CN103055659B - A kind of trapping carbon dioxide in flue gas system and method - Google Patents
A kind of trapping carbon dioxide in flue gas system and method Download PDFInfo
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- CN103055659B CN103055659B CN201210572964.4A CN201210572964A CN103055659B CN 103055659 B CN103055659 B CN 103055659B CN 201210572964 A CN201210572964 A CN 201210572964A CN 103055659 B CN103055659 B CN 103055659B
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Abstract
The present invention relates to a kind of system and method trapping carbon dioxide in flue gas, wherein method comprises advanced promoting the circulation of qi body adsorption step, then carries out gas desorption step; System comprises 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, in the below of described carbon dioxide adsorption layer, makes flue gas first by water vapor adsorption layer, then by carbon dioxide adsorption layer.A kind of system and method trapping carbon dioxide in flue gas provided by the invention, also removes the steam in flue gas while being separated the carbon dioxide in flue gas.It is advantageous that: in advance need not fill a drying equipment more more and just while catching carbon dioxide, also together the method that steam is removed, can greatly can reduce the cost that pressure-variable adsorption catches carbon dioxide.
Description
Technical field
The present invention relates to a kind of system and method trapping carbon dioxide in flue gas, particularly relate to a kind of system and method utilizing multi-layer vacuum pressure swing adsorption to trap the high humidify carbon dioxide in flue gas.
Background technology
Pressure-variable adsorption separating-purifying CO
2technology can from multiple containing CO
2source of the gas in catch purification CO
2, meet CO
2multiple industrial use.There is the advantages such as energy consumption is low, adsorbent life cycle is long, technological process is simple, automaticity is high, environmental benefit is good, pollution-free generation.
CO is trapped about utilizing Vacuum Pressure Swing Adsorption
2the selection of adsorbent in technology, the most frequently used adsorbent being also most has superiority is 13X zeolite molecular sieve at present.It is under the prerequisite of dry gas that but current great majority research nearly all concentrates on hypothesis industrial waste gas.
But containing impurity such as the saturated steam of about 10%, trace sulfide, nitride and particles in real flue gas.
But, when 13X adsorbent bed passes through containing (>5%H during high wet flue gas
2o), 13X adsorption capacity can greatly reduce.
Traditional method utilizes drying equipment before waste gas is by adsorbent bed, remove saturated steam in flue gas, 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 increase trapping CO greatly
2cost.
The application for a patent for invention Publication Specification of Chinese Patent Application No. 200680033169.0 discloses, a kind of method of purification of carbon dioxide, the method comprises: make the low-purity air-flow that will carry out processing by least one adsorbent bed, and described adsorbent bed contains and is at least two-layerly selected from following adsorption layer: the zeolite of drier, zeolite or its ion exchange form and activated carbon.But the method has only included gas absorption step, and the absorption of this gas absorption step is other foreign gas instead of carbon dioxide.
At present, the research that great majority remove steam about multilayer pressure-variable adsorption is also only limitted to trace level in air purification system (ppm level) saturated steam containing quantifier elimination, and in the present invention, in the flue gas of use, the content of steam is between 520%.Summary of the invention
The technical problem to be solved in the present invention is the principle utilizing multilayer pressure-variable adsorption, first with strongly hydrophilic and the adsorbent of easily desorb retains the steam in flue gas in same adsorbent bed, protects main CO
2adsorption layer.CO
2adsorption layer is selected for CO
2there is the adsorbent of the highest adsorptive selectivity.Finally reach only with a set of adsorbent equipment Separation of Water steam and CO simultaneously
2, finally realize high concentration trapping CO
2method.
The present invention includes the following step:
(1) airintake direction of adsorbent equipment design is that flue gas just flows to by below adsorbent bed from the bottom up, and is not flowed out by above adsorbent bed by the waste gas (mainly containing nitrogen) adsorbed.
(2) direction of desorb is from top to bottom, is desorbed the CO got off
2and H
2o and a small amount of N
2flow out by below adsorbent bed.
(3) the concentrated carbon dioxide of resolving from adsorbent bed is depressurized device and throws products pot into.
Wherein, humidity sensor is installed in the lower inlet place of adsorbent bed, monitoring air inlet and be desorbed the humidity of gas, and in the present invention, in flue gas, the volumetric concentration of steam is 5-20%.
CO within the scope of variable concentrations
2concentration sensor is separately mounted on air inlet place, gas outlet place and products pot place, monitors CO in air inlet, waste gas and gas product at any time
2instantaneous concentration.Wherein CO in flue gas
2shared percent by volume is 5-30%
Temperature sensor, current meter and pressure sensor are arranged on the force value of gas temperature, flow velocity and gas in different unit under the different cycling condition of monitoring respectively.Wherein the temperature of flue gas is 20-150 ° of C, and charge flow rate is 50-500L/min, and the absolute pressure value run within the positive pressure range of transformation operation is 100-300kPa, and the absolute pressure value run within range of negative pressure of transformation operation is 1-100kPa.
Obtained by decompressor and be used for the negative pressure of desorb.
In order to realize the cycling of various step, at adsorbent bed two, pneumatic changeover valve is all respectively installed.By the closed mutual conversion that can realize between different operating step of the conversion valve under programme-control.
Operation sequence is controlled by GEFANUC PLC operating system, and computer display interface is controlled by Citect/SCADA.
Absorbent material in the present invention is selected from activated alumina, active oxidation silica-alumina material, silica gel and combination thereof.
In the present invention, it inhales CO
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.
In the present invention, the specific area of adsorbent, pore volume and pore size all pass through adsorption tester ASAP2010(Micromeritics, USA) under liquid nitrogen temperature (77K) measure.Before test, sample activates 12h under 350 ° of C vacuum conditions, the steam adsorbed before removing sample and other impurity, ensures that the aperture of the front sample of test is clean.BET method is used to calculation sample at P/P
obe the specific area S under 0.05 – 0.25 condition
bET.Density Functional Theory (DFT) model based on aperture set factor is used to the pore size distribution of calculation sample.
First flue gas pass through at least one deck absorbent material layer, then passes through at least one deck and inhale CO
2material layer.
In the present invention, adsorbent equipment operates according to two steps, three steps, four step rule, six steps or nine footworks.
After in the present invention, the trapping of carbon dioxide occurs in flue gas dedusting and desulphurization denitration.
CO in adsorbent bed end gas outlet place waste gas in the present invention
2concentration range is at percent by volume 0.1-10%.
Provided by the invention a kind of trap carbon dioxide in flue gas method and the decorum to comprise following technical scheme as follows:
(1) trap a method for carbon dioxide in flue gas, comprise gas absorption step and gas desorption procedure; Described gas absorption step is by flue gas by multilayer pressure-swing absorption apparatus, in the adsorbent bed of described multilayer pressure-swing absorption apparatus by steam and carbon dioxide adsorption on adsorption layer, and do not flowed out described adsorbent bed by the waste gas adsorbed; Described gas desorption step is that the pressure reduced in described adsorbent bed makes carbon dioxide desorb from adsorption layer.
(2) method Gen Ju (1), realizes reducing the pressure in described adsorbent bed by decompressor.
(3) method according to any one 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, first by water vapor adsorption layer, then passes through carbon dioxide adsorption layer.
(4) method according to any one 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 the method described in any one of (1)-(4), the airintake direction of described multilayer pressure-swing absorption apparatus is that flue gas flows to by below adsorbent bed from the bottom up, and not by the waste gas that adsorbs by flowing out above adsorbent bed; The direction of desorb is from top to bottom, and the gas being desorbed out flows out by below adsorbent bed.
(6) method according to any one of (1)-(5), also comprises gas product rinsing step after gas absorption step, before gas desorption step.
(7) method according to any one 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 the method described in any one of (1)-(7), described flue gas contains and accounts for the carbon dioxide of 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) method according to any one of (1)-(8), also comprised flue gas dust removal step and desulphurization denitration step before gas absorption step.
(10) method according to any one of (1)-(9), transformation operation runs within positive pressure range, and its absolute pressure value is 100-300kPa.
(11) method according to any one of (1)-(10), transformation operation runs within range of negative pressure, and its absolute pressure value is 1-100kPa.
(12) trap a system for carbon dioxide in flue gas, comprise 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, in the below of described carbon dioxide adsorption layer, makes flue gas first by water vapor adsorption layer, then by carbon dioxide adsorption layer.
(13) system Gen Ju (12), the airintake direction of described multilayer pressure-swing absorption apparatus is that flue gas flows to by below adsorbent bed from the bottom up, and not by the waste gas that adsorbs by flowing out above adsorbent bed; The direction of desorb is from top to bottom, and the gas being desorbed out flows out by below adsorbent bed.
(14) system according to any one 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) system according to any one of (12)-(14), has all installed pneumatic changeover valve at the two ends of described adsorbent bed, by the closed mutual conversion realized between different operating step of described pneumatic changeover valve.
(16) system according to any one of (12)-(15), also comprise decompressor, described decompressor is connected with adsorbent bed, for reducing the air pressure in adsorbent bed.
(17) according to the system described in any one of (12)-(17), also comprise temperature sensor, current meter and pressure sensor and be arranged in different unit the gas temperature, flow velocity and the force value that detect under different cycling condition respectively.
(18) method according to any one of (1)-(17) or system, volume ratio (the water vapor adsorption agent: CO of bi-material
2adsorbent) upper range (R
on) be 1:2.5, lower range (R
under) be 1:4.
(19) method according to any one of (1)-(18) or system, the upper range (T of the intake air temperature of flue gas
on) be 80-150 ° of C, lower range (T
under) be 20-70 ° of C.
(20) method according to any one of (1)-(19) or system, the upper range (L of the induction air flow ratio of flue gas
on) be 300-500L/min, lower range (T
under) be 20-70 ° of C.
(21) method according to any one of (1)-(20) or system, the upper range (L of the induction air flow ratio of flue gas
on) be 300-500L/min, lower range (L
under) be 50-200L/min.
(22) method according to any one of (1)-(21) or system, adsorptive pressure upper range (P
on h-) be 150-200kPa, lower range (P
under h-) be 100-140kPa.
(23) method according to any one of (1)-(22) or system, desorption pressures upper range (P
on L-) be 8-15kPa, the lower range (P of desorption pressures
under L-) be 0-5kPa.
(24) method according to any one of (1)-(23) or system, CO
2upper range (the C of volumetric concentration
on) be 15-30%, lower range (C
under) be 5-15%.
(25) method according to any one of (1)-(24) or system, the upper range (W of the volumetric concentration of steam
on) be 10-20%, lower range (W
under) 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 R is made with lower range
under.Volume ratio (the water vapor adsorption agent: CO of bi-material
2adsorbent) upper range (R
on) be 1:2.5, R within the scope of this
oncan lower than 1:2, ideal value is 1:2.2%; R
oneven can lower than 1:2.4, ideal value is 1:2.3.CO
2lower range (the R of the volume ratio of bi-material
under) be 1:4, R within the scope of this
undercan higher than 1:3.8, ideal value is 1:3.6; R
undereven can 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 T is made with a lower range
under.Upper range (the T of the intake air temperature of flue gas
on) be 80-150 ° of C, T within the scope of this
oncan lower than 120 ° of C, ideal value is 110 ° of C; T
oneven can lower than 100 ° of C, ideal value is 80 ° of C.Lower range (the T of flue gas intake air temperature
under) be 20-70 ° of C, T within the scope of this
undercan higher than 60 ° of C, ideal value is 50 ° of C; T
undereven can higher than 40 ° of C, ideal value is 30 ° of C.
Flue gas induction air flow ratio has a upper range namely to make L
onnamely L is made with a lower range
under.Upper range (the L of the induction air flow ratio of flue gas
on) be 300-500L/min, L within the scope of this
oncan lower than 450L/min, ideal value is 400L/min; L
oneven can lower than 350L/min, ideal value is 300L/min.Lower range (the L of the volumetric concentration of steam
under) be 50-200L/min, L within the scope of this
undercan higher than 60L/min, ideal value is 80L/min; L
undereven can higher than 100L/min, ideal value is 150L/min.
The adsorptive pressure P of adsorption process
ha upper range is had namely to make P
on h-namely P is made with a lower range
under h-.Adsorptive pressure upper range (P
on h-) be 150-200kPa, P within the scope of this
on h-can lower than 190kPa, ideal value is 180kPa; P
on h-even can lower than 170kPa, ideal value is 160kPa.Lower range (the P of desorption pressures
under h-) be 100-140kPa, P within the scope of this
under h-can higher than 105kPa, ideal value is 110kPa; P
under h-even can higher than 120kPa, ideal value is 130kPa.
The desorption pressures P of desorption process
la upper range is had namely to make P
on L-namely P is made with a lower range
under L-.Desorption pressures upper range (P
on L-) be 8-15kPa, P within the scope of this
on L-can lower than 13kPa, ideal value is 12kPa; P
on h-even can lower than 10kPa, ideal value is 9kPa.Lower range (the P of desorption pressures
under L-) be 0-5kPa, P within the scope of this
under L-can higher than 0.5kPa, ideal value is 1kPa; P
under L-even can higher than 2kPa, ideal value is 3kPa.
In Vacuum Pressure Swing Adsorption specific implementation process, each factor value can select higher limit and lower limit, and can select arbitrarily between higher limit and lower limit.Volumetric concentration as CO2 in flue gas can at C
onand C
underbetween select arbitrarily; In flue gas, the concentration of steam can at W
onand W
underbetween select arbitrarily; Flue gas induction air flow ratio can at L
onand L
underbetween select arbitrarily; The adsorptive pressure of air inlet can at P
on h-and P
under h-between select arbitrarily; Desorption pressures in desorption process can at P
on L-and P
under L-between select arbitrarily.
Table 1 contains some concrete combinations of five parameters above that the present invention relates to of use.
Table 1
In specific implementation process, the CO in flue gas
2volumetric concentration has a upper range namely to make C
onnamely C is made with lower range
under.CO
2upper range (the C of volumetric concentration
on) be 15-30%, C within the scope of this
oncan lower than 25%, ideal value is 22%; C
oneven can lower than 22%, ideal value is 18%.CO
2lower range (the C of volumetric concentration
under) be 5-15%, C within the scope of this
undercan higher than 6%, ideal value is 8%; C
oneven can higher than 10%, ideal value is 12%.
In flue gas, the volumetric concentration of saturated steam has a upper range namely to make W
onnamely W is made with a lower range
under.Upper range (the W of the volumetric concentration of steam
on) be 10-20%, W within the scope of this
oncan lower than 18%, ideal value is 15%; W
oneven can lower than 14%, ideal value is 12%.Lower range (the W of the volumetric concentration of steam
under) be 5-10%, W within the scope of this
undercan higher than 6%, ideal value is 7%; W
undereven can higher than 8%, ideal value is 9%.
Table 2 contains some concrete combinations of two parameters above that the present invention relates to of use.
Table 2
| Embodiment sequence number | CO in flue gas 2Concentration | Water vapor concentration in flue gas |
| 1 | On C | On W |
| 2 | Under C | On W |
| 3 | On C | Under W |
| 4 | Under C | Under W |
A kind of system and method trapping carbon dioxide in flue gas provided by the invention, also removes the steam in flue gas while being separated the carbon dioxide in flue gas.It is advantageous that: in advance need not fill a drying equipment more more and just while catching carbon dioxide, also together the method that steam is removed, can greatly can reduce the cost that pressure-variable adsorption catches carbon dioxide.Be elected to be for adsorption layer material before adsorb water vapor in the present invention and there is easy desorption, anticorrosive, not easily deliquescing and the hydrophilic adsorbent that can operate at low temperatures.And main adsorption layer selection has the adsorbent compared with high adsorption capacity and adsorptive selectivity to CO2.
Detailed description of the invention
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.The adsorbent bed that three pressure-swing absorption apparatus are assembled by stainless steel iron pipe is wrapped up by heat-barrier material, avoid the thermal loss in sorption and desorption process, and 7 (Ttype) thermocouples (see TE1-TE7 in figure) have been installed in an adsorbent bed wherein from top to bottom, thermocouple, by the hollow position evenly packed in adsorbent bed, is used for monitoring the variations in temperature at diverse location place in adsorbent bed.Adsorbent bed is also tied with heating tape and insulating rubber material to control the temperature of adsorbent bed.The effective length of adsorbent bed is 1100mm, and internal diameter is 76mm, and bed wall thickness is 5mm.
The airintake direction of this experimental provision design is that namely power plant flue gas flows to by below adsorbent bed from the bottom up, and is not flowed away by above adsorbent bed by the waste gas (mainly containing nitrogen) adsorbed.And the direction of desorb is from top to bottom, be desorbed the CO got off
2and H
2o and a small amount of N
2to be extracted out by vacuum pump pressure device by flowing out below adsorbent bed and to throw products pot into.Humidity sensor is installed in the lower inlet place 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 separately mounted on air inlet place, gas outlet place and products pot place, can monitor CO in air inlet, waste gas and gas product at any time
2instantaneous concentration.Flowmeter and pressure sensor are arranged on the instantaneous pressure value of gas flow rate in different unit lines under the different cycling condition of monitoring and gas respectively.In addition, in order to realize the cycling of various step, at adsorbent bed two, pneumatic changeover valve has all respectively been installed.By the closed mutual conversion that just can realize between different operating step of the conversion valve under programme-control.All programme-control and the preservation of data are all controlled by Advantech DataAcquisition and Control System, thus reach the object 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
2.Just steam is taken out of when dry waste gas is equipped with the water column of distilled water by one.The content of steam is realized by the temperature of control water column.
In product gas, the concentration of carbon dioxide is monitored by gas concentration sensor.And CO
2the rate of recovery calculated by following formula:
In formula:
the rate of recovery;
cO in air inlet
2content, mol;
cO in waste gas
2content, mol.
These three adsorbent equipments form primarily of five parts, are respectively: adsorbent bed, air admission unit, waste gas unit, vacuum pump pressure device (desorb) unit and flushing unit.Adsorbent bed is built with adsorbent, and flue enters the process of adsorbent bed from air admission unit, the most of CO in flue gas
2caught by adsorbent, be not discharged via waste gas unit by the gas adsorbed.Adsorbent is all filled CO
2after, the valve closing of air admission unit and waste gas unit, air inlet terminates.Before desorption procedure, for improving CO
2purity, can rinsing step be increased.Because also have the space existed between some absorbent particles in adsorbent bed, the great majority be full of in these spaces are that gas componant in air inlet is (with N
2be main), like this with the CO that concentration is higher
2after (80 – 95%) rinses, will by CO in space
2take.The another one advantage of rinsing is exactly can make in adsorbent space by the N adsorbed
2be substituted, because N
2and the active force between adsorbent is more weak, like this as stronger dense CO
2when molecule passes through, more weak N can be replaced
2molecule, also can improve CO further
2purity.Flushing process is, rinses the valve open of unit and waste gas unit, makes sub-fraction CO
2the gas product that concentration is higher flows through adsorbent beds at short notice to the effect of rinsing.Be the gas desorption stage after flushing terminates, the valve of this stage desorption unit and vacuum pump pressure device are opened, and vacuum pump pressure device makes the pressure in adsorbent bed diminish instantaneously, the CO made in adsorbent bed that diminishes of pressure
2got off by most of desorb, be driven into products pot via after vacuum pump pressure device.
The advantage of three adsorbent beds and single adsorbent bed is the increase in pressure equalization step.That is, when an adsorbent bed is in absorption or desorb, what two other adsorbent bed carried out is isostasy, so just can reduce the capacity loss in adsorption process, and improve CO
2purity.After each adsorbent bed completes Adsorption and desorption, pressure balance and a flushing, a cycling terminates, and then repeat to catch up with the duplicate circulation step of a cycling, the ceaselessly continuity work of pressure-variable adsorption that namely realizes of cycling.
The parameter of three adsorbent equipments and the operational factor of device are in table 3.
Table 3
Selecting active silica-alumina oxide (trade name Sorbead) to be absorbent material, selecting 13X zeolite molecular sieve for inhaling CO
2material.
Embodiment 2:
Six step operating process.
Six step pressure swing adsorption operations structure arrangements are shown in Fig. 2, and detailed process is:
Step 1: a 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 inlet absorption, all the other two isostasies;
Step 4: a bed vacuum desorption, all the other two isostasies;
Step 5: No. two bed air inlet absorption, all the other two isostasies;
Step 6: No. three bed vacuum desorptions, all the other two isostasies.
After six step operations terminate, complete the sorption and desorption of three adsorbent beds, a cycling terminates, and then carries out the cycling of next round.
Pressure equalization step is added in three six step operations.That is, when an adsorbent bed is in absorption or desorb, what two other adsorbent bed carried out is isostasy, and isostasy can reduce the capacity loss in adsorption process, and improves CO
2desorb purity.
Embodiment 3:
As described in Figure 3, nine step operating process.
Nine step operations operate unlike adding gas product rinsing step in operating procedure with six steps, and detailed nine step processes are as follows:
Step 1: a bed air inlet absorption, all the other adsorbent beds are balanced;
Step 2: No. two bed gas products rinse, all the other two isostasies;
Step 3: No. two bed vacuum desorptions, all the other two isostasies;
Step 4: No. three bed air inlet absorption, all the other two adsorbent bed equilibriums;
Step 5: a bed gas product rinses, all the other two isostasies;
Step 6: a bed vacuum desorption, all the other two isostasies;
Step 7: No. two bed air inlet absorption, all the other two adsorbent bed equilibriums;
Step 8: No. three bed gas products rinse, all the other two isostasies;
Step 9: No. three bed vacuum desorptions, all the other two isostasies;
After nine step operations terminate, each adsorbent bed is completed once absorption, gas product rinses and desorb, and one takes turns circulation end of operation, then carries out the cycling of next round, and whole pressure swing adsorption technique like this cycling always goes down.
The difference that nine step operations and six steps operate adds during nine steps are tested to utilize gas product to rinse the step of adsorbent bed before desorption procedure, so just greatly can improve CO
2purity.Before reason is desorption procedure, also have the space existed between some absorbent particles in adsorbent bed, the great majority be full of in these spaces are that gas componant in air inlet is (with N
2be main), like this with the higher CO of concentration
2after (80 – 95%) rinses, will by CO in space
2take.The another one advantage of rinsing can make in adsorbent space by the N adsorbed
2be substituted, because N
2and the active force between adsorbent is more weak, like this as the CO that active force is stronger and dense
2when molecule passes through, more weak N will inevitably be replaced
2molecule, improves CO further
2purity.
Under table 4 summarizes six kinds of different operating conditions (comprise four more sharp and three invention profit) CO
2separating effect.
Table 4
System vacuum pressure minimum under each sequence number condition is 3.5kPa, and during high humidity air inlet, water inspissation degree controls in volumetric concentration about 8%.But different comparing results that is more sharp and invention profit is as follows:
(1), under dry inlet air conditions, single 13X adsorption layer 6 step experiment (see sequence number I) can obtain comparatively ideal CO
2purity and the rate of recovery are 78.4% and 86.5% respectively.But single 13X adsorption layer and under high humidity inlet air conditions (see sequence number VI), the 13X in whole adsorbent bed can be polluted and inactivation by steam.
(2) known to the sequence number I and sequence number II that has a competition, even if add Sorbead adsorption layer, CO
2separating effect be not subject to too large impact, CO
2purity declines slightly to some extent, because Sorbead is to CO
2also more weak adsorption capacity is had.Therefore, no matter be six steps or the operation of nine steps, adding of front layer sorbent material Sorbead obviously can not have influence on overall CO
2separating effect.
(3) sequence number II and III and sequence number IV and V is contrasted, in double-deck pressure-variable adsorption experiment, under steam is trapped within front layer adsorbent prerequisite, compared with dry air inlet, CO during high humidity air inlet
2purity and the rate of recovery slightly decline, but 13X still has greater activity carrys out separation of C O
2.Thus this double-deck pressure swing adsorption technique has double action, can remove the steam in flue gas and carbon dioxide simultaneously.
(4) compared (sequence number II and IV and sequence number III and V) by different operating step condition, although nine step operations employ gas product rinse adsorbent bed, CO
2the rate of recovery slightly decline, but nine steps operation can substantially increase CO
2the rate of recovery.Even if under high humidity inlet air conditions, CO
2purity also can from six steps operations 72.3% be increased to 86.9% under nine step practical operations works.
(5) last, contrast sequence number V and VI, when in rinsing step adsorbent bed, Pressure Drop is low to moderate 35kPa, although CO
2the rate of recovery can decline, but the comparatively pure carbon dioxide of 96.1% can be obtained.
Above-described embodiment is not the exhaustive of detailed description of the invention; also can there is other embodiment; above-described embodiment object is the present invention is described, but not limits the scope of the invention, and all application 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 is manufactured and uses the present invention.This invents the content that delegatable scope comprises detailed description of the invention in the content of claims and description and other embodiment.These other examples also should belong to the scope of claims of the present invention, as long as they contain the technical characteristic described by the identical written language of claim, or they include with claim without essence difference similar literal language described by technical characteristic.
All patents, the full content of patent application and other bibliography should be incorporated to present specification by reference.But if a term in the application conflicts mutually with the term including bibliography in, preferential with the term of the application.
All scopes disclosed herein all comprise end points, and are combine independently of one another between end points.
It should be noted that " first ", " second " or similar vocabulary do not represent any order, quality or importance, are only used to distinguish different technical characteristics.The qualifier " approximately " used in conjunction with quantity comprises the implication that described value and content context are specified.(such as: it includes error when measuring specific quantity).
Accompanying drawing explanation
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;
In figure, 1 is air inlet (dry air), and 2 is water vapor generation device, and 3 is air inlet tank, and 4 is 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 is the flow chart of three bed pressure swing adsorption cycles one of them adsorbent beds of six steps not with gas product flushing.
Fig. 3 is the flow chart of three one of them adsorbent beds of pressure swing adsorption cycles that nine steps are rinsed with gas product.
Claims (15)
1. trap a method for carbon dioxide in flue gas, it is characterized in that: comprise gas absorption step and gas desorption procedure; Described gas absorption step is by flue gas by multilayer pressure-swing absorption apparatus, in the adsorbent bed of described multilayer pressure-swing absorption apparatus by steam and carbon dioxide adsorption on adsorption layer, and do not flowed out described adsorbent bed by the waste gas adsorbed; Described gas desorption step is that the pressure reduced in described adsorbent bed makes carbon dioxide desorb from adsorption layer;
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, first by water vapor adsorption layer, then passes through carbon dioxide adsorption layer;
Gas product rinsing step is also comprised after gas absorption step, before gas desorption step;
Water vapor adsorption agent material and CO
2the volume ratio that sorbent material loads in adsorbent bed is 1:2.5-1:4, or 1:2.2, or 1:2.3;
Wherein, the multilayer pressure-swing absorption apparatus containing three adsorbent beds, job step is as follows:
Step 1: a bed air inlet absorption, all the other adsorbent beds are balanced;
Step 2: No. two bed gas products rinse, all the other two isostasies;
Step 3: No. two bed vacuum desorptions, all the other two isostasies;
Step 4: No. three bed air inlet absorption, all the other two adsorbent bed equilibriums;
Step 5: a bed gas product rinses, all the other two isostasies;
Step 6: a bed vacuum desorption, all the other two isostasies;
Step 7: No. two bed air inlet absorption, all the other two adsorbent bed equilibriums;
Step 8: No. three bed gas products rinse, all the other two isostasies;
Step 9: No. three bed vacuum desorptions, all the other two isostasies.
2. method according to claim 1, is characterized in that: realize reducing the pressure in described adsorbent bed by decompressor.
3. method according to claim 1, 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.
4. method according to claim 1, is characterized in that: the airintake direction of described multilayer pressure-swing absorption apparatus for from the bottom up, flue gas by flowing to below adsorbent bed, and not by the waste gas that adsorbs by flowing out above adsorbent bed; The direction of desorb is from top to bottom, and the gas being desorbed out flows out by below adsorbent bed.
5. the method according to any one of claim 1-4, 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.
6. the method according to any one of claim 1-4, is characterized in that: described flue gas contains and accounts for the carbon dioxide of cumulative volume 5-30% and the steam of 5-20%; The temperature of described flue gas is 20-150 DEG C, and flow is 50-500L/min.
7. the method according to any one of claim 1-4, is characterized in that: before gas absorption step, also comprise flue gas dust removal step and desulphurization denitration step.
8. the method according to any one of claim 1-4, is characterized in that: transformation operation runs within positive pressure range, and its absolute pressure value is 100-300kPa.
9. the method according to any one of claim 1-4, is characterized in that: transformation operation runs within range of negative pressure, and its absolute pressure value is 1-100kPa.
10. one kind traps the system of carbon dioxide in flue gas, it is characterized in that: comprise 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, in the below of described carbon dioxide adsorption layer, makes flue gas first by water vapor adsorption layer, then by carbon dioxide adsorption layer;
Water vapor adsorption agent material and CO
2the volume ratio that sorbent material loads in adsorbent bed is 1:2.5-1:4, or 1:2.2, or 1:2.3;
Wherein, the multilayer pressure-swing absorption apparatus containing three adsorbent beds, job step is as follows:
Step 1: a bed air inlet absorption, all the other adsorbent beds are balanced;
Step 2: No. two bed gas products rinse, all the other two isostasies;
Step 3: No. two bed vacuum desorptions, all the other two isostasies;
Step 4: No. three bed air inlet absorption, all the other two adsorbent bed equilibriums;
Step 5: a bed gas product rinses, all the other two isostasies;
Step 6: a bed vacuum desorption, all the other two isostasies;
Step 7: No. two bed air inlet absorption, all the other two adsorbent bed equilibriums;
Step 8: No. three bed gas products rinse, all the other two isostasies;
Step 9: No. three bed vacuum desorptions, all the other two isostasies.
11. systems according to claim 10, is characterized in that: the airintake direction of described multilayer pressure-swing absorption apparatus for from the bottom up, flue gas by flowing to below adsorbent bed, and not by the waste gas that adsorbs by flowing out above adsorbent bed; The direction of desorb is from top to bottom, and the gas being desorbed out flows out by below adsorbent bed.
12. systems according to claim 10, 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.
13. systems according to any one of claim 10-12, is characterized in that: all installed pneumatic changeover valve at the two ends of described adsorbent bed, by the closed mutual conversion realized between different operating step of described pneumatic changeover valve.
14. systems according to claim 13, is characterized in that: also comprise decompressor, described decompressor is connected with adsorbent bed, for reducing the air pressure in adsorbent bed.
15. systems according to claim 14, is characterized in that: also comprise temperature sensor, current meter and pressure sensor and be arranged in different unit the gas temperature, flow velocity and the force value that detect under different cycling condition respectively.
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| DE102015008993B4 (en) * | 2015-07-15 | 2022-01-05 | Drägerwerk AG & Co. KGaA | Method for operating an air drying device for drying air, an air drying device for drying air and a compressed air system |
| CN107045001A (en) * | 2017-01-09 | 2017-08-15 | 天津大学 | A kind of device for measuring carbon dioxide adsorption heat |
| CN113680173B (en) * | 2021-08-23 | 2023-01-13 | 无锡碳谷科技有限公司 | Device and method for directly capturing carbon dioxide by air |
| CN114669163B (en) * | 2022-03-23 | 2023-03-21 | 浙江师范大学 | Method for capturing carbon dioxide from flue gas |
| 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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