CN110131964A - A kind of chemical chain air separating method and its system - Google Patents

A kind of chemical chain air separating method and its system Download PDF

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Publication number
CN110131964A
CN110131964A CN201910422338.9A CN201910422338A CN110131964A CN 110131964 A CN110131964 A CN 110131964A CN 201910422338 A CN201910422338 A CN 201910422338A CN 110131964 A CN110131964 A CN 110131964A
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oxygen
reactor
reaction
inhaling
outlet end
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CN110131964B (en
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李玖重
孙志钦
高晓红
高跃成
郜建松
周天宇
张婧帆
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Sinopec Engineering Group Co Ltd
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Sinopec Engineering Group Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/066—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of nitrogen

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The present invention provides a kind of chemical chain air separating method and its systems, belong to technical field of air separation.Separation method includes pressing oxygen-absorbing reaction in carrying out micro- oxygen oxygen carrier and air, obtains oxygen denuded air and oxygen-enriched oxygen carrier.Oxygen-enriched oxygen carrier is subjected to oxygen release reaction, obtains oxygen deprivation oxygen carrier and oxygen rich gas.Oxygen denuded air is carried out high pressure oxygen-inhaling with oxygen deprivation oxygen carrier to react, obtains micro- oxygen oxygen carrier and nitrogen-rich gas.Separation system includes middle pressure oxygen-absorbing reaction system, puts oxygen reaction system and high pressure oxygen-inhaling reaction system, high pressure oxygen-inhaling reaction system respectively with middle pressure oxygen-absorbing reaction system and put oxygen reactor and connect.Circulation of the achievable oxygen carrier of separation system under the conditions of High Pressure Difference, using the irreversibility of oxygen-absorbing reaction under the conditions of high pressure low temperature, while the oxygen and nitrogen of high-purity, improve the efficiency and economic performance of chemical chain air separation technology.Its energy consumption is lower, and operation method is simple, and it is convenient to operate.

Description

A kind of chemical chain air separating method and its system
Technical field
The present invention relates to technical field of air separation, in particular to a kind of chemical chain air separating method and its are System.
Background technique
Oxygen and nitrogen are important chemical raw material, have extensively in fields such as chemical industry, metallurgy, oil refining, medical treatment and military affairs Application, the preparation of oxygen and nitrogen is a very crucial technology.Currently used air separation produces oxygen and nitrogen Technology have cryogenic rectification technology, membrane separation technique and pressure swing adsorption.Cryogenic rectification technology is air most mature at present Isolation technics, principle is the boiling point difference using nitrogen in air with oxygen, after air liquefaction, carries out cryogenic rectification and reaches The purpose of separation of nitrogen and oxygen, the technological investment is big, at high cost, and energy consumption is high, complicated for operation.Pressure swing adsorption air isolation technics The disadvantages of low high with energy consumption there are production capacity.Membrane separation technique there are membrane material preparation is difficult, it is at high cost the disadvantages of.
Chemical chain air separation technology is a kind of new air separation technology, compared to conventional air separation technology, Have many advantages, such as that low energy consumption, starting is fast, at low cost, operation is convenient.But current chemical chain air separation technology, which concentrates on, produces oxygen The research of gas, however the defects of the prior art exists mostly that energy consumption is higher, economy is poor, oxidation purity is lower.In addition, producing The purity of nitrogen is lower in the oxygen denuded air formed after oxygen, even if still can not obtain higher by conventional subsequent processing Nitrogen gas purity.
Summary of the invention
The first object of the present invention includes providing a kind of chemical chain air separating method, which can be realized high pressure Oxygen carrier circulates under the conditions of difference, and reaction speed is fast, and system energy consumption is low, simple and convenient, and can produce height simultaneously The oxygen and nitrogen of purity effectively improve the efficiency and economic performance of chemical chain air separation technology.
The second object of the present invention includes providing a kind of chemical chain air-seperation system, which is respectively adopted height Pressure, middle pressure, low-pressure reactor complete circulation of oxygen carrier under the conditions of High Pressure Difference, utilize oxygen-absorbing reaction under the conditions of high pressure low temperature Irreversibility, while the oxygen and nitrogen of high-purity, improve the efficiency and economic performance of chemical chain air separation technology.
The third object of the present invention include provide it is a kind of utilize above-mentioned chemical chain air-seperation system carry out air separation Method, this method energy consumption is lower, and it is convenient to operate.
The present invention solves its technical problem and adopts the following technical solutions to realize:
The present invention proposes a kind of chemical chain air separating method, comprising:
Oxygen-absorbing reaction will be pressed in micro- oxygen oxygen carrier and air progress, obtains oxygen denuded air and oxygen-enriched oxygen carrier.
Oxygen-enriched oxygen carrier is subjected to oxygen release reaction, obtains oxygen deprivation oxygen carrier and oxygen rich gas.
Oxygen denuded air is carried out high pressure oxygen-inhaling with oxygen deprivation oxygen carrier to react, obtains micro- oxygen oxygen carrier and nitrogen-rich gas.
Wherein, the pressure of middle pressure oxygen-absorbing reaction is 1-3MPa, and temperature is 650-1000 DEG C；The pressure of oxygen release reaction is 0.1- 0.5MPa, temperature are 600-990 DEG C；The pressure of high pressure oxygen-inhaling reaction is 3-5MPa, and temperature is 500-900 DEG C.
In some preferred embodiments, the high 2- of pressure of oxygen-absorbing reaction is pressed in the pressure ratio of high pressure oxygen-inhaling reaction The temperature of 5MPa, high pressure oxygen-inhaling reaction are 100-500 DEG C lower than the temperature of middle pressure oxygen-absorbing reaction.
The present invention proposes a kind of chemical chain air-seperation system,
Middle pressure oxygen-absorbing reaction system, for pressing oxygen-absorbing reaction to obtain oxygen denuded air in carrying out micro- oxygen oxygen carrier and air With oxygen-enriched oxygen carrier.
Oxygen reaction system is put, for oxygen-enriched oxygen carrier to be carried out oxygen release reaction, obtains oxygen deprivation oxygen carrier and oxygen rich gas.
High pressure oxygen-inhaling reaction system reacts for oxygen denuded air to be carried out high pressure oxygen-inhaling with oxygen deprivation oxygen carrier, obtains micro- oxygen Oxygen carrier and nitrogen-rich gas.
Wherein, high pressure oxygen-inhaling reaction system includes high pressure oxygen-inhaling reactor, and middle pressure oxygen-absorbing reaction system includes middle pressure oxygen uptake Reactor, putting oxygen reaction system includes putting oxygen reactor, high pressure oxygen-inhaling reactor respectively with middle pressure oxygen-absorbing reaction device and to put oxygen anti- Device is answered to connect.
The reaction pressure of high pressure oxygen-inhaling reactor is not less than the reaction pressure of middle pressure oxygen-absorbing reaction device, and middle pressure oxygen-absorbing reaction The reaction pressure of device is higher than the reaction pressure for putting oxygen reactor；Preferably, the reaction pressure of high pressure oxygen-inhaling reactor is 3-5MPa, Reaction temperature is 500-900 DEG C；The reaction pressure of middle pressure oxygen-absorbing reaction device is 1-3MPa, and reaction temperature is 650-1000 DEG C；It puts The reaction pressure of oxygen reactor is 0.1-0.5MPa, and reaction temperature is 600-990 DEG C.
In some embodiments, the pressure ratio of high pressure oxygen-inhaling reactor in press oxygen-absorbing reaction device the high 2- of pressure The temperature of 5MPa, high pressure oxygen-inhaling reactor are 100-500 DEG C lower than the temperature of middle pressure oxygen-absorbing reaction device.
Further, when high pressure oxygen-inhaling reactor, middle pressure oxygen-absorbing reaction device and to put oxygen reactor be fluidized-bed reaction When device, high pressure oxygen-inhaling reaction system further includes gas turbine, the first pre-heating device and the first booster apparatus；Middle pressure oxygen-absorbing reaction system System further includes the second pre-heating device, the second collector, transformation feed appliance and the second booster apparatus；Putting oxygen reaction system further includes Three collectors, third pre-heating device and cooling equipment.
The outlet with the outlet end of transformation feed appliance and the second booster apparatus respectively of the arrival end of high pressure oxygen-inhaling reactor End connection, the outlet end of high pressure oxygen-inhaling reactor and the arrival end of gas turbine connect, the arrival end difference of the first pre-heating device It is connect with the outlet end of the outlet end of gas turbine and the first booster apparatus.
The outlet with the outlet end of the first pre-heating device and middle pressure oxygen-absorbing reaction device respectively of the arrival end of second pre-heating device End connection, the outlet end of the second pre-heating device are connect with the arrival end of middle pressure oxygen-absorbing reaction device and the second booster apparatus respectively.
The arrival end of transformation feed appliance respectively with it is middle pressure oxygen-absorbing reaction device outlet end and third collector outlet end Connection, the arrival end of the second collector are connect with the outlet end of the outlet end of transformation feed appliance and third pre-heating device respectively, The outlet end of third pre-heating device is also connect with cooling equipment, the arrival end of third pre-heating device and the outlet end for putting oxygen reactor Connection, the arrival end for putting oxygen reactor are connect with the outlet end of the outlet end of the second collector and third pre-heating device respectively.
Further, when high pressure oxygen-inhaling reactor, middle pressure oxygen-absorbing reaction device and to put oxygen reactor be moving bed reaction When device, high pressure oxygen-inhaling reaction system further include the first transformation feed appliance, first rising buffer tank, gas turbine, first preheating set It is standby；Middle pressure oxygen-absorbing reaction system further includes the second transformation feed appliance, the second pre-heating device, the second rising buffer tank；Put oxygen reaction System further includes third transformation feed appliance, third rising buffer tank and third pre-heating device.
The outlet end of high pressure oxygen-inhaling reactor is connect with gas turbine and the first rising buffer tank respectively, and gas turbine goes out Mouth end is connect with the arrival end of the first pre-heating device, the outlet with the second pre-heating device respectively of the arrival end of high pressure oxygen-inhaling reactor The outlet end connection at end, the first transformation feed appliance.
The arrival end of middle pressure oxygen-absorbing reaction device respectively with the outlet end of the second pre-heating device and the second transformation feed appliance Outlet end connection, the arrival end of the second transformation feed appliance are connect with the outlet end of the first rising buffer tank, middle pressure oxygen-absorbing reaction device Outlet end respectively with the arrival end of the second pre-heating device and second rising buffer tank connect, the arrival end of the second pre-heating device Also it is connect with the outlet end of the first pre-heating device.
Put the arrival end outlet with the outlet end of third transformation feed appliance and third pre-heating device respectively of oxygen reactor End connection, the arrival end of third transformation feed appliance are connect with the outlet end of the second rising buffer tank, put the outlet end of oxygen reactor The arrival end of the arrival end and third pre-heating device that rise buffer tank with third respectively is connect, and third rises the outlet of buffer tank End is connect with the arrival end of the first transformation feed appliance.
In addition, the invention also provides a kind of method for carrying out air separation using above-mentioned chemical chain air-seperation system, Include the following steps:
The air entered after micro- oxygen oxygen carrier and pressurized heat exchange heating aoxidize instead in middle pressure oxygen-absorbing reaction device It answers, generates oxygen denuded air and oxygen-enriched oxygen carrier.
Oxygen reactor is put into the oxygen-enriched oxygen carrier input of generation and oxygen-enriched oxygen carrier is being put into the vapor in oxygen reactor Dilution is lower to carry out oxygen release reaction, generates oxygen deprivation oxygen carrier and oxygen rich gas；Gas-liquid separation is carried out to oxygen rich gas, collection is isolated Oxygen.
Oxygen denuded air is inputted into high pressure oxygen-inhaling reactor and by the oxygen deprivation oxygen carrier in oxygen denuded air and high pressure oxygen-inhaling reactor Body is reacted, and generates micro- oxygen oxygen carrier, while oxygen denuded air loses oxygen and is converted into nitrogen, collects nitrogen.
The beneficial effect of chemical chain air separating method provided by the present application and its system includes:
First, system energy consumption is low, at low cost, operation is convenient.Chemical chain air-seperation system realizes oxygen carrier under High Pressure Difference The recycling of body, system operation cost are only booster apparatus power consumption and partial heat energy, and system operation cost is lower, low energy consumption； For oxygen part processed, micro- oxygen oxygen carrier under high pressure, higher than occurring oxygen-absorbing reaction under conditions of its oxygen release temperature, oxygen carrier from Body temperature has been higher than oxygen release temperature, puts oxygen reactor into low pressure, and oxygen release reaction spontaneous can carry out, and provide heat without external Amount, oxygen cost processed can reduce by 6% than normal pressure chemical chain oxygenerating technology；Meanwhile it can be made while present invention process oxygen producing High-purity nitrogen is taken, the efficiency and economy of air separation further increase, the operating cost compared with regular air isolation technics 1/3 or so are reduced, and system operation is simple, operation is convenient.
Second, the nitrogen of 99% or more purity and the oxygen of 99% or more purity can be made simultaneously.Present invention process uses High pressure, middle pressure, low-pressure reactor complete circulation of oxygen carrier under the conditions of High Pressure Difference, and utilize high pressure low temperature condition oxygen-absorbing reaction Irreversibility, separation i.e. can simultaneously obtain 99% or more purity nitrogen and 99% or more purity oxygen.With existing chemistry Chain oxygen technique is compared, and the nitrogen of high-purity can be isolated while high-purity oxygen, further improves chemistry The separative efficiency and economy of chain separation technology.
Third, separative efficiency it is high, it can be achieved that under the conditions of High Pressure Difference air separation process continuous and steady operation.Work of the present invention Skill realizes oxygen carrier using moving bed, fluidized bed and transformation feed appliance and circulates reaction, oxygen carrier under the conditions of High Pressure Difference Body contacts with each other in reactor at a flow way with reaction gas to react, mass-and heat-transfer effect and temperature of reactor uniformity It is greatly improved compared with fixed bed reactors, reaction rate and reaction depth effectively enhance；And add with fixed bed reactors chemical chain Compacting oxygen technique is compared, and without the process of frequent switching valve, avoids valve frequent switching to system stability and reliability Influence.Therefore, present invention process can realize the high-efficiency and continuous stable operation of air separation process.
Detailed description of the invention
It, below will be to use required in embodiment in order to illustrate more clearly of the technical solution of embodiment of the present invention Attached drawing be briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not to be seen as It is the restriction to range, it for those of ordinary skill in the art, without creative efforts, can be with root Other relevant attached drawings are obtained according to these attached drawings.
Fig. 1 is the first structural schematic diagram of chemical chain air-seperation system provided by the embodiments of the present application；
Fig. 2 is second of structural schematic diagram of chemical chain air-seperation system provided by the embodiments of the present application；
Fig. 3 is the structural schematic diagram of Fig. 2 mesohigh oxygen-absorbing reaction components of system as directed；
Fig. 4 is the structural schematic diagram of middle pressure oxygen-absorbing reaction components of system as directed in Fig. 2；
Fig. 5 is the structural schematic diagram that oxygen reaction system part is put in Fig. 2.
Icon: 100- chemical chain air-seperation system；10- high pressure oxygen-inhaling reaction system；11- high pressure oxygen-inhaling reactor； 111- high pressure oxygen-inhaling reactor first entrance；112- high pressure oxygen-inhaling reactor second entrance；113- high pressure oxygen-inhaling reactor first Outlet；114- high pressure oxygen-inhaling reactor second outlet；12- gas turbine；The first pre-heating device of 13-；The first pre-heating device of 131- First entrance；132- the first pre-heating device second entrance；133- the first pre-heating device first outlet；The first pre-heating device of 134- Two outlets；The first booster apparatus of 14-；The first gas-solid separation equipment of 15-；151- the first gas-solid separation equipment first outlet；152- First gas-solid separation equipment second outlet；16- transition holding vessel；Oxygen-absorbing reaction system is pressed in 20-；Oxygen-absorbing reaction device is pressed in 21-； Oxygen-absorbing reaction device first entrance is pressed in 211-；Oxygen-absorbing reaction device second entrance is pressed in 212-；Oxygen-absorbing reaction device first is pressed in 213- Outlet；Oxygen-absorbing reaction device second outlet is pressed in 214-；The second pre-heating device of 22-；221- the second pre-heating device first entrance；222- Second pre-heating device second entrance；223- the second pre-heating device first outlet；224- the second pre-heating device second outlet；23- Two collectors；24- transformation feed appliance；241- transformation feed appliance first entrance；242- transformation feed appliance second entrance；243- transformation Feed appliance third entrance；244- the first transformation feed appliance；245- the second transformation feed appliance；246- third transformation feed appliance；25- Two booster apparatus；30- puts oxygen reaction system；31- puts oxygen reactor；311- oxygen carrier entrance；The steam inlet 312-；313- puts oxygen Reactor first entrance；314- puts oxygen reactor second entrance；315- puts oxygen reactor first outlet；316- puts oxygen reactor Two outlets；32- third collector；33- third pre-heating device；331- third pre-heating device first entrance；The preheating of 332- third is set Standby second entrance；333- third pre-heating device first outlet；334- third pre-heating device second outlet；34- cools down equipment；341- Cooling equipment first outlet；342- cools down equipment second outlet；The first collector of 41-；First communicating pipe of 42-；43- filter； The second gas-solid separation equipment of 44-；The first riser of 45-；The second riser of 46-；The first valve of 51-；The second valve of 52-；53- Three valves；The 4th valve of 54-；The 5th valve of 55-；The 6th valve of 56-；61- first rises buffer tank；62- second rises caching Tank；63- third rises buffer tank；The first surge tank of 71-；The second surge tank of 72-；73- third surge tank.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is A part of the embodiment of the present invention, instead of all the embodiments.The present invention being usually described and illustrated herein in the accompanying drawings is implemented The component of example can be arranged and be designed with a variety of different configurations.
Therefore, the detailed description of the embodiment of the present invention provided in the accompanying drawings is not intended to limit below claimed The scope of the present invention, but be merely representative of selected embodiment of the invention.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without creative efforts belongs to the model that the present invention protects It encloses.
In the description of the present invention, it should be noted that the orientation or position of the instructions such as term " on ", "lower", "inner", "outside" Set relationship be based on the orientation or positional relationship shown in the drawings or the invention product using when the orientation or position usually put Relationship is set, is merely for convenience of description of the present invention and simplification of the description, rather than the device or element of indication or suggestion meaning are necessary It with specific orientation, is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.In addition, term " first ", " second " etc. are only used for distinguishing description, are not understood to indicate or imply relative importance.
In addition, the terms such as term " vertical " are not offered as requiring component absolute upright, but can be slightly tilted.As " hung down Directly " only refer to that its direction is more vertical with respect to for "horizontal", be not indicate the structure have to it is completely vertical, but can To be slightly tilted.
In the description of the present invention, it is also necessary to which explanation is unless specifically defined or limited otherwise, term " setting ", " installation ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integrally connect It connects；It can be mechanical connection, be also possible to be electrically connected；It can be directly connected, can also indirectly connected through an intermediary, it can To be the connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood with concrete condition Concrete meaning in the present invention.
Embodiment 1
The present embodiment provides a kind of chemical chain air separating method, can include:
Oxygen-absorbing reaction will be pressed in micro- oxygen oxygen carrier and air progress, obtains oxygen denuded air and oxygen-enriched oxygen carrier.By oxygen-enriched load Oxysome carries out oxygen release reaction, obtains oxygen deprivation oxygen carrier and oxygen rich gas.Oxygen denuded air and oxygen deprivation oxygen carrier are subjected to high pressure oxygen-inhaling Reaction, obtains micro- oxygen oxygen carrier and nitrogen-rich gas.
In high pressure oxygen-inhaling reaction process, oxygen carrier oxygen-absorbing reaction is irreversible, namely oxygen carrier will not be released under this condition Oxygen reacts, and oxygen can be completely absorbed in mixed gas.
During middle pressure oxygen-absorbing reaction, the reaction of oxygen carrier oxygen release and oxygen-absorbing reaction carry out simultaneously, oxygen when balance in gas Volume content can be 0-20.8%, preferably 5-15%.
It is worth noting that irreversible oxygen uptake could occur is anti-for condition when oxygen deprivation or micro- oxygen oxygen carrier in high pressure low temperature It answers, i.e. oxygen release reaction will not occur, and the oxygen in mixed gas can be reacted completely.Irreversible reaction can make oxygen carrier will Oxygen in mixed gas reacts completely, and nitrogen gas purity is made to be higher than 99% or more.
In some embodiments, the pressure of middle pressure oxygen-absorbing reaction can be 1-3MPa, and temperature can be 650-1000 DEG C； The pressure of oxygen release reaction can be 0.1-0.5MPa, and temperature can be 600-990 DEG C；The pressure of high pressure oxygen-inhaling reaction can be 3- 5MPa, temperature can be 500-900 DEG C.Specifically, pressure difference and reaction temperature are different according to different types of oxygen carrier.
In some embodiments, the high 2-5MPa of pressure of oxygen-absorbing reaction, high pressure are pressed in the pressure ratio of high pressure oxygen-inhaling reaction The temperature of oxygen-absorbing reaction is 100-500 DEG C lower than the temperature of middle pressure oxygen-absorbing reaction.
Optionally, oxygen carrier includes metal oxygen carrier or nonmetallic oxygen carrier, and metal oxygen carrier includes copper-based oxygen carrier One of body, iron-based oxygen carrier and manganese base load oxysome are a variety of, and nonmetallic oxygen carrier includes GaSO4Oxygen carrier and perovskite carry One of oxysome is a variety of.
It can refer to ground, oxygen carrier can be selected from CoO, Co2O3、Co3O4；Fe2O3、FeO、Fe3O4、MnO、MnO2、Mn2O3Or calcium Titanium ore etc., above-mentioned oxygen carrier all have micro- oxygen, oxygen-enriched and oxygen deprivation state.
In some embodiments, oxygen-enriched oxygen carrier is CuO, and oxygen deprivation oxygen carrier is Cu2O, micro- oxygen oxygen carrier be CuO and Cu2The mixture of O, the mass fraction of CuO can be 30-50% in mixture.
Further, chemical chain air separating method further include: the oxygen carrier that high pressure oxygen-inhaling reaction generates is used for middle pressure Oxygen-absorbing reaction.
And cryogenic rectification technology is different with the boiling point of oxygen using nitrogen in air in regular air isolation technics, by air It after liquefaction, carries out cryogenic rectification and achievees the purpose that separation of nitrogen and oxygen, technological investment is big, at high cost, and energy consumption is high, and operation is multiple It is miscellaneous.The disadvantages of pressure swing adsorption air isolation technics is low high with energy consumption there is also production capacity.There are membrane materials to prepare hardly possible for membrane separation technique, The disadvantages of at high cost, therefore compared to regular air isolation technics, chemical chain air separating method provided by the present application can make into This reduction.
It holds, chemical chain air separating method provided in this embodiment is simple, and it is convenient to operate, can high-purity simultaneously Oxygen and nitrogen improve the efficiency and economic performance of chemical chain air separation technology.
Embodiment 2
Please with reference to Fig. 1 and Fig. 2, chemical chain air-seperation system 100 provided in this embodiment includes that high pressure oxygen-inhaling is anti- It answers system 10, middle pressure oxygen-absorbing reaction system 20 and puts oxygen reaction system 30.
Wherein, middle pressure oxygen-absorbing reaction system 20 is used for micro- oxygen oxygen carrier and pressure oxygen-absorbing reaction in air progress is poor to obtain Oxygen air and oxygen-enriched oxygen carrier.Oxygen reaction system 30 is put for oxygen-enriched oxygen carrier to be carried out oxygen release reaction, obtains oxygen deprivation oxygen carrier And oxygen rich gas.High pressure oxygen-inhaling reaction system 10 is used to oxygen denuded air carrying out high pressure oxygen-inhaling with oxygen deprivation oxygen carrier to react, and obtains Micro- oxygen oxygen carrier and nitrogen-rich gas.
High pressure oxygen-inhaling reaction system 10 includes high pressure oxygen-inhaling reactor 11, and middle pressure oxygen-absorbing reaction system 20 includes middle pressure oxygen uptake Reactor 21, putting oxygen reaction system 30 includes putting oxygen reactor 31, high pressure oxygen-inhaling reactor 11 respectively with middle pressure oxygen-absorbing reaction device 21 and put oxygen reactor 31 connection.
Wherein, the reaction pressure of high pressure oxygen-inhaling reactor 11 not less than it is middle pressure oxygen-absorbing reaction device 21 reaction pressure, and in The reaction pressure of pressure oxygen-absorbing reaction device 21 is higher than the reaction pressure for putting oxygen reactor 31.
Optionally, the reaction pressure of high pressure oxygen-inhaling reactor 11 for example can be 3-5MPa, and reaction temperature for example may be used Think 500-900 DEG C.The reaction pressure of middle pressure oxygen-absorbing reaction device 21 for example can be 1-3MPa, and reaction temperature for example can be 650-1000℃.The reaction pressure for putting oxygen reactor 31 can be for example 0.1-0.5MPa, and reaction temperature for example can be 600- 990℃.Specifically, pressure difference and reaction temperature are different according to different types of oxygen carrier.
Preferably, the pressure ratio of high pressure oxygen-inhaling reactor 11 in press oxygen-absorbing reaction device 21 the high 2-5MPa of pressure, high pressure The temperature of oxygen-absorbing reaction device 11 is 100-500 DEG C lower than the temperature of middle pressure oxygen-absorbing reaction device 21.
By high pressure oxygen-inhaling reaction system 10, middle pressure oxygen-absorbing reaction system 20 and the cooperation of oxygen reaction system 30 is put for making to carry Oxysome circular flow is with oxygen producing and nitrogen.
The specific choice of oxygen carrier can refer to embodiment 1.
The air separating method of above-mentioned chemical chain air-seperation system 100 can include: will in middle pressure oxygen-absorbing reaction device 21 The air entered after micro- oxygen oxygen carrier and pressurized heat exchange heating carries out oxidation reaction, generates oxygen denuded air and oxygen-enriched oxygen carrier.
Oxygen reactor 31 is put into the oxygen-enriched oxygen carrier input of generation and oxygen-enriched oxygen carrier is being put into the water in oxygen reactor 31 Oxygen release reaction is carried out under vapor dilution, generates oxygen deprivation oxygen carrier and oxygen rich gas；Gas-liquid separation is carried out to oxygen rich gas, collects and divides The oxygen separated out.
By oxygen denuded air input high pressure oxygen-inhaling reactor 11 and by oxygen denuded air with it is oxygen-enriched in high pressure oxygen-inhaling reactor 11 Oxygen carrier is reacted, and generates micro- oxygen oxygen carrier, while oxygen denuded air loses oxygen and is converted into nitrogen, collects nitrogen.
Wherein, the volume flow of air is fully converted to the theoretical flow of oxygen-enriched oxygen carrier lower than oxygen deprivation oxygen carrier, non-to work as Amount is 0.6-0.95 than coefficient.
Embodiment 3
In conjunction with the embodiments 2, please continue to refer to Fig. 1, when the high pressure oxygen-inhaling reactor in chemical chain air-seperation system 100 11, middle pressure oxygen-absorbing reaction device 21 and when putting oxygen reactor 31 and being fluidized-bed reactor, high pressure oxygen-inhaling reaction system 10 also wraps Gas turbine 12, the first pre-heating device 13 and the first booster apparatus 14 are included, middle pressure oxygen-absorbing reaction system 20 further includes the second preheating Equipment 22, the second collector 23, transformation feed appliance 24 and the second booster apparatus 25, putting oxygen reaction system 30 further includes that third is collected Device 32, third pre-heating device 33 and cooling equipment 34.
The arrival end of high pressure oxygen-inhaling reactor 11 respectively with the outlet end of transformation feed appliance 24 and the second booster apparatus 25 Outlet end connection.The outlet end of high pressure oxygen-inhaling reactor 11 is connect with the arrival end of gas turbine 12.First pre-heating device 13 Arrival end connect respectively with the outlet end of the outlet end of gas turbine 12 and the first booster apparatus 14.
The arrival end of second pre-heating device 22 respectively with the outlet end of the first pre-heating device 13 and middle pressure oxygen-absorbing reaction device 21 Outlet end connection, the outlet end of the second pre-heating device 22 enters with middle pressure oxygen-absorbing reaction device 21 and second booster apparatus 25 respectively The connection of mouth end.
The arrival end of transformation feed appliance 24 respectively with the outlet end of middle pressure oxygen-absorbing reaction device 21 and third collector 32 Outlet end connection, the arrival end of the second collector 23 respectively with the outlet end of transformation feed appliance 24 and third pre-heating device 33 Outlet end connection, the outlet end of third pre-heating device 33 also connects with cooling equipment 34, the arrival end of third pre-heating device 33 and The outlet end connection for putting oxygen reactor 31, put the arrival end of oxygen reactor 31 respectively with the outlet end of the second collector 23 and the The outlet end of three pre-heating devices 33 connects.
High pressure oxygen-inhaling reaction system 10 further includes the first gas-solid separation equipment 15 and transition holding vessel 16, high pressure oxygen-inhaling reaction The outlet end of device 11 is connect with the arrival end of the first gas-solid separation equipment 15, the outlet end of the first gas-solid separation equipment 15 respectively with The arrival end of gas turbine 12 is connected with the arrival end of transition holding vessel 16, the outlet end of transition holding vessel 16 also with middle pressure oxygen uptake Reactor 21 connects, and the arrival end of transition holding vessel 16 is also connect with the outlet end of the second pre-heating device 22.
Further, it is also connected with the first collector 41 between transformation feed appliance 24 and middle pressure oxygen-absorbing reaction device 21, first It was connected with for the first communicating pipe 42 between collector 41 and middle pressure oxygen-absorbing reaction device 21.Middle pressure oxygen-absorbing reaction device 21 is set with the second preheating Filter 43 is also connected between standby 22.
Further, it puts to be additionally provided with the second gas-solid separation equipment 44 in oxygen reactor 31 and put oxygen reactor 31 and also distinguish Equipped with steam inlet 312 and oxygen carrier entrance 311, oxygen carrier entrance 311 is connect with the outlet end of the second collector 23, and steam enters Mouth 312 is connect with the outlet end of third pre-heating device 33.
As reference, the present embodiment mesohigh oxygen-absorbing reaction device 11 has 111 He of high pressure oxygen-inhaling reactor first entrance High pressure oxygen-inhaling reactor second entrance 112.First pre-heating device 13 is preheated with the first pre-heating device first entrance 131, first Equipment second entrance 132, the first pre-heating device first outlet 133 and the first pre-heating device second outlet 134.Second pre-heating device 22 have the second pre-heating device first entrance 221, the second pre-heating device second entrance 222, the second pre-heating device first outlet 223 And the second pre-heating device second outlet 224.Middle pressure oxygen-absorbing reaction device 21 has middle pressure oxygen-absorbing reaction device first entrance 211 in Press oxygen-absorbing reaction device second entrance 212.Transformation feed appliance 24 has transformation feed appliance first entrance 241, transformation feed appliance second Entrance 242, transformation feed appliance third entrance 243.Third pre-heating device 33 has third pre-heating device first entrance 331, third Pre-heating device second entrance 332, third pre-heating device first outlet 333 and third pre-heating device second outlet 334.Cooling equipment 34 have cooling equipment first outlet 341 and cooling equipment second outlet 342.
High pressure oxygen-inhaling reactor first entrance 111 is connect with the outlet end of the second booster apparatus 25, high pressure oxygen-inhaling reactor Second entrance 112 is connect with the outlet end of transformation feed appliance 24, the outlet end of high pressure oxygen-inhaling reactor 11 and the first gas solid separation The arrival end of equipment 15 connects.The upper outlet of first gas-solid separation equipment 15 is connect with the arrival end of gas turbine 12, the first gas Gu the lower outlet of separation equipment 15 is connect with the second entrance of transition holding vessel 16.
First pre-heating device first entrance 131 is connect with the outlet end of the first booster apparatus 14, the first pre-heating device 13 Second entrance is connect with the outlet end of gas turbine 12, and the first pre-heating device first outlet 133 enters with the second pre-heating device first Mouth 221 connects, and the first pre-heating device second outlet 134 is for exporting nitrogen.
Second pre-heating device second entrance 222 is connect with the outlet end of filter 43, the second pre-heating device first outlet 223 It is divided into arranged side by side two, one connect with the first entrance of middle pressure oxygen-absorbing reaction device 21, and another and the of transition holding vessel 16 The connection of one entrance.The second outlet of second pre-heating device 22 is connect with the arrival end of the second booster apparatus 25.Transition holding vessel 16 Outlet end with it is middle pressure oxygen-absorbing reaction device 21 second entrance connect.
Transformation feed appliance first entrance 241 is connect with the outlet end of the first collector 41, transformation feed appliance second entrance 242 It is connect with the outlet end of third collector 32, transformation feed appliance third entrance 243 is for being passed through oxygen denuded air and vapor.Transformation The outlet end of feed appliance 24 is divided into two, and one connect with high pressure oxygen-inhaling reactor second entrance 112, and another is collected with second The arrival end of device 23 connects.
The first outlet for putting oxygen reactor 31 is connect with the arrival end of third collector 32, and put oxygen reactor 31 second goes out Mouth is connect with the first entrance of third pre-heating device 33.
Third pre-heating device second entrance 332 is connect with cooling equipment first outlet 341, third pre-heating device first outlet 333 connect with the arrival end of cooling equipment 34, third pre-heating device second outlet 334 and the oxygen carrier entrance for putting oxygen reactor 31 311 connections.
Further, the first riser 45 is equipped between third pre-heating device second outlet 334 and oxygen carrier entrance 311, It puts and is equipped with the second riser 46 between oxygen reactor first outlet 315 and the arrival end of third collector 32.
Further, the first valve is equipped between the outlet end of the first collector 41 and transformation feed appliance first entrance 241 Door 51 is equipped with the second valve 52, transformation feed appliance between the outlet end of transformation feed appliance 24 and the arrival end of the second collector 23 The 4th valve 54, the outlet end of third collector 32 are equipped between 24 outlet end and high pressure oxygen-inhaling reactor second entrance 112 Third valve 53 is equipped between transformation feed appliance second entrance 242.
It can refer to ground, the method for operation of above-mentioned chemical chain air-seperation system 100 can be for (it is worth noting that below It is related in the bracket of data area specific data and is integrally formed a specific embodiment, similarly hereinafter):
(non-equivalent proportion coefficient is 0.6-0.95 to ambient air, such as 0.9) enters the first booster apparatus 14, pressure rise Enter the first pre-heating device 13 by the first pre-heating device first entrance 131 afterwards to 1-3MPa (such as 1.5MPa) to change with high temperature nitrogen Heat is warming up to the first pre-heating device after 200-550 DEG C (such as 500 DEG C) by connecting with the second pre-heating device first entrance 221 First outlet 133 enters the second pre-heating device 22, is increased to 600-950 DEG C (such as 900 DEG C) with high temperature oxygen denuded air heat-exchange temperature, Most of middle pressure oxygen-absorbing reaction device first entrance 211 for therefrom pressing 21 bottom of oxygen-absorbing reaction device presses oxygen-absorbing reaction device 21 in entering, Enter transition holding vessel 16 from 16 first entrance of transition holding vessel of 16 bottom of transition holding vessel on a small quantity.
500-900 DEG C of (such as 850 DEG C) micro- oxygen oxygen carrier (CuO/ after 15 gas solid separation of the first gas-solid separation equipment Cu2O) by gas-solid separation equipment dipleg (the first gas-solid separation equipment second outlet 152) through 16 second entrance of transition holding vessel into Enter transition holding vessel 16, micro- oxygen oxygen carrier in transition holding vessel 16 under the promotion of 600-950 DEG C of (such as 900 DEG C) air through with Oxygen-absorbing reaction device 21 is pressed in the communicating pipe entrance that middle pressure oxygen-absorbing reaction device second entrance 212 connects.Oxygen carrier 1-3MPa (such as Under pressure 1.5MPa), oxidation reaction occurs in the following rising edge of the fluidization of air and air, and release heat, generate The oxygen-enriched oxygen carrier of oxygen denuded air and 650-1000 DEG C (such as 950 DEG C) that temperature is 650-1000 DEG C (such as 950 DEG C).Oxygen-absorbing reaction Equation it is as follows,
The oxygen denuded air of 650-1000 DEG C (such as 950 DEG C) therefrom presses 21 top of oxygen-absorbing reaction device to filter oxygen carrier through filter 43 Enter the second pre-heating device 22 through the second pre-heating device second entrance 222 after body particle, temperature is reduced to 300-600 DEG C (such as 500 DEG C) afterwards by the second pre-heating device second outlet 224 enter the second booster apparatus 25, pressure rise to 3-5MPa (such as 4MPa) by The high pressure oxygen-inhaling reactor first entrance 111 of 11 bottom of high pressure oxygen-inhaling reactor enters high pressure oxygen-inhaling reactor 11.
The oxygen-enriched oxygen carrier running body of 650-1000 DEG C (such as 950 DEG C) is to middle 21 top of pressure oxygen-absorbing reaction device, from the first connection Pipe 42 enters the first collector 41, (such as to 24 pressure release of transformation feed appliance to the low 10-50kPa of the first collector of pressure ratio 41 The first valve 51 is opened when 20kPa), oxygen-enriched oxygen carrier enters transformation through transformation feed appliance first entrance 241 by self gravity Feed appliance 24,24 oxygen carrier height of transformation feed appliance close the first valve 51 when reaching setting position.Transformation feed appliance 24 carries out Pressure release, and be passed through 400-650 DEG C of (such as 600 DEG C) water vapor purging air continues to be passed through water vapour after purging and pressurize, The second valve 52,640- is opened as transformation feed appliance 24 the second collector of pressure ratio, 23 pressure high 10-50kPa (such as 20kPa) 990 DEG C of (such as 940 DEG C) oxygen-enriched oxygen carriers enter the second collector 23 by self gravity.After 24 discharging of transformation feed appliance, Close the second valve 52 and pressure release, when pressure reduction to normal pressure opens third valve 53, waits charging.
(such as 940 DEG C) oxygen-enriched oxygen carrier is steamed in 400-650 DEG C (such as 600 DEG C) of water 640-990 DEG C in second collector 23 Enter through the first riser 45 from the oxygen carrier entrance 311 for putting 31 middle part of oxygen reactor under the promotion of gas.From putting oxygen reactor Under the fluidisation of the vapor of 400-650 DEG C (such as 600 DEG C) that the vapour inlets of 31 middle and lower parts enters, 0.1-0.5MPa (such as Oxygen release reaction occurs for the following rising edge of pressure 0.2MPa), and generates 500-900 DEG C of (such as 800 DEG C) oxygen deprivation oxygen carrier (Cu2O) With the oxygen rich gas of 500-900 DEG C (such as 800 DEG C).The equation of oxygen release reaction is as follows,
The oxygen rich gas of 500-900 DEG C (such as 800 DEG C) is through the second gas-solid separation equipment 44 from the top for putting oxygen reactor 31 Oxygen reactor second outlet 316 of putting draw and enter third pre-heating device 33 through third pre-heating device first entrance 331 and change with water Hot temperature is reduced to 80-150 DEG C (such as 100 DEG C), then by third pre-heating device first outlet 333 enter cooling equipment 34 into Row gas-liquid separation obtains the O of condensed water and 99% or more purity (such as 99.9%)2, O2It is collected processing.
Condensed water passes through after the cooling output of equipment first outlet 341 is mixed with moisturizing through third pre-heating device second entrance 332 enter third pre-heating device 33, become 400-650 DEG C of (such as 600 DEG C) vapor after heating.Most of vapor is anti-from oxygen is put The vapour inlet of 31 middle and lower part of device is answered to enter, the oxygen mix released as diluent gas and oxygen-enriched oxygen carrier generates oxygen rich air Body, small part promote oxygen carrier as fluidized wind.
The oxygen deprivation oxygen carrier of 500-900 DEG C (such as 800 DEG C) returns to that put oxygen anti-under the separation of the second gas-solid separation equipment 44 Answer 31 bottom of device, under the promotion of the high-temperature vapor of 400-650 DEG C (such as 600 DEG C) by with put oxygen reactor first outlet Second riser 46 of 315 connections enters third collector 32.
After 24 pressure release of transformation feed appliance opens third valve 53 to normal pressure, (such as 800 500-900 DEG C in third collector 32 DEG C) oxygen deprivation oxygen carrier by gravity by transformation feed appliance second entrance 242 enter transformation feed appliance 24.Transformation feed appliance 24 carries Oxysome height closes third valve 53 when reaching setting position.The height of 300-600 DEG C (such as 500 DEG C) is passed through to transformation feed appliance 24 Pressure oxygen denuded air pressurize, when 24 pressure ratio high pressure oxygen-inhaling reactor of transformation feed appliance, the 11 high 10-50kPa of pressure (such as The 4th valve 54 is opened when 20kPa), the oxygen deprivation oxygen carrier of 490-890 DEG C (such as 780 DEG C) is anti-by high pressure oxygen-inhaling by self gravity Device second entrance 112 is answered to enter 11 lower part of high pressure oxygen-inhaling reactor.After 24 discharging of transformation feed appliance, the 4th valve 54 is closed And pressure release is carried out, first is opened as low 10-50kPa (such as 20kPa) of 24 the first collector of pressure ratio of transformation feed appliance, 41 pressure Valve 51 waits charging.
300-600 DEG C of (such as 500 DEG C) oxygen denuded air into high pressure oxygen-inhaling reactor 11 enters with from transformation feed appliance 24 Oxygen-enriched oxygen carrier react under the pressure of 3-5MPa (such as 4MPa) and release heat.500-900 DEG C of micro- oxygen is generated to carry Oxysome, oxygen denuded air lose the nitrogen-rich gas that oxygen is converted into 500-900 DEG C (such as 850 DEG C).The equation of oxygen-absorbing reaction is such as Shown in lower,
500-900 DEG C in high pressure oxygen-inhaling reactor 11 micro- oxygen oxygen carrier of (such as 850 DEG C) under the fluidisation of oxygen denuded air into Enter the first cyclonic separation and carries out gas solid separation.Micro- oxygen oxygen carrier of 500-900 DEG C (such as 850 DEG C) by gas-solid separation equipment dipleg into Enter transition holding vessel 16 to be recycled.
By 15 top of the first gas-solid separation equipment, (the first gas solid separation is set the nitrogen-rich gas of 500-900 DEG C (such as 850 DEG C) Standby first outlet 151) draw the high temperature and pressure acting power generation that nitrogen is utilized into gas turbine 12, pressure reduction to 0.1- 0.5MPa (such as 0.2MPa), temperature are reduced to 300-700 DEG C (such as 600 DEG C) to enter by the first pre-heating device second entrance 132 First pre-heating device 13 heats air, and temperature is reduced to 50 DEG C or less to be collected processing, and nitrogen gas purity is higher than 99%.
Embodiment 4
In conjunction with the embodiments 2, please continue to refer to Fig. 2 to Fig. 5, when the high pressure oxygen-inhaling in chemical chain air-seperation system 100 is anti- Answering device 11, middle pressure oxygen-absorbing reaction device 21 and putting oxygen reactor 31 is moving-burden bed reactor；High pressure oxygen-inhaling reaction system 10 is also Rise buffer tank 61, gas turbine 12, the first pre-heating device 13 including the first transformation feed appliance 244, first；Middle pressure oxygen-absorbing reaction System 20 further includes the second transformation feed appliance 245, the second pre-heating device 22, second rising buffer tank 62；Put oxygen reaction system 30 It further include third transformation feed appliance 246, third rising buffer tank 63 and third pre-heating device 33.
The outlet end of high pressure oxygen-inhaling reactor 11 is connect with gas turbine 12 and the first rising buffer tank 61 respectively, air turbine The outlet end of machine 12 is connect with the arrival end of the first pre-heating device 13, and the arrival end of high pressure oxygen-inhaling reactor 11 is pre- with second respectively The outlet end connection of the outlet end of hot equipment 22, the first transformation feed appliance 244.
It is middle pressure oxygen-absorbing reaction device 21 arrival end respectively with the outlet end of the second pre-heating device 22 and the second transformation feeding The outlet end of device 245 connects, and the arrival end of the second transformation feed appliance 245 is connect with the outlet end of the first rising buffer tank 61, in The outlet end of oxygen-absorbing reaction device 21 is pressed to connect respectively with the arrival end of the second pre-heating device 22 and the second rising buffer tank 62, the The arrival end of two pre-heating devices 22 is also connect with the outlet end of the first pre-heating device 13.
Put the arrival end of oxygen reactor 31 respectively with the outlet end of third transformation feed appliance 246 and third pre-heating device 33 Outlet end connection, the arrival end of third transformation feed appliance 246 with second rising buffer tank 62 outlet end connect, put oxygen react The arrival end of arrival end and third pre-heating device 33 that the outlet end of device 31 rises buffer tank 63 with third respectively is connect, third The outlet end for rising buffer tank 63 is connect with the arrival end of the first transformation feed appliance 244.
Further, the first transformation feed appliance 244 and third, which rise, is equipped with the first collector 41 between buffer tank 63, and second Transformation feed appliance 245 and first rises equipped with the second collector 23 between buffer tank 61, and third transformation feed appliance 246 and second is received Third collector 32 is equipped between storage 23.
Further, high pressure oxygen-inhaling reactor 11 and first rises between buffer tank 61 equipped with the first surge tank 71, middle pressure Oxygen-absorbing reaction device 21 and second rises between buffer tank 62 equipped with the second surge tank 72, puts oxygen reactor 31 and third rises caching Third surge tank 73 is equipped between tank 63.
Further, the arrival end of the first pre-heating device 13 is also connected with the first booster apparatus 14, the second pre-heating device 22 The second booster apparatus 25 is additionally provided between high pressure oxygen-inhaling reactor 11, third pre-heating device 33 is also connected with cooling equipment 34.
As reference, the first pre-heating device 13 has the first pre-heating device first entrance 131, the first pre-heating device second Entrance 132, the first pre-heating device first outlet 133 and the first pre-heating device second outlet 134.High pressure oxygen-inhaling reactor 11 has High pressure oxygen-inhaling reactor first entrance 111, high pressure oxygen-inhaling reactor second entrance 112, high pressure oxygen-inhaling reactor first outlet 113 With high pressure oxygen-inhaling reactor second outlet 114.Second pre-heating device 22 has the second pre-heating device first entrance 221, second pre- Hot equipment second entrance 222, the second pre-heating device first outlet 223 and the second pre-heating device second outlet 224.Middle pressure oxygen uptake is anti- Answer device 21 that there is middle pressure oxygen-absorbing reaction device first entrance 211, middle pressure oxygen-absorbing reaction device second entrance 212, middle pressure oxygen-absorbing reaction device First outlet 213 and middle pressure oxygen-absorbing reaction device second outlet 214.Third pre-heating device 33 has third pre-heating device first entrance 331, third pre-heating device second entrance 332, third pre-heating device first outlet 333 and third pre-heating device second outlet 334. It puts oxygen reactor 31 and has and put oxygen reactor first entrance 313, put oxygen reactor second entrance 314, put oxygen reactor first and go out Mouthfuls 315 and put oxygen reactor second outlet 316.Cooling equipment 34 has cooling equipment first outlet 341 and cooling equipment second Outlet 342.
First pre-heating device first entrance 131 is connect with the outlet end of the first booster apparatus 14, the first pre-heating device second Entrance 132 is connect with high pressure oxygen-inhaling reactor first outlet 113, and the first pre-heating device first outlet 133 is used to export nitrogen, the One pre-heating device second outlet 134 is connect with the second pre-heating device first entrance 221.
High pressure oxygen-inhaling reactor first entrance 111 is connect with the outlet end of the first transformation feed appliance 244, high pressure oxygen-inhaling reaction Device second entrance 112 is connect with the outlet end of the second booster apparatus 25, high pressure oxygen-inhaling reactor second outlet 114 and the first buffering The arrival end of tank 71 connects.
Second pre-heating device second entrance 222 is connect with middle pressure oxygen-absorbing reaction device first outlet 213, the second pre-heating device One outlet 223 is connect with middle pressure oxygen-absorbing reaction device second entrance 212, and the second pre-heating device second outlet 224 is set with the second boosting Standby 25 arrival end connects.
Middle pressure oxygen-absorbing reaction device first entrance 211 is connect with the outlet end of the second transformation feed appliance 245, middle pressure oxygen-absorbing reaction Device second outlet 214 is connect with the arrival end of the second surge tank 72.
Third pre-heating device first entrance 331 is connect with oxygen reactor first outlet 315 is put, and third pre-heating device second enters Mouth 332 is connect with cooling equipment first outlet 341, and the arrival end of third pre-heating device first outlet 333 and cooling equipment 34 connects It connects, third pre-heating device second outlet 334 is connect with oxygen reactor second entrance 314 is put.
It puts oxygen reactor first entrance 313 to connect with the outlet end of third transformation feed appliance 246, puts oxygen reactor second and go out Mouth 316 is connect with the arrival end of third surge tank 73.
Further, the first valve 51, the first transformation are equipped between the first collector 41 and the first transformation feed appliance 244 The second valve 52, the second collector 23 and the second transformation feed appliance 245 are equipped between feed appliance 244 and high pressure oxygen-inhaling reactor 11 Between be equipped with third valve 53, equipped with the 4th valve 54 between the second transformation feed appliance 245 and middle pressure oxygen-absorbing reaction device 21, third It is equipped with the 5th valve 55 between collector 32 and third transformation feed appliance 246, third transformation feed appliance 246 and puts oxygen reactor 31 Between be equipped with the 6th valve 56.
It can refer to ground, the method for operation of above-mentioned chemical chain air-seperation system 100 can be with are as follows:
In high pressure oxygen-inhaling reaction system 10, (non-equivalent proportion coefficient is 0.6-0.95 to ambient air, such as 0.9) enters the One booster apparatus 14, pressure rise to 1-3MPa (such as 1.5MPa) enter first in advance by the first pre-heating device first entrance 131 Hot equipment 13 exchanges heat with high temperature nitrogen, temperature be increased to 200-550 DEG C (such as 500 DEG C) by with the second pre-heating device first entrance First pre-heating device second outlet 134 of 221 connections enters the second pre-heating device 22, increases with high temperature oxygen denuded air heat-exchange temperature (the middle pressure oxygen uptake of 21 top of oxygen-absorbing reaction device is therefrom pressed through the second pre-heating device first outlet 223 to 600-950 DEG C (such as 900 DEG C) Reactor second entrance 212) enter in press oxygen-absorbing reaction device 21.
First rises 500-900 DEG C of (such as 850 DEG C) micro- oxygen oxygen carrier (CuO/Cu in buffer tank 612O) by 300-650 DEG C The oxygen denuded air of (such as 500 DEG C) enters the second collector 23 through the first riser 45, and oxygen carrier enters second by gravity Transformation feed appliance 245, oxygen carrier material position closes third valve 53 after reaching setting height in the second transformation feed appliance 245.
Second transformation feed appliance 245 carries out blowdown pressure letdown, when pressure oxygen-absorbing reaction device 21 in the pressure ratio of transformation feed appliance 24 After high 10-50kPa (such as 20kPa), the 4th valve 54 is opened, temperature is micro- oxygen oxygen carrier of 500-900 DEG C (such as 850 DEG C) (CuO/Cu2O it) is therefrom pressed in middle pressure oxygen-absorbing reaction device first entrance 211 entrance on 21 top of oxygen-absorbing reaction device by self gravity Press oxygen-absorbing reaction device 21.After second transformation feed appliance, 245 discharging, the 4th valve 54 is closed, the first valve 51 is opened and charges.
The high temperature air and high temperature oxygen carrier for pressing oxygen-absorbing reaction device 21 in are under the pressure of 1-3MPa (such as 1.5MPa) It carries out oxidation reaction and simultaneously releases heat, generate oxygen denuded air that temperature is 650-1000 DEG C (such as 950 DEG C) and 650-1000 DEG C (such as 950 DEG C) oxygen-enriched oxygen carrier.The equation of oxygen-absorbing reaction is as follows,
The high pressure oxygen denuded air of 650-1000 DEG C (such as 950 DEG C) is by the middle middle pressure oxygen-absorbing reaction for pressing 21 lower part of oxygen-absorbing reaction device Device first outlet 213, which is drawn, enters the second pre-heating device 22 through the second pre-heating device second entrance 222, and temperature is reduced to 300- 600 DEG C enter the second booster apparatus 25, and pressure rise to 3-5MPa (such as 4MPa) is by the second pre-heating device second outlet 224 through height The high pressure oxygen-inhaling reactor second entrance 112 of reactor upper end is pressed to enter high-pressure reactor.
The oxygen-enriched oxygen carrier (CuO) of 650-1000 DEG C (such as 950 DEG C) is mentioned according to oxygen carrier in the second rising buffer tank 62 Lifting speed sequentially enters the second surge tank 72 by self gravity, rises buffer tank 62 subsequently into second.Second rises caching Oxygen-enriched oxygen carrier in tank 62 is transported to third through the second riser 46 by the pressure-air of 600-950 DEG C (such as 900 DEG C) and collects Device 32.
The oxygen carrier of third collector 32 enters third transformation feed appliance 246, third transformation feed appliance by gravity Oxygen carrier material position closes the 5th valve 55 after reaching setting height in 246.
Third transformation feed appliance 246 carries out pressure release, is passed through 300- to third transformation feed appliance 246 after pressure reduction to normal pressure 650 DEG C of high-temperature vapor purging airs simultaneously pressurize, when to put oxygen reactor 31 10-50kPa high for 24 pressure ratio of transformation feed appliance Afterwards, open the 6th valve 56, temperature be reduced to the oxygen-enriched oxygen carrier (CuO) of 600-990 DEG C (such as 930 DEG C) by self gravity from Oxygen reactor 31 is put in the entrance of oxygen reactor first entrance 313 of putting for putting 31 top of oxygen reactor.
After 246 discharging of third transformation feed appliance, the 6th valve 56 is closed, the 5th valve 55 is opened and charges.
It is released under the pressure of 0.1-0.5MPa (such as 0.2MPa) into the high-temperature oxygen-enriched oxygen carrier for putting oxygen reactor 31 Oxygen reaction, oxygen-enriched oxygen carrier become the oxygen deprivation oxygen carrier that temperature is 500-900 DEG C (such as 800 DEG C)；300-650 DEG C (such as 600 DEG C) Vapor through put oxygen reactor second entrance 314 enter put oxygen reactor 31 and oxygen-enriched oxygen carrier release oxygen mix, produce The oxygen rich gas of raw 500-900 DEG C (such as 800 DEG C).The equation of oxygen release reaction is as follows,
The oxygen rich gas of 500-900 DEG C (such as 800 DEG C) is put oxygen reactor first outlet 315 and third pre-heating device One entrance 331 enters third pre-heating device 33, and temperature is reduced to 80-150 DEG C (such as 100 DEG C) through third pre-heating device first outlet 333, which enter cooling equipment 34, carries out gas-liquid separation, obtains the O of condensed water and 99% or more purity (such as 99.9%)2, O2It is received Collection processing.The condensed water that cooling equipment first outlet 341 exports mixed with moisturizing after through third pre-heating device second entrance 332 into Enter third pre-heating device 33 heat up after become 300-650 DEG C of (such as 600 DEG C) vapor put again oxygen reactor second entrance 314 into Enter to put oxygen reactor 31.
Oxygen deprivation oxygen carrier (the Cu of 500-900 DEG C (such as 800 DEG C)2O) rise oxygen carrier in buffer tank 63 according to third to mention Lifting speed is put oxygen reactor second outlet 316 by self gravity and sequentially enters third surge tank 73, subsequently into third It rises buffer tank 63 and is promoted to the first collector 41 through third riser by the vapor of 300-650 DEG C (such as 600 DEG C).
The oxygen carrier of first collector 41 enters the first transformation feed appliance 244, the first transformation feed appliance by gravity Oxygen carrier material position closes the first valve 51 after reaching setting height in 244.
First transformation feed appliance 244 carries out pressure release, is passed through 300- to the first transformation feed appliance 244 after pressure reduction to normal pressure 650 DEG C (such as 500 DEG C) of oxygen denuded air purging vapor simultaneously pressurizes, when 24 pressure ratio high pressure oxygen-inhaling of transformation feed appliance reacts After device 11 10-50kPa high (such as 20kPa), the second valve 52 is opened, temperature is reduced to 490-890 DEG C (such as 780 DEG C) of oxygen deprivation to carry Oxysome enters high pressure oxygen-inhaling from the high pressure oxygen-inhaling reactor first entrance 111 of 11 upper end of high pressure oxygen-inhaling reactor by self gravity Reactor 11.
It after first transformation feed appliance, 244 discharging, closes the second valve 52 and carries out pressure discharge operations, the near normal pressure of pressure is opened First valve 51 charges.
Into high pressure oxygen-inhaling reactor 11 high-temperature oxygen-enriched oxygen carrier (CuO) under the pressure of 3-5MPa (such as 4MPa) with it is poor Oxygen air reacts and releases heat, generates micro- oxygen oxygen carrier of 500-900 DEG C (such as 850 DEG C), oxygen denuded air loses oxygen It is converted into the nitrogen-rich gas of 500-900 DEG C (such as 850 DEG C).The equation of oxygen-absorbing reaction is as follows,
The nitrogen of 500-900 DEG C (such as 850 DEG C) is gone out by the high pressure oxygen-inhaling reactor first of 11 lower part of high pressure oxygen-inhaling reactor Mouth 113, which is drawn, enters gas turbine 12, is done work and is generated electricity using the high temperature and pressure of nitrogen, pressure reduction to 0.1-0.5MPa is (such as 0.2MPa), temperature is reduced to 300-700 DEG C (such as 600 DEG C) to enter the first pre-heating device through the first pre-heating device second entrance 132 13 heating air, temperature are reduced to 50 DEG C or less to be collected processing, and nitrogen gas purity is higher than 99%.
The promotion speed that micro- oxygen oxygen carrier of 500-900 DEG C (such as 850 DEG C) rises oxygen carrier in buffer tank 61 according to first The first surge tank 71 is sequentially entered through high pressure oxygen-inhaling reactor second outlet 114 by self gravity, is risen subsequently into first Buffer tank 61 completes a circulation of oxygen carrier.
In conclusion high pressure, middle pressure, low pressure reaction is respectively adopted in chemical chain air-seperation system 100 provided by the present application Device is completed circulation of oxygen carrier under the conditions of High Pressure Difference and is made simultaneously using the irreversibility of oxygen-absorbing reaction under the conditions of high pressure low temperature The oxygen and nitrogen for taking high-purity improve the efficiency and economic performance of chemical chain air separation technology.Its operation method is simple, It is convenient to operate.
The foregoing is merely the preferred embodiment of the present invention, are not intended to restrict the invention, for this field For technical staff, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of chemical chain air separating method characterized by comprising
Oxygen-absorbing reaction will be pressed in micro- oxygen oxygen carrier and air progress, obtains oxygen denuded air and oxygen-enriched oxygen carrier；
The oxygen-enriched oxygen carrier is subjected to oxygen release reaction, obtains oxygen deprivation oxygen carrier and oxygen rich gas；
The oxygen denuded air is carried out high pressure oxygen-inhaling with the oxygen deprivation oxygen carrier to react, obtains micro- oxygen oxygen carrier and nitrogen-rich gas；
Wherein, the pressure of middle pressure oxygen-absorbing reaction is 1-3MPa, and temperature is 650-1000 DEG C；The pressure of oxygen release reaction is 0.1- 0.5MPa, temperature are 600-990 DEG C；The pressure of high pressure oxygen-inhaling reaction is 3-5MPa, and temperature is 500-900 DEG C；
Preferably, the high 2-5MPa of pressure of oxygen-absorbing reaction, the temperature of high pressure oxygen-inhaling reaction are pressed in the pressure ratio of high pressure oxygen-inhaling reaction Press the temperature of oxygen-absorbing reaction 100-500 DEG C low than in；
Preferably, the chemical chain air separating method further include: be used for the micro- oxygen oxygen carrier that high pressure oxygen-inhaling reaction generates Press oxygen-absorbing reaction.
2. a kind of chemical chain air-seperation system characterized by comprising
Middle pressure oxygen-absorbing reaction system, for pressing oxygen-absorbing reaction to obtain oxygen denuded air and richness in carrying out micro- oxygen oxygen carrier and air Oxygen oxygen carrier；
Oxygen reaction system is put, for the oxygen-enriched oxygen carrier to be carried out oxygen release reaction, obtains oxygen deprivation oxygen carrier and oxygen rich gas；
High pressure oxygen-inhaling reaction system is reacted for the oxygen denuded air to be carried out high pressure oxygen-inhaling with the oxygen deprivation oxygen carrier, is obtained Micro- oxygen oxygen carrier and nitrogen-rich gas；
Preferably, the high pressure oxygen-inhaling reaction system includes high pressure oxygen-inhaling reactor, during medium pressure oxygen-absorbing reaction system includes Press oxygen-absorbing reaction device, the oxygen reaction system of putting includes putting oxygen reactor, the high pressure oxygen-inhaling reactor respectively with medium pressure Oxygen-absorbing reaction device and the oxygen reactor of putting connect；
The reaction pressure of the high pressure oxygen-inhaling reactor is not less than the reaction pressure of medium pressure oxygen-absorbing reaction device, and medium pressure The reaction pressure of oxygen-absorbing reaction device is higher than the reaction pressure for putting oxygen reactor；Preferably, the high pressure oxygen-inhaling reactor Reaction pressure is 3-5MPa, and reaction temperature is 500-900 DEG C；The reaction pressure of medium pressure oxygen-absorbing reaction device is 1-3MPa, instead Answering temperature is 650-1000 DEG C；The reaction pressure for putting oxygen reactor is 0.1-0.5MPa, and reaction temperature is 600-990 DEG C；
Preferably, the high 2-5MPa of pressure of the pressure ratio medium pressure oxygen-absorbing reaction device of the high pressure oxygen-inhaling reactor, the height Press the temperature of oxygen-absorbing reaction device 100-500 DEG C lower than the temperature of medium pressure oxygen-absorbing reaction device.
3. chemical chain air-seperation system according to claim 2, which is characterized in that the high pressure oxygen-inhaling reactor, institute Stating middle pressure oxygen-absorbing reaction device and the oxygen reactor of putting is fluidized-bed reactor；
The high pressure oxygen-inhaling reaction system further includes gas turbine, the first pre-heating device and the first booster apparatus；Medium pressure is inhaled Oxygen reaction system further includes the second pre-heating device, the second collector, transformation feed appliance and the second booster apparatus；It is described to put oxygen reaction System further includes third collector, third pre-heating device and cooling equipment；
The arrival end of the high pressure oxygen-inhaling reactor is set with the outlet end of the transformation feed appliance and second boosting respectively Standby outlet end connection, the outlet end of the high pressure oxygen-inhaling reactor are connect with the arrival end of the gas turbine, and described first The arrival end of pre-heating device is connect with the outlet end of the outlet end of the gas turbine and first booster apparatus respectively；
The arrival end of second pre-heating device respectively with the outlet end of first pre-heating device and medium pressure oxygen-absorbing reaction The outlet end of device connects, and the outlet end of second pre-heating device is boosted with medium pressure oxygen-absorbing reaction device and described second respectively The arrival end of equipment connects；
The arrival end of the transformation feed appliance respectively with the outlet end of medium pressure oxygen-absorbing reaction device and the third collector Outlet end connection, the arrival end of second collector is pre- with the outlet end of the transformation feed appliance and the third respectively The outlet end of hot equipment connects, and the outlet end of the third pre-heating device is also connect with the cooling equipment, the third preheating The arrival end of equipment is connect with the outlet end for putting oxygen reactor, and the arrival end for putting oxygen reactor is respectively with described second The outlet end of collector and the connection of the outlet end of the third pre-heating device.
4. chemical chain air-seperation system according to claim 3, which is characterized in that the high pressure oxygen-inhaling reaction system is also Including the first gas-solid separation equipment and transition holding vessel, the outlet end of the high pressure oxygen-inhaling reactor and first gas solid separation The arrival end of equipment connects, the outlet end of first gas-solid separation equipment respectively with the arrival end of the gas turbine and described The arrival end of transition holding vessel connects, and the outlet end of the transition holding vessel is also connect with medium pressure oxygen-absorbing reaction device, described The arrival end of transition holding vessel is also connect with the outlet end of second pre-heating device.
5. chemical chain air-seperation system according to claim 3, which is characterized in that the transformation feed appliance and it is described in The first collector is also connected between pressure oxygen-absorbing reaction device；
And/or filter is also connected between medium pressure oxygen-absorbing reaction device and second pre-heating device.
6. chemical chain air-seperation system according to claim 3, which is characterized in that described put is equipped with the in oxygen reactor The two gas-solid separation equipments and oxygen reactor of putting further respectively has steam inlet and oxygen carrier entrance, the oxygen carrier entrance with The outlet end of second collector connects, and the steam inlet is connect with the outlet end of the third pre-heating device.
7. chemical chain air-seperation system according to claim 2, which is characterized in that the high pressure oxygen-inhaling reactor, institute Stating middle pressure oxygen-absorbing reaction device and the oxygen reactor of putting is moving-burden bed reactor；
The high pressure oxygen-inhaling reaction system further includes that the first transformation feed appliance, the first rising buffer tank, gas turbine and first are pre- Hot equipment；Medium pressure oxygen-absorbing reaction system further includes the second transformation feed appliance, the second pre-heating device and the second rising buffer tank； The oxygen reaction system of putting further includes third transformation feed appliance, third rising buffer tank and third pre-heating device；
The outlet end of the high pressure oxygen-inhaling reactor is connect with the gas turbine and the first rising buffer tank respectively, described The outlet end of gas turbine is connect with the arrival end of first pre-heating device, the arrival end difference of the high pressure oxygen-inhaling reactor It is connect with the outlet end of the outlet end of second pre-heating device, the first transformation feed appliance；
The arrival end of medium pressure oxygen-absorbing reaction device respectively with the outlet end of second pre-heating device and second transformation The outlet end of feed appliance connects, and the outlet end of the arrival end of the second transformation feed appliance and the first rising buffer tank connects It connects, the outlet end of medium pressure oxygen-absorbing reaction device rises with the arrival end of second pre-heating device and described second slow respectively Tank connection is deposited, the arrival end of second pre-heating device is also connect with the outlet end of first pre-heating device；
The arrival end for putting oxygen reactor is set with the outlet end of the third transformation feed appliance and third preheating respectively Standby outlet end connection, the arrival end of the third transformation feed appliance are connect with the outlet end of the second rising buffer tank, institute It states and puts the outlet end of oxygen reactor and rise the arrival end of buffer tank and entering for the third pre-heating device with the third respectively The connection of mouth end, the outlet end that the third rises buffer tank are connect with the arrival end of the first transformation feed appliance.
8. chemical chain air-seperation system according to claim 7, which is characterized in that the first transformation feed appliance and institute It states third to rise equipped with the first collector between buffer tank, the second transformation feed appliance and described first rises between buffer tank Equipped with the second collector, third collector is equipped between the third transformation feed appliance and second collector.
9. chemical chain air-seperation system according to claim 7, which is characterized in that the high pressure oxygen-inhaling reactor and institute It states and is equipped with the first surge tank between the first rising buffer tank, medium pressure oxygen-absorbing reaction device and described second rises between buffer tank Equipped with the second surge tank, described put is equipped with third surge tank between oxygen reactor and third rising buffer tank.
10. the method for carrying out air separation using any chemical chain air-seperation system of claim 2-9, feature exist In including the following steps:
The air entered after micro- oxygen oxygen carrier and pressurized heat exchange heating aoxidize instead in medium pressure oxygen-absorbing reaction device It answers, generates oxygen denuded air and oxygen-enriched oxygen carrier；
Oxygen reactor is put described in the oxygen-enriched oxygen carrier input by generation and the oxygen-enriched oxygen carrier is put into oxygen reaction described Oxygen release reaction is carried out under water vapor atmosphere in device, generates oxygen deprivation oxygen carrier and oxygen rich gas；Gas is carried out to the oxygen rich gas Liquid separation, collects the oxygen isolated；
The oxygen denuded air is inputted into the high pressure oxygen-inhaling reactor and by the oxygen denuded air and the high pressure oxygen-inhaling reactor Interior oxygen deprivation oxygen carrier is reacted, and generates micro- oxygen oxygen carrier, while oxygen denuded air loses oxygen and is converted into nitrogen, collects nitrogen Gas；
Preferably, the volume flow of the air is fully converted to the theory of the oxygen-enriched oxygen carrier lower than the oxygen deprivation oxygen carrier Flow, non-equivalent proportion coefficient are 0.6-0.95.
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