水蒸气改善钙基CO2吸收剂循环活性的研究

对钙基CO2吸收剂的循环活性改善进行了研究,分析了水蒸气处理对吸收剂的最大转化率、比表面积及孔分布等微观结构变化的影响。结果表明,经水蒸气处理后,钙基CO2吸收剂的循环活性得到了改善,最大转化率比未经水蒸气处理可提高约50百分点;水蒸气处理可大大提高钙基CO2吸收剂的比表面积,并有效改善其孔径分布状态,可使其稳定保持较高的转化率;含碳能源直接制氢过程可在不需要任何添加剂或辅助手段的条件下,有效保持钙基CO2吸收剂的循环活性。     

生物质能利用技术控制污染物排放的作用

化石燃料燃烧利用过程中排放的大量毒害气体和CO2对生态环境造成重大危害,由此产生的环境问题越来越引起世界各国的关注,相应的控制排放技术不断发展,其中生物质能利用由于其CO2零排放成为最有发展潜力的技术之一.采用LCA方法,选择生物质气化联合循环发电、生物质热裂解发电、生物质与煤混烧发电3种方案与燃煤发电进行了对比,分析生物质利用过程减排温室气体CO2、毒性气体(SOX、NOX)的作用.结果表明,在生产1 kW*h电能的生命周期中,3种生物质发电方案的CO2排放量远远小于燃煤发电,特别是生物质气化联合循环发电和生物质热裂解发电两种方案减排CO2达到了87%～94%.由于生物质低硫和低氮特性,该两种方案中NOX和SOX的减排量也非常显著,即使是生物质与煤按1∶9(质量比)混燃都可以达到25.2%和8.9%的减排效果.综合而言,生物质能的利用,不论是气化、热解或者共燃都是减排CO2、NOX和SOX有效措施.     

活性氧化铝负载DBU吸附CO2

为了减少燃煤电厂烟气CO2排放,对浸渍法制备的活性氧化铝(Al2O3)负载1,8-二氮杂二环[5,4,0]十一碳-7-烯(DBU)吸附剂及其固定床吸附CO2性能进行了研究,采用全自动气体吸附分析仪和同步热重分析仪对吸附剂比表面积、总孔容、平均孔径和热稳定性进行了表征。实验结果表明,Al2O3负载DBU吸附剂具有较大的比表面积和发达的孔隙结构,在低于140℃时具有良好的热稳定性;在室温条件下,DBU负载率为11.75%时,吸附剂对CO2吸附量最高可达18.11mg/g;经过8次吸附-脱附循环实验后,吸附剂仍保持较好的CO2吸附性能。     

CO2捕集回收技术研究

主要介绍了常用的胺化合物吸收法、钙基吸收剂法、金属氧化物法等CO2捕集回收技术的最新研究进展及存在的问题,综合对比了各种方法的优缺点:胺化合物吸收法吸收速率快,但再生能耗较高,因此开发"高效低耗"的复合吸收剂成为研究的重点;钙基吸收剂法在高温环境下对CO2的吸收有较好的效果,但吸收剂的碳酸化转化率及热稳定性是有待解决的关键问题;金属氧化物法具有高的CO2吸收效率,但成本较高.在此基础上,探索了CO2捕集回收技术改进工艺,提出改善吸收剂性能、开发高效低耗的CO2选择性吸收剂将成为今后CO2捕集回收技术的研究方向.     

木质素基水凝胶对亚甲基蓝染料的吸附性能

以木质素磺酸钠(LS-Na)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)为原料,采用微波辐射法,通过接枝共聚反应合成了生物质LS-g-PAMPS/AA水凝胶吸附剂,利用FTIR分析了水凝胶的结构。研究了吸附剂用量、染料初始浓度、吸附时间对亚甲基蓝(MB)染料的吸附性能的影响,结果显示,在MB初始浓度为1 000 mg/L,吸附剂为0.1 g时,吸附量和吸附率分别达1 914 mg/g和95%。平衡吸附数据满足Langmuir吸附等温模型,吸附动力学曲线较好地符合准二级动力学反应模型。木质素水凝胶对MB染料废水具有显著的吸附效果,可以作为阳离了染料废水处理用的生物质吸附剂。     

不同热解温度下污泥基生物炭的性质及对Cd~(2+)的吸附特性

以市政污泥为原料,在300、500和700℃无氧气氛下热解制备污泥基生物炭,探讨不同热解温度对污泥基生物炭性质的影响,研究污泥基生物炭对水溶液中重金属Cd~(2+)的吸附特性。结果表明,随着热解温度升高,污泥基生物炭的产率降低,pH值增大,碳、氢、氧和氮含量降低,芳香化程度增强,亲水性和极性降低,稳定性增强;随热解温度的升高,比表面积不断增大,生物炭表面变得粗糙并且出现明显的孔隙,但平均孔径呈现先增大后减小。在700℃下制备的污泥基生物炭对水溶液中Cd~(2+)的吸附效果优于其他制备温度下获得的生物炭,温度为298.15 K时,最大吸附容量为27.47 mg·g~(-1)。污泥基生物炭对Cd~(2+)的吸附动力学符合准二级动力学方程模型,吸附速率主要由化学吸附控制。污泥基生物炭对Cd~(2+)的吸附表现为快速吸附过程,生物炭前10 min的吸附量超过饱和吸附量的80%。Langmuir吸附等温模型能很好的描述污泥基生物炭对Cd~(2+)的吸附行为,吸附容量随热解温度升高而增大。     

生物膜细菌藻酸盐对Cu2+的吸附动力学研究

以生物膜中提取的细菌藻酸盐为原料制备藻酸钙为吸附剂,对水溶液中的Cu2+进行了吸附动力学研究.试验结果表明,吸附时间、溶液初始pH和吸附剂投加量对藻酸钙吸附Cu2+影响显著.当溶液初始pH为4.0、Cu2+初始质量浓度为100 mg/L、吸附剂投加量为0.7 g/L时,藻酸钙对Cu2+的平衡吸附量为56.15 mg/g.水溶液中Cu2+在藻酸钙上的吸附动力学过程可用准二级动力学方程来模拟.吸附等温线研究表明,藻酸钙吸附Cu2+的过程可用Langmuir和Freundlich模型来描述.100 mmol/L 乙二胺四乙酸(EDTA)可有效解吸95.6%的Cu2+,实现Cu2+的回收与吸附剂的重复利用.     

湿法再生吸附剂制备及用于大气CO_2的直接捕集

基于湿法再生吸附技术,利用强碱性季铵盐树脂材料制备了异相吸附剂薄膜,应用于大气中极低CO2的直接分离,以对抗全球变暖。通过滴定法分析吸附剂材料的电荷密度和吸附容量,利用SEM分析不同工况下制备出来的膜材料的表观结构,并对膜材料进行CO2吸附性能的测试。结果发现,热处理能够明显提高膜材料的吸附性能,还研究吸附剂制备对吸附速率,吸附量和机械强度等性能的影响,发现粒径小于43μm的树脂粉末,按60%质量分数制成的500μm厚膜材料具有较优的综合性能。     

生物质炭对溶液中Cd~(2+)的吸附

以玉米秸秆、稻壳在350~500℃制成的生物质炭作为吸附剂,研究其对溶液中Cd2+的吸附特性。通过模拟实验,考察了初始p H、生物质炭用量、吸附时间和Cd2+的起始浓度对吸附的影响。结果表明,2种生物质炭对Cd2+的吸附反应适应p H范围较宽(4.0~7.0);玉米秸秆炭和稻壳炭对Cd2+的吸附速度较快,分别在10和20 min时达到吸附平衡;玉米秸秆炭对溶液中Cd2+的吸附遵循Langmuir等温线模型,而稻壳炭对Cd2+的吸附遵循Freundlich等温线模型。在实验设定的条件下,玉米秸秆炭对溶液中Cd2+的吸附能力强于稻壳炭。     

污泥-秸秆基活性炭的制备及其对渗滤液COD的吸附

以市政污泥与玉米秸秆为原料,采用化学活化法热解制备污泥-秸秆基活性炭,研究其物化性质、热解动力学特性及对渗滤液中COD的吸附性能。考察吸附剂投加量、吸附时间和溶液p H对COD去除率的影响,并用吸附等温线对吸附数据进行了拟合。结果表明,秸秆比例越高,活性炭的吸附碘值和BET比表面积越大,最大可达663 mg/g和902 m2/g;活性炭表面呈不规则的多孔状;秸秆比例为45%的活性炭在最佳实验条件下对COD的吸附去除率为82%;活性炭对COD的吸附符合Langmuir和Freundlich等温模型。     

Laboratory study on the high-temperature capture of HCl gas by dry-injection of calcium-based sorbents

This is a laboratory study on the reduction of combustion-generated hydrochloric acid (HCl) emissions by in-furnace dry-injection of calcium-based sorbents. HCl is a hazardous gaseous pollutant emitted in significant quantities by municipal and hazardous waste incinerators, coal-fired power plants, and other industrial furnaces. Experiments were conducted in a laboratory furnace at gas temperatures of 600-1000 degrees C. HCl gas diluted with N2, and sorbent powders fluidized in a stream of air were introduced into the furnace concurrently. Chlorination of the sorbents occurred in the hot zone of the furnace at gas residence times approximately 1 s. The sorbents chosen for these experiments were calcium formate (CF), calcium magnesium acetate (CMA), calcium propionate (CP), calcium oxide (CX), and calcium carbonate (CC). Upon release of organic volatiles, sorbents calcine to CaO at approximately 700 degrees C, and react with the HCl according to the reaction CaO + 2HCl <=> CaCl2 + H2O. At the lowest temperature case examined herein, 600 degrees C, direct reaction of HCl with CaCO3 may also be expected. The effectiveness of the sorbents to capture HCl was interpreted using the "pore tree" mathematical model for heterogeneous diffusion reactions. Results show that the thin-walled, highly porous cenospheres formed from the pyrolysis and calcination of CF, CMA, and CP exhibited high relative calcium utilization at the upper temperatures of this study. Relative utilizations under these conditions reached 80%. The less costly low-porosity sorbents, calcium carbonate and calcium oxide also performed well. Calcium carbonate reached a relative utilization of 54% in the mid-temperature range, while the calcium oxide reached an 80% relative utilization at the lowest temperature examined. The data matched theoretical predictions of sorbent utilization using the mathematical model, with activation energy and pre-exponential factors for the calcination reaction of 17,000 K and 300,000 (g gas/cm2/s/atm gas), respectively. Thus, the kinetics of the calcination reaction were found to be much faster (approximately 500 times) than those of the sulfation reaction examined previously in this laboratory.     

白云石的硫化氢高温脱除性能研究

用天然白云石制备了半焙烧白云石和全焙烧白云石,并在固定床上对这些白云石进行硫化氢的高温脱除性栽能研究,同时考察了反应温度、空速、粒子粒径对白云石脱硫性能的影响.用X射线衍射(XRD)、热重分析(TG)和气体吸附等测试手段,对脱硫剂的物相组成、结构、比表面积和孔容进行了表征.结果表明,白云石是一种很好的吸硫剂.在同样条件下,3种白云石中半焙烧白云石具有最好的脱硫效果;而对于同一种白云石,反应条件的差异也会导致其脱硫效果的变化.白云石的脱硫性能与其微观结构有密切关系.     

An Urban Airshed Model for Predicting Carbon Monoxide Concentrations in Tucson,Arizona

ABSTRACT

The Electric Power Research Institute (EPRI) is conducting research to investigate mercury removal in utility flue gas using sorbents. Bench-scale and pilot-scale tests have been conducted to determine the abilities of different sor-bents to remove mercury in simulated and actual flue gas streams. Bench-scale tests have investigated the effects of various sorbent and flue gas parameters on sorbent performance. These data are being used to develop a theoretical model for predicting mercury removal by sorbents at different conditions. This paper describes the results of parametric bench-scale tests investigating the removal of mercuric chloride and elemental mercury by activated carbon.

Results obtained to date indicate that the adsorption capacity of a given sorbent is dependent on many factors, including the type of mercury being adsorbed, flue gas composition, and adsorption temperature. These data provide insight into potential mercury adsorption mechanisms and suggest that the removal of mercury involves both physical and chemical mechanisms. Understanding these effects is important since the performance of a given sorbent could vary significantly from site to site depending on the coal- or gas-matrix composition.     

Performance of Copper Chloride-Impregnated Sorbents on Mercury Vapor Control in an Entrained-Flow Reactor System

Abstract

An entrained-flow system has been designed and constructed to simulate in-flight mercury (Hg) capture by sorbent injection in ducts of coal-fired utility plants. The test conditions of 1.2-sec residence time, 140 °C gas temperature, 6.7 m/sec (22 ft/sec) gas velocity, and 0–0.24 g/m³ (0–15 lbs of sorbent per 1 million actual cubic feet of flue gas [lb/MMacf]) sorbent injection rates were chosen to simulate conditions in the ducts. Four kinds of sorbents were used in this study. Darco Hg-LH served as a benchmark sorbent with which Hg control capability of other sorbents could be compared. Also, Darco-FGD was used as a representative raw activated carbon sorbent. Two different copper chloride-impregnated sorbents were developed in our laboratory and tested in the entrained-flow system to examine the possibility of using these sorbents at coal-fired power plants. The test results showed that one of the copper chloride sorbents has remarkable elemental mercury (Hg⁰) oxidation capability, and the other sorbent demonstrated a better performance in Hg removal than Darco Hg-LH.     

Low Concentration Mercury Sorption Mechanisms and Control by Calcium-Based Sorbents: Application in Coal-Fired Processes

ABSTRACT

The capture of elemental mercury (Hg⁰) and mercuric chloride (HgCl₂) by three types of calcium (Ca)-based sor-bents was examined in this bench-scale study under conditions prevalent in coal-fired utilities. Ca-based sorbent performances were compared with that of an activated carbon. Hg⁰ capture of about 40% (nearly half that of the activated carbon) was achieved by two of the Ca-based sorbents. The presence of sulfur dioxide (SO₂) in the simulated coal combustion flue gas enhanced the Hg⁰ capture from about 10 to 40%. Increasing the temperature in the range of 65-100 °C also caused an increase in the Hg⁰ capture by the two Ca-based sorbents. Mercuric chloride (HgCl₂) capture exhibited a totally different pattern. The presence of SO₂ inhibited the HgCl₂ capture by Ca-based sorbents from about 25 to less than 10%. Increasing the temperature in the studied range also caused a decrease in HgCl₂ capture. Upon further pilot-scale confirmations, the results obtained in this bench-scale study can be used to design and manufacture more cost-effective mercury sorbents to replace conventional sorbents already in use in mercury control.     

Preparation of activated carbon using low temperature carbonisation and physical activation of high ash raw bagasse for acid dye adsorption

Activated carbons were prepared from bagasse through a low temperature (160 degrees C) chemical carbonisation treatment and gasification with carbon dioxide at 900 degrees C. The merit of low temperature chemical carbonisation in preparing chars for activation was assessed by comparing the physical and chemical properties of activated carbons developed by this technique to conventional methods involving the use of thermal and vacuum pyrolysis of bagasse. In addition, the adsorption properties (acid blue dye) of these bagasse activated carbons were also compared with a commercial activated carbon. The results suggest that despite the high ash content of the precursor, high surface areas (614-1433 m2 g(-1)) and microporous (median pore size from 0.45 to 1.2 nm) activated carbons can be generated through chemical carbonisation and gasification. The micropore area of the activated carbon developed from chars prepared by the low temperature chemical carbonisation provides favourable adsorption sites to acid blue dye (391 mg g(-1) of carbon). The alkalinity of the carbon surface and total surface area were shown to have complementary effects in promoting the adsorption of acid blue dye. Adsorption of the anionic coloured component of the acid dye was shown to be promoted in carbon exhibiting alkaline or positively charged surfaces. This study demonstrates that activated carbons with high acid dye adsorption capacities can be prepared from high ash bagasse based on low temperature chemical carbonisation and gasification.     

废活性炭微波再生新工艺的研究

提出用微波加热-二氧化碳活化法再生乙酸乙烯合成用触媒载体废活性炭工艺.采用条件实验法研究了活化时间、二氧化碳流量和微波功率对活性炭碘吸附值,亚甲基蓝吸附值和再生得率的影响,得到微波辐射加热二氧化碳活化再生乙酸乙烯用触媒载体废活性炭的最佳工艺条件为活化时间25 min,二氧化碳流量0.2 L/min,微波功率700 W.在此条件下制得的活性炭碘吸附值为1158.02 mg/g、亚甲基蓝吸附值为240 mg/g、得率为74.19%.并对活性炭进行了比表面积的测定和孔结构的分析,活性炭的比表面积为1308.13 m2/g,总孔容为0.76 mL/g.     

Experimental design methodology for the preparation of carbonaceous sorbents from sewage sludge by chemical activation--application to air and water treatments

The objective of this study is to optimize experimental conditions of sorbent preparation from sewage sludge using experimental design methodology. Series of carbonaceous sorbents have been prepared by chemical activation with sulfuric acid. The sorbents produced were characterized, and their properties (surface chemistry, porous and adsorptive properties) were analyzed as a function of the experimental conditions (impregnation ratio, activation temperature and time). Carbonaceous sorbents developed from sludge allow copper ion, phenol and dyes (Acid Red 18 and Basic Violet 4) to be removed from aqueous solution as well as VOC from gas phase. Indeed, according to experimental conditions, copper adsorption capacity varies from 77 to 83 mg g(-1), phenol adsorption capacity varies between 41 and 53 mg g(-1) and VOC adsorption capacities (acetone and toluene) range from 12 to 54 mg g(-1). Each response has been described by a second-order model that was found to be appropriate to predict most of the responses in every experimental region. The most influential factors on each experimental design response have been identified. Regions in which optimum values of each factor were achieved for preparation of activated carbons suitable for use in wastewater and gas treatments have been determined using response surfaces methodology. In order to have a high mass yield and to minimize the energetic cost of the process, the following optimal conditions, 1.5 g of H2SO4 g(-1) of sludge, 700 degrees C and 145 min are more appropriate for use of activated carbon from sludge in water and gas treatments.     

Pore structure effects on Ca-based sorbent sulfation capacity at medium temperatures: activated carbon as sorbent/catalyst support

The reaction between three different Ca-based sorbents and SO2 were studied in a medium temperature range (473-773 K). The largest SO2 capture was found with Ca(OH)2 at 773 K, 126.31 mg SO2 x g Ca(OH)2(-1), and the influence of SO2 concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sulfated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO2, one kind of CaO/ activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO2 than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO2 and Ca-based sorbents and the prepared CaO/AC sorbents/catalysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the desulfurization reaction. AC acting as the support can play a role to supply O2 to increase the affinity to SO2. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO2 adsorption.     

Effects of water vapor pretreatment time and reaction temperature on CO(2) capture characteristics of a sodium-based solid sorbent in a bubbling fluidized-bed reactor

CO(2) capture from flue gas using a sodium-based solid sorbent was investigated in a bubbling fluidized-bed reactor. Carbonation and regeneration temperature on CO(2) removal was determined. The extent of the chemical reactivity after carbonation or regeneration was characterized via (13)C NMR. In addition, the physical properties of the sorbent such as pore size, pore volume, and surface area after carbonation or regeneration were measured by gas adsorption method (BET). With water vapor pretreatment, near complete CO(2) removal was initially achieved and maintained for about 1-2min at 50 degrees C with 2s gas residence time, while without proper water vapor pretreatment CO(2) removal abruptly decreased from the beginning. Carbonation was effective at the lower temperature over the 50-70 degrees C temperature range, while regeneration more effective at the higher temperature over the 135-300 degrees C temperature range. To maintain the initial 90% CO(2) removal, it would be necessary to keep the regeneration temperature higher than about 135 degrees C. The results obtained in this study can be used as basic data for designing and operating a large scale CO(2) capture process with two fluidized-bed reactors.