CN101774876B - Method for preparing aromatic hydrocarbon by aromatizing methane and special-purpose reaction system thereof - Google Patents
Method for preparing aromatic hydrocarbon by aromatizing methane and special-purpose reaction system thereof Download PDFInfo
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- CN101774876B CN101774876B CN 201010102634 CN201010102634A CN101774876B CN 101774876 B CN101774876 B CN 101774876B CN 201010102634 CN201010102634 CN 201010102634 CN 201010102634 A CN201010102634 A CN 201010102634A CN 101774876 B CN101774876 B CN 101774876B
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Abstract
The invention discloses a method for preparing aromatic hydrocarbon by aromatizing methane and a special-purpose reaction system thereof. In the method, aromatic hydrocarbon is separated from the outlet gas of the methane aromatization reaction system, residual tail gas (methane containing about 20 percent of hydrogen) and CO2 carry out methanation reaction on supported metal catalyst in a fluidized bed, so that the tail gas is changed into methane and water again, hydrogen is almost completely converted, and after the water is separated, the methane can be recycled. The technique not only effectively solves the problem that the cost of separating methane from hydrogen is high in the process of independent aromatization, but also can effectively utilize CO2 to produce aromatic hydrocarbon, the process is shortened, the investment is less, the material cost is low, and thereby the cost of preparing aromatic hydrocarbon is greatly reduced.
Description
Technical field
The present invention relates to a kind of method and special-purpose reaction system thereof of preparing aromatic hydrocarbon by aromatizing methane.
Background technology
Benzene and other aromatic hydrocarbon product are important basic chemical industry raw materials, and be main by the petroleum refining process by-product at present.Recently along with the global crude oil price continue raise up and the increase of aromatic hydrocarbons derived product demand the holding at high price of benzene and other aromatic hydrocarbons.The China's oil shortage of resources, the demand gap of automobile oil (gasoline, diesel oil, kerosene and lubricated wet goods) is large, and ethene, propylene, divinyl etc. are sought-after, so the output for preparing aromatic hydrocarbons from petroleum path is more and more restricted.In order to satisfy all kinds of Chemical products productions of China to the rapid increase of benzene and other aromatic hydrocarbons demands, be necessary very much to seek the aromatic hydrocarbons syntheti c route of suitable non-petroleum sources.
Utilize metal-molecular sieve composite catalyst, can be in oxygen-free environment be aromatic hydrocarbons with methane conversion.Take the Mo/HZSM-5 catalyzer as example, under 973K and normal pressure, methane conversion is approximately 16%, and the selectivity of aromatic hydrocarbons is greater than 90%, and wherein the selectivity of benzene reaches again 90% in the aromatic hydrocarbons, and other aromatic hydrocarbon products are a small amount of toluene and naphthalene.Because the benzene purposes is wide, demand is large, and this route becomes in the world lasting study, the potential chemical industry route of tool.
Yet in the past twenties years, various countries scientist's research work mainly concentrates on the manufacturing of catalyzer, and aspects such as reaction and deactivation mechanism.The preparative-scale of aromatization is in laboratory microreactor conceptual phase, there is no the through engineering approaches report.Wherein one of major technique bottleneck of through engineering approaches difficulty is, because thermodynamics equilibrium limit, the per pass conversion lower (about 16%) of the aromatization that carries out under 600-700 ℃ contains 22% hydrogen and 78% methane approximately in the gas of generation.Because this route is not yet realized industrialization at present, there is not the report about the isolation technique of methane and hydrogen in this particular system.From general technical standpoint, the method for available pressure-variable adsorption realizes the methane cycle reuse with hydrogen and methane separation.But this separation costs is higher, and power consumption.Simultaneously, in specific system, the hydrogen of generation is useless, and its storage is a very large problem.
Summary of the invention
The reactive system that the purpose of this invention is to provide a kind of preparing aromatic hydrocarbon by aromatizing methane.
The reactive system of preparing aromatic hydrocarbon by aromatizing methane provided by the present invention, separation system 2, methanation reaction system 3 and methane and water separating system 4 by methane aromatization system 1, aromatic hydrocarbons and methane, hydrogen form, and are connected by pipeline successively between them;
Wherein, the reactor in the described methanation reaction system 3 is fluidized-bed reactor; The catalyzer that adopts in the described methanation reaction system 3 is metal load type catalyst, described metal is selected from the alloy of following at least a metal or following at least two kinds of metals formation: Ni, Fe, Co, Re, Mo, W, Cr, Mn and Rh, the carrier in the described metal load type catalyst is selected from following at least a: Al
2O
3, SiO
2And ZrO
2, the massfraction of metal is 10-30% in the described metal load type catalyst; The intensity of described metal load type catalyst is Mohs' hardness 6-10, and particle diameter is the 50-500 micron, and tap density is 500-1500kg/m
3, specific surface area is 150-400m
2/ g.
Described methane aromatization system 1 comprises the fluidized-bed reactor of methane aromatizing, the reactor of aromatized catalyst charcoal regeneration and handling equipment and the pipeline that the catalyzer between two reactors is carried back and forth;
The separation system 2 of described aromatic hydrocarbons and methane, hydrogen is comprised of interchanger and the transferpump of organic solvent with the organic solvent of absorption tower, desorption tower and the differing temps of the described organic solvent of carrying.
Described methane and water separating system 4 are comprised of interchanger and air water separator.
A further object of the present invention provides a kind of method of preparing aromatic hydrocarbon by aromatizing methane.
The method of preparing aromatic hydrocarbon by aromatizing methane provided by the present invention comprises the steps:
1) makes in the methane aromatization system 1 of methane in reactive system provided by the present invention and carry out aromatization, obtain the mixed gas of aromatic hydrocarbons, methane and hydrogen;
2) described mixed gas is passed in the separation system 2 of aromatic hydrocarbons and methane, hydrogen, organic solvent or solvent oil in the separated system 2 of aromatic hydrocarbons in the described mixed gas are absorbed, obtain the mixed gas of methane and hydrogen; Then, with the desorb from described organic solvent or solvent oil of described aromatic hydrocarbons, obtain aromatic hydrocarbons;
3) with step 2) methane that obtains and the mixed gas of hydrogen introduce in the fluidized-bed reactor of methanation reaction system 3, and pass into simultaneously CO
2, make hydrogen and CO
2Catalyzer in described fluidized-bed reactor reacts, and obtains the mixed gas of methane and water vapour;
Described catalyzer is metal load type catalyst, and described metal can be selected from the alloy of following at least a metal or following at least two kinds of metals formation: Ni, Fe, Co, Re, Mo, W, Cr, Mn and Rh, the carrier in the described metal load type catalyst can be selected from following at least a: Al
2O
3, SiO
2And ZrO
2, the massfraction of metal is 10-30% in the described metal load type catalyst, specifically can be 10%-20%, 20%-30%; The intensity of described metal load type catalyst is Mohs' hardness 6-10, and particle diameter is the 50-500 micron, specifically can be 50-200 micron, 200-500 micron, and tap density is 500-1500kg/m
3, specifically can be 500-900,900-1500kg/m
3, specific surface area is 150-400m
2/ g specifically can be 150-300m
2/ g, 300-400m
2/ g;
4) with step 3) methane that obtains and the mixed gas of water vapour introducing methane and water separating system 4, by interchanger water vapor is cooled off, then through air water separator with methane and moisture from, methane is returned in the methane aromatization system 1 by pipeline recycle at last.
Wherein, the boiling point of organic solvent and described solvent oil step 2) all is higher than 140 ℃; Described organic solvent specifically can be Three methyl Benzene, tetramethyl-benzene, pentamethylbenzene, hexamethyl-benzene etc., described solvent oil specifically can be the multiple high boiling paraffinic hydrocarbons that satisfies this boiling range, the mixture of naphthenic hydrocarbon or aromatic hydrocarbon is such as the 190# among the GB1992-80 (88), 260# solvent oil or methylnaphthalene, acenaphthene etc.The temperature that organic solvent in the separated system 2 of aromatic hydrocarbons in the described mixed gas or solvent oil absorb can be 20-30 ℃; The temperature of described aromatic hydrocarbons desorb from described organic solvent or solvent oil can be 140-160 ℃.
Step 3) hydrogen and CO in
2The temperature of reaction that catalyzer in described fluidized-bed reactor reacts can be 250-450 ℃, and the absolute pressure of described reaction is 0.02-1MPa, specifically can be 0.02-0.1MPa, 0.1-1.0MPa; Hydrogen and CO in the reaction system of described reaction
2Mol ratio be 3.8-4.2, CO
2Volume space velocity be 100-10000h
-1, specifically can be 100-1000h
-1, 2000-5000h
-1, 7000-10000h
-1Step 3) volume fraction of hydrogen is lower than 1% in the methane that obtains and the mixed gas of water vapour.
The step 2 of aforesaid method) in, from organic solvent or solvent oil after the desorb, remaining organic solvent or solvent oil can return in the separation system 2 and continue to recycle with aromatic hydrocarbons.
The step 3 of aforesaid method) in, the temperature of the fluidized-bed reactor in the methanation system 3 is by saturated cooling water control or saturated water coolant and superheated vapour control, the high temperature that obtains (200-400 ℃) steam is used for methane aromatization system 1 Raw gas is carried out preheating, or as the thermal source of aromatic hydrocarbons desorb in the separation system 2 of aromatic hydrocarbons and methane, hydrogen.
Aforesaid method step 1) in, make the concrete grammar of methane aromatizing be: aromatized catalyst (is contained Cu, Fe, Ni, Mn, Mo, the metals such as Ga, with ZSM-5 molecular sieve, the content of metal is 4-10%) be packed in the methane aromatizing fluidized-bed reactor, be warming up to 600-750 ℃, then methane is passed into and react, control methane air speed is 1000-3000L/gcat/h, the aromatic hydrocarbons that generates, hydrogen exports out the methane aromatization system with unconverted methane from fluidized-bed reactor. when the carbon deposition quantity of aromatized catalyst greater than 3% the time, through piping and e Foerderanlage, move to the catalyst regeneration fluidized-bed reactor and regenerate that (regenerating medium is air, the control regeneration temperature is 500-600 ℃), make the content carbon of catalyzer be lower than 0.1% after, by pipeline and e Foerderanlage, be transmitted back to the methane aromatizing fluidized-bed reactor, carry out successive reaction.
Methane provided by the present invention prepares in the method for aromatic hydrocarbons, the exit gas of methane aromatization system is isolated aromatic hydrocarbon product after, with residual exhaust (methane that contains approximately 20% hydrogen) and CO
2Metal load type catalyst in fluidized-bed carries out methanation reaction, makes tail gas again become methane and water, realizes that approaching fully of hydrogen transforms, and realizes the recycle of methane behind the Separation of Water.Above-mentioned technology both can effectively solve the high problem of methane in the independent aromatization process and Hydrogen Separation cost, can effectively utilize CO again
2Produce aromatic hydrocarbons, shorten flow process, less investment, raw materials cost is low, makes the cost decrease of preparation aromatic hydrocarbons.
The method of preparing aromatic hydrocarbon by aromatizing methane provided by the present invention is compared with existing method has following advantage:
1, method of the present invention does not need to arrange the recovery system of methane and hydrogen, has not only reduced the isolation technique difficulty, and has significantly saved facility investment.
2, method of the present invention is being utilized CO
2Methanation is carried out in the process of methane cycle utilization, calculates with the maximum aromatic hydrocarbons (benzene) that generates, and is equivalent to former cause 6mol methane is generated 1mol benzene and 9mol H
2Reaction, become 2.25mol CO
2With the process of 3.75mol methane generation 1mol benzene and 4.5mol water, saved 40% methane feed gas, and can effectively utilize the CO in the stack gas
2Gas is equivalent to use CO
2Produce aromatic hydrocarbons, the gas raw material expense Billy of this technology reduces 25%-30% with the expense that the pure methane raw material prepares aromatic hydrocarbons.
3, CO
2With H
2Methanation reaction be strong exothermal reaction, utilize this reaction heat can by-product high-pressure steam, be used for the desorb of aromatic hydrocarbons and organic solvent, or the preheating of methane aromatizing unstripped gas, or the further separation of aromatic hydrocarbon product, can make aromatic hydrocarbons production cost reduction 5-8% per ton.
Description of drawings
Fig. 1 is the synoptic diagram of the reactive system of preparing aromatic hydrocarbon by aromatizing methane provided by the present invention.
Embodiment
Describe below by the method for specific embodiment to preparing aromatic hydrocarbon by aromatizing methane provided by the present invention, but the present invention is not limited thereto.Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
Following each embodiment step 3) used metal load type catalyst can prepare by the following method in: use basic solution (such as volatile salt the corresponding nitrate of the metal in one or more reactive metals and the carrier, muriate or organic compound etc., bicarbonate of ammonia, urea, NaOH, KOH, Na
2CO
3, ammonium sulfate etc.) and carry out the coprecipitation method preparation, through super-dry, roasting obtains; Perhaps directly use carrier (Al
2O
3And/or SiO
2And/or ZrO
2), with the nitrate of reactive metal, muriate or organic compound etc. flood thereon, then filter, and drying, roasting obtains.
Embodiment 1, preparing aromatic hydrocarbon by aromatizing methane
In reactive system shown in Figure 1, be prepared.
1) with aromatized catalyst (as: Mo/ZSM-5, the massfraction of Mo is 6%) be packed in the methane aromatizing fluidized-bed reactor, be warming up to 700 ℃, then methane being passed into fluidized-bed reactor reacts, control methane air speed is 1000L/ (gcath), the aromatic hydrocarbons that generates, hydrogen exports out the methane aromatization system with unconverted methane from fluidized-bed reactor.When the carbon deposition quantity of aromatized catalyst greater than 3% the time, through piping and e Foerderanlage, move to the catalyst regeneration fluidized-bed reactor and regenerate that (regenerating medium is air, the control regeneration temperature is 500 ℃), after making the content carbon of catalyzer be lower than 0.1%, by pipeline and e Foerderanlage, be transmitted back to the methane aromatizing fluidized-bed reactor, carry out successive reaction.
2) high-temperature gas (mainly containing aromatic hydrocarbons, methane and hydrogen) of methane aromatization system 1 outlet is introduced separation system 2, after cooling, utilize Three methyl Benzene to absorb aromatic hydrocarbons at 20 ℃, tail gas after qualified (mainly is methane and hydrogen, aromatic free almost) goes out separation system 2, under 140 ℃, with aromatic hydrocarbons desorb from organic solvent, obtain aromatic hydrocarbon product, can continue to recycle after the organic solvent cooling.
3) with in the single hop fluidized-bed reactor in the tail gas after qualified (methane and hydrogen) the introducing methanation system 3, simultaneously with CO
2Introduce in the fluidized-bed, make CO
2With hydrogen at Ni/Mn/Al
2O
3React on the catalyzer that (massfraction of Ni is that the massfraction of 25%, Mn is 5% in the catalyzer, and all the other are Al
2O
3Catalyst grain size is 250um, and specific surface area is 200m
2/ g, hardness is 7, tap density is 500kg/m
3), temperature of reaction is 320 ℃, pressure is 0.1MPa (gauge pressure), CO
2Volume is that air speed is 2000h
-1, H
2/ CO
2Be 3.8; Be controlled at the gas (CH of methanation system 3 outlets
4, H
2, CO
2With H
2The mixture of O) H in
2Volume fraction is lower than 0.8%; Above-mentioned exit gas is introduced separation system 4 separate, methane passes into reactive system 1 and recycles after being drawn by separation system 4.
The temperature of fluidized-bed is by saturated water coolant indirect heat exchange control in the methanation system, to become temperature be 250-270 ℃ high temperature and high pressure steam to saturated water coolant after the heat exchange, will be for the aromatic hydrocarbons of benzene and methane and Hydrogen Separation system 2 and the thermal source of organic solvent desorption under high temperature unit.
Embodiment 2, preparing aromatic hydrocarbon by aromatizing methane
1) with aromatized catalyst (as: Mo/ZSM-5, the massfraction of Mo is 6%) be packed in the methane aromatizing fluidized-bed reactor, be warming up to 680 ℃, then methane being passed into fluidized-bed reactor reacts, control methane air speed is 1500L/ (gcath), the aromatic hydrocarbons that generates, hydrogen exports out the methane aromatization system with unconverted methane from fluidized-bed reactor. when the carbon deposition quantity of aromatized catalyst greater than 3% the time, through piping and e Foerderanlage, move to the catalyst regeneration fluidized-bed reactor and regenerate that (regenerating medium is air, the control regeneration temperature is 560 ℃), after making the content carbon of catalyzer be lower than 0.1%, by pipeline and e Foerderanlage, be transmitted back to the methane aromatizing fluidized-bed reactor, carry out successive reaction.
2) high-temperature gas (mainly containing aromatic hydrocarbons, methane and hydrogen) of methane aromatization system 1 outlet is introduced separation system 2, after cooling, utilize tetramethyl-benzene to absorb aromatic hydrocarbons at 25 ℃, tail gas after qualified (mainly is methane and hydrogen, aromatic free almost) goes out separation system 2, under 145 ℃, with aromatic hydrocarbons desorb from organic solvent, obtain aromatic hydrocarbon product, can continue to recycle after the organic solvent cooling.
3) with in the two-stage fluidized bed reactor in the tail gas after qualified (methane and hydrogen) the introducing methanation system 3, simultaneously with CO
2Introduce in the fluidized-bed, make CO
2With hydrogen at Ni/Mo/Al
2O
3React on the catalyzer that (massfraction of Ni is that the massfraction of 15%, Mo is 3% in the catalyzer, and all the other are Al
2O
3Catalyst grain size is 50um, and specific surface area is 400m
2/ g, hardness is 10, tap density is 1500kg/m
3), the temperature of reaction of two-section flowing bed first paragraph is controlled to be 250 ℃, and the temperature of reaction of second segment is controlled to be 450 ℃, and pressure is 1MPa (gauge pressure), CO
2Volume is that air speed is 10000h
-1, H
2/ CO
2Be 3.9; Be controlled at the gas (CH of methanation system 3 outlets
4, H
2, CO
2With H
2The mixture of O) H in
2Volume fraction is lower than 0.05%; Above-mentioned exit gas is introduced separation system 4 separate, methane passes into reactive system 1 and recycles after being drawn by separation system 4.
In the methanation system in the two-section flowing bed temperature of first paragraph by the control of saturated water coolant indirect heat exchange, to become temperature be 200 ℃ high temperature and high pressure steam to saturated water coolant after the heat exchange, the temperature of second segment is carried out heat exchange control with above-mentioned high-temperature steam, finally obtains overheated high-temperature steam as the thermal source of the methane feed gas preheating in the methane aromatization system 1.
Embodiment 3, preparing aromatic hydrocarbon by aromatizing methane
In reactive system shown in Figure 1, be prepared.
1) with aromatized catalyst (as: Ni/Mo/ZSM-5, Ni, the massfraction of Mo is respectively 2%, 4%) is packed in the methane aromatizing fluidized-bed reactor, be warming up to 700 ℃, then methane is passed into and react, control methane air speed is 1500L/ (gcath), the aromatic hydrocarbons that generates, hydrogen exports out the methane aromatization system with unconverted methane from fluidized-bed reactor. when the carbon deposition quantity of aromatized catalyst greater than 3% the time, through piping and e Foerderanlage, move to catalyst regeneration fluidized-bed reactor regenerate (regenerating medium is air, control regeneration temperature be 550 ℃), after making the content carbon of catalyzer be lower than 0.1%, by pipeline and e Foerderanlage, be transmitted back to the methane aromatizing fluidized-bed reactor, carry out successive reaction.
2) high-temperature gas (mainly containing aromatic hydrocarbons, methane and hydrogen) of methane aromatization system 1 outlet is introduced separation system 2, after cooling, utilize pentamethylbenzene to absorb aromatic hydrocarbons at 30 ℃, tail gas after qualified (mainly is methane and hydrogen, aromatic free almost) goes out separation system 2, under 150 ℃, with aromatic hydrocarbons desorb from organic solvent, obtain aromatic hydrocarbon product, can continue to recycle after the organic solvent cooling.
3) with in the two-stage fluidized bed reactor in the tail gas after qualified (methane and hydrogen) the introducing methanation system 3, simultaneously with CO
2Introduce in the fluidized-bed, make CO
2With hydrogen at Co/Fe/W/ZrO
2-Al
2O
3(massfraction of Co is that the massfraction of 25%, Fe is that the massfraction of 3%, W is 2% to catalyzer in the catalyzer, and all the other are ZrO
2-Al
2O
3Catalyst grain size is 100um, and specific surface area is 300m
2/ g, hardness is 8, tap density is 1000kg/m
3) on react, the temperature of reaction of two-section flowing bed first paragraph is controlled to be 350 ℃, the temperature of reaction of second segment is controlled to be 250 ℃, pressure is 0.5MPa (gauge pressure), CO
2Volume is that air speed is 5000h
-1, H
2/ CO (mol ratio) is 4.0; Be controlled at the gas (CH of methanation system 3 outlets
4, H
2, CO
2With H
2The mixture of O) H in
2Volume fraction is lower than 0.2%; Above-mentioned exit gas is introduced separation system 4 separate, methane passes into reactive system 1 and recycles after being drawn by separation system 4.
In the methanation system in the two-section flowing bed temperature of second segment by the control of saturated water coolant indirect heat exchange, to become temperature be 200 ℃ high temperature and high pressure steam to saturated water coolant after the heat exchange, the temperature of first paragraph is carried out heat exchange control with above-mentioned steam, finally obtains overheated high-temperature steam as the thermal source of the methane feed gas preheating in the methane aromatization system 1.
Embodiment 4, preparing aromatic hydrocarbon by aromatizing methane
In reactive system shown in Figure 1, be prepared.
1) with aromatized catalyst (as: Ga/ZSM-5, the massfraction of Ga is 6%) be packed in the methane aromatizing fluidized-bed reactor, be warming up to 720 ℃, then methane is passed into and react, control methane air speed is 2500L/gcat/h, the aromatic hydrocarbons that generates, hydrogen exports out the methane aromatization system with unconverted methane from fluidized-bed reactor. when the carbon deposition quantity of aromatized catalyst greater than 3% the time, through piping and e Foerderanlage, move to the catalyst regeneration fluidized-bed reactor and regenerate that (regenerating medium is air, the control regeneration temperature is 580 ℃), after making the content carbon of catalyzer be lower than 0.1%, by pipeline and e Foerderanlage, be transmitted back to the methane aromatizing fluidized-bed reactor, carry out successive reaction.
2) high-temperature gas (mainly containing aromatic hydrocarbons, methane and hydrogen) of methane aromatization system 1 outlet is introduced separation system 2, after cooling, utilize hexamethyl-benzene to absorb aromatic hydrocarbons at 23 ℃, tail gas after qualified (mainly is methane and hydrogen, aromatic free almost) goes out separation system 2, under 155 ℃, with aromatic hydrocarbons desorb from organic solvent, obtain aromatic hydrocarbon product, can continue to recycle after the organic solvent cooling.
3) with in the single hop fluidized-bed reactor in the tail gas after qualified (methane and hydrogen) the introducing methanation system 3, simultaneously with CO
2Introduce in the fluidized-bed, make CO
2With hydrogen at Ni/Re/SiO
2-Al
2O
3React on the catalyzer that (massfraction of Ni is that the massfraction of 8%, Re is 2% in the catalyzer, and all the other are SiO
2-Al
2O
3Catalyst grain size is 200um, and specific surface area is 300m
2/ g, hardness is 6.5, tap density is 800kg/m
3), the temperature of reaction of fluidized-bed is controlled to be 300 ℃, and pressure is 0.02MPa (gauge pressure), CO
2Volume is that air speed is 500h
-1, H
2/ CO (mol ratio) is 3.9; Be controlled at the gas (CH of methanation system (c) outlet
4, H
2, CO
2With H
2The mixture of O) H in
2Volume fraction is lower than 0.4%; Above-mentioned exit gas is introduced separation system 4 separate, methane passes into reactive system 1 and recycles after being drawn by separation system 4.
The temperature of fluidized-bed is by the control of saturated water coolant indirect heat exchange in the methanation system, and to become temperature be 250 ℃ high temperature and high pressure steam to saturated water coolant after the heat exchange, the thermal source that further separates as aromatic hydrocarbons.
Embodiment 5, preparing aromatic hydrocarbon by aromatizing methane
In reactive system shown in Figure 1, be prepared.
1) with aromatized catalyst (as: Fe/Mo/ZSM-5, Fe, the massfraction of Mo is 1%, 3%) is packed in the methane aromatizing fluidized-bed reactor, be warming up to 680 ℃, then methane is passed into and react, control methane air speed is 1800L/ (gcath), the aromatic hydrocarbons that generates, hydrogen exports out the methane aromatization system with unconverted methane from fluidized-bed reactor. when the carbon deposition quantity of aromatized catalyst greater than 3% the time, through piping and e Foerderanlage, move to catalyst regeneration fluidized-bed reactor regenerate (regenerating medium is air, control regeneration temperature be 500 ℃), after making the content carbon of catalyzer be lower than 0.1%, by pipeline and e Foerderanlage, be transmitted back to the methane aromatizing fluidized-bed reactor, carry out successive reaction.
2) high-temperature gas (mainly containing aromatic hydrocarbons, methane and hydrogen) of methane aromatization system 1 outlet is introduced separation system 2, after cooling, utilize the mixture (mass ratio of methylnaphthalene and acenaphthene is 1: 3) of methylnaphthalene and acenaphthene to absorb aromatic hydrocarbons at 21 ℃, tail gas after qualified (mainly is methane and hydrogen, aromatic free almost) goes out separation system 2, under 150 ℃, with aromatic hydrocarbons desorb from organic solvent, obtain aromatic hydrocarbon product, can continue to recycle after the organic solvent cooling.
3) with in the single hop fluidized-bed reactor in the tail gas after qualified (methane and hydrogen) the introducing methanation system 3, simultaneously with CO
2Introduce in the fluidized-bed, make CO
2With hydrogen at Fe/Cr/Al
2O
3React on the catalyzer that (massfraction of Fe is that the massfraction of 15%, Cr is 15% in the catalyzer, and all the other are Al
2O
3Catalyst grain size is 250um, and specific surface area is 150m
2/ g, hardness is 7.5, tap density is 750kg/m
3), the temperature of reaction of fluidized-bed is controlled to be 280 ℃, and pressure is 0.03MPa (gauge pressure), CO
2Volume is that air speed is 100h
-1, H
2/ CO (mol ratio) is 3.9; Be controlled at the gas (CH of methanation system (c) outlet
4, H
2, CO
2With H
2The mixture of O) H in
2Volume fraction is lower than 0.1%; Above-mentioned exit gas is introduced separation system 4 separate, methane passes into reactive system 1 and recycles after being drawn by separation system 4.
The temperature of fluidized-bed is by the control of saturated water coolant indirect heat exchange in the methanation system, and to become temperature be 240 ℃ high temperature and high pressure steam to saturated water coolant after the heat exchange, the thermal source that further separates as aromatic hydrocarbons.
Embodiment 6, preparing aromatic hydrocarbon by aromatizing methane
In reactive system shown in Figure 1, be prepared.
1) with aromatized catalyst (as: Mn/Mo/ZSM-5, Mn, the massfraction of Mo is respectively 1%, 3%) is packed in the methane aromatizing fluidized-bed reactor, be warming up to 720 ℃, then methane is passed into and react, control methane air speed is 2000L/gcat/h, the aromatic hydrocarbons that generates, hydrogen exports out the methane aromatization system with unconverted methane from fluidized-bed reactor. when the carbon deposition quantity of aromatized catalyst greater than 3% the time, through piping and e Foerderanlage, move to catalyst regeneration fluidized-bed reactor regenerate (regenerating medium is air, control regeneration temperature be 520 ℃), after making the content carbon of catalyzer be lower than 0.1%, by pipeline and e Foerderanlage, be transmitted back to the methane aromatizing fluidized-bed reactor, carry out successive reaction.
2) high-temperature gas (mainly containing aromatic hydrocarbons, methane and hydrogen) of methane aromatization system 1 outlet is introduced separation system 2, after cooling, utilize 190# solvent oil (boiling range is 160-190 ℃) to absorb aromatic hydrocarbons at 22 ℃, tail gas after qualified (mainly is methane and hydrogen, aromatic free almost) goes out separation system 2, under 145 ℃, with aromatic hydrocarbons desorb from organic solvent, obtain aromatic hydrocarbon product, can continue to recycle after the organic solvent cooling.
3) with in the two-stage fluidized bed reactor in the tail gas after qualified (methane and hydrogen) the introducing methanation system 3, simultaneously with CO
2Introduce in the fluidized-bed, make CO
2With hydrogen at Co/Rh/SiO
2React on the catalyzer that (massfraction of Co is that the massfraction of 15%, Rh is 3% in the catalyzer, and all the other are SiO
2Catalyst grain size is 400um, and specific surface area is 350m
2/ g, hardness is 7, tap density is 900kg/m
3), the temperature of reaction of two-section flowing bed first paragraph is controlled to be 400 ℃, and the temperature of reaction of second segment is controlled to be 260 ℃, and pressure is 0.6MPa (gauge pressure), CO
2Volume is that air speed is 8000h
-1, H
2/ CO (mol ratio) is 4.2; Be controlled at the gas (CH of methanation system (c) outlet
4, H
2, CO
2With H
2The mixture of O) H in
2Volume fraction is lower than 0.5%; Above-mentioned exit gas is introduced separation system 4 separate, methane passes into reactive system 1 and recycles after being drawn by separation system 4.
In the methanation system in the two-section flowing bed temperature of second segment by the control of saturated water coolant indirect heat exchange, to become temperature be 200 ℃ high temperature and high pressure steam to saturated water coolant after the heat exchange, the temperature of first paragraph is carried out heat exchange control with above-mentioned steam, finally obtains overheated high-temperature steam as the thermal source of the methane feed gas preheating in the methane aromatization system 1.
Embodiment 7, preparing aromatic hydrocarbon by aromatizing methane
In reactive system shown in Figure 1, be prepared.
1) with aromatized catalyst (as: Cu/Cr/Mo/ZSM-5, Cu, Cr, the massfraction of Mo is respectively 3%, 2%, 3%) is packed in the methane aromatizing fluidized-bed reactor, be warming up to 700 ℃, then methane is passed into and react, control methane air speed is 3000L/gcat/h, the aromatic hydrocarbons of generation, hydrogen exports out the methane aromatization system with unconverted methane from fluidized-bed reactor. when the carbon deposition quantity of aromatized catalyst greater than 3% the time, through piping and e Foerderanlage, move to catalyst regeneration fluidized-bed reactor regenerate (regenerating medium is air, control regeneration temperature be 750 ℃), after making the content carbon of catalyzer be lower than 0.1%, by pipeline and e Foerderanlage, be transmitted back to the methane aromatizing fluidized-bed reactor, carry out successive reaction.
2) high-temperature gas (mainly containing aromatic hydrocarbons, methane and hydrogen) of methane aromatization system 1 outlet is introduced separation system 2, after cooling, utilize 260# solvent oil (boiling range 195-260 ℃) to absorb aromatic hydrocarbons at 25 ℃, tail gas after qualified (mainly is methane and hydrogen, aromatic free almost) goes out separation system 2, under 160 ℃, with aromatic hydrocarbons desorb from organic solvent, obtain aromatic hydrocarbon product, can continue to recycle after the organic solvent cooling.
3) with in the stage fluidized bed reactor in the tail gas after qualified (methane and hydrogen) the introducing methanation system 3, simultaneously with CO
2Introduce in the fluidized-bed, make CO
2With hydrogen at Ni/Al
2O
3React on the catalyzer that (massfraction of Ni is 20% in the catalyzer, and all the other are Al
2O
3Catalyst grain size is 80um, and specific surface area is 270m
2/ g, hardness is 8.4, tap density is 1300kg/m
3), the temperature of reaction of stage fluidized bed first paragraph is controlled to be 420 ℃, and the temperature of reaction of second segment is controlled to be 350 ℃, and the 3rd section temperature of reaction is controlled to be 250 ℃, and pressure is 0.6MPa (gauge pressure), CO
2Volume is that air speed is 7000h
-1, H
2/ CO (mol ratio) is 3.8; Be controlled at the gas (CH of methanation system 3 outlets
4, H
2, CO
2With H
2The mixture of O) H in
2Volume fraction is lower than 0.01%; Above-mentioned exit gas is introduced separation system 4 separate, methane passes into reactive system 1 and recycles after being drawn by separation system 4.
The 3rd section temperature is by saturated water coolant indirect heat exchange control in stage fluidized bed in the methanation system 3, to become temperature be 200 ℃ high temperature and high pressure steam to saturated water coolant after the heat exchange, then introduce second segment heat exchange temperature control, introduce again first paragraph heat exchange temperature control, finally obtain overheated high-temperature steam as the thermal source of the methane feed gas preheating in the methane aromatization system (a).
Claims (8)
1. the reactive system of a preparing aromatic hydrocarbon by aromatizing methane, separation system (2), methanation reaction system (3) and methane and water separating system (4) by methane aromatization system (1), aromatic hydrocarbons and methane, hydrogen form, and are connected by pipeline successively between them; Wherein, described methanation reaction system (3) comprises fluidized-bed reactor and catalyzer, described catalyzer is metal load type catalyst, described metal is selected from the alloy of following at least a metal or following at least two kinds of metals formation: Ni, Fe, Co, Re, Mo, W, Cr, Mn and Rh, the carrier in the described metal load type catalyst is selected from following at least a: Al
2O
3, SiO
2And ZrO
2, the massfraction of metal is 10-30% in the described metal load type catalyst; The intensity of described metal load type catalyst is Mohs' hardness 6-10, and particle diameter is the 50-500 micron, and tap density is 500-1500kg/m
3, specific surface area is 150-400m
2/ g;
Fluidized-bed reactor in the described methanation reaction system (3) is single hop fluidized-bed reactor or multiple stage fluidized-bed reactor;
Described methane aromatization system (1) comprises the reactor of fluidized-bed reactor, aromatized catalyst charcoal regeneration and handling equipment and the pipeline that the catalyzer between two reactors is carried back and forth;
The separation system of described aromatic hydrocarbons and methane, hydrogen (2) comprise organic solvent, with the carrying described organic solvent absorption tower and desorption tower and transferpump and interchanger; The boiling point of described organic solvent all is higher than 140 ℃;
Described methane and water separating system (4) comprise interchanger and air water separator.
2. the method for a preparing aromatic hydrocarbon by aromatizing methane comprises the steps:
1) makes methane in methane aromatization system claimed in claim 1 (1), carry out aromatization, obtain the mixed gas of aromatic hydrocarbons, methane and hydrogen;
2) described mixed gas is passed in the separation system (2) of aromatic hydrocarbons claimed in claim 1 and methane, hydrogen, the organic solvent in the separated system of aromatic hydrocarbons (2) in the described mixed gas is absorbed, obtain the mixed gas of methane and hydrogen; Then, with the desorb from described organic solvent of described aromatic hydrocarbons, obtain aromatic hydrocarbons;
3) with step 2) methane that obtains and the mixed gas of hydrogen introduce in the fluidized-bed reactor of methanation reaction system claimed in claim 1 (3), and pass into simultaneously CO
2, make hydrogen and CO
2Catalyzer in described fluidized-bed reactor reacts, and obtains the mixed gas of methane and water vapour; Described catalyzer is metal load type catalyst, and described metal is selected from the alloy of following at least a metal or following at least two kinds of metals formation: Ni, Fe, Co, Re, Mo, W, Cr, Mn and Rh, the carrier in the described metal load type catalyst is selected from following at least a: Al
2O
3, SiO
2And ZrO
2, the massfraction of metal is 10-30% in the described metal load type catalyst; The intensity of described metal load type catalyst is Mohs' hardness 6-10, and particle diameter is the 50-500 micron, and tap density is 500-1500kg/m
3, specific surface area is 150-400m
2/ g;
4) with step 3) methane that obtains and the mixed gas of water vapor introduce methane claimed in claim 1 and water separating system (4) through the heat exchange cooling, and in air water separator, separate, then methane is returned in the methane aromatization system (1) by pipeline and recycle.
3. method according to claim 2 is characterized in that: step 2) described in the boiling point of organic solvent all be higher than 140 ℃; The temperature that organic solvent in the separated system of aromatic hydrocarbons in the described mixed gas (2) absorbs is 20-30 ℃; The temperature of described aromatic hydrocarbons desorb from described organic solvent is 140-160 ℃.
4. it is characterized in that: step 3 according to claim 2 or 3 described methods) massfraction of metal is 10-20% or 20-30% in the described catalyzer;
The particle diameter of described catalyzer is 50-200 micron or 200-500 micron;
The tap density of described catalyzer is 500-900kg/m
3Or 900-1500kg/m
3
The specific surface area of described catalyzer is 150-300m
2/ g or 300-400m
2/ g;
5. method according to claim 4 is characterized in that: step 3) middle hydrogen and CO
2The temperature of reaction that catalyzer in described fluidized-bed reactor reacts is 250-450 ℃ or 250-300 ℃ or 350-450 ℃;
The absolute pressure of described reaction is 0.02-1.0MPa or 0.02-0.1MPa or 0.1-1.0MPa;
Step 3) CO in
2Volume space velocity be 100-10000h
-1Or 100-10000h
-1Or 100-1000h
-1Or 2000-5000h
-1Or 7000-10000h
-1
Hydrogen and CO in the reaction system of described reaction
2Mol ratio be 3.8-4.2.
6. method according to claim 5 is characterized in that: step 3) volume fraction of hydrogen is lower than 1% in the methane that obtains and the mixed gas of water vapour.
7. method according to claim 6 is characterized in that: step 2) in described aromatic hydrocarbons from described organic solvent after the desorb, described organic solvent returns in the separation system (2) and recycles.
8. method according to claim 7, it is characterized in that: step 3) in the temperature of fluidized-bed reactor in the methanation reaction system (3) control by saturated cooling water control or saturated water coolant and superheated vapour, the temperature that obtains is that 200-400 ℃ of steam is used for methane aromatization system (1) Raw gas is carried out preheating, or as the thermal source of aromatic hydrocarbons with the middle aromatic hydrocarbons desorb of separation system (2) of methane, hydrogen.
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| CN101580449A (en) * | 2008-05-15 | 2009-11-18 | 中国石油天然气股份有限公司 | Method and device for preparing aromatics through methane aromatization |
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| CN101580449A (en) * | 2008-05-15 | 2009-11-18 | 中国石油天然气股份有限公司 | Method and device for preparing aromatics through methane aromatization |
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