Modification of CaO-based sorbents prepared from calcium acetate for CO_2 capture at high temperature

CaO-based sorbent is considered to be a promising candidate for capturing CO_2 at high temperature. However,the adsorption capacity of CaO decreases sharply with the increase of the carbonation/calcination cycles. In this study, CaO was derived from calcium acetate(CaAc_2), which was doped with different elements(Mg, Al,Ce, Zr and La) to improve the cyclic stability. The carbonation conversion and cyclic stability of sorbents were tested by thermogravimetric analyzer(TGA). The sorbents were characterized by N_2 isothermal adsorption measurements, scanning electron microscopy(SEM) and X-ray diffraction(XRD). The results showed that the cyclic stabilities of all modified sorbents were improved by doping elements, while the carbonation conversions of sorbents in the 1st cycle were not increased by doping different elements. After 22 cycles, the cyclic stabilities of CaO–Al, CaO–Ce and CaO–La were above 96.2%. After 110 cycles, the cyclic stability of CaO–Al was still as high as 87.1%. Furthermore, the carbonation conversion was closely related to the critical time and specific surface area.

CO_(2) capture by double metal modified CaO-based sorbents from pyrolysis gases

High-temperature pyrolysis technology can effectively solve the problem of municipal solid waste pollution.However,the pyrolysis gas contains a large amount of CO_(2),which would adversely affect the subsequent utilization.To address this problem,a novel method of co-precipitation modification with Ca,Mg and Zr metals was proposed to improve the CO_(2)capture performance.X-ray diffraction(XRD)patterns and energy dispersive X-ray spectroscopy analysis showed that the two inert supports MgO and CaZrO_(3)were uniformly distributed in the modified calcium-based sorbents.In addition,the XRD results indicated that CaZrO_(3)was produced by the reaction of ZrO_(2)and CaO at high temperatures.The effects of doping ratios,adsorption temperature,calcination temperature,CO_(2)concentration and calcination atmosphere on the adsorption capacity and cycle stability of the modified calcium-based sorbent were studied.The modified calcium-based sorbent achieved the best CO_(2)capture performance when the doping ratio was 10:1:1 with carbonation at 700℃ under 20%CO_(2)/80%N_(2)atmosphere and calcination at 900℃ under100%N_(2)atmosphere.After ten cycles,the average carbonation conversion rate of Ca-10 sorbent was 72%.Finally,the modified calcium-based sorbents successfully reduced the CO_(2)concentration of the pyrolysis gas from 37%to 5%.

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 modi fied CaObased sorbent was investigated by thermogravimetric analyzer(TGA).The modi fied CaO-based sorbents with CaAc_2 as precursor were respectively doped with different elements(Mg,Al,Ce,Zr and La).The speci fic surface area,pore volume and pore size distribution were tested by N_2 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°C for 5 h in air by the muf fle 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.

Influence of CaO-based expansive agent,superabsorbent polymers and curing temperature on pore structure evolution of early-age cement paste

Cracks easily generate in concrete at early age owing to the shrinkage deformation.CaO-based expansion agent(CEA)and superabsorbent polymers(SAP)have been extensively used for the mitigation of concrete shrinkage.The macroscopic properties of concrete are highly determined by the microstructure.In this study,the influence of CEA and SAP addition on the pore structure evolution of cement paste under different curing temperatures was evaluated via low-field nuclear magnetic resonance spectroscopy.Test results indicated that,in cement paste,a higher CEA content led to a higher porosity and a larger most probable pore diameter(MPPD).Meanwhile,SAP addition increased the porosity and MPPD of CEA cement paste at early age but decreased them after 7 d,and a higher SAP content always brought a higher porosity and MPPD.Furthermore,the addition of SAP led to a lower porosity and MPPD of CEA cement paste than that of plain cement paste after 14 d.Moreover,the porosity and MPPD of CEA cement paste decreased first and subsequently increased as the curing temperature raised.

The Al_(2)O_(3)and Mn/Al_(2)O_(3)sorbents highly utilized in destructive sorption of NF_(3)

NF_(3)is commonly used as an etching and cleaning gas in semiconductor industry,however it is a strongly greenhouse gas.Therefore,the destruction of disposal NF_(3)is an urgent task to migrate the greenhouse effect.Among the technologies for NF_(3)abatement,the destructive sorption of NF_(3)over metal oxides sorbents is an effective way.Thus,the search for a highly reactive and utilized sorbent for NF_(3)destruction is in great demand.In this work,AlOOH supported on carbon-sphere(AlOOH/CS)as precursors were synthesized hydrothermally and heat-treated to prepare the Al_(2)O_(3)sorbents.The influence of AlOOH/CS hydrothermal temperatures on the reactivity of derived Al_(2)O_(3)sorbents for NF_(3)destruction was investigated,and it is shown that the Al2O3 from AlOOH/CS hydro-thermalized at 120℃is superior to others.Subsequently,the optimized Al_(2)O_(3)was covered by Mn(OH)x to prepare Mn/Al_(2)O_(3)sorbents via changing hydrothermal temperatures and Mn loadings.The results show that the Mn/Al_(2)O_(3)sorbents are more utilized than bare Al_(2)O_(3)in NF_(3)destructive sorption due to the promotional effect of Mn_(2)O_(3)as surface layer on the fluorination of Al_(2)O_(3)as substrate,especially the optimal 5%Mn/Al2O3(160℃)exhibits a utilization percentage as high as 90.4%,and remarkably exceeds all the sorbents reported so far.These findings are beneficial to develop more efficient sorbents for the destruction of NF_(3).

Effect of Strong Basic Oxide（ Li2O,Na2O,K2O and BaO）on Property of CaO-Based Flux

It is found that strong basic oxides including Li2O,Na2O,K2O and BaO,which are used to replace a part of CaO in CaO-based fluxes,can lower the melting point and the viscosity and enhance the dephosphorizing ability. The mechanism was analysed and the addition of Li2O to CaO based fluxes was recommended.

Effect of Ca/Mg molar ratio on the calcium-based sorbents

Steelmaking industry faces urgent demands for both steel slag utilization and CO_(2)abatement.Ca and Mg of steel slag can be extracted by acid solution and used to prepare sorbents for CO_(2)capture.In this work,the calcium-based sorbents were prepared from stainless steel slag leachate by co-precipitation,and the initial CO_(2)chemisorption capacity of the calcium-based sorbent prepared from steel slag with the Ca and Mg molar ratio of 3.64:1 was 0.40 g/g.Moreover,the effect of Ca/Mg molar ratio on the morphology,structure,and CO_(2)chemisorption capacity of the calcium-based sorbents were investigated.The results show that the optimal Ca/Mg molar ratio of sorbent for CO_(2)capture was4.2:1,and the skeleton support effect of MgO in calcium-based sorbents was determined.Meanwhile,the chemisorption kinetics of the sorbents was studied using the Avrami-Erofeev model.There were two processes of CO_(2)chemisorption,and the activation energy of the first stage(reaction control)was found to be lower than that of the second stage(diffusion control).

Calcium looping heat storage performance and mechanical property of CaO-based pellets under fluidization

The CaO-based pellets were fabricated using extrusion-spheronization method for calcium looping thermochemical heat storage under the fluidization.The effects of adhesive,biomass-based pore-forming agent,binder and particle size on the heat storage performance and mechanical property of the CaObased pellets were investigated in a bubbling fluidized bed reactor.The addition of 2%(mass)polyvinylpyrrolidone as an adhesive not only helps granulate,but also improves the heat storage capacity of the pellets.All biomass-templated CaO-based pellets display higher heat storage capacity than biomass-free pellets,indicating that the biomass-based pore-forming agent is beneficial for heat storage under the fluidization.Especially,bagasse-templated pellets show the highest heat storage conversion of 0.61 after 10 cycles.Moreover,Al_(2)O_(3)as a binder for the pellets helps obtain high mechanical strength.The CaO-based pellets doped with 10%(mass)bagasse and 5%(mass)Al_(2)O_(3)reach the highest heat storage density of 1621 kJ·kg^(-1) after 30 cycles and the highest crushing strength of 4.98 N.The microstructure of the bagasse-templated pellets appears more porous than that of biomass-free pellets.The bagassetemplated CaO-based pellets doped with Al_(2)O_(3)seem promising for thermochemical heat storage under the fluidization,owing to the enhanced heat storage capacity,excellent mechanical strength,and simplicity of the synthesis procedure.

Studies of Adsorption of Cadmium Ions by Biowaste Adsorbent from Aqueous Solutions with Ion-Selective Electrodes and ICP-OES

Using environment-friendly and low-cost biowaste adsorbents as toxic metal ion removal substrates from aqueous solutions has a great economic advantage. This work evaluated pumpkin and potato peel biowastes for the adsorption of cadmium ions. The biowastes were treated with acid or base. Batch experiments were carried out by introducing a known concentration of metal ion solution into the biowaste sorbent at various pH levels. The pH and metal ion concentration was monitored with pH and cadmium ion-selective electrode continuously for two hours, and the final concentration for the metal ion after 24 hours was measured with the cadmium electrode and then confirmed with ICP-OES. L-type isotherms were obtained that fit to Freundlich model. Adsorption isotherms showed chemical adsorption and the kinetics following the second order model. Equilibrium adsorption capacity is higher than 29 mg/g at pH 5.6 when the initial concentration is 220 ppm. Dynamic cadmium adsorption capacity is 17 mg/g from aqueous solution when the feed solution is 220 ppm with pumpkin peel biowaste sorbent. The biowaste materials can be regenerated with acid washing.

失活石灰石自活化增强循环捕集CO_(2)特性

钙循环工艺是一种低成本高效率捕集CO_(2)技术,运行过程需不断补充新鲜吸收剂并排出失活吸收剂,实现失活钙基吸收剂原位资源化利用具有重要意义。为研究颗粒状石灰石失活后自活化特性,运用双固定床反应器制备了失活石灰石,分析了自活化后石灰石碳酸化转化率随循环次数的变化规律,采用XRD、SEM、N_(2)吸附等分析测试手段探究了自活化提高失活石灰石循环捕集CO_(2)性能机理。结果表明,失活石灰石置于环境中可吸收空气中水分生成Ca(OH)_(2),吸水率φ达100%后,继续吸水生成氢氧化钙水合物,极限吸水率为130%。不同程度自活化后的石灰石循环捕集CO_(2)性能均有不同程度提高,随吸水率变化呈线性升高趋势。与分析纯CaCO3相比,失活石灰石对吸水率变化更敏感,随吸水率升高其循环捕集CO_(2)性能提高更快。吸水率为130%时,自活化后石灰石循环捕集CO_(2)性能甚至优于新鲜石灰石。微观结构分析结果显示:新鲜石灰石因高温烧结而失活过程中,CaO晶粒尺寸由41.9 nm长大至72.2 nm,孔隙结构发生坍塌阻塞,比孔容和比表面积显著降低。经过自活化,煅烧后的石灰石中CaO晶粒尺寸降低,原本密实的表面重新生成孔隙结构;吸水率为130%时,晶粒尺寸降至35.1 nm,比孔容和比表面积分别恢复至新鲜石灰石的70.5%和107.6%,特别是10~100 nm孔隙得以再生,因此失活石灰石循环捕集CO_(2)性能恢复。虽然自活化过程会加剧失活石灰石颗粒磨损速率,但吸水率100%的自活化石灰石磨损导致直径每小时减小量仅为颗粒直径的0.55%。综上所述,自活化后的失活石灰石完全可替代新鲜石灰石,作为补充钙基吸收剂用于钙循环捕集CO_(2)。

三种血清学方法和qPCR方法在鸡滑液囊支原体检测中的综合应用研究

为评价不同方法对鸡滑液囊支原体(MS)活疫苗免疫和非免疫状态鸡群的监测效果,研究分别采用HI、SPA与ELISA三种抗体检测方法和qPCR方法同步对某养殖场A、B和C三组鸡群进行MS感染和抗体水平监测,其中A鸡群23日龄免疫MS活疫苗(MS-H株),B、C鸡群不免疫MS疫苗。结果显示:三种血清学检测方法所测MS抗体阳性率趋势基本一致,HI抗体效价变化规律和ELISA抗体效价变化规律相似,但血清学方法相对于qPCR方法具有一定的滞后性,qPCR可以最早发现MS野毒感染,且在使用活疫苗免疫的情况下对疫苗和野毒进行鉴别检测。研究提示:在条件允许的情况下,qPCR可以作为MS首选的监测方法;当检测条件受限时,上述三种血清学方法同样也可以用于评估MS野毒感染状况,但对结果的判断受母源抗体水平、疫苗免疫状况、野毒感染时间等多重因素的影响,在结果判断时应进行综合分析。

基于核酸适体LYGV1c的酶联吸附法检测石斑鱼虹彩病毒感染

【目的】利用核酸适体LYGV1c构建可快速、准确识别石斑鱼虹彩病毒(Grouper iridovirus Guangxi strain,SGIV-Gx)感染的酶联吸附法(Aptamer LYGV1c-based enzyme-linked apta-sorbent assay,LYGV1c-ELASA),为提高水产疫病检测及防控效率提供理论支持。【方法】基于生物素标记的LYGV1c(Bio-LYGV1c)开发核酸适体酶联吸附法(LYGV1c-ELASA)检测SGIV-Gx,通过对Bio-LYGV1c特异性、灵敏性、稳定性等实验评估其检测性能。通过珍珠龙胆石斑鱼(Epinephelus fuscoguttatus♀×Epinephelus lanceolatus♂)SGIV-Gx感染试验进行活体验证,同时用荧光定量PCR(qPCR)测定衣壳蛋白基因(MCP)的表达,与LYGV1c-ELASA进行比较,验证该酶联吸附法检测的可信度。【结果】LYGV1c-ELASA的方法可特异性地识别SGIV的感染,Bio-LYGV1c识别SGIV感染的最适工作浓度为500 nmol/L,最适孵育时间为20 min,最适结合温度为4~28℃,LYGV1c-ELASA最低检测限为5×103 mL-1。活体验证结果表明,随着注射的SGIV-Gx浓度的升高,LYGV1c-ELASA检测出的石斑鱼体内病毒450 nm处的光密度(OD450)的值升高;qPCR结果表明,SGIV-Gx的MCP的表达量升高,与LYGV1c-ELASA检测结果相一致。【结论】建立的LYGV1c-ELASA技术不仅可用于体外检测,同时也适用于活体检测。LYGV1c-ELASA技术可实现对石斑鱼养殖过程中石斑鱼虹彩病毒病的快速诊断、实时监控。

Synthesis of highly reactive sorbent from industrial wastes and its CO_2 capture capacity

A kind of industrial solid waste, i.e., carbide slag, was used as CaO precursor to synthesize CO2 sorbent. The highly reactive synthetic sorbent was prepared from carbide slag, aluminum nitrate hydrate and glycerol water solution by the combustion synthesis method. The results show that the synthetic sorbent exhibits a much higher CO2 capture capacity compared with carbide slag. The CO2 capture capacity and the carbonation conversion of the synthetic sorbent are 0. 38 g/g and 0. 70 after 50 cycles, which are 1.8 and 2. 1 times those of carbide slag. The average carbonation conversion and the CO2 capture efficiency of the synthetic sorbent are higher than those of carbide slag with the same sorbent flow ratios. The required sorbent flow ratios are lower for synthetic sorbent to achieve the same CO2 capture efficiency compared with carbide slag. With the same sorbent flow ratio and CO2 capture efficiency, the energy requirement in calciner for the synthetic sorbent is less than that for carbide slag.

CCUS技术及镁基功能材料在其中的应用

综述了碳捕集、利用与存储(CCUS)技术的研究进展,特别是分析了MgO、Mg/Al水滑石等镁基功能材料在CO_(2)捕集和碳资源转化中的应用研究。讨论了不同类型的镁基材料所具有的不同理化性质和特征结构以及其在不同的应用领域展现出理想的应用效果,介绍了研究者在镁基材料上面的改性修饰工作,总结展望了CCUS技术和镁基功能材料未来的发展趋势。

惰性载体对钙基吸附剂脱碳性能增强作用的研究进展

大规模二氧化碳(CO_(2))排放会造成一系列环境与气候问题。钙基吸附剂由于成本低、理论吸附容量大,成为最具潜力的规模化烟气CO_(2)脱除手段之一。然而,钙基吸附剂存在高温烧结导致CO_(2)吸附能力逐渐衰减的技术瓶颈。因此,提升钙基吸附剂的抗烧结性能成为研究热点。该文总结钙基吸附剂的高温烧结机理,综述基于惰性载体提升钙基吸附剂抗烧结性能方法的研究现状。根据载体前体物与钙基吸附剂是否发生反应,将惰性载体分为双金属氧化物和单一相金属氧化物两类,重点介绍Ca-Al混合氧化物、CaZrO3和MgO等3种典型载体对钙基吸附剂抗烧结性能提升的作用机制。最后,对惰性载体强化钙基吸附剂脱碳性能的研究进行展望。

弱极性超微孔Sc/In-CPM-66A用于CH_(4)/N_(2)吸附分离性能

低浓度煤层气的提质利用对缓解国内天然气不足的现状具有重要意义,然而煤层气中存在的氮气杂质限制了该类资源的进一步应用,进行低浓度煤层气中CH_(4)/N_(2)混合物的分离至关重要。制备了两种具有弱极性超微孔的金属有机框架材料Sc-CPM-66A和In-CPM-66A,研究材料从CH_(4)/N_(2)混合物中富集CH_(4)的性能,利用PXRD、77 K N_(2)吸附、TGA和FTIR光谱对材料的结构进行了表征。IAST选择性计算表明,In-CPM-66A和Sc-CPM-66A的CH_(4)/N_(2)选择性达到6.0。受益于材料表面存在的大量的甲基基团,两种材料对CH_(4)的吸附热低于被报道的大部分材料,材料与甲烷分子之间弱的相互作用有利于吸附剂的脱附再生。穿透实验进一步表明,CPM-66A可以实现动态条件下CH_(4)/N_(2)混合物的分离,循环穿透实验显示该类材料具有良好的可重复性。

熔盐改性氧化镁吸附剂制备及固定床低浓度CO_(2)吸附捕集

针对吸附法捕集烟道气CO_(2)成本和能耗较高问题,研究采用六水氯化镁和碳酸氢钠通过沉淀法制备碱式碳酸镁并煅烧制得氧化镁粉体,再通过硝酸钠和碳酸钠浸渍改性并成型为(Na NO_(3))_(0.1)-Mg O和(Na NO_(3))_(0.1)(Na_(2)CO_(3))_(0.05)-Mg O颗粒状吸附剂。采用X射线衍射等表征手段对两种吸附剂颗粒微观结构进行分析,并结合热重实验评估了CO_(2)吸附/解吸动力学和循环稳定性。进行了硝酸钠/碳酸钠改性氧化镁吸附剂颗粒填充床低浓度CO_(2)气体的吸附解吸实验研究,分析了氧化镁表面负载的硝酸盐和碳酸盐对低浓度CO_(2)条件下捕集的强化作用。结果表明,在300℃左右,硝酸钠能够在氧化镁表面形成熔盐层,显著强化了CO_(2)吸附性能;硝酸钠熔盐层内存在CO_(2)扩散阻力,需要一定的CO_(2)分压作为通过熔盐层所需的传质推动力,进而降低了低浓度CO_(2)吸附量;碳酸钠的添加可降低CO_(2)通过熔盐层所需的传质推动力,提高低浓度CO_(2)吸附量。

Mixed plastics waste valorization to high-added value products via thermally induced phase separation and spin-casting

Plastic waste is an underutilized resource that has the potential to be transformed into value-added materials.However,its chemical diversity leads to cost-intensive sorting techniques,limiting recycling and upcycling opportunities.Herein,we report an open-loop recycling method to produce graded feedstock from mixed polyolefins waste,which makes up 60%of total plastic waste.The method uses heat flow scanning to quantify the composition of plastic waste and resolves its compatibility through controlled dissolution.The resulting feedstock is then used to synthesize blended pellets,porous sorbents,and superhydrophobic coatings via thermally induced phase separation and spin-casting.The hybrid approach broadens the opportunities for reusing plastic waste,which is a step towards creating a more circular economy and better waste management practices.

大型海藻微波热解制氢特性研究

大型海藻无需耕地、不含难热解的木质素,是降碳减排、生产小分子生物燃料的理想原料。对大型海藻(包括海带、蜈蚣藻、孔石莼和海黍子)进行微波热解,并与落叶松进行对比。研究了微波热解过程的升温行为、气体释放行为及氢气生成曲线,比较了微波热解的产物分布、气体组成和气化指标,进一步利用Ca-Al(CaO-Al_(2)O_(3))吸附剂原位吸收海带微波热解产生的二氧化碳(CO_(2)),强化海带的定向转化制氢。结果表明,大型海藻比落叶松具有更快的升温行为、更好的制氢效果,尤其海带的氢气产率(16.40 g/kg)为落叶松的3倍。添加Ca-Al吸附剂能够进一步增强海带的微波热解制氢效率,当海带与Ca-Al吸附剂的质量比为1.0:3.0时,氢气产率达到44.24 g/kg,气化效率可达68.57%,气体产物中氢气含量高达77.24%。

紫象草原花青素的大孔吸附树脂纯化、平均聚合度及体外抗氧化活性测定

试验旨在利用大孔吸附树脂获得紫象草原花青素粗提物的纯化条件,并探究在此条件下获得纯化物的平均聚合度和体外抗氧化活性。试验采用单因素试验设计,通过比较3种大孔吸附树脂D101、HP-20、ADS-17的吸附与解吸特性,选择最优吸附树脂类型,对紫象草原花青素粗提物进行洗脱浓度、上样体积和洗脱体积的筛选,之后利用静态和动态吸附与解吸试验确定纯化条件,制备紫象草原花青素纯化物;采用盐酸-香草醛法测定纯化物原花青素的平均聚合度及其对1,1-二苯基-2三硝基肼(DPPH·)和羟自由基(·OH)的体外清除率。结果表明:采用φ2.6 cm×30.0 cm玻璃层析柱,选择D101型大孔吸附树脂、90%(V/V)浓度乙醇为洗脱剂,上样体积480 mL,洗脱体积155 mL时纯化效果较好,纯化后原花青素B2含量由纯化前10.01 mg/g提升至13.82 mg/g,提升了36.06%;紫象草原花青素粗提物经乙酸乙酯萃取后,获得水相和乙酸乙酯相的平均聚合度分别为26.87、13.63,纯化物的平均聚合度为14.67。当紫象草原花青素纯化物质量浓度为100 mg/mL时,DPPH·、·OH清除能力分别为99.55%、97.72%,相当于1 mg/mL维生素C,并且紫象草原花青素纯化物体外抗氧化活性显著高于粗提物(P<0.05)。综上所述,试验获得了大孔吸附树脂纯化紫象草原花青素的条件,纯化处理基本不影响原花青素提取物的平均聚合度,并发现原花青素纯化物具有良好的体外抗氧化活性。