonium hydroxide is 1:0.066: 0.27.
specifically, 1g of modified ZSM-5 molecular sieve catalyst was loaded into a fixed bed, nitrogen was introduced to a pressure of 1.0MPa, and the pressure was raised to 350 ℃ under the protection of nitrogen flow, and then benzene and lower olefins (i.e., a mixed gas of ethylene, propylene, and nitrogen) were introduced while adjusting the benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, the space velocity is 0.47h-1。
Example 7
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
In the embodiment of the present application, the low-carbon aromatic hydrocarbon is benzene which is a model compound; the low-carbon olefin is a mixed gas of 15% of ethylene, 10% of propylene and 75% of nitrogen in volume fraction, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
dissolving aluminum isopropoxide in desalted water, performing ultrasonic dispersion for 0.5h, and then stirring in a water bath at 85 ℃ for 3h to obtain a first solution; aluminum isopropoxide provides the source of aluminum;
mixing a tetrapropyl ammonium hydroxide solution and a tetraethyl orthosilicate solution, and stirring the mixture in a water bath at the temperature of 35 ℃ for 3 hours to obtain a second solution; wherein tetrapropylammonium hydroxide is used as a template agent, and tetraethoxysilane is used as a silicon source;
and (2) dropwise adding the first solution into the second solution, stirring the solution in a water bath at the temperature of 35 ℃ for 1 hour, keeping the solution at the temperature of 80 ℃ for 0.5 hour, removing ethanol generated by hydrolysis, adding water to the original liquid level, uniformly stirring and mixing the solution at the temperature of 35 ℃, adding the solution into a crystallization reaction kettle with a polytetrafluoroethylene lining, heating the reaction kettle at the temperature of 170 ℃ for 72 hours, separating the crystallized mixture, washing the mixture to be neutral, drying the mixture at the temperature of 100 ℃ overnight, and roasting the mixture at the temperature of 540 ℃ for 6 hours to remove a template agent to obtain the modified ZSM-5 molecular sieve catalyst. The particle size of the modified ZSM-5 molecular sieve catalyst is 210 nm.
Specifically, the mole ratio of tetraethyl orthosilicate, aluminum isopropoxide and tetrapropylammonium hydroxide is 1:0.066: 0.20.
specifically, 1g of modified ZSM-5 molecular sieve catalyst was loaded into a fixed bed, nitrogen was introduced to a pressure of 1.0MPa, and the pressure was raised to 350 ℃ under the protection of nitrogen flow, and then benzene and lower olefins (i.e., a mixed gas of ethylene, propylene, and nitrogen) were introduced while adjusting the benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, the space velocity is 0.47h-1。
Example 8
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
In the embodiment of the present application, the low-carbon aromatic hydrocarbon is benzene which is a model compound; the low-carbon olefin is a mixed gas of 15% of ethylene, 10% of propylene and 75% of nitrogen in volume fraction, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
dissolving aluminum isopropoxide in desalted water, performing ultrasonic dispersion for 0.5h, and then stirring in a water bath at 85 ℃ for 3h to obtain a first solution; aluminum isopropoxide provides the source of aluminum;
mixing a tetrapropyl ammonium hydroxide solution and a tetraethyl orthosilicate solution, and stirring the mixture in a water bath at the temperature of 35 ℃ for 3 hours to obtain a second solution; wherein tetrapropylammonium hydroxide is used as a template agent, and tetraethoxysilane is used as a silicon source;
and (3) dropwise adding the first solution into the second solution, stirring for 0.5 hour in a water bath at 35 ℃, then keeping for 0.5 hour at 80 ℃, removing ethanol generated by hydrolysis, then adding water to the original liquid level, stirring and mixing uniformly at 35 ℃, then adding into a crystallization reaction kettle with a polytetrafluoroethylene lining, heating for 72 hours at 170 ℃, separating the crystallized mixture, washing to be neutral, drying overnight at 100 ℃, and roasting for 6 hours at 540 ℃ to remove a template agent, thus obtaining the modified ZSM-5 molecular sieve catalyst. The particle size of the modified ZSM-5 molecular sieve catalyst is 310 nm.
Specifically, the mole ratio of tetraethyl orthosilicate, aluminum isopropoxide and tetrapropylammonium hydroxide is 1:0.066: 0.17.
specifically, 1g of modified ZSM-5 molecular sieve catalyst was loaded into a fixed bed, nitrogen was introduced to a pressure of 1.0MPa, and the pressure was raised to 350 ℃ under the protection of nitrogen flow, and then benzene and lower olefins (i.e., a mixed gas of ethylene, propylene, and nitrogen) were introduced while adjusting the benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, the space velocity is 0.47h-1。
Example 9
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
In the embodiment of the present application, the low-carbon aromatic hydrocarbon is benzene which is a model compound; the low-carbon olefin is a mixed gas of 15% of ethylene, 10% of propylene and 75% of nitrogen in volume fraction, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a gallium-loaded ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
mixing the modified ZSM-5 molecular sieve catalyst prepared in the example 1 with gallium nitrate to obtain a mixture; wherein the mass of the gallium element accounts for 1% of the mass of the mixture;
and (3) mixing the mixture according to the solid-to-liquid ratio of 1 g: dispersing 50mL of the catalyst into deionized water, rotationally evaporating the mixture in a water bath kettle at 50 ℃ to dryness, drying the mixture at 100 ℃ overnight, calcining the mixture in a muffle furnace at 540 ℃ for 5 hours, and reducing the calcined mixture at 500 ℃ for 4 hours in a hydrogen atmosphere to obtain the gallium-loaded ZSM-5 molecular sieve catalyst.
Specifically, 1.0g of a gallium-loaded ZSM-5 molecular sieve catalyst is weighed and filled in a fixed bed, nitrogen is introduced until the pressure is 2.0MPa, the temperature is raised to 250 ℃ under the protection of nitrogen flow, then benzene and low-carbon olefin (namely, mixed gas of ethylene, propylene and nitrogen) are introduced at the same time, and the benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, space velocity of 1.18h-1。
Example 10
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
In the embodiment of the present application, the low-carbon aromatic hydrocarbon is benzene which is a model compound; the low-carbon olefin is a mixed gas of 15% of ethylene, 10% of propylene and 75% of nitrogen in volume fraction, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a gallium-loaded ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
mixing the modified ZSM-5 molecular sieve catalyst prepared in the example 1 with gallium nitrate to obtain a mixture; wherein the mass of the gallium element accounts for 2 percent of the mass of the mixture;
and (3) mixing the mixture according to the solid-to-liquid ratio of 1 g: dispersing 50mL of the catalyst into deionized water, rotationally evaporating the mixture in a water bath kettle at 50 ℃ to dryness, drying the mixture at 100 ℃ overnight, calcining the mixture in a muffle furnace at 540 ℃ for 5 hours, and reducing the calcined mixture at 500 ℃ for 4 hours in a hydrogen atmosphere to obtain the gallium-loaded ZSM-5 molecular sieve catalyst.
Specifically, 1.0g of a gallium-loaded ZSM-5 molecular sieve catalyst is weighed and filled in a fixed bed, nitrogen is introduced until the pressure is 2.0MPa, the temperature is raised to 250 ℃ under the protection of nitrogen flow, then benzene and low-carbon olefin (namely, mixed gas of ethylene, propylene and nitrogen) are introduced at the same time, and the benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, space velocity of 1.18h-1。
Example 11
The invention provides a method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon, which comprises the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein, the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a ZSM-5 molecular sieve catalyst loaded with gallium.
In the embodiment of the present application, the low-carbon aromatic hydrocarbon is benzene which is a model compound; the low-carbon olefin is a mixed gas of 15% of ethylene, 10% of propylene and 75% of nitrogen in volume fraction, wherein the low-carbon olefin is used as an alkylating agent in the reaction.
In the embodiment of the application, the adopted molecular sieve catalyst is a gallium-loaded ZSM-5 molecular sieve catalyst, and the preparation method comprises the following steps:
mixing the modified ZSM-5 molecular sieve catalyst prepared in the example 1 with gallium nitrate to obtain a mixture; wherein the mass of the gallium element accounts for 3% of the mass of the mixture;
and (3) mixing the mixture according to the solid-to-liquid ratio of 1 g: dispersing 50mL of the catalyst into deionized water, rotationally evaporating the mixture in a water bath kettle at 50 ℃ to dryness, drying the mixture at 100 ℃ overnight, calcining the mixture in a muffle furnace at 540 ℃ for 5 hours, and reducing the calcined mixture at 500 ℃ for 4 hours in a hydrogen atmosphere to obtain the gallium-loaded ZSM-5 molecular sieve catalyst.
Specifically, 1.0g of a gallium-loaded ZSM-5 molecular sieve catalyst is weighed and filled in a fixed bed, nitrogen is introduced until the pressure is 2.0MPa, the temperature is raised to 250 ℃ under the protection of nitrogen flow, then benzene and low-carbon olefin (namely, mixed gas of ethylene, propylene and nitrogen) are introduced at the same time, and the benzene: ethylene: propylene molar ratio 1.0: 1.0: 0.7, space velocity of 1.18h-1。
The aromatic hydrocarbon components in the aviation kerosene were synthesized from the low-carbon aromatic hydrocarbons according to the methods of examples 1 to 11, and the conversion rates (C-mol%) of propylene, ethylene and benzene in the different examples were measured, wherein the conversion rate is the ratio of the number of moles of carbon consumed for a certain substance to the number of moles of carbon charged for the substance, and the results are shown in table 1 below.
TABLE 1-conversion of propylene, ethylene and benzene (C-mol%) in the different examples
Figure BDA0002711937430000151
Figure BDA0002711937430000161
As is apparent from Table 1, in examples 1 to 5, the results of the evaluation of the alkylation reaction performance at different Si/Al ratios are shown, and in examples 1 to 5, the Si/Al ratio is increased in the order of increasing the Si/Al ratio, and the higher the Si/Al ratio is when the alkylation reaction is carried out with catalysts having different Si/Al ratios, the weaker the acidity of the catalyst is (the acidity of the silicoaluminophosphate molecular sieve is derived from [ AlO ]4]The structural unit is negatively charged, but the charge is not limited to [ AlO ]4]The structural units are dispersed through the skeleton transmission action to generate long-range interaction (long-range interaction), in short, the silicon-aluminum ratio is improved, the density of acid centers is reduced, the density of electron clouds on a single acid center is also reduced, and the acidity is correspondingly reducedWeaker), the more difficult the reaction proceeds, and the conversion of benzene decreases with increasing silica to alumina ratio. However, under all conditions of the silicon-aluminum ratio, the conversion rate of the olefin is almost the same and is always kept at about 99C-mol%, and the possible reasons are that the electron cloud density of the benzene ring of the aromatic hydrocarbon with the branched chain is high, the carbocation is more easily attracted to generate the alkylation reaction, and the olefin participates in the multi-alkylation reaction. Examples 6-8 are the results of the evaluation of the alkylation reaction performance of catalysts with different crystal grain sizes, and the crystal grains of the catalysts of examples 6-8 are sequentially increased, and it can be seen that the conversion rate of benzene is also sequentially increased along with the gradual increase of the crystal grains of the catalysts. The particle size has little influence on the conversion rate of the olefin, and the conversion rate of the olefin is kept to be about 99C-mol% under all particle size conditions. Examples 9-11 show the effect of the Ga modified catalyst on the alkylation performance, the conversion of olefins was about 100% with different Ga loading catalysts, and the change was small, which indicates that a small amount of Ga loading did not affect the conversion of olefins, because the requirement for acidity was not high when the high carbon aromatics were alkylated with olefins. Along with the increase of Ga loading, the conversion rate of benzene is increased from 38.27C-mol% to 41.75C-mol% and then is reduced to 34.54C-mol%, and the rule that the conversion rate is increased and then reduced is presented, which shows that the capacity of the catalyst for converting benzene can be obviously improved by Ga with certain loading. The direct reason is that more benzene participates in the reaction, the polyalkylation reaction and the olefin oligomerization reaction are inhibited, and the deeper reason is that the acidity of the Ga modified ZSM-5 molecular sieve is changed to a certain extent. Meanwhile, when 2 wt.% Ga catalyst was used (example 10), the highest benzene conversion was due to the increased probability of contact due to the small amount of metal ions remaining in the pores in the metal-supported catalyst migrating out of the pores and the active centers migrating out of the pores at the proper temperature.
The selectivity of the products of the different examples was tested by using the aromatic hydrocarbon component of the low carbon aromatic hydrocarbon synthesized aviation kerosene according to the methods of the above examples 1 to 11, wherein the selectivity is expressed by carbon mole percentage (C-mol), and the carbon mole percentage is the ratio of the carbon mole number of a certain product to the carbon mole number of all the products, and the results are shown in table 2.
TABLE 2 product Selectivity of different examples
Figure BDA0002711937430000171
Figure BDA0002711937430000181
As can be seen from Table 2, the overall selectivity of C1-C5 in examples 1-5 gradually increased with increasing Si/Al ratio because side reactions such as olefin oligomerization and cracking of high carbon number aromatic hydrocarbons occurred with decreasing acid sites. The selectivity of C8-C15 total aromatics is not greatly changed along with the ratio of silicon to aluminum. Examples 6-8 are reaction results with catalysts having different particle sizes, the selectivity of the target products C8-C15 is about 56C-mol%, while the selectivity of C8 is 35C-mol%, 37C-mol% and 40C-mol%, respectively, and the selectivity of C10 is 5C-mol%, 7C-mol% and 10C-mol%, respectively, which indicates that the smaller the particle size, the smaller the proportion of the low carbon aromatic hydrocarbon product. Meanwhile, the sum of the selectivities of C11 to C13 gradually decreases from small to large, indicating that smaller particle sizes favor the shift of the carbon number of the aromatic hydrocarbon product toward higher carbon numbers. Examples 9-11 are the results of evaluations of different Ga loadings and although the selectivity of the target product does not change much, the product distribution has a clear law: the smaller and smaller C8 fraction and the larger and larger C9 fraction with increasing Ga loading indicates that the acid strength required for the reaction of benzene with propylene is not as great as the acid strength required for the reaction of benzene with ethylene.
The aromatic hydrocarbon components in the aviation kerosene are synthesized by using the low-carbon aromatic hydrocarbons according to the methods of the above examples 1 to 11, and the yields (C-mol%) of the C8-C15 aromatic hydrocarbons in different examples are respectively tested, wherein the yields of the C8-C15 aromatic hydrocarbons are ratios of the total carbon moles of all C8-C15 aromatic hydrocarbon products to the carbon moles of the input raw materials, and the results are shown in table 3.
TABLE 3 yield (C-mol%) of C8-C15 aromatics for different examples
Examples Yield (C-mol%) of C8-C15 aromatic hydrocarbon
Example 1 34.3
Example 2 32.7
Example 3 31.54
Example 4 30.74
Example 5 28.62
Example 6 34.3
Example 7 30.39
Example 8 30.44
Example 9 52.66
Example 10 55.44
Example 11 46.39
As can be seen from Table 3, the Si/Al ratio of the alkylation experiments (examples 1-5) showed the highest yield of the target product compared to the smallest catalyst (example 1), which is caused by the higher acid content of the low Si/Al ratio catalyst, and the higher benzene conversion rate. Examples 6-8 are C8-C15 aromatics yields for catalysts with different particle sizes, the smaller the particle size of the catalyst, the higher the yield of the desired product, since the alkylation product is not more restricted when flowing inside the molecular sieve particles after the catalyst particles have been reduced, and can flow rapidly into and out of the interior of the catalyst particles, and thus the likelihood of cracking is reduced. Meanwhile, the external surface area is increased due to the fact that catalyst particles are reduced, acid sites of the catalyst can be exposed, and therefore reactants can be more easily contacted with the acid sites, and the alkylation reaction can be smoothly carried out. In addition, the small crystal grains are stacked to form intercrystalline mesopores, so that space is provided for the increase of the carbon chain of the alkylation product, and the yield of the target product aromatic hydrocarbon can be improved. Examples 9-11 are comparisons of the performance of catalysts with different Ga loadings, and as the Ga loading increases, the yield of the target aromatic hydrocarbon increases first and then decreases, the gallium-loaded ZSM-5 molecular sieve catalyst in example 10 shows the highest yield of C8-C15 aromatic hydrocarbons, which is 55.44C-mol%, indicating that a moderate decrease in acidity is beneficial to the alkylation reaction and effectively inhibits side reactions such as olefin oligomerization and cracking, while an excessive decrease in catalyst acidity is not beneficial to the alkylation reaction, and thus example 10 has the pore size and acidity most suitable for benzene alkylation to prepare the key components of aviation kerosene aromatic hydrocarbon.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbon is characterized by comprising the following steps:
carrying out gas-phase heterogeneous reaction on low-carbon aromatic hydrocarbon and low-carbon olefin in a fixed bed reactor filled with a molecular sieve catalyst;
wherein the molecular sieve catalyst is a modified ZSM-5 molecular sieve catalyst or a gallium-loaded ZSM-5 molecular sieve catalyst.
2. The method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons according to claim 1, wherein the preparation method of said modified ZSM-5 molecular sieve catalyst is as follows:
dissolving aluminum isopropoxide in desalted water, and uniformly stirring to obtain a first solution;
mixing a tetrapropyl ammonium hydroxide solution and a tetraethyl orthosilicate solution, and uniformly stirring to obtain a second solution;
and dropwise adding the first solution into the second solution, uniformly stirring, placing in a reaction kettle for hydrothermal reaction, and separating, washing and drying after the reaction is finished to obtain the modified ZSM-5 molecular sieve catalyst.
3. The method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons according to claim 2, wherein the preparation method of said gallium-loaded ZSM-5 molecular sieve catalyst comprises:
mixing the modified ZSM-5 molecular sieve catalyst with gallium salt, dispersing the mixture into water, heating the mixture, and evaporating the mixture to dryness;
and calcining the evaporated substances, and reducing in a hydrogen atmosphere to obtain the gallium-loaded ZSM-5 molecular sieve catalyst.
4. The method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons according to claim 1, characterized in that the gas-phase heterogeneous reaction conditions are as follows: the molar ratio of the low-carbon aromatic hydrocarbon to the low-carbon olefin is 0.5: 1-3: 1, the temperature is 200-400 ℃, the pressure is 1-4 MPa, and the space velocity is 0.2-2 h-1。
5. The method for synthesizing aromatic hydrocarbon components in aviation kerosene according to claim 1, wherein the low-carbon aromatic hydrocarbons include aromatic hydrocarbons of C6-C7, and the low-carbon olefins include olefins of C2-C3.
6. The method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons according to claim 1, wherein the particle size of the modified ZSM-5 molecular sieve catalyst is 50-1000 nm.
7. The method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons as claimed in claim 2, wherein the first solution is dripped into the second solution, the mixture is stirred uniformly and then placed in a reaction kettle for hydrothermal reaction, and after the reaction is finished, the mixture is separated, washed and dried and then calcined at 520-550 ℃ for 5-10 hours to obtain the modified ZSM-5 molecular sieve catalyst; wherein the temperature of the hydrothermal reaction is 150-180 ℃ and the time is 60-80 h.
8. The method for synthesizing aromatic hydrocarbon components in aviation kerosene using low-carbon aromatic hydrocarbons according to claim 1, wherein before passing the low-carbon aromatic hydrocarbons and the low-carbon olefins through the fixed bed reactor filled with the molecular sieve catalyst, the method further comprises: and introducing nitrogen into the fixed bed reactor filled with the molecular sieve catalyst until the pressure is 1-1.2 MPa, and heating to 320-360 ℃.
9. The method for synthesizing aromatic hydrocarbon components in aviation kerosene by using low-carbon aromatic hydrocarbons as claimed in claim 3, wherein the modified ZSM-5 molecular sieve catalyst is dispersed in water after being mixed with gallium salt, heated to 50-60 ℃, evaporated to dryness and then dried at 100-110 ℃; and calcining the dried substance at 530-550 ℃ for 4-8 h, and reducing at 480-510 ℃ in a hydrogen atmosphere to obtain the gallium-loaded ZSM-5 molecular sieve catalyst.
10. The method for synthesizing an aromatic hydrocarbon component in aviation kerosene using low-carbon aromatic hydrocarbons as claimed in claim 3, wherein the molar ratio of tetraethyl orthosilicate, aluminum isopropoxide and tetrapropylammonium hydroxide is 1 (0.002-0.3) to (0.1-1).
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