CN101559348A - For removing moisture from a substrate containing CH4And/or N2To separate CO from the gas2Adsorbent, preparation method and application thereof - Google Patents
For removing moisture from a substrate containing CH4And/or N2To separate CO from the gas2Adsorbent, preparation method and application thereof Download PDFInfo
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- CN101559348A CN101559348A CNA2009100328180A CN200910032818A CN101559348A CN 101559348 A CN101559348 A CN 101559348A CN A2009100328180 A CNA2009100328180 A CN A2009100328180A CN 200910032818 A CN200910032818 A CN 200910032818A CN 101559348 A CN101559348 A CN 101559348A
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- 238000000926 separation method Methods 0.000 claims abstract description 35
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- 229960000892 attapulgite Drugs 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
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- 238000003756 stirring Methods 0.000 claims description 2
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- 238000001354 calcination Methods 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- 238000010521 absorption reaction Methods 0.000 description 25
- 239000007789 gas Substances 0.000 description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
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- 230000004913 activation Effects 0.000 description 6
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- 238000007789 sealing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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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
- 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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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the field of gas separation and disclosesFor removing moisture from a substrate containing CH4And/or N2To separate CO from the gas2The preparation method and the application of the adsorbent. The adsorbent is prepared by the following method: pulverizing attapulgite clay, adding acid solution, modifying at constant temperature of 60-90 deg.C for a certain time, washing to pH 7, drying, and calcining. The adsorbent can effectively adsorb and separate CH4And/or N2CO in the gas of (2)2. The preparation method is simple and easy to operate, and the prepared adsorbent can adsorb CO2The adsorption capacity is large and the adsorption separation effect is obvious. The adsorbent can be used for CH4And/or N2CO in the System2Separation, the separation coefficient is: alpha is alphaCO2/CH4>8、αCO2/N2>25。
Description
Technical field
The invention belongs to the gas separation field, relate to a kind of being used for from containing CH
4And/or N
2Gas in separation of C O
2Adsorbent and its production and application.
Background technology
Natural gas is important chemical material and clean energy resource, and along with the adjustment of energy resource structure, the human wants amount constantly increases.Natural gas is as one of three big fossil energies, and half a century also was taken as a kind of byproduct of oil exploitation in the past usually, and its value and crude oil almost are equal to now.Find the discovery chance of the opportunity of natural gas much larger than oil from now on, along with the worsening shortages and the good human requirement to preserving the ecological environment of scientific and technological progress of petroleum resources, the world continues to increase the demand of natural gas.The proportion of natural gas in world's primary energy structure by 1970 17% rise to 1994 23%, expect 2010 and will reach 25%, so also the someone thinks that 21 century will become the natural gas epoch.The energy resource structure of China is very unreasonable, natural gas utilize degree very low, China's natural gas accounts for 2% of energy total amount, and external ratio reaches 20%.The main component of natural gas is a methane, but the new natural gas of gathering contains a certain amount of CO usually
2Because CO
2Existence, not only reduced the calorific value of natural gas, its faintly acid has very important corrosiveness for the conveyance conduit and the reservoir vessel of natural gas simultaneously.
According to different CO
2Separate and purification CO in the source
2Technology have 20 surplus kind, but more common at present having: cryogenic rectification method, absorption process (Physical Absorption method and chemical absorption method), membrane separation process and absorption method.
Carbon dioxide is a kind of important chemical raw materials for production, and it is of many uses, as is used to produce methyl alcohol and urea; In industrial waste and water treatment procedure, carbon dioxide is important environment composition, and available carbon dioxide replaces sulfuric acid control pH value etc.; On the other hand, carbon dioxide content surge in recent years causes greenhouse effects, global warming, and sea level rise; Also can contain a large amount of CO in the flue gas that also has boiler, gas turbine, lime to store
2, more than a large amount of CO
2Discharging all can cause huge threat to environment, all need to isolate CO in the purification of natural gas, biogas, coal gas, cellar for storing things gas, fermentation gas, industrial waste gas processing etc.
2, and from flue gas, deviate from and reclaim CO
2Gas etc., existing Many researchers has been done research to this, so from aspects such as commercial Application and environmental protection adsorbing separation CO as can be known
2It is particularly important that gas all seems.
Summary of the invention
The object of the present invention is to provide a kind of can being used for from containing CH
4And/or N
2Gas in separation of C O
2Adsorbent.
Another object of the present invention provides above-mentioned preparation of adsorbent method.
A further object of the invention provides the application of above-mentioned adsorbent.
Purpose of the present invention realizes by following technical proposal:
A kind of being used for from containing CH
4And/or N
2Gas in separation of C O
2Adsorbent, this adsorbent prepares by following method:
Get the Concave-convex clay rod raw material, pulverize, add acid solution, appropriate time is handled in 60-90 ℃ of constant temperature modification, wash to the pH value be 7, drying, roasting and getting.
Described adsorbent, wherein this adsorbent raw material adopts the Concave-convex clay rod that natural attapulgite clay or process removal of impurities are purified.
Described adsorbent, wherein removal of impurities is purified and adopted following method: the natural attapulgite clay is pulverized, and adds dispersant and water, stirs, and makes it form suspension, leaves standstill 24-48h, gets the supernatant liquid centrifugation and obtains the Concave-convex clay rod that removal of impurities is purified.The dispersant that adds is one or more in sodium pyrophosphate, sodium metasilicate, calgon, the Sodium Polyacrylate, addition is the 3%-6% of the excellent stone clay of recessed soil quality, can also work in coordination with simultaneously ultrasonic processing together, the particle that utilizes ultrasonic " cavitation " effect to disperse Concave-convex clay rod to reunite.
Described adsorbent, wherein the solid-to-liquid ratio of Concave-convex clay rod and acid solution is 1: 5-1: 20 (g/100ml), acid is HCl, HNO
3, H
2SO
4, H
3PO
4, H
2C
2O
4In a kind of or two kinds, when acid was a kind of, concentration was 0.2-1mol/L, when acid was two kinds, total acid concentration was respectively 0.2-1mol/L, perhaps acid solution pH is 2-4.
This adsorbent is used for adsorbing separation CO
2Activation condition be 200-400 ℃ of heating 1-8h and/or vacuumize 2-4h, adsorb under the normal temperature.
Described preparation of adsorbent method comprises the following steps: to get the Concave-convex clay rod raw material, pulverizes, and adds acid solution, and appropriate time is handled in 60-90 ℃ of constant temperature modification, wash to the pH value be 7, drying, roasting and getting.
Described adsorbent is used for from containing CH
4And/or N
2Gas in adsorbing separation CO
2
Beneficial effect of the present invention:
Raw material sources of the present invention are abundant, cost is low, operation is simple, to CO
2Adsorption capacity big, CO
2With CH
4And N
2Good separating effect, can be used for from containing CH
4And/or N
2Gas in separation of C O
2
1, the simple easy operating of preparation method, and cost is low.
2, prepared adsorbent crystal structure is complete, look whiteness height, purity height, and agglomeration obviously reduces, and impurity also obviously reduces, good dispersion.
3, prepared adsorbent specific area and pore volume have very big raising, CO absorption with respect to the Concave-convex clay rod raw material
2Amount significantly improve, and to CH
4And N
2Adsorbance little, can be used for CH
4And/or N
2Middle CO
2Separation.
The specific area of raw material Concave-convex clay rod is 100m
2About/g, the specific area after the modification is 200-400m
2/ g; Pore volume before and after the modification is for being respectively 0.4cm
3About/g and 0.9cm
3About/g; Look whiteness before and after the modification has obvious variation, and the look whiteness is higher after the modification; And the Concave-convex clay rod after the modification than modification before the adsorbed gas performance improve a lot, be determined under the pressure of 760mmHg (1 standard atmospheric pressure) Concave-convex clay rod CO absorption before the modification under the room temperature
2Amount be 13cm
3About/g, and the CO after the modification
2Adsorbance is greater than 33cm
3/ g, CH simultaneously
4, N
2The adsorbance of gas all is not more than 4cm
3/ g (see Fig. 4, the data of Fig. 4 are to be vacuumized after 2 hours through normal temperature by adsorbent at room temperature to measure on OMNISORP 100CX specific surface and aperture absorption instrument).The separation α of this adsorbent
CO2/CH4>8, α
CO2/N2>25.
Description of drawings
Fig. 1 is the process chart of preparation adsorbent.
Fig. 2 is the sem photograph of natural attapulgite clay.
Fig. 3 is the Concave-convex clay rod sem photograph after purification and the chemical modification.
Fig. 4 adsorbent is at normal temperatures to CO
2, N
2, CH
4The adsorption isotherm of pure component equilibrium adsorption.
Wherein: ■ is a Concave-convex clay rod CO absorption after the modification
2Amount, ● be Concave-convex clay rod CO absorption before the modification
2Amount, ▲ be Concave-convex clay rod absorption CH after the modification
4Amount,
Be Concave-convex clay rod absorption N after the modification
2Amount.
Fig. 5 mist adsorbing separation determinator schematic diagram.
Wherein: 1. raw material gas cylinder 2. nitrogen cylinders 3. argon bottles 4. dry post 5. adsorption column 6-8. pressure-reducing valve 9-15. control valves 16. flow control valves 17. activation furnaces 18. vacuum meters 19. precision pressure gauges 20. vavuum pumps 21. spinner flowmeters 22. six-way valves 23. gas chromatographs 24. soap film flowmeters 25. programmed temperature control instruments.
The specific embodiment
The invention will be further elaborated by the following examples.
Separation is measured:
Take by weighing adsorbent 0.1-1g at 200-400 ℃ of heating 1-8h and/or vacuumize 2-4h, under normal temperature, same pressure, be used for adsorbing separation CO then
2, CH
4, N
2Gas, separation is calculated as follows:
Wherein: 1 represents different gas respectively with 2.For equilibrium adsorption situation (pure component gas), X
1, X
2Be equilibrium adsorption capacity (ml/g); For dynamic absorption (blending ingredients gas), X
1, X
2For penetrating adsorbance (ml/g) accordingly; Y
1, Y
2, be respectively the percentage composition of respective components in blending ingredients gas.
After embodiment 1 adopts the natural attapulgite clay to purify again modification prepare adsorbent
As shown in Figure 1, get 10g natural attapulgite clay pit, add 1000ml deionized water and sodium hexametaphosphate dispersant, the dispersant quality is 3% of a natural attapulgite clay quality, fully mix, make it form suspension, leave standstill 36h, get the supernatant liquid centrifugation, oven dry, the Concave-convex clay rod that must purify, 200 orders that grind, sieve, standby.The HCl solution that takes by weighing purification Concave-convex clay rod that 2g sieves and 2000ml concentration and be 0.6mol/L mixes, the water bath with thermostatic control of putting into temperature and be 90 ℃ keeps 12h, carry out modification, spend deionised water to pH be 7,200 orders of drying, grind, sieve, extruding slivering roasting (200-400 ℃, 4-8h) shaping obtains adsorbent, and sealing is preserved.Fig. 2 is the sem photograph of natural attapulgite clay.Fig. 3 is the Concave-convex clay rod sem photograph after purification and the chemical modification.
The adsorbent of preparation can be at 200-400 ℃ of heating 4-8h activates (the adsorbent activation condition of following examples preparations all condition) for this reason or/and vacuumize 2-4h, carries out determining adsorption under the normal temperature.The adsorbent that sealing is preserved after 200-400 ℃ of 4-8h roasting in the preparation process has been in the state of activation.
Get the 0.5g adsorbent and be used for absorption test, obtain the separation α of this adsorbent under the normal temperature and pressure according to the ratio of the maximum adsorption value of pure component
CO2/CH4Be 8.6, α
CO2/N2Be 26.2.
All at 100 ℃ used adsorbent vacuumized 1h after adsorbent has adsorbed at every turn and regenerate, CO absorption under the normal temperature of regeneration back
2Value is 32.8cm
3/ g, 32.6cm
3/ g, 32.5cm
3/ g, 32.5cm
3/ g, adsorbance does not change basically, and regenerability is good.
Get 15g natural attapulgite clay pit, add 1000ml deionized water and dispersant sodium pyrophosphate, the consumption of dispersant is 4% of a natural attapulgite clay pit quality, fully mix, supernatant liquid is got in centrifugation, oven dry, the Concave-convex clay rod that must purify, pulverize, 200 orders that sieve, standby.Taking by weighing sieve Concave-convex clay rod and 1500ml concentration of 3g is the H of 0.8mol/L
2SO
4Solution mixes, and the water bath with thermostatic control of putting into temperature and be 80 ℃ keeps 8h, and washing is to neutral, 200 orders of drying, grind, sieve, and the extruding slivering, roasting (200-400 ℃, 4-8h) be shaped and obtain adsorbent, sealing is preserved.
Get the 0.4g adsorbent and be used for absorption test, record the separation α of this adsorbent under the normal temperature and pressure according to the ratio of the maximum adsorption value of pure component
CO2/CH4Be 8.7, α
CO2/N2Be 25.9.
All at normal temperature used adsorbent vacuumized 3h after adsorbent has adsorbed at every turn and regenerate, CO absorption under the normal temperature of regeneration back
2Value be 33.2cm
3/ g, 33.1cm
3/ g, 33cm
3/ g, 33cm
3/ g, adsorbance does not change basically, and regenerability is good.
Embodiment 3 directly adopts the natural attapulgite clay alteration to prepare adsorbent
Getting the natural attapulgite clay pit is raw material 100g, pulverize, and be that the natural attapulgite raw clay to be joined pH in 1: 20 be 3 HNO by the solid-to-liquid ratio (g/100ml) of Concave-convex clay rod raw material and acid solution
3In the solution, mix, keep 12h in 70 ℃ of waters bath with thermostatic control, spending deionised water is 7 to pH, 200 orders of drying, grind, sieve, and the extruding slivering, roasting (200-400 ℃, 4-8h) shaping obtains adsorbent, and sealing is preserved.
Get the 1g adsorbent and be used for absorption test, obtain the separation α of this adsorbent under the normal temperature and pressure according to the ratio of the maximum adsorption value of pure component
CO2/CH4Be 8.3, α
CO2/N2Be 26.1.
The adsorbent reactivation condition all vacuumizes 0.5h at 200 ℃ to used adsorbent at every turn after having adsorbed, CO absorption under the normal temperature of regeneration back
2Value be 32.6cm
3/ g, 32.5cm
3/ g, 32.4cm
3/ g, 32.4cm
3/ g, adsorbance does not change basically, and regenerability is good.
Embodiment 4 adopts natural attapulgite clay purification post-modification to prepare adsorbent
Getting natural attapulgite clay pit 20g is raw material, pulverize, add deionized water and dispersant sodium metasilicate, the consumption of sodium metasilicate is 5% of a Concave-convex clay rod quality, fully mix, make it form suspension, leave standstill 36h, get the supernatant liquid centrifugation, oven dry, the Concave-convex clay rod that must purify grinds, crosses 200 mesh sieves, and is standby.
Take by weighing the purification Concave-convex clay rod that 5g sieves, solid-to-liquid ratio (g/100mL) by 1: 10 is mixed with the HCl solution of 0.8mol/L, keep 12h in 90 ℃ the water bath with thermostatic control, spend deionised water to pH be 7,200 orders of drying, grind, sieve, extrusion molding, 340~400 ℃ of roasting 5h in Muffle furnace, obtain adsorbent, sealing is preserved.
Get the 1g adsorbent and be used for absorption test, obtain the separation α of this adsorbent under the normal temperature and pressure according to the ratio of the maximum adsorption value of pure component
CO2/CH4Be 8.4, α
CO2/N2Be 25.3.
All used adsorbent vacuumized after the each absorption of adsorbent is finished and regenerated CO absorption under the normal temperature in 10 minutes at 300 ℃
2Value be 32.9cm
3/ g, 32.8cm
3/ g, 32.5cm
3/ g, 32.5cm
3/ g, adsorbance does not change basically, and regenerability is good.
Embodiment 5 adopts the adsorbent of the Concave-convex clay rod preparation after purifying to carry out the absorption of three components
Adopt the post dynamic method to measure three component CO
2, N
2And CH
4Adsorption separation performance, calculate the adsorbance of each component according to the exit concentration breakthrough point.
Three component mist adsorbing separation determinator such as Fig. 5.
CO in the raw material gas cylinder 1
2And CH
4Mist is removed moisture content by dry post 4, with the N in the nitrogen cylinder 2
2, argon bottle 3 the mixed atmosphere formed through pressure-reducing valve 6-8 and control valve 9-11 respectively of Ar by adsorption column 5, adopt gas chromatograph 23 to measure each components contents in the mixed atmospheres, do not added mixed atmosphere before the adsorbent and formed and add CO behind the adsorbent
2, N
2And CH
4Adsorbance, the adsorbance that gas composition before the absorption and mensuration obtain sees Table 1.The activation of adsorbent can vacuumize by activation furnace 17 heating and/or by vavuum pump 20 with regeneration to be carried out, and the temperature of activation furnace 17 is regulated by program temperature instrument 25, and the degree that vacuumizes can be observed by vacuum meter 18.Mixed atmosphere by adsorption column 5 after control valve 14, flow control valve 16, spinner flowmeter 21, six siphunculus 22 to soap film flowmeter 24, are measured exit concentrations in the sampling of six siphunculus, 22 places through gas chromatograph 23.
Adsorbent adopts the adsorbent of embodiment 4 preparations.
Obtain CO by the adsorbance data in the table 1
2/ N
2Separation be 100, CO
2/ CH
4Separation be 9.
Table 1
Wherein adsorbent is to CO
2/ N
2The separation of the dynamic absorption separation during much larger than the pure component equilibrium adsorption, be because dynamically there is the displacement relation in absorption, because three components are adsorbed simultaneously and had competitive Adsorption, the N that begins to adsorb
2Gradually by CO
2Or CH
4Replace, cause adsorbance originally with regard to little N
2Adsorbance is littler, so separation differs greatly, the while is owing to the difference of adsorption capacity power, for CH
4Separation do not have great influence.
Claims (8)
1, a kind of being used for from containing CH
4And/or N
2Gas in separation of C O
2Adsorbent, it is characterized in that this adsorbent prepares by following method:
Get the Concave-convex clay rod raw material, pulverize, add acid solution, appropriate time is handled in 60-90 ℃ of constant temperature modification, wash to the pH value be 7, drying, roasting and getting.
2, adsorbent according to claim 1, the Concave-convex clay rod that its feature adopts the natural attapulgite clay or purifies through removal of impurities at this adsorbent raw material.
3, adsorbent according to claim 2, it is characterized in that the following method of removal of impurities purification employing: the natural attapulgite clay is pulverized, and adds dispersant and water, stir, make it form suspension, leave standstill 24-48h, get the supernatant liquid centrifugation and obtain the Concave-convex clay rod that removal of impurities is purified.
4, adsorbent according to claim 3 is characterized in that dispersant is one or more in sodium pyrophosphate, sodium metasilicate, calgon, the Sodium Polyacrylate, and addition is the 3%-6% of the excellent stone clay of recessed soil quality.
5, adsorbent according to claim 1, the solid-to-liquid ratio that it is characterized in that Concave-convex clay rod and acid solution is 1: 5-1: 20 (g/100ml), acid is HCl, HNO
3, H
2SO
4, H
3PO
4, H
2C
2O
4In a kind of or two kinds, when acid was a kind of, concentration was 0.2-1mol/L, when acid was two kinds, total acid concentration was respectively 0.2-1mol/L, perhaps acid solution pH is 2-4.
6, the described adsorbent of claim 1 is characterized in that this adsorbent is used for adsorbing separation CO
2Activation condition be 200-400 ℃ and heat and/or vacuumize 2-4h, adsorb under the normal temperature.
7, the described preparation of adsorbent method of claim 1, this method comprises the following steps: to get the Concave-convex clay rod raw material, pulverizes, and adds acid solution, appropriate time is handled in 60-90 ℃ of constant temperature modification, wash to the pH value be 7, drying, roasting and getting.
8, the described adsorbent of claim 1 is used for from containing CH
4And/or N
2Gas in adsorbing separation CO
2
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