CN107684811B - A kind of rotary cyclic carbon capturing device and method based on three reactions - Google Patents
A kind of rotary cyclic carbon capturing device and method based on three reactions Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 83
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 31
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 19
- 239000002250 absorbent Substances 0.000 claims abstract description 58
- 230000002745 absorbent Effects 0.000 claims abstract description 57
- 230000004044 response Effects 0.000 claims abstract description 34
- 230000004087 circulation Effects 0.000 claims abstract description 21
- 238000005265 energy consumption Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- 239000003546 flue gas Substances 0.000 claims description 26
- 230000008929 regeneration Effects 0.000 claims description 25
- 238000011069 regeneration method Methods 0.000 claims description 25
- 230000009719 regenerative response Effects 0.000 claims description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 14
- 230000037452 priming Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000012495 reaction gas Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 230000009257 reactivity Effects 0.000 claims description 5
- 238000009423 ventilation Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 238000005242 forging Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 18
- 230000009467 reduction Effects 0.000 abstract description 12
- 239000006096 absorbing agent Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 229910052925 anhydrite Inorganic materials 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000006378 damage Effects 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 33
- 239000000292 calcium oxide Substances 0.000 description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 23
- 239000007787 solid Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 6
- 235000010216 calcium carbonate Nutrition 0.000 description 6
- 239000000306 component Substances 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000002779 inactivation Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
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- 241000196324 Embryophyta Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 reactor Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary reactants
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention belongs to carbon capture technology relevant device fields, more particularly to a kind of rotary continuous cyclic carbon capturing device reacted based on three, it includes rotary shaft and one or more groups of circular response units, every group of circular response unit includes three reactors, reactor is circumferentially arranged side by side and is uniformly distributed in rotary shaft, each inside reactor is respectively provided with cavity for placing absorbent, air inlet is additionally provided at the top of each reactor, bottom is provided with gas outlet, and the air inlet is connected to the cavity of inside reactor with gas outlet.The invention also discloses a kind of methods for carrying out circulation carbon capture using above-mentioned apparatus.The present invention, which solves calcium-base absorbing agent high temperature sintering, leads to hole reduction, SO2Reaction generates CaSO4The advantages that impurity causes the problem of absorption property reduction caused by the reasons such as pore structure destruction, while solving absorbent wear problem, considerably reduces energy consumption, and equipment is compact, has both economy and environment friendly.
Description
Technical field
The invention belongs to carbon capture technology relevant device fields, more particularly, to a kind of rotation reacted based on three
The continuous cyclic carbon capturing device of formula and method.
Background technique
It is well known that the activity of the mankind, such as industrial processes, steam power plant, cement plant, steel mill etc. are formed by dioxy
Changing carbon emission is to cause the main reason of global warming.The CO generated by fossil energy burning2It is total that total amount accounts for about greenhouse gases
82% or so of amount, the concern with countries in the world to Global Greenhouse Effect problem reduce CO2 emission and increasingly cause weight
Depending on, and become the most important measure that people cope with global warming.
The discharge of carbon dioxide gas is reduced it has already been proposed many science and technology.Current existing carbon dioxide
Capture method mainly has O2/CO2Method trapping, pre-combustion capture and three kinds of post-combustion capture, wherein post-combustion capture be using compared with
For universal method.So-called post-combustion capture is divided in flue gas caused by system is burnt in air from primary fuel
From CO2, including pressure-variable adsorption, UF membrane, Physical Absorption and chemical absorbing etc., existing equipment can be directly applied to, is put into
Relatively fewer, principle is simple, applied widely.For example, chemical absorption method is used for CO due to the presence of chemical reaction2When trapping,
Absorbability is strong, and equilibrium partial pressure is low, and sufficiently high mass transfer force can be maintained in absorption process, it can be ensured that high arresting efficiency, tool
There are higher operability and vast market prospect.
Based on flue gas CO after the burning of calcium circularly trapping2Technology is considered as CO after a kind of most promising burning2It catches
One of collection technology.Its working principle is that：Contain low concentration CO2Flue gas be passed through in adsorptive reactor, CaO adsorbent absorb CO2,
Then CaCO is generated3Product is transported in the higher regeneration reactor of another temperature by serial dual fluidized bed system, and CaO inhales
Attached dose is regenerated, while obtaining the CO of high concentration2, and then compress, transport and seal up for safekeeping, and the CaO adsorbent after regenerating is again
It is transported to progress flue gas CO in adsorptive reactor2Trapping.Capture CO is recycled based on calcium2Technology, reaction equation are：It is carbonating
In reactor, CaO+CO2 → CaCO3；In calcination reactor, CaCO3→CaO+CO2。
Studies have shown that the amine of comercial operation washes method absorption CO at present2Cost be 55 $/ton CO2, and calcium circulation is caught
CO after collection burning2Cost be 20 $/ton CO2.And calcium circulating technology also has many technological merits, absorbent raw material
It is wide in earth distribution, it is cheap；Kinetics superior performance, theoretical absorption capacity are high；Without redesigning boiler, only
It only needs to install a carbon capture module additional in tail gas part；Natural pollution-free, absorbent can be used as cement plant, steel after inactivation
The raw material of factory, boiler flue gas desulfurization island, water treatment plant and construction industry, will not generate secondary pollution.
However, further investigations have shown that, which still has following technical problem：(1) calcium-base absorbing agent is multiple
During recycling, absorbent is because high temperature sintering causes the reduction of absorbent specific surface area, and porosity is reduced, and hole is blocked
Deng, and then the activity of absorbent is caused to reduce, absorptive capacity reduces sharply；(2) absorbent needs anti-in carbonation reactor and regeneration
It answers and is shifted between device, calcium-base absorbing agent causes particles collision serious wear because of more crisp, further increases the pressure of dedusting
Power；(3) SO present in flue gas2Competitive reaction can occur with absorbent, due to H2SO4Acidity ratio H2CO3By force, thus absorbent compared with
Easily and SO2And the O in air2Generate the difficult CaSO decomposed4, the aperture of absorbent is blocked, the pore structure of absorbent is destroyed.
Since there are drawbacks described above and deficiency, this field needs to make and further improve, preferably to send out
Wave Ca-base adsorbent circularly trapping CO2The advantage of technology.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of cyclic carbons of rotary packed bed to catch
Acquisition means and method, wherein the reduction of calcium-base absorbing agent hole, serious wear etc. lead to its adsorption capacity when combining circulation carbon capture
The characteristics of reduction, accordingly devise it is a kind of carry out cyclic carbon capture method and equipment using rotary packed bed, and by circulation
Each process involved in carbon capture and as the specific of the components such as reactor, air inlet/outlet in the capturing device of key component
Structure, arrangement etc. are studied and are designed, and accordingly can effectively solve the reduction of calcium-base absorbing agent hole leads to active drop
Low, serious wear, SO2 reaction generate the problem of absorption property caused by the reasons such as impurity reduces, and improve W-response rate, together
When have many advantages, such as equipment it is compact, have both economy and environment friendly, be therefore particularly suitable for the trapping of carbon dioxide.
To achieve the above object, according to one aspect of the present invention, a kind of cyclic carbon with rotary packed bed is provided
Capturing device, which is characterized in that it includes a vertical rotary shaft, and around one or more groups of the following of rotary shaft setting
Ring reaction member, wherein：
Circular response unit described in every group includes three reactors, and the reactor is circumferentially arranged side by side in rotary shaft,
And be uniformly distributed, each inside reactor is respectively provided with cavity for placing absorbent, at the top of each reactor
It is additionally provided with air inlet, bottom is provided with gas outlet, and the air inlet and gas outlet connect with the cavity of inside reactor
Logical, rotary shaft rotation drives above-mentioned reactor to turn to different operating positions, and the air inlet introduces different reaction gas,
It is discharged after being reacted in reactor through gas outlet.
Specifically, rotary continuous cyclic carbon capturing device, by three carbon captures as system core component
The concrete composition structure and its set-up mode of recirculation reactor group are designed, and drive three reactors using the rotary shaft at center
Rotation, each reactor is arranged in parallel, and under the rotation of central axis, is passed through differential responses gas, realizes carbonation reactor, regeneration
The function of reactor and absorbent activated reactor is rotated vertical after the reactor being connected in parallel to each other executes corresponding function by center
Axis drives three reactor rotations to realize successively and alternately replaces；Fixing packed bed design, avoids absorbent and occurs because of collision
Abrasion, it is not necessary to gas solid separation be carried out by cyclone separator, also avoid the short grained generation of PM2.5, and then fill without dedusting
It sets；The components such as transfer and cyclone separator without material, system run all right, and the device integrate absorption system, equipment
It is compact, the advantages that having both economy and environment friendly.
It is further preferred that the multiple groups circular response unit is along rotary shaft longitudinal direction when circular response unit is multiple groups
It sets gradually or is circumferentially uniformly set gradually along rotary shaft, and be separately provided between circular response unit described in each group.It will follow
The quantity and structure of ring reaction member are set in the manner described above, can satisfy the trapping of the cyclic carbon of different demands, and
It is respectively independently arranged, facilitates individually operated and management.
Preferably, the reactor is fan-shaped column structure.By setting fan-shaped column structure for reactor, can make anti-
Device is answered to collectively form cylindrical structure, so that the more compact structure of the cyclic carbon capturing device.
Other side according to the invention proposes a kind of method of continuous circulation carbon capture reacted based on three,
It is characterized in that, it uses cyclic carbon capturing device as described above, described this method specifically includes following steps：
S1 places absorbent CaO for any one reactor in every group of circular response unit in internal cavities, into
Port is passed through flue gas, the absorbent CaO in the reactor and the CO in flue gas2Carbonation reaction occurs and produces calcium carbonate, from anti-
The gas outlet of device bottom is answered to be discharged without CO2Flue gas；
S2 rotates rotary shaft, and the reactor after carbonation reaction goes to subsequent work position, at this time anti-
It answers and is passed through O in the air inlet of device2And water vapour, it by calcination and regeneration is CaO by calcium carbonate, gas after reaction is from bottom outlet
Mouth discharge；
S3 rotates the reactor after regenerative response to subsequent work position, and the air inlet of the reactor is passed through at this time
Activated media, the activated media pass through reactor at high temperature, enhance the reactivity of CaO absorbent, then through bottom
Gas outlet discharge；
The sequence circulation that each reactor of S4 presses step S1-S3 carries out carbonation reaction, regenerative response and priming reaction,
And above-mentioned reaction carries out simultaneously in three reactors of every group of circular response unit, and as the rotary shaft constantly rotates, institute
State reactor in circular response unit successively alternately above-mentioned carbonating, regeneration and priming reaction.
The sequence circulation that each reactor of S4 presses step S1-S3 carries out carbonation reaction, regenerative response and priming reaction,
And above-mentioned reaction carries out simultaneously in three reactors of every group of circular response unit, and as the rotary shaft constantly rotates, institute
State the reactor successively alternately above-mentioned reaction in circular response unit.
Specifically, this method cooperates by the rotation of three reactors in circular response unit and is passed through different reaction gas
Body can circuit sequentially realization carbonation reactor, the function of regeneration reactor and absorbent activated reactor, and pass through
This method can reduce the temperature and energy consumption of regenerative response, slow down the inactivation of absorbent at high temperature, after improving its multiple circulation
Absorption efficiency, prolong its service life；And solid absorbent and reaction product are held in relatively-stationary space, i.e.,
CO2Absorption and desorption process can carry out in situ, accordingly can eliminate from the root what solid particle occurred because mutually colliding
Abrasion, can significantly improve W-response efficiency compared with existing continuous carbon Trapping ways, and the circulation for greatly improving absorbent is living
Property, eliminate the abrasion that solid sorbent particles occur by collision；And the progress of priming reaction then enables to absorbent to be destroyed
Pore structure be switched on again, to further increase the reactivity of absorbent.
It is further preferred that in step sl, the reaction temperature when reactor carries out carbonation reaction is 650 DEG C-
700℃；In step s 2,750 DEG C -800 DEG C of running temperature when the reactor progress regenerative response；In step s3, institute
State 700 DEG C -750 DEG C of running temperature when reactor carries out priming reaction.
Above-mentioned selected reaction temperature can matched well three reactors in parallel execute respective functions, and by close etc.
The reaction condition of temperature, makes three road parallel reactors run (temperature difference of three reactors is less than 150 DEG C) under nearly isothermy, greatly
Amplitude greatly reduces energy consumption caused by the not isothermal temperature difference of system lower than the reactor temperature difference (being greater than 300 DEG C) of common calcium circulation；
Carbonating is exothermic reaction, and each functioning reactor executes corresponding function in the identical position of correspondence, can be abundant
Utilize this partial heat.Compared with traditional more energy efficient environmental protection of interconnected fluidized bed reactor, the cascade utilization of thermal energy may be implemented.And
The activation temperature of activated reactor is set as between carbonation reactor and regeneration reactor；Energy consumption can be reduced, is activated simultaneously
Absorbent.
Preferably, in step sl, when carrying out carbonation reaction, the reactor provides positive pressure by supercharging device.?
In carbonation reaction, improves pressure and be conducive to carbonation reaction to positive reaction progress, that is, be conducive to the production of calcium carbonate.Moreover,
Improve the temperature of carbonation reaction by increasing pressure, while by reducing regeneration temperature, it can be achieved that differential responses process
Nearly isothermal, to achieve the purpose that the dissipation for reducing heat when switching between not isothermal furnace body.In addition, in carbonation reaction
In, due to increasing with temperature, the equilibrium partial pressure of CO2 is also increased, when equilibrium partial pressure be higher than practical flue gas CO2 partial pressure when
It waits, reaction will be carried out to back reaction, and CaCO3 is caused to decompose.Therefore, it by adjusting pressure size, may be implemented between reactor
Carbonation reaction rate and regenerative response between rate-matched.
Preferably, in step sl, when carrying out carbonation reaction, it is complete as the Control of chemical reaction stage to set its reaction time
At the time.This is because CaO and CO2Reaction by very short Control of chemical reaction stage and veryer long product layer diffusion control
Stage composition processed, when calcium oxide reaches a critical product layer thickness, the reduction of gas-solid reaction rate sharply.
Preferably, in step s 2, the air inlet is passed through O2Gaseous fuel, the gas are also passed through while with water vapour
Fluid fuel carries out oxygen-enriched combusting and discharges heat.It is passed through oxygen and vapor is conducive to the quick progress of regenerative response, and regenerate anti-
Institute's calorific requirement in device is answered to be provided by oxygen-enriched combusting mode, fuel heat release in burning also provides temperature condition for regenerative response.
Preferably, in step s 2, when carrying out regenerative response, the reactor provides negative pressure by negative pressure ventilation device.
In regeneration reactor, since temperature has a great impact to absorbent calcining and decomposing rate, when temperature increases, decomposition rate is anxious
Acute increase, but absorbent is easy to happen serious sintering in the high temperature environment and causes to absorb active reduction.It thus proposes logical
Setting subnormal ambient is crossed, conducive to the progress of calcining, while the regeneration temperature of regeneration reactor is reduced, slows down the inactivation of absorbent.
Preferably, in step s 2, the gas that regenerative response generates is high concentration CO2, condensed collection.By will be high
Concentration C O2Condensation collection is carried out, it can be achieved that it is recycled.
Preferably, in step s3, the activated media is HBr steam or water vapour, is purged using spray head mode.
The activated medias such as vapor have a great impact to the circulation activity of absorbent, and vapor can be improved the absorption of calcium-base absorbing agent
Activity and cyclical stability, but it is obvious that the mechanical strength of absorbent is declined；Using this filled type fixed-bed design, benefit
With the activation effect of vapor, while avoiding being mutually displaced for absorbent and causing broken and wear.Steam activation not only mentions
The circulation activity of high-selenium corn agent, and SO can be mitigated2Destruction to calcium-base absorbing agent.SO2With CaO and O2Reaction, shape
The CaSO decomposed at hardly possible4, CaSO4Molal volume ratio CaO, Ca (OH)2,CaCO3It is all big, so that CaO hole is blocked, cause to live
Property decline.Vapor makes absorbent aperture again, CO2Still it can participate in reacting with kernel CaO.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, have the following advantages that and
Beneficial effect：
(1) reduction of calcium-base absorbing agent hole, serious wear etc. lead to its adsorption capacity when the present invention combines circulation carbon capture
The characteristics of reduction, accordingly devise it is a kind of carry out cyclic carbon capture method and equipment using cyclic pac king bed, and by circulation
Each process involved in carbon capture and as the specific of the components such as reactor, air inlet/outlet in the capturing device of key component
Structure, arrangement etc. are studied and are designed, and accordingly can effectively solve the reduction of calcium-base absorbing agent hole leads to active drop
Low, serious wear, SO2 reaction generate the problem of absorption property caused by the reasons such as impurity reduces, and improve W-response rate, together
When have many advantages, such as equipment it is compact, have both economy and environment friendly, be therefore particularly suitable for the trapping of carbon dioxide.
(2) this method is cooperated by the rotation of three reactors in circular response unit and is passed through different reaction gas, made
It can circuit sequentially realization carbonation reactor, the function of regeneration reactor and absorbent activated reactor, in this way,
The temperature and energy consumption that can reduce regenerative response slow down the inactivation of absorbent at high temperature, improve its absorption after repeatedly recycling
Efficiency prolongs its service life, and reduces production cost.
(3) rotary shaft of the present invention drives three reactor rotations, is held in solid absorbent and reaction product relatively
In fixed space namely CO2Absorption and desorption process can carry out in situ, can accordingly eliminate from the root solid particle because
The abrasion mutually collided and occurred, W-response efficiency can be significantly improved compared with existing continuous carbon Trapping ways, is mentioned significantly
The circulation activity of high-selenium corn agent, eliminates the abrasion that solid sorbent particles occur by collision.And without going through cyclone separator
Gas solid separation is carried out, also avoids the short grained generation of PM2.5, and then be not necessarily to dust-extraction unit；Transfer and rotation without material
The components such as wind separator, system run all right.
(4) present invention uses steam activation, not only improves the circulation activity of absorbent, but also can mitigate SO2To calcium
The destruction of base absorbant.SO2With CaO and O2Reaction forms the difficult CaSO decomposed4, CaSO4Molal volume ratio CaO, Ca
(OH)2,CaCO3It is all big, so that CaO hole is blocked, cause active decline.And vapor makes absorbent in priming reaction
Again aperture, CO2Still it can participate in reacting with kernel CaO.The Life cycle of entire absorbent obtains good utilization,
Absorbent after inactivation can be used as the absorbent of SO2 trapping, can also be used as the raw material of cement industry, well recycling.
(5) present invention run three road parallel reactors under nearly isothermy (temperature difference of three reactors is less than 150
DEG C), significantly lower than the reactor temperature difference of common calcium circulation (being greater than 300 DEG C), substantially reducing reduces the system not isothermal temperature difference
Caused by energy consumption, improve the economic performance of system, realize the cascade utilization of thermal energy.And the activation temperature of activated reactor is set as
Between carbonation reactor and regeneration reactor；Energy consumption, while activated absorption agent can be reduced.
Preferably optimal reaction temperature and time are chosen in each reaction, make full use of the dynamics Controlling rank of absorbent
Section reduces SO2To the destroying infection of absorbent pore structure；Pass through the matched carbonating of setting efficiency, regeneration and activation rank
Section realizes that the ladder of energy utilizes using the exothermic heat of reaction of carbonating and the heat release of activation stage.
(6) reaction gas circuit of the invention switching smoothly, can make flue gas CO2Purifying；Regeneration reactor is vented through being subcooled
After solidifying, almost pure CO can be obtained2Gas can carry out resource utilization or seal up for safekeeping.And the device of the invention be easy to
Existing flue gas desulfurization device combines, and constructs " desulfurization-carbon dioxide fixation " integrated apparatus.Also there is facility compact；Convenient for mould
The advantages of blockization is installed is suitble to large-scale promotion to use.
Detailed description of the invention
Fig. 1 is to be illustrated in the prior art based on absorbent lime agent flue gas carbon capture circulating fluidized bed system main structure
Figure；
Fig. 2 is according to three bed reactor system of parallel connection constructed by the preferred embodiment for the present invention.
In all the appended drawings, identical appended drawing reference is used to denote the same element or structure, wherein：
1- rotary shaft, 2- reactor, 3- air inlet, the gas outlet 4-, 5- circular response unit, A- flue gas, B- heat, C- without
CO2Tail gas, the high-purity CO of D-2, M- carbonation reactor, N- regeneration reactor, O- flue gas, P- activated media, Q- heat, O2/
H2O, X- are without CO2Tail gas, Y- discharge activated media, Z-CO2/H2O。
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Fig. 1 shows the main structure signal of the alternating temperature carbon capture fluidized system based on solid absorbent in the prior art
Figure.As shown in fig. 1, in this traditional serial double-fluidized-bed reactor, carbonation reactor and regeneration reactor are all point
The different location set in response path is opened up, solid absorbent must be constantly subjected to displacement along response path, because of mutually collision
And the abrasion or reduction ratio occurred is more serious, directly influences whole reaction efficiency；And following for this traditional process
For loop device, absorption and the temperature difference of desorption reaction between the two are often larger, are such as about using the absorption of CaO and the desorption temperature difference
350 DEG C, be about 250 DEG C, etc. using the absorption and the desorption temperature difference of MgO.
Fig. 2 is according to the continuous cyclic carbon trapping system reacted constructed by the preferred embodiment for the present invention based on three
Agent structure schematic diagram.It includes a vertical rotary shaft 1, and around one or more groups of circulations of the rotary shaft 1 setting
Reaction member 5, wherein：
Circular response unit 5 described in every group includes three reactors 2, and the reactor 2 is circumferentially set in rotary shaft 1 side by side
It sets, and is uniformly distributed, cavity is respectively provided with inside each reactor 2 for placing absorbent, in each reactor 2
Top is additionally provided with air inlet 3, and bottom is provided with gas outlet 4, and the air inlet 3 is with gas outlet 4 and inside reactor 2
Cavity connection, the rotation of above-mentioned rotary shaft 1 drives above-mentioned reactor 2 to turn to different operating positions, and the air inlet 3 introduces
Different reaction gas is discharged after reacting in reactor 2 through gas outlet 4, and the reactor 2 is fan-shaped column structure.
Carbonation reactor air inlet is flue gas after burning, and regeneration reactor air inlet is preferably O2/H2O steam, activated reactor
Air inlet is preferably H2O steam.By top-down mode, gas circuit is by O, and P, Q are each led into each reactor, after reaction
Gas is drawn by X, Y, Z；Also, it is connected with negative pressure ventilation device with regeneration reactor, and is mutually reelected with carbonation reactor
Selecting property is provided with supercharging device.Contained CO2After being absorbed, flue gas can discharge atmosphere；And H after regeneration reactor2O/
CO2Mixed gas obtains almost pure CO by condensation2Utilization can be trapped or sealed up for safekeeping.
The present invention also provides a kind of methods of continuous circulation carbon capture reacted based on three, which is characterized in that it is adopted
With rotary cyclic carbon capturing device as described above, described this method specifically includes following steps：
S1 places absorbent CaO for any one reactor in every group of circular response unit in internal cavities, into
Port is passed through flue gas, the absorbent CaO in the reactor and the CO in flue gas2Carbonation reaction occurs and produces calcium carbonate, from anti-
The gas outlet of device bottom is answered to be discharged without CO2Flue gas；
S2 rotates rotary shaft, and the reactor after carbonation reaction goes to subsequent work position, at this time anti-
It answers and is passed through O in the air inlet of device2And water vapour, it by calcination and regeneration is CaO by calcium carbonate, gas after reaction is from bottom outlet
Mouth discharge；
S3 rotates the reactor after regenerative response to subsequent work position, and the air inlet of the reactor is passed through at this time
Activated media, the activated media pass through reactor at high temperature, enhance the reactivity of CaO absorbent, then through bottom
Gas outlet discharge；
The sequence circulation that each reactor of S4 presses step S1-S3 carries out carbonation reaction, regenerative response and priming reaction,
And above-mentioned reaction carries out simultaneously in three reactors of every group of circular response unit, and as the rotary shaft constantly rotates, institute
State reactor in circular response unit successively alternately above-mentioned carbonating, regeneration and priming reaction.
In one particular embodiment of the present invention, in step sl, anti-when the reactor progress carbonation reaction
Answering temperature is 650 DEG C -700 DEG C；In step s 2,750 DEG C -800 DEG C of running temperature when the reactor progress regenerative response；
In step s3,700 DEG C -750 DEG C of running temperature when the reactor progress priming reaction.
In another specific embodiment of the invention, in step sl, when carrying out carbonation reaction, the reactor is logical
It crosses supercharging device and positive pressure is provided.
In another specific embodiment of the invention, in step s 2, the air inlet is passed through O2It is same with water vapour
When be also passed through gaseous fuel, the gaseous fuel carries out oxygen-enriched combusting and discharges heat.
In another specific embodiment of the invention, in step s 2, when carrying out regenerative response, the reactor passes through
Negative pressure ventilation device provides negative pressure.
In another specific embodiment of the invention, in step s 2, the gas that regenerative response generates is high concentration
CO2, condensed collection.
In another specific embodiment of the invention, in step s3, the activated media is that HBr steam or water steam
Vapour is purged using spray head mode.
To sum up, characteristic of the invention is：The first, the CO of solid absorbent2It absorbs and regenerative process carries out in situ,
Solid particle is eliminated from the root because colliding and the abrasion of generation, enables the device to utilize cheap wearability well
Very poor alkali and alkaline earth metal ions oxide carries out CO2Trapping；The second, flue gas first passes through increasing before entering adsorptive reactor
Add blower to be pressurized, improves adsorption reaction rate；Setting air-introduced machine is exported in regeneration reactor and takes out negative pressure, improves desorption reaction
The effect of efficiency, this targeted design can reach further transformation enhancing adsorption-desorption；Third reduces regenerative response temperature
Degree slows down the high temperature sintering of absorbent；4th, nearly isothermal system reduces the not isothermal temperature difference energy consumption of system.5th, device utilizes
The packed bed of rotation designs, optimization system structure, facility compact；Convenient for modularization installation；6th, regeneration reactor is set, it is excellent
Change the circular response activity of absorbent.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (6)
1. a kind of rotary cyclic carbon capturing device, which is characterized in that it includes a vertical rotary shaft (1), and is surrounded
One or more groups of circular response units (5) of the rotary shaft (1) setting, wherein：
Circular response unit (5) described in every group includes three reactors (2), and the reactor (2) is circumferential side by side in rotary shaft (1)
Setting, and be uniformly distributed, cavity is respectively provided with inside each reactor (2) for placing absorbent CaO, each described anti-
The top of device (2) is answered to be additionally provided with air inlet (3), bottom is provided with gas outlet (4), the air inlet (3) and gas outlet
(4) cavity internal with reactor (2) is connected to, and it is different that above-mentioned rotary shaft (1) rotation drives above-mentioned reactor (2) to turn to
Operating position, the air inlet (3) introduce different reaction gas, are discharged after reaction through gas outlet (4) in reactor (2)；
The air inlet of each reactor (2) passes first into flue gas, the absorbent CaO in reactor and the CO in flue gas2It carbonates
Reaction generates calcium carbonate, and reaction temperature is 650 DEG C -700 DEG C, and reactor provides positive pressure by supercharging device when carbonation reaction；
Reactor after carbonation reaction goes to subsequent work position, is passed through O from air inlet2, water vapour and gaseous fuel, carry out
Regenerative response makes calcium carbonate be regenerated as CaO, and reactor provides negative pressure by negative pressure ventilation device when regenerative response, and carries out oxygen-enriched
Burning, reaction temperature are 750 DEG C -800 DEG C；Reactor after regenerative response is rotated to subsequent work position, from air inlet
It is passed through activated media and carries out priming reaction, to enhance the reactivity of CaO absorbent, reaction temperature is 700 DEG C -750 DEG C；Three
Reactor is run under nearly isothermy, and the temperature difference reduces energy consumption caused by the not isothermal temperature difference, realize the ladder of thermal energy less than 150 DEG C
Grade utilizes.
2. rotary cyclic carbon capturing device as described in claim 1, which is characterized in that when circular response unit (5) is more
When group, the multiple groups circular response unit (5) longitudinally sets gradually or circumferential uniformly successively along rotary shaft (1) along rotary shaft (1)
Setting, and be separately provided between circular response unit (5) described in each group.
3. rotary cyclic carbon capturing device as claimed in claim 1 or 2, which is characterized in that the reactor (2) is sector
Column structure.
4. a kind of method for the continuous circulation carbon capture reacted based on three, which is characterized in that it uses claim 1-3 such as to appoint
Rotary cyclic carbon capturing device, described this method described in one specifically include following steps：
S1 places absorbent CaO, in air inlet for any one reactor in every group of circular response unit in internal cavities
It is passed through flue gas, the absorbent CaO in the reactor and the CO in flue gas2Carbonation reaction occurs and produces calcium carbonate, from reactor
The gas outlet of bottom is discharged without CO2Flue gas, reaction temperature is 650 DEG C -700 DEG C, and reactor passes through pressurization when carbonation reaction
Device provides positive pressure；
S2 rotates rotary shaft, and the reactor after carbonation reaction goes to subsequent work position, at this time in reactor
Air inlet in be passed through O2, water vapour and gaseous fuel, gaseous fuel carries out oxygen-enriched combusting and discharges heat, by calcium carbonate by forging
Burning is regenerated as CaO, and the gas after reaction is discharged from bottom gas outlet, and reaction temperature is 750 DEG C -800 DEG C, and when regenerative response reacts
Device provides negative pressure by negative pressure ventilation device；
S3 rotates the reactor after regenerative response to subsequent work position, and the air inlet of the reactor is passed through activation at this time
Medium, the activated media pass through reactor at high temperature, enhance the reactivity of CaO absorbent, then through the outlet of bottom
Mouth discharge, reaction temperature are 700 DEG C -750 DEG C；
The sequence that each reactor of S4 presses step S1-S3, which recycles, carries out carbonation reaction, regenerative response and priming reaction, and on
Reaction is stated in three reactors of every group of circular response unit while being carried out, it is described to follow as the rotary shaft constantly rotates
Reactor in ring reaction member successively alternately above-mentioned carbonating, regeneration and priming reaction.
5. method as claimed in claim 4, which is characterized in that in step s 2, the gas that regenerative response generates is high concentration
CO2, condensed collection.
6. method as claimed in claim 4, which is characterized in that in step s3, the activated media is that HBr steam or water steam
Vapour is purged using spray head mode.
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| CN113697841B (en) * | 2020-05-21 | 2023-06-02 | 江西理工大学 | Method for preparing rare earth oxide by low-temperature decomposition method |
| CN111729470B (en) * | 2020-07-03 | 2021-12-31 | 东北大学 | CO for purifying metallurgical waste gas2Cyclic capture system and method |
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| CN1336846A (en) * | 1999-10-20 | 2002-02-20 | 阿尔斯通电力株式会社 | Regenerative type carbon dioxide separator and carbon dioxide separating system |
| JP2009138186A (en) * | 2007-11-14 | 2009-06-25 | Ihi Corp | Method and apparatus for co2 recovery and gasification |
| CN107057797A (en) * | 2017-03-28 | 2017-08-18 | 大连理工大学 | A kind of composite oxygen carrier, preparation method and its application in solid fuel gasification |
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| CN1336846A (en) * | 1999-10-20 | 2002-02-20 | 阿尔斯通电力株式会社 | Regenerative type carbon dioxide separator and carbon dioxide separating system |
| JP2009138186A (en) * | 2007-11-14 | 2009-06-25 | Ihi Corp | Method and apparatus for co2 recovery and gasification |
| CN107057797A (en) * | 2017-03-28 | 2017-08-18 | 大连理工大学 | A kind of composite oxygen carrier, preparation method and its application in solid fuel gasification |
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