CN116393098A - CO adsorption modified by amine 2 Preparation method and application of acid-activated attapulgite material - Google Patents

CO adsorption modified by amine 2 Preparation method and application of acid-activated attapulgite material Download PDF

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CN116393098A
CN116393098A CN202310447997.4A CN202310447997A CN116393098A CN 116393098 A CN116393098 A CN 116393098A CN 202310447997 A CN202310447997 A CN 202310447997A CN 116393098 A CN116393098 A CN 116393098A
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acid
adsorption
attapulgite
amine
tepa
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何忠
杨忠胜
张静波
余顺新
杨明
余梦
李卓智
罗晶
陈楚龙
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CCCC Second Highway Consultants Co Ltd
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Abstract

The invention belongs to the technical field of carbon dioxide trapping and sealing, and particularly discloses an amine modified CO adsorption method 2 Preparation method of acid-activated attapulgite material and CO in flue gas of coal-fired power plant 2 Applications in the collection. The invention adopts Attapulgite (ATP) as raw material, and after acid activation, tetraethylenepentamine (TEPA) is adopted to modify the raw material by an impregnation method to obtain the CO adsorption modified by amine 2 Acid-activated attapulgite of (a)Soil material. Compared with the common adsorbent, the TEPA material has excellent water resistance and cycle stability, and can keep better carbon dioxide adsorption performance under different carbon dioxide concentrations, so that the TEPA material has practical significance for developing the carbon dioxide adsorbent which operates efficiently and stably for a long time.

Description

CO adsorption modified by amine 2 Preparation method and application of acid-activated attapulgite material
Technical Field
The invention belongs to the technical field of carbon dioxide trapping and sealing, and in particular relates to an amine modified CO adsorption method 2 Preparation method of acid-activated attapulgite material and CO in flue gas of coal-fired power plant 2 Applications in the collection.
Background
CO 2 Is the most dominant greenhouse gas in the world, CO in the atmosphere 2 The greenhouse effect caused by the increase in concentration has become one of the major environmental problems. Fossil fuel power plants are the largest source of carbon dioxide emissions. In order to control carbon dioxide emissions, a great deal of research has been conducted. Among these, carbon dioxide capture and sequestration (CCS) technology is a sustainable strategy for reducing short-term and mid-term carbon dioxide emissions. The process aims at CO discharged in large industrial facilities by different methods such as physical absorption method, chemical solvent method, low-temperature method, membrane system and the like 2 Capturing is performed before entering the atmosphere. Among these methods, adsorption techniques based on liquid amines have been widely studied and are also industrially used for decades. However, the method has the defects of solvent loss, equipment corrosion, high regeneration energy consumption and the like. Thus, to avoid these drawbacks, much research has focused on carbon dioxide capture by solid amine adsorbents. The amine is loaded on different solid matrixes to absorb CO by a chemical grafting and physical impregnation method 2 . The solid amine adsorbent has high adsorption capacity, high selectivity and high stabilityLow energy consumption and the like.
In these solid amine adsorbents, different high specific surface area porous materials were found to be useful for CO capture 2 Including molecular sieves, activated carbon, organic frameworks, and clays. Among them, clay minerals are receiving a great deal of attention because of their availability, low cost, good adsorption properties, good chemical stability and thermal stability. The silane coupling agent is reacted with the attapulgite to prepare CO with good selectivity 2 A capture agent. Attapulgite is considered to be an ideal material because of low cost and good performance, and the main source of the attapulgite is attapulgite clay. The attapulgite clay mainly comprises 70% -80% of attapulgite, and also contains a small amount of kaolinite, montmorillonite, quartz, sepiolite, hydromica and opal. The theoretical chemical formula of the attapulgite is Mg 5 Si 8 O 20 (OH) 2 (OH 2 ) 4 ·4H 2 O is a chain structure water-containing magnesium aluminum silicate clay mineral, and belongs to 2:1 type clay minerals. The chains aggregate in two dimensions, forming a semi-closed gallery, unlike other clay minerals. Because of this unique structure, attapulgite has a variety of special physicochemical properties, including mainly adsorption, catalysis, ion exchange, rheology, and plasticity. In CO 2 In adsorption, li and the like are utilized to modify the attapulgite to simulate CO in methane 2 Selective adsorption of CO 2 The adsorption capacity is more than 2mmol/g.
The introduction of amine is also an important component of the preparation of solid amine adsorbents, and the modification method is mainly divided into an impregnation method and a grafting method. The impregnation method is to soak the porous material in organic amine solution to load the organic amine onto the surface and pore canal of the material, thereby improving the CO absorption of the adsorbent 2 Adsorption selectivity and adsorption capacity of (a). Typical impregnating organic amines are Mainly Ethanolamine (MEA), diethanolamine (DEA), tetraethylenepentamine (TEPA), polyethylenimine (PEI), n-Methyldiethanolamine (MDEA), and the like. The impregnation method of Khail and the like is used for loading the MEA on the active carbon, and the surface of the impregnated active carbon is found to form a plurality of active sites, thereby improving CO 2 Adsorption capacity and selectivity. Ardhylarini et al found that when MDEA impregnates the surface of mesoporous carbon negativeAt a loading of 43wt%, CO 2 The adsorption increased from 1.60mmol/g to 2.63mmol/g, whereas CO was increased at a MDEA loading of 50wt% 2 The adsorption amount was reduced to 1.76mmol/g. This is because the organic amine is loaded too much, which causes serious blockage of the pore structure of the material and is unfavorable for CO 2 And (5) adsorption. Therefore, it is necessary to reasonably control the loading of the organic amine. The grafting method is to connect the nitrogen-containing functional group to the surface of the adsorption material through the action of chemical bond. The method can effectively reduce the volatilization of the organic amine, but has more complicated steps. Bamdad et al grafted aminopropyl triethyloxysilane (APTES) onto the oxidized biomass activated carbon surface, found that the N content in the grafted activated carbon increased from 0.15 (%) to 3.90 (%) for CO at room temperature 2 The maximum adsorption amount of (C) was 3.70mmol/g.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide an amine-modified adsorption method for CO 2 A preparation method and application of the acid-activated attapulgite material. The invention prepares the CO which is efficient, stable, low in cost and capable of being recycled 2 The adsorption material adopts Attapulgite (ATP) with lower cost as raw material, and is modified by Tetraethylenepentamine (TEPA) impregnation method after acid activation to obtain good CO 2 Adsorption capacity and stability in flue gas.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
CO adsorption modified by amine 2 The preparation method of the acid-activated attapulgite material comprises the following steps:
(1) Preparing acid activated attapulgite: activating the attapulgite by acid to obtain acid-activated attapulgite;
(2) Amine modification: impregnating the acid-activated attapulgite obtained in the step (2) with tetraethylenepentamine, and drying to obtain the product with modified adsorption of CO by amine 2 Is an acid activated attapulgite material.
Preferably, in the step (1), the attapulgite is sieved by a 50-mesh sieve, preferably by a 50-200-mesh sieve, more preferably by a 50-100-mesh sieve; the attapulgite is subjected to deionized water washing and filtering pretreatment before acid activation so as to remove water-soluble impurities.
Further, in the step (1), the concentration of the acid is 1-5mol/L, wherein the ratio of the material to the liquid, namely the ratio of the mass of the attapulgite to the volume of the acid is 1:10-1:20, g/mL, and the acid is any one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and acetic acid, preferably hydrochloric acid, more preferably 2mol/L hydrochloric acid.
Further, in the step (2), the tetraethylenepentamine is dissolved in an organic solvent and then used for impregnating the acid-activated attapulgite obtained in the step (2), wherein the ratio of the tetraethylenepentamine to the organic solvent is (0.6-1.2) g: (8-15) mL, preferably (0.6-1.2) g:10mL of the organic solvent is methanol.
Further, in the step (2), the ratio of the mass of tetraethylenepentamine to the mass of the acid-activated attapulgite is 20% to 40%, preferably 25% to 35%, more preferably 30%.
Further, in the step (2), the dipping time is 10 to 15 hours, preferably 12 hours.
The amine modified adsorption CO prepared by the method 2 Is characterized in that the acid activated attapulgite material is CO in flue gas 2 Applications in the collection.
Further, the flue gas is flue gas of a coal-fired power plant.
Further, CO 2 The trapping temperature is 40 to 70 ℃, preferably 50 to 60 ℃, more preferably 60 ℃.
Further, CO in the flue gas 2 The concentration range is 10 to 20vol%.
Further, the amine modified adsorption of CO in flue gas under dry conditions 2 Is used for adsorbing CO by the acid activated attapulgite material 2 The mechanism is as follows: 1molCO 2 React with 2mol amine groups to form stable carbamates. The adsorption of CO by amine modification 2 The acid activated attapulgite material of (2) adsorbs CO when water vapor exists in the flue gas 2 The mechanism is changed, CO 2 The reaction with the amino group 1:1 generates bicarbonate, improves the utilization rate of the amino group, and is beneficial to improving the adsorption capacity of the adsorbent; on the other hand, carbamates can also react with carbon dioxide in the presence of waterReact with water to form bicarbonate, promote CO reaction 2 Is adsorbed by the adsorbent. Thus, preferably, the flue gas contains water vapour under humid conditions or in the flue gas.
Compared with the prior art, the invention has the following advantages:
(1) The specific surface area and the number of active sites are increased by changing the structure of the attapulgite through acid activation;
(2) TEPA modification can obviously improve the CO content of HATP 2 Providing more active sites;
(3) The material has excellent water resistance and cycle stability;
(4) Can keep better carbon dioxide adsorption performance under different carbon dioxide concentrations.
Drawings
Fig. 1: XRD patterns of ATP, HATP and TEPA/HATP adsorbents in different TEPA ratios.
Fig. 2: infrared spectra of ATP, HATP and TEPA/HATP adsorbents in different TEPA ratios.
Fig. 3: SEM profile of ATP, HATP and TEPA/HATP adsorbent at different TEPA ratios, wherein: (a) is ATP, (b) is HATP, (c) is 20TEPA/HATP, (d) is 30TEPA/HATP, and (e) is 40 TEPA/HATP.
Fig. 4: thermal gravimetric maps of ATP, HATP and TEPA/HATP adsorbents with different TEPA ratios.
Fig. 5: ATP, HATP and different TEPA ratio of TEPA/HATP adsorbent N 2 Adsorption-desorption curves and pore size distribution curves.
Fig. 6: breakthrough curves for ATP, HATP and TEPA/HATP at different TEPA ratios and CO 2 Adsorption capacity.
Fig. 7: reaction temperature vs. 30TEPA/HATP adsorbent CO 2 Influence of adsorption properties.
Fig. 8: CO 2 Concentration to 30TEPA/HATP adsorbent CO 2 Influence of adsorption properties.
Fig. 9: steam vs. HATP and 30TEPA/HATP adsorbent CO 2 Influence of adsorption properties.
Fig. 10: 1 of 30TEPA/HATP adsorbent at 60℃0 times CO 2 Adsorption cycle stability.
Detailed Description
The following is a further description of the technical solution of the present invention by applicant in conjunction with specific embodiments and accompanying drawings, but the scope of protection of the present invention as claimed is not limited to the embodiments.
The starting materials used in the following examples: attapulgite (ATP) is purchased from Yixiang New Material Co., ltd, and all the attapulgite is crushed by a crusher to pass through a 50-mesh sieve for standby. The original attapulgite is tested by an X-ray fluorescence spectrometer (XRF) to measure that the attapulgite contains a large amount of SiO 2 And other various metal oxides, wherein the contents of O and Si are 45.50% and 26.39%, respectively, and the contents of Ca, fe, al and Mg are more than the contents of other metal elements, and 9.32%, 6.27%, 5.62% and 4.20%, respectively.
Example 1: CO adsorption modified by amine 2 The preparation method of the acid-activated attapulgite material comprises the following steps:
(1) Pretreatment of ATP: taking 20g of attapulgite which is crushed to pass through a 50-mesh sieve, washing and filtering the attapulgite with deionized water, and repeating the washing and filtering for 3 times; another 5g of attapulgite crushed to pass through a 50-mesh sieve is washed by deionized water, filtered and repeated for 3 times, and then directly put into a baking oven at 105 ℃ for drying for 12 hours, the sample is marked as ATP, and the test is carried out: its specific surface area is 91.06m 2 g -1 Pore volume of 0.233cm 3 g -1 。
(2) Acid activation of ATP: taking undried ATP after washing and filtering by deionized water in the step (1), and adding 300mL of 2mol/L hydrochloric acid into the undried ATP, wherein: the feed-liquid ratio is 1:15, the feed-liquid ratio refers to the ratio of the mass (g) of the attapulgite to the volume (mL) of the hydrochloric acid, and the stirring speed is 1200rpm when the magnetic stirring is carried out for 4 hours at 70 ℃. After stirring, filtering, washing to neutrality, drying in an oven at 105 ℃ for 12 hours to obtain acid-activated ATP, labeled HATP, tested: its specific surface area is 179.96m 2 g -1 Pore volume of 0.293cm 3 g -1 。
(3) TEPA modification: 0.6g, 0.9g, 1.2g Tetraethylenepentamine (TEPA) were dissolved in 10mLAdding 3g of ATP activated by acid in (2) into tetraethylenepentamine methanol solution, magnetically stirring at room temperature for 12h at 1200rpm, directly drying in a 75 ℃ oven for 6h after stirring to obtain amine modified adsorption CO 2 The samples were labeled as 20TEPA/HATP, 30TEPA/HATP and 40TEPA/HATP adsorbents, respectively, and the specific surface area and pore volume data are shown in Table 1.
Example 2: characterization of the adsorbent Performance
FIG. 1 shows XRD patterns of ATP, HATP and TEPA/HATP adsorbents in varying amounts of TEPA, observing the crystal structure. It was found that all materials showed peaks of attapulgite, which confirmed that the addition of acid and TEPA did not change the crystal structure of ATP. In the ATP spectra, the characteristic peaks of dolomite are 32.1 °, 42.2 °, 46.1 ° and 52.2 °, respectively. After HCl treatment, activated ATP (HATP) had no distinct dolomite peaks. This phenomenon shows that 2mol/LHCl activation can remove impurity dolomite in attapulgite on the premise of not damaging the crystal structure of ATP, thereby increasing the pore structure of ATP, releasing more active sites and facilitating the addition of TEPA. Meanwhile, after the acid treatment, al 3+ 、Ca 2+ 、Mg 2+ The plasma impurity ions are dissolved in a large quantity, the aperture and the specific surface area of the ATP are increased, and the adsorption capacity is improved. As the amount of the TEPA modifier increases, the characteristic peak intensity of the attapulgite is obviously increased, which indicates that the TEPA promotes the crystallization of ATP. The improvement of the crystallinity can promote the adsorption of the gas on the surface of the adsorbent, thereby obtaining better CO 2 The removal rate.
In order to observe the functional groups of the attapulgite, the introduction of TEPA was confirmed, and FTIR experiments were performed, the curves being shown in fig. 2. From the untreated ATP spectrum, it was detected that the respective sample was at 3606cm -1 、3570cm -1 And 3516cm -1 There are three peaks which are associated with different hydroxyl groups. Mg-O at 1288cm -1 There appears a distinct stretching vibration peak, which disappears after the acid treatment. Indicating that HCl activation can remove impurities in ATP, increasing the number of active sites, consistent with XRD results. In addition, 944cm -1 The peak at which is attributable to SStretching vibration of i-O, 1599cm -1 And 744cm -1 The peak at which is related to the surface hydroxyl groups. After TEPA impregnation, some new peaks appear in the TEPA/HATP spectrum. Wherein 2890cm -1 、1530cm -1 And 1420cm -1 The tensile vibration peaks for C-H, N-H and C-N, respectively, indicate a significant loading of the amine. A large amount of TEPA may also lead to a stronger peak in the spectrum. Thus, FTIR results confirm successful introduction of TEPA, with possible interactions as follows:
Si-OH+RNH 2 →Si-O - N + H 3 R(1)
the surface morphology of ATP, HATP and TEPA/HATP adsorbents with different amounts of TEPA were observed by SEM and the results are shown in fig. 3, wherein: (a) is ATP, (b) is HATP, (c) is 20TEPA/HATP, (d) is 30TEPA/HATP, and (e) is 40 TEPA/HATP. Untreated ATP can be observed as a fibrous structure with fibers densely packed together. After acid treatment, HATP fibers are more dispersed, which means that acid modification can disperse dense and ordered fibers in the attapulgite, thereby increasing the specific surface area and enhancing the adsorption capacity of the adsorbent. After TEPA loading, some aggregation of ATP fibers was observed on the attapulgite, indicating amine deposition on the attapulgite. Interestingly, the addition of TEPA can re-order the fiber distribution. This can be attributed to the interaction of attapulgite with amines as in formula (1). The TEPA compound can be coated on the surface of clay mineral to promote fiber aggregation. This phenomenon results in a decrease in the BET surface area of the ATP sample.
The thermostability of the original and modified ATP was investigated with TG and the results are shown in FIG. 4. The weightlessness process of the unmodified ATP material is divided into three stages on the TG curve. The weight loss below 300 ℃ (8.4%) can be interpreted as the removal of physically absorbed water and carbon dioxide, and the weight loss from 300 ℃ to 550 ℃ (4.1%) can be attributed to the overflow of chemically absorbed water. The final stage above 550 ℃ (9.5%) is the stage of decomposition of impurities in the ATP sample. The TG curve of the HATP sample below 550 ℃ is similar to ATP, but when the temperature increases, the TG curve remains stable as impurities have been removed by the acid. For the TEPA-modified HATP material, the weight loss is more pronounced in the initial stage due to the excellent wet adsorption capacity of the TEPA molecules. Above 120 ℃, the loss of weight of the TEPA/HATP curve is more pronounced, which is related to evaporation and decomposition of the amine. The losses on the curve are most pronounced from 100℃to 250 ℃. The total weight loss rates for 20TEPA/HATP, 30TEPA/HATP and 40TEPA/HATP were 21.0%, 26.9% and 36.5%, respectively, indicating that the decrease in weight loss rate was related to the amount of modified TEPA used.
Through N 2 Adsorption-desorption experiments characterize the structural properties of different ATP adsorbents. The isotherm is shown in fig. 5 (a), and the pore size distribution obtained by the BJH method is shown in fig. 5 (b). BET specific surface area and pore volume data for ATP, HATP and TEPA/HATP are summarized in Table 1. As can be seen from FIG. 5 (a), both ATP and the modified material exhibit typical type iv isotherms, N when the relative pressure P/P0 is greater than 0.4 2 Obvious H3 type hysteresis loop appears on adsorption-desorption isotherm, which indicates that a crack type mesoporous structure appears in the ATP material. This fissured mesoporous structure is believed to provide more active sites for the TEPA molecule. The presence of hysteresis loops in mesoporous materials can be explained by capillary condensation. As can be seen from Table 1, the specific surface area of ATP after acidic treatment was 91.06m 2 The/g is increased significantly to 179.96m 2 Per gram, pore volume is also from 0.233cm 3 The/g was increased to 0.293cm 3 And/g. This can be explained by the fact that the acidic treatment removes impurities (Mg 2+ ，Al 3+ Etc.), thereby increasing BET area and pore volume, facilitating TEPA loading and CO absorption 2 . This conclusion is consistent with XRD and SEM results. However, after loading with different amounts of TEPA, and with larger amounts of addition, the BET area and pore volume of the TEPA/ATP adsorbent are significantly reduced. BET areas of 20TEPA/ATP and 30TEPA/ATP were 70.01m, respectively 2 /g and 61.25m 2 Per g, while the BET area of 40TEPA/ATP drops sharply to 39.17m 2 And/g. The possible reason is that the introduced amine occupies and fills the surface pores, resulting in pore blocking of ATP. From the pore size distribution of FIG. 5 (b), it can be seen that all samples have a peak centered at 28-29nm and that there are multiple pore sizes. After TEPA modification, the peak intensity is obviously reduced, confirming the amine molecule to enterInto the pores of the ATP.
TABLE 1 BET specific surface area and pore volume results for ATP, HATP and TEPA/HATP
Figure BDA0004196385460000061
Example 3: adsorption performance experiment of adsorbent
1g of adsorbent was placed in the middle of a quartz reaction tube having a length of 0.4m and an inner diameter of 20mm. First, with high purity N 2 (40 mL/min) pretreating the adsorbent at 100deg.C for 1 hr, removing CO adsorbed on the adsorbent surface in air 2 And H 2 O; the reactor temperature was then reduced to the specified reaction temperature and the gas replaced with 15% CO 2 /85％N 2 Is simulated (40 mL/min). The intake air flow is regulated by a mass flow controller. By CO 2 Analyzer measuring outlet CO 2 Concentration. By maintaining the simulated flue gas stream pre-wetted at 60 ℃ in a water bath, the effect of water vapor on the adsorbent performance is achieved. According to CO 2 Breakthrough curve calculation of different ATP adsorbents versus CO 2 The adsorption capacity of (2) is as follows:
Figure BDA0004196385460000071
in the formula (2), Q is CO 2 Adsorption capacity (mmol/g), F is gas flow rate (mL/min), M is the weight of ATP adsorbent (g), V is 22.4mL/mmol, C 0 For import CO 2 Concentration (vol.%), C is outlet CO 2 Concentration (vol%).
1. For CO under dry conditions 2 Influence of adsorption Capacity
Breakthrough curves for ATP, HATP and TEPA/HATP at different TEPA ratios and CO 2 The adsorption capacity is shown in FIG. 6. As can be seen from fig. 6 (a), acidic activation increases the breakthrough time of ATP, while the addition of TEPA further increases the breakthrough time of ATP. However, when the TEPA loading is increased to 40%, its breakthrough time is reduced, but still slightly above 20TEPA/HATP. In FIG. 6 (b) is calculated from the breakthrough curveDifferent adsorbents for CO 2 Is used as the adsorption amount of the catalyst. In all materials, the raw material ATP versus CO 2 The adsorption amount of (2) was the lowest (1.07 mmol/g), and the adsorption amount of HATP was 1.37mmol/g. This is probably due to the removal of impurities in the ATP well by the acid, the specific surface area increases, and adsorption of carbon dioxide is facilitated. In addition, removal of impurities also favors the loading of TEPA on ATP. The adsorption amounts of 20TEPA/HATP and 30TEPA/HATP were significantly increased to 2.1mmol/g and 3.28mmol/g, respectively. The possible reason is that the supported amine can react with CO 2 The reaction produces stable carbamates, providing more active sites on the material. The reaction equation is as follows:
CO 2 +2RNH 2 →RNH 3 + +RNHCOO - (3)
CO 2 +2R 2 NH→R 2 NH 2 + +R 2 NCOO - (4)
from formulas (3) and (4), it can be inferred that loading TEPA is beneficial in promoting carbon dioxide capture. In samples with TEPA loadings of 20% and 30%, CO was adsorbed with increasing amine levels 2 Is enhanced. However, when the TEPA level was further increased to 40%, CO 2 Capture capacity drops to 2.58mmol/g, which may be due to clogging with excess amine, the pores of the ATP material are filled with TEPA, adsorbing CO 2 Is smaller. Thus, in all samples, 30% tepa is the most suitable carbon dioxide capture. In addition, table 2 is the previous literature and the present study of CO of amine modified adsorbents under dry conditions 2 Adsorption capacity comparison. It was found that in the different amine modified materials, 30TEPA/HATP CO 2 The trapping performance is best.
Temperature plays a key role in carbon dioxide adsorption. During the adsorption process, the temperature affects the equilibrium of the adsorption reaction and mass transfer. Higher temperatures favor mass transfer, but high temperatures are detrimental to adsorption because the adsorption reaction is exothermic. To reveal temperature CO adsorption on 30TEPA/HATP adsorbent 2 The performance was tested at 40, 50, 60 and 70℃for its breakthrough curve and CO 2 The adsorption capacity results are shown in FIG. 7. As shown in fig. 7 (a), breakthrough occursThe time sequence is 60 DEG C>50℃>70℃>40 ℃, elucidation of CO on 30TEPA/HATP 2 The adsorption amount increases and then decreases with increasing temperature. Calculated CO at 40 ℃, 50 ℃, 60 ℃ and 70 DEG C 2 The adsorption amounts of (C) were 2.05mmol/g, 2.86mmol/g, 3.28mmol/g and 2.27mmol/g, respectively. 60℃was determined as CO 2 Optimum temperature for trapping. This is probably because an increase in temperature not only increases the activity of TEPA, but also accelerates the rate of movement of carbon dioxide molecules, thereby promoting diffusion of carbon dioxide in the pores and increasing the chance of contact with the adsorbent active sites. Therefore, the adsorption amount increases with an increase in temperature. However, CO 2 Is exothermic. When the temperature is further increased to 70 ℃, the adsorption process is mainly controlled by the heat mechanics rather than the dynamics, the adsorption balance moves towards the desorption direction, and the adsorption capacity is reduced.
In actual flue gas, CO 2 Is not constant but floats within a certain range. In order to obtain better application value, the adsorbent is required to be used in different COs 2 The content (10 vol%, 15vol%, 20 vol%) showed good CO 2 Capture performance. CO 2 Concentration pair 30TEPA/HATP sample CO 2 Breakthrough curve of adsorption performance and CO 2 As shown in FIG. 8, the carbon dioxide concentration was varied from 10 to 20vol%. As can be seen from FIG. 8 (b), CO under three conditions 2 There was no significant difference in trapping performance. CO 2 At concentrations of 10vol%, 15vol% and 20vol%, CO 2 The adsorption amounts were 3.18mmol/g, 3.28mmol/g and 3.39mmol/g, respectively. CO 2 The concentration increase can only lead to CO 2 The adsorption capacity is slightly improved. Interestingly, the breakthrough curves were significantly different. When CO 2 The breakthrough time was significantly shortened when the concentration was increased from 10vol% to 20vol%. The possible reasons are CO 2 Every 5vol% increase in concentration, CO per unit volume 2 The content also increases. Higher CO 2 Concentration can make more CO 2 The molecules react with amine groups within a certain time, helping to shorten the breakthrough time. However, the amine group content in 30TEPA/HATP is unchanged, and finally CO 2 Adsorption capacityIs basically unchanged. Thus, 30TEPA/HATP material was found to be CO-rich in various materials 2 Has good stability of CO under concentration 2 Adsorption capacity of but higher CO 2 The content is favorable for shortening the adsorption time.
Table 2 amine modified absorbent CO under dry conditions 2 Comparison of adsorption Capacity
Figure BDA0004196385460000081
Reference is made to:
[1]Gómez-Pozuelo,G.；Sanz-Pérez,E.S.；Arencibia,A.；Pizarro,P.；Sanz,R.；Serrano,D.P.CO 2 adsorption on amine-functionalizedclays.Microporous Mesoporous Mater.2019,282,38-47.
[2]Niu,M.；Yang,H.；Zhang,X.；Wang,Y.；Tang,A.Amine Impregnated Mesoporous Silica Nanotube as an Emerging Nanocomposite for CO 2 Capture.ACS Appl.Mater.Interfaces 2016,8(27),17312-17320.
[3]Wang,X.；Ma,X.；Song,C.；Locke,D.R.；Siefert,S.；Winans,R.E.；Mollmer,J.；Lange,M.；Moller,A.；Glaser,R.Molecular basket sorbents polyethylenimine-SBA-15 for CO 2 capture from flue gas:Characterization and sorption properties.Microporous Mesoporous Mater.2013,169,103-111.
[4]Horri,N.；Sanz-Perez,E.S.；Arencibia,A.；Sanz,R.；Frini-Srasra,N.；Srasra,E.Amine grafting of acid-activated bentonite for carbon dioxide capture.Appl.Clay Sci.2019,180,105195.
[5]Yuan,M.；Gao,G.；Hu,X.；Luo,X.；Huang,Y.；Jin,B.；Liang,Z.Premodified Sepiolite Functionalized with Triethylenetetramine as anEffective and Inexpensive Adsorbent for CO 2 Capture.Ind.Eng.Chem.Res.2018,57(18),6189-620
[6]Liu,L.；Chen,H.；Shiko,E.；Fan,X.；Zhou,Y.；Zhang,G.；Luo,X.；Hu,X.Low-cost DETA impregnation of acid-activated sepiolitefor CO 2 capture.Chem.Eng.J.2018,353,940-948.
2. for CO under humid conditions 2 Influence of adsorption Capacity
Steam is an unavoidable component of actual flue gas. To simulate actual flue gas, 15% CO at 60℃ 2 /85％N 2 The mixture was pre-wet in a water bath (with a water bath consisting of N 2 The content of the water vapor is controlled by the temperature of the evaporation device, and then the water vapor passes through the gas mixing tank and CO 2 Mixed), study of steam versus HATP and 30TEPA/HATP sample CO 2 Influence of adsorption properties. As can be seen from fig. 9: when water vapor is introduced into the simulated flue gas, the breakthrough time of HATP is slightly shortened compared with that of the dry flue gas; CO of HATP in dry flue gas 2 The adsorption amount was 1.37mmol/g and that in wet flue gas was 1.13mmol/g. Possible reasons are H 2 O forms a water film on the adsorbent, plugs the pores, reduces the number of active sites, and eventually leads to a decrease in adsorption performance. As can be seen from fig. 9: the breakthrough time of 30TEPA/HATP in wet flue gas is longer than that in dry flue gas, the breakthrough time is prolonged from 6 minutes to 7 minutes, the total adsorption amount is increased from 3.28mmol/L to 3.82mol/L, and the water vapor enhances the CO of 30TEPA/HATP 2 Is used for the adsorption capacity of the catalyst. CO of 30TEPA/HATP sample in the presence of Water 2 The adsorption amount is increased by 16.5%, which shows that the promotion effect of the water vapor is remarkable. This is probably due to the change in adsorption mechanism of the 30TEPA/HATP material in the presence of water vapor. Under dry conditions of 1mol CO 2 With 2mol of amine groups [ formula (3) and formula (4)]In contrast, CO 2 Reacts with an amino group 1:1 to generate bicarbonate, improves the utilization rate of the amino group, and contributes to improving the adsorption capacity of the adsorbent [ formula (5) and formula (6)]. In addition, the carbamates of formula (3) and (4) react with carbon dioxide and water to form bicarbonate in the presence of water, promoting the reaction of CO 2 Adsorption of [ formula (7) and formula (8) ]]. The reaction equation is as follows:
CO 2 +RNH 2 +H 2 O→RNH 3 + +HCO 3 - (5)
CO 2 +R 2 NH+H 2 O→R 2 NH 2 + +HCO 3 - (6)
CO 2 +R 2 NCOO - +2H 2 O→R 2 NH 2 + +2HCO 3 - (7)
CO 2 +RNHCOO - +2H 2 O→RNH 2 + +2HCO 3 - (8)
example 4: recycling regeneration of adsorbents
In practical flue gas applications, the regenerability of the adsorbent is important because it determines the life of the material and the frequency of replacement, thereby affecting the CO 2 Cost of trapping. CO from spent TEPA/HATP adsorbent 2 After adsorption, the mixture was subjected to 40mL/min at 100 DEG C 2 Regenerating under atmosphere. FIG. 10 is a graph of carbon dioxide adsorption at 60℃and N at 100℃for a 30TEPA/HATP adsorbent 2 The adsorption amount was desorbed in the atmosphere for 10 repeated cycles. The results show that in the first cycle, CO 2 The adsorption capacity of the catalyst is 3.28mmol/g, and the adsorption capacity slightly decreases with the increase of the cycle times; this may be related to degradation and volatilization of impregnated TEPA. After 10 cycles, the adsorption of TEPA was 3.04mmol/g, which was only 7.0% lower, indicating a strong chemical interaction between TEPA and acid-activated ATP. In general, after 10 cycles of adsorption and desorption experiments, the 30TEPA/HATP adsorbent was subjected to CO 2 The adsorption capacity is not obviously reduced, and higher adsorption performance is still maintained, so that the catalyst has good circulation stability and industrial application value.

Claims (10)

1. CO adsorption modified by amine 2 The preparation method of the acid-activated attapulgite material is characterized by comprising the following steps:
(1) Preparing acid activated attapulgite;
(2) Impregnating the acid-activated attapulgite obtained in the step (2) with tetraethylenepentamine, and drying to obtain the product with modified adsorption of CO by amine 2 An acid-activated attapulgite material;
in the step (2), the ratio of the mass of the tetraethylenepentamine to the mass of the acid-activated attapulgite is 20% -40%, preferably 25% -35%, more preferably 30%.
2. An amine modified CO adsorption according to claim 1 2 The preparation method of the acid-activated attapulgite material is characterized in that in the step (2), tetraethylenepentamine is dissolved in an organic solvent and then used for impregnating the acid-activated attapulgite obtained in the step (2).
3. An amine modified CO adsorption according to claim 2 2 The preparation method of the acid-activated attapulgite material is characterized in that the organic solvent is methanol.
4. An amine modified CO adsorption according to claim 2 2 The preparation method of the acid-activated attapulgite material is characterized in that in the step (2), the soaking time is 10-15h.
5. An amine modified CO adsorption according to claim 2 2 The preparation method of the acid-activated attapulgite material is characterized in that in the step (1), the acid is used for activating the attapulgite to obtain the acid-activated attapulgite; the attapulgite is sieved by a 50-mesh sieve; the attapulgite is subjected to deionized water washing and filtering pretreatment before acid activation.
6. An amine modified CO adsorption according to claim 5 2 The preparation method of the acid-activated attapulgite material is characterized in that in the step (1), the concentration of acid is 1-5mol/L, and the ratio of the mass of the attapulgite to the volume of the acid is 1:10-1:20, g/mL.
7. An amine modified CO adsorption according to claim 6 2 The preparation method of the acid-activated attapulgite material is characterized in that the acid is any one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and acetic acid.
8. Amine modified prepared by the process of any one of claims 1 to 7Sexual adsorption of CO 2 Is characterized in that the acid activated attapulgite material is CO in flue gas 2 Applications in the collection.
9. The use according to claim 8, characterized in that CO 2 The trapping temperature is 40 to 70 ℃, preferably 50 to 60 ℃, more preferably 60 ℃.
10. The use according to claim 9, characterized in that the CO in the flue gas 2 The concentration range is 10-20vol%;
use according to claim 9, characterized in that the flue gas contains water vapour under humid conditions or in the flue gas;
the use according to claim 8, wherein the flue gas is coal fired power plant flue gas.
CN202310447997.4A 2023-04-24 2023-04-24 CO adsorption modified by amine 2 Preparation method and application of acid-activated attapulgite material Pending CN116393098A (en)

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