CN107721801B - The system and method for propylene is prepared using chemical chain oxidative dehydrogenation of propane - Google Patents

The system and method for propylene is prepared using chemical chain oxidative dehydrogenation of propane Download PDF

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CN107721801B
CN107721801B CN201710919420.3A CN201710919420A CN107721801B CN 107721801 B CN107721801 B CN 107721801B CN 201710919420 A CN201710919420 A CN 201710919420A CN 107721801 B CN107721801 B CN 107721801B
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gas
gaseous mixture
oxygen
propane
fixed bed
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CN107721801A (en
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于庆波
吴天威
王坤
秦勤
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Northeastern University China
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor

Abstract

The present invention relates to a kind of system and methods that propylene is prepared using chemical chain oxidative dehydrogenation of propane.Above system includes two fixed beds, two reversal valves, gaseous mixture dehydration equipment, mixed gas separation equipment, and two fixed beds are connected to two reversal valves.The above method is that two reversal valves link so that two fixed beds are alternately as dehydrogenation reactor and oxidation reactor.It is reacted at high temperature when fixed bed is as dehydrogenation reactor for oxygen carrier granule and propane, generation contains the oxygen carrier granule after propylene, the gaseous mixture of vapor and COx gas and oxygen loss, oxidation reaction is carried out at high temperature with oxygen-containing gas for the oxygen carrier granule after oxygen loss when fixed bed is as oxidation reactor, generates regenerated oxygen carrier granule.Gaseous mixture is dried in gaseous mixture dehydration equipment, and mixed gas separation equipment separates propylene from gaseous mixture.The system and method for preparing propylene using chemical chain oxidative dehydrogenation of propane of the invention have many advantages, such as efficiently, it is energy-saving and environmental protection, economy, safe.

Description

The system and method for propylene is prepared using chemical chain oxidative dehydrogenation of propane
Technical field
The present invention relates to a kind of system and methods that propylene is prepared using chemical chain oxidative dehydrogenation of propane.
Background technique
Propylene is the base stock of three big synthetic materials, is a kind of important petrochemical materials, furthermore propylene also can be used In other important chemical products such as production polypropylene, acrylonitrile and acrylic acid.The production technology of propylene is mainly petroleum at present The either catalytic cracking (FCC) of the steam cracking of brain and heavy crude, both propylene production technologies account for entire production of propylene row 80% or so of industry.But what both propylene production technologies mainly produced is ethylene and product oil, propylene wherein only with A kind of form of by-product and generate, therefore propylene yield is severely limited.It flows down derivative recently as propylene Consumption quicklys increase, and propylene demand persistently rises, and imbalance between supply and demand becomes clear day by day.
To alleviate propylene imbalance between supply and demand, some emerging production of propylene technologies such as coal propylene (MTO), preparing propylene from methanol (MTP), propane direct dehydrogenation (DHP) and oxidative dehydrogenation of propane (ODHP) come into being, at present China have a small amount of MTO, MTP and DHP put into production.But there is also some problems, MTO and MTP as emerging coal chemical technology for these emerging technologies, Coal/CH need to be undergone4- synthesis gas-methanol-propylene multistep process, therefore producing process is complex, product purity it is lower and Equipment investment is higher, if while can also generate high water consume and high CO by raw material of coal2, NOx emission the problems such as.DHP is by heating power The restriction for learning balance, generally requires and carries out under the conditions of high-temperature low-pressure, reaction condition is more harsh, and once-through propylene yield is not high (generally below 30%), and catalyst inactivates seriously under these conditions, needs repeated regeneration.ODHP is existing for the catalyst In the case of, oxygen is passed through simultaneously to reactor and propane makes propane react generation propylene and water, the technology with oxygen can overcome de- Thermodynamical equilibrium limitation during hydrogen, therefore can be carried out under conditions of milder.But propane is in the presence of oxygen Excessive oxidation reaction easily occurs and generates COx (carbon monoxide and carbon dioxide) so that the yield of propylene can be reduced, while oxygen In the presence of also will increase operating cost, it is unfavorable for the safe operation of equipment, furthermore the technology also needs expensive air separation plant to protect Demonstrate,prove the lasting supply of oxygen.
Therefore seek efficient one kind, energy-saving and environmental protection, economy, the propylene preparation system of safety and method to be badly in need of as current It solves the problems, such as.
Summary of the invention
(1) technical problems to be solved
The purpose of the present invention is to provide a kind of efficient, energy-saving and environmental protection, economy, the propylene preparation system of safety and methods.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
The present invention provides a kind of system for preparing propylene using chemical chain oxidative dehydrogenation of propane, including the first fixed bed, Two fixed beds, entrance reversal valve, outlet reversal valve, gaseous mixture dehydration equipment, mixed gas separation equipment；Wherein, the first fixed bed Be capable of fixing oxygen carrier granule in the second fixed bed, the first fixed bed and the second fixed bed with entrance reversal valve and outlet Reversal valve connection, entrance reversal valve and outlet reversal valve linkage are so that the first fixed bed and the second fixed bed are anti-alternately as dehydrogenation Device and oxidation reactor are answered, it can be for oxygen carrier granule therein when the first fixed bed and the second fixed bed are as dehydrogenation reactor It is reacted at high temperature with into propane therein, generates gaseous mixture and oxygen loss containing propylene, vapor and COx gas Oxygen carrier granule afterwards, dehydrogenation reactor can export gaseous mixture, and the first fixed bed and the second fixed bed are as oxidation reactor When can carry out at high temperature oxidation reaction for the oxygen carrier granule after wherein oxygen loss and into oxygen-containing gas therein, generate poor Carrier of oxygen and regenerated oxygen carrier granule simultaneously export Poor oxygen gas；Wherein, gaseous mixture dehydration equipment can do gaseous mixture It is dry；Wherein, mixed gas separation equipment can isolate propylene from the gaseous mixture after drying.
According to the present invention, the first fixed bed and the second fixed bed all have gas access and gas vent；Entrance reversal valve With oxygen-containing gas entrance, propane inlet, the first gas outlet and the second gas outlet, the gas of the first gas outlet and the first fixed bed Entrance connection, the second gas outlet is connected to the gas access of the second fixed bed；Export reversal valve have the first air inlet, second into Port, mixed gas outlet and Poor oxygen gas outlet, the first air inlet are connected to the gas vent of the first fixed bed, the second air inlet It is connected to the gas vent of the second fixed bed；Wherein, the oxygen-containing gas entrance of entrance reversal valve is connected to and third with the first gas outlet While alkane entrance is connected to the second gas outlet, the mixed gas outlet of control outlet reversal valve is connected to and first with the second air inlet Air inlet and Poor oxygen gas outlet；Wherein, the oxygen-containing gas entrance of entrance reversal valve is connected to and propane with the second gas outlet While entrance is connected to the first gas outlet, control outlet reversal valve mixed gas outlet be connected to the first air inlet and second into Port and Poor oxygen gas outlet.
According to the present invention, further includes: gaseous mixture heat exchanger, gaseous mixture heat exchanger have gaseous mixture entrance, mixed gas outlet, Propane inlet, propane outlets, connection gaseous mixture entrance and the mixed gas passage of mixed gas outlet and it is connected to propane inlet and third The gaseous mixture entrance in the propane channel of alkane outlet, gaseous mixture heat exchanger is connected to the mixed gas outlet of outlet reversal valve, gaseous mixture The propane outlets of heat exchanger are connected to the propane inlet of entrance reversal valve, what gaseous mixture heat exchanger can be exported for dehydrogenation reactor Gaseous mixture exchanges heat with the propane that will be fed into dehydrogenation reactor；Gaseous mixture waste heat boiler, gaseous mixture waste heat boiler have mixing The gaseous mixture entrance of gas entrance and mixed gas outlet, gaseous mixture waste heat boiler is connected to the mixed gas outlet of gaseous mixture heat exchanger, Gaseous mixture waste heat boiler can the gaseous mixture after heat exchanging carry out waste heat recycling；Wherein, gaseous mixture dehydration equipment has gaseous mixture The gaseous mixture entrance of entrance and mixed gas outlet, gaseous mixture dehydration equipment is connected to the mixed gas outlet of gaseous mixture waste heat boiler.
According to the present invention, mixed gas separation equipment can also isolate COx gas and not from the gaseous mixture after drying The propane of reaction, mixed gas separation equipment have gaseous mixture entrance, propylene outlet, COx gas vent and propane outlets, mixing The gaseous mixture entrance of gas separation equipment is connected to the mixed gas outlet of gaseous mixture dehydration equipment, and the propane of mixed gas separation equipment goes out Mouth is connected to the propane inlet of gaseous mixture heat exchanger.
According to the present invention, further includes: Poor oxygen gas heat exchanger, Poor oxygen gas heat exchanger have Poor oxygen gas entrance, oxygen deprivation Gas vent, oxygen-containing gas entrance, oxygen-containing gas outlet, connection Poor oxygen gas entrance and the Poor oxygen gas of Poor oxygen gas outlet are logical The oxygen-containing gas channel in road, connection oxygen-containing gas entrance and oxygen-containing gas outlet, the Poor oxygen gas entrance of Poor oxygen gas heat exchanger With the Poor oxygen gas outlet of outlet reversal valve, the oxygen-containing gas of Poor oxygen gas heat exchanger exports oxygen-containing with entrance reversal valve Gas access connection, Poor oxygen gas heat exchanger can will be fed into for the Poor oxygen gas that exports in oxidation reactor and oxidation reaction Oxygen-containing gas heat exchange in device；Poor oxygen gas waste heat boiler, Poor oxygen gas waste heat boiler have Poor oxygen gas entrance and oxygen deprivation gas Body outlet, the Poor oxygen gas entrance of Poor oxygen gas waste heat boiler and the Poor oxygen gas outlet of Poor oxygen gas heat exchanger, oxygen deprivation Gas waste-heat boiler can the Poor oxygen gas after heat exchanging carry out waste heat recycling.
It according to the present invention, is gold in the described first fixed oxygen carrier granule with filling fixed in second fixed bed Belong to oxide oxygen carrier granule or perovskite oxygen carrier granule；When using metal oxide oxygen carrier granule, metal oxidation Object selects Mn2O3/Mn3O4、Mn3O4/MnO、V2O5/VO2、VO2/V2O3、Co3O4/CoO、CoO/Co、CuO/Cu2O、MoO3/MoO2、 MoO3/Mo、Fe2O3/Fe3O4、SbO2/Sb2O3、CdO/Cd、WO3/WO2With one of NiO/Ni etc. or a variety of, oxygen carrier is prepared Inert carrier select Al2O3、SiO2、TiO2、ZrO2、Y2O3, zeolite, molecular sieve, one of spinelle and sepiolite or more Kind, the content of metal oxide is in 5-70wt%；When using perovskite oxygen carrier granule, RBaCo is selected2O5(R=Y, Pr- Ho)、RBaCo4O7(R=Y, Dy-Lu), RSrR1O4(R=La, Ln；R1=Co, Cu, Ni) etc.；Oxygen carrier using mechanical mixing, Coprecipitation, sol-gel method, infusion process, solid reaction process, spray drying process, hydro-thermal method or citric acid method etc. are made, oxygen carrier Body particle diameter is 200~1000 μm.
Another aspect of the present invention provides a kind of method for preparing propylene using chemical chain oxidative dehydrogenation of propane, and method is using upper The system for stating any one, entrance reversal valve and outlet reversal valve linkage, make the first fixed bed and the second fixed bed alternately as de- Hydrogen reactor and oxidation reactor；In the fixed bed as dehydrogenation reactor, propane carries out at high temperature with oxygen carrier granule Reaction, generation contain the oxygen carrier granule after propylene, the gaseous mixture of vapor and COx gas and oxygen loss；Anti- as oxidation It answers in the fixed bed of device, the oxygen carrier granule after oxygen loss and oxygen-containing gas carry out oxidation reaction, generate Poor oxygen gas and regenerated Oxygen carrier granule, and export Poor oxygen gas；Gaseous mixture is dried in gaseous mixture dehydration equipment；Mixed gas separation equipment is from drying Propylene is isolated in gaseous mixture afterwards.
According to the present invention, unreacted propane is also contained in gaseous mixture；Mixed gas separation equipment is from the gaseous mixture after drying In respectively be isolated by propylene, propane and COx gas, the propane isolated is sent into dehydrogenation reactor.
According to the present invention, it first will be fed into dehydrogenation reactor by the gaseous mixture of the output of the fixed bed as dehydrogenation reactor and i.e. Propane exchange heat in gaseous mixture heat exchanger, then by gaseous mixture be sent into gaseous mixture waste heat boiler carry out waste heat recycling, lead to again later Mixing qi exhaustion wetting system is crossed gaseous mixture is dried.
According to the present invention, it will be fed into oxidation reactor by the Poor oxygen gas of the output of the fixed bed as oxidation reactor and i.e. In oxygen-containing gas exchange heat in Poor oxygen gas heat exchanger, Poor oxygen gas after heat exchange is sent into more than Poor oxygen gas waste heat boiler carries out Recuperation of heat.
According to the present invention, in the fixed bed as dehydrogenation reactor, reaction temperature that propane is reacted with oxygen carrier granule It is 300-700 DEG C；The temperature of propane after being exchanged heat by gaseous mixture heat exchanger is 100-300 DEG C, the temperature of the gaseous mixture after heat exchange Degree is 300-600 DEG C, and the temperature by gaseous mixture waste heat boiler waste heat gaseous mixture after the recovery is 100-200 DEG C；As oxygen In the fixed bed for changing reactor, the reaction temperature of oxidation reaction is 300-700 DEG C；Containing after being exchanged heat by Poor oxygen gas heat exchanger The temperature of carrier of oxygen is 100-300 DEG C, and the Poor oxygen gas after heat exchange is 300-600 DEG C, more than Poor oxygen gas waste heat boiler The temperature of Poor oxygen gas after recuperation of heat is 20-100 DEG C.
(3) beneficial effect
The beneficial effects of the present invention are:
Using the system provided by the invention for preparing propylene using chemical chain oxidative dehydrogenation of propane, first, as dehydrogenation The certain embodiments carried out in the fixed bed of reactor can be by by-product H2It is oxidized to water, eliminates thermodynamics in dehydrogenation reaction process The limitation of balance improves once-through propylene yield, while by-product H2The heat discharged in oxidation process can also be provided to de- Hydrogen reaction, reduces the energy consumption in dehydrogenation reaction；Second, the Main By product in certain embodiments is vapor, favorably In the separation of subsequent products, while also reducing the energy consumption of subsequent products separation；Third, as raw material propane it is from a wealth of sources, The propylene that low value-added propane is converted to high added value had into very big economic benefit；4th, propane is directly prepared into third Alkene, process flow is short, and equipment investment is small and product quality is good；5th, oxygen and reactant propane and product propylene are eliminated Directly contact, reduce excessive oxidation reaction progress, be conducive to improve propylene yield, while also increase operability and Safety；6th, compared to using coal as a large amount of CO of stock discharge2And NOx, the COx gas that this system generates is less, does not generate NOx, it is more environmentally-friendly；7th, using two fixed beds, entrance reversal valve and outlet reversal valve, both do not have to carry out oxygen carrier granule Conveying and the subsequent removal particles work to gaseous mixture and Poor oxygen gas, and persistently carry out generating propane in guarantee system Reaction, simplifies the structure of system, has saved raw material, reduce energy consumption.
It is provided by the invention to be prepared in the method for propylene using oxidative dehydrogenation of propane, first, it can will be secondary in certain embodiments Product H2It is oxidized to water, eliminates the limitation of thermodynamical equilibrium in dehydrogenation reaction process, improves once-through propylene yield, while is secondary Product H2The energy consumption reduced in dehydrogenation reaction to dehydrogenation reaction can also be provided in the heat discharged in oxidation process；The Two, the Main By product in certain embodiments is vapor, is conducive to the separation of subsequent products, while also reducing subsequent products Isolated energy consumption；Third, as raw material propane it is from a wealth of sources, by low value-added propane be converted to high added value propylene have There is very big economic benefit；4th, propane is directly prepared into propylene, process flow is short, and equipment investment is small and product quality is good；The Five, it eliminates oxygen to contact with reactant propane and the direct of product propylene, reduces the progress of excessive oxidation reaction, be conducive to The yield of propylene is improved, while also increasing operability and safety；6th, a large amount of compared to by stock discharge of coal CO2And NOx, the COx gas that this method generates is less, does not generate NOx, more environmentally-friendly；7th, utilize two fixed beds, entrances Reversal valve and outlet reversal valve both do not have to the conveying and the subsequent removal to gaseous mixture and Poor oxygen gas that carry out oxygen carrier granule Particles work, and persistently carry out generating the reaction of propane in guarantee system, processing step is simplified, raw material has been saved, is reduced Energy consumption.
To sum up, chemical chain oxidative dehydrogenation of propane of the invention prepare propylene system and method efficiently, energy-saving and environmental protection, warp Ji, safety.
Detailed description of the invention
Fig. 1 is the schematic illustration of the system and method for the invention that propylene is prepared using chemical chain oxidative dehydrogenation of propane；
Fig. 2 is the structural schematic diagram for the system that propylene is prepared using chemical chain oxidative dehydrogenation of propane that embodiment one provides；
Fig. 3 is in the system in Fig. 2, and the first fixed bed is as oxidation reactor, the second fixed bed as dehydrogenation reactor Schematic diagram；
Fig. 4 is in the system in Fig. 2, and the first fixed bed is as dehydrogenation reactor, the second fixed bed as oxidation reactor Schematic diagram.
[appended drawing reference]
1: the first fixed bed；2: the second fixed beds；3: entrance reversal valve；4: outlet reversal valve；5: Poor oxygen gas heat exchanger； 6: Poor oxygen gas waste heat boiler；7: gaseous mixture heat exchanger；8: gaseous mixture waste heat boiler；9: gaseous mixture dehydration equipment；10: gaseous mixture Separation equipment；11:COx gas reservoir；12: propylene reservoir；13: oxygen-containing gas valve；14: propane valve；15: heating Body；16: feed inlet；17: gas access；18: drain hole；19: gas vent；20: the second gas outlets；21: propane inlet；22: First gas outlet；23: oxygen-containing gas entrance；24: mixed gas outlet；25: the second air inlets；26: Poor oxygen gas outlet；27: the One air inlet；28: Poor oxygen gas entrance；29: Poor oxygen gas outlet；30: oxygen-containing gas entrance；31: oxygen-containing gas outlet；32: Gaseous mixture entrance；33: propane outlets；34: mixed gas outlet；35: propane inlet；36: gaseous mixture entrance；37: propane outlets； 38:COx gas vent；39: propylene outlet.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair It is bright to be described in detail.Wherein, the directional terminologies such as "top", "bottom" involved in this paper are orientated reference with shown in Figure 2.
Embodiment one
Referring to Figures 1 and 2, the present embodiment provides a kind of systems for preparing propylene using chemical chain oxidative dehydrogenation of propane, should System includes the first fixed bed 1, the second fixed bed 2, entrance reversal valve 3, outlet reversal valve 4, gaseous mixture heat exchanger 7, gaseous mixture Waste heat boiler 8, gaseous mixture dehydration equipment 9, mixed gas separation equipment 10, COx gas reservoir 11, propylene reservoir 12, oxygen deprivation Gas heat exchanger 5, Poor oxygen gas waste heat boiler 6.
Oxygen carrier granule is capable of fixing in first fixed bed 1 and the second fixed bed 2, the first fixed bed 1 and second is fixed Bed 2 is connected to entrance reversal valve 3 and outlet reversal valve 4, and entrance reversal valve 3 and the outlet linkage of reversal valve 4 are so that first is fixed Bed 1 and the second fixed bed 2 are alternately as dehydrogenation reactor and oxidation reactor, i.e., the first fixed bed 1 is alternately as dehydrogenation reaction Device and oxidation reactor, the second fixed bed 2 are made alternately as dehydrogenation reactor and oxidation reactor, and in the first fixed bed 1 The second fixed bed 2 is used as oxidation reactor while for dehydrogenation reactor, while the first fixed bed 1 is as oxidation reactor Second fixed bed 2 is used as dehydrogenation reactor.
When first fixed bed 1 and the second fixed bed 2 are as dehydrogenation reactor, propane can be received, and can be for Oxygen carrier granule therein and entrance propane therein are reacted at high temperature, a portion propane and oxygen carrier granule hair Raw oxidative dehydrogenation, the oxygen carrier granule after generating propylene, vapor and oxygen loss, it is anti-that deep oxidation occurs for another part propane It answers, generates vapor and COx gas, the byproduct that COx gas is reacted as propane with oxygen carrier granule.As dehydrogenation reactor Fixed bed can export oxidative dehydrogenation generation propylene and vapor and deep oxidation reaction generate vapor and Gaseous mixture is collectively formed in COx gas, and the oxygen carrier granule after oxygen loss is still fixed in the fixed bed as dehydrogenation reactor and The fixed bed cannot be discharged.It is understood that above-mentioned " high temperature " refer to can occur above-mentioned oxidative dehydrogenation and deep oxidation reaction Temperature.It is understood that gaseous mixture is not limited to only comprising vapor, COx gas and propylene, it is such as anti-in dehydrogenation in the present embodiment It answers the propane carried out in device 3 and there are unreacted propane in oxygen carrier granule reaction, then can also include propane in gaseous mixture, because This, gaseous mixture is the summation of gaseous material in dehydrogenation reactor.
Wherein, the oxidative dehydrogenation conducted in dehydrogenation reactor are as follows:
MexOy+C3H8=MexOy-1+C3H6+H2O(g)
Wherein, the deep oxidation reaction conducted in dehydrogenation reactor are as follows:
7MexOy+C3H8=7MexOy-1+3CO+4H2O(g)
10MexOy+C3H8=10MexOy-1+3CO2+4H2O(g)
Gaseous mixture heat exchanger 7 is connected to outlet reversal valve 4, by the movement of outlet reversal valve 4, so that gaseous mixture heat exchanger 7 are connected to by exporting reversal valve 4 with as dehydrogenation reactor always, that is, follow the work of the first fixed bed 1 and the second fixed bed 2 The change of state is connected to by exporting reversal valve 4 with the fixed bed as dehydrogenation reactor always, can receive dehydrogenation reaction The gaseous mixture of device output.The gaseous mixture that gaseous mixture heat exchanger 7 is exported for dehydrogenation reactor with will be fed into dehydrogenation reactor Propane exchanges heat wherein, is preheated with treating reactant propane, gaseous mixture heat exchanger 7 can export respectively heat exchange after propane and Gaseous mixture after heat exchange.Also, gaseous mixture heat exchanger 7 is connected to entrance reversal valve 3, by the movement of entrance reversal valve 3, so that Gaseous mixture heat exchanger 7 is connected to the fixed bed as dehydrogenation reactor always, and the propane after exchanging heat is sent into dehydrogenation reactor Participate in reaction.Specifically, in gaseous mixture heat exchanger 7, the propane of low temperature absorbs heat from the gaseous mixture of high temperature, carries gaseous mixture Partial heat out returns in dehydrogenation reactor through propane cycles.
Gaseous mixture waste heat boiler 8 is connected to gaseous mixture heat exchanger 7, can receive the gaseous mixture after heat exchange and carry out to it Waste heat recycling.Gaseous mixture waste heat boiler 8 can export the gaseous mixture after recovery waste heat.
Gaseous mixture dehydration equipment 9 is connected to gaseous mixture waste heat boiler 8, can receive the output of gaseous mixture waste heat boiler 8 Gaseous mixture after recovery waste heat, and gaseous mixture can be dried.Specific in the present embodiment, gaseous mixture dehydration equipment 9 For condenser, the vapor in gaseous mixture can be condensed into liquid water removing by condenser, to remove the vapor in gaseous mixture, Realize the drying to gaseous mixture, condenser can export the gaseous mixture after liquid water and water vapor removing respectively.Certainly, for pair The equipment that gaseous mixture is dried is not limited to condenser, can also be that any dry set may be implemented in other in the prior art It is standby.
Mixed gas separation equipment 10 is connected to gaseous mixture dehydration equipment 9, with receive it is dry after gaseous mixture, at this point, because to There are unreacted propane in dehydrogenation reactor, gaseous mixture is made of propane, COx gas and propylene.Mixed gas separation equipment 10 COx gas, propane and propylene can respectively be isolated by and export three respectively.Wherein, in the present embodiment, mixed gas separation Equipment 10 is a separator, can isolate COx gas, propane and propylene simultaneously.Certainly, not limited to this, in other realities Apply in example, mixed gas separation equipment 10 may also comprise multiple separators, can respectively be isolated by by multiple separators COx gas, Propane and propylene.Wherein, mixed gas separation equipment 10 is connected to gaseous mixture heat exchanger 7, can mix the propane isolated warp It returns in dehydrogenation reactor and reuses through entrance reversal valve 3 again after the conjunction acquisition heat of gas heat exchanger 7, save raw material.As a result, In the present embodiment, it is changed for recycling the connection of propane by gaseous mixture between dehydrogenation reactor and mixed gas separation equipment 10 Hot device 7 and entrance reversal valve 3 are completed, but in other embodiments, dehydrogenation reactor and mixed gas separation equipment 10 can directly lead to Cross the connection of entrance reversal valve 3.
COx gas reservoir 11 is connected to mixed gas separation equipment 10, is isolated with to receive mixed gas separation equipment 10 COx gas.Certainly, the COx gas that mixed gas separation equipment 10 is isolated also can be directly used for subsequent chemical industry synthesis.
Propylene reservoir 12 is connected to mixed gas separation equipment 10, with receive that mixed gas separation equipment 10 is isolated third Alkene.Certainly, the propylene that mixed gas separation equipment 10 is isolated also can be directly used for subsequent chemical industry synthesis.
When first fixed bed 1 and the second fixed bed 2 are as oxidation reactor, before oxygen carrier granule therein has been subjected to Dehydrogenation reaction becomes the oxygen carrier granule after oxygen loss.Fixed bed as oxidation reactor can receive oxygen-containing gas, and can Oxidation reaction is carried out at high temperature for the oxygen carrier granule after wherein oxygen loss and into oxygen-containing gas therein, generates Poor oxygen gas With regenerated oxygen carrier granule and export Poor oxygen gas.Wherein, above-mentioned " high temperature " refer to make oxygen carrier granule after oxygen loss with Oxygen-containing gas occurs oxidation reaction, obtains the temperature that oxygen forms oxygen carrier granule again.The oxygen carrier granule after oxygen loss obtains oxygen as a result, It is still fixed in former fixed bed after regenerating oxygen carrier granule afterwards.It is understood that 2 alternate play of the first fixed bed 1 and the second fixed bed Dehydrogenation reactor and oxidation reactor can be such that the oxygen loss of oxygen carrier granule therein carries out in same fixed bed with oxygen is obtained, Without exporting oxygen carrier granule.
Wherein, the oxidation reaction conducted in oxidation reactor are as follows:
MexOy-1+0.5O2(g)→MexOy
Poor oxygen gas heat exchanger 5 is connected to outlet reversal valve 4, by the movement of outlet reversal valve 4, so that Poor oxygen gas changes Hot device 5 is connected to by exporting reversal valve 4 with oxidation reactor always, i.e., so that Poor oxygen gas heat exchanger 5 follows the first fixed bed 1 It is connected to always by outlet reversal valve 4 with the fixed bed as oxidation reactor with the change of the working condition of the second fixed bed 2, The Poor oxygen gas of oxidation reactor output can be received.Also, Poor oxygen gas heat exchanger 5 can for Poor oxygen gas with will give Enter in oxidation reactor oxygen-containing gas heat exchange, and by after heat exchange Poor oxygen gas and oxygen-containing gas export respectively.Oxygen deprivation gas Body heat exchanger 5 is connected to entrance reversal valve 3, by the movement of entrance reversal valve 3, so that Poor oxygen gas heat exchanger 5 passes through always Entrance reversal valve 3 is connected to oxidation reactor, i.e., so that Poor oxygen gas heat exchanger 5 follows the first fixed bed 1 and the second fixed bed 2 The change of working condition be connected to the fixed bed as oxidation reactor by entrance reversal valve 3 always, can will exchange heat Oxygen-containing gas afterwards is sent into oxidation reactor.Wherein, oxygen-containing gas absorbs the heat in high temperature Poor oxygen gas, and by the heat band Return oxidation reactor.
Poor oxygen gas waste heat boiler 6 is connected to Poor oxygen gas heat exchanger 5, can receive the Poor oxygen gas and right after heat exchange It carries out waste heat recycling, and can export the Poor oxygen gas after recovery waste heat.
To sum up, using the system provided in this embodiment for preparing propylene using oxidative dehydrogenation of propane, first, as dehydrogenation What is carried out in the fixed bed of reactor can be by by-product H in certain embodiments2It is oxidized to water, is eliminated hot in dehydrogenation reaction process The limitation of mechanical balance improves once-through propylene yield, while by-product H2The heat discharged in oxidation process can also be provided To dehydrogenation reaction, the energy consumption in dehydrogenation reaction is reduced；Second, the Main By product in certain embodiments is vapor, Be conducive to the separation of subsequent products, while also reducing the energy consumption of subsequent products separation；Third, as raw material propane source it is wide It is general, the propylene that low value-added propane is converted to high added value is had into very big economic benefit；4th, propane is directly prepared into Propylene, process flow is short, and equipment investment is small and product quality is good；5th, oxygen and reactant propane and product propylene are eliminated Direct contact, reduce the progress of excessive oxidation reaction, be conducive to the yield for improving propylene, while also increasing operability And safety；6th, compared to using coal as a large amount of CO of stock discharge2And NOx, the COx gas that this system generates is less, also not NOx is generated, it is more environmentally-friendly；7th, using two fixed beds, entrance reversal valve 3 and outlet reversal valve 4, both do not have to carry out oxygen carrier The conveying of body particle and the subsequent removal particles work to gaseous mixture and Poor oxygen gas, and persistently generated in guarantee system The reaction of propane simplifies the structure of system, has at least saved (main for removing the solid particle in gaseous mixture and Poor oxygen gas If the oxygen carrier granule after the oxygen carrier granule/oxygen loss brought out) equipment；Raw material has been saved (without because of oxygen carrier granule Conveyance loss and oxygen carrier granule is supplemented into dehydrogenation reactor)；Reduce energy consumption.
Also, it is exchanged heat, the heat recovery and utilization in gaseous mixture can either be made entrained by propane using gaseous mixture and propane Heat for being used in dehydrogenation reactor, saved the energy；Energy consumption when subsequent water vapor removing can be reduced again.
Also, further energy regenerating is on the one hand carried out, on the other hand can be reduced subsequent using the waste heat in gaseous mixture Energy consumption when water vapor removing.
Also, it is exchanged heat using Poor oxygen gas and oxygen-containing gas, the heat recovery and utilization in Poor oxygen gas can either be made to contain Heat entrained by carrier of oxygen is used for oxidation reactor, has saved the energy.
Also, the temperature for being emitted into the Poor oxygen gas of atmosphere can be further reduced using the waste heat in Poor oxygen gas, is dropped The low influence to environment.
To sum up, system high efficiency (propylene output efficiency is high), the section that propylene is prepared using oxidative dehydrogenation of propane of the present embodiment Energy, environmental protection, economic, safety.
In the present embodiment, the first fixed bed 1 and the second fixed bed 2 all have gas access 17 and gas vent 19, gas The top of fixed bed is arranged in body entrance 17, and supplied gas enters fixed bed；The bottom of fixed bed is arranged in gas vent 19, gas supply Fixed bed is discharged in body.Entrance reversal valve 3 has oxygen-containing gas entrance 23, propane inlet 21, the first gas outlet 22 and the second outlet Mouth 20, the first gas outlet 22 is connected to the gas access 17 of the first fixed bed 1, the gas of the second gas outlet 20 and the second fixed bed 2 Body entrance 17 is connected to.Exporting reversal valve 4 has the first air inlet 27, the second air inlet 25, mixed gas outlet 24 and Poor oxygen gas Outlet 26, the first air inlet 27 is connected to the gas vent 19 of the first fixed bed 1, the second air inlet 25 and the second fixed bed 2 Gas vent 19 is connected to.
Wherein, referring to Fig. 3, the first working condition of entrance reversal valve 3 and outlet reversal valve 4 are as follows: entrance reversal valve 3 While oxygen-containing gas entrance 23 is connected to the first gas outlet 22 and propane inlet 21 is connected to the second gas outlet 20, control outlet The mixed gas outlet 24 of reversal valve 4 is connected to the second air inlet 25 and the first air inlet 27 is connected to Poor oxygen gas outlet 26.
At this point, oxygen-containing gas is by the oxygen-containing gas entrance 23 of entrance reversal valve 3, the first gas outlet of entrance reversal valve 3 22, the gas access 17 of the first fixed bed 1 enters in the first fixed bed 1, and Poor oxygen gas is gone out by the gas of the first fixed bed 1 Mouth 19, the first air inlet 27 for exporting reversal valve 4 and the Poor oxygen gas outlet 26 for exporting reversal valve 4 are sent to Poor oxygen gas heat exchanger 5, the first fixed bed 1 is used as oxidation reactor as a result,.
At this point, propane is solid by the propane inlet 21 of entrance reversal valve 3, the second gas outlet 20, second of entrance reversal valve 3 The gas access 17 of fixed bed 2 enters the second fixed bed 2, gas vent 19, outlet reversal valve of the gaseous mixture by the second fixed bed 2 4 the second air inlet 25, the mixed gas outlet 24 for exporting reversal valve 4 are sent to gaseous mixture heat exchanger 7, and the second fixed bed 2 is made as a result, For dehydrogenation reactor.
Wherein, referring to Fig. 4, second of working condition of entrance reversal valve 3 and outlet reversal valve 4 are as follows: entrance reversal valve 3 While oxygen-containing gas entrance 23 is connected to the second gas outlet 20 and propane inlet 21 is connected to the first gas outlet 22, control outlet The mixed gas outlet 24 of reversal valve 4 is connected to the first air inlet 27 and the second air inlet 25 is connected to Poor oxygen gas outlet 26.
At this point, oxygen-containing gas is by the oxygen-containing gas entrance 23 of entrance reversal valve 3, the second gas outlet 20 of reversal valve, the The gas access 17 of two fixed beds 2 enters in the second fixed bed 2, Poor oxygen gas by the gas vent 19 of the second fixed bed 2, The Poor oxygen gas outlet 26 of the second air inlet 25 and outlet reversal valve 4 of outlet reversal valve 4 is sent to Poor oxygen gas heat exchanger 5, by This, the second fixed bed 2 is used as oxidation reactor.
At this point, propane is solid by the propane inlet 21 of entrance reversal valve 3, the first gas outlet 22, first of entrance reversal valve 3 The gas access 17 of fixed bed 1 enters the first fixed bed 1, gas vent 19, outlet reversal valve of the gaseous mixture by the first fixed bed 1 4 the first air inlet 27, the mixed gas outlet 24 for exporting reversal valve 4 are sent to gaseous mixture heat exchanger 7, and the first fixed bed 1 is made as a result, For dehydrogenation reactor.
It is understood that entrance reversal valve 3 and outlet reversal valve 4 the first above-mentioned working condition and second working condition it Between switch, i.e., controllable first fixed bed 1 and the second fixed bed 2 are alternately as dehydrogenation reactor and oxidation reactor.Wherein, it Guarantee that entrance reversal valve 3 and outlet reversal valve 4 switch respective communication direction while property, to guarantee the first fixed bed 1 and the Reaction atmosphere in two fixed beds 2 can change simultaneously.
In the present embodiment, the top sidewall of the first fixed bed 1 and the second fixed bed 2 is equipped with feed inlet 16, and first is solid Be additionally provided with drain hole 18 in the bottom sidewall of fixed bed 1 and the second fixed bed 2, feed inlet 16 and drain hole 18 and it is horizontal in 20 °- 70 ° of angle.Calandria 15 is additionally provided on the outer wall of first fixed bed 1 and the second fixed bed 2.First fixed bed 1 and second is solid The reaction temperature that fixed bed 2 can be born is at least 300-700 DEG C, i.e. at least can be carried out in the first fixed bed 1 and the second fixed bed 2 300-700 DEG C of reaction such as needs it is also possible to higher.
Wherein, the oxygen carrier granule of the participation reaction of fixed filling can be gold in the first fixed bed 1 and the second fixed bed 2 Belong to oxide oxygen carrier granule or perovskite oxygen carrier granule.When using metal oxide, Mn can be selected2O3/Mn3O4、 Mn3O4/MnO、V2O5/VO2、VO2/V2O3、Co3O4/CoO、CoO/Co、CuO/Cu2O、MoO3/MoO2、MoO3/Mo、Fe2O3/ Fe3O4、SbO2/Sb2O3、CdO/Cd、WO3/WO2With one of substances such as NiO/Ni or a variety of, wherein substance generation before "/" Table reacted in dehydrogenation reactor before oxygen carrier, oxygen carrier is just reduced into the subsequent substance of "/" after dehydrogenation reaction, and It is passed into oxidation reactor and is reacted.Al can be selected in the inert carrier for preparing oxygen carrier2O3、SiO2、TiO2、ZrO2And Y2O3 One of equal compounds such as oxides and zeolite, molecular sieve, spinelle and sepiolite are a variety of, and metal oxide contains Amount is in 5-70wt% or so.When using perovskite oxygen carrier, RBaCo can be selected2O5(R=Y, Pr-Ho), RBaCo4O7(R =Y, Dy-Lu), RSrR1O4(R=La, Ln；R1=Co, Cu, Ni) etc..Mechanical mixing, coprecipitation, molten can be used in oxygen carrier Glue-gel method, infusion process, solid reaction process, spray drying process, hydro-thermal method or citric acid method etc. are made, oxygen carrier granule diameter It is 200~1000 μm.
Further, gaseous mixture heat exchanger 7 has the gaseous mixture entrance 32 entered for gaseous mixture, defeated for the gaseous mixture after exchanging heat It is mixed gas outlet 34 out, the propane inlet 35 entered for propane, mixed for the propane outlets 33 of the propane output after heat exchange, connection Gas entrance 32 is closed with the mixed gas passage of mixed gas outlet 34 and is connected to the propane channels of propane inlet 35 and propane outlets 33, It is not connected to but can exchange heat between mixed gas passage and propane channel, so that propane and gaseous mixture heat exchange.Preferably, by propane Entrance 35 be directed toward propane outlets 33 in the direction opposite by gaseous mixture entrance 32 be directed toward mixed gas outlet 33 direction, be more conducive to Heat exchange.The gaseous mixture entrance 32 of gaseous mixture heat exchanger 7 is connected to the mixed gas outlet 24 of outlet reversal valve 4 to receive dehydrogenation reaction The gaseous mixture exported in device, the propane outlets 33 of gaseous mixture heat exchanger 7 are connected to the propane inlet 21 of entrance reversal valve 3 will change Propane after heat is sent into dehydrogenation reactor.Certainly, the propane inlet 35 of gaseous mixture heat exchanger 7 also by pipeline and removes gaseous mixture Other propane sources connection other than separation equipment is equipped with propane flow valve 14 to meet the supply of propane feed on the pipeline. The temperature for the gaseous mixture being discharged after the heat exchange of gaseous mixture heat exchanger 7 from its mixed gas outlet 34 is 300-600 DEG C.By mixing The temperature for the propane that gas heat exchanger 7 is discharged after exchanging heat from its propane outlets 33 is 100-300 DEG C.
Further, gaseous mixture waste heat boiler 8 is with the gaseous mixture entrance entered for gaseous mixture, the mixing exported for gaseous mixture Gas outlet and other waste heat boiler common structures, the gaseous mixture entrance of gaseous mixture waste heat boiler 8 and mixing for gaseous mixture heat exchanger 7 Gas outlet is closed, to receive the gaseous mixture by heat exchange.It is arranged after the heat exchange of gaseous mixture waste heat boiler 8 from its mixed gas outlet The temperature of gaseous mixture out is 100-200 DEG C.When the waste heat that gaseous mixture waste heat boiler 8 recycles needs to heat when separating gaseous mixture It can be used for mixed gas separation equipment 10.
Gaseous mixture dehydration equipment 9 is with the gaseous mixture entrance entered for gaseous mixture, the mixed gas outlet being discharged for gaseous mixture And connection gaseous mixture entrance and mixed gas outlet mixed gas passage, the gaseous mixture entrance of gaseous mixture dehydration equipment 9 with mix The mixed gas outlet of gas waste heat boiler 8 is connected to, to receive the gaseous mixture after recovery waste heat.Wherein, gaseous mixture dehydration equipment 9 also has There is the discharge of liquid water out feed flow state water.Also have in gaseous mixture dehydration equipment 9 condensing medium inlet entered for cooling medium, The condensing medium outlet being discharged for the cooling medium after heat exchange and connection are between condensing medium inlet and condensing medium outlet Cooling medium channel, be not connected to but can exchange heat between cooling medium channel and mixed gas passage, in cooling medium channel The cooling medium of flowing exchanges heat with the gaseous mixture that flows in mixed gas passage, the vapor in gaseous mixture be condensed into liquid water from Gaseous mixture removing, cooling medium heat absorption.In the present embodiment, oxygen-containing gas can be selected as cooling medium, containing after heat absorption Carrier of oxygen can be used as the oxygen-containing gas for feeding oxidation reactor.Further, the volumetric concentration of oxygen is 1- in oxygen-containing gas 99%, preferably air or oxygen containing industrial smoke.The temperature of the liquid water formed in gaseous mixture dehydration equipment 9 is at 60-80 DEG C, warp The supplement water that can be used as waste heat boiler (gaseous mixture waste heat boiler 8 and/or Poor oxygen gas waste heat boiler 6) after deoxygenation is added to waste heat In boiler.Certainly, the present invention is not limited to this, and the mode of absorption can also be used in gaseous mixture dehydration equipment 9 in other embodiments Water vapor removing.
Mixed gas separation equipment 10 is with the gaseous mixture entrance 36 entered for gaseous mixture, the COx gas exported for COx gas Outlet 38 exports 39 for the propylene that propylene exports and for the propane outlets 37 that propane exports, the mixing of mixed gas separation equipment 10 Gas entrance 36 is connected to the mixed gas outlet of gaseous mixture dehydration equipment 9, to receive the gaseous mixture after drying.Propane outlets 39 and mixed The propane inlet 35 for closing gas heat exchanger 7 is connected to.
COx gas reservoir 11 has the gas access COx entered for COx gas, the COx gas of COx gas reservoir 11 Body entrance is connected to the COx gas vent of mixed gas separation equipment 10, to receive the COx gas isolated from gaseous mixture.When So, the COx gas vent of mixed gas separation equipment 10 can be also connected to downstream chemical industry synthesis equipment.The chemical industry synthesis of COx gas Including synthetic oil, methanol and ethylene glycol etc. using COx gas as in the chemical industry synthesis of raw material.
Propylene reservoir 12 has the propylene entrance entered for propylene, the propylene entrance and gaseous mixture point of propylene reservoir 12 Propylene outlet from equipment 10, to receive the propylene isolated from gaseous mixture.Certainly, the third of mixed gas separation equipment 10 Alkene outlet can be also connected to downstream chemical industry synthesis equipment.The chemical industry synthesis of propylene includes synthesis polypropylene, acrylic acid and acrylonitrile Deng using propylene as in the chemical industry synthesis of raw material.
Poor oxygen gas heat exchanger 5 has the Poor oxygen gas entrance 28 entered for Poor oxygen gas, for the Poor oxygen gas after exchanging heat Output Poor oxygen gas outlet 29, for oxygen-containing gas enter oxygen-containing gas entrance 30, for heat exchange after oxygen-containing gas output Oxygen-containing gas outlet 31, connection Poor oxygen gas entrance 28 and Poor oxygen gas export 29 Poor oxygen gas channel, be connected to oxygen-containing gas The oxygen-containing gas channel of entrance 30 and oxygen-containing gas outlet 31, is not connected between Poor oxygen gas channel and oxygen-containing gas channel and only changes Heat, so that Poor oxygen gas exchanges heat with oxygen-containing gas.Preferably, Poor oxygen gas entrance 28 is directed toward Poor oxygen gas outlet 29 In the direction opposite oxygen-containing gas entrance 30 be directed toward oxygen-containing gas outlet 31 direction.
The Poor oxygen gas entrance 28 of Poor oxygen gas heat exchanger 5 is connected to the Poor oxygen gas outlet 26 of outlet reversal valve 4, to connect Receive the Poor oxygen gas of high temperature.The oxygen-containing gas entrance 30 of Poor oxygen gas heat exchanger 5 is connected to by pipeline with oxygen-containing gas source, at this Pipeline is equipped with oxygen-containing gas flow valve 13, to control the intake of oxygen-containing gas, and then controls the reaction in oxidation reactor. The oxygen-containing gas outlet 31 of Poor oxygen gas heat exchanger 5 is connected to the oxygen-containing gas entrance 23 of entrance reversal valve 3.By Poor oxygen gas The temperature for the Poor oxygen gas that heat exchanger 5 is discharged after exchanging heat from its Poor oxygen gas outlet 29 is 300-600 DEG C.It is changed by Poor oxygen gas The temperature for the oxygen-containing gas that hot device 5 is discharged after exchanging heat from its oxygen-containing gas outlet 31 is 100-300 DEG C.
Poor oxygen gas waste heat boiler 6 has the Poor oxygen gas entrance entered for Poor oxygen gas, for the oxygen deprivation after recovery waste heat The Poor oxygen gas outlet of gas discharge and other waste heat boiler common structures, the Poor oxygen gas of Poor oxygen gas waste heat boiler 6 enter The Poor oxygen gas outlet of mouth and Poor oxygen gas heat exchanger 5, to receive the Poor oxygen gas after heat exchange.By Poor oxygen gas waste heat The temperature for the Poor oxygen gas that boiler 6 is discharged after exchanging heat from the outlet of its Poor oxygen gas is 20-100 DEG C.
When oxygen-containing gas is that air etc. will not be to the gas that environment impacts, the oxygen deprivation of Poor oxygen gas waste heat boiler 6 Gas vent is communicated with the atmosphere, and the Poor oxygen gas that will have cooled down is discharged into atmosphere, will not impact to environment.When Poor oxygen gas is When cannot be directly discharged into the gas of atmosphere, the Poor oxygen gas outlet of Poor oxygen gas waste heat boiler 6 can also be connected to collection device.
In the system of the present embodiment, it may also include control device, control device and entrance reversal valve 3 and outlet reversal valve 4 Communication connection, to control the linkage of the two.
In the system of the present embodiment, above-mentioned " connection " can be two components and be directly connected to and be connected, and be also possible to Two components are connected to by pipeline, and other component also can be set on pipeline, as long as being able to achieve the biography of corresponding material It is defeated.
Embodiment two
The present embodiment provides a kind of method for preparing propylene using chemical chain oxidative dehydrogenation of propane, this method uses embodiment System in one, entrance reversal valve 3 and outlet reversal valve 4 link, and make the first fixed bed 1 and the second fixed bed 2 alternately as de- Hydrogen reactor and oxidation reactor, i.e. the first fixed bed 1 are alternately as dehydrogenation reactor and oxidation reactor, the second fixed bed 2 Alternately as dehydrogenation reactor and oxidation reactor, and the second fixation while the first fixed bed 1 conduct dehydrogenation reactor Bed 2 is used as oxidation reactor, and the second fixed bed 2 is used as dehydrogenation reactor while the first fixed bed 1 is as oxidation reactor.
Wherein, in the fixed bed as dehydrogenation reactor, propane is reacted at high temperature with oxygen carrier granule, wherein Oxidative dehydrogenation occurs for a part of propane and oxygen carrier granule, the oxygen carrier granule after generating propylene, vapor and oxygen loss, separately Deep oxidation reaction occurs for a part of propane, generates vapor and COx gas, and export third generated containing oxidative dehydrogenation The gaseous mixture of vapor and COx gas and the propane not reacted completely that alkene and vapor, deep oxidation reaction generate.? In the present embodiment, the propane unreacted being passed through in the fixed bed as dehydrogenation reactor is complete, and propane is also contained in gaseous mixture. Oxidative dehydrogenation and the reaction temperature of deep oxidation reaction are 300-700 DEG C
Wherein, in the fixed bed as oxidation reactor, oxygen carrier granule and oxygen-containing gas after oxygen loss are at high temperature Oxidation reaction is carried out, generates Poor oxygen gas and regenerated oxygen carrier granule, and export Poor oxygen gas.The reaction temperature of oxidation reaction It is 300-700 DEG C.
Gaseous mixture heat exchanger 7 receives the gaseous mixture exported as the fixed bed of dehydrogenation reactor through outlet reversal valve 4, and makes The part gaseous mixture exchanges heat in gaseous mixture heat exchanger 7 with the propane that will be fed into the fixed bed as dehydrogenation reactor.Then Gaseous mixture after output heat exchange, the temperature of the gaseous mixture after exchanging heat at this time are 300-600 DEG C, and by the propane after heat exchange through entering Mouth reversal valve 3 is sent into dehydrogenation reactor, and the temperature of the propane after being exchanged heat at this time by gaseous mixture heat exchanger 7 is 100-300 DEG C.
Gaseous mixture waste heat boiler 8 receives the gaseous mixture that gaseous mixture heat exchanger 7 exports, this part gaseous mixture is in gaseous mixture waste heat Waste heat recycling is carried out in boiler 8, then exports the gaseous mixture after recovery waste heat.After being recycled by 8 waste heat of gaseous mixture waste heat boiler Gaseous mixture temperature be 100-200 DEG C.
Gaseous mixture dehydration equipment 9 receives the gaseous mixture after the recovery waste heat that gaseous mixture waste heat boiler 8 exports, part mixing Gas is dried in gaseous mixture dehydration equipment 9, the gaseous mixture after then output is dry.
Mixed gas separation equipment 10 receives the gaseous mixture after the drying that gaseous mixture dehydration equipment 9 exports and therefrom separates respectively Propylene, propane and COx gas out, the propane isolated through entrance reversal valve 3 send work back to after sending into gaseous mixture heat exchanger 7 heat exchange For in the fixed bed of dehydrogenation reactor.
Poor oxygen gas heat exchanger 5 receives the Poor oxygen gas of the fixed bed output as oxidation reactor, and by the oxygen deprivation gas Body exchanges heat in Poor oxygen gas heat exchanger 5 with the oxygen-containing gas that will be fed into the fixed bed as oxidation reactor, after heat exchange Poor oxygen gas and oxygen-containing gas export respectively.The temperature of oxygen-containing gas after being exchanged heat by Poor oxygen gas heat exchanger 5 is 100- 300 DEG C, the Poor oxygen gas after heat exchange is 300-600 DEG C.
Poor oxygen gas waste heat boiler 6 receives the Poor oxygen gas that Poor oxygen gas heat exchanger 5 exports, and the Poor oxygen gas after heat exchange exists Waste heat recycling is carried out in Poor oxygen gas waste heat boiler 6, is then exported the Poor oxygen gas after recovery waste heat, is passed through Poor oxygen gas waste heat The temperature of 6 waste heat of boiler Poor oxygen gas after the recovery is 20-100 DEG C.
Preferably, the partial size of oxygen carrier granule fixed in the first fixed bed 1 and the second fixed bed 2 is 200-1000 μm. Oxygen carrier granule can be metal oxide oxygen carrier granule or perovskite oxygen carrier granule.It, can when using metal oxide Select Mn2O3/Mn3O4、Mn3O4/MnO、V2O5/VO2、VO2/V2O3、Co3O4/CoO、CoO/Co、CuO/Cu2O、MoO3/MoO2、 MoO3/Mo、Fe2O3/Fe3O4、SbO2/Sb2O3、CdO/Cd、WO3/WO2With one of substances such as NiO/Ni or a variety of, wherein Substance before "/" represents the oxygen carrier before reacting in dehydrogenation reactor, and oxygen carrier is just reduced into after dehydrogenation reaction The subsequent substance of "/", and be passed into oxidation reactor and reacted.Al can be selected in the inert carrier for preparing oxygen carrier2O3、 SiO2、TiO2、ZrO2And Y2O3One of equal compounds such as oxides and zeolite, molecular sieve, spinelle and sepiolite are more Kind, the content of metal oxide is in 5-70wt% or so.When using perovskite oxygen carrier, RBaCo can be selected2O5(R=Y, Pr-Ho)、RBaCo4O7(R=Y, Dy-Lu), RSrR1O4(R=La, Ln；R1=Co, Cu, Ni) etc..Oxygen carrier can be used mechanical mixed The system such as legal, coprecipitation, sol-gel method, infusion process, solid reaction process, spray drying process, hydro-thermal method and citric acid method , oxygen carrier granule diameter is 200~1000 μm.
To sum up, using the method provided in this embodiment for preparing propylene using chemical chain oxidative dehydrogenation of propane, first, de- It can be by by-product H during hydrogen2It is oxidized to water, the limitation of thermodynamical equilibrium in dehydrogenation reaction process is eliminated, makes once-through propylene Yield improves, while by-product H2The heat discharged in oxidation process can also be provided to dehydrogenation reaction, reduce dehydrogenation reaction In energy consumption；Second, the Main By product in certain embodiments is vapor, is conducive to the separation of subsequent products, simultaneously Also reduce the energy consumption of subsequent products separation；Third, as raw material propane it is from a wealth of sources, low value-added propane is converted to The propylene of high added value has very big economic benefit；4th, propane is directly prepared into propylene, process flow is short, equipment investment Small and product quality is good；5th, it eliminates oxygen to contact with reactant propane and the direct of product propylene, reduces excessive oxidation The progress of reaction is conducive to the yield for improving propylene, while also increasing operability and safety；6th, compared to coal For a large amount of CO of stock discharge2And NOx, the COx gas of this method discharge is less, and does not generate NOx, more environmentally-friendly；7th, Using two fixed beds, entrance reversal valve 3 and outlet reversal valve 4, the conveying of oxygen carrier granule and subsequent right is not both had to carry out The removal particles work of gaseous mixture and Poor oxygen gas, and persistently carry out generating the reaction of propane in guarantee system, simplify technique Step, at least saved for remove the solid particle in gaseous mixture and Poor oxygen gas (oxygen carrier granule mainly brought out/ Oxygen carrier granule after oxygen loss) the step of；Raw material has been saved (without the conveyance loss because of oxygen carrier granule to dehydrogenation reactor Middle supplement oxygen carrier granule)；Reduce energy consumption.
Also, it is exchanged heat, the heat recovery and utilization in gaseous mixture can either be made entrained by propane using gaseous mixture and propane Heat for being used in dehydrogenation reactor, saved the energy；Energy consumption when subsequent water vapor removing can be reduced again.
Also, further energy regenerating is on the one hand carried out, on the other hand can be reduced subsequent using the waste heat in gaseous mixture Energy consumption when water vapor removing.
Also, it is exchanged heat using Poor oxygen gas and oxygen-containing gas, the heat recovery and utilization in Poor oxygen gas can either be made to contain Heat entrained by carrier of oxygen is used for oxidation reactor, has saved the energy.
Also, the temperature for being emitted into the Poor oxygen gas of atmosphere can be further reduced using the waste heat in Poor oxygen gas, is dropped The low influence to environment.
To sum up, the method for preparing propylene using oxidative dehydrogenation of propane efficient (propylene output efficiency is high) of the present embodiment, section Energy, environmental protection, economic, safety.
To sum up, technological core of the invention is the redox property using oxygen carrier, with third under the conditions of no gaseous oxygen Alkane occurs oxidative dehydrogenation and prepares propylene, then carries out oxidation regeneration to oxygen carrier under oxygen-containing gas atmosphere.
It is understood that, when production just starts, needing first to start a fixation in the system and method for above-described embodiment Bed is used as dehydrogenation reactor, starts another fixed bed when the fixed bed becomes oxidation reactor to take over as dehydrogenation reaction Device, when produce stablize after, the first fixed bed 1 and the second fixed bed 2 form above-mentioned alternately as dehydrogenation reactor and oxidation reaction The state of device.
It is understood that being to obtain the step that oxygen is carried out as clue using the oxygen loss of oxygen carrier granule (participating in dehydrogenation)-in the above-mentioned methods Rapid description.It is emphasized that either how to describe the present invention, claimed content core is will with oxygen carrier granule Propylene is made in propane, without that should be explained with limiting the invention property of describing mode.
Method as follows, that the system progress using embodiment one is further described with an experiment.Wherein with propylene annual output For 60,000 tons of dehydrogenation systems, the specific implementation step of method is as follows:
S1, the suitable oxygen carrier of selection, select partial size at 200~1000 μm the oxygen carrier granule prepared after screening The particle of left and right is added in fixed bed by the feed inlet 16 at 2 top of the first fixed bed 1 and the second fixed bed.In the present embodiment In, select metal oxide V2O5With inert carrier Al2O3, the adding proportion of metal oxide is 10wt%, using dipping legal system Standby oxygen carrier, sieves the oxygen carrier of preparation, selects partial size in 2 tons of oxygen carrier granule of 400~500 μm.
S2, the heating member 15 for opening the first fixed bed 1 and the second fixed bed 2, rise rapidly the temperature inside fixed bed And reaction temperature is maintained, in the present embodiment, reaction temperature is 600 DEG C.
S3, propane valve 14, adjustment entrance reversal valve 3 and the circulating direction for exporting reversal valve 4 are opened, makes propane by entrance Reversal valve 3 enters in the second fixed bed 2, and reacts in the second fixed bed 2 with the oxygen carrier granule in bed；? The gaseous mixture generated in two fixed beds 2 is discharged from the gas vent 19 of fixed bed bottom, enters gaseous mixture by outlet reversal valve 4 In heat exchanger 7, after being exchanged heat in gaseous mixture heat exchanger 7 with the propane wait react, through gaseous mixture waste heat boiler 8 and gaseous mixture Dehydration equipment 9 enters mixed gas separation equipment 10, and the propane isolated in mixed gas separation equipment 10 is through gaseous mixture heat exchanger 7 It being backed in the second fixed bed 2 with entrance reversal valve 3, propylene and COx gas have respectively entered in respective reservoir, or Directly carry out chemical industry synthesis.
More specifically, the change of the circulating direction of entrance reversal valve 3 and outlet reversal valve 4, makes propane pass through gaseous mixture Second gas outlet 20 of the heat exchanger 7 successively propane inlet 21 through entrance reversal valve 3, entrance reversal valve 3 is from the second fixed bed 2 Gas access 17 enters in the second fixed bed 2；Propane is aoxidized with the oxygen carrier granule in bed in the second fixed bed 2 Dehydrogenation reaction generates propylene and vapor, while part propane occurs deep oxidation reaction and generates COx gas and vapor, oxygen carrier Body particle is reduced the oxygen carrier granule after forming oxygen loss；The gaseous mixture generated in the second fixed bed 2 is from 2 bottom of the second fixed bed The gas vent 19 in portion is discharged, and is exported the mixed gas outlet 24 of reversal valve 4 from mixed by the second air inlet 25 of outlet reversal valve 4 The gaseous mixture entrance 32 for closing gas heat exchanger 7 enters in gaseous mixture heat exchanger 7, with to be reacted third in gaseous mixture heat exchanger 7 Alkane exchanges heat, and the mixture temperature after heat exchange is 400 DEG C, propane temperature is 200 DEG C, and the gaseous mixture after heat exchange is through more than gaseous mixture Temperature is passed through in gaseous mixture dehydration equipment 9 after being down to 120 DEG C after 8 recovery waste heat of heat boiler, is condensed out in gaseous mixture dehydration equipment 9 Gaseous mixture be passed through in mixed gas separation equipment 10, the temperature of the liquid water being condensed out is 80 DEG C and the supplement as waste heat boiler Water enters in the oxygen-eliminating device of waste heat boiler；The propane isolated in mixed gas separation equipment 10 is changed by propane outlets 37 through gaseous mixture Hot device 7 and entrance reversal valve 3 back in the second fixed bed 2, and propylene enters propylene reservoir 12 by propylene outlet 39 In carry out storage or directly carry out chemical industry synthesis, COx gas enters in COx gas reservoir 11 by COx gas vent 38 It carries out storage or directly carries out chemical industry synthesis.
As a result, in this step, the second fixed bed temporarily has neither part nor lot in reaction as dehydrogenation reactor, the first fixed bed.
S4, after reaction a period of time (in the present embodiment for half an hour after), oxygen-containing gas valve 13 is opened, adjusts entrance The circulating direction of reversal valve 3 and outlet reversal valve 4, enters oxygen-containing gas in second fixed bed 2 by entrance reversal valve 3；? In second fixed bed 2, oxygen-containing gas be reduced after oxygen carrier occur oxidation reaction realize oxygen carrier oxidation regeneration, through anti- Air after answering becomes oxygen denuded air；Meanwhile second the oxygen denuded air generated in fixed bed 2 from the gas vent of fixed bed bottom 19 discharges, are entered in Poor oxygen gas heat exchanger 5 by outlet reversal valve 4, in Poor oxygen gas heat exchanger 5 with it is to be reacted oxygen-containing It enters after gas converting heat in Poor oxygen gas waste heat boiler 6, is directly vented after recovery waste heat in Poor oxygen gas waste heat boiler 6. Propane gas becomes successively through gaseous mixture heat exchanger 7, entrance reversal valve 3, into the first fixed bed 1, with the first fixed bed 1 simultaneously In oxygen carrier occur oxidative dehydrogenation.Gas vent of the gaseous mixture generated in the first fixed bed 1 from fixed bed bottom 19 discharges, are entered in gaseous mixture heat exchanger 7 by outlet reversal valve 4, are carried out in gaseous mixture heat exchanger 7 with propane to be reacted After heat exchange, mixed gas separation equipment 10 is entered through gaseous mixture waste heat boiler 8 and gaseous mixture dehydration equipment 9, mixed gas separation is set The propane isolated in standby 10 backs in the first fixed bed 1 through gaseous mixture heat exchanger 7 and entrance reversal valve 3, propylene and COx gas has respectively entered in respective reservoir, or directly carries out chemical industry synthesis.
More specifically, referring to Fig. 4, the change of entrance reversal valve 3 and the circulating direction of outlet reversal valve 4 makes oxygenous Body (in the present embodiment be air) passes through Poor oxygen gas heat exchanger 5 and successively the oxygen-containing gas entrance 23 through entrance reversal valve 3 and enters Second gas outlet 20 of mouth reversal valve 3 enters in the second fixed bed 2 from the gas access 17 of the second fixed bed 2；It is solid second In fixed bed 2, the oxidation of oxidation reaction realization oxygen carrier occurs for oxygen-containing gas again with the oxygen carrier after being reduced in a previous step It is raw, it is reacted after oxygen-containing gas become Poor oxygen gas；The Poor oxygen gas generated in second fixed bed 2 is from 2 bottom of the second fixed bed The gas vent 19 in portion is discharged, by the second air inlet 25 of outlet reversal valve 4 exported the Poor oxygen gas outlet 26 of reversal valve 4 into Enter into Poor oxygen gas heat exchanger 5, the temperature of the Poor oxygen gas after heat exchange is 300 DEG C, the temperature of oxygen-containing gas is 200 DEG C, is changed Poor oxygen gas after heat recovery waste heat, temperature in Poor oxygen gas waste heat boiler 6 are cooled to room temperature direct emptying；Entrance changes simultaneously To valve 3 and outlet reversal valve 4 circulating direction change so that propane successively the propane outlets 33 through gaseous mixture heat exchanger 7, enter Mouthful propane inlet 21 of reversal valve 3, the first gas outlet 22 of entrance reversal valve 3, the first fixed bed 1 gas access 17 enter the In one fixed bed 1, and oxidative dehydrogenation occurs with the oxygen carrier granule in the first fixed bed 1；It is generated in the first fixed bed 1 Gaseous mixture from the gas vent 19 of 1 bottom of the first fixed bed be discharged, by outlet reversal valve 4 the first air inlet 27 through outlet change It enters in gaseous mixture heat exchanger 7, is mixing from the gaseous mixture entrance 32 of gaseous mixture heat exchanger 7 to the mixed gas outlet 24 of valve 4 It exchanging heat in gas heat exchanger 7 with propane to be reacted, the mixture temperature after heat exchange is 400 DEG C, propane temperature is 200 DEG C, Gaseous mixture after heat exchange is passed through gaseous mixture dehydration equipment 9 after temperature is down to 120 DEG C after 8 recovery waste heat of gaseous mixture waste heat boiler In, it is passed through in mixed gas separation equipment 10 in the gaseous mixture that gaseous mixture dehydration equipment 9 is condensed out, the temperature for the liquid water being condensed out Supplement water for 80 DEG C and as waste heat boiler enters in the oxygen-eliminating device of waste heat boiler；It is isolated in mixed gas separation equipment 10 Propane is backed in the first fixed bed 1 by propane outlets 37 through gaseous mixture heat exchanger 7 and entrance reversal valve 3, and propylene is by third Alkene outlet 39, which enters in propylene reservoir 12, to be carried out storage or directly carries out chemical industry synthesis, and COx gas is by COx gas vent 38 enter in COx gas reservoir 11 carry out storage or directly carry out chemical industry synthesis.
As a result, in this step, the second fixed bed 2 is used as oxidation reactor, and the first fixed bed 1 takes over the second fixed bed 2 As dehydrogenation reactor.
S5, after reaction a period of time (in the present embodiment for half an hour after), adjustment entrance reversal valve 3 and outlet reversal valve 4 circulating direction enters propane in second fixed bed 2 by entrance reversal valve 3, and in the second fixed bed 2 and in bed Oxygen carrier granule react；The gaseous mixture generated in the second fixed bed 2 is discharged from the gas vent 19 of fixed bed bottom, It is entered in gaseous mixture heat exchanger 7 by outlet reversal valve 4, after being exchanged heat in gaseous mixture heat exchanger 7 with the propane wait react, Mixed gas separation equipment 10 is entered through gaseous mixture waste heat boiler 8 and gaseous mixture dehydration equipment 9, is divided in mixed gas separation equipment 10 The propane separated out backs in the second fixed bed 2 through gaseous mixture heat exchanger 7 and entrance reversal valve 3, propylene and COx gas point It does not enter in respective reservoir, or directly carries out chemical industry synthesis.Meanwhile making oxygen-containing gas through Poor oxygen gas heat exchanger 5, entering Mouth reversal valve 3 enters in the first fixed bed 1；In the first fixed bed 1, with the oxygen carrier after being reduced oxygen occurs for oxygen-containing gas Change reaction realize oxygen carrier oxidation regeneration, it is reacted after air become oxygen denuded air；Meanwhile the interior generation of the first fixed bed 1 Oxygen denuded air from the gas vent 19 of fixed bed bottom be discharged, entered in Poor oxygen gas heat exchanger 5 by outlet reversal valve 4, It is entered in Poor oxygen gas waste heat boiler 6 after the oxygen-containing gas heat exchange wait react in Poor oxygen gas heat exchanger 5, in oxygen deprivation gas It is directly vented after recovery waste heat in body waste heat boiler 6.
More specifically, referring to Fig. 3, the change of entrance reversal valve 3 and the circulating direction of outlet reversal valve 4 wears propane Second gas outlet 20 of the successively propane inlet 21 through entrance reversal valve 3, entrance reversal valve 3 is crossed after gaseous mixture heat exchanger 7 from The gas access of two fixed beds 2 enters in the second fixed bed 2；Oxygen carrier in the second fixed bed 2 in propane and bed Grain occurs oxidative dehydrogenation and generates propylene and vapor, at the same part propane occur deep oxidation reaction generate COx gas and Vapor, oxygen carrier granule are reduced the oxygen carrier granule after forming oxygen loss.The gaseous mixture generated in second fixed bed 2 is from second The gas vent 19 of 2 bottom of fixed bed is discharged, by the second air inlet 25 of outlet reversal valve 4 through exporting the gaseous mixture of reversal valve 4 Outlet 24 enters in gaseous mixture heat exchanger 7 from the gaseous mixture entrance 32 of gaseous mixture heat exchanger 7, in gaseous mixture heat exchanger 7 with Propane to be reacted exchanges heat, and the mixture temperature after heat exchange is 400 DEG C, propane temperature is 200 DEG C, the gaseous mixture after heat exchange Temperature is passed through in gaseous mixture dehydration equipment 9 after being down to 120 DEG C after 8 recovery waste heat of gaseous mixture waste heat boiler, is dehydrated in gaseous mixture The gaseous mixture that equipment 9 is condensed out is passed through in mixed gas separation equipment 10, and the temperature for the liquid water being condensed out is 80 DEG C and as remaining The supplement water of heat boiler enters in the oxygen-eliminating device of waste heat boiler；The propane isolated in mixed gas separation equipment 10 is by propane outlets 37 back in the second fixed bed 2 through gaseous mixture heat exchanger 7 and entrance reversal valve 3, and propylene is entered by propylene outlet 39 Storage is carried out in propylene reservoir 12 or directly carries out chemical industry synthesis, and COx gas enters COx gas by COx gas vent 38 Storage is carried out in body reservoir 11 or directly carries out chemical industry synthesis.Meanwhile the circulating direction of reversal valve 3 and outlet reversal valve 4 Change the oxygen-containing gas after making oxygen-containing gas (being air in the present embodiment) pass through Poor oxygen gas heat exchanger 5 by entrance reversal valve 3 Entrance 23 enters the first fixed bed 1 from the gas access 17 of the first fixed bed 1 through the first gas outlet 22 of entrance reversal valve 3 In；In the first fixed bed 1, the oxygen carrier granule after being reduced in oxygen-containing gas and previous step occurs oxidation reaction and realizes load The oxidation regeneration of oxysome particle, it is reacted after oxygen-containing gas become Poor oxygen gas；The Poor oxygen gas generated in first fixed bed 1 It is discharged from the gas vent 19 of 1 bottom of the first fixed bed, by the first air inlet 27 of outlet reversal valve 4 through outlet reversal valve 4 Poor oxygen gas outlet 26 enters in Poor oxygen gas heat exchanger 5, and the temperature of the Poor oxygen gas after heat exchange is 300 DEG C, oxygen-containing gas Temperature be 200 DEG C, Poor oxygen gas after heat exchange recovery waste heat, temperature in Poor oxygen gas waste heat boiler 6 are cooled to room temperature directly Connect emptying.As a result, in this step, the first fixed bed 1 is used as oxidation reactor, and the second fixed bed 2 is used as dehydrogenation reactor.
S6, return step S4 circulation execute, and keep entering the first fixed bed 1, the second fixed bed 2 after system stable operation The flow of oxygen-containing gas is 1000m3/ h, propane flow 800m3The flow of/h, oxygen-containing gas and propane remains unchanged, according to journey Sequence (such as the program being stored in control device) automatically switches entrance reversal valve 3 and exports the circulating direction of reversal valve 4.
After S7, system are out of service, oxygen-containing gas valve 13 and propane valve 14 are closed, passes through two fixed bed lower parts Drain hole 19 drains the oxygen carrier granule in bed respectively.
In the above method, the chemical industry synthesis of propylene include synthesis polypropylene, acrylic acid and acrylonitrile etc. with propylene be original In the chemical industry synthesis of material, the chemical industry synthesis of COx includes synthetic oil, methanol and ethylene glycol etc. using COx as in the chemical industry synthesis of raw material.
The above is only a preferred embodiment of the present invention, for those of ordinary skill in the art, according to the present invention Thought, there will be changes in the specific implementation manner and application range, and the content of the present specification should not be construed as to the present invention Limitation.

Claims (7)

1. a kind of system for preparing propylene using chemical chain oxidative dehydrogenation of propane, which is characterized in that including the first fixed bed (1), Second fixed bed (2), entrance reversal valve (3), outlet reversal valve (4), gaseous mixture dehydration equipment (9), mixed gas separation equipment (10)；
Wherein, oxygen carrier granule, first fixed bed (1) are capable of fixing in the first fixed bed (1) and the second fixed bed (2) It is additionally provided with calandria (15) on the outer wall of second fixed bed (2), first fixed bed (1) and second fixed bed (2) it is connected to the entrance reversal valve (3) and the outlet reversal valve (4), the entrance reversal valve (3) and the outlet are changed It is linked to valve (4) so that first fixed bed (1) and second fixed bed (2) are anti-alternately as dehydrogenation reactor and oxidation Device is answered, the first fixed bed (1) and the second fixed bed (2) can be for oxygen carrier granule therein and entrance when being used as dehydrogenation reactor Propane therein is reacted at high temperature, and generation contains the load after propylene, the gaseous mixture of vapor and COx gas and oxygen loss Oxysome particle, the dehydrogenation reactor can export the gaseous mixture, first fixed bed (1) and second fixed bed (2) as oxidation reactor when can for after wherein oxygen loss oxygen carrier granule and enter oxygen-containing gas therein at high temperature into Row oxidation reaction generates Poor oxygen gas and regenerated oxygen carrier granule and exports the Poor oxygen gas；
Wherein, the gaseous mixture can be dried in the gaseous mixture dehydration equipment (9)；
Wherein, the mixed gas separation equipment (10) can isolate propylene from the gaseous mixture after drying；
First fixed bed (1) and second fixed bed (2) all have gas access and gas vent；
The entrance reversal valve (3) has oxygen-containing gas entrance, propane inlet, the first gas outlet and the second gas outlet, and described the One gas outlet is connected to the gas access of first fixed bed (1), second gas outlet and second fixed bed (2) Gas access connection；
The outlet reversal valve (4) has the first air inlet, the second air inlet, mixed gas outlet and Poor oxygen gas outlet, described First air inlet is connected to the gas vent of first fixed bed (1), second air inlet and second fixed bed (2) Gas vent connection；
Wherein, the oxygen-containing gas entrance of the entrance reversal valve (3) be connected to first gas outlet and the propane inlet with While second gas outlet is connected to, the mixed gas outlet and second air inlet for controlling outlet reversal valve (4) connect Logical and described first air inlet and the Poor oxygen gas outlet；
Wherein, the oxygen-containing gas entrance of the entrance reversal valve (3) be connected to second gas outlet and the propane inlet with While first gas outlet is connected to, the mixed gas outlet and first air inlet for controlling outlet reversal valve (4) connect Logical and described second air inlet and the Poor oxygen gas outlet；
The system for preparing propylene using chemical chain oxidative dehydrogenation of propane further include:
Gaseous mixture heat exchanger (7), the gaseous mixture heat exchanger (7) have gaseous mixture entrance, mixed gas outlet, propane inlet, third Alkane outlet, connection gaseous mixture entrance are with the mixed gas passage of mixed gas outlet and are connected to the propane of propane inlet and propane outlets Channel, the gaseous mixture entrance of the gaseous mixture heat exchanger (7) is connected to the mixed gas outlet of outlet reversal valve (4), described The propane outlets of gaseous mixture heat exchanger (7) are connected to the propane inlet of the entrance reversal valve (3), the gaseous mixture heat exchanger (7) gaseous mixture that can be exported for the dehydrogenation reactor exchanges heat with the propane that will be fed into the dehydrogenation reactor；
Gaseous mixture waste heat boiler (8), the gaseous mixture waste heat boiler (8) has gaseous mixture entrance and mixed gas outlet, described mixed The gaseous mixture entrance for closing gas waste heat boiler (8) is connected to the mixed gas outlet of the gaseous mixture heat exchanger (7), more than the gaseous mixture Heat boiler (8) can the gaseous mixture after heat exchanging carry out waste heat recycling；
Wherein, the gaseous mixture dehydration equipment (9) has gaseous mixture entrance and mixed gas outlet, the gaseous mixture dehydration equipment (9) gaseous mixture entrance is connected to the mixed gas outlet of the gaseous mixture waste heat boiler (8)；
The mixed gas separation equipment (10) can also isolate COx gas and unreacted third from the gaseous mixture after drying Alkane, the mixed gas separation equipment (10) has gaseous mixture entrance, propylene outlet, COx gas vent and propane outlets, described The gaseous mixture entrance of mixed gas separation equipment (10) is connected to the mixed gas outlet of the gaseous mixture dehydration equipment (9), described mixed The propane outlets for closing gas separation equipment (10) are connected to the propane inlet of the gaseous mixture heat exchanger (7)；
The system for preparing propylene using chemical chain oxidative dehydrogenation of propane further include:
There is Poor oxygen gas entrance, Poor oxygen gas to export, is oxygen-containing for Poor oxygen gas heat exchanger (5), the Poor oxygen gas heat exchanger (5) Gas access, oxygen-containing gas outlet, connection Poor oxygen gas entrance exported with Poor oxygen gas Poor oxygen gas channel, be connected to it is oxygenous Body entrance and oxygen-containing gas outlet oxygen-containing gas channel, the Poor oxygen gas entrance of the Poor oxygen gas heat exchanger (5) with it is described Export the Poor oxygen gas outlet of reversal valve (4), oxygen-containing gas outlet and the entrance of the Poor oxygen gas heat exchanger (5) The oxygen-containing gas entrance of reversal valve (3) is connected to, and the Poor oxygen gas heat exchanger (5) can be for exporting in the oxidation reactor Poor oxygen gas exchanges heat with the oxygen-containing gas that will be fed into the oxidation reactor；
There is Poor oxygen gas entrance and Poor oxygen gas to go out for Poor oxygen gas waste heat boiler (6), the Poor oxygen gas waste heat boiler (6) Mouthful, the Poor oxygen gas of the Poor oxygen gas entrance of the Poor oxygen gas waste heat boiler (6) and the Poor oxygen gas heat exchanger (5) exports Connection, the Poor oxygen gas waste heat boiler (6) can the Poor oxygen gas after heat exchanging carry out waste heat recycling.
2. the system according to claim 1 for preparing propylene using chemical chain oxidative dehydrogenation of propane, which is characterized in that
The oxygen carrier granule of fixed filling is metal oxide in first fixed bed (1) and second fixed bed (2) Oxygen carrier granule or perovskite oxygen carrier granule；
When using metal oxide oxygen carrier granule, metal oxide selects Mn2O3/Mn3O4、Mn3O4/MnO、V2O5/VO2、 VO2/V2O3、Co3O4/CoO、CoO/Co、CuO/Cu2O、MoO3/MoO2、MoO3/Mo、Fe2O3/Fe3O4、SbO2/Sb2O3、CdO/ Cd、WO3/WO2With one of NiO/Ni or a variety of, the inert carrier for preparing oxygen carrier selects Al2O3、SiO2、TiO2、ZrO2、 Y2O3, zeolite, molecular sieve, one of spinelle and sepiolite or a variety of, the content of metal oxide is in 5-70wt%；
When using perovskite oxygen carrier granule, RBaCo is selected2O5(R=Y, Pr-Ho), RBaCo4O7(R=Y, Dy-Lu), RSrR1O4(R=La, Ln；R1=Co, Cu, Ni)；
Oxygen carrier uses mechanical mixing, coprecipitation, sol-gel method, infusion process, solid reaction process, spray drying process, water Thermal method or citric acid method are made, and oxygen carrier granule diameter is 200~1000 μm.
3. a kind of method for preparing propylene using chemical chain oxidative dehydrogenation of propane, which is characterized in that the method is wanted using right System described in any one of 1-2, the entrance reversal valve (3) and the outlet reversal valve (4) linkage are asked, makes described first to consolidate Fixed bed (1) and second fixed bed (2) are alternately as dehydrogenation reactor and oxidation reactor；
In the fixed bed as the dehydrogenation reactor, propane is reacted at high temperature with oxygen carrier granule, and generation contains Propylene, the gaseous mixture of vapor and COx gas and the oxygen carrier granule after oxygen loss, wherein propane is reacted with oxygen carrier granule Reaction temperature be 300-700 DEG C；
In the fixed bed as the oxidation reactor, oxygen carrier granule and oxygen-containing gas after oxygen loss carry out oxidation reaction, Poor oxygen gas and regenerated oxygen carrier granule are generated, and exports the Poor oxygen gas, wherein the reaction temperature of the oxidation reaction It is 300-700 DEG C；
Gaseous mixture is dried in the gaseous mixture dehydration equipment (9)；
The mixed gas separation equipment (10) isolates propylene from the gaseous mixture after drying.
4. the method according to claim 3 for preparing propylene using chemical chain oxidative dehydrogenation of propane, which is characterized in that
Also contain unreacted propane in the gaseous mixture；
The mixed gas separation equipment (10) respectively is isolated by propylene, propane and COx gas from the gaseous mixture after drying, separation Propane out is sent into dehydrogenation reactor.
5. the method according to claim 3 for preparing propylene using chemical chain oxidative dehydrogenation of propane, which is characterized in that
First it will be fed into the propane of dehydrogenation reactor in gaseous mixture by the gaseous mixture of the output of the fixed bed as dehydrogenation reactor and i.e. Heat exchange in heat exchanger (7), then the gaseous mixture is sent into gaseous mixture waste heat boiler (8) and carries out waste heat recycling, later again by mixed Qi exhaustion wetting system (9) are closed gaseous mixture is dried.
6. the method according to claim 5 for preparing propylene using chemical chain oxidative dehydrogenation of propane, which is characterized in that
The Poor oxygen gas of fixed bed as oxidation reactor output is existed with the oxygen-containing gas that will be fed into oxidation reactor Heat exchange in Poor oxygen gas heat exchanger (5), the Poor oxygen gas after heat exchange are sent into Poor oxygen gas waste heat boiler (6) and carry out waste heat recycling.
7. the method according to claim 6 for preparing propylene using chemical chain oxidative dehydrogenation of propane, which is characterized in that
The temperature of propane after being exchanged heat by gaseous mixture heat exchanger (7) is 100-300 DEG C, and the temperature of the gaseous mixture after heat exchange is 300-600 DEG C, the temperature by gaseous mixture waste heat boiler (8) waste heat gaseous mixture after the recovery is 100-200 DEG C；
The temperature of oxygen-containing gas after being exchanged heat by Poor oxygen gas heat exchanger (5) is 100-300 DEG C, the Poor oxygen gas after heat exchange It is 300-600 DEG C, the temperature by Poor oxygen gas waste heat boiler (6) waste heat Poor oxygen gas after the recovery is 20-100 DEG C.
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