CN103055659A - System and method for capturing carbon dioxide in flue gas - Google Patents
System and method for capturing carbon dioxide in flue gas Download PDFInfo
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- CN103055659A CN103055659A CN2012105729644A CN201210572964A CN103055659A CN 103055659 A CN103055659 A CN 103055659A CN 2012105729644 A CN2012105729644 A CN 2012105729644A CN 201210572964 A CN201210572964 A CN 201210572964A CN 103055659 A CN103055659 A CN 103055659A
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Abstract
The invention relates to a system and a method for capturing carbon dioxide in flue gas. The method comprises a first step of gas adsorption and a second step of gas desorption. The system comprises a multilayer pressure swing adsorption apparatus. The multilayer pressure swing adsorption apparatus contains at least one adsorption bed; each adsorption bed contains at least a steam adsorption layer and at least a carbon dioxide adsorption layer, wherein the steam adsorption layer is arranged below the carbon dioxide adsorption layer, and the flue gas is allowed to pass through the steam adsorption layer first and the carbon dioxide adsorption layer next. With the system and the method for capturing carbon dioxide in the flue gas provided by the invention, steam in the flue gas is removed while carbon dioxide is being separated from the flue gas. The invention has the following advantage: since steam can be removed during capturing of carbon dioxide without additional arrangement of a drying device in advance in the method, cost for pressure swing adsorption and capture of carbon dioxide is substantially reduced.
Description
Technical field
The present invention relates to a kind of system and method that captures carbon dioxide in flue gas, relate in particular to a kind of system and method that utilizes the multi-layer vacuum pressure swing adsorption to capture the high humidify carbon dioxide in the flue gas.
Background technology
Pressure-variable adsorption separating-purifying CO
2Technology can be from the multiple CO that contains
2Source of the gas in catch purification CO
2, satisfy CO
2Multiple industrial use.Have the advantages such as energy consumption is low, the adsorbent life cycle is long, technological process is simple, automaticity is high, environmental benefit is good, pollution-free generation.
About utilizing Vacuum Pressure Swing Adsorption to capture CO
2The selection of adsorbent in the technology, at present the most frequently used also is that the adsorbent that has advantage most is the 13X zeolite molecular sieve.But present great majority research nearly all concentrates on and supposes that industrial waste gas is under the prerequisite of dry gas.
But contain the impurity such as saturated steam, trace sulfide, nitride and particle about 10% in the real flue gas.
Yet, as 13X adsorbent bed (〉 5%H when containing high wet flue gas
2O), 13X adsorption capacity can greatly reduce.
Traditional method is to utilize drying equipment to remove saturated steam in the flue gas before waste gas is by adsorbent bed, and the steam treatment amount of high humidity is very large, the timely activation of drier and to upgrade also be problem, and this also can greatly increase and captures CO
2Cost.
The application for a patent for invention Publication Specification of Chinese patent application numbers 200680033169.0 discloses, a kind of method of purification of carbon dioxide, the method comprises: make the low-purity air-flow that will process by at least one adsorbent bed, described adsorbent bed contains the two-layer at least following adsorption layer that is selected from: the zeolite of drier, zeolite or its ion exchange form and activated carbon.But the method has included only the gas absorption step, and this gas absorption step absorption is other foreign gas rather than carbon dioxide.
At present, great majority also only limit to the research of trace level in the air purification system (ppm level) saturated steam content about the research of multilayer pressure-variable adsorption removal steam, and in the present invention, the content of steam is between 520% in the flue gas of use.Summary of the invention
The technical problem to be solved in the present invention is to utilize the principle of multilayer pressure-variable adsorption, holds back steam in the flue gas with the adsorbent of strongly hydrophilic and easily desorb first in same adsorbent bed, protects main CO
2Adsorption layer.CO
2Adsorption layer is selected for CO
2Has the adsorbent of high adsorptive selectivity.Finally reach only with cover adsorbent equipment while Separation of Water steam and a CO
2, realize that finally high concentration captures CO
2Method.
The present invention includes the following step:
(1) airintake direction of adsorbent equipment design is for from the bottom up, and flue gas is just flow to by the adsorbent bed below, and the waste gas that is not adsorbed (mainly containing nitrogen) is flowed out by the adsorbent bed top.
(2) direction of desorb is desorbed the CO that gets off for from top to bottom
2And H
2O and a small amount of N
2Flowed out by the adsorbent bed below.
The concentrated carbon dioxide of (3) resolving from adsorbent bed is depressurized device and throws products pot into.
Wherein, humidity sensor is installed in the porch, lower end of adsorbent bed, monitoring air inlet and be desorbed the humidity of gas, among the present invention in the flue gas volumetric concentration of steam be 5-20%.
CO in the variable concentrations scope
2Concentration sensor is mounted respectively at the air inlet place, the gas outlet is located and the products pot place, monitors at any time CO in air inlet, waste gas and the gas product
2Instantaneous concentration.CO in the flue gas wherein
2Shared percent by volume is 5-30%
Temperature sensor, current meter and pressure sensor are installed in respectively the force value of gas temperature, flow velocity and the gas under the different cycling conditions of monitoring in the different unit.Wherein the temperature of flue gas is 20-150 ° of C, and charge flow rate is 50-500L/min, and the absolute pressure value of moving within the malleation scope of transformation operation is 100-300kPa, and the absolute pressure value of moving within range of negative pressure of transformation operation is 1-100kPa.
Obtain the negative pressure of desorb by decompressor.
In order to realize the cycling of various steps, pneumatic changeover valve has been installed respectively all at adsorbent bed two.Closure by the conversion valve under the programme-control can realize the mutual conversion between the different operating step.
Operation sequence is by the control of GEFANUC PLC operating system, and the computer display interface is controlled by Citect/SCADA.
Absorbent material among the present invention is selected from activated alumina, active oxidation silica-alumina material, silica gel and combination thereof.
It inhales CO among the present invention
2Sorbing material be selected from 13X zeolite molecular sieve, LiX zeolite molecular sieve, CaX zeolite molecular sieve, active carbon, metal organic frame class material (MOF), hydrotalcite-like material (Hydrotalcite-like compounds) and combination thereof.
The specific area of adsorbent, pore volume and pore size all pass through adsorption tester ASAP2010(Micromeritics, USA among the present invention) (77K) mensuration under liquid nitrogen temperature.Before the test, sample activates 12h under 350 ° of C vacuum conditions, removes steam and other impurity of adsorbing before the sample, guarantees that the aperture of the front sample of test is clean.The BET method is used to calculation sample at P/P
oBe the specific area S under 0.05 –, 0.25 condition
BETBe used to the pore size distribution of calculation sample based on Density Functional Theory (DFT) model of aperture set factor.
Flue gas is at first passed through at least one deck absorbent material layer, then passes through at least one deck suction CO
2Material layer.
Adsorbent equipment is according to two steps, three steps, four step rule, six steps or the operation of nine footworks among the present invention.
The capture of carbon dioxide occurs in after flue gas dedusting and the desulphurization denitration among the present invention.
CO in place, the terminal gas outlet of the adsorbent bed waste gas among the present invention
2Concentration range is at percent by volume 0.1-10%.
It is as follows that a kind of method that captures carbon dioxide in flue gas provided by the invention and the decorum comprise following technical scheme:
(1) a kind of method that captures carbon dioxide in flue gas comprises gas absorption step and gas desorption procedure; Described gas absorption step is that flue gas is passed through the multilayer pressure-swing absorption apparatus, in the adsorbent bed of described multilayer pressure-swing absorption apparatus steam and carbon dioxide are adsorbed on the adsorption layer, and the waste gas that is not adsorbed flows out described adsorbent bed; Described gas desorption step is that the pressure that reduces in the described adsorbent bed makes carbon dioxide desorb from adsorption layer.
(2) according to (1) described method, realize reducing pressure in the described adsorbent bed by decompressor.
(3) according to each described method of (1)-(2), described multilayer pressure-swing absorption apparatus contains at least one adsorbent bed, and each adsorbent bed contains at least one deck water vapor adsorption layer and at least one deck carbon dioxide adsorption layer; Flue gas is first by the water vapor adsorption layer, then by the carbon dioxide adsorption layer.
(4) according to each described method of (1)-(3), described water vapor adsorption layer contains absorbent material, is selected from activated alumina, active oxidation silica-alumina material, silica gel and combination thereof; Described carbon dioxide adsorption layer contains sorbing material, is selected from 13X zeolite molecular sieve, LiX zeolite molecular sieve, CaX zeolite molecular sieve, active carbon, metal organic frame class material, hydrotalcite-like material and combination thereof.
(5) according to each described method of (1)-(4), the airintake direction of described multilayer pressure-swing absorption apparatus is for from the bottom up, and flue gas is flow to by the adsorbent bed below, and the waste gas that is not adsorbed is flowed out by the adsorbent bed top; The direction of desorb is for from top to bottom, and the gas that is desorbed is out flowed out by the adsorbent bed below.
(6) according to (1)-(5) each described methods, after the gas absorption step, before the gas desorption step, also comprise the gas product rinsing step.
(7) according to each described method of (1)-(6), described multilayer pressure-swing absorption apparatus contains at least two adsorbent beds, and an adsorbent bed carries out gas absorption step or gas desorption step, and other adsorbent bed carries out pressure equalization step.
(8) according to (1)-(7) each described methods, described flue gas contains the carbon dioxide that accounts for cumulative volume 5-30% and the steam of 5-20%; The temperature of described flue gas is 20-150 ° of C, and flow is 50-500L/min.
(9) according to each described method of (1)-(8), before the gas absorption step, also comprise flue gas dust removal step and desulphurization denitration step.
(10) according to each described method of (1)-(9), the transformation operation is to move within the malleation scope, and its absolute pressure value is 100-300kPa.
(11) according to each described method of (1)-(10), the transformation operation is to move within range of negative pressure, and its absolute pressure value is 1-100kPa.
(12) a kind of system that captures carbon dioxide in flue gas comprises the multilayer pressure-swing absorption apparatus, and described multilayer pressure-swing absorption apparatus contains at least one adsorbent bed, and each adsorbent bed contains at least one deck water vapor adsorption layer and at least one deck carbon dioxide adsorption layer; Described water vapor adsorption layer makes flue gas first by the water vapor adsorption layer, then by the carbon dioxide adsorption layer below described carbon dioxide adsorption layer.
(13) according to (12) described system, the airintake direction of described multilayer pressure-swing absorption apparatus is for from the bottom up, and flue gas is flow to by the adsorbent bed below, and the waste gas that is not adsorbed is flowed out by the adsorbent bed top; The direction of desorb is for from top to bottom, and the gas that is desorbed is out flowed out by the adsorbent bed below.
(14) according to each described system of (12)-(13), described water vapor adsorption layer contains absorbent material, is selected from activated alumina, active oxidation silica-alumina material, silica gel and combination thereof; Described carbon dioxide adsorption layer contains sorbing material, is selected from 13X zeolite molecular sieve, LiX zeolite molecular sieve, CaX zeolite molecular sieve, active carbon, metal organic frame class material, hydrotalcite-like material and combination thereof.
(15) according to each described system of (12)-(14), at the two ends of described adsorbent bed pneumatic changeover valve has been installed all, by the mutual conversion between the closure realization different operating step of described pneumatic changeover valve.
(16) according to each described system of (12)-(15), also comprise decompressor, described decompressor links to each other with adsorbent bed, is used for reducing the air pressure of adsorbent bed.
(17) according to each described system of (12)-(17), comprise that also temperature sensor, current meter and pressure sensor are installed in respectively gas temperature, flow velocity and the force value that detects in the different unit under the different cycling conditions.
(18) according to (1)-(17) each described method or system, (the water vapor adsorption agent: CO of the volume ratio of bi-material
2Adsorbent) upper range (R
On) be 1:2.5, lower range (R
Lower) be 1:4.
(19) according to (1)-(18) each described method or system, the upper range (T of the intake air temperature of flue gas
On) be 80-150 ° of C, lower range (T
Lower) be 20-70 ° of C.
(20) according to (1)-(19) each described method or system, the upper range (L of the induction air flow ratio of flue gas
On) be 300-500L/min, lower range (T
Lower) be 20-70 ° of C.
(21) according to (1)-(20) each described method or system, the upper range (L of the induction air flow ratio of flue gas
On) be 300-500L/min, lower range (L
Lower) be 50-200L/min.
(22) according to (1)-(21) each described method or system, adsorptive pressure upper range (P
On the h-) be 150-200kPa, lower range (P
Under the h-) be 100-140kPa.
(23) according to (1)-(22) each described method or system, desorption pressures upper range (P
On the L-) be 8-15kPa, the lower range (P of desorption pressures
Under the L-) be 0-5kPa.
(24) according to (1)-(23) each described method or system, CO
2Upper range (the C of volumetric concentration
On) be 15-30%, lower range (C
Lower) be 5-15%.
(25) according to (1)-(24) each described method or system, the upper range (W of the volumetric concentration of steam
On) be 10-20%, lower range (W
Lower) be 5-10%.
In specific implementation process, water vapor adsorption agent material and CO
2The volume ratio that sorbent material loads in adsorbent bed has a upper range namely to make R
OnNamely make R with lower range
Lower(the water vapor adsorption agent: CO of the volume ratio of bi-material
2Adsorbent) upper range (R
On) be 1:2.5, R in this scope
OnCan be lower than 1:2, ideal value is 1:2.2%; R
OnEven can be lower than 1:2.4, ideal value is 1:2.3.CO
2Lower range (the R of the volume ratio of bi-material
Lower) be 1:4, R in this scope
LowerCan be higher than 1:3.8, ideal value is 1:3.6; R
LowerEven can be higher than 1:3.4, ideal value is 1:3.2.
The intake air temperature of flue gas has a upper range namely to make T
OnNamely make T with a lower range
LowerUpper range (the T of the intake air temperature of flue gas
On) be 80-150 ° of C, T in this scope
OnCan be lower than 120 ° of C, ideal value is 110 ° of C; T
OnEven can be lower than 100 ° of C, ideal value is 80 ° of C.Lower range (the T of flue gas intake air temperature
Lower) be 20-70 ° of C, T in this scope
LowerCan be higher than 60 ° of C, ideal value is 50 ° of C; T
LowerEven can be higher than 40 ° of C, ideal value is 30 ° of C.
The flue gas induction air flow ratio has a upper range namely to make L
OnNamely make L with a lower range
LowerUpper range (the L of the induction air flow ratio of flue gas
On) be 300-500L/min, L in this scope
OnCan be lower than 450L/min, ideal value is 400L/min; L
OnEven can be lower than 350L/min, ideal value is 300L/min.Lower range (the L of the volumetric concentration of steam
Lower) be 50-200L/min, L in this scope
LowerCan be higher than 60L/min, ideal value is 80L/min; L
LowerEven can be higher than 100L/min, ideal value is 150L/min.
The adsorptive pressure P of adsorption process
hThere is a upper range namely to make P
On the h-Namely make P with a lower range
Under the h-Adsorptive pressure upper range (P
On the h-) be 150-200kPa, P in this scope
On the h-Can be lower than 190kPa, ideal value is 180kPa; P
On the h-Even can be lower than 170kPa, ideal value is 160kPa.Lower range (the P of desorption pressures
Under the h-) be 100-140kPa, P in this scope
Under the h-Can be higher than 105kPa, ideal value is 110kPa; P
Under the h-Even can be higher than 120kPa, ideal value is 130kPa.
The desorption pressures P of desorption process
LThere is a upper range namely to make P
On the L-Namely make P with a lower range
Under the L-Desorption pressures upper range (P
On the L-) be 8-15kPa, P in this scope
On the L-Can be lower than 13kPa, ideal value is 12kPa; P
On the h-Even can be lower than 10kPa, ideal value is 9kPa.Lower range (the P of desorption pressures
Under the L-) be 0-5kPa, P in this scope
Under the L-Can be higher than 0.5kPa, ideal value is 1kPa; P
Under the L-Even can be higher than 2kPa, ideal value is 3kPa.
Each factor value can be selected higher limit and lower limit in the Vacuum Pressure Swing Adsorption specific implementation process, and can select arbitrarily between higher limit and lower limit.Volumetric concentration such as CO2 in the flue gas can be at C
OnAnd C
LowerBetween select arbitrarily; The concentration of steam can be at W in the flue gas
OnAnd W
LowerBetween select arbitrarily; The flue gas induction air flow ratio can be at L
OnAnd L
LowerBetween select arbitrarily; The adsorptive pressure of air inlet can be at P
On the h-And P
Under the h-Between select arbitrarily; Desorption pressures in the desorption process can be at P
On the L-And P
Under the L-Between select arbitrarily.
Table 1 has comprised some concrete combinations of top five parameters that the present invention relates to of using.
Table 1
In specific implementation process, the CO in the flue gas
2Volumetric concentration has a upper range namely to make C
OnNamely make C with lower range
LowerCO
2Upper range (the C of volumetric concentration
On) be 15-30%, C in this scope
OnCan be lower than 25%, ideal value is 22%; C
OnEven can be lower than 22%, ideal value is 18%.CO
2Lower range (the C of volumetric concentration
Lower) be 5-15%, C in this scope
LowerCan be higher than 6%, ideal value is 8%; C
OnEven can be higher than 10%, ideal value is 12%.
The volumetric concentration of saturated steam has a upper range namely to make W in the flue gas
OnNamely make W with a lower range
LowerUpper range (the W of the volumetric concentration of steam
On) be 10-20%, W in this scope
OnCan be lower than 18%, ideal value is 15%; W
OnEven can be lower than 14%, ideal value is 12%.Lower range (the W of the volumetric concentration of steam
Lower) be 5-10%, W in this scope
LowerCan be higher than 6%, ideal value is 7%; W
LowerEven can be higher than 8%, ideal value is 9%.
Table 2 has comprised some concrete combinations of top two parameters that the present invention relates to of using.
Table 2
| The embodiment sequence number | CO in the flue gas 2Concentration | Water vapor concentration in the flue gas |
| 1 | On the C | On the W |
| 2 | Under the C | On the W |
| 3 | On the C | Under the W |
| 4 | Under the C | Under the W |
A kind of system and method that captures carbon dioxide in flue gas provided by the invention is also removed the steam in the flue gas in the carbon dioxide in separating flue gas.It is advantageous that: needn't fill the method that a drying equipment just can also can be removed steam together in advance when catching carbon dioxide more more, can greatly reduce the cost that pressure-variable adsorption is caught carbon dioxide.The front adsorption layer material that is used for the adsorbed water steam among the present invention be elected to be have easy desorption, anticorrosive, the hydrophily adsorbent that is difficult for deliquescing and can operates at low temperatures.And main adsorption layer selects that CO2 is had adsorbent than high adsorption capacity and adsorptive selectivity.
The specific embodiment
Embodiment 1:
As shown in Figure 1, a kind of three pressure-swing absorption apparatus comprise air inlet (dry air) 1, water vapor generation device 2, air inlet tank 3, reuse circuit 4, vavuum pump 5, products pot 6, irrigation lines 7, adsorbent bed 8, gas tank 9 and tail gas 10.Three pressure-swing absorption apparatus are wrapped up by heat-barrier material by the adsorbent bed of stainless steel iron pipe assembling, avoid the thermal loss in the sorption and desorption process, and 7 (Ttype) thermocouples have been installed in adsorbent bed therein from top to bottom (have been seen TE1 among the figure-TE7), thermocouple is evenly packed into the hollow position in the adsorbent bed, is used for monitoring the variations in temperature at diverse location place in the adsorbent bed.Also be tied with heating tape and electro-insulating rubber material on the adsorbent bed and control the temperature of adsorbent bed.The effective length of adsorbent bed is 1100mm, and internal diameter is 76mm, and the bed wall thickness is 5mm.
The airintake direction of this experimental provision design is for from the bottom up, and namely power plant flue gas is flow to by the adsorbent bed below, and the waste gas that is not adsorbed (mainly containing nitrogen) is flowed away by the adsorbent bed top.And the direction of desorb is desorbed the CO that gets off for from top to bottom
2And H
2O and a small amount of N
2Extracted and throw into out products pot by the outflow of adsorbent bed below by the vavuum pump decompressor.Humidity sensor is installed in the porch, lower end of adsorbent bed, can monitor the humidity (water vapor concentration) of air inlet and resolved gas.The CO of variable concentrations scope
2Concentration sensor is mounted respectively at the air inlet place, the gas outlet is located and the products pot place, can monitor at any time CO in air inlet, waste gas and the gas product
2Instantaneous concentration.Flowmeter and pressure sensor are installed in respectively the gas flow rate under the different cycling conditions of monitoring and the instantaneous pressure value of gas in the different unit lines.In addition, in order to realize the cycling of various steps, pneumatic changeover valve has been installed respectively all at adsorbent bed two.Closure by the conversion valve under the programme-control just can realize the mutual conversion between the different operating step.All programme-control and the preservation of data are all controlled by Advantech DataAcquisition and Control System, thereby reach the purpose of cycling.
Dry power plant flue gas is the mixture of carbon dioxide and dry air.The source of carbon dioxide is the industrial liquid CO of interior compression
2Dry waste gas is just taken steam out of during by a water column that distilled water is housed.The content of steam is to realize by the temperature of controlling water column.
The concentration of carbon dioxide is monitored by gas concentration sensor in the product gas.And CO
2The rate of recovery calculate by following formula:
In the formula:
The rate of recovery;
These three adsorbent equipments mainly are comprised of five parts, are respectively: adsorbent bed, air admission unit, waste gas unit, vavuum pump decompressor (desorb) unit and flushing unit.Adsorbent is housed in the adsorbent bed, and flue enters the process of adsorbent bed from air admission unit, the most of CO in the flue gas
2Be adsorbed agent and catch, the gas that is not adsorbed is discharged from via the waste gas unit.Adsorbent all is filled CO
2After, the valve closing of air admission unit and waste gas unit, air inlet finishes.Before the desorption procedure, for improving CO
2Purity, can increase rinsing step.Because also have the space that exists between some absorbent particles in the adsorbent bed, the great majority that are full of in these spaces are that gas componant in the air inlet is (with N
2Be main), like this with the higher CO of concentration ratio
2After (80 – 95%) flushing, will be by CO in the space
2Take.The another one advantage of flushing is exactly to make the N that is adsorbed in the adsorbent space
2Be substituted, because N
2And the active force between the adsorbent a little less than, dense CO that like this ought be stronger
2When molecule passes through, can replace weak N
2Molecule also can further improve CO
2Purity.Flushing process is that the valve open of flushing unit and waste gas unit makes sub-fraction CO
2The gas product that concentration is higher is flowed through adsorbent beds at short notice to the effect of washing.Be the gas desorption stage after flushing finishes, valve and the vavuum pump decompressor of this desorb unit are opened in stage, and the vavuum pump decompressor diminishes the pressure moment in the adsorbent bed, and the diminishing of pressure makes the CO in the adsorbent bed
2Got off by most of desorb, via being driven into products pot behind the vavuum pump decompressor.
The advantage of three adsorbent beds and single adsorbent bed is to have increased pressure equalization step.That is to say when an adsorbent bed in absorption or during desorb, what two other adsorbent bed carried out is isostasy, so just can reduce the ability loss in the adsorption process, and raising CO
2Purity.After each adsorbent bed is finished Adsorption and desorption, pressure balance and a flushing, a cycling finishes, and then repeat to catch up with the duplicate circulation step of a cycling, ceaselessly the continuity work of the pressure-variable adsorption namely realized of cycling.
The parameter of three adsorbent equipments and the operational factor of device see Table 3.
Table 3
Selecting active silica-alumina oxide (trade name Sorbead) is absorbent material, selects the 13X zeolite molecular sieve for inhaling CO
2Material.
Embodiment 2:
Six step operating process.
Six step pressure swing adsorption operations structure arrangements are seen Fig. 2, and detailed process is:
Step 1: bed air inlet absorption, all the other two isostasies;
Step 2: No. two bed vacuum desorptions, all the other two isostasies;
Step 3: No. three bed air inlets absorption, all the other two isostasies;
Step 4: a bed vacuum desorption, all the other two isostasies;
Step 5: No. two bed air inlets absorption, all the other two isostasies;
Step 6: No. three bed vacuum desorptions, all the other two isostasies.
Behind the six step EOs, finished the sorption and desorption of three adsorbent beds, a cycling finishes, and then carries out the cycling of next round.
Increased pressure equalization step in three six steps operations.That is to say when an adsorbent bed in absorption or during desorb, what two other adsorbent bed carried out is isostasy, isostasy can reduce the ability loss in the adsorption process, and improves CO
2Desorb purity.
Embodiment 3:
As described in Figure 3, nine step operating process.
What the operation of nine steps was different from the operation of six steps is to increase the gas product rinsing step in operating procedure, and detailed nine step processes are as follows:
Step 1: bed air inlet absorption, all the other adsorbent beds are balanced;
Step 2: No. two bed gas product flushings, all the other two isostasies;
Step 3: No. two bed vacuum desorptions, all the other two isostasies;
Step 4: No. three bed air inlets absorption, all the other two adsorbent bed equilibriums;
Step 5: a bed gas product flushing, all the other two isostasies;
Step 6: a bed vacuum desorption, all the other two isostasies;
Step 7: No. two bed air inlets absorption, all the other two adsorbent bed equilibriums;
Step 8: No. three bed gas product flushings, all the other two isostasies;
Step 9: No. three bed vacuum desorptions, all the other two isostasies;
Behind the nine step EOs, each adsorbent bed has been finished once absorption, gas product flushing and desorb, and one takes turns the circulation end of operation, then carries out the cycling of next round, and whole pressure swing adsorption technique like this always cycling goes down.
The operation of nine steps is to have increased the step of utilizing gas product flushing adsorbent bed before desorption procedure in the experiment of nine steps with the difference of six steps operation, so just can greatly improve CO
2Purity.Reason is before the desorption procedure, and also having the space that exists between some absorbent particles, the great majority that are full of in these spaces in the adsorbent bed is that gas componant in the air inlet is (with N
2Be main), like this with the higher CO of concentration
2After (80 – 95%) flushing, will be by CO in the space
2Take.The another one advantage of flushing is to make the N that is adsorbed in the adsorbent space
2Be substituted, because N
2And the active force between the adsorbent a little less than, like this as the stronger and dense CO of active force
2When molecule passes through, will inevitably replace weak N
2Molecule further improves CO
2Purity.
Table 4 has been summed up under six kinds of different operating conditions (comprising four relatively more sharp and three invention profits) CO
2Separating effect.
Table 4
Minimum system vacuum pressure is 3.5kPa under each sequence number condition, and water inspissation degree is controlled at volumetric concentration about 8% during the high humidity air inlet.But different comparing results relatively more sharp and that invention is sharp is as follows:
(1) under the dry inlet air conditions, single 13X adsorption layer 6 step experiments (seeing sequence number I) can obtain comparatively ideal CO
2Purity and the rate of recovery are respectively 78.4% and 86.5%.But (see sequence number VI) under single 13X adsorption layer and the high humidity inlet air conditions, the 13X in the whole adsorbent bed can be polluted and inactivation by steam.
(2) to having a competition sequence number I and sequence number II as can be known, even added Sorbead adsorption layer, CO
2Separating effect be not subject to too large impact, CO
2Purity descends slightly to some extent, because Sorbead is to CO
2Weak adsorption capacity is also arranged.Therefore, no matter be six steps or the operation of nine steps, the adding of anterior layer sorbent material Sorbead can obviously not have influence on whole CO
2Separating effect.
(3) contrast sequence number II and III and sequence number IV and V in double-deck pressure-variable adsorption experiment, are trapped within the anterior layer adsorbent prerequisite at steam, compare CO during the high humidity air inlet with dry air inlet
2Purity and the rate of recovery decline is slightly arranged, come separation of C O but 13X still has greater activity
2Thereby this double-deck pressure swing adsorption technique has double action, can remove simultaneously steam and carbon dioxide in the flue gas.
(4) compare (sequence number II and IV and sequence number III and V) by different operating step condition, although gas product flushing adsorbent bed, CO have been used in the operation of nine steps
2The rate of recovery slightly descend, but nine step operations can improve CO greatly
2The rate of recovery.Even under the high humidity inlet air conditions, CO
2Purity also can from six step operations lower 72.3% be increased to 86.9% under the nine steps practical operations work.
(5) last, contrast sequence number V and VI are when rinsing step adsorbent bed internal pressure is reduced to 35kPa, although CO
2The rate of recovery can descend, but can obtain 96.1% than pure carbon dioxide.
Above-described embodiment is not the exhaustive of the specific embodiment; the embodiment that other also can be arranged; above-described embodiment purpose is to illustrate the present invention, and unrestricted protection scope of the present invention, all application that come by simple change of the present invention all drop in protection scope of the present invention.
This patent specification use-case goes to show the present invention, comprising optimal mode, and those of ordinary skill in the art are made and uses the present invention.This invents delegatable scope and comprises the content of claims and the content of the specific embodiment in the specification and other embodiment.These other examples also should belong to the scope that patent right of the present invention requires, as long as they contain the described technical characterictic of the identical written language of claim, perhaps they include and the similar literal language described technical characterictic of claim without essence difference.
All patents, the full content of patent application and other list of references should be incorporated present specification by reference into.If but a term among the application conflicts mutually with the term of including list of references in, and is preferential with the application's term.
All scopes disclosed herein all comprise end points, and are to make up independently of one another between the end points.
It should be noted that " first ", " second " or similar vocabulary do not represent any order, and quality or importance just are used for distinguishing different technical characterictics.The implication that comprises described value and content context appointment in conjunction with the qualifier " approximately " of quantity use.(for example: it includes the error when measuring specific quantity).
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is the structural representation of three pressure-swing absorption apparatus;
1 is air inlet (dry air) among the figure, and 2 is water vapor generation device, and 3 are the air inlet tank, and 4 are the reuse circuit, and 5 is vavuum pump, and 6 is products pot, and 7 is irrigation lines, and 8 is adsorbent bed, and 9 is gas tank, and 10 is tail gas.
Fig. 2 six goes on foot the circulate flow chart of one of them adsorbent bed of three pressure-variable adsorptions of carries product gas flushing not.
Fig. 3 was nine steps with the circulate flow chart of one of them adsorbent bed of three pressure-variable adsorptions of gas product flushing.
Claims (17)
1. a method that captures carbon dioxide in flue gas is characterized in that: comprise gas absorption step and gas desorption procedure; Described gas absorption step is that flue gas is passed through the multilayer pressure-swing absorption apparatus, in the adsorbent bed of described multilayer pressure-swing absorption apparatus steam and carbon dioxide are adsorbed on the adsorption layer, and the waste gas that is not adsorbed flows out described adsorbent bed; Described gas desorption step is that the pressure that reduces in the described adsorbent bed makes carbon dioxide desorb from adsorption layer.
2. method according to claim 1 is characterized in that: realize reducing pressure in the described adsorbent bed by decompressor.
3. method according to claim 1, it is characterized in that: described multilayer pressure-swing absorption apparatus contains at least one adsorbent bed, and each adsorbent bed contains at least one deck water vapor adsorption layer and at least one deck carbon dioxide adsorption layer; Flue gas is first by the water vapor adsorption layer, then by the carbon dioxide adsorption layer.
4. method according to claim 3, it is characterized in that: described water vapor adsorption layer contains absorbent material, is selected from activated alumina, active oxidation silica-alumina material, silica gel and combination thereof; Described carbon dioxide adsorption layer contains sorbing material, is selected from 13X zeolite molecular sieve, LiX zeolite molecular sieve, CaX zeolite molecular sieve, active carbon, metal organic frame class material, hydrotalcite-like material and combination thereof.
5. method according to claim 1 is characterized in that: the airintake direction of described multilayer pressure-swing absorption apparatus is for from the bottom up, and flue gas is flow to by the adsorbent bed below, and the waste gas that is not adsorbed is flowed out by the adsorbent bed top; The direction of desorb is for from top to bottom, and the gas that is desorbed is out flowed out by the adsorbent bed below.
6. each described method according to claim 1-5 is characterized in that: also comprise the gas product rinsing step after the gas absorption step, before the gas desorption step.
7. each described method according to claim 1-5, it is characterized in that: described multilayer pressure-swing absorption apparatus contains at least two adsorbent beds, and an adsorbent bed carries out gas absorption step or gas desorption step, and other adsorbent bed carries out pressure equalization step.
8. each described method according to claim 1-5 is characterized in that: described flue gas contains the carbon dioxide that accounts for cumulative volume 5-30% and the steam of 5-20%; The temperature of described flue gas is 20-150 ° of C, and flow is 50-500L/min.
9. each described method is characterized in that: also comprised flue gas dust removal step and desulphurization denitration step before the gas absorption step according to claim 1-5.
10. each described method according to claim 1-5 is characterized in that: the transformation operation is to move within the malleation scope, and its absolute pressure value is 100-300kPa.
11. each described method according to claim 1-5 is characterized in that: the transformation operation is to move within range of negative pressure, and its absolute pressure value is 1-100kPa.
12. system that captures carbon dioxide in flue gas, it is characterized in that: comprise the multilayer pressure-swing absorption apparatus, described multilayer pressure-swing absorption apparatus contains at least one adsorbent bed, and each adsorbent bed contains at least one deck water vapor adsorption layer and at least one deck carbon dioxide adsorption layer; Described water vapor adsorption layer makes flue gas first by the water vapor adsorption layer, then by the carbon dioxide adsorption layer below described carbon dioxide adsorption layer.
13. system according to claim 12 is characterized in that: the airintake direction of described multilayer pressure-swing absorption apparatus is for from the bottom up, and flue gas is flow to by the adsorbent bed below, and the waste gas that is not adsorbed is flowed out by the adsorbent bed top; The direction of desorb is for from top to bottom, and the gas that is desorbed is out flowed out by the adsorbent bed below.
14. system according to claim 12 is characterized in that: described water vapor adsorption layer contains absorbent material, is selected from activated alumina, active oxidation silica-alumina material, silica gel and combination thereof; Described carbon dioxide adsorption layer contains sorbing material, is selected from 13X zeolite molecular sieve, LiX zeolite molecular sieve, CaX zeolite molecular sieve, active carbon, metal organic frame class material, hydrotalcite-like material and combination thereof.
15. each described system according to claim 12-14, it is characterized in that: pneumatic changeover valve has all been installed at the two ends at described adsorbent bed, and the closure by described pneumatic changeover valve realizes the mutual conversion between the different operating step.
16. system according to claim 15 is characterized in that: also comprise decompressor, described decompressor links to each other with adsorbent bed, is used for reducing the air pressure of adsorbent bed.
17. system according to claim 16 is characterized in that: comprise that also temperature sensor, current meter and pressure sensor are installed in respectively gas temperature, flow velocity and the force value that detects in the different unit under the different cycling conditions.
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| CN115671951B (en) * | 2022-07-19 | 2023-04-07 | 原初科技（北京）有限公司 | Carbon dioxide combined capturing method |
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