CN115779860A - Chitosan and organic amine composite solid adsorbent for adsorbing carbon dioxide in coal-fired flue gas, and preparation method, application and regeneration method thereof - Google Patents
Chitosan and organic amine composite solid adsorbent for adsorbing carbon dioxide in coal-fired flue gas, and preparation method, application and regeneration method thereof Download PDFInfo
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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
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for adsorbing CO in coal-fired flue gas 2 The chitosan and organic amine composite solid adsorbent and the preparation method, the application and the regeneration method thereof. One preparation method comprises the following steps: 1) Dissolving chitosan in dilute acetic acid to prepare a transparent homogeneous chitosan solution; 2) Loading the uniformly mixed chitosan solution to the degassed mesoporous material; 3) Dissolving organic amine in absolute ethyl alcohol, and uniformly mixing to obtain an organic alcohol amine solution; 4) Adding the chitosan-impregnated porous support material to an organic amine solution to prepare CO 2 A solid adsorbent. According to the invention, chitosan and organic amine are used as active components to be loaded on the inner surface of the porous material pore channel, so that the mechanical strength of the original carrier is kept unchanged and the pore structure is complete, and the method is favorable for gas to be in the adsorbentThe mass transfer process of (2); amino group and CO 2 The adsorbent has high selectivity and adsorption capacity for complex flue gas of coal-fired power plants.
Description
Technical Field
The invention relates to a method for adsorbing CO in coal-fired flue gas 2 The chitosan and organic amine composite solid adsorbent is prepared by adsorbing CO in tail flue gas of a coal-fired power plant 2 Belonging to the fields of porous material adsorption and coal-fired flue gas purification.
Background
CO produced by fossil energy combustion 2 Is the most main source of greenhouse gases in the atmosphere and aims at the flue gas pair CO after the coal of a thermal power plant is combusted 2 The technology of capture and sequestration is currently considered to be one of the most promising technologies for the reduction of greenhouse gases in the atmosphere.
Among the various methods for capturing carbon dioxide at present, the solid adsorption method has the advantages of simple equipment, low regeneration energy consumption, mild reaction conditions, no equipment corrosion and the like, and has better application prospect. The main solid adsorbents at present comprise carbon-based adsorbents, silicon-based adsorbents, MOFs and the like, and the main adsorption effects are micropores of the adsorbents and CO 2 Molecular forces between molecules, however, in CO 2 The coal-fired flue gas with low partial pressure and complex components is subjected to N 2 Influence of moistureResulting in lower selectivity and thermal stability of the adsorbent. At present, in the field of gas-solid adsorption catalysis, loading cheap and easily-obtained active components on the surface of a porous solid adsorbent is an efficient method, so that the number of active sites on the adsorption surface can be obviously increased, the adsorption effect is changed from physical adsorption to main adsorption into chemical adsorption mainly comprising stable chemical bonds, and the CO can be effectively increased 2 Selectivity and thermal stability of the solid adsorbent.
Amino group (-NH) 2 ) With CO 2 A reversible reaction to form carbamate occurs, and the specific reaction formula is as follows:
the reaction between the carbamate and the carbamic acid is an acid-base equilibrium reaction between the carbamate and the amine, and is a reversible reaction, and the reverse reaction rate increases with the increase in temperature, so that the regeneration of the adsorbent can be performed by desorbing carbon dioxide by increasing the temperature, and the recycling of the adsorbent can be realized. Compared with the traditional solid adsorbent, the adsorbent loaded with amino as an active component can effectively improve the adsorption selectivity and can eliminate the existence of moisture to CO in the environment of complex flue gas of a coal-fired power plant 2 Influence of adsorption properties.
The chitosan is a macromolecular structure generated by deacetylating chitin, is widely and easily obtained in nature, contains rich amino and hydroxyl groups, is nontoxic, odorless and degradable, and has excellent biocompatibility. Organic amine is an active component which is more applied in the field of carbon adsorption, but an organic amine compound is an offensive odor pollutant next to organic sulfide, and can cause environmental pollution; compared with organic amine, the chitosan is rich in amino groups. Meanwhile, the composite material has biocompatibility, can effectively reduce the process flow and economic cost of wastewater treatment, and has the potential of realizing industrial large-scale application.
In recent years, many researchers at home and abroad apply chitosan to CO 2 The separation fields such as ionic liquid absorption, chitosan cross-linking agent coupling membrane separation method, solid framework adsorption and the like, which indicate that the chitosan has the function of adsorbing CO 2 For example, in "a method for preparing chitosan-based carbon dioxide adsorption aerogel" (patent No. CN 107952415A), the aerogel is prepared by quaternizing chitosan, loading carbonate ions, crosslinking with graphene oxide, and freeze-drying; and a preparation method of the carbon dioxide adsorbent with the chitosan skeleton, namely mixing a chitosan solution and resin particles loaded with carbonate ions, solidifying, and freeze-drying to form a skeleton structure. However, the technology does not aim at complex components in coal-fired flue gas, a mechanical structure is not enough to support industrial long-term cyclic absorption/desorption, a preparation flow is complex, the repeated preparation economy and time cost are too high, and large-scale industrial application is difficult to achieve.
Thus, in CO 2 Low partial pressure and complex composition in coal-fired flue gas, N 2 、O 2 And the influence of moisture and other trace gases causes the selectivity and thermal stability of the adsorbent to be low, so that the preparation cost is low on the premise of ensuring rapid dynamic adsorption, and the solid adsorbent with high selectivity and adsorption capacity is one of the important directions of the following researches.
Disclosure of Invention
In order to solve at least one of the technical problems, the invention provides a method for adsorbing CO in coal-fired flue gas 2 The preparation method of the chitosan and organic amine composite solid adsorbent and the application thereof in tail flue gas in coal-fired power plants.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of chitosan and organic amine composite solid adsorbent for adsorbing CO2 in coal-fired flue gas comprises the following steps:
s1, preparing a chitosan solution: dissolving chitosan in dilute acetic acid, stirring, and ultrasonically oscillating to fully dissolve the chitosan to obtain a uniform chitosan solution;
s2, loading chitosan: degassing the porous material in a vacuum drying oven at high temperature, and adding the degassed porous material into deionized water to form a suspension; and under the condition of stirring, dropwise adding the chitosan solution into the porous material suspension, uniformly mixing by ultrasonic oscillation, heating in a water bath for a period of time to ensure that the chitosan is fully impregnated, then cooling in an ice water bath, centrifuging to obtain solid particles, washing the solid particles to be neutral by using deionized water, and drying in a vacuum drying oven overnight to obtain the chitosan-loaded solid adsorbent.
S3, organic amine loading: adding organic amine into absolute ethyl alcohol, and stirring at room temperature until the organic amine is uniformly mixed to obtain a homogeneous organic amine solution; adding the chitosan-loaded solid adsorbent into an organic amine solution, continuously stirring, distilling by rotary distillation to remove redundant absolute ethyl alcohol, and finally putting the mixture into a vacuum drying oven to dry overnight to obtain CO 2 A solid adsorbent.
Alternatively, the preparation method comprises the following steps:
s1, organic amine loading: adding organic amine into absolute ethyl alcohol, and stirring at room temperature until the organic amine is uniformly mixed to obtain a homogeneous organic amine solution; degassing the porous material in a vacuum drying oven at high temperature, adding the degassed porous material into absolute ethyl alcohol, and stirring to obtain a uniform suspension; slowly dripping the organic amine solution into the suspension, and continuously stirring to fully impregnate; performing rotary distillation to evaporate redundant absolute ethyl alcohol, and finally putting the absolute ethyl alcohol into a vacuum drying oven for drying to obtain the solid adsorbent loaded with organic amine;
s2, preparing a chitosan solution: dissolving chitosan in dilute acetic acid, stirring, and ultrasonically oscillating to fully dissolve the chitosan to obtain a transparent homogeneous chitosan solution;
s3, loading chitosan: adding the solid adsorbent loaded with organic amine into deionized water to form a suspension; dropwise adding the chitosan solution to the porous material under stirringUltrasonically oscillating and uniformly mixing the material suspension, heating and stirring the material suspension in a water bath for a period of time to fully impregnate the chitosan, cooling the material suspension in an ice water bath, centrifuging the material suspension to obtain solid particles, washing the solid particles to be neutral by using deionized water, and drying the solid particles in a vacuum drying oven to obtain CO 2 A solid adsorbent.
In the technical scheme, the chitosan containing amino groups is adopted to replace part of organic amine to modify the porous material, so that CO is reduced 2 The adsorption/desorption temperature is about 35 ℃ as the best adsorption temperature, about 75 ℃ as the desorption temperature, basically stable in adsorption capacity after 10 times of circulation, and can be used for adsorbing CO in coal-fired flue gas 2 The selectivity is high.
On the basis of the technical scheme, the invention can be improved as follows.
Specifically, the chitosan is one or two of chitosan with a deacetylation degree of 75% or more, preferably chitosan with a deacetylation degree of 95% or more; the volume concentration of the dilute acetic acid is 1-3%; the mass concentration of the prepared chitosan solution is 0.5wt% -5 wt%. Acetic acid is an effective solvent for dissolving chitosan, and the properties of chitosan such as deacetylation degree, temperature, molecular weight and the like can influence the dissolving behavior. In acidic aqueous solutions, chitosan exists as an electrolyte. At this time, the chitosan forms ammonium salt through the action of protons in the acid and amino groups on the chitosan, thereby breaking hydrogen bonds between chitosan molecules and further realizing the dissolution process. The degree of deacetylation is an important factor affecting the properties of chitosan. The amino group in chitosan determines the change of the charging property of chitosan with the change of pH value, and the group determines the change of the charging property of chitosan with the change of pH value. When the pH value is low, the amino groups are protonated and positively charged, so that the chitosan becomes water-soluble cationic polyelectrolyte.
Specifically, the Porous material is one or two or more of Porous materials with the Pore diameter of 2nm-20nm, such as SBA-15, SBA-16, MCM-41, KIT-6, resin, carbon-based molecular sieves, activated carbon, mesoporous silica, MOFs, aerogel, columnar clay, metal oxide, phosphate, etc., or a hierarchical Pore molecular sieve material with micropores and mesopores, for example, a hierarchical Pore Zeolite molecular sieve disclosed in "Stable, ports, and bulk Particles with High External Surface and Large Pore Volume from Self-assembly of Zeolite Nanocrystals with catalysis Polymer" by Song et al; hierarchical porous ZSM-5, Y-type zeolite molecular sieves and the like disclosed in the literature, namely design synthesis, catalytic performance and computer simulation research of hierarchical porous zeolite; a hierarchical pore SAPO-11 molecular sieve disclosed in the patent of nanometer hierarchical pore SAPO-11 molecular sieve and the preparation method and application thereof (patent number CN 114054082B); a hierarchical porous carbon material and the like disclosed in the patent of a preparation method, a product and an application of a high-adsorption material (patent No. CN 112645329A).
Specifically, the organic amine includes one or more of polyethyleneimine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ethylenediamine, tertiary amine N-methyl glycol amine, ethanolamine, diethanolamine, N-methyl glycol amine, and the like. Adsorption method for capturing and separating CO 2 The key point of the method is the advantages and disadvantages of the adsorbent, and the CO has application value 2 The adsorbent should have the following conditions: excellent selectivity, high adsorption capacity, good mechanical strength and thermal stability, regenerability, good adsorption kinetics and low price cost. The porous material has the advantages of no toxicity, large specific surface area, mature preparation process, adjustable pore size according to requirements, large adsorption capacity and the like, but the adsorption performance is quickly reduced along with the rise and fall of temperature due to physical adsorption; especially zeolite molecular sieve material with strong adsorption to water and CO 2 Form competitive adsorption, thereby limiting the separation of CO from flue gas 2 The use of (1).
The porous material is modified, chitosan or organic amine containing amino groups is loaded on the premise of not influencing the mass transfer effect of adsorbate in pores, and the porous material which has a larger pore diameter (larger than 2 nm), controllable pore diameter, narrow distribution and a higher specific surface area or contains both mesopores and micropores is required to be adopted, and is selected as described above.
Specifically, the porous material is subjected to vacuum high-temperature degassing at 100-150 ℃ for 6-12 h. Degassing treatment is carried out before chitosan is loaded, so that some gas adsorbed by the carrier in the storage process can be removed, and the chitosan and organic amine can be more fully loaded on the surface of the adsorbent.
Specifically, the concentration of the porous material in the suspension is 10-15 g/L; s2, heating the water bath at 50-60 ℃ for 4-10 h; the cooling time of the ice water bath in the step S2 is 1-2 h; and in the step S2, the drying temperature is 50-70 ℃, and the drying time is 6-15 h. The temperature of the water bath and the drying heating are both kept in a milder range under the influence of the thermal stability of the chitosan.
Specifically, the concentration of the organic amine solution prepared in the step S3 is 2 g/L-10 g/L; the temperature of the rotary distillation process in the step S3 is 40-60 ℃, and the rotating speed of a distillation instrument is 400-1000rpm. When the organic amine is loaded, absolute ethyl alcohol is used as a solvent, redundant absolute ethyl alcohol is required to be removed after the impregnation is finished, and a rotary distillation mode is adopted.
Specifically, the ultrasonic oscillation time in the steps S1 to S3 is 20min to 60min; and in the stirring process from S1 to S3, the rotating speed of the magnetic stirrer is 400 to 1000rpm, and the time is 1 to 6 hours.
Specifically, the aperture of the adsorbent prepared in the step S3 is 0.5-4 nm, the maximum saturated adsorption capacity can reach 4.3mmol/g, and CO in the adsorbed gas can be adsorbed 2 The selectivity is over 95 percent.
Specifically, the adsorbent prepared in the step S3 is applied to CO in coal-fired flue gas 2 Capture of flue gas CO 2 The concentration is 5 to 30 percent, and the airspeed is 1000 to 1500h -1 When in use, the coal-fired flue gas can be discharged into CO 2 The concentration is reduced to be below 0.25 percent, and the method has great application prospect; the adsorption temperature is 25-40 ℃, and the desorption temperature is 75-90 ℃. The adsorption/desorption is carried out for 10 times in a circulating way, and the adsorption capacity is kept above 95 percent; the adsorption/desorption is carried out for 50 times in a circulating way, and the adsorption capacity is kept above 80 percent.
Specifically, when the adsorption capacity of the prepared adsorbent in the step S3 is lower than 75% of the initial adsorption capacity after multiple cycles, the adsorbent can be regarded as large in failure degree, purging is performed at 200 ℃ for 3 hours in a nitrogen atmosphere, then the adsorbent can be regenerated by soaking a small amount of chitosan, and the adsorption capacity after regeneration can reach 90% -100% of the initial adsorption capacity.
In the solid adsorbent prepared by the invention, the mass ratio of the chitosan to the organic amine to the porous material is (0.1-0.4): (0.4-0.1): 1.
The invention has the beneficial effects that:
1) A large amount of amino and hydroxyl, C3-OH and C2-NH, exist between molecules and in molecules of the unimpregnated chitosan 2 Functional groups such as C6-OH and the like can form intramolecular and intermolecular hydrogen bonds, so that free amino groups are not too many, and more groups can be utilized by dissolving in acetic acid and then impregnating, therefore, chitosan is loaded on the porous material by an impregnation method, and the utilization rate of amino groups in the chitosan can be obviously improved;
2) The mechanical strength and the pore structure of the original porous material are reserved, the rapid diffusion of flue gas in the pore diameter is facilitated, and the intact framework structure after the industrial repeated recycling can be ensured;
3) Active sites on the surface of the original porous material are increased, physical adsorption of the porous material is converted into chemical adsorption, and the problem that the original porous solid adsorbent is poor in selectivity and thermal stability is solved;
4) The chitosan is adopted to replace a part of organic amine for modification, so that the CO is reduced 2 The adsorption/desorption temperature is about 35 ℃, the desorption temperature is about 75 ℃, the adsorption capacity is basically stable after 10 times of circulation, the adsorbent is renewable, the circulation energy consumption is low, and the adsorbent is biodegradable, and has the potential of industrial large-scale application and higher ecological economic benefit.
Drawings
FIG. 1 is a CO of the present invention 2 A flow chart of a preparation method of the adsorbent;
FIG. 2 is a CO of the present invention 2 A schematic diagram of a penetrating absorption performance detection device;
FIG. 3 is CO of the present invention 2 And (4) a cyclic adsorption performance diagram.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
the embodiment provides a method for adsorbing CO in coal-fired flue gas 2 The chitosan and organic amine composite solid adsorbent and the preparation method thereof specifically comprise the following steps:
s1, preparing a chitosan solution: mixing 0.6g of chitosan with deacetylation degree of more than 95% with 2vol% of 1g of 100mL in a mass-to-volume ratio, stirring for 4 hours at room temperature by using a magnetic stirrer, and then carrying out ultrasonic oscillation for 20min to fully dissolve the chitosan to obtain a uniform chitosan solution;
s2, loading chitosan: degassing 1.5g of SBA-15 in a vacuum drying oven at 110 ℃ for 6h, and uniformly mixing the degassed molecular sieve and deionized water according to the mass ratio of 1; dropwise adding the chitosan solution obtained in the step S1 into the suspension under the stirring condition, carrying out ultrasonic bath for 20min, and uniformly mixing; heating the obtained suspension in water bath to 60 ℃, keeping the temperature for 6h, and cooling the suspension in ice water bath for 1h to ensure that the chitosan is fully impregnated into the porous material; obtaining adsorbent solid particles loaded with chitosan under the centrifugal action of 5000rpm, washing the adsorbent solid particles to be neutral by using deionized water, and drying the adsorbent solid particles in a vacuum drying oven at 50 ℃ overnight to obtain CO loaded with chitosan 2 A solid adsorbent.
S3, organic amine loading: mixing 0.9g of ethanolamine (MEA) and absolute ethanol according to the mass volume ratio of 1g; s2 the chitosan-loaded CO 2 Adding the solid adsorbent into the organic amine solution, and continuously stirring for 6 hours at 600rpm of a magnetic stirrer; distilling off excessive anhydrous ethanol at 50 deg.C with rotary distiller, and drying in vacuum oven at 50 deg.C overnight to obtain CO 2 Solid adsorbent, about 3g.
Example 2:
the embodiment provides a method for adsorbing CO in coal-fired flue gas 2 The chitosan and organic amine composite solid adsorbent and the preparation method thereof comprise the following steps:
s1, preparing a chitosan solution: mixing 0.6g of chitosan with the deacetylation degree of more than 95% with 2vol% of 1g of 100mL, stirring for 4 hours at room temperature by using a magnetic stirrer, and then carrying out ultrasonic oscillation for 20min to fully dissolve the chitosan to obtain a uniform chitosan solution;
s2, loading chitosan: degassing 1.5g of MCM-41 in a vacuum drying oven at 110 ℃ for 6h, and uniformly mixing the degassed molecular sieve and deionized water according to the mass ratio of 1; dropwise adding the chitosan solution in the S1 into the suspension under the stirring condition, and uniformly mixing the chitosan solution in an ultrasonic bath for 20 min; heating the obtained suspension in water bath to 60 ℃, keeping the temperature for 6h, and cooling the suspension in ice water bath for 1h to ensure that the chitosan is fully impregnated into the porous material; obtaining adsorbent solid particles loaded with chitosan under the centrifugal action of 5000rpm, washing the adsorbent solid particles to be neutral by using deionized water, and drying the adsorbent solid particles in a vacuum drying oven at 50 ℃ overnight to obtain CO loaded with chitosan 2 A solid adsorbent.
S3, organic amine loading: mixing 0.9g of Polyethyleneimine (PEI) with absolute ethyl alcohol according to a mass volume ratio of 1g; s2 the chitosan-loaded CO 2 Adding the solid adsorbent into the organic amine solution, and continuously stirring for 6 hours by a magnetic stirrer at 600 rpm; distilling off excessive anhydrous ethanol at 50 deg.C with rotary distiller, and drying in vacuum oven at 50 deg.C overnight to obtain CO 3g 2 A solid adsorbent.
Example 3:
the embodiment provides a method for adsorbing CO in coal-fired flue gas 2 The chitosan and organic amine composite solid adsorbent and the preparation method thereof specifically comprise the following steps:
s1, preparing a chitosan solution: mixing 0.6g of chitosan with deacetylation degree of more than 95% with 2vol% of 1g of 100mL in a mass-to-volume ratio, stirring for 4 hours at room temperature by using a magnetic stirrer, and then carrying out ultrasonic oscillation for 20min to fully dissolve the chitosan to obtain a uniform chitosan solution;
s2, loading chitosan: 1.5g of mesoporous SiO 2 Degassing at 110 deg.C for 6 hr in vacuum drying oven, mixing with deionized water1, and uniformly mixing in a mass ratio of 50 to form a suspension; dropwise adding the chitosan solution obtained in the step S1 into the suspension under the stirring condition, carrying out ultrasonic bath for 20min, and uniformly mixing; heating the obtained suspension in water bath to 60 ℃, keeping the temperature for 6h, and cooling the suspension in ice water bath for 1h to ensure that the chitosan is fully impregnated into the porous material; obtaining adsorbent solid particles loaded with chitosan under the centrifugal action of 5000rpm, washing the adsorbent solid particles to be neutral by using deionized water, and drying the adsorbent solid particles in a vacuum drying oven at 50 ℃ overnight to obtain CO loaded with chitosan 2 A solid adsorbent.
S3, organic amine loading: mixing 0.9g of Tetraethylenepentamine (TEPA) with absolute ethyl alcohol according to a mass volume ratio of 1g to 200mL, and continuously stirring for 1h at room temperature by using a magnetic stirrer at a rotating speed of 600rpm until the mixture is uniformly mixed to obtain an organic amine solution; s2 the chitosan-loaded CO 2 Adding the solid adsorbent into the organic amine solution, and continuously stirring for 6 hours at 600rpm of a magnetic stirrer; evaporating excessive anhydrous ethanol at 50 deg.C with rotary distiller, and drying in vacuum oven at 50 deg.C overnight to obtain about 3g CO 2 A solid adsorbent.
Example 4
The embodiment provides a method for adsorbing CO in coal-fired flue gas 2 The chitosan and organic amine composite solid adsorbent and the preparation method thereof specifically comprise the following steps:
s1, organic amine loading: mixing 0.9g of Polyethyleneimine (PEI) with absolute ethyl alcohol according to a mass-volume ratio of 1g to 200mL, and continuously stirring for 1h at a rotating speed of 600rpm of a magnetic stirrer at room temperature until the mixture is uniformly mixed to obtain an organic amine solution; degassing 1.5g of MCM-41 in a vacuum drying oven at 110 ℃ for 6h, and uniformly mixing the degassed molecular sieve and absolute ethyl alcohol according to the mass ratio of 1; slowly adding the organic amine solution into the suspension under the stirring condition, and continuously stirring for 6 hours by using a magnetic stirrer; removing excessive anhydrous ethanol at 50 deg.C with a rotary distiller, and drying in a vacuum oven at 50 deg.C overnight to obtain CO loaded with organic amine 2 A solid adsorbent.
S2, preparing a chitosan solution: mixing 0.6g of chitosan with the deacetylation degree of more than 95% with 2vol% of 1g of 100mL, stirring for 4 hours at room temperature by using a magnetic stirrer, and then carrying out ultrasonic oscillation for 20min to fully dissolve the chitosan to obtain a uniform chitosan solution;
s3, loading chitosan: the CO loaded with organic amine and described in S1 2 Uniformly mixing a solid adsorbent and deionized water according to the mass ratio of 1; dropwise adding the chitosan solution obtained in the step S2 into the suspension under the stirring condition, carrying out ultrasonic bath for 20min, and uniformly mixing; heating the obtained suspension in water bath to 60 ℃, keeping the temperature for 6h, and cooling the suspension in ice water bath for 1h to ensure that the chitosan is fully impregnated into the porous material; centrifuging at 5000rpm to obtain chitosan-loaded adsorbent solid particles, washing with deionized water to neutrality, and drying in vacuum oven at 50 deg.C overnight to obtain about 3g CO 2 A solid adsorbent.
Detection of CO prepared in examples 1 to 4 2 The structural parameters and detection results of the solid adsorbent are shown in Table 1. Wherein the specific surface area and pore size structure of the adsorbent are measured by a specific surface area and pore size distribution tester (ASAP 2020, michkok, USA); the average pore diameter is obtained by multiplying the pore volume by 4 divided by the BET area; for physical adsorption, CO 2 The adsorption of (a) occurs mainly within the micropores of the adsorbent; for chemisorption, in addition to being related to the specific surface area and pore size of the adsorbent, there is a close relationship mainly to the number of active functional groups on the surface of the adsorbent.
Detection of CO prepared in examples 1 to 4 2 CO of solid adsorbent 2 The adsorption performance and the detection result are shown in Table 2. Wherein, CO 2 The method for detecting the adsorption performance comprises the following steps: 1) The saturated adsorption capacity adopts a thermogravimetric adsorption method, a sample is dried in a vacuum drying oven at 50 ℃ overnight in advance so as to remove residual water and air impurities in the pore channel of the adsorbent, about 10mg of the sample is taken for analysis, the pretreatment process is completed by blowing in a high-purity nitrogen atmosphere of 50mL/min, the temperature is raised to 75 ℃ from room temperature at the heating rate of 5 ℃/min, and then the sample is kept at constant temperature for 30min so as to remove residual impurity gases in the pore channel of the adsorbent; cooling to 35 deg.C at a rate of 5 deg.C/min and standing at constant temperature for 30min to stabilize the temperature. Then high purity N is added 2 Switching to high purity CO 2 Adsorbing at the rate of 70mL/min until the quality is not obviously changed; 2) The penetrating adsorption quantity is detected by adopting an adsorption device shown in the following figure, about 2g of adsorbent is taken for experiment, the purging is completed in a high-purity nitrogen atmosphere of 100mL/min, the temperature is increased from room temperature to 75 ℃ at the temperature rise rate of 5 ℃/min, and then the adsorbent stays for 30min at constant temperature so as to remove the residual impurity gas in the pore channel of the adsorbent; cooling to 35 deg.C at a rate of 5 deg.C/min, and standing at constant temperature for 30min to stabilize the temperature; then N is added 2 Switching to mixed gas of coal-fired flue gas, each gas component being 15% CO 2 、100ppmSO 2 、500ppmNO X 、6％O 2 、3％H 2 O, and the balance of protective gas N 2 The breakthrough adsorption is carried out with a total gas flow of 100mL/min until the CO is discharged 2 Stopping when the concentration reaches the same concentration as the inlet concentration. Heating and desorbing the adsorbed sample by using TGA (thermal gas chromatography), circularly adsorbing/desorbing for multiple times, and calculating to obtain CO according to a concentration change curve 2 The amount of adsorption.
Table 1 example CO 2 Pore size structure of adsorbent
TABLE 2 different examples CO 2 Adsorption effect of adsorbent
The results show that the chitosan prepared by the above examples has CO after loading with organic amine 2 The solid adsorbent still has higher specific surface area and ordered pore structure, and CO is carried out 2 During the adsorption, CO can still be ensured 2 Mass transfer flow in the adsorbent pore channel so as to ensure that the adsorbent can carry out CO separation 2 The adsorption capacity of (A) is CO with prospect 2 A low temperature solid adsorbent material. The chitosan is used for replacing a part of organic amine for modification, so that CO is reduced 2 The optimum adsorption temperature is about 35 ℃, and the desorption temperature is about 75 DEG CAnd on the right, the adsorption capacity is still kept above 95% after 10 times of circulation, the adsorbent is renewable and has low circulating energy consumption, the chitosan is degradable, the environmental pollution is small, and the method has the potential of industrial large-scale application and higher ecological economic benefit.
The CO of the chitosan and organic amine modified porous material disclosed by the embodiment of the invention 2 Adsorbent preparation method and CO 2 The sorbent and its use are described in detail herein, and the principles and embodiments of the present invention are illustrated herein using specific examples, which are intended to be merely CO useful in understanding the present invention 2 Preparation method of solid adsorbent and CO 2 Adsorbent and its application and core idea; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. Adsorption of CO in coal-fired flue gas 2 The preparation method of the chitosan and organic amine composite solid adsorbent is characterized by comprising the following steps:
s1, preparing a chitosan solution: dissolving chitosan in dilute acetic acid, stirring, and ultrasonically oscillating to fully dissolve the chitosan to obtain a transparent homogeneous chitosan solution;
s2, loading chitosan: degassing a porous material in a vacuum drying oven at high temperature, and adding the porous material into deionized water to form a suspension; dropwise adding the chitosan solution into the porous material suspension under the stirring condition, uniformly mixing by ultrasonic oscillation, heating in a water bath, stirring for a period of time to fully impregnate the chitosan, cooling in an ice water bath, centrifuging to obtain solid particles, washing with deionized water to be neutral, and drying in a vacuum drying oven to obtain a chitosan-loaded solid adsorbent;
s3, organic amine loading: adding organic amine into absolute ethyl alcohol, and stirring at room temperature until the organic amine is uniformly mixed to obtain a homogeneous organic amine solution; adding the chitosan-loaded solid adsorbent into an organic amine solution, continuously stirring for full impregnation, and rotatingDistilling to remove excessive anhydrous ethanol, and drying in a vacuum drying oven to obtain CO 2 A solid adsorbent;
or:
s1, organic amine loading: adding organic amine into absolute ethyl alcohol, and stirring at room temperature until the organic amine is uniformly mixed to obtain a homogeneous organic amine solution; degassing the porous material in a vacuum drying oven at high temperature, adding the degassed porous material into absolute ethyl alcohol, and stirring to obtain a uniform suspension; slowly dripping the organic amine solution into the suspension, and continuously stirring to fully impregnate; performing rotary distillation to evaporate redundant absolute ethyl alcohol, and finally putting the absolute ethyl alcohol into a vacuum drying oven for drying to obtain the solid adsorbent loaded with organic amine;
s2, preparing a chitosan solution: dissolving chitosan in dilute acetic acid, stirring, and ultrasonically oscillating to fully dissolve the chitosan to obtain a transparent homogeneous chitosan solution;
s3, loading chitosan: adding the solid adsorbent loaded with organic amine into deionized water to form a turbid liquid; under the stirring condition, dropwise adding the chitosan solution into the porous material suspension, uniformly mixing by ultrasonic oscillation, heating in a water bath and stirring for a period of time to fully impregnate the chitosan, cooling in an ice water bath, centrifuging to obtain solid particles, washing with deionized water to neutrality, and drying in a vacuum drying oven to obtain CO 2 A solid adsorbent.
2. The preparation method of the chitosan and organic amine composite solid adsorbent for adsorbing CO2 in coal-fired flue gas according to claim 1, wherein the chitosan is one or two of chitosan with deacetylation degree of 75% or more, preferably chitosan with deacetylation degree of 95% or more; the volume concentration of the dilute acetic acid is 1-3%; the mass concentration of the prepared chitosan solution is 0.5wt% -5 wt%.
3. The method for adsorbing CO in coal-fired flue gas according to claim 1 2 The preparation method of the chitosan and organic amine composite solid adsorbent is characterized by comprising the following steps:
the porous material comprises but is not limited to one or two or more of porous materials SBA-15, SBA-16, MCM-41, KIT-6, resin, carbon-based molecular sieves, activated carbon, mesoporous silica, aerogel, pillared clay, alumina, phosphate, MOFs and the like with the pore diameter of 2nm-20 nm;
or, the porous material is a hierarchical pore molecular sieve material with micropores and mesopores simultaneously;
the organic amine includes, but is not limited to, one or two or more of polyethyleneimine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ethylenediamine, ethanolamine, diethanolamine, and N-methyl glycol amine.
4. The preparation method of the chitosan and organic amine composite solid adsorbent for adsorbing CO2 in coal-fired flue gas according to claim 1, wherein in the step S2:
in the suspension, the concentration of the porous material is 5-20 g/L;
the water bath heating temperature is 50-70 ℃, and the heating time is 4-10 h;
the cooling time of the ice-water bath is 1-2 h;
the drying temperature is 50-70 ℃, and the drying time is 6-15 h.
5. The method for adsorbing CO in coal-fired flue gas according to claim 1 2 The preparation method of the chitosan and organic amine composite solid adsorbent is characterized by comprising the following steps:
the concentration of the homogeneous organic amine solution prepared in the step S3 or S1 is 2 g/L-10 g/L;
the temperature of the rotary distillation process in the step S3 or S1 is 50-70 ℃, and the rotating speed of a distillation instrument is 400-1000r/min;
the ultrasonic oscillation time of the steps S1 to S3 is respectively 20min to 60min;
in the stirring process of the steps S1 to S3, the rotating speed of the magnetic stirrer is 400 to 1000rpm, and the time is 1 to 6 hours.
6. CO produced by the production method according to any one of claims 1 to 5 2 An adsorbent.
7. CO according to claim 6 2 An adsorbent characterized by:
the aperture of the adsorbent is 0.5 nm-5 nm;
the maximum saturated adsorption capacity is 4.3mmol/g;
adsorption of CO from gases 2 The selectivity is over 95 percent;
the adsorption/desorption is carried out for 10 times in a circulating way, and the adsorption capacity is kept above 95 percent; circulating absorption/desorption for 50 times, and keeping the absorption capacity above 80%; the adsorption/desorption is carried out for 1000 times in a circulating way, and the adsorption capacity is 10 to 30 percent.
8. A CO according to any one of claims 6 or 7 2 Use of an adsorbent, characterized in that: CO as coal-fired flue gas 2 An adsorbent.
9. Use according to claim 8, characterized in that:
CO applied to coal-fired flue gas 2 Capture of CO in coal-fired flue gas 2 The concentration is 5-30%, the adsorption temperature is 25-40 ℃, and the desorption temperature is 75-90 ℃;
CO applied to coal-fired flue gas 2 Trapping at a space velocity of 1000-1500 h -1 Coal-fired flue gas outlet CO 2 The concentration is reduced to below 0.25 percent.
10. A CO according to any one of claims 6 or 7 2 A method for regenerating an adsorbent, characterized by: when the adsorption capacity is lower than 70% of the initial adsorption capacity, purging is carried out for 3h at 200-225 ℃ in a nitrogen atmosphere, then 5-8 wt% of chitosan is soaked, the adsorbent is regenerated, and the adsorption capacity after regeneration is 90-100% of the initial adsorption capacity.
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