CN105418347A - Method for preparing arene via biological methane photoactivation and non-oxidative aromatization - Google Patents
Method for preparing arene via biological methane photoactivation and non-oxidative aromatization Download PDFInfo
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Abstract
The invention provides a method for preparing arene via biological methane photoactivation and non-oxidative aromatization. The method comprises biological methane carbon dioxide separation, multi-stage serial photoactivation reaction, aromatisation reaction, hydrogen permeation palladium membrane separation, multi-stage condensation heat exchange and heat recovery, and gas-liquid separation, wherein part of gas from a tail end outlet of a photoactivation reactor is returned via a gas pump, the other part of the gas enters an aromatisation reactor; methane which is not converted in a primary reaction system enters a secondary reaction system; hydrogen permeated from a hydrogen permeation palladium membrane separator is recycled via a vacuum pump, while after non-permeated micromolecular alkane and arene are subjected to heat recovery and liquid arene recovery, non-condensated part is returned via the air pump. The method has the advantages that the byproduct hydrogen can be recovered; as a low temperature photoactivation reaction is adopted, the methane conversion rate is improved, small quantities of ethylene, ethane and propane generated in the reaction system can serve as auxiliary reactants of methane and initiators of free radical reactions, the aromatisation temperature of methane is lowered, the energy consumption is lowered, and the production cost is greatly reduced.
Description
Technical field
The present invention relates to the series connection photoactive reaction body system that aromatic hydrocarbons is prepared in a kind of serialization, belong to chemical technology field.
Background technology
Along with the consumption of oil, along with improving constantly of biological methane at a specified future date (i.e. biogas) and construction of natural gas fields ability, biogas and Sweet natural gas cause great interest as the energy and petrochemical material in recent years, main component based on biogas and Sweet natural gas is methane, the former is based on civilian, and the latter is with civilian and industrial utilization, and industrial utilization is mainly used for producing synthetic gas, in oxidizing atmosphere, use O
2, H
2o or CO
2as oxygenant, synthetic gas is for the product favourable on high temperature and thermodynamics of methane, and therefore the production of synthetic gas avoids the challenge of methane conversion in kinetics and selectivity, but needs the construction cost bearing great number, it is reported, synthetic gas facility accounts for 50% of GTL for Gas To Liquids factory construction cost.
Aromatic hydrocarbon product is important Organic Chemicals, obtain mainly through oil and coking by-product at present, because oil is Nonrenewable resources, and coking by-product crude benzol by steel industry depressed affect larger, therefore oil and coking route are restricted, and biological methane such as biogas is renewable energy source, the restriction that the utilization of large-sized biogas is transported, at present mainly as fuel, and the Utilization prospects of renewable energy source is very wide, therefore biological methane is made liquid fuel such as gasoline and industrial chemicals and there is important economy and social effect.
The main component of biological methane is methane, and its composition is general containing methane 55 ~ 70%, CO
228 ~ 44%, H
2s0.034%, process remove CO
2methane afterwards adopts M/HZSM-5 catalyst series aromizing under anaerobic, can obtain aromatic hydrocarbons as benzene, toluene etc.; Because the c h bond of methane can be comparatively large, be 436kJ/mol, and 2CH
4→ C
2h
4+ 2H
2, Δ G
0 298K=68.6kJ/mol, therefore on thermodynamics, reaction is difficult to carry out, and carries out methane aromatization under 600 ~ 800 DEG C of high temperature, transformation efficiency is lower by only about 10%, and in the gross product of generation, hydrogen is not recycled, and causes the waste of hydrogen energy source.
In the past thirty years, the methane direct conversion that people take huge effort exploitation alternative is the route of petroleum chemicals, but methane is symmetric a, non-polar molecule, functionally ruptured by c h bond and inevitably introduce asymmetry, increase the possibility of reaction further, the relation of some methane direct conversion route transformation efficiency-optionally can be expressed as: A → B → C first order reaction, and the operational path of two most studies is methane oxidative coupling production ethene OCM, catalytic partial oxidation of methane is methyl alcohol processed and formaldehyde directly.And oxygen-free dehydrogenating aromatization of methane aromatic hydrocarbons can be expressed as: 6CH
4→ 9H
2+ C
6h
6; Modal catalyzer has: M/HZSM-5, and wherein M is single-component or polycomponent transition metal or precious metal; If M is MoO
3cause methane dimerization, first methane is at MoO
3surface is activated, and ethene is principal reaction intermediate, and aromizing is reacted at zeolite surface through ethene, and methane is activated generation methyl free radicals, and reaction generates ethene, C further
2h
6be the primary product of methane activation, first generate Mo
2c; 2CH
4→ C
2h
4+ 2H
2, infer MoO
3or the carbide complexes of inactivation be active centre as methane activation, without unit process step and kinetic rate expression formula, speed is first order reaction for methane partial pressure.Methane reaction is the acidic catalyst reaction on HZSM-5 surface, at Mo
2the ethene of C Surface Creation, gas phase methane and H
2in Bronsted acid site particle successive reaction, ethene is adsorbed and protonated at Bronsted acid particle, generates ethyl carbonium ion.
C
2h
4+ HZSM-5 (s) → C
2h
5 +s () is the rate determining step of ethylene conversion, activated disfunction is 88.2kJ/mol, and the chainpropagation of alkene is primarily of C
2h
5 +catalysis, and C
2h
5 +surface concn is crucial, due to high reactivity obstacle, infers that surface concn is lower.
Ethene carbonium ion and ethene react further in zeolite channels, after oligomerisation reaction, cause chainpropagation to generate larger carbonium ion C
4h
9 +, continue and ethene successive reaction, generate normal alkane C
6h
12, in initial gas phase reaction, hexane continues to follow two reaction paths, and hexane dehydrogenation generates hexyl carbonium ion and H
2molecule, hydride is at C
6h
12and C
2h
5 +between transmit, produce initial gas phase alkyl, as seen in this reaction mechanism, hexane transform determined by dehydrogenation step.
According to another report, methane can be also light olefin [CatalystsToday, 2011,171:211 ~ 220] from haloalkane or methanol conversion; CN104148101 describes a kind of methane anaerobic directly method of alkene processed and catalyzer thereof, and its temperature of reaction is, 750 ~ 1200 DEG C.CN104844403 describes methane in conventional fluidized-bed reactor, carries out conversion and obtain high-temperature gas product (aromatic hydrocarbons, hydrogen and methane), through being cooled to 300 DEG C, with the CO passed in 700 DEG C and catalyzer Mo/ZSM-5
2enter methanation system together, by H
2and CO
2methanation is reclaimed, wherein CO
2and H
2the methane cycle generated, and the water generated is discharged.And CN104193573 describes a kind of method methane conversion being become alkylated aromatic hydrocarbons, in charging, add the C of <5%
3+ hydrocarbon.CN104998587 discloses the microchannel reaction unit of a kind of continuous production alkene and aromatic hydrocarbons, by microchannel effect, heat and mass transfer enhancement, continuously monobromethane is made alkene.Bibliographical information [JournalofEnvironmentalSciences, 2009,21:736 ~ 740] Methane dehydro aromatization gas on Mo/H-MFI becomes the catalyzer of liquid.CN1559683 discloses nonoxidation catalytic dehydrogenation aromatization of methane aromatic hydrocarbons loaded catalyst, methane conversion 15 ~ 20%, benzene selective 60 ~ 70%.
Summary of the invention
Have that methane dehydrogenation temperature is high 700 ~ 900 DEG C, consume energy large problem to overcome prior art, the present invention aims to provide a kind of methane prepares aromatic hydrocarbons method through photo catalytic activation, oxygen-free aromatization reaction, recovery heat and separator, through the alkane such as a small amount of ethane and propane of photo catalytic activation, generation, can as the coreagent of methane in aromatization reactor, for methane dehydrogenation provides the initiator of methyl free radicals, thus reduce temperature and the reaction difficulty of methane aromatizing.The methane mixed gas part that methane photoactive reaction device exports is returned and repeatedly circulates, part enters aromatization reactor by the preheating of multi-stage condensing cooling heat exchanger and reclaims heat, aromizing temperature is 350 ~ 550 DEG C, aromizing exit gas through palladium permeable hydrogen membrane separator 300 ~ 400 DEG C of separation, after extracting hydrogen out, pass through condensing heat exchanger, transfer heat to photoactive reaction device exit gas, the aromatic hydrocarbons of condensing cooling is separated, the methane be not condensed enters recycled system and continues reaction, exit gas enters aromatization reactor 350 ~ 550 DEG C through preheating, enter palladium permeable hydrogen membrane separator again.
The device of preparing aromatic hydrocarbon by aromatizing methane comprises: the biological methane from storage tank pumps into biological methane CO2 by air pump 1a and removes system 1, with air pump 1b, the methane of emergence work is squeezed into series connection photoactive reaction device 3a-c again, the methane obtained is exported from photoactive reaction device, ethane, ethene, hydrogen, propane mixture, a part is returned by circulation air pump 1n, a part is by water cooler 8a-b, condenser 7 and the aromatization products gas mixture that condenser 6 interchanger is indirect and palladium dehydrogenation membrane separation apparatus exports carry out heat exchange, after methane mixed gas being preheated to 350 ~ 550 DEG C with air pump 1d by preheater 11, enter methane aromatization device 4, or directly enter aromatization reactor 4 by air pump 1m and preheater 11, methane is exported to obtain by aromatization, aromatic hydrocarbons, ethane, hydrogen, propane and ethene gas mixture, this gas mixture air pump 1e containing aromatic hydrocarbons is pumped into palladium permeable hydrogen membrane separator 5, palladium air-permeable envelope separator use temperature is 300 ~ 400 DEG C, its infiltration outlet is hydrogen, extract out with hydrogen vacuum pump 10 and recycle, not by permeate for methane, aromatic hydrocarbons and ethane, propane and ethene, respectively by air pump 1e, 1f, 1g enters condenser 6, condenser 7 and water cooler 8a-b heat exchange, the gas-liquid mixture be condensed enters gas-liquid separator 9, its entrance cooler outlet, at gas-liquid separator by aromatic hydrocarbons and methane, ethane, propane and ethene mixed gas separation, liquid aromatic hydrocarbon benzene and a small amount of toluene is obtained bottom gas-liquid separator, the uncooled gas of aromatic free is discharged from gas-liquid separator top, mainly contain after methane, ethane, propane and ethene mixed with methane photoactive reaction device exit gas by circulation air pump 1h pump, through air pump 1i, 1j, 1k and condensing cooling interchanger 8a-b, 7,6 and 11 indirect heat exchange Posterior circle apply mechanically.
Photoactive reaction device 3a-c adopts high voltage mercury lamp, LEDUV light source, and photocatalyst has gallium, tungsten, molybdenum, lanthanum and cerium, or load is on carrier, and as HZSM-5, photoactive reaction device use temperature is room temperature.
The invention provides acquisition methane, aromatic hydrocarbons, ethane, hydrogen, ethene, the gas mixture of propane and butane, by thtee-stage shiplock photoactive reaction device 3a-c, in room temperature, under UV and photocatalyst effect, methane moiety is converted into ethane, propane and butane, and as methane dehydrogenation reaction initiator and coreagent, UV light source is high voltage mercury lamp, power is 10 ~ 1000W, methane conversion is 10 ~ 30%, containing ethane in generation product gas mixture is 0.1 ~ 10%, propane 0.1 ~ 10%, ethene 0.1 ~ 5%, butane 0.1 ~ 5%, hydrogen 0.1 ~ 5%, methane photoactive reaction device catalyzer is: gallium, cerium, lanthanum, molybdenum and zinc metal, or it is supported, carrier is HZSM-5.
Compared with prior art, the present invention has following advantages:
1) the Gibbs free energy Δ G that auxiliary agent hydro carbons can reduce Methane activation process is provided
t 0, reduce methane conversion temperature;
2) in photoactivation methane reaction, owing to belonging to middle low-temperature activation, large energy is saved;
3) methane is by repeatedly circulation light activation provocative reaction, can obtain enough reaction promoter hydro carbons ethane, ethene, propane and butane;
4) this methane photoactive reaction device carbides-free generate, while preparing small molecules alkane, recyclable hydrogen gas byproduct;
5) without the need to buying ethane, ethene, propane and butane, methane photo-activation products, after heat recuperation, directly turns back in aromatization reactor, saves the cost that methane conversion is aromatic hydrocarbons.
Technical scheme of the present invention
Fig. 1 is the schematic flow sheet that biological methane photoactivation aromizing prepares aromatic hydrocarbon system, and 1a, 1b, 1c, 1d, 1e, 1f, 1g, 1i, 1j, 1k are air pump, and 1h, 1m, 1n circulation air pump, 2 biological methanes remove CO
2system, 3a-c thtee-stage shiplock photoactivation quartz reactor, 4 aromatization reactors, 5 palladium permeable hydrogen membrane separators, 6-7 condenser, 8a-b water cooler, 9 gas-liquid separators, 10 hydrogen vacuum pumps, 11 preheaters.
First the biological methane air pump 1a from storage tank is pumped into CO
2remove system 2, then will without CO
2methane gas pass in three sections of series connection photoactivation quartz reactor 3a-c with air pump 1b under 0.1MPa, built-in light source is high voltage mercury lamp, wavelength is 200 ~ 400nm, power is 10 ~ 1000W, at room temperature, be filled with in the reactor of photocatalyst, the catalyzer contained is metal Ce, W, Mo, Ga, or it is supported, carrier is HZSM-5 zeolite molecular sieve, through three sections of series connection photoactive reactions, a part of reaction gas is returned by air pump 1c, 1n, and a part enters circulation air pump 1m or water cooler 8a-b; Controlling methane conversion is 10 ~ 30%, and controlling this lower methane conversion object is avoid reactor carbon distribution, containing methane 70 ~ 90% in the gas mixture product obtained, ethane 0.1 ~ 10%, propane 0.1 ~ 10%, ethene 0.1 ~ 5%, butane 0.1 ~ 5%, hydrogen 0.1 ~ 5%.
Above-mentioned photoactive reaction device 3a-c is exported a part of gas mixture containing methane and ethane etc., by air pump 1i, 1j, 1k is successively through supercooler 8a-b, condenser 7, condenser 6 and preheater 11 indirect heat exchange, be preheated to 350 ~ 550 DEG C, enter in methane aromatization device 4, the built-in secondary light source of reactor is high voltage mercury lamp, wavelength is 200 ~ 400nm, power is 20 ~ 2000W, the catalyzer loaded in reactor has metal molybdenum and ruthenium, carrier is HZSM-5 or HMCM-22, it is 0.1 ~ 0.15MPa that reactant gases enters pressure, temperature of reaction is 350 ~ 550 DEG C, through aromatization reactor catalyzed reaction, containing methane 40 ~ 50% in reactor outlet gas mixture, aromatic hydrocarbons 10 ~ 30%, ethane 0.1 ~ 10%, propane 0.1 ~ 10%, butane 0.1 ~ 5%, ethene 0.1 ~ 5%, hydrogen 0.2 ~ 10%.
This gas mixture product pumps into palladium permeable hydrogen membrane separator 5 by air pump 1d, remove hydrogen with hydrogen vacuum pump 10 at 300 ~ 400 DEG C and reclaim, residue mixed gas is containing methane, aromatic hydrocarbons, ethane, propane and butane and a small amount of hydrogen, after entering condenser 6, condenser 7, water cooler 8a-b heat exchange successively by air pump 1e, 1f and 1g, enter gas-liquid separator 9, from gas-liquid separator bottom part from condensed fluid mainly containing benzene and a small amount of toluene, the methane that top is not cooled and small molecules alkane, apply mechanically with feed gas mixing Posterior circle with circulation air pump 1h.
Condensing heat exchanger is B-grade condensation, photoactive reaction device 3a-c outlets products gas mixture is adopted to be refrigerant containing methane, ethane and propane, this refrigerant is heated in heat transfer process, water cooler 8b interchanger adopts recirculated water to be heat-eliminating medium, cooling temperature is room temperature, cooled gas mixture, by obtaining liquid aromatic hydrocarbon crude product benzene and a small amount of toluene bottom gas-liquid separator 9, gas-liquid separator top is unconverted methane and small molecules straight chain hydrocarbon, by air pump 1h recycled.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet (embodiment 1) 1a, 1b, 1c, 1d, 1e, 1f, 1g, 1i, 1j, 1k air pump that biological methane photoactivation aromizing prepares aromatic hydrocarbon system, and 1h, 1m, 1n circulation air pump, 2 remove CO
2system, 3a-c thtee-stage shiplock photoactivation quartz reactor, 4 aromatization reactors, 5 palladium permeable hydrogen membrane separators, 6-7 condenser, 8a-b water cooler, 9 gas-liquid separators, 10 hydrogen vacuum pumps, 11 preheaters;
Embodiment
Remove CO
2biological methane, by adopting thtee-stage shiplock photo catalytic activation reactor, part mixture back light activated reactor, methane conversion is made to become ethane, propane and butane as the activator of methane dehydrogenation free radical reaction and initiator, part mixture is drawn, impel the energy of oxygen-free aromatization reaction of methane to reduce, increase transformation efficiency and the selectivity of aromatization, in total reaction: 6CH
4→ 9H
2+ C
6h
6a certain amount of hydrogen is had to need to separate from reaction system, this reduces gathering of hydrogen for continuous reaction and circulating reaction, the equilibrium conversion increasing methane aromatizing is favourable, carry out reverse indirect multi-stage condensing cool and heat recuperation by exporting gas mixture with photoactive reaction device, eliminate the heat in aromatization products, aromatic hydrocarbons crude product is obtained through gas-liquid separator, uncooled methane and the recycle of small molecules straight chain hydrocarbon thereof, the whole technological process of production does not have byproduct emission, greatly reduces production cost.
Embodiment 1
First the biological methane air pump 1a from storage tank is pumped into CO
2remove system 2, then will without CO
2methane gas pass in three sections of series connection photoactivation quartz reactor 3a-c with air pump 1b under 0.1MPa, built-in light source is high voltage mercury lamp, wavelength is 200 ~ 400nm, power is 10 ~ 1000W, at room temperature, be filled with in the reactor of photocatalyst, the catalyzer contained is metal Ce, W, Mo, Ga, or it is supported, carrier is HZSM-5 zeolite molecular sieve, through three sections of series connection photoactive reactions, a part of reaction gas is returned by air pump 1c, 1n, and a part enters circulation air pump 1m or water cooler 8a-b; Controlling methane conversion is 10 ~ 30%, and controlling this lower methane conversion object is avoid reactor carbon distribution, containing methane 70 ~ 90% in the gas mixture product obtained, ethane 0.1 ~ 10%, propane 0.1 ~ 10%, ethene 0.1 ~ 5%, butane 0.1 ~ 5%, hydrogen 0.1 ~ 5%.
Above-mentioned photoactive reaction device 3a-c is exported a part of gas mixture containing methane and ethane etc., by air pump 1i, 1j, 1k is successively through supercooler 8a-b, condenser 7, condenser 6 and preheater 11 indirect heat exchange, be preheated to 350 ~ 550 DEG C, enter in methane aromatization device 4, the built-in secondary light source of reactor is high voltage mercury lamp, wavelength is 200 ~ 400nm, power is 20 ~ 2000W, the catalyzer loaded in reactor has metal molybdenum and ruthenium, carrier is HZSM-5 or HMCM-22, it is 0.1 ~ 0.15MPa that reactant gases enters pressure, temperature of reaction is 350 ~ 550 DEG C, through aromatization reactor catalyzed reaction, containing methane 40 ~ 50% in reactor outlet gas mixture, aromatic hydrocarbons 10 ~ 30%, ethane 0.1 ~ 10%, propane 0.1 ~ 10%, butane 0.1 ~ 5%, ethene 0.1 ~ 5%, hydrogen 0.2 ~ 10%.
This gas mixture product pumps into palladium permeable hydrogen membrane separator 5 by air pump 1d, remove hydrogen with hydrogen vacuum pump 10 at 300 ~ 400 DEG C and reclaim, residue mixed gas is containing methane, aromatic hydrocarbons, ethane, propane and butane and a small amount of hydrogen, after entering condenser 6, condenser 7, water cooler 8a-b heat exchange successively by air pump 1e, 1f and 1g, enter gas-liquid separator 9, from gas-liquid separator bottom part from condensed fluid mainly containing benzene and a small amount of toluene, the methane that top is not cooled and small molecules alkane, apply mechanically with feed gas mixing Posterior circle with circulation air pump 1h.
Condensing heat exchanger is B-grade condensation, photoactive reaction device 3a-c outlets products gas mixture is adopted to be refrigerant containing methane, ethane and propane, this refrigerant is heated in heat transfer process, water cooler 8b interchanger adopts recirculated water to be heat-eliminating medium, cooling temperature is room temperature, cooled gas mixture, by obtaining liquid aromatic hydrocarbon crude product benzene and a small amount of toluene bottom gas-liquid separator 9, gas-liquid separator top is unconverted methane and small molecules straight chain hydrocarbon, by air pump 1h recycled.
Claims (9)
1. biological methane photoactivation anaerobic aromatization prepares a method for aromatic hydrocarbons, and its first order reaction system comprises biological methane CO
2separation system, thtee-stage shiplock photoactive reaction device, air pump, interchanger, aromatization reactor, palladium permeable hydrogen membrane separator, air pump, multi-stage condensing water cooler and heat recuperation, gas-liquid separator.
2. prepare the method for aromatic hydrocarbons according to claim 1 biological methane photoactivation anaerobic aromatization, its thtee-stage shiplock photoactive reaction device outlet gas mixture is returned by an air pump part, and a part enters aromatization reactor by air pump.
3. according to claim 1, the thtee-stage shiplock photoactive reaction device that first order reaction system comprises is silica glass, internal high-voltage mercury lamp light source, wavelength 200 ~ 400nm, power 10 ~ 1000W; Photocatalyst has metal Ga, W, Mo, La and Ce or supported, and carrier is SiO
2, Al
2o
3, TiO
2, HZSM-5, photoactive reaction temperature is room temperature.
4. the method for aromatic hydrocarbons is prepared according to claim 1 biological methane photoactivation anaerobic aromatization, the unconverted methane of its first order reaction system enters second order reaction system and comprises air pump, interchanger, aromatization reactor, palladium permeable hydrogen membrane separator, air pump, multi-stage condensing water cooler and heat recuperation, gas-liquid separator, the like.
5. according to claim 4, the methane aromatization device that I and II reaction system comprises is silica glass, built-in secondary light source high voltage mercury lamp, wavelength 200 ~ 400nm, power 20 ~ 2000W; Catalyzer has metal M o, W and supported protonic acid as H
+, carrier is HZSM-5 and HMCM-22 molecular sieve, and aromizing temperature is 350 ~ 550 DEG C.
6. according to claim 4, the palladium permeable hydrogen membrane separator that I and II reaction system comprises, its use temperature are 300 ~ 400 DEG C, the hydrogen oozed out from permeate end is recycled through hydrogen vacuum pump, reaction product ethane, ethene, propane, benzene and the toluene etc. that do not permeate reclaim after aromatic hydrocarbons through aromatics seperation device, isolated small-numerator olefin and alkane circulation and methane merge, and enter secondary reaction system.
7. according to claim 4, the condensate cooler that I and II reaction system comprises is multi-stage condensing cooling heat exchanger, gas mixture (300 ~ 400 DEG C) is indirectly condensed cooling wherein, condensing cooling medium is respectively photoactive reaction device outlet gas mixture containing methane, ethane and propane and recirculated water, after multi-stage condensing cooling heat exchanger and gas-liquid separator, aromatic hydrocarbons is liquefied Separation and Recovery, and the gas be not condensed is that methane, small-numerator olefin and paraffinic hydrocarbons are recycled by air pump and apply mechanically.
8. according to claim 4, the gas-liquid separator that I and II reaction system comprises, the product liquid reclaimed that is condensed bottom gas-liquid separator is aromatic hydrocarbons benzene and a small amount of toluene, and the small molecules alkane be not condensed from separator top and methane mixed gas are recycled by air pump and apply mechanically.
9. according to claim 4, the condenser that I and II reaction system comprises and cooler heat exchangers, the unconverted methane circulated by preheating material and recovery and small molecules paraffinic hydrocarbons carry out heat recuperation.
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