CN104844403B - System and method for directly preparing aromatic hydrocarbon from methane - Google Patents
System and method for directly preparing aromatic hydrocarbon from methane Download PDFInfo
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- CN104844403B CN104844403B CN201510134637.4A CN201510134637A CN104844403B CN 104844403 B CN104844403 B CN 104844403B CN 201510134637 A CN201510134637 A CN 201510134637A CN 104844403 B CN104844403 B CN 104844403B
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Abstract
The invention discloses a system and a method for directly preparing aromatic hydrocarbon from methane. The system comprises a methane aromatization sub system, a methanation reaction sub system and a separating sub system. The method comprises the following steps: cooling a high-temperature gas mixture of hydrogen gas, methane and aromatic hydrocarbon from the outlet of the methane aromatization sub system; directly reacting the cooled gas mixture with CO2 in the methanation reaction sub system to obtain a mixture of methane, CO2, water and aromatic hydrocarbon; and performing gas-liquid separation on the mixture to obtain aromatic hydrocarbon, wherein the methane can be recycled. According to the system and the method, the problems of high energy consumption of the separation of the gas and the aromatic hydrocarbon in an independent aromatization process and high cost are effectively solved, heat energy contained in the gas from the outlet of the aromatization system is effectively utilized, and the advantages of low methane consumption, short process, less investment, and the capacity of greatly utilizing CO2 and greatly reducing the cost of the aromatic hydrocarbon are achieved.
Description
Technical field
The invention belongs to chemical technology field, more particularly to a kind of methane directly prepares the System and method for of aromatic hydrocarbons.
Background technology
Aromatic hydrocarbon product is important basic chemical industry raw material, main at present to be obtained by petroleum path.But due to alkene production
And oil product (petrol and diesel oil etc.) production has raw material competitive relation, the yield for preparing aromatic hydrocarbons from petroleum path is increasingly restricted.I
State needs every year the substantial amounts of aromatic hydrocarbons of import.
With methane as raw material, with metal-molecular sieve bifunctional catalyst conversion under oxygen-free environment, it is possible to obtain benzene, first
The important aromatic hydrocarbons such as benzene and naphthalene.But because thermodynamical equilibrium is limited, the conversion per pass of the aromatization carried out at 600-700 DEG C
Relatively low (about 16%), containing about 22% hydrogen and 78% methane in the gas of generation.The method of pressure-variable adsorption by hydrogen and methane separation,
Cost is higher, and consumes energy.Meanwhile, in specific system, the hydrogen of generation is useless, and its storage is one and very big asks
Topic.Early stage patent report generates the technology of methane using CO2 and the methane reaction of hydrogen, efficiently solves this difficult problem.
But a large amount of methane are separated with the aromatic hydrocarbons of low content with hydrogen and need absorption and desorption technology, high energy consumption, long flow path.Need handle simultaneously
The high-temperature tail gas of aromatisation system outlet, first cool down, and after being separated, then heat up and carry out methanation reaction, and energy consumption is very high.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide one kind methane directly prepares aromatic hydrocarbons
System and method for, by the tail gas of methane aromatization system outlet after heat exchange, directly and CO2In Suitable ranges
Reaction, then again with isolation technics aromatic hydrocarbons, water and gas (methane, containing remaining a small amount of hydrogen) separation, methane gas can be real
Existing conversion and cycle, not only avoids aromatic hydrocarbons and the high difficult problem of methane, hydrogen separating energy consumption, flow process is simplified, while being effectively utilized
Process heat energy, with equipment investment is both reduced, reduces the advantage of aromatics production cost again.
To achieve these goals, the technical solution used in the present invention is：
The system that a kind of methane directly prepares aromatic hydrocarbons, including：
Methane aromatizing subsystem 1, its system entry connects methane, and outlet obtains the gaseous mixture of methane, hydrogen and aromatic hydrocarbons；
Methanation reaction subsystem 2, its entrance meets the outlet of methane aromatizing subsystem 1 and CO2, its outlet obtains first
Alkane, aromatic hydrocarbons, water and remaining hydrogen；
Isolated subsystem 3, its entrance connects the outlet of methanation reaction subsystem 2, by methane, aromatic hydrocarbons, water and residual hydrogen
Edema caused by disorder of QI is from wherein separating obtained methane and remaining hydrogen are recycled to methane aromatizing subsystem 1 and recycle.
The methanation reaction subsystem 2 is using multistage alternating temperature fixed bed reactors or multistage alternating temperature fluidized-bed reactor
(multistage refers to two sections to more than two sections), the temperature of reactor is controlled with saturation cooling water or Low Temperature Steam, the high-temperature steam for obtaining
Unstripped gas for methane aromatization system 1 is preheated.
Metal load type catalyst used in the methanation reaction subsystem 2, wherein metal be Ni, Cu, Fe, Pt, Pd,
One kind in Co, Re, Mo, W, Cr, Mn and Rh or by various alloys for being formed, carrier is Al2O3、SiO2And ZrO2In
It is a kind of or by various mixture for being formed, using alkali metal and rare earth element as auxiliary agent, the quality of metal in the catalyst
Fraction is 0.1-10%, and alkali-metal mass fraction is 0.01-2%, and the mass fraction of rare earth element is 0.01-2%, and remaining is
Catalyst carrier.
The alkali metal is K or Na, and the rare earth element is La or Ce.
Present invention also offers the method that aromatic hydrocarbons is directly prepared based on the system methane, by methane in methane aromatizing
The high-temperature gas mixture that aromatisation obtains methane, hydrogen and aromatic hydrocarbons is carried out in subsystem 1, the high-temperature gas mixture is cooled to into 300-
350 DEG C, with CO2The reaction wherein of methanation reaction subsystem 2 is sent into together obtains methane, aromatic hydrocarbons, water and remaining hydrogen
Compounding substances, then compounding substances feeding isolated subsystem 3 is separated, isolated methane is recycled to remaining hydrogen
Methane aromatizing subsystem 1 is recycled, and aromatic hydrocarbons is with water as final products.
In the compounding substances, remaining hydrogen is less than 1%, CO with the Volume fraction of methane2With the volume fraction of methane
Than less than 0.05%.
The methanation reaction subsystem 2 adopts multistage alternating temperature fixed bed reactors or multistage alternating temperature fluidized-bed reactor,
The temperature of reactor is controlled with saturation cooling water or Low Temperature Steam, and the high-temperature steam for obtaining is used for methane aromatization system 1
Unstripped gas preheating；Metal load type catalyst used in methanation reaction subsystem 2, wherein metal be Ni, Cu, Fe, Pt,
One kind in Pd, Co, Re, Mo, W, Cr, Mn and Rh or by various alloys for being formed, carrier is Al2O3、SiO2And ZrO2In
One kind or by various mixture for being formed, using alkali metal and rare earth element as auxiliary agent, the quality of metal point in catalyst
Number is 0.1-10%, and alkali-metal mass fraction is 0.01-2%, and the mass fraction of rare earth element is 0.01-2%, and remaining is to urge
Agent carrier, reaction condition is：Using temperature 200-350 DEG C, pressure 0.1-1MPa (absolute pressure).
The operational approach of the reactor of the methanation reaction subsystem 2：By CO2Become from multistage with the high-temperature gas mixture
The high-temperature region of warm fixed bed reactors or multistage alternating temperature fluidized-bed reactor is passed through, centre by heat exchange control temperature, finally from
Low-temperature space goes out methanation reaction subsystem 2, wherein high-temperature region temperature range 300-350 DEG C, low-temperature space temperature range 200-250
℃。
Compared with prior art, the invention has the beneficial effects as follows：
1st, the aromatic hydrocarbons that need not arrange low content is separated with a large amount of gases (hydrogen and methane), it is not required that arrange methane
With the piece-rate system of hydrogen, isolation technics difficulty is not only reduced, and equipment investment is greatly saved.
2nd, methanation system is directly connect after methane aromatizing subsystem, it is to avoid first cooling and the energy for heating up again of gas
Consumption.The gas raw material expense of the technology reduces 30%-40% than the expense that aromatic hydrocarbons is prepared with pure methane raw material.
3rd, using various alternating temperature fluid beds or fixed bed reactors, CO can effectively be converted2With H2, it is to avoid CO2To pipe
The sour corrosion in road.
4th, using the methanation catalyst containing alkalinous metal and rare earth element, can adapt to the first under aromatic hydrocarbons existence condition
Alkylation reaction, make first to carry out methanation, laggard water-filling and aromatic hydrocarbons, methane etc. is separated into possibility, greatly shortens flow process.
5th, hydrogen do not converted completely, makes residual hydrogen on the premise of methane aromatizing effect is not affected, directly and methane
Methane aromatizing subsystem is back to, plant investment and energy consumption is saved.
Description of the drawings
Fig. 1 is the structured flowchart of the system that present invention methane directly prepares aromatic hydrocarbons.
Specific embodiment
Describe embodiments of the present invention in detail with reference to the accompanying drawings and examples.
As shown in figure 1, the system that a kind of methane of the present invention directly prepares aromatic hydrocarbons, including：
Methane aromatizing subsystem 1, its system entry connects methane, and outlet obtains the gaseous mixture of methane, hydrogen and aromatic hydrocarbons；
Methanation reaction subsystem 2, its entrance meets the outlet of methane aromatizing subsystem 1 and CO2, its outlet obtains first
Alkane, aromatic hydrocarbons, water and remaining hydrogen；
Isolated subsystem 3, its entrance connects the outlet of methanation reaction subsystem 2, by methane, aromatic hydrocarbons, water and residual hydrogen
Edema caused by disorder of QI is from wherein separating obtained methane and remaining hydrogen are recycled to methane aromatizing subsystem 1 and recycle.
Wherein, in methane aromatizing subsystem 1, with methane or with the mixture of a small amount of other gases (such as residual hydrogen, inertia
Gas (such as nitrogen, argon etc.)) it is used as reaction raw materials.Catalyst is being reported (as divided in fluid bed or fixed bed reactors
The upper carried metal of son sieve, such as metal Mo, Ga, Cu, Au, Ag, Fe, Ni, Mn even loads are on ZSM-5 or MCM-22 is first-class) on it is anti-
Answer (general temperature control is at 600-1000 DEG C), reactor outlet obtains the (mixing of methane, aromatic hydrocarbons and hydrogen of high-temperature product gas
Thing).After catalyst inactivation, point two methods regeneration, one kind is in fluidized bed reaction system, to move on to special regeneration reactor
Charcoal regeneration, then returns again to aromatization reactor.If using fixed bed reaction system, reaction mass cut out, carry out
After atmosphere displacement, logical oxygen-containing gas carries out regeneration and burns carbon (general regeneration temperature is controlled to 500-700 DEG C), and then again Jing atmosphere is put
After changing, it is passed through reaction mass and continues reaction at appropriate temperatures.)
Methanation reaction subsystem 2 is using multistage alternating temperature fixed bed reactors or multistage alternating temperature fluidized-bed reactor (multistage
Refer to two sections to more than two sections), the temperature of reactor is controlled with saturation cooling water or Low Temperature Steam, and the high-temperature steam for obtaining is used for first
The unstripped gas preheating of alkane aromatization system 1.
In isolated subsystem 3, methane, aromatic hydrocarbons, water and the mixture of remaining hydrogen are first passed through and cooled, according to dew point
Difference, in common gas-liquid separator, makes gas (methane and remaining hydrogen) be separated with liquid (aromatic hydrocarbons and water).Methane
Circulation is can be carried out with residual hydrogen through necessary drying (removing residual liquid with adsorbent such as in fixed bed).Institute
Liquid (aromatic hydrocarbons and water) is obtained in 20-40 DEG C of stratification of normal pressure.The liquid rich in aromatic hydrocarbons is extracted, using rectification or other separation sides
Method removes remaining water, obtains aromatic hydrocarbon product；The liquid rich in water is extracted, using rectification or adsorption method virtue therein is removed
Hydrocarbon, obtains that the water of process can be sent outside).
Based on said system, aromatic hydrocarbons can be directly prepared with methane, specific embodiment is as follows.
Embodiment 1
It is enterprising in existing catalyst (Mo/ZSM-5) at 700 DEG C by methane in conventional fluidized bed reactor system
Row conversion, obtains high-temperature product gas (aromatic hydrocarbons, hydrogen and methane).
Methane aromatizing subsystem 1 is mixed into High Temperature Gas (aromatic hydrocarbons, methane, hydrogen) through being cooled to 300 DEG C, with CO2One
Rise and be passed through methanation reaction subsystem 2, (Ni/K/Ce/Al is filled with from two sections of alternating temperature fluid beds2O3(Ni, K, Ce are being urged catalyst
Mass fraction in agent is respectively 10%, 0.01%, 2%)；350 DEG C of high temperature section；200 DEG C of low-temperature zone, reactor is by indirect
Heat exchange control temperature, reactor pressure 1MPa (absolute pressure)), the compounding substances (CH of the outlet of methanation reaction subsystem 2 after reaction4,
H2, H2The mixture of O and aromatic hydrocarbons) in H2With CH4Volume fraction be less than 1%, CO2With CH4Volume fraction be less than
0.05%.The compounding substances are passed through isolated subsystem 3 and are separated, and after methane is drawn with a small amount of hydrogen by isolated subsystem 3, lead to
Enter methane aromatizing subsystem 1 and be circulated to use.After aromatic hydrocarbons is separated from water, product is formed.
The temperature of the fluidized-bed reactor in methanation reaction subsystem 2 saturation cooling water control, the high temperature for obtaining steams
Vapour is used for the unstripped gas of methane aromatizing subsystem 1 and preheats.
Embodiment 2
It is enterprising in existing catalyst (Mo/ZSM-5) at 750 DEG C by methane in conventional fixed bed reactor system
Row conversion, obtains high-temperature product gas (aromatic hydrocarbons, hydrogen and methane).
Methane aromatizing subsystem 1 is mixed into High Temperature Gas (aromatic hydrocarbons, methane, hydrogen) through being cooled to 350 DEG C, with CO2One
Rise and be passed through methanation reaction subsystem 2, (Ni/Mo/K/La/Al is filled with from two sections of alternating temperature fixed beds2O3Catalyst (Ni, Mo, K,
La mass fractions in the catalyst are respectively 1%, 5%, 2%, 2%)；350 DEG C of high temperature section；200 DEG C of low-temperature zone, reactor leads to
Cross indirect heat exchange control temperature, reactor pressure 0.6MPa (absolute pressure)), the mixing of the outlet of methanation reaction subsystem 2 after reaction
Material (CH4, H2, H2The mixture of O and aromatic hydrocarbons) in H2With CH4Volume fraction be less than 1%, CO2With CH4Volume fraction
Less than 0.05%.The compounding substances are passed through isolated subsystem 3 and are separated, and methane is drawn with a small amount of hydrogen by isolated subsystem 3
Afterwards, it is passed through methane aromatizing subsystem 1 and is circulated and uses.After aromatic hydrocarbons is separated from water, product is formed.
The temperature of the fixed bed reactors in methanation reaction subsystem 2 saturation cooling water control, the high temperature for obtaining steams
Vapour is used for the unstripped gas of methane aromatizing subsystem 1 and preheats.
Embodiment 3
Methane aromatizing subsystem 1 is mixed into High Temperature Gas (aromatic hydrocarbons, methane, hydrogen) through being cooled to 300 DEG C, with CO2One
Rise and be passed through methanation reaction subsystem 2, (Co/W/K/Ce/ZrO is filled with from three sections of alternating temperature fluid beds2Catalyst (Co, W, K, Ce
Mass fraction in the catalyst is respectively 3%, 3%, 1.2%, 0.8%)；350 DEG C of high temperature section；280 DEG C of middle-temperature section, low-temperature zone
250 DEG C, reactor controls temperature, reactor pressure 0.5MPa (absolute pressure) by indirect heat exchange), methanation reaction subsystem after reaction
Compounding substances (the CH of the outlet of system 24, H2, H2The mixture of O and aromatic hydrocarbons) in H2With CH4Volume fraction be less than 1%, CO2With
CH4Volume fraction be less than 0.05%.The compounding substances are passed through isolated subsystem 3 and are separated, methane and a small amount of hydrogen by
After isolated subsystem 3 is drawn, it is passed through methane aromatizing subsystem 1 and is circulated and use.After aromatic hydrocarbons is separated from water, product is formed.
The Low Temperature Steam control of the temperature of the fluidized-bed reactor in methanation reaction subsystem 2, the high-temperature steam for obtaining
Unstripped gas for methane aromatizing subsystem 1 is preheated.
Embodiment 4
Methane aromatizing subsystem 1 is mixed into High Temperature Gas (mainly containing aromatic hydrocarbons, methane, hydrogen) through being cooled to 320 DEG C, with
CO2Methanation reaction subsystem 2 is passed through together, and (Ni/Mn/Na/Ce/ZrO is filled with from four sections of alternating temperature fixed beds2-Al2O3Catalysis
(Ni, Mn, Na, Ce mass fraction in the catalyst is respectively 2%, 2%, 0.01%, 0.01%) for agent；High temperature section is to low-temperature zone
Temperature be followed successively by 350,320,240,200 DEG C, reactor controls temperature by indirect heat exchange, and reactor pressure 0.4MPa is (absolutely
Pressure)), the compounding substances (CH of the outlet of methanation reaction subsystem 2 after reaction4, H2, H2The mixture of O and aromatic hydrocarbons) in H2With CH4's
Volume fraction is less than 1%, CO2With CH4Volume fraction be less than 0.05%.The compounding substances are passed through isolated subsystem 3 and carry out
Separate, after methane is drawn with a small amount of hydrogen by isolated subsystem 3, be passed through methane aromatizing subsystem 1 and be circulated and use.Aromatic hydrocarbons
After being separated from water, product is formed.
The temperature of the fixed bed reactors in methanation reaction subsystem 2 saturation cooling water control, the high temperature for obtaining steams
Vapour is used for the unstripped gas of methane aromatizing subsystem 1 and preheats.
Embodiment 5
Methane aromatizing subsystem 1 is mixed into High Temperature Gas (mainly containing aromatic hydrocarbons, methane, hydrogen) through being cooled to 310 DEG C, with
CO2Methanation reaction subsystem 2 is passed through together, and (Fe/Ni/Cr/K/La/SiO is filled with from five sections of alternating temperature fixed beds2Catalyst
(Fe, Ni, Cr, K, La mass fraction in the catalyst is respectively 1%, 6%, 0.5%, 0.5%, 0.2%)；High temperature section is to low
Temperature section temperature is followed successively by 350 DEG C, and 320,280,250,200 DEG C, reactor controls temperature, reactor pressure by indirect heat exchange
0.3MPa (absolute pressure)), the compounding substances (CH of the outlet of methanation reaction subsystem 2 after reaction4, H2, H2The mixture of O and aromatic hydrocarbons)
Middle H2With CH4Volume fraction be less than 1%, CO2With CH4Volume fraction be less than 0.05%.The compounding substances are passed through separation
Subsystem 3 is separated, and after methane is drawn with a small amount of hydrogen by isolated subsystem 3, is passed through methane aromatizing subsystem 1 and is followed
Ring is used.After aromatic hydrocarbons is separated from water, product is formed.
The Low Temperature Steam control of the temperature of the fixed bed reactors in methanation reaction subsystem 2, the high-temperature steam for obtaining
Unstripped gas for methane aromatizing subsystem 1 is preheated.
Embodiment 6
Methane aromatizing subsystem 1 is mixed into High Temperature Gas (mainly containing aromatic hydrocarbons, methane, hydrogen) through being cooled to 350 DEG C, with
CO2Methanation reaction subsystem 2 is passed through together, and (Fe/Ni/Rh/K/La/Al is filled with from five sections of alternating temperature fluid beds2O3-SiO2Urge
(Fe, Ni, Rh, K, La mass fraction in the catalyst is respectively 4%, 0.1%, 2.5%, 0.5% to agent, 0.2%)；High temperature
Section is followed successively by 350,330,270,230,200 DEG C to low-temperature zone temperature, reactor pressure 0.8MPa (absolute pressure)), methane after reaction
Change the compounding substances (CH of the reaction outlet of subsystem 24, H2, H2The mixture of O and aromatic hydrocarbons) in H2With CH4Volume fraction be less than
1%, CO2With CH4Volume fraction be less than 0.05%.The compounding substances are passed through isolated subsystem 3 and are separated, methane with it is few
After amount hydrogen is drawn by isolated subsystem 3, it is passed through methane aromatizing subsystem 1 and is circulated and use.After aromatic hydrocarbons is separated from water, shape
Into product.
The temperature of the fluidized-bed reactor in methanation reaction subsystem 2 is controlled with saturation cooling water or Low Temperature Steam, is obtained
The high-temperature steam for arriving is used for the unstripped gas of methane aromatizing subsystem 1 and preheats.
Embodiment 7
Methane aromatizing subsystem 1 is mixed into High Temperature Gas (mainly containing aromatic hydrocarbons, methane, hydrogen) through being cooled to 330 DEG C, with
CO2Methanation reaction subsystem 2 is passed through together, and (Rh/K/Ce/Al is filled with from three sections of alternating temperature fixed beds2O3Catalyst (Rh, K,
Ce mass fractions in the catalyst are respectively 0.1%, 2%, 2%)；High temperature section to the temperature of low-temperature zone is respectively 350,270,
200 DEG C, reactor pressure 0.1MPa (absolute pressure)), the compounding substances (CH of the outlet of methanation reaction subsystem 2 after reaction4, H2, H2O
With the mixture of aromatic hydrocarbons) in H2With CH4Volume fraction be less than 1%, CO2With CH4Volume fraction be less than 0.05%.Should
Compounding substances are passed through isolated subsystem 3 and are separated, and after methane is drawn with a small amount of hydrogen by isolated subsystem 3, are passed through methane virtue
Structure sub-systems 1 are circulated and use.After aromatic hydrocarbons is separated from water, product is formed.
The temperature of the fixed bed reactors in methanation reaction subsystem 2 saturation cooling water control, the high temperature for obtaining steams
Vapour is used for the unstripped gas of methane aromatization subsystem (1) and preheats.
Embodiment 8
Methane aromatizing subsystem 1 is mixed into High Temperature Gas (mainly containing aromatic hydrocarbons, methane, hydrogen) through being cooled to 350 DEG C, with
CO2Methanation reaction subsystem 2 is passed through together, and (Pt/Fe/K/Ce/Al is filled with from four sections of alternating temperature fluid beds2O3Catalyst (Pt,
Fe, K, Ce mass fraction in the catalyst is respectively 0.2%, 3%, 2%, 2%)；High temperature section to the temperature of low-temperature zone is distinguished
For 350,310,270,200 DEG C, reactor pressure 0.1MPa (absolute pressure)), the mixing of the outlet of methanation reaction subsystem 2 after reaction
Material (CH4, H2, H2The mixture of O and aromatic hydrocarbons) in H2With CH4Volume fraction be less than 1%, CO2With CH4Volume fraction
Less than 0.05%.The compounding substances are passed through isolated subsystem 3 and are separated, and methane is drawn with a small amount of hydrogen by isolated subsystem 3
Afterwards, it is passed through methane aromatizing subsystem 1 and is circulated and uses.After aromatic hydrocarbons is separated from water, product is formed.
The Low Temperature Steam control of the temperature of the fluidized-bed reactor in methanation reaction subsystem 2, the high-temperature steam for obtaining
Unstripped gas for methane aromatization subsystem (1) is preheated.
Embodiment 9
Methane aromatizing subsystem 1 is mixed into High Temperature Gas (mainly containing aromatic hydrocarbons, methane, hydrogen) through being cooled to 320 DEG C, with
CO2Methanation reaction subsystem 2 is passed through together, and (Pd/W/K/La/Al is filled with from three sections of alternating temperature fixed beds2O3-ZrO2Catalyst
(Pd, W, K, La mass fraction in the catalyst is respectively 0.7%, 2%, 2%, 0.01%)；300 DEG C of high temperature section；Middle-temperature section
260 DEG C, 200 DEG C of low-temperature zone, reactor pressure 0.9MPa (absolute pressure)), the mixture of the outlet of methanation reaction subsystem 2 after reaction
Matter (CH4, H2, H2The mixture of O and aromatic hydrocarbons) in H2With CH4Volume fraction be less than 1%, CO2With CH4Volume fraction it is little
In 0.05%.The compounding substances are passed through isolated subsystem 3 and are separated, after methane is drawn with a small amount of hydrogen by isolated subsystem 3,
It is passed through methane aromatizing subsystem 1 and is circulated and uses.After aromatic hydrocarbons is separated from water, product is formed.
The temperature of the fixed bed reactors in methanation reaction subsystem 2 saturation cooling water control, the high temperature for obtaining steams
Vapour is used for the unstripped gas of methane aromatizing subsystem 1 and preheats.
Claims (3)
1. a kind of method that methane directly prepares aromatic hydrocarbons, it is characterised in that the device for being used includes：
Methane aromatizing subsystem (1), its system entry connects methane, and outlet obtains the gaseous mixture of methane, hydrogen and aromatic hydrocarbons；
Methanation reaction subsystem (2), its entrance meets the outlet of methane aromatizing subsystem (1) and CO2, its outlet obtains first
Alkane, aromatic hydrocarbons, water and remaining hydrogen；
Isolated subsystem (3), its entrance connects the outlet of methanation reaction subsystem (2), by methane, aromatic hydrocarbons, water and residual hydrogen
Edema caused by disorder of QI is from wherein separating obtained methane and remaining hydrogen are recycled to methane aromatizing subsystem (1) recycling；The methanation
Reaction subsystem (2) uses full using multistage alternating temperature fixed bed reactors or multistage alternating temperature fluidized-bed reactor, the temperature of reactor
Control with cooling water or Low Temperature Steam, the high-temperature steam for obtaining is used for the unstripped gas of methane aromatization system (1) and preheats；
Metal load type catalyst used in the methanation reaction subsystem (2), wherein metal be Ni, Cu, Fe, Pt, Pd,
One kind in Co, Re, Mo, W, Cr, Mn and Rh or by various alloys for being formed, carrier is Al2O3、SiO2And ZrO2In
It is a kind of or by various mixture for being formed, using alkali metal and rare earth element as auxiliary agent, the quality of metal in the catalyst
Fraction is 0.1-10%, and alkali-metal mass fraction is 0.01-2%, and the mass fraction of rare earth element is 0.01-2%, and remaining is
Catalyst carrier, the alkali metal is K or Na, and the rare earth element is La or Ce；
Methane is carried out into the high-temperature gas mixture that aromatisation obtains methane, hydrogen and aromatic hydrocarbons in methane aromatizing subsystem (1), will
The high-temperature gas mixture is cooled to 300-350 DEG C, with CO2Wherein reaction obtains first to send into methanation reaction subsystem (2) together
The compounding substances of alkane, aromatic hydrocarbons, water and remaining hydrogen, then compounding substances feeding isolated subsystem (3) are separated, separate
The methane for obtaining is recycled to methane aromatizing subsystem (1) recycling with remaining hydrogen, and aromatic hydrocarbons is with water as final products, institute
In stating compounding substances, remaining hydrogen is less than 1%, CO with the Volume fraction of methane2It is less than with the Volume fraction of methane
0.05%.
2. the method for directly preparing aromatic hydrocarbons with methane according to claim 1, it is characterised in that the methanation reaction subsystem
System (2) is using multistage alternating temperature fixed bed reactors or multistage alternating temperature fluidized-bed reactor, the temperature saturation cooling water of reactor
Or Low Temperature Steam is controlled, the high-temperature steam for obtaining is used for the unstripped gas of methane aromatization system (1) and preheats；Methanation reaction
Metal load type catalyst used in subsystem (2), wherein metal be Ni, Cu, Fe, Pt, Pd, Co, Re, Mo, W, Cr, Mn and
One kind in Rh or by various alloys for being formed, carrier is Al2O3、SiO2And ZrO2In one kind or by it is various formed it is mixed
Compound, using alkali metal and rare earth element as auxiliary agent, the mass fraction of metal is 0.1-10% in catalyst, alkali-metal matter
Amount fraction is 0.01-2%, and the mass fraction of rare earth element is 0.01-2%, and remaining is catalyst carrier, and reaction condition is：Make
With temperature 200-350 DEG C, pressure 0.1-1MPa.
3. the method for directly preparing aromatic hydrocarbons with methane according to claim 1, it is characterised in that the methanation reaction subsystem
The operational approach of the reactor of system (2)：By CO2With the high-temperature gas mixture from multistage alternating temperature fixed bed reactors or multistage alternating temperature
The high-temperature region of fluidized-bed reactor is passed through, and centre finally goes out methanation reaction subsystem by heat exchange control temperature from low-temperature space
(2), wherein high-temperature region temperature range 300-350 DEG C, low-temperature space temperature range 200-250 DEG C.
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