CN107418619A - A kind of preparation method of aromatic naphtha - Google Patents
A kind of preparation method of aromatic naphtha Download PDFInfo
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- CN107418619A CN107418619A CN201710369011.0A CN201710369011A CN107418619A CN 107418619 A CN107418619 A CN 107418619A CN 201710369011 A CN201710369011 A CN 201710369011A CN 107418619 A CN107418619 A CN 107418619A
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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
- 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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- 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
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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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- 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
- B01J29/42—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
- 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
Abstract
This application provides a kind of preparation method 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, obtains aromatic naphtha；Described to contain in methane atmosphere, the volume ratio of methane is 1%~100%；The aromatized catalyst is the molecular sieve catalysts of ZSM 5 of carried metal.The preparation method of the present invention is simple and easy, is advantageous to large-scale production；And, the preparation method of the present invention is combined methane atmosphere with the molecular sieve catalysts of ZSM 5 of carried metal, the catalytic action of catalyst and the activation of methane mutually cooperate with collocation, the aromatization of feedstock oil can be promoted, feed stock conversion and aromatics yield are effectively improved, especially improves the selectivity and yield of benzene therein, toluene and dimethylbenzene these light aromatics；In addition, there is high-octane rating according to aromatic naphtha made from the preparation method of the present invention, there are good anti-knock properties as gasoline, be advantageous to improve engine power and save fuel.
Description
Technical field
The invention belongs to chemical field, more particularly to a kind of preparation method of aromatic naphtha.
Background technology
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 carry
The effective ways of high alkane value, and one of mode for utilizing of carbon resource Optimum Synthesis.In aromatic hydrocarbons, the carbon of phenyl ring connection
Chain length is longer for heavy aromatics, and the carbon chain lengths that phenyl ring connects are shorter for light aromatic hydrocarbons, in general, more than C10 aromatic hydrocarbons
For heavy aromatics, on the contrary is light aromatic hydrocarbons, and such as benzene, toluene are common light aromatic hydrocarbons.In recent years, abundant light hydrocarbon resource is being catalyzed
Under agent effect, reacted by a series of complex to be converted into the aromatic hydrocarbons such as the benzene of high added value, toluene and dimethylbenzene, 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 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 light aromatics such as benzene, toluene and dimethylbenzene is especially obtained and is of great significance and value.
The method of some alkane aromatizations generation 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%
The complex carrier conduct of rare earth oxide, 1%~7% phosphorus, antimony and bismuth and zeolite and 30%~80% binding agent composition
Catalyst, C9+ heavy arenes in raw material can be made full use of, making it, together catalyzed conversion forms benzene, toluene and two with lighter hydrocarbons
The aromatic hydrocarbons such as toluene.Publication No. CN102030605B patent 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, then boil by Hydrogen mercerising
Stone catalyst reaction area, the catalytic reaction twice through two kinds of catalyst, obtain the aromatic hydrocarbons such as benzene and dimethylbenzene.However, these are existing
Preparation technology is typically more complicated, and condition requires harsh, or conversion ratio and product yield it is 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.
The content of the invention
In view of this, it is an object of the invention to provide a kind of preparation method of aromatic naphtha, preparation technology of the invention letter
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 invention provides a kind of preparation method of aromatic naphtha, comprise the following steps：
Under containing methane atmosphere, will be enriched in the feedstock oil of alkane component, to carry out aromatisation under aromatized catalyst effect anti-
Should, 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.
Preferably, it is described to be made up 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, the one kind of metal in Zn, Ga, Ag, Ru
It is or several.
Preferably, 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.
Preferably, in the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Zn and Ga, Zn accounts for ZSM-5 molecules
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
It is that the mass ratio that 0.5%~5%, Ga accounts for ZSM-5 molecular sieve is 0.5%~5% to measure ratio；
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
It is that the mass ratio that 1%~10%, Ru accounts for ZSM-5 molecular sieve is 0.5%~5% to measure ratio.
Preferably, in the ZSM-5 molecular sieve catalyst of the carried metal, when metal is Zn and Ga, ZSM-5 molecular sieve is
The molecular sieve being modified through 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 invention provides a kind of preparation method of aromatic naphtha, under containing methane atmosphere, will be enriched in the raw material of alkane component
Oil carries out aromatization under aromatized catalyst effect, obtains aromatic naphtha；It is described to contain in methane atmosphere, the volume ratio of methane
For 1%~100%；The aromatized catalyst is the ZSM-5 molecular sieve catalyst of carried metal.The preparation method letter of the present invention
It is single easy, be advantageous to large-scale production；Moreover, the preparation method of the present invention is by methane atmosphere and the ZSM-5 molecules of 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, there is high-octane rating according to aromatic naphtha made from the preparation method of the present invention, have as gasoline
Good anti-knock properties, be advantageous to improve engine power and save fuel.
Embodiment
The invention provides a kind of preparation method of aromatic naphtha, comprise the following steps：
Under containing methane atmosphere, will be enriched in the feedstock oil of alkane component, to carry out aromatisation under aromatized catalyst effect anti-
Should, 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.
The preparation method of the present invention is combined methane atmosphere 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
There is high-octane rating according to aromatic naphtha made from the preparation method of the present invention, there are good anti-knock properties as gasoline, be advantageous to
Improve engine power and save fuel；In addition, the preparation method of the present invention is simple and easy, be advantageous to large-scale production.
In the present invention, aromatization is carried out under containing methane atmosphere, described to contain in methane atmosphere, the volume ratio of methane is
1%~100%, preferably 50%~100%.Aromatization, activation and the alkane aromatization of methane 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 up of containing methane atmosphere methane and inert gas 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 aromatization is carried out, preferably control the air pressure containing methane atmosphere for 0.1~
5.0MPa, that is, it is 0.1~5.0MPa to control reaction pressure.
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 is preferably selected from raffinating 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 interval
The material quantity of agent processing, its formula are：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 by the comprehensive function of each side, it is necessary to be determined, and suitable mass space velocity can also be beneficial to reaction effect
Lifting.
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 the one or more in 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 conventional loaded catalyst in this area, 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
The 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
In case dry 6~10h, with after in air atmosphere at 400~700 DEG C calcine 2~4h, you can obtain loaded Ag-Ga's
ZSM-5 molecular sieve catalyst；Wherein, the addition of silver nitrate and gallium nitrate is with the content of Ag, Ga in final catalyst
Metering is learned to weigh.When preparing the catalyst for loading other metals, above-mentioned precursor solution is replaced with into respective metal
Precursor solution, then to preparation condition accommodation.
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 to 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 be preferably 0.5%~5%, Ce account for Zn, Ga with
The quality of ZSM-5 molecular sieve and the ratio between be 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 in general modified load-type catalyst；Specifically, can be by following
Mode obtains：After Zn-Ga/ZSM-5 molecular sieves are obtained, by cerous nitrate (III valency) dissolving in deionized water, by Zn-Ga/
ZSM-5 molecular sieve is added in the aqueous solution, is adjusted to after 3.5~4.0 PH with watery hydrochloric acid, is fully 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, dry, dry at 90~100 DEG C
Do after calcining 2~3h at 550~650 DEG C, obtain the Zn-Ga/ZSM-5 molecular sieve catalysts that P and Ce is modified.
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 to 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 be preferably 1%~70%.The present invention
In, the preparation method of the above-mentioned Ag-Ga/ZSM-5 molecular sieve catalysts for being modified with silica is not particularly limited, can be according to this
The preparation method of in general modified catalyst in field；Specifically, it can obtain in the following manner：Obtaining support type
After molecular sieve-4 A g-Ga/ZSM-5, it is placed in the ethanol solution dissolved with silane, stirs 2~6h at ambient temperature, then at
4~8h is dried in 100~120 DEG C of baking oven, 3~5h is calcined at 400~600 DEG C afterwards, obtains being modified with silica
Ag-Ga/ZSM-5 catalyst.Wherein, the silane is preferably APTES or tetraethoxysilane.This
In invention, when using APTES, the addition of APTES is preferably controlled
Mass ratio with Ag-Ga/ZSM-5 molecular sieves is 10%~60%, and what is obtained is modified with the Ag-Ga/ZSM-5 molecules of silica
In sieve catalyst, SiO2Account for integer catalyzer (i.e. SiO2+ Ag-Ga/ZSM-5 molecular sieves) mass ratio be preferably 1%~15%；
When using tetraethoxysilane, the addition of tetraethoxysilane is preferably controlled with the mass ratio of Ag-Ga/ZSM-5 molecular sieves
For 100%~300%, what is obtained is modified with the Ag-Ga/ZSM-5 molecular sieve catalysts of silica, SiO2Account for overall catalysis
Agent (i.e. SiO2+ Ag-Ga/ZSM-5 molecular sieves) 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 to account for the mass ratio of ZSM-5 molecular sieve be preferably 0.5%~5% to 1%~10%, Ru.
In the present invention, it is above-mentioned contain methane atmosphere under and aromatized catalyst in the presence of carry out aromatization when, it is excellent
The temperature of selected control system reaction is 300~400 DEG C.In the present invention, reaction unit can be slurry used by the aromatization
State bed or fixed bed reactors, preferably batch (-type) 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 catalyst action, the activation of methane promotes the aromatization of feedstock oil, will be enriched in alkane
Feedstock oil convert for the aromatic naphtha rich in aromatic hydrocarbons, and effectively increase the selectivity of benzene, toluene and dimethylbenzene light aromatics
And yield；Moreover, gained aromatic naphtha has higher octane number, there can be good explosion-proof when being used as gasoline, have
Beneficial to raising engine power and save fuel.In addition, the preparation method of the present invention is simple and easy, be advantageous to large-scale production.
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply 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 sieves are 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, reaction time 60min, after reaction terminates, obtains aromatic naphtha.Gained aromatic hydrocarbons oil ingredient is examined
Survey, as a result show, 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%, C9 and the aromatic hydrocarbons of the above in aromatic naphtha
The relative amount of compound is 4.46%；The octane number of gained aromatic naphtha is 72.79, and 24.85% is improved compared to raw material.
Embodiment 2
To raffinate oil as raw material, Zn-Ga/ZSM-5 molecular sieves are 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, after reaction terminates, obtain aromatic naphtha.Gained aromatic hydrocarbons oil ingredient is entered
Row detection, as a result shows, 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%, C9 and the above in aromatic naphtha
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
Using hydrogasoline as raw material, the Zn-Ga/ZSM-5 molecular sieves being modified through P and Ce are catalyst (silica alumina ratio 80, Zn
The mass ratio for accounting for ZSM-5 molecular sieve is that the mass ratio that 5%, Ga accounts for ZSM-5 molecular sieve is that 1%, P accounts for Zn-Ga/ZSM-5 molecular sieves
Mass ratio be that 2.5%, Ce accounts for the mass ratioes of Zn-Ga/ZSM-5 molecular sieves as 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
It is 400 DEG C, reaction pressure 5.0MPa, reaction time 60min to answer temperature, after reaction terminates, obtains aromatic naphtha.To gained virtue
Hydrocarbon ils component is detected, and is as a result shown, 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 C9 and the aromatic compound of the above is 45.15%；The octane number of gained aromatic naphtha is 90.83, is carried compared to raw material
It is high by 17.67%.
Embodiment 4
To raffinate oil as raw material, Zn-Ru/ZSM-5 molecular sieves are 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, reaction time 60min, after reaction terminates, obtains aromatic naphtha.Gained aromatic hydrocarbons oil ingredient is examined
Survey, as a result show, 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%, C9 and the aromatic hydrocarbons of the above in aromatic naphtha
The relative amount of compound is 11.21%；The octane number of gained aromatic naphtha is 94.01, and 61.25% is improved compared to raw material.
Embodiment 5
To raffinate oil as raw material, Ag-Ga/ZSM-5 molecular sieves are 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 1% methane and the mixed atmosphere of 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, reaction pressure 0.1MPa, reaction time 60min, after reaction terminates, obtains aromatic naphtha.To gained
Aromatic hydrocarbons oil ingredient is detected, and is as a result shown, 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 24.48%, C9 and the aromatic compound of the above 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 sieves of modification are that (silica alumina ratio is catalyst
80, the Ag mass ratioes for accounting for ZSM-5 molecular sieve are that the mass ratio that 1%, Ga accounts for ZSM-5 molecular sieve is 1%, SiO2Account for Zn-Ga/ZSM-
The mass ratio of 5 molecular sieves is 8.1%, SiO2There is provided by APTES), under 100% methane atmosphere,
Aromatization is carried out in batch (-type) slurry reactor kettle；The mass space velocity of feedstock oil is 2h-1, catalyst amount 0.1g,
Reaction temperature is 400 DEG C, reaction pressure 3.0MPa, reaction time 60min, after reaction terminates, obtains aromatic naphtha.To gained
Aromatic hydrocarbons oil ingredient is detected, and is as a result shown, 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 84.08%, C9 and the aromatic compound of the above 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 sieves of modification be catalyst (silica alumina ratio 80,
The mass ratio that Ag accounts for ZSM-5 molecular sieve is that the mass ratio that 1%, Ga accounts for ZSM-5 molecular sieve is 1%, SiO2Account for Zn-Ga/ZSM-5 points
The mass ratio of son sieve is 8.1%, SiO2There is provided by APTES), under 100% methane atmosphere,
Aromatization is carried out in batch (-type) slurry reactor kettle；The mass space velocity of feedstock oil is 2h-1, catalyst amount 0.1g, instead
It is 400 DEG C, reaction pressure 3.0MPa, reaction time 60min to answer temperature, after reaction terminates, obtains aromatic naphtha.To gained virtue
Hydrocarbon ils component is detected, and is as a result shown, 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 C9 and the aromatic compound of the above is 27.02%；The octane number of gained aromatic naphtha is 110.15, is carried 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 sieves of modification be catalyst (silica alumina ratio 23,
The mass ratio that Ag accounts for ZSM-5 molecular sieve is that the mass ratio that 1%, Ga accounts for ZSM-5 molecular sieve is 1%, SiO2Account 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 batch (-type) slurry
Aromatization is carried out in bed reactor；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, after reaction terminates, obtain aromatic naphtha.Gained aromatic hydrocarbons oil ingredient is entered
Row detection, as a result shows, 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%, C9 and the above in aromatic naphtha
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
Reacted under different atmosphere
To raffinate oil as raw material, Ag-Ga/ZSM-5 molecular sieves are that (silica alumina ratio 80, Ag accounts for ZSM-5 molecular sieve to catalyst
Mass ratio be 1%, Ga account for the mass ratio of ZSM-5 molecular sieve for 1%), be respectively placed in 100% nitrogen atmosphere (being designated as 9-1#),
The nitrogen (being designated as 9-2#) of 1% methane+99%, 50% nitrogen of methane+50% (being designated as 9-3#), 100% methane atmosphere
In (being designated 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, reaction pressure 0.1MPa, reaction time 60min, after reaction terminates, obtains virtue
Hydrocarbon ils (being 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 the gained aromatic naphtha of 1 embodiment of table 9
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
Reacted under different catalysts
To raffinate oil as raw material, using Zn-Ga/ZSM-5 molecular sieves as catalyst, (silica alumina ratio 80, Zn account for ZSM-5 points respectively
Son sieve mass ratio be that the mass ratio that 5%, Ga accounts for ZSM-5 molecular sieve is 1%, be designated as 10-1#), with Zn-Pt/ZSM-5 molecular sieves
For catalyst, (silica alumina ratio 80, the mass ratio that Zn accounts for ZSM-5 molecular sieve are that the mass ratio that 5%, Pt accounts for ZSM-5 molecular sieve is
1%, it is designated as 10-2#), using Mg-Ga/ZSM-5 molecular sieves as catalyst, (silica alumina ratio 80, Mg account for the mass ratio of ZSM-5 molecular sieve
The mass ratio that ZSM-5 molecular sieve is accounted for for 5%, Ga is 1%, is designated as 10-3#), using ZSM-5 molecular sieve as catalyst, (silica alumina ratio is
80, it is designated 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, after reaction terminates, obtain aromatic naphtha (being respectively sample 10-1#, 10-2#, 10-3#, 10-4#).Respectively to gained aromatic hydrocarbons
Oil ingredient is detected, as a result referring to table 2.
The testing result of the gained aromatic naphtha of 2 embodiment of table 10
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, according to the preparation method of the present invention, feed stock conversion i.e. product can be effectively improved and received
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 explanation of above example is only intended to help the method and its core concept for understanding the present invention.To these embodiments
A variety of modifications will be apparent for those skilled in the art, generic principles defined herein can be with
Without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to the most wide model consistent with principles disclosed herein and features of novelty
Enclose.
Claims (10)
1. a kind of preparation method of aromatic naphtha, it is characterised in that comprise 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.
2. preparation method according to claim 1, it is characterised in that the methane atmosphere that contains is by methane and inert gas group
Into.
3. preparation method according to claim 2, it is characterised in that the inert gas is selected from nitrogen, argon gas or helium.
4. according to preparation method according to any one of claims 1 to 3, it is characterised in that in the reaction, containing methane atmosphere
Air pressure be 0.1~5.0MPa.
5. preparation method according to claim 4, it is characterised 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, it is characterised in that the temperature of the reaction is 300~400 DEG C.
7. preparation method according to claim 1, it is characterised in that the ZSM-5 molecular sieve catalyst of the carried metal
In, one or more of the metal in Zn, Ga, Ag, Ru.
8. preparation method according to claim 7, it is characterised in that the ZSM-5 molecular sieve catalyst of the carried metal
In, metal is Zn and Ga, or is Ag and Ga, or is Zn and Ru.
9. preparation method according to claim 8, it is characterised in that the ZSM-5 molecular sieve catalyst of the carried metal
In, when metal is Zn and Ga, the mass ratio that Zn accounts for ZSM-5 molecular sieve is the mass ratio that 1%~10%, Ga accounts for ZSM-5 molecular sieve
For 0.5%~5%；
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
The mass ratio that ZSM-5 molecular sieve is accounted for for 0.5%~5%, Ga is 0.5%~5%；
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
The mass ratio that ZSM-5 molecular sieve is accounted for for 1%~10%, Ru is 0.5%~5%.
10. preparation method according to claim 8 or claim 9, it is characterised in that the ZSM-5 molecular sieve of the carried metal is urged
In agent, when metal is Zn and Ga, ZSM-5 molecular sieve is the molecular sieve being modified through P and Ce；Wherein, P accounts for Zn, Ga and ZSM-5 points
Son 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 molecules 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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