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.     

钙基烟气脱硫剂制备的实验研究

采用正交实验 ,研究了水合制备高效钙基烟气脱硫剂时各制备条件对产物的影响。结果表明 ,水合时间、水合温度Ca(OH) 2 /CaSO4的质量比 ,以及飞灰 / (Ca(OH) 2 +CaSO4)质量比四个条件对脱硫剂比表面积的形成有显著的影响 ;从而由单因素实验得出一最佳钙基脱硫剂制备条件组合。此外 ,通过XDR分析 ,测定了脱硫剂的物相组成 ,扫描电镜观察显示飞灰和水合吸收剂具有不同的表面形态     

钙基烟气脱硫剂制备的实验研究

采用正交试验,研究了水合制备高效钙基烟气脱硫剂时各制备条件对产物的影响。结果表明,水合时间、水合温度Ca(OH)2/CaSO4的质量比,以及飞灰／（Ca(OH)2 CaSO4）质量比四个条件对脱硫剂比表面积的形成有显著的影响;从而由单因素实验得出一最佳钙基脱硫剂制备条件组合。此外,通过XDR分析,测定了脱硫剂的物相组成,扫描电镜观察显示飞灰和水合吸收剂具有不同的表面形态。     

密相半干法低温同时脱硫脱硝影响因素

针对90~160℃的低温条件下,SO₂对钙基吸收剂吸收NO_x的影响进行了实验研究,分析了烟气温度T、含氧率、含湿量等对SO₂促进钙基吸收剂吸收NO_x的影响。实验结果表明,当烟气中SO₂浓度的升高可促进钙基吸收剂对NO_x的吸收;同时,维持反应系统在9.2%的含湿量;保证烟气温度在结露点以上,使系统在90~100℃的温度区间;控制系统漏风率,防止含氧率的升高;保证前端电除尘效率的同时,将一部分电除尘捕集到的灰尘作为钙基脱硫剂的添加剂,并使之参与脱硫反应器内的钙基吸收剂循环过程中;可较多地脱除烟气中的污染物质。     

钙基吸附剂捕集生物质燃气中的二氧化碳

生物质热解燃气中CO2的捕集,是提高燃气热值和实现碳减排的关键问题之一。为利用生物质热解燃气温度偏高的特点,拟通过化学吸附方法,捕集燃气中高浓度的CO2。为此,利用不同钙基前驱物制备了系列钙基固体吸附剂,系列钙基固体吸附剂对CO2的单次吸附和循环吸附实验结果表明,含钙和镁氧化物混合物的吸附剂具有较稳定的循环吸附特性以及较大的吸附负荷。孔结构特性分析表明,适宜于CO2吸附的有效孔径范围可能为小于4 nm。因此,可以通过对天然白云石的改性获得合适孔径的钙镁基固体吸附剂,达到有效捕集生物质燃气中CO2的目的。     

多循环CCRs法在分离燃煤锅炉尾部烟气中CO2方面的应用

随着温室效应和全球变暖的加剧,煤燃烧所排出的CO2作为引起温室效应的主要气体而引起人们的密切关注.由于燃煤锅炉所排放的尾气中所含的CO2的体积份额低、排放量大,而且处于微负压状态,因此目前控制和分离吸收CO2的方法,包括各类吸收法、吸附法、膜分离法和O2/CO2燃烧技术等,能够经济可行地适用于电力工业燃煤锅炉尾部烟气中CO2分离的方法非常少.与上述各类方法相比,钙基吸收剂CCRs(calcination/carbonation reactions)法是一种新兴的经济可行的分离燃煤锅炉尾部烟气中CO2的方法.对采用该法时,吸收剂的选择、吸收剂在多次CCRs过程中结构特点的变化、提高吸收剂对CO2的吸收容量以及防止吸收剂反应性的衰减等方面进行了详细的阐述.     

多循环CCRs法在分离燃煤锅炉尾部烟气中CO2方面的应用

随着温室效应和全球变暖的加剧，煤燃烧所排出的CO2作为引起温室效应的主要气体而引起人们的密切关注。由于燃煤锅炉所排放的尾气中所含的CO2的体积份额低、排放量大，而且处于微负压状态，因此目前控制和分离吸收CO2的方法，包括各类吸收法、吸附法、膜分离法和O2／CO2燃烧技术等，能够经济可行地适用于电力工业燃煤锅炉尾部烟气中CO2分离的方法非常少。与上述各类方法相比，钙基吸收剂CCRs（calcination／carbonation reactions）法是一种新兴的经济可行的分离燃煤锅炉尾部烟气中CO2的方法。对采用该法时，吸收剂的选择、吸收剂在多次CCRs过程中结构特点的变化、提高吸收剂对CO2的吸收容量以及防止吸收剂反应性的衰减等方面进行了详细的阐述。     

Cu-Mn-O制备条件对其催化燃烧甲苯性能的影响

以甲苯催化燃烧为模型反应,考察了Cu-Mn-O催化剂共沉淀制备方法中沉淀剂、滴加方式和焙烧温度对其催化活性的影响.结果表明,以Na2CO3为沉淀剂、反滴(金属离子溶液滴加到碱液)、500℃焙烧所制得的催化剂具有较高的活性,其甲苯完全燃烧(甲苯转化率98%以上)温度为220℃.多晶粉末衍射(XRD)和比表面积(BET)表征发现,在Cu1.5Mn1.5O4晶相中掺杂少量的CuO晶相可以有效地提高催化剂活性,催化剂的比表面积(BET)越大,活性越高.     

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。     

Fe/Ga2O3-Al2O3催化甲烷还原NO的性能

以甲烷为还原剂的选择性催化脱硝技术(SCR-CH_4)是一种很有潜力的新的脱硝方法,但催化剂的催化活性比较低。为了提高催化剂的活性以及抗水能力,可使用Fe对Al_2O_3负载的Ga_2O_3催化剂进行改性。采用共沉淀法,制备了xFe/Ga_2O_3-Al_2O_3催化剂,在固定床反应器中测试其选择性催化CH_4还原NO的性能。使用XRD、N_2吸附脱附、XPS、H_2-TPR、Py-IR等方法进行表征。结果表明:经过Fe改性后的催化剂提高了中高温的催化活性,提高了催化剂的N_2选择性,并改善了催化剂的抗水特性;5Fe/Ga_2O_3-Al_2O_3催化剂在500℃、富氧条件下,达到76%的NO转化率和100%的N_2选择性;在5%水蒸气条件下,5Fe/Ga_2O_3-Al_2O_3在500℃仍保持60%以上的NO转化率。N_2吸附脱附结果显示,引入Fe后,催化剂保持了原有比表面积,并且大大增加了催化剂孔径,可提高催化剂抗水能力。XPS与UV-vis显示,5Fe/Ga_2O_3-Al_2O_3具有高含量的游离态Fe~(3+),可提高催化剂的中高温活性。H2-TPR结果显示,Fe的引入提高了催化剂氧化还原能力,增强了原有Ga_2O_3-Al_2O_3中高温的还原活性。Py-FT-IR结果显示,催化剂表面同时存在Lewis酸和Br?nsted酸,铁的引入增加了催化剂表面的Lewis酸量。因此,Fe修饰Ga_2O_3-Al_2O_3是提高Ga_2O_3-Al_2O_3催化剂的SCR-CH_4脱硝性能的有效方法。     

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.     

Pore Structure Effects on Ca-Based Sorbent Sulfation Capacity at Medium Temperatures: Activated Carbon as Sorbent/Catalyst Support

Abstract

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?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 sul-fated 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/cata-lysts 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 des-ulfurization 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.     

Characterization of flue gas cleaning residues from European solid waste incinerators: assessment of various Ca-based sorbent processes

For the first time, a set of samples of European flue gas cleaning residues, mainly from the incineration of municipal solid waste (MSW), has undergone a mineralogical study. The residues are the result of the neutralization of acid flue gases by lime, the predominant method adopted in Europe, using dry and semi-dry washing processes. The study protocol combines physico-chemical analytical techniques (XRD, FTIR, DSC/TGA) and global chemical analysis enabling identification of the chemical composition of the main constituents, particularly chlorinated Ca-based phases, as well as establishment of modal distributions of the represented phases, both crystalline and amorphous. The samples are slightly hydrated and values vary for trapped Cl, S and even CO(2). The main crystalline phases are NaCl, KCl, CaSO(4), CaCO(3), Ca(OH)(2) and calcium hydroxychloride CaOHCl. CaOHCl is the main chlorine phase, regardless of the treatment process, filtration mode, and specific surface of the Ca-based sorbent. This phase develops during neutralization of HCl by excess lime present according to the reaction Ca(OH)(2)+HCl-->CaOHCl+H(2)O, to the detriment of a complete yield involving the two lime OH groups with formation of CaCl(2).2H(2)O. In addition, it seems that gas temperatures above 150 degrees C increase competition between lime-based neutralization of HCl, SO(2) acid flue gases and CO(2) trapping, thus reducing washing efficiency.     

Preparation and characterisation of activated carbon from waste tea by physical activation using steam

ABSTRACT

In this study, the feasibility of preparing activated carbon from waste tea by physical activation using steam was investigated. The effects of activation temperature on yield and pore properties of the prepared activated carbon were studied. The yield decreased with increased activation temperature owing to the decomposition of cellulose and hemicellulose. The specific surface area and pore volume of the activated carbon were estimated using the Brunauer–Emmett–Teller method, Langmuir equation, and t-plot method. The specific surface area and micropore volume increased with increases in activation temperature, as additional volatile materials were released. The specific surface area significantly decreased at first but slightly increased with increasing activation time. The maximum specific surface area reached 995 m²/g at an activation temperature of 800 °C with a water flow rate of 0.075 g/min and a constant hold time of 0.5 hr. According to the nitrogen adsorption isotherms, micropores mainly developed when the activation temperature was below 800 °C, and both micropores and mesopores developed when it was above 800 °C. The results showed that activation temperature significantly affected micropore and mesopore volumes, as well as the specific surface area of the activated carbon. Overall, waste tea was found to be an attractive raw material for producing low-cost activated carbon.

Implications: Every year, a large amount of waste tea is generated after extraction. The high carbon content of waste tea showed that it can be used as raw material to produce activated carbon. This study investigated the feasibility of preparing activated carbon from waste tea by physical activation using steam. Temperature and time were found to have clear effects on pore properties. Our proposed method and raw material are more environmentally friendly and involve low cost. Furthermore, this offers a potential solution to the problems of waste tea disposal and low-cost activated carbon production.     

Preparation of calcium silicate absorbent from iron blast furnace slag

Calcium silicate hydrate (CSH) solids were prepared from hydrated lime and iron blast furnace slag in an aqueous agitated slurry at 92 degrees C. While it was hoped a minimal lime/slag ratio could be used to create near-amorphous CSH, the surface area of the product improved by increasing the lime/slag weight ratio to 2. The addition of gypsum to the lime/slag system dramatically improved the formation of surface area, creating solids with 139 m2/g after 30 hr of reaction when only a minimal amount of lime was present. The SO2 reactivity of solids prepared with gypsum greatly exceeded that of hydrated lime, achieving greater than 70-80% conversion of the alkalinity after 1 hr of reaction with SO2. The use of CaCl2 as an additive to the lime/slag system, in lieu of gypsum, also produced high-surface-area solids, 115 m2/g after 21 hr of reaction. However, the SO2 reactivity of these sorbents was relatively low given the high surface area. This emphasized that the correlation between surface area and SO2 reactivity was highly dependent on the solid phase, which was subsequently dependent on slurry composition.     

Production of hydrogen-rich gas from methane by thermal plasma reform

This study investigated the reforming characteristics and optimum operating condition of the high-temperature plasma torch (so called plasmatron) for hydrogen-rich gas (syngas) production. At the optimum condition, the composition of produced syngas was 45.4% hydrogen (H2), 6.9% carbon monoxide (CO), 1.5% carbon dioxide (CO2), and 1.1% acetylene (C2H2). The H2/CO ratio was 6.6, hydrogen yield was 78.8%, and the energy conversion rate was 63.6%. To obtain the optimum operating condition, parametric studies were carried out examining the effects of O2/CH4 ratio, steam/CH4 ratio, and Ni catalyst addition in reactor. When the steam/CH4 ratio was 1.23, the production of hydrogen was maximized and the methane conversion rate was 99.7%. The syngas composition was determined to be 50.4% H2, 5.7% CO, 13.8% CO2, and 1.1% C2H2. The H2/CO ratio was 9.7, hydrogen yield was 93.7%, and the energy conversion rate was 78.8%. Hydrogen production with catalyst was effective, compared with no catalyst.     

Preparation of carbonaceous adsorbent from straw and its adsorption performance for H2S removal

ABSTRACT

Activated carbonaceous were prepared from high-carbon, abandoned straw biomass. With hydrogen sulfide gas as the target pollutant, single factor experiments were employed to assess the effects of activator type, activation temperature, activation time, and liquid-material ratio on the adsorption performance of the prepared carbonaceous adsorbent. The materials were characterized using elemental analysis, SEM, FTIR, and BET. The results showed -OH, -CH-, and -C = O groups exist on the surface of the prepared adsorbent, specific surface area can reach 1104.84 m²?g^?1, total pore volume can reach 0.261 cm³?g^?1 and, where the pore volume is greater than 80%, well-developed pore structures were present that facilitated adsorption. The experimental results showed the adsorption time could reach 198 min with optimal ZnCl₂ activator concentration (30%), carbonization temperature (550°C), and liquid-to-material ratio (3:1). Compared with the existing activated carbon adsorbents, the adsorption effects and preparation cost of this absorbent are advantageous, and the absorbent has prospects for broad market application.     

Utilization of agricultural waste corn cob for the preparation of carbon adsorbent

In the present study, a series of activated carbons were prepared from agricultural waste corn cob by chemical and physical activations with potassium hydroxide (KOH)/potassium carbonate (K2CO3) and carbon dioxide (CO2). The effect of process variables such as impregnation ratio, impregnation time, activation temperature and soaking time of CO2 was studied in order to relate these preparation parameters with the physical properties of final carbon products. The resulting activated carbons were characterized by nitrogen adsorption-desorption isotherms at 77 K. The surface areas and pore volumes of carbons were estimated by the BET equation, the Langmuir equation and the t-plot method. Under the experimental conditions investigated, the main parameters in the activation of corn cob were found to be the impregnation ratio and activation temperature. The soaking time of CO2 is another important variable, which had a strong effect on the pore volume development. The BET surface area and total pore volume were as large as about 2000 m2/g and about 1.0 cm3/g, respectively. This study showed that the activation of agricultural waste corn cob with KOH/K2CO3 and CO2 was suitable for the preparation of large-surface-area activated carbons.     

Preparation of sulfurized powdered activated carbon from waste tires using an innovative compositive impregnation process

The objective of this study is to develop an innovative compositive impregnation process for preparing sulfurized powdered activated carbon (PAC) from waste tires. An experimental apparatus, including a pyrolysis and activation system and a sulfur (S) impregnation system, was designed and applied to produce sulfurized PAC with a high specific surface area. Experimental tests involved the pyrolysis, activation, and sulfurization of waste tires. Waste-tire-derived PAC (WPAC) was initially produced in the pyrolysis and activation system. Experimental results indicated that the Brunauer-Emmett-Teller (BET) surface area of WPAC increased, and the average pore radius of WPAC decreased, as water feed rate and activation time increased. In this study, a conventional direct impregnation process was used to prepare the sulfurized PAC by impregnating WPAC with sodium sulfide (Na2S) solution. Furthermore, an innovative compositive impregnation process was developed and then compared with the conventional direct impregnation process. Experimental results showed that the compositive impregnation process produced the sulfurized WPAC with high BET surface area and a high S content. A maximum BET surface area of 886 m2/g and the S content of 2.61% by mass were obtained at 900 degrees C and at the S feed ratio of 2160 mg Na2S/g C. However, the direct impregnation process led to a BET surface area of sulfurized WPAC that decreased significantly as the S content increased.