CN108636059A - A kind of collecting carbonic anhydride and regenerated integrated apparatus and method - Google Patents
A kind of collecting carbonic anhydride and regenerated integrated apparatus and method Download PDFInfo
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- B01D53/32—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 electrical effects other than those provided for in group B01D61/00
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
- F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
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Abstract
The invention discloses a kind of collecting carbonic anhydride and regenerated integrated apparatus and method, apparatus of the present invention are made of water vapourizer, flue gas and vapor mixing arrangement, Gas Ionizer, carbon dioxide collection and adsorbent reactivation device, gas-solid separating device；It is heated by flue gas, carbon dioxide adsorption, sorbent circulation regeneration, the trapping recycling of the carbon dioxide in flue gas is realized, to reduce the discharge capacity of carbon dioxide.Low grade heat energy heating water and adsorbent are recycled from flue gas, vapor is formed and carbon dioxide is promoted to inhale, and realize recycling for carbon dioxide absorber, and then improve the source benefit of entire absorbing process process.It is additionally arranged Gas Ionizer in flue gas and vapor mixing arrangement, makes gas ionization, promotes the absorption of gas.The present invention has equipment simple, small, compact-sized, invests low, the high advantage of adsorbent utilization ratio, suitable for being applied in coal-burning power plant's stack gas cleaning and carbon dioxide collection.
Description
Technical field
The present invention relates to a kind of collecting carbonic anhydride and regenerated integrated apparatus and methods, belong to the recycling of carbon dioxide
Utilize field.
Background technology
The carbon dioxide that combustion of fossil fuel generates is considered as one of most important greenhouse gases.Atmospheric greenhouse gas
Concentration increase cause greenhouse effects to increase year by year, and cause that global warming, sea level rise, the environment such as Melting Glacierss are asked
Topic.To coal-burning power plant, the CO in the large size flue gas source such as cement plant2It carries out trapping and storage will be helpful to reduce carbon dioxide row
It puts, alleviates greenhouse effects.CO simultaneously2It is also a kind of potential carbon resource.Current tellurian resource growing tension, many scholars
It is dedicated to CO2The research for capturing and sealing up for safekeeping and utilize, wherein the separation and collection CO from flue gas2More and more it is concerned by people.
Currently, many collecting carbonic anhydride technologies are widely studied, including chemical absorbing, chemisorption and UF membrane etc..
Wherein, liquid amine absorption process CO2Trapping process has been actually applied, and this method has many advantages, such as efficient, and uptake is big.But
It is that this method still limits it and be widely used there are many disadvantage, is volatilized as alkanolamine solution is easy to happen oxidative degradation so that absorbing
Reduced performance；The strong basicity of solution has heavy corrosion effect to instrument and equipment；The shortcomings of alkanolamine solution regeneration consumption is big.
In order to overcome these disadvantages, alkanolamine solution absorption process CO is substituted2Trapping technique, there has been proposed utilize porous material
CO is carried out as solid absorbent2Adsorb set method.The active charcoal of common porous material（AC）, zeolite, alkalinous metal oxidation
Object (MxOy), metal organic framework (MOF) and covalent organic framework (COF), mesoporous silica-base material etc..Solid absorbent is due to it
Operating method is relatively simple and weak to equipment corrosion and is taken seriously, however these adsorbents usually have poor selectivity, inhale
The attached low disadvantage of amount.In order to further increase CO2Adsorption capacity and adsorption/desorption rate consider liquid organic amine to pass through object
Reason dipping or chemical grafting load on porous carrier, to be prepared into amine solid adsorbent.
With directly using porous material as adsorbent compared with, solid amine absorption agent can be inhaled with high selectivity by chemical action
Attached CO2, there is higher adsorption/desorption rate, and improve the water-resistance of adsorbent, and study according to scholar,
Under the conditions of having existing for vapor, the interaction of vapor and organic amine, carbon dioxide can improve solid amine absorption agent pair
CO2Adsorbance.Compared with liquid amine solution absorption method, solid amine absorption method also has that easy to operate, regeneration energy consumption is low, pair sets
It is standby to corrode the advantages that small, adsorption desorption rate is fast.Chinese patent CN104258828A is related to
Carrier exploitation amine solid adsorbent is for capturing flue gas CO2.And in terms of solid amine detaches carbon dioxide process device, in
State patent CN104162341A is related to collecting the device and method of carbon dioxide in a kind of gas from industrial flue, by using heating
Machine and cooler carry out cold-heat treatment to adsorbent, realize the recycling of adsorbent, but the plant energy consumption increases, and separately sets feed
Machine and riser make adsorbent complete cyclic process, but adsorption process complex procedures, device disperse.
Invention content
The present invention is intended to provide a kind of collecting carbonic anhydride and regenerated integrated apparatus and method, are realized in flue gas
The trapping of carbon dioxide, to reduce the discharge capacity of carbon dioxide.
The present invention makes full use of a large amount of low grade residual heats contained in flue gas to heat water and generates vapor, improves absorption
Adsorbance of the agent to carbon dioxide.Heating regeneration is carried out to adsorbent using flue gas middle-low grade waste heat simultaneously, to realize
Carbon dioxide absorber recycles, and then improves the source benefit of entire technical process.
The present invention provides a kind of collecting carbonic anhydride and regenerated integrated apparatus, including water vapourizer, flue gas
With vapor mixing arrangement, Gas Ionizer, carbon dioxide collection and adsorbent generating apparatus, gas-solid separating device；
The water vapourizer, outside are positive truncated rectangular pyramids structure, and central upper portion is equipped with waste gas inlet, and bottom goes out equipped with flue gas
Mouth and steam outlet, side are equipped with water supply port；In being divided into inside device, in, it is three layers outer, the annular channel of outer layer is flue
The annular channel in gas channel, middle level is aquaporin, and the channel of internal layer is water vapor channel, and waste gas inlet leads directly to flue gas
In channel, water supply port connects aquaporin by pipeline, and steam outlet is equipped in water vapor channel bottom；
Flue gas channels carry out heating vaporization on the outside of aquaporin, to water；
Connection flue gas and vapor mixing arrangement below the device；
The flue gas and vapor mixing arrangement, the device are rectangular parallelepiped structure, and the flue gas of top and water vapourizer goes out
Mouth, steam outlet communicate, and bottom centre is equipped with mixed gas outlet；The device is internally provided with baffle, and baffle point multilayer is uniformly put down
Row setting；It is connect with Gas Ionizer on the outside of the device；The inner wall of the device is equipped with insulating layer, to prevent whole device band
Electricity；Connection carbon dioxide collection and adsorbent reactivation device below the device；
The both sides of the carbon dioxide collection and adsorbent reactivation device are separately connected carbon dioxide-cyclone separator and exhaust gas-
The top center of cyclone separator, carbon dioxide-cyclone separator and exhaust gas-cyclone separator is equipped with gas vent, lower end side
Face is equipped with adsorbent outlet, and the upper end of the side opposite with adsorbent outlet is equipped with gas feed；
The carbon dioxide collection and adsorbent reactivation device, are made of upper and lower two chambers, and upper and lower two chambers are by obstructing
Plate separates, and prevents the carbon dioxide of heating adsorbent release from entering the device upper chamber, and upper chamber is rectangular parallelepiped structure, under
Portion's chamber is semicylinder, and the semi-cylindrical of semicylinder connects with baffler, and upper chamber is divided into interlayer and middle layer, interlayer
For insulating layer（The inside is common thermal insulation material）, the left side of upper chamber is equipped with adsorbent supply port, is set on the right side of upper chamber
There are waste gas outlet, waste gas outlet to connect exhaust gas-cyclone separator；
The left bottom of lower chamber is equipped with carbon dioxide outlet, and carbon dioxide outlet connects carbon dioxide-cyclone separator；
The rotation gear with longer sawtooth is equipped in carbon dioxide collection and adsorbent reactivation device, gear shaft is arranged on top
Between chamber and lower chamber, the both ends of gear shaft are fixed on the left and right sides wall between upper chamber and lower chamber, and
Gear shaft is arranged in parallel with baffler, is recycled in the device by gear rotary adsorbent；The outside of lower chamber is
Flue gas heating interlayer, interlayer bottom centre are equipped with waste gas inlet, and interlayer side is equipped with flue gas outlet, the flue gas outlet
It is connect with water vapourizer by pipeline；
The Gas Ionizer includes discharge electrode and collector, and flue gas is with the first layer baffle in vapor mixing arrangement
The baffle of discharge electrode, the other side opposite with discharge electrode is collector.
The reason of carbon dioxide collection and adsorbent reactivation device, lower chamber is arranged to semi-cylindrical structure
It is：Adsorbent in upper and lower chamber will lean on the long sawtooth of gear to drive, could be in upper and lower cavity indoor circulation, if lower chamber
And as upper chamber be cuboid, in the lower corner of cuboid, gear serrations are not achieved, and will make to enter lower chamber
Adsorber section be retained in lower chamber turning, upper chamber cannot be recycled to.
In above-mentioned apparatus, the adsorbent in the carbon dioxide collection and adsorbent reactivation device is solid amine absorption agent.
In above-mentioned apparatus, the insulating layer is rubber or ceramics.
Two pieces of resistances are equipped in above-mentioned apparatus, between the upper and lower part of the carbon dioxide collection and adsorbent reactivation device
Partition board, each one piece of gear shaft both sides are flexible rubber material, and two pieces of bafflers are not solid close to the side of gear shaft
It is fixed, it is fixed between upper chamber and lower chamber close to the side of carbon dioxide collection and adsorbent reactivation device front and rear wall
Front and back inner wall on.
All cogged sawtooth in upper and lower chamber, the baffler being provided with is the soft flexible length of rubber material
Square plate, two pieces of bafflers are not fixed close to the side of gear shaft, but are contacted with gear shaft.Close to carbon dioxide collection and suction
The side of attached dose of regenerating unit front and rear wall is fixed on the front and back inner wall between upper chamber portion and lower chamber.Turn in gear
When dynamic, longer sawtooth can bend soft flexible baffler along lower cavity wall, and after waiting sawtooth to turn over, baffler can be under
A sawtooth is returned to origin-location before reaching above baffler.The presence of baffler does not influence gear rotation.
In above-mentioned apparatus, the rotation gear in the carbon dioxide collection and adsorbent reactivation device has 2 ~ 4 sawtooth.
In above-mentioned apparatus, the carbon dioxide-cyclone separator connects two by pipeline respectively with exhaust gas-cyclone separator
Carbonoxide is collected and adsorbent reactivation device.
In above-mentioned apparatus, a length of 200mm ~ 1000mm of top sides of water vapourizer, a length of 1000mm of bottom sides ~
2000mm。
The present invention provides a kind of collecting carbonic anhydride and regeneration methods to be included the following steps using above-mentioned apparatus：
（1）Flue gas is introduced in from the waste gas inlet of water vapourizer top center in water vapourizer；Disguise in steam
In setting, water storage interlayer outer wall of the flue gas out of this device passes through, and is heated to water using flue gas waste heat, makes water vapor shape
At vapor, vapor and flue gas enter flue gas by the flue gas outlet and steam outlet of the device lower part and are steamed with water
In gas mixing arrangement；
（2）It is ionized first by Gas Ionizer into flue gas and the flue gas and vapor of vapor mixing arrangement, in baffle
Under the action of flue gas and vapor be sufficiently mixed, then gaseous mixture passes through flue gas and vapor mixing arrangement bottom centre
Outlet enters carbon dioxide collection and adsorbent reactivation device；
（3）Vapor and the gaseous mixture of flue gas are introduced in carbon dioxide collection and adsorbent reactivation device top, gaseous mixture
In carbon dioxide be in the device rotate gear sawtooth between solid amine absorption agent adsorbed, after removing removing carbon dioxide
Flue gas by waste-gas adsorbant gas-solid mixture outlet enter exhaust gas-cyclone separator, exhaust gas carry a small amount of adsorbent quilt
It is reentered in the upper chamber of carbon dioxide collection and adsorbent reactivation device by pipeline after separation, exhaust gas is by exhaust gas-rotation
The pure waste gas outlet of wind separator top center is discharged into air；
（4）By the rotation of carbon dioxide collection and adsorbent reactivation device inward turning rotating disk, the absorption after carbon dioxide is adsorbed
Agent is brought into lower chamber, and flue gas is introduced in carbon dioxide collection and adsorbent reactivation from the waste gas inlet of bottom
In the flue gas heating interlayer of device lower chamber；It adsorbs the adsorbent after carbon dioxide to be heated by the flue gas in interlayer, release
Release carbon dioxide, the device underflue gas heating interlayer discharge flue gas by pipeline enter in water vapourizer with its
In flue gas converge, the carbon dioxide come out by carbon emissions carries a small amount of adsorbent and passes through carbon dioxide absorber gas-solid mixing
Object outlet enters carbon dioxide-cyclone separator, pure dioxy of the carbon dioxide isolated from gas-solid separating device top center
Change carbon outlet discharge to collect, a small amount of adsorbent entrained by carbon dioxide reenters carbon dioxide by pipeline after being detached and receives
In the upper chamber of collection and adsorbent reactivation device；The adsorbent for releasing carbon dioxide follows rotation gear to be again introduced into
Portion's chamber carries out the circulation absorption of carbon dioxide.
In the above method, the flue gas comes from cement kiln factory of coal-burning power plant or coke-oven plant.
Beneficial effects of the present invention：
（1）The present invention realizes effective trapping of carbon dioxide in flue gas, to reduce the discharge capacity of carbon dioxide；
（2）Heating is carried out to water present invention utilizes flue gas middle-low grade thermal energy and generates vapor, improves adsorbent to dioxy
Change the adsorption effect of carbon；
（3）Present invention utilizes flue gas middle-low grade waste heats to carry out heating regeneration to adsorbent, improves entire adsorption process
Source benefit, while realizing recycling for carbon dioxide absorber, there is higher adsorbent utilization ratio；
（4）Apparatus of the present invention equipment is simple, small, compact-sized, and investment is low.
（5）It is additionally arranged Gas Ionizer in flue gas and vapor mixing arrangement, makes gas ionization, is conducive to gas quilt
Adsorbent adsorbs.
Description of the drawings
Fig. 1 is the overall structure diagram of circular regeneration collecting carbonic anhydride integrated apparatus；
Fig. 2 is the relative position vertical view of gear shaft and baffler.
Fig. 3 is the side view of carbon dioxide collection and adsorbent reactivation device.
In figure, 1：Water vapourizer, 1.1：Waste gas inlet, 1.2：Water supply port, 1.3：Water storage interlayer, 1.4：Flue gas
Outlet, 1.5：Steam outlet；2：Flue gas and vapor mixing arrangement, 2.1：Baffle, 2.2：Mixed gas outlet, 2.3：Insulation
Layer；3：Gas Ionizer, 3.1：Discharge electrode, 3.2：Collector；4：Carbon dioxide collection and adsorbent reactivation device, 4.1：Barrier
Plate, 4.2：Upper chamber, 4.3：Lower chamber；4.4：Insulating layer, 4.5：Flue gas heating interlayer, 4.6：Waste gas inlet,
4.7：Flue gas outlet, 4.8：Waste gas outlet, 4.9：Adsorbent supply port, 4.10：Carbon dioxide outlet, 4.11：Pipeline,
4.12：Sawtooth, 4.13：Rotate gear；5：Carbon dioxide-cyclone separator, 5.1：Pure carbon dioxide exports, and 5.2：Titanium dioxide
Carbon import, 5.3：Adsorbent outlet； 6：Exhaust gas-cyclone separator, 6.1：Pure waste gas outlet, 6.2：Adsorbent outlet, 6.3：It is useless
Gas import.
Specific implementation mode
It is further illustrated the present invention below by embodiment, but is not limited to following embodiment.
Embodiment 1：
As shown in Fig. 1 ~ 3, a kind of circular regeneration collecting carbonic anhydride integrated apparatus, including water vapourizer 1, flue gas and water
Steam mixer 2, Gas Ionizer 3, carbon dioxide collection and adsorbent reactivation device 4, carbon dioxide-cyclone separator 5,
Exhaust gas-cyclone separator 6；
The water vapourizer, the device truncated rectangular pyramids shape, central upper portion are equipped with waste gas inlet 1.1, and bottom face is equipped with cigarette
Road gas outlet 1.4 and steam outlet 1.5, middle part side are equipped with water supply port 1.2, and device is internally provided with truncated rectangular pyramids shape water storage folder
Layer 1.3, flue gas passes through from 1.3 outer wall of water storage interlayer, and heating and gasifying is carried out to water；Connection flue gas and vapor below the device
Mixing arrangement 2；
The flue gas and vapor mixing arrangement, the device are the cubic bodily form, and top passes through flue gas outlet 1.4 and vapor
Outlet 1.5 is connect with water vapourizer 1, which is internally provided with baffle 2.1, and bottom centre is equipped with mixed gas outlet 2.2, described
Baffle point multilayer is uniformly laterally arranged, which connects Gas Ionizer 3；The inner wall of the device is equipped with a layer insulating
2.3, to prevent whole device from charging；Link carbon dioxide collection and adsorbent reactivation device 4 below the device；
The carbon dioxide collection and adsorbent reactivation device, the device top are the cubic bodily form, and lower part is semi-cylinder, lower end side
Face is equipped with carbon dioxide outlet 4.10, and medial side face is equipped with waste gas outlet 4.8, carbon dioxide outlet 4.10 and waste gas outlet 4.8
The both sides of the device are located at, baffler 4.1, the barrier are equipped between the upper chamber 4.2 and lower chamber 4.3 of the device
The carbon dioxide that plate is used for preventing lower part heating adsorbent from releasing enters the device upper chamber 4.2, and device is internally provided with
Rotation gear 4.13 with sawtooth 4.12, is rotated by gear, and the adsorbent between sawtooth is recycled in the device；
The device lower outside is equipped with flue gas heating interlayer 4.5, and interlayer bottom centre is equipped with waste gas inlet 4.6, and interlayer side is set
There is flue gas outlet 4.7, which is connect by pipeline 4.11 with water vapourizer 1；
The Gas Ionizer 3 includes discharge electrode 3.1 and collector 3.2, on the inside of flue gas and vapor mixing arrangement upper end
First layer baffle is discharge electrode, and the baffle of the other side opposite with discharge electrode is collector；
Carbon dioxide-the cyclone separator, top center are equipped with pure carbon dioxide and export 5.1, and upper side is equipped with titanium dioxide
Carbon import 5.2, the side lower end opposite with carbon dioxide inlet are equipped with adsorbent outlet 5.3, and adsorbent outlet 5.3 passes through pipeline
Connect carbon dioxide collection and adsorbent reactivation device top；
Exhaust gas-the cyclone separator, top center are equipped with pure waste gas outlet 6.1, and upper side is equipped with exhaust gas inlet 6.3, with
The opposite side lower end of exhaust gas entrance is equipped with adsorbent outlet 6.2, and adsorbent outlet 6.2 connects carbon dioxide collection by pipeline
And adsorbent reactivation device top.
In above-mentioned apparatus, the adsorbent in the carbon dioxide collection and adsorbent reactivation device 4 is solid amine absorption agent.
In above-mentioned apparatus, the insulating layer 2.3 is rubber or ceramics.
In above-mentioned apparatus, the baffler 4.1 in the carbon dioxide collection and adsorbent reactivation device 4 is flexible
Rubber material, two pieces of bafflers are not fixed close to the side of gear shaft, close to carbon dioxide collection and adsorbent reactivation device
The side of front and rear wall is fixed on the front and back inner wall between upper chamber portion and lower chamber.
In above-mentioned apparatus, the rotation gear 4.13 in the carbon dioxide collection and adsorbent reactivation device 4 has 2 ~ 4
Sawtooth 4.12.
In above-mentioned apparatus, the carbon dioxide-cyclone separator connects two by pipeline respectively with exhaust gas-cyclone separator
Carbonoxide is collected and adsorbent reactivation device.
Its effect of water vapourizer is：Allow flue gas be introduced into from the entrance of the device top center, flue gas from this
The outer wall of water storage interlayer inside device passes through, and is heated to water using flue gas waste heat；Water vapor is set to form vapor, water
Steam and flue gas enter flue gas by the flue gas outlet and steam outlet of the bottom of device and mix dress with vapor
In setting；
Flue gas and vapor mixing arrangement, the vapor and flue gas of vaporization are introduced into the device, and effect is：Into this
The vapor and flue gas of device is arranged on the Gas Ionizer ionization of the device upper end, then the baffle in the device
Under effect, vapor and flue gas is made to be sufficiently mixed；Gaseous mixture enters carbon dioxide by the outlet at the bottom of device center
In collection and adsorbent reactivation device；
The gaseous mixture of carbon dioxide collection and adsorbent reactivation device, vapor and flue gas is introduced into the device top, makees
With being：Solid amine absorption agent between making the carbon dioxide in gaseous mixture be in the sawtooth of device rotation gear is adsorbed, and is gone
Flue gas after removing carbon dioxide is entered by waste gas outlet in exhaust gas-cyclone separator, a small amount of adsorbent quilt entrained by exhaust gas
The device top is reentered by pipeline after separation, pure exhaust gas is arranged by the gas vent of exhaust gas-cyclone separator top center
Enter air；By the rotation of the rotation gear in the device, adsorbs the adsorbent after carbon dioxide and is brought into the device lower part,
The adsorbent after carbon dioxide is adsorbed by the flue gas heating by the device lower part interlayer, releases carbon dioxide, the device
The flue gas of underflue gas heating interlayer discharge by pipeline enter in water vapourizer with from integrated apparatus top center
The flue gas being introduced into water vapourizer is converged, and the carbon dioxide released by heating carries a small amount of adsorbent and passes through dioxy
Change carbon outlet and enter carbon dioxide-cyclone separator, the pure carbon dioxide detached is from the top of carbon dioxide-cyclone separator
The gas vent discharge of the heart is collected, and a small amount of adsorbent that carbon dioxide carries is reentered by pipeline on the device after being detached
Portion；The adsorbent for releasing carbon dioxide follows the top that the rotation of rotation gear is re-introduced into the device to carry out titanium dioxide
Carbon adsorption recycles；
Gas Ionizer, effect are：The gas ionization in flue gas and vapor；Wherein flue gas mixes dress with vapor
It is discharge electrode to set the first layer baffle on the inside of upper end, and the baffle of the other side opposite with discharge electrode is collector；
Carbon dioxide-the cyclone separator is cyclone separator, and effect is：Carbon dioxide and adsorbent mixtures are from side
It enters in cyclone separator, by cyclonic separation, isolated carbon dioxide goes out from cyclone separator top center gas
Mouth discharge is collected, what the adsorbent under detaching was connect from cyclone separator bottom with carbon dioxide collection and adsorbent reactivation device
Pipeline enters in carbon dioxide collection and adsorbent reactivation device.
Exhaust gas-the cyclone separator is cyclone separator, and effect is：Exhaust gas and adsorbent mixtures enter from side
Into cyclone separator, by cyclonic separation, exhaust gas is discharged into air from cyclone separator top center gas vent, under detaching
The pipeline that adsorbent is connect from cyclone separator bottom with carbon dioxide collection and adsorbent reactivation device enters carbon dioxide
In collection and adsorbent reactivation device.
Use above-mentioned apparatus carry out carbon dioxide catch and regenerate collect method for：
Solid amine absorption agent is put into from adsorbent supply port in carbon dioxide collection and adsorbent reactivation device first, is opened
Gear is rotated, adsorbent is allowed to form cycle in carbon dioxide collection and adsorbent reactivation device.Then water is disguised from steam
The water supply port set is injected into water storage interlayer, and water storage height is no more than the height of water filling port.
Then the flue stack gas from coal-burning power plant or similar place from the flue of water vapourizer top center
Gas entrance is introduced in water vapourizer；The water vapourizer upper table surface length of side can be 200mm ~ 1000mm, the following table length of side
1000mm ~ 2000mm, in water device, the outer wall of water storage interlayer of the flue gas out of this device passes through, and utilizes flue gas
Waste heat heats water, so that water vapor is formed vapor, passes through the dress to recycle flue gas waste heat, vapor and flue gas
It sets the flue gas outlet of lower part and steam outlet enters in flue gas and vapor mixing arrangement.
Into flue gas in vapor mixing arrangement flue gas and vapor ionized first by Gas Ionizer, then
Flue gas and vapor are sufficiently mixed under the action of the device Internal baffle, and then gaseous mixture is mixed by flue gas with vapor
The mixed gas outlet at bottom of device center enters in carbon dioxide collection and adsorbent reactivation device.
Vapor and the gaseous mixture of flue gas are introduced in the upper chamber of carbon dioxide collection and adsorbent reactivation device,
The solid amine absorption agent that carbon dioxide in gaseous mixture is between the sawtooth for rotating gear in the device is adsorbed, and dioxy is removed
Change the flue gas after carbon to be entered in exhaust gas-adsorbent gas-solid separating device by waste gas outlet, a small amount of adsorbent that exhaust gas carries
It is reentered in upper chamber by pipeline after exhaust gas-adsorbent gas-solid separating device separation, pure exhaust gas is by exhaust gas-adsorbent
The pure waste gas outlet 6.1 of gas-solid separating device top center is discharged into air；
By the rotation of carbon dioxide collection and adsorbent reactivation device inward turning rotating disk, the adsorbent quilt after carbon dioxide is adsorbed
It is brought into lower chamber, flue gas is introduced in from the waste gas inlet of bottom under carbon dioxide collection and adsorbent reactivation device
In the flue gas heating interlayer of portion's chamber；It adsorbs the adsorbent after carbon dioxide to be heated by the flue gas in interlayer, releases two
Carbonoxide, the device underflue gas heating interlayer discharge flue gas by pipeline enter in water vapourizer with cigarette therein
Road gas converges, and the carbon dioxide being released enters in carbon dioxide-adsorbent gas-solid separating device, by carbon dioxide-suction
The pure carbon dioxide that attached dose of gas-solid separating device is isolated from the outlet of the pure carbon dioxide of top center, collect by 5.1 discharge, dioxy
Change and upper chamber is reentered by pipeline after a small amount of adsorbent entrained by carbon is detached；Release the absorption of carbon dioxide
Agent follows rotation gear to be again introduced into upper chamber and carries out carbon dioxide adsorption cycle.
Claims (9)
1. a kind of collecting carbonic anhydride and regenerated integrated apparatus, it is characterised in that：Including water vapourizer, flue gas and water
Steam mixer, Gas Ionizer, carbon dioxide collection and adsorbent reactivation device, gas-solid separating device；
The water vapourizer, outside are positive truncated rectangular pyramids structure, and central upper portion is equipped with waste gas inlet, and bottom goes out equipped with flue gas
Mouth and steam outlet, side are equipped with water supply port；In being divided into inside device, in, it is three layers outer, the annular channel of outer layer is flue
The annular channel in gas channel, middle level is aquaporin, and the channel of internal layer is water vapor channel, and waste gas inlet leads directly to flue gas
In channel, water supply port connects aquaporin by pipeline, and steam outlet is equipped in water vapor channel bottom；
Connection flue gas and vapor mixing arrangement below the device；
The flue gas and vapor mixing arrangement, the device are rectangular parallelepiped structure, and the flue gas of top and water vapourizer goes out
Mouth, steam outlet communicate, and bottom centre is equipped with mixed gas outlet；The device is internally provided with baffle, and baffle point multilayer is uniformly put down
Row setting；It is connect with Gas Ionizer on the outside of the device；The inner wall of the device is equipped with insulating layer, to prevent whole device band
Electricity；Connection carbon dioxide collection and adsorbent reactivation device below the device；
The both sides of the carbon dioxide collection and adsorbent reactivation device are separately connected carbon dioxide-cyclone separator and exhaust gas-
The top center of cyclone separator, carbon dioxide-cyclone separator and exhaust gas-cyclone separator is equipped with gas vent, lower end
Side is equipped with adsorbent outlet, and gas feed is equipped with the upper end of adsorbent outlet opposite side；
The carbon dioxide collection and adsorbent reactivation device, are made of upper and lower two chambers, and upper and lower two chambers are by obstructing
Plate separates, and upper chamber is rectangular parallelepiped structure, and lower chamber is semicylinder, semi-cylindrical and the baffler phase of semicylinder
It connects, upper chamber is divided into interlayer and middle layer, and interlayer is insulating layer, and the left side of upper chamber is equipped with adsorbent supply port, top
The right side of chamber is equipped with waste gas outlet, and waste gas outlet connects exhaust gas-cyclone separator；
The left bottom of lower chamber is equipped with carbon dioxide outlet, and carbon dioxide outlet connects carbon dioxide-cyclone separator,
The rotation gear with long sawtooth is equipped in carbon dioxide collection and adsorbent reactivation device, gear shaft is arranged in upper chambers
On the joint face of room and lower chamber, the both ends of gear shaft are fixed on the left and right sides wall of upper chamber and lower chamber, and
Gear shaft is arranged in parallel with baffler, is carried out in carbon dioxide collection and adsorbent reactivation device by gear rotary adsorbent
Cycle；The outside of lower chamber is flue gas heating interlayer, and interlayer bottom centre is equipped with waste gas inlet, and interlayer side is equipped with cigarette
Road gas outlet, the flue gas outlet are connect by pipeline with water vapourizer；
The Gas Ionizer includes discharge electrode and collector, and flue gas is to put with the first layer baffle in vapor mixing arrangement
The baffle of electrode, the other side opposite with discharge electrode is collector.
2. collecting carbonic anhydride according to claim 1 and regenerated integrated apparatus, it is characterised in that：The titanium dioxide
Adsorbent in carbon collection and adsorbent reactivation device is solid amine absorption agent.
3. collecting carbonic anhydride according to claim 1 and regenerated integrated apparatus, it is characterised in that：The insulating layer
For rubber or ceramics.
4. collecting carbonic anhydride according to claim 1 and regenerated integrated apparatus, it is characterised in that：The titanium dioxide
Two pieces of bafflers are equipped between carbon collection and the upper chamber and lower chamber of adsorbent reactivation device, in gear shaft both sides each one
Block, baffler are rectangular slab, are flexible rubber material, and baffler is that activity is arranged close to one end of gear shaft, barrier
The other end of plate is fixed on the inner wall between upper chamber and lower chamber；When gear shaft rotates, baffler activity setting
One end is swung up and down with gear shaft.
5. collecting carbonic anhydride according to claim 1 and regenerated integrated apparatus, it is characterised in that：The titanium dioxide
Rotation gear in carbon collection and adsorbent reactivation device has 2 ~ 4 sawtooth.
6. collecting carbonic anhydride according to claim 1 and regenerated integrated apparatus, it is characterised in that：The titanium dioxide
Carbon-cyclone separator connects carbon dioxide collection and adsorbent reactivation device by pipeline respectively with exhaust gas-cyclone separator.
7. collecting carbonic anhydride according to claim 1 and regenerated integrated apparatus, it is characterised in that：Water vapourizer
The a length of 200mm ~ 1000mm of top sides, a length of 1000mm ~ 2000mm of bottom sides.
8. a kind of collecting carbonic anhydride and regeneration method, using claim 1 ~ 7 any one of them collecting carbonic anhydride and
Regenerated integrated apparatus, it is characterised in that：Include the following steps：
（1）Flue gas is introduced in from the waste gas inlet of water vapourizer top center in water vapourizer；Disguise in steam
In setting, water storage interlayer outer wall of the flue gas out of this device passes through, and is heated to water using flue gas waste heat, makes water vapor shape
At vapor, vapor and flue gas enter flue gas by the flue gas outlet and steam outlet of the device lower part and are steamed with water
In gas mixing arrangement；
（2）It is ionized first by Gas Ionizer into flue gas and the flue gas and vapor of vapor mixing arrangement, in baffle
Under the action of flue gas and vapor be sufficiently mixed, then gaseous mixture passes through flue gas and vapor mixing arrangement bottom centre
Outlet enters carbon dioxide collection and adsorbent reactivation device；
（3）Vapor and the gaseous mixture of flue gas are introduced in the upper chamber of carbon dioxide collection and adsorbent reactivation device
In, the solid amine absorption agent that the carbon dioxide in gaseous mixture is between the sawtooth for rotating gear in the device is adsorbed, and is removed
Flue gas after carbon dioxide enters exhaust gas-cyclone separator by the outlet of waste-gas adsorbant gas-solid mixture, and what exhaust gas carried lacks
Amount adsorbent is reentered in the upper chamber of carbon dioxide collection and adsorbent reactivation device after being detached by pipeline, exhaust gas
Air is discharged by the pure waste gas outlet of exhaust gas-cyclone separator top center；
（4）By the rotation of carbon dioxide collection and adsorbent reactivation device inward turning rotating disk, the absorption after carbon dioxide is adsorbed
Agent is brought into lower chamber, and flue gas is introduced in carbon dioxide collection and adsorbent reactivation from the waste gas inlet of bottom
In the flue gas heating interlayer of device lower chamber；It adsorbs the adsorbent after carbon dioxide to be heated by the flue gas in interlayer, release
Release carbon dioxide, the device underflue gas heating interlayer discharge flue gas by pipeline enter in water vapourizer with its
In flue gas converge, the carbon dioxide come out by carbon emissions carries a small amount of adsorbent and passes through carbon dioxide absorber gas-solid mixing
Object outlet enters carbon dioxide-cyclone separator, and the carbon dioxide isolated is from carbon dioxide-cyclone separator top center
Pure carbon dioxide outlet discharge is collected, and a small amount of adsorbent entrained by carbon dioxide by pipeline reenters dioxy after being detached
In the upper chamber for changing carbon collection and adsorbent reactivation device；The adsorbent for releasing carbon dioxide follows rotation gear again
The circulation absorption of carbon dioxide is carried out into upper chamber.
9. collecting carbonic anhydride according to claim 8 and regeneration method, it is characterised in that：The flue gas carrys out spontaneous combustion
Coal-fired plant, cement kiln factory or coke-oven plant.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113086944A (en) * | 2021-03-31 | 2021-07-09 | 重庆朗福环保科技有限公司 | Carbon dioxide capture and conversion fuel device |
| CN114191933A (en) * | 2021-12-16 | 2022-03-18 | 安徽华塑股份有限公司 | Carbon dioxide capture system of lime kiln |
| CN114225678A (en) * | 2021-11-25 | 2022-03-25 | 浙江涌原新能科技股份有限公司 | Low-carbon treatment device for industrial power supply and distribution system |
| WO2023151355A1 (en) * | 2022-02-09 | 2023-08-17 | 西安热工研究院有限公司 | System and method for continuously capturing carbon dioxide by means of direct air capture |
| CN116870885A (en) * | 2023-06-30 | 2023-10-13 | 贵州绿色产业技术研究院 | Multi-space desorption device and solid amine carbon capture system |
| CN117085456A (en) * | 2023-10-16 | 2023-11-21 | 太原理工大学 | Device and method for capturing flue gas in well |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298023A (en) * | 2008-06-17 | 2008-11-05 | 东南大学 | Device for removing CO2 of flue gas by highly active potassium-base absorbing agent dry method and method thereof |
| CN101325995A (en) * | 2005-08-16 | 2008-12-17 | Co2Crc技术股份有限公司 | Plant and process for removing carbon dioxide from gas streams |
| CN102198360A (en) * | 2011-05-26 | 2011-09-28 | 清华大学 | Process and equipment for removing CO2 in flue gas by utilizing amine solid adsorbent |
| US20120000365A1 (en) * | 2010-06-24 | 2012-01-05 | Seibu-Giken Co., Ltd | Apparatus for removing carbon dioxide from a gas |
| CN102553433A (en) * | 2012-01-20 | 2012-07-11 | 东华大学 | Device and method for removing CO2 in coal-fired flue gas |
| CN105344200A (en) * | 2015-11-09 | 2016-02-24 | 广西桂晟新能源科技有限公司 | Technology for raising capture efficiency of carbon dioxide in flue gas by utilization of water vapor |
| CN105617855A (en) * | 2014-10-27 | 2016-06-01 | 陕西玉航电子有限公司 | Solid-state amine fluidized bed reactor |
| CN106163636A (en) * | 2013-12-31 | 2016-11-23 | 彼得·艾森伯格尔 | For removing CO from air2rotation many materials all in one piece bed mobile system |
-
2018
- 2018-05-03 CN CN201810412872.7A patent/CN108636059B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101325995A (en) * | 2005-08-16 | 2008-12-17 | Co2Crc技术股份有限公司 | Plant and process for removing carbon dioxide from gas streams |
| CN101298023A (en) * | 2008-06-17 | 2008-11-05 | 东南大学 | Device for removing CO2 of flue gas by highly active potassium-base absorbing agent dry method and method thereof |
| US20120000365A1 (en) * | 2010-06-24 | 2012-01-05 | Seibu-Giken Co., Ltd | Apparatus for removing carbon dioxide from a gas |
| CN102198360A (en) * | 2011-05-26 | 2011-09-28 | 清华大学 | Process and equipment for removing CO2 in flue gas by utilizing amine solid adsorbent |
| CN102553433A (en) * | 2012-01-20 | 2012-07-11 | 东华大学 | Device and method for removing CO2 in coal-fired flue gas |
| CN106163636A (en) * | 2013-12-31 | 2016-11-23 | 彼得·艾森伯格尔 | For removing CO from air2rotation many materials all in one piece bed mobile system |
| CN105617855A (en) * | 2014-10-27 | 2016-06-01 | 陕西玉航电子有限公司 | Solid-state amine fluidized bed reactor |
| CN105344200A (en) * | 2015-11-09 | 2016-02-24 | 广西桂晟新能源科技有限公司 | Technology for raising capture efficiency of carbon dioxide in flue gas by utilization of water vapor |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113086944A (en) * | 2021-03-31 | 2021-07-09 | 重庆朗福环保科技有限公司 | Carbon dioxide capture and conversion fuel device |
| CN114225678A (en) * | 2021-11-25 | 2022-03-25 | 浙江涌原新能科技股份有限公司 | Low-carbon treatment device for industrial power supply and distribution system |
| CN114191933A (en) * | 2021-12-16 | 2022-03-18 | 安徽华塑股份有限公司 | Carbon dioxide capture system of lime kiln |
| WO2023151355A1 (en) * | 2022-02-09 | 2023-08-17 | 西安热工研究院有限公司 | System and method for continuously capturing carbon dioxide by means of direct air capture |
| CN116870885A (en) * | 2023-06-30 | 2023-10-13 | 贵州绿色产业技术研究院 | Multi-space desorption device and solid amine carbon capture system |
| CN116870885B (en) * | 2023-06-30 | 2024-03-26 | 贵州绿色产业技术研究院 | Multi-space desorption device and solid amine carbon capture system |
| CN117085456A (en) * | 2023-10-16 | 2023-11-21 | 太原理工大学 | Device and method for capturing flue gas in well |
| CN117085456B (en) * | 2023-10-16 | 2024-01-12 | 太原理工大学 | Device and method for capturing flue gas in well |
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