CN102327725B - Method for adsorbing and trapping CO2 by using steric effect - Google Patents

Method for adsorbing and trapping CO2 by using steric effect Download PDF

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CN102327725B
CN102327725B CN2011101833004A CN201110183300A CN102327725B CN 102327725 B CN102327725 B CN 102327725B CN 2011101833004 A CN2011101833004 A CN 2011101833004A CN 201110183300 A CN201110183300 A CN 201110183300A CN 102327725 B CN102327725 B CN 102327725B
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absorption
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CN102327725A (en
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李明
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Nantong San Intellectual Property Service Co ltd
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Wuxi Greenstek Co ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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Abstract

The invention provides a method for adsorbing and trapping CO2 by using a steric effect. According to the method, stable adsorption capacity to medium and high temperature mixed gases from an industrial exhaust source is achieved, and favorable CO2 selective adsorption relative to other gases in the gases is expressed. The method is characterized in that CO2 in the mixed gases is adsorbed by adopting a pressure varying adsorption technology and the steric effect, with a 3A zeolite molecular sieve with the aperture of about 0.3-0.34nm as an adsorbent.

Description

A kind of use steric effect adsorbing and trapping CO 2Method
Technical field
The present invention relates to CO 2The technical field of capture method is specially a kind of use steric effect adsorbing and trapping CO 2Method.
Background technology
The world today, CO 2A large amount of dischargings make that greenhouse effects are more and more serious, for this reason, for containing CO 2Concentration and temperature be higher industrial emission source all, adopts suitable technology to carry out CO 2Separate to reclaim and seem particularly necessary.
In the prior art, adopt the pressure swing adsorption technique of physical absorbent to capture CO 2Be subjected to extensive attention, 5A zeolite molecular sieve, 13X zeolite molecular sieve are widely used as adsorbent, and wherein the 5A zeolite molecular sieve has CO in the equilibrium adsorption 2Adsorbance raises with temperature and the characteristic that significantly reduces, and adsorption capacity was poor when it at high temperature used: when being elevated to 175 ℃ when temperature, and the CO of 5A zeolite molecular sieve 2Adsorbance only be 25 ℃ 24%; The 13X zeolite molecular sieve is for containing low concentration CO 2During gaseous mixture, its CO absorption 2Measure low, so its selective absorption CO 2Ability.For this reason, press for find a kind of to CO 2Good adsorbance is arranged, and remaining gas shows specific CO in the relative mist under middle hot conditions 2The adsorbent of selective absorption, and definite its brought into play optimal adsorption capture CO under the reasonable process condition 2Method.
Summary of the invention
At the problems referred to above, the invention provides a kind of use steric effect adsorbing and trapping CO 2Method, it makes the middle high-temperature gas mixture body to industrial emission source have stable adsorbance, and relatively in the mist remaining gas show good CO 2Selective absorption.
A kind of use steric effect adsorbing and trapping CO 2Method, its technical scheme is such:
It is characterized in that: be adsorbent with the 3A zeolite molecular sieve of aperture about 0.3～0.34nm, adopt pressure swing adsorption, by the CO in the steric effect absorption mist 2
It is further characterized in that: the adsorption temp in the described pressure swing adsorption is at 80 ℃～300 ℃, and adsorptive pressure is at 0.2MPa～1MPa;
It further is characterised in that:
It comprises at least two adsorption towers, and the adsorbent in the adsorption tower is the 3A zeolite molecular sieve of aperture about 0.3～0.34nm, CO absorption 2The time, wherein at least one adsorption tower participates in absorption, at least one adsorption tower participates in desorb, and the method step of described pressure swing adsorption is as follows:
A feeds unstripped gas in the adsorption tower that participates in absorption and adsorbs adsorption temp: 80 ℃～300 ℃, and adsorptive pressure: 0.2MPa～1MPa, adsorption time: 200 seconds～300 seconds, be adsorbed CO 2After gas flow out from the outlet of this adsorption tower;
The desorb of the absorption of the adsorption tower of b participation absorption and the adsorption tower of participation desorb is finished simultaneously, and the corresponding single adsorption tower of finishing that adsorbed of the adsorption tower that single desorb is afterwards finished is all pressed, and all the pressure time is 5 seconds～10 seconds;
After c all pressed and finishes, the adsorption tower that absorption is just finished carried out desorb by step-down, desorption pressures: 0MPa～0.1MPa, CO by the pipeline connection outside 2Be discharged from this adsorption tower, the 3A zeolite molecular sieve regeneration in this adsorption tower, its desorption time is identical with its adsorption time, and this moment, other adsorption tower adsorbed synchronously;
The adsorption tower that the firm desorb of d is finished carries out the pressurising first time by another adsorption tower of finishing adsorption process simultaneously, feeds part then and is adsorbed CO 2Product gas this adsorption tower is pressurized to adsorptive pressure: 0.2MPa～1MPa;
Above-mentioned job step is carried out in this adsorption tower circulation that pressurising is finished after the e.
After adopting method of the present invention, the aperture is loaded in adsorption tower at the 3A zeolite molecular sieve about 0.3～0.34nm, removes CO in the unstripped gas 2Outside other gas molecule diameter all greater than 0.34nm(N 2The molecule effective diameter is 0.364nm, O 2The molecule effective diameter is 0.346nm, CH 4The molecule effective diameter is 0.38nm), so N 2, O 2, CH 4Be difficult for adsorbing in 3A zeolite molecular sieve micropore Deng gas, it passes through adsorption layer along the gap between the 3A zeolite molecular sieve, and CO 2Effective diameter is 0.33nm, and its kinetic energy by molecular motion enters the micropore in the 3A zeolite molecular sieve, is adsorbed capture.This method improves selective, the actual arresting efficiency of increase adsorbent of adsorbent, to handle CO 2Content is 10% CO 2And N 2Gaseous mixture is example, CO of the present invention 2Effectively adsorbance is 5 times of the 13X zeolite molecular sieve used always, and CO in the stripping gas 2Concentration also surpass 95%, reached the level of direct liquefaction substantially, thereby realized CO 2The efficient capture utilization of gas.The present invention has stable equilibrium adsorption capacity to the mist of industrial emission source, and the remaining gas in the relative mist shows specific CO 2Selective absorption.And in the prior art, the 3A zeolite molecular sieve only is used as adsorption moisture.
Description of drawings
Fig. 1 is four tower pressure swing adsorption process flow chart of the present invention;
Fig. 2 is that the adsorption tower exit gas is formed in the specific embodiment one;
Fig. 3 is that the adsorption tower exit gas is formed in the specific embodiment two.
The specific embodiment
It comprises at least two adsorption towers, and the adsorbent in the adsorption tower is the 3A zeolite molecular sieve of aperture about 0.3～0.34nm, CO absorption 2The time, wherein at least one adsorption tower participates in absorption, at least one adsorption tower participates in desorb, and the method step of described pressure swing adsorption is as follows:
A feeds unstripped gas in the adsorption tower that participates in absorption and adsorbs adsorption temp: 80 ℃～300 ℃, and adsorptive pressure: 0.2MPa～1MPa, adsorption time: 200 seconds～300 seconds, be adsorbed CO 2After gas flow out from the outlet of this adsorption tower;
The desorb of the absorption of the adsorption tower of b participation absorption and the adsorption tower of participation desorb is finished, and the corresponding single adsorption tower of finishing that adsorbed of the adsorption tower that single desorb is afterwards finished is all pressed, and all the pressure time is 5 seconds～20 seconds;
After c all pressed and finishes, the adsorption tower that absorption is just finished carried out desorb by step-down, desorption pressures: 0MPa～0.1MPa, CO by the pipeline connection outside 2Be discharged from this adsorption tower, the 3A zeolite molecular sieve regeneration in this adsorption tower, its desorption time is identical with its adsorption time, and this moment, other adsorption tower adsorbed synchronously;
The adsorption tower that the firm desorb of d is finished carries out the pressurising first time by another adsorption tower of finishing adsorption process simultaneously, feeds then and is removed CO 2Product gas this adsorption tower is pressurized to adsorptive pressure: 0.2MPa～1MPa;
Above-mentioned job step is carried out in this adsorption tower circulation that pressurising is finished after the e.
Specific embodiment one:
Adopt the absorption of four tower transformations to carry out CO in steam power plant's flue gas 2Capture, steam power plant's smoke characteristic is:
Treating capacity is big: in 1,440 ten thousand degree that generate electricity day, the discharging flue gas is about 532.4m 3/ s;
Temperature is higher: the mean temperature of flue gas is 100 ℃, and induced-draught fan outlet cigarette temperature is 130 ℃ after dedusting, and chimney breast cigarette temperature is between 70-90 ℃;
Pressure is lower; Exhanst gas outlet is generally normal pressure, and pressure is 0.1～0.15 MPa;
Composition is than complexity and contain CO 2Concentration is lower, and smoke components is: 13% CO 2, 73% N 2, 10% H 2O, 3% O 2With all contaminations matter that is less than 1%;
After pre-dehydration and supercharging, adopt the absorption of four tower transformations to carry out CO 2Capture, see Fig. 1, it comprises adsorption tower 1, adsorption tower 2, adsorption tower 3, adsorption tower 4, product gas tank 5, the aperture is loaded in adsorption tower 1, adsorption tower 2, adsorption tower 3, adsorption tower 4 at the 3A zeolite molecular sieve about 0.3～0.34nm, and the existing work period with adsorption tower 1 is illustrated whole adsorbing and trapping process:
When a began to adsorb, the adsorption temp in the adsorption tower 1 was that 80 ℃, adsorptive pressure are 0.2MPa, unstripped gas is fed in the adsorption tower 1 adsorb, and adsorption time 200 seconds is adsorbed CO 2After gas flow out from the outlet of adsorption tower 1, feed product gas tank 5;
Adsorption tower 1 and the adsorption tower 2 of having finished desorb are all pressed after the b, all press the time: 20 seconds;
C makes adsorption tower 1 by desorb pipeline connection outside, bottom then, is depressurized to normal pressure and carries out desorb, CO 2Be discharged from this adsorption tower, the 3A zeolite molecular sieve regeneration in this adsorption tower, desorption time: 200 seconds;
Adsorption tower 1 carries out the pressurising first time by the adsorption tower 2 of finishing desorb after the d, and product gas tank 5 is pressurized to close to 0.2MPa this adsorption tower to adsorption tower 1 feeding gas then;
Above-mentioned job step is carried out in this adsorption tower 1 circulation that pressurising is finished after the e.
Final outlet CO behind adsorbing and trapping 2Account for total volume fraction and can drop to 2% following (see figure 2), CO 2Removal efficiency is higher than 85%, and its carbon arresting efficiency is 5 times of the 13X zeolite molecular sieve used always.The CO that after desorb, obtains 2Concentration is convenient to further to CO more than 95% 2Carry and seal up for safekeeping.
Specific embodiment two:
Adopt the absorption of four tower transformations to carry out CO in the coking plant circulating air 2Capture, the circulating air main component in the coking plant dry coke quenching technology is inert gas N 2, contain the CO of 10-16% 2With a small amount of CO that is no more than 7%.Become 900 ℃ high-temperature flue gas after circulating air and the heat exchange of burnt layer, after processes such as one-time dedusting, waste heat exchange, final dusting, circulate next time.CO during heat exchange in the circulating air 2Can generate CO with red burnt reaction, cause the coke scaling loss.Handled circulating air essential condition is as follows: temperature is 0.1-0.12 MPa, CO at 160 ℃, pressure 2%:N 2%:CO%=15:79:6.
Adopt the absorption of four tower transformations to carry out CO 2Capture, see Fig. 1, it comprises adsorption tower 1, adsorption tower 2, adsorption tower 3, adsorption tower 4, product gas tank 5, the aperture is loaded in adsorption tower 1, adsorption tower 2, adsorption tower 3, adsorption tower 4 at the 3A zeolite molecular sieve about 0.3～0.34nm, and the existing work period with adsorption tower 1 is illustrated whole adsorbing and trapping process:
When a began to adsorb, the adsorption temp in the adsorption tower 1 was that 160 ℃, adsorptive pressure are 0.4MPa, unstripped gas is fed in the adsorption tower 1 adsorb, and adsorption time 300 seconds is adsorbed CO 2After gas flow out from the outlet of adsorption tower 1, feed product gas tank 5;
Adsorption tower 1 and the adsorption tower 3 of having finished desorb are all pressed after the b, all press the time: 5 seconds;
C makes adsorption tower 1 vacuumize by bottom desorb pipeline then, and the vacuum that is depressurized to 0MPa is carried out desorb, CO 2Be discharged from this adsorption tower, the 3A zeolite molecular sieve regeneration in this adsorption tower, desorption time: 300 seconds;
Adsorption tower 1 carries out the pressurising first time by the adsorption tower 3 of finishing desorb after the d, and product gas tank 5 feeds gas to adsorption tower 1 this adsorption tower is pressurized to 0.4MPa then;
Above-mentioned job step is carried out in this adsorption tower 1 circulation that pressurising is finished after the e.
Final outlet CO 2Concentration in 2% following (see figure 3), removal efficiency reaches 88.3%, can reduce the coke burn out rate significantly.The CO that after desorb, obtains 2Concentration is convenient to further to CO more than 96% 2Carry and seal up for safekeeping.
Specific embodiment three:
Adopt the absorption of four tower transformations to carry out CO in the coke-stove gas of coke oven 2Capture, coke-stove gas is mixture, its productive rate with form because of the different difference to some extent with the coking condition of coal for coking quality.Its main component is hydrogen and methane, also contains a certain amount of carbon monoxide, carbon dioxide, nitrogen etc. in addition.Handled oven gas essential condition is as follows: temperature is at 300 ℃, and pressure is 0.1-0.12 MPa, mainly forms H 2: CH 4: CO:CO 2: N 2=55%:25%:8%:10%:2%.
Adopt the absorption of four tower transformations to carry out CO 2Capture, see Fig. 1, it comprises adsorption tower 1, adsorption tower 2, adsorption tower 3, adsorption tower 4, product gas tank 5, the 3A zeolite molecular sieve tegillum of aperture about 0.3～0.34nm fills in adsorption tower 1, adsorption tower 2, adsorption tower 3, the adsorption tower 4, and the existing work period with adsorption tower 1 is illustrated whole adsorbing and trapping process:
When a began to adsorb, the adsorption temp in the adsorption tower 1 was that 300 ℃, adsorptive pressure are 1MPa, unstripped gas is fed in the adsorption tower 1 adsorb, and adsorption time 200 seconds is adsorbed CO 2After gas flow out from the outlet of adsorption tower 1, feed product gas tank 5;
Adsorption tower 1 and the adsorption tower 4 of having finished desorb are all pressed after the b, all press the time: 10 seconds;
C makes adsorption tower 1 vacuumize by bottom desorb pipeline then, is depressurized to 0.1MPa and carries out desorb, CO 2Be discharged from this adsorption tower, the 3A zeolite molecular sieve regeneration in this adsorption tower, desorption time: 200 seconds;
Adsorption tower 1 carries out the pressurising first time by the adsorption tower 4 of finishing desorb after the d, and product gas tank 5 feeds gas to adsorption tower 1 this adsorption tower is pressurized to 1MPa then;
Above-mentioned job step is carried out in this adsorption tower circulation 1 that pressurising is finished after the e.

Claims (1)

1. one kind is used steric effect adsorbing and trapping CO 2Method, it is characterized in that: be adsorbent with the aperture at the 3A of 0.3～0.34nm zeolite molecular sieve, adopt pressure swing adsorption, by the CO in the steric effect absorption mist 2Adsorption temp in the described pressure swing adsorption is at 80 ℃～300 ℃, and adsorptive pressure is at 0.2MPa～1MPa; It comprises at least two adsorption towers, and the adsorbent in the adsorption tower is that the aperture is in the 3A of 0.3～0.34nm zeolite molecular sieve, CO absorption 2The time, wherein at least one adsorption tower participates in absorption, at least one adsorption tower participates in desorb, and the method step of described pressure swing adsorption is as follows:
Adsorb adsorption temp in a, the adsorption tower with unstripped gas feeding participation absorption: 80 ℃～300 ℃, adsorptive pressure: 0.2MPa～1MPa, adsorption time: 200 seconds～300 seconds, be adsorbed CO 2After gas flow out from the outlet of this adsorption tower;
The desorb of the adsorption tower of the absorption of the adsorption tower of b, participation absorption and participation desorb is finished simultaneously, and the corresponding single adsorption tower of finishing that adsorbed of the adsorption tower that single desorb is afterwards finished is all pressed, and all the pressure time is 5 seconds～10 seconds;
C, all press finish after, the adsorption tower that absorption is just finished carries out desorb by step-down, desorption pressures: 0MPa～0.1MPa, CO by the pipeline connection outside 2Be discharged from this adsorption tower, the 3A zeolite molecular sieve regeneration in this adsorption tower, its desorption time is identical with its adsorption time, and this moment, other adsorption tower adsorbed synchronously;
The adsorption tower that d, desorb are just finished carries out the pressurising first time by another adsorption tower of finishing adsorption process simultaneously, feeds then and is adsorbed CO 2Product gas this adsorption tower is pressurized to adsorptive pressure: 0.2MPa～1MPa;
Above-mentioned job step is carried out in this adsorption tower circulation that e, pressurising are afterwards finished.
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JP6663024B2 (en) * 2016-08-22 2020-03-11 フタバ産業株式会社 Carbon dioxide supply device
CN109012029B (en) * 2018-10-17 2021-02-26 齐鲁工业大学 Carbon dioxide adsorption recovery method

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EP0904825A2 (en) * 1997-09-30 1999-03-31 The Boc Group, Inc. Removal of carbon dioxide from air
US5897686A (en) * 1997-10-22 1999-04-27 Air Products And Chemicals, Inc. Synthesis gas drying and CO2 removal
CN1230452A (en) * 1998-03-12 1999-10-06 波克股份有限公司 Removal of carbon dioxide from gas streams

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KR0173399B1 (en) * 1996-08-28 1999-02-01 손영목 Method for manufacturing carbon dioxide by pressure swing absorption

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Publication number Priority date Publication date Assignee Title
EP0904825A2 (en) * 1997-09-30 1999-03-31 The Boc Group, Inc. Removal of carbon dioxide from air
US5897686A (en) * 1997-10-22 1999-04-27 Air Products And Chemicals, Inc. Synthesis gas drying and CO2 removal
CN1230452A (en) * 1998-03-12 1999-10-06 波克股份有限公司 Removal of carbon dioxide from gas streams

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