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1.
The effect of the regeneration temperature (150°, 250°, and 350°C) during multiple CO2 cyclic sorption-regeneration cycles of a K2CO3/Al2O3 solid sorbent in a bubbling fluidized bed reactor was evaluated in terms of the CO2 capture capacity and chemical composition of the solid sorbent. The CO2 capture capacity after regeneration at 150° and 250°C decreased with increasing cycle numbers, reaching approximately 57 and 78%, respectively, and 19.0 and 39.3%, respectively, of the original capacity after one and five regeneration cycles. This decline in the CO2 capture capacity was due to the accumulation of KHCO3 (at 150°C) and KAl(CO3)2(OH)2 (150° and 250°C) from their incomplete degradation back to the K2CO3/Al2O3 solid sorbent. When regenerated at 350°C, the CO2 capture capacity remained essentially constant in each cycle number because of complete desorption (no residual KHCO3 and KAl(CO3)2(OH)2). The formation mechanism of complex structure occurred similar to the one in a fixed bed reactor/thermogravimetric analyzer with lower regeneration temperature. The general operation conditions for K2CO3/Al2O3 solid sorbents are summarized.  相似文献   

2.
Armin Hassanzadeh 《Fuel》2010,89(6):1287-1297
Highly reactive and mechanically strong low-cost regenerable MgO-based sorbents were prepared by modification of dolomite which involved partial calcinations followed by impregnation with a potassium-based salt. The sorbents are capable of removing CO2 from gasification-based processes such as Integrated Gasification Combined Cycle (IGCC). The sorbents have high reactivity and good capacity toward CO2 absorption in the temperature range of 300-450 °C at 20 atm. and can be easily regenerated at 500 °C. The reaction appears to be first order with respect to CO2 concentration with an activation energy of 44 kJ/mol. The reactivity and the absorption capacity of the sorbents increase with increasing temperature, as long as the partial pressure of CO2 is above the equilibrium value for sorbent carbonation. The reactivity of the sorbents appears to improve in the presence of steam, which is likely due to the increase in the BET surface area and the porosity of the sorbent. A two-zone expanding grain model, consisting of a high-reactivity outer shell and a low-reactivity inner core is shown to provide an excellent fit to the TGA experimental data on sorbent carbonation at various operating conditions.  相似文献   

3.
The water gas shift reaction was evaluated in the presence of novel carbon dioxide (CO2) capture sorbents, both alone and with catalyst, at moderate reaction conditions (i.e., 300-600 °C and 1-11.2 atm). Experimental results showed significant improvements to carbon monoxide (CO) conversions and production of hydrogen (H2) when CO2 sorbents are incorporated into the water gas shift reaction. Results suggested that the performance of the sorbent is linked to the presence of a Ca(OH)2 phase within the sorbent. Promoting calcium oxide (CaO) sorbents with sodium hydroxide (NaOH) as well as pre-treating the CaO sorbent with steam appeared to lead to formation of Ca(OH)2, which improved CO2 sorption capacity and WGS performance. Results suggest that an optimum amount of NaOH exists as too much leads to a lower capture capacity of the resultant sorbent. During capture, the NaOH-promoted sorbents displayed a high capture efficiency (nearly 100%) at temperatures of 300-600 °C. Results also suggest that the CaO sorbents possess catalytic properties which may augment the WGS reactivity even post-breakthrough. Furthermore, promotion of CaO by NaOH significantly reduces the regeneration temperature of the former.  相似文献   

4.
Potassium carbonate supported on alumina is used as a solid sorbent for CO2 capture at low temperatures. However, its CO2 capture capacity decreases immediately after the first cycle. This regeneration problem is due to the formation of the by-product [KAl(CO3)(OH)2] during CO2 sorption. To overcome this problem, a new regenerable potassium-based sorbent was fabricated by CO2 thermal treatment of sorbents prepared by the impregnation of δ-alumina with K2CO3 in the presence of 10 vol% CO2 and 10 vol% H2O. The CO2 capture capacities of the new regenerable sorbents were maintained over multiple CO2 sorption tests. These results can be explained by the fact that the sorbent prepared by CO2 thermal treatment did not form any by-product during CO2 sorption. Based on these results, we suggest that the regeneration properties of potassium-based sorbents using δ-alumina could be significantly improved by the use of the CO2 thermal treatment developed in this study.  相似文献   

5.
Carbonation of fly ash in oxy-fuel CFB combustion   总被引:1,自引:0,他引:1  
Chunbo Wang  Yewen Tan 《Fuel》2008,87(7):1108-1114
Oxy-fuel combustion of fossil fuel is one of the most promising methods to produce a stream of concentrated CO2 ready for sequestration. Oxy-fuel FBC (fluidized bed combustion) can use limestone as a sorbent for in situ capture of sulphur dioxide. Limestone will not calcine to CaO under typical oxy-fuel circulating FBC (CFBC) operating temperatures because of the high CO2 partial pressures. However, for some fuels, such as anthracites and petroleum cokes, the typical combustion temperature is above 900 °C. At CO2 concentrations of 80-85% (typical of oxy-fuel CFBC conditions with flue gas recycle) limestone still calcines, but when the ash cools to the calcination temperature, carbonation of fly ash deposited on cool surfaces may occur. This phenomenon has the potential to cause fouling of the heat transfer surfaces in the back end of the boiler, and to create serious operational difficulties. In this study, fly ash generated in a utility CFBC boiler was carbonated in a thermogravimetric analyzer (TGA) under conditions expected in an oxy-fuel CFBC. The temperature range investigated was from 250 to 800 °C with CO2 concentration set at 80% and H2O concentrations at 0%, 8% and 15%, and the rate and the extent of the carbonation reaction were determined. Both temperature and H2O concentrations played important roles in determining the reaction rate and extent of carbonation. The results also showed that, in different temperature ranges, the carbonation of fly ash displayed different characteristics: in the range 400 °C < T ? 800 °C, the higher the temperature the higher the CaO-to-carbonate conversion ratio. The presence of H2O in the gas phase always resulted in higher CaO conversion ratio than that obtainable without H2O. For T ? 400 °C, no fly ash carbonation occurred without the presence of H2O in the gas phase. However, on water vapour addition, carbonation was observed, even at 250 °C. For T ? 300 °C, small amounts of Ca(OH)2 were found in the final product alongside CaCO3. Here, the carbonation mechanism is discussed and the apparent activation energy for the overall reaction determined.  相似文献   

6.
Vasilije Manovic 《Fuel》2011,90(1):233-239
CaO-based pellets supported with aluminate cements show superior performance in carbonation/calcination cycles for high-temperature CO2 capture. However, like other CaO-based sorbents, their CO2 carrying activity is reduced after increasing numbers of cycles under high-temperature, high-CO2 concentration conditions. In this work the feasibility of their reactivation by steam or water and remaking (reshaping) was investigated. The pellets, prepared from three limestones, Cadomin and Havelock (Canada) and Katowice (Poland, Upper Silesia), were tested in a thermogravimetric analyzer (TGA). The cycles were performed under realistic CO2 capture conditions, which included calcination in 100% CO2 at temperatures up to 950 °C. Typically, after 30 cycles, samples were hydrated for 5 min with saturated steam at 100 °C in a laboratory steam reactor (SR). Moreover, larger amounts of pellets were cycled in a tube furnace (TF), hydrated with water and reshaped, and tested to determine their CO2 capture activity in the TGA. It was found that, after the hydration stage, pellets recovered their activity, and more interestingly, pellets that had experienced a longer series of cycles responded more favorably to reactivation. Moreover, it was found that conversion of pellets increased after about 70 cycles (23%), reaching 33% by about cycle 210, with no reactivation step. Scanning electron microscope (SEM) analyses showed that the morphology of the low-porosity shell formed at the pellet surface during cycles, which limits conversion, was eliminated after a short period (5 min) of steam hydration. The nitrogen physisorption analyses (BET, BJH) of reshaped spent pellets from cycles in the TF confirmed that sorbent surface area and pore size distribution were similar to those of the original pellets. The main alumina compound in remade pellets as determined by XRD was mayenite (Ca12Al14O33). These results showed that, with periodic hydration/remaking steps, pellets can be used for extended times in CO2 looping cycles, regardless of capture/regeneration conditions.  相似文献   

7.
Catalytic pyrolysis of pine wood was carried out in a fixed-bed reactor heated slowly from room temperature to 700 °C under a stream of purging argon to examine the effects of the physically mixed K2CO3 or Ca(OH)2 on the pyrolysis behaviors. K2CO3 demonstrated a stronger catalysis for decomposition of hemicellulose, cellulose and lignin constituents, leading to the reduced yield of liquid product in conjunction with the increased yields of gaseous and char products because of the promoted secondary reactions of liquid product. With the addition of 17.7 wt.% of K2CO3, none of saccharides, aldehydes and alcohols was formed and the formation of acids, furans and guaiacols was substantially reduced, whereas the yields of alkanes and phenols were increased. Potassium led to an increase in the cumulative yields of H2, CO2 and CO at 700 °C. Ca(OH)2 somewhat promoted the decomposition of cellulose and lignin constituents, and the effect of Ca(OH)2 on the yields of liquid and char was opposite to that of K2CO3. With the addition of 22.2 wt.% Ca(OH)2, some groups of liquid product such as acids and aldehydes disappeared completely and the yields of saccharides, furans and guaiacols were somewhat reduced, while the yield of alcohols was remarkably increased in contrast to the result of K2CO3. The addition of Ca(OH)2 did not significantly change the total yield of gaseous product at 700 °C but enhanced the yield of H2.  相似文献   

8.
Adsorption is considered a promising method for carbon capture. CO2 adsorbents take a variety of forms - but one approach is to fill mesoporous substrates with a polymeric CO2 selective sorbent. SBA-15 and mesocellular siliceous foam (MCF) are high pore volume, high surface area ordered mesoporous materials for which modification with amine should result in high capacity, highly selective adsorbents. SBA-15 and MCF were separately loaded with approximately one pore volume equivalent of linear polyethyleneimine (PEI) (Mw = 2500) or branched PEI (Mn = 1200). CO2 adsorption/desorption isotherms under dry CO2 were obtained at 75, 105 and 115 °C. The CO2 adsorption/desorption kinetics were improved with temperature, though the CO2 capacities generally decreased. The adsorption capacity for MCF loaded with branched PEI at 105 and 115 °C were 151 and 133 mg/g adsorbent, respectively (in 50% CO2/Ar, 20 min adsorption time). These are significantly higher than the adsorption capacity observed for SBA-15 loaded with branched PEI under same conditions, which were 107 and 83 mg/g adsorbent, respectively. Thus the results indicate that, on a unit mass basis, amine modified MCF's are potentially better adsorbents than amine modified SBA-15 for CO2 capture at modestly elevated temperature in a vacuum swing adsorption process.  相似文献   

9.
This study examines the CO2 capture behavior of KMnO4-doped CaO-based sorbent during the multiple calcination/carbonation cycles. The cyclic carbonation behavior of CaCO3 doped with KMnO4 and the untreated CaCO3 was investigated. The addition of KMnO4 improves the cyclic carbonation rate of the sorbent above carbonation time of 257 s at each carbonation cycle. When the mass ratio of KMnO4/CaCO3 is about 0.5-0.8 wt.%, the sorbent can achieve an optimum carbonation conversion during the long-term cycles. The carbonation temperature of 660-710 °C is beneficial to cyclic carbonation of KMnO4-doped CaCO3. The addition of KMnO4 improves the long-term performance of CaCO3, resulting in directly measured conversion as high as 0.35 after 100 cycles, while the untreated CaCO3 retains conversion less than 0.16 at the same reaction conditions. The addition of KMnO4 decreases the surface area and pore volume of CaCO3 after 1 cycle, but it maintains the surface area and pores between 26 nm and 175 nm of the sorbent during the multiple cycles. Calculation reveals that the addition of KMnO4 improves the CO2 capture efficiency significantly using a CaCO3 calcination/carbonation cycle and decreases the amount of the fresh sorbent.  相似文献   

10.
In order to increase the use of carpet wastes (pre- and/or post-consumer wastes), this work studies for the first time the preparation and characterisation of a microporous material from a commercial carpet (pile fiber content: 80% wool/20% nylon; primary and secondary backings: woven polypropylene; binder: polyethylene) and its application for CO2 capture. The porous material was prepared from an entire carpet material using a standard chemical activation with KOH and then, characterised in terms of their porous structure and surface functional groups. Adsorption of CO2 was studied using a thermogravimetric analyser at several temperatures (25-100 °C) and under different CO2 partial pressures (i.e. pure CO2 flow and a ternary mixture of 15% CO2, 5% O2 and 80% N2). In order to examine the adsorbent regenerability, multiple CO2 adsorption/desorption cycles were also carried out. The surface area and micropore volume of the porous adsorbent were found to be 1910.17 m2 g− 1 and 0.85 cm3 g− 1, respectively. The CO2 adsorption profiles illustrate that the maximum CO2 capture on the sample was reached in less than 10 min. CO2 adsorption capacities up to 8.41 wt.% and 3.37 wt.% were achieved at 25 and 70 °C, respectively. Thermal swing regeneration studies showed that the prepared adsorbent has good cyclic regeneration capacities.  相似文献   

11.
A bubbling fluidized bed reactor was used to study CO2 capture from flue gas by using a potassium-based solid sorbent, sorbKX35 which was manufactured by the Korea Electric Power Research Institute. A dry sorbent, sorbKX35, consists of K2CO3 for absorption and supporters for mechanical strength. To increase initial CO2 removal, some amount of H2O was absorbed in the sorbent before injecting simulated flue gas. It was possible to achieve 100% CO2 removal for more than 10 minutes at 60°C and a residence time of 2 s with H2O pretreatment. When H2O pretreatment time was long enough to convert K2CO3 of sorbKX35 into K2CO3 · 1.5H2O, CO2 removal was excellent. The results obtained in this study can be used as basic data for designing and operating a large scale CO2 capture process with two fluidized bed reactors. This work was presented at the 6 th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.  相似文献   

12.
The effect of bed height on CO2 capture was investigated by carbonation/regeneration cyclic operations using a bubbling fluidized bed reactor. We used a potassium-based solid sorbent, SorbKX35T5 which was manufactured by the Korea Electric Power Research Institute. The sorbent consists of 35% K2CO3 for absorption and 65% supporters for mechanical strength. We used a fluidized bed reactor with an inner diameter of 0.05 m and a height of 0.8 m which was made of quartz and placed inside of a furnace. The operating temperatures were fixed at 70 °C and 150 °C for carbonation and regeneration, respectively. The carbonation/regeneration cyclic operations were performed three times at four different L/D (length vs diameter) ratios such as one, two, three, and four. The amount of CO2 captured was the most when L/D ratio was one, while the period of maintaining 100% CO2 removal was the longest as 6 minutes when L/D ratio was three. At each cycle, CO2 sorption capacity (g CO2/g sorbent) was decreased as L/D ratio was increased. The results obtained in this study can be applied to design and operate a large scale CO2 capture process composed of two fluidized bed reactors. This work was presented at the 7 th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.  相似文献   

13.
To demonstrate process feasibility of in situ CO2 capture from combustion of fossil fuels using Ca-based sorbent looping technology, a flexible atmospheric dual fluidized bed combustion system has been constructed. Both reactors have an ID of 100 mm and can be operated at up to 1000 °C at atmospheric pressure. This paper presents preliminary results for a variety of operating conditions, including sorbent looping rate, flue gas stream volume, CaO/CO2 ratio and combustion mode for supplying heat to the sorbent regenerator, including oxy-fuel combustion of biomass and coal with flue gas recirculation to achieve high-concentration CO2 in the off-gas. It is the authors' belief that this study is the first demonstration of this technology using a pilot-scale dual fluidized bed system, with continuous sorbent looping for in situ CO2 capture, albeit at atmospheric pressure. A multi-cycle test was conducted and a high CO2 capture efficiency (> 90%) was achieved for the first several cycles, which decreased to a still acceptable level (> 75%) even after more than 25 cycles. The cyclic sorbent was sampled on-line and showed general agreement with the features observed using a lab-scale thermogravimetric analysis (TGA) apparatus. CO2 capture efficiency decreased with increasing number of sorbent looping cycles as expected, and sorbent attrition was found to be another significant factor to be limiting sorbent performance.  相似文献   

14.
Ni modified K2CO3/MoS2 catalyst was prepared and the performance of higher alcohol synthesis catalyst was investigated under the conditions: T = 280–340 °C, H2/CO (molar radio) = 2.0, GHSV = 3000 h 1, and P = 10.0 MPa. Compared with conventional K2CO3/MoS2 catalyst, Ni/K2CO3/MoS2 catalyst showed higher activity and higher selectivity to C2+OH. The optimum temperature range was 320–340 °C and the maximum space-time yield (STY) of alcohol 0.30 g/ml h was obtained at 320 °C. The selectivity to hydrocarbons over Ni/K2CO3/MoS2 was higher, however, it was close to that of K2CO3/MoS2 catalyst as the temperature increased. The results indicated that nickel was an efficient promoter to improve the activity and selectivity of K2CO3/MoS2 catalyst.  相似文献   

15.
Calcium-carbonate powders were coprecipitated with Al3+ and then decomposed in air and/or under a CO2 flux between 590 °C and 1150 °C. The data were analysed using a consecutive-decomposition-dilatometer method and the kinetic results were discussed according to the microstructure analysis done by N2 adsorption isotherms (78 K), SEM and FT-IR measurements. Below 1000 °C, CaCO3 particle thermal-decomposition was pseudomorphic, resulting in the formation of a CaO grain porous network. When the CaO grains were formed, the Al3+ diffused among them, producing AlO4 groups that promoted the CaO grain coarsening and reduced O2− surface sites available to CO2 adsorbed molecules to form CO32−. In pure CaO, CO32− diffused through the grain boundary, enhancing Ca2+ and O2− mobility; AlO4 groups reduced CO32− penetration and CaO sintering rate. Above 1000 °C, the sintering rate of the doped samples exceeded that of the undoped, likely because of Al3+ diffusion in CaO and viscous flow.  相似文献   

16.
One promising method for the capture of CO2 from point sources is through the usage of a lime-based sorbent. Lime (CaO) acts as a CO2 carrier, absorbing CO2 from the flue gas (carbonation) and releasing it in a separate reactor (calcination) to create a pure stream of CO2 suitable for sequestration. One of the challenges with this process is the decay in calcium utilization (CO2 capture capacity) during carbonation/calcination cycling. The reduction in calcium utilization of natural limestone over large numbers of cycles (>250) was studied. Cycling was accomplished using pressure swing CO2 adsorption in a pressurized thermogravimetric reactor (PTGA). The effect of carbonation pressure on calcium utilization was studied in CO2 with the reactor operated at 1000 °C. The pressure was cycled between atmospheric pressure for calcination, and 6, 11 or 21 bar for carbonation. Over the first 250 cycles, the calcium utilization reached a near-asymptotic value of 12.5-27.7%, depending on the cycling conditions. Pressure cycling resulted in improved long-term calcium utilization compared to temperature swing or CO2 partial pressure swing adsorption under similar conditions. An increased rate of de-pressurization caused an increase in calcium utilization, attributed to fracturing of the sorbent particle during the rapid calcination, as observed via SEM analysis.  相似文献   

17.
The effects of CuO, Li2CO3 and CaTiO3 additives on the densification, microstructure and microwave dielectric properties of CaSiO3–1 wt% Al2O3 ceramics for low-temperature co-fired applications were investigated. With a single addition of 1 wt% Li2CO3, the CaSiO3–1 wt% Al2O3 ceramic required a temperature of at least 975 °C to be dense enough. Large amount addition of Li2CO3 into the CaSiO3–1 wt% Al2O3 ceramics led to the visible presence of Li2Ca3Si6O16 and Li2Ca4Si4O13 second phases. Fixing the Li2CO3 content at 1 wt%, a small amount of CuO addition significantly promoted the sintering process and lowered the densification temperature to 900 °C whereas its addition deteriorated the microwave dielectric properties of CaSiO3–1 wt% Al2O3 ceramics. Based on 10 wt% CaTiO3 compensation in temperature coefficient, good microwave dielectric properties of εr=8.92, Q×f=19,763 GHz and τf=−1.22 ppm/°C could be obtained for the 0.2 wt% CuO and 1.5 wt% Li2CO3 doped CaSiO3–1 wt% Al2O3 ceramics sintered at 900 °C. The chemical compatibility of the above ceramics with silver during the cofiring process has also been investigated, and the result showed that there was no chemical reaction between silver and ceramics, indicating that the as-prepared composite ceramics were suitable for low-temperature co-fired ceramics applications.  相似文献   

18.
The phase diagram of the Al2O3-HfO2-Y2O3 system was first constructed in the temperature range 1200-2800 °C. The phase transformations in the system are completed in eutectic reactions. No ternary compounds or regions of appreciable solid solution were found in the components or binaries in this system. Four new ternary and three new quasibinary eutectics were found. The minimum melting temperature is 1755 °C and it corresponds to the ternary eutectic Al2O3 + HfO2 + Y3Al5O12. The solidus surface projection, the schematic of the alloy crystallization path and the vertical sections present the complete phase diagram of the Al2O3-HfO2-Y2O3 system.  相似文献   

19.
Plate-like α-Al2O3 single-crystal particles were successfully synthesized in NaCl–KCl flux using Al(OH)3 powders as starting materials, and the influence of pre-calcining of Al(OH)3 powders on the phase formation and morphology of α-Al2O3 powders was focused. When Al(OH)3 powders are used as starting materials, the synthesized product at 900 °C is mainly composed of α-Al2O3 and κ-Al2O3, and most synthesized particles show alveolate morphology. At 1100 °C, single-phase α-Al2O3 powders are developed, in which there are many aggregations of intensively bound plate-like particles. In contrast, using porous amorphous Al2O3 powders obtained by pre-calcining Al(OH)3 powders at 550 °C for 3 h as the starting material, plate-like α-Al2O3 single-crystal particles can be well developed above 900 °C. The reason of the influence of pre-calcining of Al(OH)3 powders on the phase formation and morphology of α-Al2O3 powders is also discussed in the paper.  相似文献   

20.
This study focuses on enhancing CO2 uptake by modifying limestone with acetate solutions under pressurized carbonation condition. The multicycle tests were carried out in an atmospheric calcination/pressurized carbonation reactor system at different temperatures and pressures. The pore structure characteristics (BET and BJH) were measured as a supplement to the reaction studies. Compared with the raw limestone, the modified sorbent showed a great improvement in CO2 uptake at the same reaction condition. The highest CO2 uptake was obtained at 700 °C and 0.5 MPa, by 88.5% increase over the limestone at 0.1 MPa after 10 cycles. The structure characteristics of the sorbents on N2 absorption and SEM confirm that compared with the modified sorbent, the effective pores of limestone are greatly driven off by sintering, which hinders the easy access of CO2 molecules to the unreacted-active sites of CaO. The morphological and structural properties of the modified sorbent did not reveal significant differences after multiple cycles. This would explain its superior performance of CO2 uptake under pressurized carbonation. Even after 10 cycles, the modified sorbent still achieved a CO2 uptake of 0.88.  相似文献   

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