负载型K2CO3/Al2O3二氧化碳吸收剂的碳酸化反应特性

The carbonation characteristics of K₂CO₃/Al₂O₃ supported sorbent for CO₂ capture was investigated with thermogravimetric apparatus（TGA）,X-ray diffraction（XRD）,scanning electron microscopy analysis（SEM）and N₂ adsorption.The results showed that the carbonation rate of K₂CO₃ before being loaded on Al₂O₃ was slow.However,the K₂CO₃/Al₂O₃ upported sorbent showed excellent carbonation performance.The difference in carbonation behavior between K₂CO₃ nd K₂CO₃/Al₂O₃ supported sorbent was analyzed from the microscopic view.The analytical reagent K₂CO₃ sample was of monoclinic crystal structure and could react quickly with H₂O in the experimental carbonation environment to produce K₂CO₃•1.5H₂O,which was unfavorable to carbonation reaction.When K₂CO₃was loaded on Al₂O₃,the surface area and porosity of the sorbent was improved greatly.So the carbonation properties of the K₂CO₃/Al₂O₃ supported sorbent was also improved.     

高温下改性钙基吸附剂固定床反应器从烟气中捕捉二氧化碳(英文)

Four kinds of Ca-based sorbents were prepared by calcination and hydration reactions using different precursors: calcium hydroxide, calcium carbonate, calcium acetate monohydrate and calcium oxide. The CO2 absorption capacity of those sorbents was investigated in a fixed-bed reactor in the temperature range of 350-650℃. It was found that all of those sorbents showed higher capacity for CO2 absorption when the operating temperature higher than 450℃. The CaAc2-CaO sorbent showed the highest CO2 absorption capacity of 299mg·g-1. The morphology of those sorbents was examined by scanning electron microscope (SEM), and the changes of composition before and after carbonation were also determined by X-ray diffraction (XRD). Results indicated that those sorbents have the similar chemical compositions and crystalline phases before carbonation reaction [mainly Ca(OH)2], and CaCO3 is the main component after carbonation reaction. The SEM morphology shows clearly that the sorbent pores were filled with reaction products after carbonation reaction, and became much denser than before. The N2 adsorption-desorption isotherms indicated that the CaAc2-CaO and CaCO3-CaO sorbents have higher specific surface area, larger pore volume and appropriate pore size distribution than that of CaO-CaO and Ca(OH)2-CaO.     

Effect of pre-calcination for modified CaO-based sorbents on multiple carbonation/calcination cycles

In the present work,the effect of pre-calcination on carbonation conversion and cyclic stability of modified CaO-based sorbent was investigated by thermogravimetric analyzer (TGA).The modified CaO-based sorbents with CaAc2 as precursor were respectively doped with different elements (Mg,Al,Ce,Zr and La).The specfic surface area,pore volume and pore size distribution were tested by N2 isothermal adsorption measurements.The phase compositions of sorbents were characterized by X-ray diffraction (XRD).The results showed that the cyclic stabilities of the sorbents were improved by pre-calcination.The pre-calcination was conducted at 900 ℃ for 5 h in air by the muffle furnace.With pre-calcination,the cyclic stabilities of sorbents could be as high as 96％after 22 cycles,such as CaO-Al,CaO-Ce and CaO-La.After contact with air,the carbonation conversions of spent sorbents with pre-calcination suddenly increased by about one-sixth due to the change of channel structure by hydration.Both the cyclic stability of sorbent and the durability of reactivation were related to the structural stability of sample,especially the stability of mesopores between 2 nm and 5.5 nm.The present work also provided an easy and low-cost method for reactivating the spent CaO-based sorbents.     

硅酸钠溶液分步碳分制备高纯沉淀氧化硅

By using industrial sodium silicate solution as raw material,high purity SiO₂ powder was successfully synthesized by the split-step carbonation method.The relations between pH value of end point and the removal percentage of impurity at the first carbonation and the purity and yield of product SiO₂ powder at the second carbonation were studied.The SiO₂ powder was characterized by using XRD,SEM,IR and composition analysis.The results showed that when the pH value of end point at the first carbonation was 10.9,the purity of SiO₂ prepared was up to 99.9%.The SiO₂ powder synthesized was amorphous with regular sphere shape,uniform size and no reunion.The reaction mechanism was also discussed.     

CO2跨临界双级压缩制冷循环的热力学分析

Two-stage vapor compression refrigeration cycle was accomplished with an intercooler.The state of the refrigerant vapor leaving the intercooler affects the system performance.The thermodynamic analysis of the trans-critical two-stage refrigeration cycle using CO₂ as the refrigerant was made with a condensing temperature of 35℃.When the intercooler operated at about the geometric mean of the evaporating and condensing pressures,compared with the single stage cycle,the coefficient of performance（COP）of the two-stage cycle was improved.As the degree of superheating of the CO₂ vapor leaving the intercooler increased,the COP of the two-stage system decreased.     

288 K下Li+,K+//CO2-3,B4O2-7-H2O四元体系的相平衡

Solubilities and properties (density, conductivity and pH value) of solutions in the quaternary system Li⁺,K⁺//CO^2-₃,B₄O^2-₇-H₂O at 288 K were experimentally studied with the isothermal equilibrium method. The phase diagram of the system consisted of two invariant points E and F, five univariant curves, and four crystallization fields that belonged to K₂CO₃·3/2H₂O,Li₂B₄O₇·3H₂O,K₂B₄O₇·4H₂O and Li₂CO₃. The composition of the solution corresponding to E was w（CO^2-₃）=2.27 %,w（B₄O^2-₇）=6.05 %,w（K⁺ ）=4.30%,w(Li⁺)=0.30 % and the equilibrium solids were Li₂B₄O₇· 3H₂O+K ₂B₄O₇·4H₂O+Li₂CO₃;The composition of the solution for F was w(CO^2-₃)=22.45%,w(B₄O^2-₇)=1.88%,w(K⁺ )=29.96%,w(Li⁺ )=0.03% and the equilibrium solids were K₂CO₃·3/2H₂O+K ₂B₄O₇·4H₂O+Li₂CO₃. K₂CO₃ possesses strong salting-out effect on K₂B₄O₇,Li₂CO₃ and Li₂B₄O₇.     

煅烧升温速率对于钙基吸收剂脱碳性能的影响

A wire-mesh reactor capable of heating samples at a given heating-rate (1—1000 K•s^-1) was used to investigate the effect of heating-rate on Ca-based absorbent performance of CO₂ capture.BET method was used to analyze the morphology of the produced CaO, and the capabilities of the absorbent were compared.It was found that CaO calcined at a higher heating-rate had more appropriate pore distribution for CO₂ capture, and the capability of CaO calcined at 1000 K•s^-1 was 15% higher than that calcined at 1 K•s^-1 determined by TGA.     

Effect of different organic compounds on the preparation of CaO-based CO2 sorbents derived from wet mixing combustion synthesis

CaO based sorbents have great potential for commercial use to capture CO_2 of power plants. In the demand of producing sorbents with better cyclic performance, CaO-based sorbents derived from different kinds of calcium precursors, containing calcium carbonate(CC-CaO), calcium gluconate monohydrate(CG-CaO), calcium citrate(CCi-CaO) and calcium acetate monohydrate(CA-CaO), were tested cyclically and compared using simultaneous thermal analyzer(STA). And further study was conducted on the sorbents modified with citric acid monohydrate and 50% gluconic acid solution by wet mixing combustion synthesis. The modified sorbents showed better performance and higher pore parameters as well as porous microstructure with more organic acid added. After 20 cycles of carbonation and calcination, the C2CCi8(CaO: citric acid = 2:8 by mass ratio) and C2G8(CaO: gluconic acid = 2:8 by mass ratio) sorbent possess CO_2 capture capacity of 0.45 g·g~(-1)(g CO_2 per g sorbents) and 0.52 g·g~(-1) respectively. The citric acid was more effective for modification than gluconic acid for extended 50 cycles. Furthermore, good linear relationship between CaO conversion and specific surface area as well as pore volume were determined, of which the specific surface area showed closer correlation with CaO conversion.     

Enhancement of CO2 capture and microstructure evolution of the spent calcium-based sorbent by the self-reactivation process

The effect of self-reactivation on the CO_2 capture capacity of the spent calcium based sorbent was investigated in a dual-fixed bed reactor.The sampled sorbents from the dual-fixed bed reactor were sent for XRD,SEM and N_2 adsorption analysis to explain the self-reactivation mechanism.The results show that the CaO in the spent sorbent discharged from the calciner absorbs the vapor in the air to form Ca(OH)_2 and further Ca(OH)_2·2 H_2 O under environmental conditions,during which process the CO_2 capture capacity of the spent sorbent can be self-reactivated.The microstructure of the spent sorbent is improved by the self-reactivation process,resulting in more porous microstructure,higher BET surface area and pore volume.Compared with the calcined spent sorbent that has experienced 20 cycles,the pore volume and BET surface area are increased by 6.69 times and 56.3% after self-reactivation when φ=170%.The improved microstructure makes it easier for the CO_2 diffusion and carbonation reaction in the sorbent.Therefore,the CO_2 capture capacity of the spent sorbent is enhanced by self-reactivation process.A self-reactivation process coupled with calcium looping process was proposed to reuse the discharged spent calcium based sorbent from the calciner.Higher average carbonation conversion and CO_2 capture efficiency can be achieved when self-reactivated spent sorbent is used as supplementary sorbent in the calciner rather than fresh CaCO_3 under the same conditions.     

碳酸化法制备α-Al(OH)3包覆CaCO3复合晶须

A carbonation process was developed to coat Al(OH)₃ on aragonite whisker. Al(OH)₃ coating was obtained in a suspension,which contained 3Cao·Al₂O₃·6H₂O(C₃AH₆)-NaOH prepared by adding Ca(OH)₂ to NaAlO₂ aqueous solution.The CaCO₃ whiskers coated with fine particles of Al(OH)₃ were prepared by blowing CO₂ gas into the suspension.The formed Al(OH)₃ adhered to the CaCO₃ fibers as the substrate.In order to coat α -Al(OH)₃ on aragonite whisker , the pH value of the solution must be higher than 10.5.The formation of C₃AH₆ and complexation of calcium carbonate molecule with C₃A were the domain factors to get single aragonite phase whisker. Micro-analysis demonstrated that the existence of Al(OH)₃ crystal coating on the surface of aragonite-type calcium carbonate whisker.After the coated whiskers were treated strongly in an ultrasonic water bath.Al(OH)₃ still adhered to the CaCO₃ whiskers well.The reaction mechanism was also mentioned in this paper.     

负载型钾基CO2吸收剂的结构表征和碳酸化反应特性

CO2减排已成为21世纪人类面临的焦点问题.而在我国燃煤电厂作为CO2排放量最大、排放最集中的化石燃料燃烧场所,对其进行CO2减排技术的研究和开发势在必行.     

钾基CO2吸收剂的碳酸化反应特性

对钾基CO₂吸收剂的碳酸化反应机理进行研究。利用热重分析、XRD、扫描电镜和氮吸附仪进行试验。结果表明：分析纯碳酸钾的组分为K₂CO₃·1.5H₂O,碳酸化反应速率缓慢;先将分析纯碳酸钾样品脱除结晶水后再进行碳酸化反应时,K₂CO₃与气氛中的水蒸气迅速生成K₂CO₃·1.5H₂O,不利于碳酸化反应的进行;由KHCO₃分解产生的K₂CO₃却表现出优越的碳酸化反应性能,20 min内转化率高达85%以上,经过多次循环试验后吸收剂仍保持很高的活性。从微观角度分析了两种改性钾基CO₂吸收剂碳酸化反应机理差异的原因,通过拟合计算得到了这3种钾基吸收剂的碳酸化反应速率常数,为干法K₂CO₃/KHCO₃循环脱除CO₂的研究提供了一定的基础数据。     

纳米钙基CO2吸附剂反应吸附与分解动力学

采用TGA测定纳米钙基CO₂吸附剂在500～650℃温度范围内,CO₂分压0.015～0.025 MPa氮气气氛中的吸附反应动力学。针对纳米钙基CO₂吸附剂吸附CO₂反应特征,提出以两倍最大吸附速率对应的时间点前后分别为快速反应段与慢速反应段。分别采用Boltzmann方程与Avrami-Erofeev方程拟合快速反应段与慢速反应段吸附反应动力学方程,得到纳米钙基CO₂吸附剂在快速反应段与慢速反应段的活化能分别为27.52、70.25 kJ·mol^-1。吸附率拟合与实验值平均相对误差分别为10.29％、4. 17%。研究测试了纳米钙基CO₂吸附剂在650～800℃温度范围内,N₂,0.02、0.04 MPa CO₂分压氮气气氛中的分解反应动力学。忽略反应过程中传热、传质影响,采用收缩核模型,分别求得吸附剂在N₂,0.02、0.04 MPa CO₂分压氮气气氛中的活化能为141.9、34.7、113.2 kJ·mol^-1。碳酸钙分解率与实验值比较平均相对误差分别小于5.66% 、7.82%、5.01%。     

CO2载体CaO循环煅烧/碳酸化反应的分形特征

捕捉煤燃烧释放出的CO₂时,作为CO₂载体的CaO微观结构特性对其循环碳酸化性能具有显著影响。采用分形维数作为表征CaO微观结构的特征参数,研究在循环煅烧/碳酸化反应过程中CaO的分形特征及其对CO₂捕捉性能的影响规律。结果表明,随着循环次数的增加CaO分形维数逐渐下降,CaO孔道也由粗糙和不规则变得越来越平滑和有规则性。煅烧温度升高则CaO分形维数下降。分形维数较大的CaO具有较高的碳酸化速率。在碳酸化过程的前10 min内CaO的分形维数迅速减小,此后随时间变化缓慢。在分形维数D≤2.61的实验范围内,CaO分形维数与其循环碳酸化转化率呈线性正相关;当D＞2.61时,可能存在临界分形维数D_cr,当D＞D_cr时随着分形维数的进一步增大CaO转化率反而减小。     

钙基CO_2吸收剂循环活性衰减原因初探

对钙基CO2吸收剂的循环活性衰减进行了实验研究,考察了随着循环次数的增加,吸收剂的表面形态、吸收剂分子孔径及比表面积等微观结构的变化,分析了钙基CO2吸收剂循环活性衰减的原因。结果表明,随着循环次数的增加,吸收剂晶粒中的片状结构已经完全消失,取而代之的是正方体状的大晶粒,晶粒生长严重,大量空隙被封闭。而由此引起的吸收剂的比表面积的不断减小和孔容积的降低以及孔分布的改变,导致了吸收剂循环活性的衰减,吸收剂的循环转化率降低。     

沉淀法SiO2包覆纳米CaCO3吸附剂性能

以CO₂为沉淀剂,Na₂SiO₃为硅源,制备了SiO₂包覆纳米CaCO₃吸附剂。TEM测试证实纳米CaCO₃表面包覆一层SiO₂膜, 用SEM & EDX 测试5个包硅样品Si含量为0.67%～4.93%。采用TGA考察吸附剂的分解温度及600℃、20% CO₂条件下的吸附性能。结果表明：采用CO₂沉淀法包覆SiO₂后,与未包硅的纳米CaCO₃相比,分解温度降低9～42℃。纳米SiO₂/CaCO₃吸附剂的循环吸附率、吸附容量、吸附速率均随Si含量的减小先增加后降低。Si含量为1.05%的纳米SiO₂/CaCO₃吸附剂显示最佳吸附性能,第1、5次循环吸附容量分别为8.9、6.0 mol·kg^-1,与未包覆SiO2的纳米CaCO₃相比,分别提高11%、50%,同时在第5次循环快反应段吸附速率较纳米CaCO₃提高10%。与纳米CaCO₃相比,包硅后的吸附剂具有较高的吸附容量和循环吸附率,循环稳定性较好。     

钙基CO2吸收剂的循环特性

对钙基CO₂吸收剂的循环特性进行了实验研究，考察了煅烧温度和碳酸化（吸收）温度对吸收剂最大转化率的影响，比较了常压煅烧-碳酸化（CC）过程和煅烧-水合-碳酸化（CHC）过程中吸收剂的最大吸收能力，并就添加剂对吸收剂循环性能的影响进行了实验研究.结果表明，随着循环次数的增加，吸收剂的吸收能力明显下降，未经处理的吸收剂，循环10次后，其吸收能力基本都下降到20％左右;温和的煅烧温度和较高的吸收温度下，吸收剂的最大转化率比较高;CC过程中吸收剂的最大转化率明显低于CHC过程;添加了氯化钠和碳酸钠的吸收剂的吸收能力急剧下降，但循环性能稳定;多次循环后对吸收剂进行再活化，可使其活性恢复到初始的95％.     

EtOH-H2O对钙基吸收剂分离CO2的影响

采用不同体积浓度的乙醇溶液分别对石灰石和石灰石的煅烧产物CaO进行调质处理,研究它们的碳酸化反应,并与水合调质CaO的碳酸化进行比较。通过SEM和N2吸附法考察吸收剂多次煅烧的微观结构特性,进一步揭示了乙醇溶液促进CaO碳酸化的机理。结果表明：随着循环反应次数的增加,乙醇溶液调质后CaO的碳酸化转化率明显高于石灰石和水合调质的CaO,对于石灰石,乙醇溶液则没有明显的调质效果。CaO经乙醇溶液调质后在650～700℃内有利于碳酸化的进行。乙醇浓度越高,则经调质后CaO的转化率越高,抗烧结性能越好。经乙醇溶液调质的CaO煅烧后比表面积和比孔容均比单纯水合大,远高于煅烧后的石灰石;比孔容分布和孔比表面积分布明显优于煅烧后的水合CaO和石灰石。乙醇溶液调质对CaO的孔有明显的增扩效应。