CN110156016A - The combined recovery device and method of carbon dioxide in flue gas, nitrogen and oxygen - Google Patents
The combined recovery device and method of carbon dioxide in flue gas, nitrogen and oxygen Download PDFInfo
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- CN110156016A CN110156016A CN201910517538.2A CN201910517538A CN110156016A CN 110156016 A CN110156016 A CN 110156016A CN 201910517538 A CN201910517538 A CN 201910517538A CN 110156016 A CN110156016 A CN 110156016A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/225—Multiple stage diffusion
- B01D53/226—Multiple stage diffusion in serial connexion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
- C01B21/0405—Purification or separation processes
- C01B21/0433—Physical processing only
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
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- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
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- C01B2210/0014—Physical processing by adsorption in solids
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention provides the combined recovery device and methods of a kind of carbon dioxide in flue gas, nitrogen and oxygen.The device includes the first CO2Film separation unit, the 2nd CO2Film separation unit, CO2Pressure-variable adsorption separative unit and O2Pressure-variable adsorption separative unit；2nd CO2The carbon dioxide enriched gas import of the first of film separation unit and the first CO2The carbon dioxide enriched gas outlet of the first of film separation unit is connected；CO2First high pressure non-permeate gas import of pressure-variable adsorption separative unit and the first CO2The first high pressure non-permeate gas outlet of film separation unit is connected；O2The carbon dioxide de degasification import of pressure-variable adsorption separative unit and CO2The carbon dioxide de degasification outlet of pressure-variable adsorption separative unit is connected.Flue gas is handled using above-mentioned apparatus, the enrichment degree of carbon dioxide is higher, and nitrogen and oxygen that can simultaneously in separating flue, while realizing the resource utilization of carbon dioxide in flue gas, nitrogen and oxygen.
Description
Technical field
The present invention relates to fume treatment technical fields, in particular to a kind of carbon dioxide in flue gas, nitrogen and oxygen
Combined recovery device and method.
Background technique
Global warming is one of current environmental problem main in the world, in the various greenhouse gases for leading to climate change
In, carbon dioxide (CO2) heating up on the earth influences maximum, control CO2Discharge has become the important technology route of reply climate warming
One of.CO in combustion product gases2Discharge has the characteristics that concentration is low, stable, collection dosis neutralisata is big, is extensive emission reduction CO2Best neck
One of domain.It meanwhile also including nitrogen (N of a large amount of concentration 70% or so in flue gas2) and oxygen (O of the concentration 8%2), concentration
Lower than the concentration of nitrogen in air and oxygen, therefore, it is difficult to utilize.
The CO of high-purity2It is a kind of important industrial gasses, the CO of separation and collection2Oil and natural gas not only can be injected
The rate of oil and gas recovery is improved in field, also can be widely applied to anthropogenics, manufacture soda etc., realizes resource utilization.
CO in flue gas2Separation and collection technical application has a extensive future, and has significant environmental benefit, economic benefit and social benefit.Cause
This, separation and collection CO2Technology is the important technology for being related to coal-burning power plant's reduction of greenhouse gas discharge.
CO at present2Trapping recovery method in, membrane separation process is one of more effective method.The main original of membrane separation process
When reason is that two or more admixture of gas passes through polymeric membrane, due to solubility and diffusion of the various gases in film
The difference of coefficient causes gas with various relative permeation rates in film variant.The wherein relatively fast gas of infiltration rate, such as two
Carbonoxide, vapor, hydrogen, helium, hydrogen sulfide etc. can be preferentially enriched with by permeable membrane；And infiltration rate is relatively slow
Gas, the delay side if the gases such as methane, nitrogen, carbon monoxide in film is enriched with, so that reaching mixed gas separates it
Purpose.It is compared with other methods, UF membrane traps CO2With without chemical reaction, will not generate pollutant, device structure is compact,
Occupied area is small, start flexibly, safeguard and run the advantages that facilitating.
However, due in flue gas nitrogen and oxygen content it is higher, and the opposite infiltration speed of oxygen and nitrogen in film
Rate difference is smaller, still there is remaining CO when resulting in membrane separation process processing flue gas2More problems, this also results in CO2Enrichment
Degree is low, and nitrogen and oxygen difficulty separate, the problem more than the wasting of resources.
Summary of the invention
The main purpose of the present invention is to provide the combined recovery device of a kind of carbon dioxide in flue gas, nitrogen and oxygen and
Method, when solving in the prior art using membrane separation process processing flue gas, CO2Enrichment degree is low, nitrogen and the separation of oxygen difficulty
Problem.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of carbon dioxide in flue gas, nitrogen and
The combined recovery device of oxygen comprising: the first CO2Film separation unit is provided with gas inlet, the first carbon dioxide enriched gas
Outlet and the outlet of the first high pressure non-permeate gas；2nd CO2Film separation unit is provided with the first carbon dioxide enriched gas import and
The outlet of one carbon dioxide product gas, the first carbon dioxide enriched gas import are connected with the first carbon dioxide enriched gas outlet；CO2Become
Adsorption separation unit is pressed, the first high pressure non-permeate gas import, the outlet of the second carbon dioxide product gas and carbon dioxide de are provided with
Degasification outlet, the first high pressure non-permeate gas import are connected with the outlet of the first high pressure non-permeate gas；And O2Pressure-variable adsorption separation is single
Member is provided with carbon dioxide de degasification import, the outlet of oxygen concentration gas and the outlet of nitrogen-rich gas, carbon dioxide de degasification import
It is connected with carbon dioxide de degasification outlet.
Further, the first high pressure non-permeate gas import and the outlet of the first high pressure non-permeate gas pass through impermeable gas delivery pipe
Road is connected；2nd CO2Film separation unit be additionally provided with the second high pressure non-permeate gas outlet, the second high pressure non-permeate gas outlet with it is non-
Letter shoot road is permeated to be connected.
Further, device further includes the first compression unit, and the air inlet pipeline of gas inlet is arranged in the first compression unit
On, for being compressed to flue gas.
Further, the first carbon dioxide enriched gas import passes through the enriched gas that is connected with the first carbon dioxide enriched gas outlet
Transfer pipeline is connected；Device further includes the second compression unit, and the second compression unit is arranged on enriched gas transfer pipeline, for pair
The carbon dioxide enriched gas of first carbon dioxide enriched gas outlet discharge is compressed.
Further, device further includes the first fume treatment unit, and the setting of the first fume treatment unit is single in the first compression
On transfer pipeline between member and gas inlet, for removing liquid impurity and solid impurity in compressed flue gas.
Further, the first fume treatment unit includes the first cooler for being sequentially connected in series setting, the first demister and
One filter.
Further, device further includes the second fume treatment unit, and the setting of the second fume treatment unit is single in the second compression
Member and the 2nd CO2On enriched gas transfer pipeline between film separation unit, for removing in compressed carbon dioxide enriched gas
Moisture.
Further, the second fume treatment unit includes the second cooler, the second demister and the second mistake being arranged in series
Filter, alternatively, the second fume treatment unit is dehydration device.
Further, the first CO2Film separation unit and the 2nd CO2Membrane module in film separation unit is separately selected from
Hollow-fibre membrane, rolled film or plate membrane.
According to a further aspect of the invention, the combined recovery side of a kind of carbon dioxide in flue gas, nitrogen and oxygen is additionally provided
Method comprising following steps: flue gas is subjected to first time CO2Membrane separation obtains carbon dioxide enriched gas and the first high pressure
Impermeable gas；Carbon dioxide enriched gas is subjected to second of CO2Membrane separation obtains first part's carbon dioxide product gas；
The separation of carbon dioxide pressure-variable adsorption is carried out to the first high pressure non-permeate gas, obtains carbon dioxide de degasification and second part titanium dioxide
Carbon products gas；And the separation of oxygen pressure-variable adsorption is carried out to carbon dioxide de degasification, obtain oxygen concentration gas and nitrogen-rich gas.
Further, second of CO2The second high pressure non-permeate gas is also obtained during membrane separation, method further includes
Second high pressure non-permeate gas is subjected to the step of carbon dioxide pressure-variable adsorption separates together with the first high pressure non-permeate gas.
Further, in the step of carbon dioxide pressure-variable adsorption separates, process conditions are as follows: treatment temperature is -10~120
DEG C, adsorptive pressure is 0.10~1.50MPa of absolute pressure, and adsorbent is one in molecular sieve, silica gel, active carbon and its modified adsorbent
Kind is a variety of；Preferably, in the step of oxygen pressure-variable adsorption separates, process conditions are as follows: treatment temperature is -10~120 DEG C, is inhaled
Enclosure pressure is 0.10~1.5MPa of absolute pressure, and adsorbent is one kind or more of molecular sieve, silica gel, active carbon and its modified adsorbent
Kind.
Further, first time CO is being carried out to flue gas2Before the process of membrane separation, method further include to flue gas into
In the step of the step of the first second compression of row, preferably the first second compression, gas pressure is made to be greater than absolute pressure 0.10MPa.
Further, in second of CO2Before the process of membrane separation, method further include to carbon dioxide enriched gas into
In the step of the step of the second second compression of row, preferably the second second compression, gas pressure is made to be greater than absolute pressure 0.10MPa.
Further, after the step of the first second compression, method further includes being handled compressed flue gas to remove
The step of solid impurity and liquid impurity therein；Preferably, the step of handling compressed flue gas includes: not by several times
Cooling, demisting and filtering are carried out to sequence to compressed flue gas.
Further, after the step of the second second compression, method further includes carrying out to compressed carbon dioxide enriched gas
The step of processing is to remove moisture therein；Preferably, the step of handling compressed carbon dioxide enriched gas include:
Cooling, demisting, filtering are carried out to compressed carbon dioxide enriched gas.
The present invention provides the combined recovery devices of a kind of carbon dioxide in flue gas, nitrogen and oxygen comprising the first CO2
Film separation unit, the 2nd CO2Film separation unit, CO2Pressure-variable adsorption separative unit and O2Pressure-variable adsorption separative unit；First CO2Film
Separative unit is provided with gas inlet, the first carbon dioxide enriched gas outlet and the outlet of the first high pressure non-permeate gas, the 2nd CO2Film
Separative unit is provided with the first carbon dioxide enriched gas import and the outlet of the first carbon dioxide product gas, and first is carbon dioxide enriched
Gas import is connected with the first carbon dioxide enriched gas outlet；CO2Pressure-variable adsorption separative unit is provided with the first high pressure non-permeate gas
Import, the outlet of the second carbon dioxide product gas and carbon dioxide de degasification outlet, the first high pressure non-permeate gas import and first high
Impermeable gas outlet is pressed to be connected；O2Pressure-variable adsorption separative unit is provided with carbon dioxide de degasification import, the outlet of oxygen concentration gas
And the outlet of nitrogen-rich gas, carbon dioxide de degasification import are connected with carbon dioxide de degasification outlet.
Flue gas is handled using above-mentioned apparatus, the enrichment degree of carbon dioxide is higher, and nitrogen that can simultaneously in separating flue
Gas and oxygen, while realizing the resource utilization of carbon dioxide in flue gas, nitrogen and oxygen.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows the combined recovery dress of carbon dioxide in flue gas according to an embodiment of the present invention, nitrogen and oxygen
The schematic diagram set.
Wherein, the above drawings include the following reference numerals:
10, the first CO2Film separation unit；20, the 2nd CO2Film separation unit；30,CO2Pressure-variable adsorption separative unit；40,O2
Pressure-variable adsorption separative unit；50, the first compression unit；60, the second compression unit；70, the first fume treatment unit；80, second
Fume treatment unit.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
As described in background technology part, when handling flue gas using membrane separation process in the prior art, there are CO2Enrichment
The problem of degree is low, nitrogen and oxygen difficulty separate.
To solve the above-mentioned problems, the present invention provides the combined recoveries of a kind of carbon dioxide in flue gas, nitrogen and oxygen
Device, as shown in Figure 1, the device includes the first CO2Film separation unit 10, the 2nd CO2Film separation unit 20, CO2Pressure-variable adsorption point
From unit 30 and O2Pressure-variable adsorption separative unit 40, the first CO2Film separation unit 10 is provided with gas inlet, the first carbon dioxide
Enriched gas outlet and the outlet of the first high pressure non-permeate gas；2nd CO2Film separation unit 20 is provided with the first carbon dioxide enriched gas
Import and the outlet of the first carbon dioxide product gas, the first carbon dioxide enriched gas import export phase with the first carbon dioxide enriched gas
Even；CO2Pressure-variable adsorption separative unit 30 is provided with the first high pressure non-permeate gas import, the second carbon dioxide product gas outlet and two
Carbonoxide removes gas outlet, and the first high pressure non-permeate gas import is connected with the outlet of the first high pressure non-permeate gas；O2Pressure-variable adsorption point
Unit 40 is provided with carbon dioxide de degasification import, the outlet of oxygen concentration gas and the outlet of nitrogen-rich gas, carbon dioxide eliminating
Gas import is connected with carbon dioxide de degasification outlet.
Different from traditional membrane separation process, present invention employs the device processing that UF membrane and pressure-variable adsorption separation combine
Flue gas.Specifically:
Utilize the first CO2Film separation unit 10 can carry out CO to flue gas first2Membrane separation is needed because of carbon capture
Exhaust gas volumn is huge, utilizes the first CO2Film separation unit 10 advantageously reduces land occupation, and simplifies treatment process.In the first CO2Film point
Under processing from unit 10, most of carbon dioxide in flue gas forms the first carbon dioxide enriched gas from first by seperation film
Carbon dioxide enriched gas outlet discharge, oxygen, nitrogen and a small amount of carbon dioxide then form the discharge of the first high pressure non-permeate gas.It utilizes
2nd CO2Film separation unit 20 can further be enriched with the carbon dioxide in the first carbon dioxide enriched gas, form one
Partial CO 2 product gas.
Secondly, utilizing CO2Pressure-variable adsorption separative unit 30 can carry out the carbon dioxide in the first high pressure non-permeate gas
Pressure-variable adsorption separation.CO2Pressure-variable adsorption separative unit 30 is by adsorbent under the conditions of transformation for CO2With oxygen, nitrogen adsorption
Power reach separation CO2Purpose.And it experienced the first CO2The processing of film separation unit 10, most of titanium dioxide in flue gas
Carbon is separated, and the gas concentration lwevel in the first high pressure non-permeate gas significantly reduces, this is advantageous for reducing CO2Transformation is inhaled
The dosage of adsorbent in attached separative unit 30, and improve the adsorbing separation effect of carbon dioxide, obtain another part carbon dioxide
Product gas.Through CO2After the processing of pressure-variable adsorption separative unit 30, the carbon dioxide in the first high pressure non-permeate gas is further divided
From the carbon dioxide de degasification of oxygen and nitrogen composition enters O2In pressure-variable adsorption separative unit 40, oxygen is directed to based on adsorbent
The adsorption rate differential separation oxygen and nitrogen of gas and nitrogen.It is compared with other methods, pressure-variable adsorption has without chemical reaction, no
It can generate pollutant, it is easy to operate, safeguard and run the advantages that facilitating.
Flue gas is handled using the above-mentioned device of the present invention, while realizing the resource of carbon dioxide in flue gas, nitrogen and oxygen
Change recycling.
In a preferred embodiment, CO2Pressure-variable adsorption separative unit 30 includes CO2Absorbing unit and CO2Desorption is single
Member, CO2Absorbing unit is used at a higher pressure to CO2It is adsorbed, CO2Desorption unit is for right at lower pressures
Adsorbent after absorption carbon dioxide is desorbed.Preferred desorption mode can be the modes such as to vacuumize.
In a preferred embodiment, O2Pressure-variable adsorption separative unit 40 includes O2Absorbing unit and O2Desorption unit,
O2Absorbing unit is used at a higher pressure to O2It is adsorbed, O2Desorption unit is for existing to the adsorbent after adsorption of oxygen
It is desorbed under lower pressure.Specific desorption mode can be the modes such as to vacuumize.
In a kind of preferred embodiment, as shown in Figure 1, the first high pressure non-permeate gas import and the first high pressure non-permeate gas
Outlet is connected by impermeable gas transfer pipeline；2nd CO2Film separation unit 20 is additionally provided with the outlet of the second high pressure non-permeate gas,
The outlet of second high pressure non-permeate gas is connected with impermeable gas transfer pipeline.Through the 2nd CO2After the processing of film separation unit 20, Ke Yijin
One step separates the carbon dioxide in carbon dioxide enriched gas, obtains the higher carbon dioxide product gas of purity.Separate remaining oxygen
Second high pressure non-permeate gas of gas, nitrogen and a small amount of carbon dioxide composition is exported from the second high pressure non-permeate gas to be discharged, into one
Step enters CO together with the first high pressure non-permeate gas2Pressure-variable adsorption separative unit 30.Be conducive to further improve in flue gas in this way
The separating effect of carbon dioxide, oxygen and nitrogen improves resource recovery.
In a preferred embodiment, the first CO2Film separation unit 10 and the 2nd CO2Film in film separation unit 20
Component is separately selected from hollow-fibre membrane, rolled film or plate membrane.Here " being separately selected from " refers to first
CO2Film separation unit 10 and the 2nd CO2Membrane module in film separation unit 20 each is selected from one of above-mentioned three kinds of membrane modules,
Three may be the same or different between each other.Preferably, the material of membrane module is high molecular polymer organic material.Phase
Than in inoranic membrane, as membrane module, using the membrane module of high molecular polymer organic material formation, its processing technology is simple, manufacture
Cost is relatively low, for the CO in large-scale separation recycling coal-fired plant flue gas2Project investment cost can be greatly reduced.Together
When, the concentration of carbon dioxide is lower (about 12%) in certain flue gases such as coal-fired plant flue gas, and the selectivity of organic film is higher, energy
Enough further increase CO2Separation and recovery rate and amount of collected.
In a preferred embodiment, above-mentioned apparatus further includes the first compression unit 50, and the first compression unit 50 is set
It sets on the air inlet pipeline of gas inlet, for being compressed to flue gas.It can be the first CO using the first compression unit 502Film
The CO of separative unit 102Infiltration further provides for pressure-driven.And it should be noted that is vacuumized compared to being utilized in per-meate side
Or the method for purging decompression, the present invention is capable of providing enough pressure differences using the first compression unit 50, enough to drive
CO2Through film, especially organic film, to further increase CO2The trapping rate of recovery.Similarly, it is highly preferred that the first titanium dioxide
The import of carbon enrichment gas is connected with the first carbon dioxide enriched gas outlet by the enriched gas transfer pipeline that is connected；Device further includes second
Compression unit 60, the second compression unit 60 are arranged on enriched gas transfer pipeline, for exporting to the first carbon dioxide enriched gas
The carbon dioxide enriched gas of discharge is compressed.
In flue gas other than carbon dioxide, oxygen and nitrogen, also carries some solid impurities (particulate matter) and liquid is miscellaneous
Matter (moisture), in order to reduce these solid impurities and liquid impurity to the first CO2Especially there is seperation film in film separation unit 10
The influence of machine seperation film, in a preferred embodiment, above-mentioned apparatus further include the first fume treatment unit 70, the first cigarette
Gas disposal unit 70 is arranged on the transfer pipeline between the first compression unit 50 and gas inlet, for removing compressed cigarette
Liquid impurity and solid impurity in gas.Seperation film, especially organic separation membrane be easy by the solid impurities such as particulate matter pollution,
Humidity is required and temperature requirement is higher, these influences can be reduced to the greatest extent using the first fume treatment unit 70, thus into one
Step improves the treatment effect of flue gas.
In one embodiment, the solid impurity and liquid impurity in filter removal flue gas be can use.More preferably
Ground, the first fume treatment unit 70 include the first cooler, the first demister and first filter for being sequentially connected in series setting.It utilizes
First cooler can further condense the liquid in flue gas, then remove wherein condensable liquid through the first demister
Foam, droplet and the solids that may be entrained, finally recycling first filter that can further remove may folder in flue gas
The objectionable impurities such as the fine liquid of band.Meanwhile the first cooler is set and also helps control flue-gas temperature, to further increase the
One CO2The operation stability of film separation unit 10.
In a kind of preferred embodiment, the first fume treatment unit 70 further includes heat exchanger, and heat exchanger is provided with to be added
Hot import and outlet to be heated, import to be heated are connected with the outlet of first filter, and outlet to be heated and gas inlet phase
Even.The flue gas after impurity can will be removed in this way to carry out heat exchange in heat exchanger and be heated, and make it away from dew point and constant
The operation temperature of system.
In a preferred embodiment, device further includes the second fume treatment unit 80, the second fume treatment unit
80 are arranged in the second compression unit 60 and the 2nd CO2On enriched gas transfer pipeline between film separation unit 20, for removing pressure
The moisture in carbon dioxide enriched gas after contracting.Be conducive to further increase the 2nd CO in this way2The operation of film separation unit 20 is steady
It is qualitative.Preferably, the second fume treatment unit 80 includes the second cooler being arranged in series, the second demister and the second filtering
Device, alternatively, the second fume treatment unit 80 is dehydration device.Second cooler, the second demister and the second filter with above
First cooler, the first demister and first filter have similar effect.
Similarly, preferably the second fume treatment unit 80 further includes heat exchanger, and heat exchanger is provided with import to be heated and to be added
Heat outlet, import to be heated are connected with the outlet of the second filter, and outlet to be heated and the 2nd CO2The of film separation unit 20
One carbon dioxide enriched gas import is connected.
Above-mentioned apparatus is not only suitable for the processing of coal-fired plant flue gas, is also applied for the low-concentration flue gas such as steel plant, cement plant
The separation and collection of middle carbon dioxide, oxygen and nitrogen.
According to another aspect of the present invention, the combined recovery of a kind of carbon dioxide in flue gas, nitrogen and oxygen is additionally provided
Method comprising following steps: flue gas is subjected to first time CO2Membrane separation obtains carbon dioxide enriched gas and first high
Press impermeable gas；Carbon dioxide enriched gas is subjected to second of CO2Membrane separation obtains first part's carbon dioxide product
Gas；The separation of carbon dioxide pressure-variable adsorption is carried out to the first high pressure non-permeate gas, obtains carbon dioxide de degasification and second part two
Carbonoxide product gas；The separation of oxygen pressure-variable adsorption is carried out to carbon dioxide de degasification, obtains oxygen concentration gas and nitrogen-rich gas.
Using method provided by the invention, by CO2UF membrane and pressure-variable adsorption combine, while realizing carbon dioxide in flue gas, nitrogen
With the resource utilization of oxygen.
In a preferred embodiment, second of CO2The non-infiltration of the second high pressure is also obtained during membrane separation
Ventilative, the above method further includes that the second high pressure non-permeate gas is carried out carbon dioxide transformation suction together with the first high pressure non-permeate gas
Fufen from the step of.Be conducive to the separating effect for further improving carbon dioxide in flue gas, oxygen and nitrogen in this way, improve resource
The rate of recovery.
In order to further increase the effect of carbon dioxide pressure-variable adsorption separation, in a preferred embodiment, dioxy
In the step of changing the separation of carbon pressure-variable adsorption, process conditions are as follows: treatment temperature is -10~120 DEG C, and processing pressure is absolute pressure 0.10
~1.50MPa (A), adsorbent are the one or more of active carbon, silica gel, molecular sieve and its modified adsorbent.Preferably, dioxy
Change carbon pressure-variable adsorption separation the step of include: using above-mentioned adsorbent under above-mentioned process conditions to the first high pressure non-permeate gas into
Row carbon dioxide pressure-variable adsorption obtains carbon dioxide de degasification and is adsorbed with the adsorbent of carbon dioxide；In the state vacuumized
Under, the above-mentioned adsorbent for being adsorbed with carbon dioxide is desorbed, second part carbon dioxide product gas is obtained.
In order to further increase the effect of oxygen pressure-variable adsorption separation, in a preferred embodiment, oxygen transformation
In the step of adsorbing separation, process conditions are as follows: treatment temperature be -10~120 DEG C, processing pressure be absolute pressure 0.10~
1.50MPa (A), adsorbent are one of active carbon, silica gel, molecular sieve and its modified adsorbent or a variety of.Preferably, oxygen
The step of pressure-variable adsorption separates includes: to carry out oxygen to carbon dioxide de degasification under above-mentioned process conditions using above-mentioned adsorbent
Pressure-variable adsorption obtains nitrogen-rich gas and the adsorbent for being adsorbed with oxygen；In the state of vacuumizing, it is aerobic to desorb above-mentioned absorption
The adsorbent of gas obtains oxygen concentration gas.
Same adsorbent is different to different component absorption properties, by taking molecular sieve as an example, within the scope of certain pressure, and molecule
The absorption property of sieve: CO2> O2> N2, therefore richness CO2It is preferential to remove after air-flow enters carbon dioxide pressure-variable adsorption separation process
CO2, in removing CO2Afterwards, air-flow enters the separation of oxygen pressure-variable adsorption, preferentially removes O2。
In a preferred embodiment, first time CO is being carried out to flue gas2Before the process of membrane separation, method
Further include the steps that carrying out the first second compression to flue gas, the step of preferably the first second compression in, so that gas pressure is greater than absolute pressure
0.10MPa(A).It in this way can be first time CO2The CO of membrane separation2Infiltration further provides for pressure-driven.Similarly, preferably
Ground is carrying out second of CO to carbon dioxide enriched gas2Before the process of membrane separation, method further includes to carbon dioxide richness
In the step of gas collection carries out the step of the second second compression, preferably the second second compression, gas pressure is made to be greater than absolute pressure 0.10MPa (A).
In flue gas other than carbon dioxide, oxygen and nitrogen, also carries some solid impurities (particulate matter) and liquid is miscellaneous
Matter (moisture), in order to reduce these solid impurities and liquid impurity to first time CO2The influence of membrane separation, a kind of preferred
Embodiment in, the step of the first second compression after, method further includes being handled compressed flue gas to remove wherein
Solid impurity and liquid impurity the step of；Preferably, the step of handling compressed flue gas includes: successively to compression
Flue gas afterwards carries out cooling, demisting and filtering.Flue gas first be cooled after, by demisting can by liquid foam condensable in flue gas,
Droplet and the solids that may be entrained removal.Then possible entrainment in flue gas can further be removed by filtration treatment
The objectionable impurities such as fine liquid.In short, can substantially more remove liquid impurity, the solid in flue gas using aforesaid way
The impurity such as grain, to further increase the trapping effect of carbon dioxide.Meanwhile it can also effectively be controlled by carrying out cooling to flue gas
Flue-gas temperature processed, to further increase the operation stability of seperation film especially organic separation membrane.
It is highly preferred that method further includes carrying out to compressed carbon dioxide enriched gas after the step of the second second compression
The step of processing is to remove moisture therein；Preferably, the step of handling compressed carbon dioxide enriched gas include:
Cooling, demisting and filtering successively are carried out to compressed carbon dioxide enriched gas.
Beneficial effects of the present invention are further illustrated by the following examples:
Embodiment 1
To certain steel plant, flue gas is tested, and accounts device shown in Fig. 1 of the present invention for low concentration CO in flue gas2
The trapping of technique and oxygen and nitrogen recycling treatment effect.
Wherein, it is all made of hollow-fibre membrane made of organic film material in carbon dioxide film separation unit, which is
Polyimides (PI)；In the step of carbon dioxide pressure-variable adsorption separates, process conditions are as follows: treatment temperature is 30 degrees Celsius, place
Reason pressure is 0.50MPa (A), and adsorbent is silica gel；In the step of oxygen pressure-variable adsorption separates, process conditions are as follows: processing temperature
Degree is 30 degrees Celsius, and processing pressure is 0.47MPa (A), and adsorbent is carbon molecular sieve.
The results are shown in Table 1 for mass balance:
Table 1
It can be seen from the above description that the above embodiments of the present invention realized the following chievements: can by table 1
Know, when the throughput of the blast furnace flue gas of processing is 10000Nm3/ h, CO2Content 27.35%, O2Content 6.23%, N2Content
When 65.99%, in the treatment process in the present embodiment, second segment CO2Film separation unit permeates gas (product gas) flow
699Nm3/ h, CO2Content is promoted to 97.11% from 27.35%.The adsorbed gas flow that pressure-swing absorption apparatus comes out is 125Nm3/ h,
O2Content is promoted to 88% from 6.23%.N2Content is promoted to 99.20% from 65.99%.Using above-mentioned apparatus handle flue gas, two
The enrichment degree of carbonoxide is higher, and nitrogen and oxygen that can simultaneously in separating flue, at the same realize carbon dioxide in flue gas,
The resource utilization of nitrogen and oxygen.The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
For those skilled in the art, the invention may be variously modified and varied.It is all the spirit and principles in the present invention it
Interior, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (16)
1. the combined recovery device of a kind of carbon dioxide in flue gas, nitrogen and oxygen characterized by comprising
First CO2Film separation unit (10) is provided with gas inlet, the first carbon dioxide enriched gas outlet and the non-infiltration of the first high pressure
Vent outlet；
2nd CO2Film separation unit (20), is provided with the first carbon dioxide enriched gas import and the first carbon dioxide product gas goes out
Mouthful, the first carbon dioxide enriched gas import is connected with the described first carbon dioxide enriched gas outlet；
CO2Pressure-variable adsorption separative unit (30) is provided with the first high pressure non-permeate gas import, the outlet of the second carbon dioxide product gas
And carbon dioxide de degasification outlet, the first high pressure non-permeate gas import are connected with the first high pressure non-permeate gas outlet；
And
O2Pressure-variable adsorption separative unit (40) is provided with carbon dioxide de degasification import, the outlet of oxygen concentration gas and nitrogen-rich gas
Outlet, the carbon dioxide de degasification import are connected with carbon dioxide de degasification outlet.
2. the apparatus according to claim 1, which is characterized in that the first high pressure non-permeate gas import and described first high
Impermeable gas outlet is pressed to be connected by impermeable gas transfer pipeline；2nd CO2Film separation unit (20) is additionally provided with second
The outlet of high pressure non-permeate gas, the second high pressure non-permeate gas outlet are connected with the impermeable gas transfer pipeline.
3. device according to claim 1 or 2, which is characterized in that described device further includes the first compression unit (50), institute
It states the first compression unit (50) to be arranged on the air inlet pipeline of the gas inlet, for compressing flue gas.
4. device according to claim 3, which is characterized in that the first carbon dioxide enriched gas import and described first
Carbon dioxide enriched gas outlet is connected by the enriched gas transfer pipeline that is connected；Described device further includes the second compression unit (60),
Second compression unit (60) is arranged on the enriched gas transfer pipeline, for going out to the described first carbon dioxide enriched gas
The carbon dioxide enriched gas of mouth discharge is compressed.
5. device according to claim 3, which is characterized in that described device further includes the first fume treatment unit (70),
The delivery pipe that first fume treatment unit (70) is arranged between first compression unit (50) and the gas inlet
On the road, for removing liquid impurity and solid impurity in the compressed flue gas.
6. device according to claim 5, which is characterized in that first fume treatment unit (70) includes being sequentially connected in series
The first cooler, the first demister and the first filter being arranged.
7. device according to claim 4, which is characterized in that described device further includes the second fume treatment unit (80),
Second fume treatment unit (80) is arranged in second compression unit (60) and the 2nd CO2Film separation unit (20)
Between the enriched gas transfer pipeline on, for removing the moisture in the compressed carbon dioxide enriched gas.
8. device according to claim 7, which is characterized in that second fume treatment unit (80) includes being arranged in series
The second cooler, the second demister and the second filter, alternatively, second fume treatment unit (80) be dehydration device.
9. the apparatus according to claim 1, which is characterized in that the first CO2Film separation unit (10) and described second
CO2Membrane module in film separation unit (20) is separately selected from hollow-fibre membrane, rolled film or plate membrane.
10. the combined reclamation method of a kind of carbon dioxide in flue gas, nitrogen and oxygen, which is characterized in that the method includes with
Lower step:
The flue gas is subjected to first time CO2Membrane separation obtains carbon dioxide enriched gas and the first high pressure non-permeate gas；
The carbon dioxide enriched gas is subjected to second of CO2Membrane separation obtains first part's carbon dioxide product gas；
The separation of carbon dioxide pressure-variable adsorption is carried out to the first high pressure non-permeate gas, obtains carbon dioxide de degasification and second
Divide carbon dioxide product gas；And
The separation of oxygen pressure-variable adsorption is carried out to the carbon dioxide de degasification, obtains oxygen concentration gas and nitrogen-rich gas.
11. according to the method described in claim 10, it is characterized in that, second of CO2It is also obtained during membrane separation
Second high pressure non-permeate gas, the method also includes by the second high pressure non-permeate gas and the first high pressure non-permeate gas
The step of carrying out carbon dioxide pressure-variable adsorption separation together.
12. method described in 0 or 11 according to claim 1, which is characterized in that the step of carbon dioxide pressure-variable adsorption separates
In, process conditions are as follows: treatment temperature is -10~120 DEG C, and adsorptive pressure is 0.10~1.50MPa of absolute pressure, and adsorbent is molecule
One of sieve, silica gel, active carbon and its modified adsorbent are a variety of；
Preferably, in the step of oxygen pressure-variable adsorption separates, process conditions are as follows: treatment temperature is -10~120 DEG C, is inhaled
Enclosure pressure is 0.10~1.5MPa of absolute pressure, and adsorbent is one kind or more of molecular sieve, silica gel, active carbon and its modified adsorbent
Kind.
13. method described in 0 or 11 according to claim 1, which is characterized in that carrying out first time CO to the flue gas2UF membrane
Before the process of processing, the method also includes carrying out the first second compression to the flue gas, the preferably described first time pressure
In the step of contracting, gas pressure is made to be greater than absolute pressure 0.10MPa.
14. method described in 0 or 11 according to claim 1, in second of CO2Before the process of membrane separation, the side
Method further includes the steps that in the step of carrying out the second second compression, preferably second second compression to the carbon dioxide enriched gas,
Gas pressure is set to be greater than absolute pressure 0.10MPa.
15. according to the method for claim 13, which is characterized in that after the step of first second compression, the method
Further include the steps that handling the compressed flue gas to remove solid impurity and liquid impurity therein；Preferably,
The step of handling the compressed flue gas includes: regardless of order to carry out cooling to the compressed flue gas, remove
Mist and filtering.
16. according to the method for claim 14, which is characterized in that after the step of second second compression, the method
Further include the steps that handling to remove moisture therein the compressed carbon dioxide enriched gas；Preferably, to pressure
The step of carbon dioxide enriched gas after contracting is handled includes: cold to the compressed carbon dioxide enriched gas progress
But, demisting, filtering.
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