CN107418619B - A kind of preparation method of aromatic naphtha - Google Patents
A kind of preparation method of aromatic naphtha Download PDFInfo
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- 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
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- 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
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- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/44—Noble metals
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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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
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
This application provides a kind of preparation methods of aromatic naphtha, and under containing methane atmosphere, the feedstock oil that will be enriched in alkane component carries out aromatization under aromatized catalyst effect, obtain aromatic naphtha；Described to contain in methane atmosphere, the volume ratio of methane is 1%~100%；The aromatized catalyst is the ZSM-5 molecular sieve catalyst of carried metal.Of the invention preparation method is simple, is conducive to large-scale production；And, preparation method of the invention is by methane atmosphere in conjunction with the ZSM-5 molecular sieve catalyst of carried metal, the catalytic action of catalyst and the activation of methane mutually cooperate with collocation, it can promote the aromatization of feedstock oil, feed stock conversion and aromatics yield are effectively improved, the selectivity and yield of benzene therein, toluene and dimethylbenzene these light aromatics are especially improved；In addition, aromatic naphtha made from preparation method according to the invention has high-octane rating, there are good anti-knock properties as gasoline, be conducive to improve engine power and save fuel.
Description
Technical field
The invention belongs to chemical field, in particular to a kind of preparation method of aromatic naphtha.
Background technique
With the reduction of petroleum-based energy, will be enriched in the resource aromatisation of alkane component to obtain the aromatic naphtha containing aromatic hydrocarbons is to mention
The effective ways and carbon resource Optimum Synthesis of high alkane utility value by the way of one of.In aromatic hydrocarbons, the carbon of phenyl ring connection
Longer chain length is heavy aromatics, and the carbon chain lengths of phenyl ring connection are shorter for light aromatic hydrocarbons, in general, the aromatic hydrocarbons of C10 or more
For heavy aromatics, on the contrary is light aromatic hydrocarbons, such as benzene, toluene are common light aromatic hydrocarbons.In recent years, abundant light hydrocarbon resource is being catalyzed
Under agent effect, the aromatic hydrocarbons such as the benzene, toluene and dimethylbenzene of high added value are converted by a series of complex reaction, have caused industry
Great attention.Benzene, toluene and dimethylbenzene are most widely used three kinds of light aromatics compounds in aromatic hydrocarbons, be may be used as unleaded
The blend component of gasoline can also be used as the important source material of Organic Chemical Industry, and therefore, the light hydrocarbon resource that will be enriched in alkane turns
Aromatic hydrocarbons is turned to, the especially light aromatics such as acquisition benzene, toluene and dimethylbenzene are of great significance and value.
The method that some alkane aromatizations generate aromatic hydrocarbons has been disclosed in the prior art, such as Publication No. CN101993320B
Patent disclose a kind of aromatization method for producing light aromatics, by 0.5%~5.0% zinc oxide, 0.1%~5.0%
Rare earth oxide, 1%~7% phosphorus, antimony and bismuth and zeolite and 30%~80% binder composition complex carrier conduct
Catalyst can make full use of C9+ heavy arene in raw material, its catalyzed conversion together with lighter hydrocarbons is made to form benzene, toluene and two
The aromatic hydrocarbons such as toluene.The patent of Publication No. CN102030605B discloses a kind of aromatizing low-carbon paraffin technique, by low-carbon raw material
By the reaction zone of at least two aromatized catalysts, the reaction zone of molecular sieve containing HZSM-5 is first passed through, is boiled using Hydrogen mercerising
Stone catalyst reaction area, the catalysis twice through two kinds of catalyst are reacted, and the aromatic hydrocarbons such as benzene and dimethylbenzene are obtained.However, these are existing
Preparation process is typically more complicated, and condition requires harsh or conversion ratio and product yield poor；And how simply to prepare virtue
Hydrocarbon, obtain good conversion rate and aromatics yield especially light aromatics yield and obtain high-quality aromatic hydrocarbon product increasingly by
To attention.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation method of aromatic naphtha, preparation process letter of the invention
It is single easy, and feed stock conversion and aromatics yield can be effectively improved, the especially yield of light aromatics, and gained aromatic naphtha
With high-octane rating.
The present invention provides a kind of preparation methods of aromatic naphtha, comprising the following steps:
It is anti-carrying out aromatisation under aromatized catalyst effect containing the feedstock oil that under methane atmosphere, will be enriched in alkane component
It answers, obtains aromatic naphtha；
Described to contain in methane atmosphere, the volume ratio of methane is 1%~100%；
The aromatized catalyst is the ZSM-5 molecular sieve catalyst of carried metal.
Preferably, described to be made of containing methane atmosphere methane and inert gas.
Preferably, the inert gas is selected from nitrogen, argon gas or helium.
Preferably, in the reaction, the air pressure containing methane atmosphere is 0.1~5.0MPa.
Preferably, the feedstock quality air speed of the feedstock oil is 1.0~3.0h-1；
The feedstock oil be selected from raffinate oil, hydrogasoline, coker gasoline or naphtha.
Preferably, the temperature of the reaction is 300~400 DEG C.
Preferably, in the ZSM-5 molecular sieve catalyst of the carried metal, metal is selected from one of Zn, Ga, Ag, Ru
Or it is several.
Preferably, in the ZSM-5 molecular sieve catalyst of the carried metal, metal is Zn and Ga, or is Ag and Ga, or be
Zn and Ru.
Preferably, in the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Zn and Ga, Zn accounts for ZSM-5 molecule
The mass ratio of sieve is that the mass ratio that 1%~10%, Ga accounts for ZSM-5 molecular sieve is 0.5%~5%；
In the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Ag and Ga, Ag accounts for the matter of ZSM-5 molecular sieve
Amount is 0.5%~5% than being the mass ratio that 0.5%~5%, Ga accounts for ZSM-5 molecular sieve；
In the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Zn and Ru, Zn accounts for the matter of ZSM-5 molecular sieve
Amount is 0.5%~5% than being the mass ratio that 1%~10%, Ru accounts for ZSM-5 molecular sieve.
Preferably, in the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Zn and Ga, ZSM-5 molecular sieve is
Through the modified molecular sieve of P and Ce；Wherein, P account for Zn, Ga and ZSM-5 molecular sieve quality and the ratio between account for for 0.5%~5%, Ce
The quality of Zn, Ga and ZSM-5 molecular sieve and the ratio between be 0.5%~5%；
In the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Ag and Ga, the ZSM-5 of the carried metal
The surface modification of molecular sieve has silica, and the silica accounts for the ZSM-5 molecular sieve and silica of the carried metal
Quality and the ratio between be 1%~70%.
The present invention provides a kind of preparation methods of aromatic naphtha will be enriched in the raw material of alkane component under containing methane atmosphere
Oil carries out aromatization under aromatized catalyst effect, obtains aromatic naphtha；It is described to contain in methane atmosphere, the volume ratio of methane
It is 1%~100%；The aromatized catalyst is the ZSM-5 molecular sieve catalyst of carried metal.Preparation method letter of the invention
It is single easy, be conducive to large-scale production；Moreover, preparation method of the invention is by the ZSM-5 molecule of methane atmosphere and carried metal
Sieve catalyst combines, and the catalytic action of catalyst and the activation of methane mutually cooperate with collocation, can promote the aromatisation of feedstock oil
Reaction, effectively improves feed stock conversion and aromatics yield, especially improves these light aromatics of benzene, toluene and dimethylbenzene therein
Selectivity and yield；In addition, aromatic naphtha made from preparation method according to the invention has high-octane rating, have as gasoline
Good anti-knock properties are conducive to improve engine power and save fuel.
Specific embodiment
The present invention provides a kind of preparation methods of aromatic naphtha, comprising the following steps:
It is anti-carrying out aromatisation under aromatized catalyst effect containing the feedstock oil that under methane atmosphere, will be enriched in alkane component
It answers, obtains aromatic naphtha；
Described to contain in methane atmosphere, the volume ratio of methane is 1%~100%；
The aromatized catalyst is the ZSM-5 molecular sieve catalyst of carried metal.
Preparation method of the invention by methane atmosphere in conjunction with the ZSM-5 molecular sieve catalyst of carried metal, catalyst
Catalytic action and the activation of methane mutually cooperate with collocation, can promote the aromatization of feedstock oil, effectively improve raw material conversion
Rate and aromatics yield especially improve the selectivity and yield of benzene therein, toluene and dimethylbenzene these light aromatics；Meanwhile
Aromatic naphtha made from preparation method according to the invention has high-octane rating, has good anti-knock properties as gasoline, is conducive to
It improves engine power and saves fuel；In addition, of the invention, preparation method is simple, is conducive to large-scale production.
In the present invention, aromatization is carried out under containing methane atmosphere, described containing in methane atmosphere, the volume ratio of methane is
1%~100%, preferably 50%~100%.Aromatization, the activation of methane and alkane aromatization are carried out under methane atmosphere
Change collaboration to carry out, the yield of light aromatics in aromatic naphtha can be effectively improved, and obtain high-octane rating aromatic naphtha.
It is described to be preferably made of methane and inert gas containing methane atmosphere in the present invention.In the present invention, the inert gas
It preferably is selected from nitrogen, argon gas or helium.
In the present invention, during carrying out aromatization, preferably control the air pressure containing methane atmosphere be 0.1~
5.0MPa, i.e. control reaction pressure are 0.1~5.0MPa.
In the present invention, aromatization is carried out as raw material using the feedstock oil rich in alkane component.It is described in the present invention
Feedstock oil be preferably selected from raffinate oil, hydrogasoline, coker gasoline or naphtha.It is excellent when carrying out aromatization in the present invention
The feedstock quality air speed of selected control feedstock oil is 1.0~3.0h-1；Feedstock quality air speed refers to urging for unit mass in the unit time
The material quantity of agent processing, formula are as follows: mass space velocity=material quality flow (kgh-1Or gh-1)/catalyst quality
(kg or g)；The factors such as feedstock quality air speed and feedstock property, catalyst performance and reaction condition are related, by various reactions because
The reciprocal effect of element needs to determine by the comprehensive function of various aspects, and suitable mass space velocity can also be beneficial to reaction effect
Promotion.
In the present invention, used aromatized catalyst is the ZSM-5 molecular sieve catalyst of carried metal.In the present invention,
The silica alumina ratio of the ZSM-5 molecular sieve is preferably 23~80.The present invention does not have special limit to the source of the ZSM-5 molecular sieve
System is general commercially available product.
In the present invention, in the catalyst, metal is preferably one or more of Zn, Ga, Ag, Ru；More preferably Zn
And Ga, or be Ag and Ga, or be Zn and Ru.Preparation method of the present invention to the ZSM-5 molecular sieve catalyst of the carried metal
It is not particularly limited, according to the preparation method of the loaded catalyst of this field routine, such as infusion process commonly used in the art,
Ion-exchange or coprecipitation etc..Such as by taking Ag-Ga/ZSM-5 catalyst as an example, it can obtain in the following manner: with infusion process
Aqueous solution dissolved with silver nitrate and gallium nitrate is added dropwise in ZSM-5 molecular sieve, gained sample is placed in 80~90 DEG C of bakings
Dry 6~10h, then calcines 2~4h at 400~700 DEG C in air atmosphere, can be obtained loaded Ag-Ga's in case
ZSM-5 molecular sieve catalyst；Wherein, the additive amount of silver nitrate and gallium nitrate is with the content of Ag, Ga in final catalyst
Metering is learned to weigh.When preparation loads the catalyst of other metals, above-mentioned precursor solution is replaced with into respective metal
Precursor solution, then preparation condition is adaptively adjusted.
In the present invention, in the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Zn and Ga, Zn accounts for ZSM-5 points
The mass ratio of son sieve is preferably that account for the mass ratio of ZSM-5 molecular sieve be preferably 0.5%~5% to 1%~10%, Ga.In the present invention,
In the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Zn and Ga, ZSM-5 molecular sieve can also be to change through P and Ce
The molecular sieve of property；Wherein, P account for Zn, Ga and ZSM-5 molecular sieve quality and the ratio between preferably 0.5%~5%, Ce account for Zn, Ga with
The quality of ZSM-5 molecular sieve and the ratio between preferably 0.5%~5%.In the present invention, the system for the catalyst that above-mentioned P and Ce are modified
Preparation Method is not particularly limited, according to the preparation method of general modified load-type catalyst；Specifically, can be by following
Mode obtains: after obtaining Zn-Ga/ZSM-5 molecular sieve, in deionized water by cerous nitrate (III valence) dissolution, by Zn-Ga/
ZSM-5 molecular sieve is added in the aqueous solution, after PH is adjusted to 3.5~4.0 with dilute hydrochloric acid, is sufficiently stirred at 90~100 DEG C
Mix 1~3h；Then, ammonium phosphate is added, continues 1~3h of stirring, is cooled to room temperature；Then, it dries, dries at 90~100 DEG C
2~3h is calcined after dry at 550~650 DEG C, obtains the modified Zn-Ga/ZSM-5 molecular sieve catalyst of P and Ce.
In the present invention, in the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Ag and Ga, Ag accounts for ZSM-5 points
The mass ratio of son sieve is preferably that account for the mass ratio of ZSM-5 molecular sieve be preferably 0.5%~5% to 0.5%~5%, Ga.The present invention
In, when metal is Ag and Ga, the surface of the ZSM-5 molecular sieve of the carried metal can also be modified with silica, wherein two
Silica account for the ZSM-5 molecular sieve of the carried metal and the quality of silica and the ratio between preferably 1%~70%.The present invention
In, the preparation method of the above-mentioned Ag-Ga/ZSM-5 molecular sieve catalyst for being modified with silica is not particularly limited, can be according to this
The preparation method of general modified catalyst in field；Specifically, can obtain in the following manner: obtaining support type
It after molecular sieve-4 A g-Ga/ZSM-5, places it in the ethanol solution dissolved with silane, stirs 2~6h at room temperature, then at
Dry 4~8h, calcines 3~5h at 400~600 DEG C later, obtains being modified with silica in 100~120 DEG C of baking oven
Ag-Ga/ZSM-5 catalyst.Wherein, the silane is preferably 3-aminopropyltriethoxysilane or tetraethoxysilane.This
In invention, when using 3-aminopropyltriethoxysilane, the additive amount of 3-aminopropyltriethoxysilane is preferably controlled
Mass ratio with Ag-Ga/ZSM-5 molecular sieve is 10%~60%, the obtained Ag-Ga/ZSM-5 molecule for being modified with silica
In sieve catalyst, SiO2Account for monolithic catalyst (i.e. SiO2+ Ag-Ga/ZSM-5 molecular sieve) mass ratio be preferably 1%~15%；
When using tetraethoxysilane, the additive amount of tetraethoxysilane and the mass ratio of Ag-Ga/ZSM-5 molecular sieve are preferably controlled
It is 100%~300%, in the obtained Ag-Ga/ZSM-5 molecular sieve catalyst for being modified with silica, SiO2Account for whole catalysis
Agent (i.e. SiO2+ Ag-Ga/ZSM-5 molecular sieve) mass ratio be preferably 10%~70%.
In the present invention, in the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Zn and Ru, Zn accounts for ZSM-5 points
The mass ratio of son sieve is preferably that account for the mass ratio of ZSM-5 molecular sieve be preferably 0.5%~5% to 1%~10%, Ru.
It is excellent above-mentioned containing under methane atmosphere and when aromatized catalyst under the action of carries out aromatization in the present invention
The temperature of selected control system reaction is 300~400 DEG C.In the present invention, reaction unit used by the aromatization can be slurry
State bed or fixed bed reactors, preferably intermittent slurry reactor kettle or continous way fixed bed reactors.
The present invention will be enriched in the feedstock oil of alkane component in the ZSM-5 molecular sieve catalyst containing methane atmosphere and carried metal
Lower carry out aromatization, under the action of catalyst, the activation of methane promote the aromatization of feedstock oil, will be enriched in alkane
Feedstock oil conversion in order to be rich in the aromatic naphtha of aromatic hydrocarbons, and effectively increase the selectivity of benzene, toluene and dimethylbenzene light aromatics
And yield；Moreover, gained aromatic naphtha octane number with higher, can have good explosion-proof, have when using as gasoline
Conducive to raising engine power and save fuel.In addition, of the invention, preparation method is simple, is conducive to large-scale production.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1
To raffinate oil as raw material, Zn-Ga/ZSM-5 molecular sieve is that (silica alumina ratio 80, Zn accounts for ZSM-5 molecular sieve to catalyst
Mass ratio is that the mass ratio that 5%, Ga accounts for ZSM-5 molecular sieve is 1%), under 100% methane atmosphere, in continous way fixed bed
Aromatization is carried out in reactor；The mass space velocity of feedstock oil is 3h-1, catalyst amount 1g, reaction temperature is 300 DEG C,
Reaction pressure is 5.0MPa, and reaction time 60min obtains aromatic naphtha after reaction.Gained aromatic hydrocarbons oil ingredient is examined
It surveys, the results show that the conversion ratio of feedstock oil is 45.86%, liquid product yield 33.95%；Wherein, benzene, toluene and diformazan
The selectivity of benzene is 15.59%, and the relative amount of benzene, toluene and dimethylbenzene is 18.74% in aromatic naphtha, the aromatic hydrocarbons of C9 or more
The relative amount of compound is 4.46%；The octane number of gained aromatic naphtha is 72.79, improves 24.85% compared to raw material.
Embodiment 2
To raffinate oil as raw material, Zn-Ga/ZSM-5 molecular sieve is that (silica alumina ratio 80, Zn accounts for ZSM-5 molecular sieve to catalyst
Mass ratio is that the mass ratio that 5%, Ga accounts for ZSM-5 molecular sieve is 1%), under 100% methane atmosphere, in continous way fixed bed
Aromatization is carried out in reactor；The mass space velocity of feedstock oil is 1.5h-1, catalyst amount 2g, reaction temperature 380
DEG C, reaction pressure 5.0MPa, reaction time 60min obtains aromatic naphtha after reaction.To gained aromatic hydrocarbons oil ingredient into
Row detection, the results show that the conversion ratio of feedstock oil is 92.93%, liquid product yield 48.17%；Wherein, benzene, toluene and
The selectivity of dimethylbenzene is 34.46%, and the relative amount of benzene, toluene and dimethylbenzene is 63.41% in aromatic naphtha, C9's or more
The relative amount of aromatic compound is 32.69%；The octane number of gained aromatic naphtha is 94.01, is improved compared to raw material
61.25%.
Embodiment 3
It is catalyst (silica alumina ratio 80, Zn through P and Ce modified Zn-Ga/ZSM-5 molecular sieve using hydrogasoline as raw material
It is that 1%, P accounts for Zn-Ga/ZSM-5 molecular sieve that the mass ratio for accounting for ZSM-5 molecular sieve, which is the mass ratio that 5%, Ga accounts for ZSM-5 molecular sieve,
Mass ratio be 2.5%, Ce account for Zn-Ga/ZSM-5 molecular sieve mass ratio be 1.2%), under 100% methane atmosphere,
Aromatization is carried out in continous way fixed bed reactors；The mass space velocity of feedstock oil is 1.5h-1, catalyst amount 2g, instead
Answering temperature is 400 DEG C, and reaction pressure 5.0MPa, reaction time 60min obtains aromatic naphtha after reaction.To gained virtue
Hydrocarbon ils component is detected, the results show that the conversion ratio of feedstock oil is 57.74%, liquid product yield 25.84%；Wherein,
The selectivity of benzene, toluene and dimethylbenzene is 19.58%, and the relative amount of benzene, toluene and dimethylbenzene is 54.24% in aromatic naphtha,
The relative amount of the aromatic compound of C9 or more is 45.15%；The octane number of gained aromatic naphtha is 90.83, is mentioned compared to raw material
It is high by 17.67%.
Embodiment 4
To raffinate oil as raw material, Zn-Ru/ZSM-5 molecular sieve is that (silica alumina ratio 80, Zn accounts for ZSM-5 molecular sieve to catalyst
Mass ratio is that the mass ratio that 5%, Ru accounts for ZSM-5 molecular sieve is 1%), under 100% methane atmosphere, in continous way fixed bed
Aromatization is carried out in reactor；The mass space velocity of feedstock oil is 3h-1, catalyst amount 1g, reaction temperature is 400 DEG C,
Reaction pressure is 5.0MPa, and reaction time 60min obtains aromatic naphtha after reaction.Gained aromatic hydrocarbons oil ingredient is examined
It surveys, the results show that the conversion ratio of feedstock oil is 93.93%, liquid product yield 58.24%；Wherein, benzene, toluene and diformazan
The selectivity of benzene is 13.31%, and the relative amount of benzene, toluene and dimethylbenzene is 19.22% in aromatic naphtha, the aromatic hydrocarbons of C9 or more
The relative amount of compound is 11.21%；The octane number of gained aromatic naphtha is 94.01, improves 61.25% compared to raw material.
Embodiment 5
To raffinate oil as raw material, Ag-Ga/ZSM-5 molecular sieve is that (silica alumina ratio 80, Ag accounts for ZSM-5 molecular sieve to catalyst
Mass ratio is that the mass ratio that 1%, Ga accounts for ZSM-5 molecular sieve is 1%), in the mixed atmosphere of 1% methane and 99% nitrogen
Under, aromatization is carried out in continous way fixed bed reactors；The mass space velocity of feedstock oil is 3h-1, catalyst amount 1g,
Reaction temperature is 400 DEG C, and reaction pressure 0.1MPa, reaction time 60min obtains aromatic naphtha after reaction.To gained
Aromatic hydrocarbons oil ingredient is detected, the results show that the conversion ratio of feedstock oil is 42.98%, liquid product yield 33.87%；Its
In, the selectivity of benzene, toluene and dimethylbenzene is 21.69%, and the relative amount of benzene, toluene and dimethylbenzene is in aromatic naphtha
The relative amount of the aromatic compound of 24.48%, C9 or more is 3.59%；The octane number of gained aromatic naphtha is 67.62, is compared
Raw material improves 15.99%.
Embodiment 6
Using coker gasoline as raw material, through SiO2The Ag-Ga/ZSM-5 molecular sieve of modification is that (silica alumina ratio is catalyst
It is 1%, SiO that 80, the Ag mass ratioes for accounting for ZSM-5 molecular sieve, which are the mass ratio that 1%, Ga accounts for ZSM-5 molecular sieve,2Account for Zn-Ga/ZSM-
The mass ratio of 5 molecular sieves is 8.1%, SiO2There is provided by 3-aminopropyltriethoxysilane), under 100% methane atmosphere,
Aromatization is carried out in intermittent slurry reactor kettle；The mass space velocity of feedstock oil is 2h-1, catalyst amount 0.1g,
Reaction temperature is 400 DEG C, and reaction pressure 3.0MPa, reaction time 60min obtains aromatic naphtha after reaction.To gained
Aromatic hydrocarbons oil ingredient is detected, the results show that the conversion ratio of feedstock oil is 71.89%, liquid product yield 51.89%；Its
In, the selectivity of benzene, toluene and dimethylbenzene is 60.60%, and the relative amount of benzene, toluene and dimethylbenzene is in aromatic naphtha
The relative amount of the aromatic compound of 84.08%, C9 or more is 15.92%；The octane number of gained aromatic naphtha is 108.18, phase
28.74% is improved than raw material.
Embodiment 7
Using naphtha as raw material, through SiO2The Ag-Ga/ZSM-5 molecular sieve of modification be catalyst (silica alumina ratio 80,
It is the mass ratio that 1%, Ga accounts for ZSM-5 molecular sieve is 1%, SiO that Ag, which accounts for the mass ratio of ZSM-5 molecular sieve,2Account for Zn-Ga/ZSM-5 points
The mass ratio of son sieve is 8.1%, SiO2There is provided by 3-aminopropyltriethoxysilane), under 100% methane atmosphere,
Aromatization is carried out in intermittent slurry reactor kettle；The mass space velocity of feedstock oil is 2h-1, catalyst amount 0.1g, instead
Answering temperature is 400 DEG C, and reaction pressure 3.0MPa, reaction time 60min obtains aromatic naphtha after reaction.To gained virtue
Hydrocarbon ils component is detected, the results show that the conversion ratio of feedstock oil is 75.56%, liquid product yield 57.38%；Wherein,
The selectivity of benzene, toluene and dimethylbenzene is 57.95%, and the relative amount of benzene, toluene and dimethylbenzene is 72.98% in aromatic naphtha,
The relative amount of the aromatic compound of C9 or more is 27.02%；The octane number of gained aromatic naphtha is 110.15, is mentioned compared to raw material
It is high by 49.11%.
Embodiment 8
To raffinate oil for raw material, through SiO2The Ag-Ga/ZSM-5 molecular sieve of modification be catalyst (silica alumina ratio 23,
It is the mass ratio that 1%, Ga accounts for ZSM-5 molecular sieve is 1%, SiO that Ag, which accounts for the mass ratio of ZSM-5 molecular sieve,2Account for Zn-Ga/ZSM-5 points
The mass ratio of son sieve is 57.5%, SiO2There is provided by tetraethoxysilane), under 100% methane atmosphere, in intermittent slurry
Aromatization is carried out in bed reaction kettle；The mass space velocity of feedstock oil is 2h-1, catalyst amount 0.1g, reaction temperature 400
DEG C, reaction pressure 3.0MPa, reaction time 60min obtains aromatic naphtha after reaction.To gained aromatic hydrocarbons oil ingredient into
Row detection, the results show that the conversion ratio of feedstock oil is 95.48%, liquid product yield 63.24%；Wherein, benzene, toluene and
The selectivity of dimethylbenzene is 44.80%, and the relative amount of benzene, toluene and dimethylbenzene is 66.25% in aromatic naphtha, C9's or more
The relative amount of aromatic compound is 30.16%；The octane number of gained aromatic naphtha is 102.50, is improved compared to raw material
75.81%.
Embodiment 9
It is reacted under different atmosphere
To raffinate oil as raw material, Ag-Ga/ZSM-5 molecular sieve is that (silica alumina ratio 80, Ag accounts for ZSM-5 molecular sieve to catalyst
Mass ratio be 1%, Ga account for ZSM-5 molecular sieve mass ratio be 1%), be respectively placed in 100% nitrogen atmosphere (being denoted as 9-1#),
Nitrogen (being denoted as 9-2#), 50%+50% nitrogen of methane (being denoted as 9-3#), 100% methane atmosphere of 1% methane+99%
In (being denoted as 9-4#), aromatization is carried out in continous way fixed bed reactors；The mass space velocity of feedstock oil is 3h-1, catalysis
Agent dosage is 1g, and reaction temperature is 400 DEG C, and reaction pressure 0.1MPa, reaction time 60min obtains virtue after reaction
Hydrocarbon ils (respectively sample 9-1#, 9-2#, 9-3#, 9-4#).Gained aromatic hydrocarbons oil ingredient is detected, as a result referring to table 1.
The testing result of 1 embodiment of table, 9 gained aromatic naphtha
Note: " octane number increase rate " refers to the octane number of gained aromatic naphtha compared to the ratio that the octane number of raw material improves in table
Example.
Embodiment 10
It is reacted under different catalysts
To raffinate oil as raw material, using Zn-Ga/ZSM-5 molecular sieve as catalyst, (silica alumina ratio 80, Zn account for ZSM-5 points respectively
The mass ratio of son sieve be the mass ratio that 5%, Ga accounts for ZSM-5 molecular sieve is 1%, is denoted as 10-1#), with Zn-Pt/ZSM-5 molecular sieve
For catalyst, (silica alumina ratio 80, Zn account for the mass ratio of ZSM-5 molecular sieve as 5%, the Pt mass ratio for accounting for ZSM-5 molecular sieve and are
1%, it is denoted as 10-2#), using Mg-Ga/ZSM-5 molecular sieve as catalyst, (silica alumina ratio 80, Mg account for the mass ratio of ZSM-5 molecular sieve
Be 1% for 5%, the Ga mass ratio for accounting for ZSM-5 molecular sieve, be denoted as 10-3#), using ZSM-5 molecular sieve as catalyst, (silica alumina ratio is
80, it is denoted as 10-4#), under 100% methane atmosphere, aromatization is carried out in continous way fixed bed reactors；Feedstock oil
Mass space velocity be 1.5h-1, catalyst amount 2g, reaction temperature is 380 DEG C, reaction pressure 5.0MPa, and the reaction time is
60min obtains aromatic naphtha (respectively sample 10-1#, 10-2#, 10-3#, 10-4#) after reaction.Respectively to gained aromatic hydrocarbons
Oil ingredient is detected, as a result referring to table 2.
The testing result of 2 embodiment of table, 10 gained aromatic naphtha
Note: " octane number increase rate " refers to the octane number of gained aromatic naphtha compared to the ratio that the octane number of raw material improves in table
Example.
As seen from the above embodiment, preparation method according to the invention can effectively improve feed stock conversion i.e. product and receive
Rate, and effectively increase the selectivity and yield of benzene, toluene and dimethylbenzene light aromatics；Moreover, gained aromatic naphtha is with higher
Octane number, integrated quality is higher.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.To these embodiments
A variety of modifications will be readily apparent to those skilled in the art, the general principles defined herein can be with
Without departing from the spirit or scope of the present invention, it realizes in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to widest model consistent with the principles and novel features disclosed in this article
It encloses.
Claims (7)
1. a kind of preparation method of aromatic naphtha, which comprises the following steps:
Under containing methane atmosphere, the feedstock oil that will be enriched in alkane component carries out aromatization under aromatized catalyst effect,
Obtain aromatic naphtha；
Described to contain in methane atmosphere, the volume ratio of methane is 1%~100%；
The aromatized catalyst is the ZSM-5 molecular sieve catalyst of carried metal；
In the ZSM-5 molecular sieve catalyst of the carried metal, metal is Zn and Ga, or is Ag and Ga, or is Zn and Ru；
In the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Zn and Ga, Zn accounts for the mass ratio of ZSM-5 molecular sieve
It is 0.5%~5% for 1%~10%, the Ga mass ratio for accounting for ZSM-5 molecular sieve；
In the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Ag and Ga, Ag accounts for the mass ratio of ZSM-5 molecular sieve
It is 0.5%~5% for 0.5%~5%, the Ga mass ratio for accounting for ZSM-5 molecular sieve；
In the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Zn and Ru, Zn accounts for the mass ratio of ZSM-5 molecular sieve
It is 0.5%~5% for 1%~10%, the Ru mass ratio for accounting for ZSM-5 molecular sieve.
2. preparation method according to claim 1, which is characterized in that the methane atmosphere that contains is by methane and inert gas group
At.
3. preparation method according to claim 2, which is characterized in that the inert gas is selected from nitrogen, argon gas or helium.
4. preparation method described in any one of claim 1 to 3, which is characterized in that in the reaction, contain methane atmosphere
Air pressure be 0.1~5.0MPa.
5. the preparation method according to claim 4, which is characterized in that the feedstock quality air speed of the feedstock oil be 1.0~
3.0h-1；
The feedstock oil be selected from raffinate oil, hydrogasoline, coker gasoline or naphtha.
6. preparation method according to claim 5, which is characterized in that the temperature of the reaction is 300~400 DEG C.
7. preparation method according to claim 1, which is characterized in that the ZSM-5 molecular sieve catalyst of the carried metal
In, when metal is Zn and Ga, ZSM-5 molecular sieve is the molecular sieve modified through P and Ce；Wherein, P accounts for Zn, Ga and ZSM-5 molecular sieve
Quality and the ratio between be 0.5%~5%, Ce account for Zn, Ga and ZSM-5 molecular sieve quality and the ratio between be 0.5%~5%；
In the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Ag and Ga, the ZSM-5 molecule of the carried metal
The surface modification of sieve has silica, and the silica accounts for the ZSM-5 molecular sieve of the carried metal and the matter of silica
Amount and the ratio between be 1%~70%.
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| CN111229299A (en) * | 2020-03-10 | 2020-06-05 | 广西华睿能源科技有限公司 | Catalyst for high-efficiency isomerization and aromatization of straight-chain paraffin and preparation method thereof |
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| CN111672535A (en) * | 2020-06-18 | 2020-09-18 | 中国石油化工股份有限公司 | Catalyst and method for heavy oil and methane modification and rich production of low-carbon aromatic hydrocarbon |
| US11725150B2 (en) | 2020-08-18 | 2023-08-15 | Kara Technologies Inc. | Method of light oil desulfurization in the presence of methane containing gas environment and catalyst structure |
| CN114073977A (en) * | 2020-08-21 | 2022-02-22 | 国家能源投资集团有限责任公司 | Noble metal supported catalyst, preparation method and application thereof, and method for improving aromatic hydrocarbon yield in process of preparing aromatic hydrocarbon from light hydrocarbon |
| CN113198522A (en) * | 2021-04-25 | 2021-08-03 | 西南化工研究设计院有限公司 | Monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane and preparation method thereof |
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