CN117181190A - Sulfur-resistant CO 2 Adsorbent and preparation method thereof - Google Patents
Sulfur-resistant CO 2 Adsorbent and preparation method thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 29
- 239000011593 sulfur Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010881 fly ash Substances 0.000 claims abstract description 48
- 239000004964 aerogel Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000011240 wet gel Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000002019 doping agent Substances 0.000 claims abstract description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003607 modifier Substances 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 7
- 239000003054 catalyst Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 18
- 239000002910 solid waste Substances 0.000 abstract description 8
- 230000001186 cumulative effect Effects 0.000 abstract description 6
- 238000001291 vacuum drying Methods 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003513 alkali Substances 0.000 description 13
- 230000004927 fusion Effects 0.000 description 13
- 239000011148 porous material Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- -1 silicon aluminum hydrochloride Chemical compound 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Abstract
The invention relates to the field of solid waste resource utilization, in particular to a sulfur-resistant CO 2 An adsorbent and a preparation method thereof; the method comprises the following steps: (1) pre-treating fly ash; (2) Extracting a silicon-aluminum precursor, and adding hydrochloric acid into the calcined product obtained in the step (1); (3) forming a wet gel; (4) ultra-low temperature vacuum drying to obtain an aerogel carrier; (5) Sulfur-resistant doping modification, and simultaneously adding modifier K 2 CO 3 And doping agent manganese acetate, (6) drying and screening, selecting a sample with a certain particle size to obtain the sulfur-resistant CO 2 An adsorbent; (1) The sulfur-resistant CO prepared by the invention 2 The adsorbent is excellent in performance even when SO is contained in the atmosphere 2 Under the condition of that the cumulative adsorption capacity is still up to 1.75mmol/g, and the good sulfur-resistant adsorption performance is maintained, and exceeds that of most CO 2 An adsorbent. The modified adsorbent prepared by the invention has the sulfur resistance, improves the recycling service life of the adsorbent, and saves the cost.
Description
Technical Field
The invention relates to the field of solid waste resource utilization, in particular to a sulfur-resistant CO 2 An adsorbent and its preparation method are provided.
Background
The coal ash is used as a combustion byproduct of the power plant, accounts for 60% -88% of the total solid waste of the coal-fired power plant, the annual global yield is estimated to be about 10 hundred million tons, and the global average utilization rate is still low despite the gradual increase of the utilization of the coal ash for many years.
The surface of the fly ash mainly consists of a compact irregular block structure, has a poor microstructure and is not beneficial to the chemical reaction. The most main chemical element in the fly ash is Si and Al, and the crystal mineral in the fly ash is mullite Al 6 Si 2 O 13 In addition, contain crystalline SiO 2 、Al 2 O 3 The existence of CaO and amorphous glass is suitable for preparing the mesoporous silica-alumina composite aerogel, and the prepared silica-alumina composite aerogel has developed microstructure, uniform and rough surface, rich pores and loose overall structure. The active component is loaded on the porous material to realize CO by utilizing the larger pore diameter and the open pore structure 2 And (5) adsorption. The structure is favorable for loading active components, is convenient for gas to diffuse in pores and is favorable for CO 2 And (3) carrying out an adsorption reaction.
CO in CCUS 2 The low-cost fly ash of the solid waste of the power plant is used in the capturing link, so that the carbon capturing cost can be greatly reduced, the discharge of the fly ash is reduced, the requirement on landfill of the waste of the power plant is reduced, and the natural resources are saved. In addition, fly ash generated in the field is directly used in the coal-fired power plant, so that logistics transportation is not needed, and the transportation cost is reduced. From this, it can be seen that CO is carried out by using coal-fired solid waste fly ash 2 Adsorption can not only reduce CO 2 The emission reduces the damage of the power plant to the environment, can reduce the landfill requirement of the power plant to the waste fly ash, and saves resources.
However, since the flue gas of the power plant contains trace amountsSO of (2) 2 Can lead to CO 2 The adsorbent is deactivated and the adsorption performance is greatly reduced.
Disclosure of Invention
The invention aims to solve the problem of SO of the conventional adsorbent 2 Disadvantages of deactivation under atmosphere and conventional sol-gel process for preparing CO 2 The technical problem of high cost during the adsorption of the adsorbent is to provide a sulfur-resistant CO 2 An adsorbent and its preparation method are provided. Sulfur-resistant CO prepared by the method of the invention 2 The adsorbent has high specific surface area and contains SO 2 The smoke can still keep better CO 2 The adsorption performance of the aerogel carrier is that manganese acetate is used as a precursor to promote the distribution of the doping agent on the surface of the aerogel carrier. Meanwhile, the invention adopts the cheap fly ash as the precursor of the adsorbent, and overcomes the defect of preparing CO by the conventional sol-gel method 2 The cost of the adsorbent is high.
In order to solve the technical problems, the invention adopts the following technical scheme: sulfur-resistant CO 2 The preparation method of the adsorbent comprises the following steps:
(1) Pre-treating the fly ash, namely mixing and calcining the fly ash with sodium carbonate serving as a pre-treating agent at high temperature;
(2) Extracting a silicon-aluminum precursor, adding hydrochloric acid into the calcined product obtained in the step (1), stirring for 1 hour, filtering and taking filtrate;
(3) Forming wet gel, adding propylene oxide into the filtrate obtained in the step (2), adjusting the pH value of the filtrate, and standing to form wet gel;
(4) The sample obtained in the step (3) is put into an ultralow temperature refrigerator for freezing and then is dried by a vacuum freeze dryer, so as to obtain an aerogel carrier;
(5) Adding the aerogel carrier obtained in the step (4) into deionized water for stirring, and simultaneously adding a modifier K 2 CO 3 And a dopant precursor manganese acetate;
(6) Drying, sieving, selecting sample with certain particle diameter to obtain sulfur-resistant CO 2 An adsorbent.
Since the aerogel prepared by using the fly ash has high specific surfaceThe manganese acetate can be loaded in the internal gaps of the aerogel after being dissolved in water, and MnO is formed in the subsequent drying step 2 Thin layer, make MnO 2 The mesoporous carbon is uniformly distributed in the surface and the internal gaps of the adsorbent without crystallization, and a large number of mesopores are beneficial to the passage of gas molecules and the progress of reaction.
Further, in the step (1), the mass ratio of the sodium carbonate to the fly ash is 0.7:1.
Further, in the step (1), the calcination temperature was 850℃and the calcination time was 3 hours.
Further, the concentration of the added hydrochloric acid in the step (2) is 3mol/L, and the mass volume ratio of the calcined product to the hydrochloric acid is 1g:10mL.
Further, in the step (3), the volume ratio of the epoxy propane to the filtrate is 1:2, and the pH value of the filtrate is 9-10.
Preferably, the freezing temperature in step (4) is-80 ℃.
Preferably, the K in step (5) 2 CO 3 The content is 30 percent of the mass of the aerogel carrier, and MnO generated by manganese acetate 2 The content is 2% of the mass of the aerogel carrier.
Preferably, the sulfur-resistant CO of step (6) 2 The adsorbent particle size was 150 microns.
In addition, the invention also provides the sulfur-resistant CO prepared by the preparation method 2 An adsorbent.
Compared with the prior art, the invention has the following beneficial effects:
(1) The sulfur-resistant CO prepared by the invention 2 The adsorbent is excellent in performance even when SO is contained in the atmosphere 2 Under the condition of that the cumulative adsorption capacity is still up to 1.75mmol/g, and the good sulfur-resistant adsorption performance is maintained, and exceeds that of most CO 2 An adsorbent.
(2) The aerogel prepared by the invention has good microstructure and BET specific surface area as high as 873.9m 2 Per gram, the average pore diameter is 2.5nm, the medium is Kong Zhanbi 80.4.4%, the micropore accounts for 19.5%, and the macropores are only 0.1%; the specific surface area of the fly ash is only 6.92m 2 Per g, medium Kong Zhanbi 39.6.6%, 60.4% of macropores, noMicropores. The invention realizes the high added value utilization of the coal-fired solid waste fly ash.
(3) Sulfur-resistant CO 2 The precursor material cost of the adsorbent was estimated. The market price of the raw materials is queried by a chemical material purchasing wholesale website (chem.1688. Com), the price of sodium carbonate is 1100 yuan/t, and the price of 31 percent industrial hydrochloric acid is 600 yuan/t. The invention prepares CO by using fly ash 2 The adsorption capacity of the adsorbent is 1.75mmol/g, according to K 2 CO 3 Theoretical loading is 30%, doping amount is 2%, and each adsorption of 1kg CO is calculated 2 12.99kg of adsorbent and 8.703kg of aerogel carrier are required. According to the experimental results, 10mL of 3mol/L hydrochloric acid was required for each 1g of aluminum aerogel, and 3.8g was required in terms of 31% industrial hydrochloric acid. Thus, 1kg CO per adsorption 2 Sodium carbonate 4.35kg,31% technical hydrochloric acid 33.07kg are required. The raw material cost is roughly estimated to be 25 yuan/kg CO 2 . If ethyl orthosilicate is used as a precursor to prepare aerogel, the price of the ethyl orthosilicate is 16 yuan/kg, and the raw material rough cost is 437 yuan/kg CO according to the same load and adsorption quantity estimation 2 . Greatly reduces the manufacturing cost.
(4) The modified adsorbent prepared by the invention has the sulfur resistance, improves the recycling service life of the adsorbent, and saves the cost.
(5) CO in CCUS 2 The low-cost fly ash of the solid waste of the power plant is used in the capturing link, so that the carbon capturing cost can be greatly reduced, the discharge of the fly ash is reduced, the requirement on landfill of the waste of the power plant is reduced, and the natural resources are saved.
(6) The fly ash generated on the site is directly used in the coal-fired power plant, so that logistics transportation is not needed, and the transportation cost is reduced.
Drawings
FIG. 1 is an X-ray diffraction pattern of coal-fired solid waste fly ash.
FIG. 2 is a graph showing the pretreatment results of fly ash at different calcination temperatures and ratios according to the examples of the present invention.
FIG. 3 is a graph showing the results of the calculation of the burn-out rate at different calcination temperatures and ratios according to the examples of the present invention.
FIG. 4 is a graph showing the extraction results of different concentrations of silicon aluminum hydrochloride precursors according to an embodiment of the invention.
FIG. 5 is a photograph of an aerogel obtained after low temperature freeze vacuum drying in accordance with an embodiment of the present invention.
FIG. 6 shows an aerogel prepared according to an embodiment of the invention with sulfur-resistant CO 2 Low temperature N of adsorbent 2 Adsorption-desorption graph.
FIG. 7 shows an aerogel prepared according to an embodiment of the present invention with sulfur-resistant CO 2 Pore size distribution of the adsorbent.
FIG. 8 is a graph of aerogel and sulfur-resistant CO prepared according to an embodiment of the invention 2 X-ray diffraction pattern of the adsorbent before and after reaction.
FIG. 9 is a graph of fly ash based sulfur-resistant CO prepared in accordance with an embodiment of the invention 2 Cumulative adsorption capacity profile for adsorbent.
Detailed Description
The invention is further illustrated below with reference to specific examples.
The fly ash raw materials of the following examples are from certain power plants in North China, chemical composition analysis of the fly ash is shown in Table 1, and crystal structure analysis of the fly ash is shown in FIG. 1 by XRD.
Table 1 fly ash chemical composition table
Examples
(1) And (5) pretreatment of the fly ash. Na having a total mass of 20g and mass ratios of 0.4, 0.5, 0.6, 0.7 and 0.8 was weighed out by a balance 2 CO 3 The mixture is fully ground and mixed with fly ash, the uniformly mixed sample is placed in a muffle furnace, and the mixture is calcined for 3 hours at 700 ℃, 800 ℃, 850 ℃, 900 ℃ and 1000 ℃ respectively, and the results of the products at different temperatures and proportions are shown in figure 2. According to the experimental results, all proportions of Na at a calcination temperature of 1000 DEG C 2 CO 3 The alkali fusion products of the mixture with the fly ash are all brown yellow substances with hard and compact structures,the material is tightly attached to the inner wall of the magnetic boat, is not easy to remove, is not easily dissolved in hydrochloric acid, and cannot be further subjected to acid leaching operation. Na when the calcination temperature is 900 DEG C 2 CO 3 : the mixture alkali fusion product of the fly ash of 0.8 is compact and is adhered to the magnetic boat; na (Na) 2 CO 3 : when the fly ash is smaller than 0.7, the alkali fusion product can be separated from the magnetic boat, and the structure becomes more crisp along with the reduction of the proportion of the alkali fusion product and the magnetic boat. At this temperature, all of the alkali fusion products were dark yellow lumps. When the calcination temperature is 850 ℃, the alkali fusion product is fine and uniform powder, and along with Na 2 CO 3 The color of the fly ash is gradually lighter than that of the fly ash, and the fly ash is white when the ratio is 0.8. When the calcining temperature is 800 ℃, all the alkali fusion products are powder samples with whitish color and loose and even structure, and are easy to recycle for the next operation, na 2 CO 3 : the color of the fly ash is the whitest when the fly ash is 0.6 and 0.7. When the calcination temperature is 700 ℃, the product is a brownish red soil block-shaped substance, and is easy to smash into powder. At this temperature, na 2 CO 3 : when the proportion of fly ash is more than 0.7, a whitish bubble-like structure can be observed on the surface.
In order to quantitatively analyze the completion degree of the alkali fusion reaction, the burning loss rate of the mixture after calcination is calculated under all conditions, and the calculation formula is shown as formula (1). The results of the burn-out quantitative analysis under all conditions are shown in FIG. 3.
Wherein, eta is the burning loss rate;
m 1 -total mass of the mixture before reaction, g;
m 2 total mass of mixture after reaction, g.
Under the condition of high-temperature calcination, the fly ash and Na 2 CO 3 The reaction occurs, and the high burning loss rate indicates that more gas is released by the reaction, so that the reaction is more complete. At the calcination temperature of 1000 ℃, the product is hard and compact and is not easy to dissolve in hydrochloric acidIndicating that the alkali fusion product under this temperature condition is not suitable for the next operation. As can be seen from FIG. 3, na is present under all temperature conditions 2 CO 3 : when the ratio of fly ash was 0.7, the burning loss rate of the mixture was the highest, which means that the alkali fusion reaction was the most sufficient at this ratio, and it was confirmed that 0.7 was Na at the time of alkali fusion 2 CO 3 Optimum proportion of fly ash. When the calcining temperature is 700 ℃, the calcining loss rate is between 12.08 and 13.53 percent, the whole is lower, which shows that under the condition of 700 ℃, the fly ash and Na are 2 CO 3 The reaction of (2) is insufficient and the calcination temperature is too low. When the calcining temperature is 800-900 ℃, the overall burning loss rate is higher, and under the same mixing proportion, the burning loss rates at different temperatures are closer. Wherein the calcination condition is that the temperature is 900 ℃ and the Na is 2 CO 3 The burn-out rate obtained when the mixing ratio with fly ash is 0.8 is 15.71%, the mixed sample products are agglomerated and adhered to the magnetic boat, and cannot be completely recovered from the magnetic boat, so that the calculated burn-out rate of the data is inaccurate, and the sample with the structure is not suitable for the next acid leaching in combination with the experimental result of fig. 2, so that the condition is not selected as the optimal alkali fusion condition, and repeated experiments are not carried out. The burn-out rate of other samples was between 15.36% and 21.50% with the exception of the special group at 800-900 ℃. When the calcination temperature is 850 ℃, na 2 CO 3 : fly ash=0.7, the maximum loss on ignition rate was 21.50% under this condition.
(2) And (5) extracting a silicon-aluminum precursor. The calcination temperature in the step (1) is 850 ℃, na 2 CO 3 : fly ash = 0.7. 2mol/L, 3mol/L, 4mol/L hydrochloric acid were added to the samples obtained, and stirred for 1 hour using a magnetic stirrer, followed by filtration to leave a filtrate, the results of which are shown in figure 4. When the concentration of the hydrochloric acid is 2mol/L, the color of the solution is lighter, and more slurry sediment which cannot be dissolved in the hydrochloric acid exists at the bottom of the beaker; when the concentration of hydrochloric acid is 3mol/L and 4mol/L, the solution in the beaker is uniform, and no precipitate is visible. The hydrochloric acid concentration increased and the color of the solution tended to yellow from white, since hydrochloric acid caused Fe in the solid sample 3+ Dissolved in hydrochloric acid, the higher the concentration of hydrochloric acid is, the Fe can be dissolved and released 3+ The more, and thus the more color of the solutionYellow. Meanwhile, in experiments, the high-concentration hydrochloric acid can cause the alkali fusion product to react more quickly, and the precipitate disappears. When the concentration of hydrochloric acid is 4mol/L, the solution starts to form gel in the acid leaching and filtering processes, the silica sol can form gel under the acidic or alkaline condition, and the aluminum gel needs to be formed under the alkaline condition, so the gel at the moment is the silica gel. The silica gel is formed too quickly under the acidic condition, so that the aluminum sol is fixed in the framework of the silica gel, and the formation of the aluminum gel is not facilitated. After stirring with a magnetic stirrer, the solution was filtered, and when the concentration of hydrochloric acid was 2mol/L, more precipitate remained on the filter paper, and when the concentration of hydrochloric acid was 3mol/L, almost no precipitate remained on the filter paper. The reaction cannot be completely carried out due to the concentration of 2mol/L hydrochloric acid, the reaction is too fast due to the concentration of 4mol/L hydrochloric acid, and when the concentration of hydrochloric acid is 3mol/L, the acid leaching reaction can be fully carried out, and a uniform solution which is easy to filter can be formed.
(3) A wet gel is formed. Adding propylene oxide into the filtrate obtained by adding 3mol/L hydrochloric acid in the step (2), regulating the pH value of the filtrate to 9-10, standing for 1 hour, and tilting the beaker by 45 degrees until no liquid flows out to indicate that wet gel is formed.
(4) And (5) carrying out ultralow-temperature vacuum drying. And (3) placing the sample obtained in the step (3) into an ultralow temperature refrigerator, freezing at the temperature of-80 ℃, and drying by using a vacuum freeze dryer to obtain the aerogel carrier with loose and porous structure, as shown in figure 5. Low temperature N of aerogel 2 The adsorption-desorption experimental graph, the pore size distribution diagram and the X-ray diffraction diagram are respectively shown in fig. 6, 7 and 8. The BET specific surface area of the aerogel prepared by the method is up to 873.9m 2 BJH cumulative pore volume of 0.35 cm/g 3 Per g, average pore diameter 2.5nm, medium Kong Zhanbi 80.4.4%, micropore ratio 19.5% and macropores only 0.1%.
(5) And (3) sulfur doping resistance modification. The aerogel carrier obtained in the step (4) and the modifier K 2 CO 3 Adding the dopant precursor manganese acetate into deionized water, stirring for 12h, and K 2 CO 3 The theoretical loading of (2) is 30%, and 2% Mn is doped by taking manganese acetate as a precursor.
(6) Drying and screening the sample obtained in the step (5), and selecting a sample with the particle size of 150 mu m to obtain the sulfur-resistant CO 2 An adsorbent. Low temperature N of adsorbent 2 The adsorption-desorption experimental graph, pore size distribution diagram, and X-ray diffraction diagram are shown in FIG. 6, FIG. 7, and FIG. 8, respectively, and the performance test of the adsorbent is shown in FIG. 9 (200 mg/Nm in atmosphere) 3 SO 2 ). CO prepared by the method 2 The cumulative adsorption amount of the adsorbent under the optimal adsorption condition is up to 1.75mmol/g.
Comparative example
The present control provides an undoped CO 2 The preparation method of the adsorbent is different from that of the embodiment in that: undoped Mn in step (5); other methods and steps are the same as those in the examples, and are not repeated here, the CO of the adsorbent in the comparative example 2 The cumulative adsorption amount was 1.36mmol/g.
Claims (9)
1. Sulfur-resistant CO 2 The preparation method of the adsorbent is characterized by comprising the following steps:
(1) Pre-treating the fly ash, namely mixing and calcining the fly ash with sodium carbonate serving as a pre-treating agent at high temperature;
(2) Extracting a silicon-aluminum precursor, adding hydrochloric acid into the calcined product obtained in the step (1), stirring for 1 hour, filtering and taking filtrate;
(3) Forming wet gel, adding propylene oxide into the filtrate obtained in the step (2), adjusting the pH value of the filtrate, and standing to form wet gel;
(4) The sample obtained in the step (3) is put into an ultralow temperature refrigerator for freezing and then is dried by a vacuum freeze dryer, so as to obtain an aerogel carrier;
(5) Adding the aerogel carrier obtained in the step (4) into deionized water for stirring, and simultaneously adding a modifier K 2 CO 3 And a dopant precursor manganese acetate;
(6) Drying, sieving, selecting sample with certain particle diameter to obtain sulfur-resistant CO 2 An adsorbent.
2. An anti-sulphur CO according to claim 1 2 Preparation of adsorbentThe preparation method is characterized in that the mass ratio of the sodium carbonate to the fly ash in the step (1) is 0.7:1.
3. An anti-sulphur CO according to claim 1 2 The preparation method of the adsorbent is characterized in that the calcination temperature in the step (1) is 850 ℃ and the calcination time is 3 hours.
4. An anti-sulphur CO according to claim 1 2 The preparation method of the adsorbent is characterized in that the concentration of the added hydrochloric acid in the step (2) is 3mol/L, and the mass volume ratio of the calcined product to the hydrochloric acid is 1g:10mL.
5. An anti-sulphur CO according to claim 1 2 The preparation method of the adsorbent is characterized in that the mass ratio of the epoxy propane to the filtrate in the step (3) is 1:2, and the pH value of the filtrate is 9-10.
6. An anti-sulphur CO according to claim 1 2 A process for the preparation of an adsorbent, characterized in that in step (4) the freezing temperature is-80 ℃.
7. An anti-sulphur CO according to claim 1 2 A process for producing an adsorbent, characterized by comprising the step (5) of reacting K with a catalyst 2 CO 3 The content is 30% of the mass of the aerogel carrier, and MnO is obtained from the precursor 2 The content is 2% of the mass of the aerogel carrier.
8. An anti-sulphur CO according to claim 1 2 A process for producing an adsorbent, characterized by comprising the step (6) of reacting sulfur-resistant CO 2 The adsorbent particle size was 150 microns.
9. Sulfur-resistant CO prepared by the preparation method according to any one of claims 1 to 8 2 An adsorbent.
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