酸碱改性对氧化铁脱硫剂脱硫性能影响的研究

通过酸碱改性制备了酸式和碱式2种不同表面性质的常温氧化铁脱硫剂,并采用FT-IR技术对其表面酸碱性质和净化硫化氢废气活性进行了研究.结果表明,表面酸碱件质不同的脱硫剂其脱硫反应行为也不同,在脱硫过程中硫化氢氧化生成的硫酸及亚硫酸会影响脱硫剂的表面酸碱性质,造成酸式脱硫剂的表面酸性更强,从而抑制了硫化氢分子在酸式脱硫剂表...     

Effectiveness and mechanisms of hydrogen sulfide adsorption by camphor-derived biochar

The characteristics and mechanisms of hydrogen sulfide (H2S) adsorption on a biochar through pyrolysis at various temperatures (100 to 500 degrees C) were investigated. The biochar used in the current study was derived from the camphor tree (Cinnamomum camphora). The samples were ground and sieved to produceparticle sizes of 0.4 mm to 1.25 mm, 0.3 mm to 0.4 mm, and <0.3 mm. The H2S breakthrough capacity was measured using a laboratory-designed test. The surface properties of the biochar were characterized using pH and Fourier-transform infrared spectroscopy (FTIR) analysis. The results obtained demonstrate that all camphor-derived biochars were effective in H2S sorption. Certain threshold ranges ofthepyrolysis temperature and surfacepH were observed, which, when exceeded, have dramatic effects on the H2S adsorption capacity. The sorption capacity ranged from 1.2 mg/g to 121.4 mg/g. The biochar with 0.3 mm to 0.4 mm particle size possesses a maximum sorption capacity at 400 degrees C. The pH and FTIR analysis results showed that carboxylic and hydroxide radical groups were responsible for H2S sorption. These observations will be helpful in designing biochar as engineered sorbents for the removal of H2S.     

Removal of carbonyl sulfide using activated carbon adsorption

Wastewater treatment plant odors are caused by compounds such as hydrogen sulfide (H2S), methyl mercaptans, and carbonyl sulfide (COS). One of the most efficient odor control processes is activated carbon adsorption; however, very few studies have been conducted on COS adsorption. COS is not only an odor causing compound but is also listed in the Clean Air Act as a hazardous air pollutant. Objectives of this study were to determine the following: (1) the adsorption capacity of 3 different carbons for COS removal; (2) the impact of relative humidity (RH) on COS adsorption; (3) the extent of competitive adsorption of COS in the presence of H2S; and (4) whether ammonia injection would increase COS adsorption capacity. Vapor phase react (VPR; reactivated), BPL (bituminous coal-based), and Centaur (physically modified to enhance H2S adsorption) carbons manufactured by Calgon Carbon Corp. were tested in three laboratory-scale columns, 6 in. in depth and 1 in. in diameter. Inlet COS concentrations varied from 35 to 49 ppmv (86-120 mg/m3). RHs of 17%, 30%, 50%, and 90% were tested. For competitive adsorption studies, H2S was tested at 60 ppmv, with COS at 30 ppmv. COS, RH, H2S, and ammonia concentrations were measured using an International Sensor Technology Model IQ-350 solid state sensor, Cole-Parmer humidity stick, Interscan Corp. 1000 series portable analyzer, and Drager Accuro ammonia sensor, respectively. It was found that the adsorption capacity of Centaur carbon for COS was higher than the other two carbons, regardless of RH. As humidity increased, the percentage of decrease in adsorption capacity of Centaur carbon, however, was greater than the other two carbons. The carbon adsorption capacity for COS decreased in proportion to the percentage of H2S in the gas stream. More adsorption sites appear to be available to H2S, a smaller molecule. Ammonia, which has been found to increase H2S adsorption capacity, did not increase the capacity for COS.     

Effectiveness and mechanisms of hydrogen sulfide adsorption by camphor-derived biochar

The characteristics and mechanisms of hydrogen sulfide (H₂S) adsorption on a biochar through pyrolysis at various temperatures (100 to 500°C) were investigated. The biochar used in the current study was derived from the camphor tree (Cinnamomum camphora). The samples were ground and sieved to produce particle sizes of 0.4 mm to 1.25 mm, 0.3 mm to 0.4 mm, and <0.3 mm. The H₂S breakthrough capacity was measured using a laboratory-designed test. The surface properties of the biochar were characterized using pH and Fourier-transform infrared spectroscopy (FTIR) analysis. The results obtained demonstrate that all camphor-derived biochars were effective in H₂S sorption. Certain threshold ranges of the pyrolysis temperature and surface pH were observed, which, when exceeded, have dramatic effects on the H₂S adsorption capacity. The sorption capacity ranged from 1.2 mg/g to 121.4 mg/g. The biochar with 0.3 mm to 0.4 mm particle size possesses a maximum sorption capacity at 400°C. The pH and FTIR analysis results showed that carboxylic and hydroxide radical groups were responsible for H₂S sorption. These observations will be helpful in designing biochar as engineered sorbents for the removal of H₂S.

Implications: This paper studies the potential of biochar derived by camphor to adsorb hydrogen sulfide at environmentally sustainable temperatures. The different sizes of the biochars and the different temperatures of pyrolysis for the camphor particle have a great impact on adsorption of hydrogen sulfide.     

活性炭吸附硫化氢及微波辐照解吸研究

研究了两种活性炭对硫化氢的平衡吸附性能力,并对活性炭床层的穿透性进行了考察;吸附饱和和活性炭在微波辐射的作用下进行解吸。实验表明,解吸效率与微波作用时间及温度有关,在本实验条件下H2S解吸效率达90．1％。     

Adsorption of hydrogen sulfide by biochars derived from pyrolysis of different agricultural/forestry wastes

The characteristics and mechanisms of hydrogen sulfide (H₂S) adsorption on three different biochars derived from agricultural/forestry wastes through pyrolysis at various temperatures (100 to 500 ºC) were investigated. In this study, the H₂S breakthrough capacity was measured using a laboratory-characterized using pH and Fourier transform infrared spectroscopy analysis. The results obtained demonstrate that all biochars were effective in H₂S sorption. The sorption capacity of the biochar for H₂S removal is related to the pyrolysis temperature and pH of the surface. Certain threshold ranges of the pyrolysis temperature (from 100 to 500 ºC) and pH of the surface are presented. It also concluded that the sorption capacity (for removing H₂S) of rice hull-derived biochar is the largest in three biochars (camphor-derived biochar, rice hull-derived biochar, and bamboo-derived biochar). These observations will be helpful in designing biochar as engineered sorbents for the removal of H₂S.Implications: This paper focuses on the adsorption of hydrogen sulfide (H₂S) by biochars derived from wastes. The characteristics and mechanisms of hydrogen sulfide (H₂S) adsorption on three different boichars derived from agricultural/forestry wastes through pyrolysis at various temperatures were investigated. In this study, the H₂S breakthrough capacity was measured using laboratory characterization with pH and Fourier-transform infrared spectroscopy analysis. The results obtained demonstrate that all biochars were effective in H₂S sorption. The sorption capacity of the biochar for H₂S removal is related to the pyrolysis temperature and pH of the surface.     

过渡金属浸渍改性ACF去除H_2S研究

为探讨活性炭纤维（ACF）去除恶臭气体H2S的性能,采用过渡金属浸渍改性ACF吸附H2S,揭示出改性ACF前后吸附H2S的性能差异及浸渍剂的浓度和种类对ACF吸附性能的影响。结果表明,通过过渡金属改性后的ACF吸附性能有显著提高,对H2S吸附是物理吸附和化学吸附共同作用的结果,改性后的ACF硫容量大小依次为：5%硝酸铜改性ACF〉5%硝酸钴改性ACF〉5%硝酸锰改性ACF。不同浓度浸渍剂改性后的ACF吸附H2S性能有所不同,硫容量呈现出随着浓度升高先增大后减小的趋势。不同浸渍剂改性后的ACF吸附穿透曲线也不同,穿透时间依次为：TCu-ACF〉TCo-ACF〉TMn-ACF。混合金属溶液改性ACF吸附H2S,5%硝酸铜-3%硝酸钴溶液改性ACF吸附性能最佳,硫容量可达166.7 mg/g;而5%硝酸铜-3%硝酸钴-1%硝酸锰溶液改性的ACF效果最差,硫容量仅为83.3 mg/g。     

酸碱盐改性对活性炭吸附油气特征的影响

采用酸碱盐溶液浸渍方法对活性炭进行改性,探究了其吸附油气的特征,考察了改性后的活性炭对油气吸附量和穿透时间的影响,采用BET、SEM、XRD及FT-IR等方法对活性炭进行了表征。结果表明：改性后的活性炭孔结构和表面化学性质发生了明显的变化,2^#样品(醋酸改性)比表面积最大为1 264.33 m²·g⁻¹,碱改性活性炭对油气的吸附性能优于其他改性方法,3^#样品(氨水改性)吸附容量最高为0.279 g·g⁻¹,拟合动力学速率常数k′值是0.096 3,5^#样品(氢氧化钾改性)穿透时间最长为130 min;改性处理后,增加了活性炭表面的—OH与C=C含量,正丁烷主要以—CH₂基团吸附在吸附剂表面。在综合酸碱盐溶液改性的基础上,利用Yoon-Nelson动力学方程对吸附曲线进行拟合,评价改性活性炭对油气的吸附性能。以上研究结果可为活性炭吸附油气的工业应用提供参考。     

Kinetics and the mass transfer mechanism of hydrogen sulfide removal by biochar derived from rice hull

The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperature has great influence on the adsorption of H₂S. At the different pyrolysis temperature, the H₂S removal efficiency of rice hull-derived biochar was different. The adsorption capacities of biochar were 2.09 mg·g^–1, 2.65 mg·g^–1, 16.30 mg·g^–1, 20.80 mg·g^–1, and 382.70 mg·g^–1, which their pyrolysis temperatures were 100 °C, 200 °C, 300 °C, 400 °C and 500 °C respectively. Based on the Yoon-Nelson model, it analyzed the mass transfer mechanism of hydrogen sulfide adsorption by biochar.

Implications: The paper focuses on the biochar derived from rice hull–removed hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperatures have great influence on the adsorption of H₂S. At the different pyrolysis temperatures, the H₂S removal efficiency of rice hull–derived biohar was different. The adsorption capacities of biochar were 2.09, 2.65, 16.30, 20.80, and 382.70 mg·g^?1, and their pyrolysis temperatures were 100, 200, 300, 400, and 500 °C, respectively. Based on the Yoon-Nelson model, the mass transfer mechanism of hydrogen sulfide adsorption by biochar was analyzed.     

改性高炉渣对甲基橙的吸附

以盐酸和十六烷基三甲基溴化铵对包钢高炉渣进行表面改性,通过XRD、SEM和N2吸附-脱附测试研究其微观结构和孔径分布,并以阴离子型染料甲基橙溶液为模拟染料废水研究其吸附性能,进而探索最佳改性制备条件。研究结果表明：有机改性高炉渣主要化学成分为SiO2,表面有明显的孔道结构,比表面积高达394.5 m2·g-1,平均孔径为12.4 nm;有机改性高炉渣对甲基橙溶液均具有较强的吸附性能,最佳改性条件为加入改性剂盐酸浓度为3 mol·L-1、十六烷基三甲基溴化铵的最终投加浓度为8 g·L-1、水热温度160 ℃和16 h,此时所制备的有机改性高炉渣吸附性能最强,吸附率为98.06%,最大吸附量达357.14 mg·g-1。等温吸附实验表明,有机改性高炉渣对甲基橙溶液的吸附属于多分子层吸附。     

Comparison of modified montmorillonite adsorbents. Part II: The effects of the type of raw clays and modification conditions on the adsorption performance

This paper builds on the preceding researches to study the effects of the type of clays (montmorillonites K10, KSF) and modifying conditions on the structure and adsorption behavior of resulting clay adsorbents. The raw clays were modified by polymeric Al/Fe species, hexadecyl-trimethylammonium (HDTMA) surfactant and a complex of polymeric Al/Fe-HDTMA. X-ray diffraction spectra was applied to analyze the structure of the raw and modified clays. After modification, the basal spacing of the clays varied, depending on the types of raw clay and modification conditions. Copper and phenol were selected as adsorbates for evaluating the adsorption performance of various clays, which was affected significantly by the types of raw clay and modification conditions. In general the inorganic contaminant (e.g., Cu) tend to be adsorbed by the polymeric Al/Fe modified clay and the organic impurities (e.g., phenol) will be preferably captured by the surfactant modified clay; both due to the specific surface properties resulting from introducing the modifiers. The complex modified clays possessed the ability of adsorbing both inorganic and organic contaminants. In addition, the d 0 0 1 spacing of modified KSF was greater than that of K10; the adsorption performance with modified KSF was thus greater than that with the modified K10. Finally, the ratio of modifiers to the clay (metal:surfactant:clay) has been observed to affect the adsorption performance; the optimal conditions have been defined.     

高锰酸钾改性球形中孔炭的甲醛吸附性能

采用球形中孔炭为载体,通过浸渍法担载高锰酸钾（KMnO4）制备高容量甲醛吸附剂。通过低温氮气吸附法、扫描电镜(SEM)、X射线光电子能谱(XPS)表征了球形中孔炭的孔结构及表面化学,并采用固定床测试了相应的球形中孔炭的动态甲醛吸附性能。实验结果表明：经过KMnO4浸渍改性后,球形中孔炭保持良好的球形度,并保留一定的比表面积和孔容,有利于甲醛的扩散以及甲醛与吸附活性位的接触;同时,表面C—O、C=O等含氧官能团数量增加,有效提高了甲醛的吸附性能。在KMnO4浓度为30%时性能最佳,吸附穿透容量和饱和容量分别为30.55 mg·g-1和66.04 mg·g-1,是未改性球形中孔炭的5.2倍和3.4倍。因此,KMnO4改性是提升球形中孔炭甲醛吸附性能的有效手段。     

Removal of azo dye from water by magnetite adsorption-Fenton oxidation.

The aim of this study is to highlight the possibility of using powder magnetite adsorption-Fenton oxidation as a method for removal of azo dye acid red B (ARB) from water. The adsorption properties of magnetite powder towards ARB were studied. The oxidation of adsorbed ARB and regeneration of magnetite adsorbent at the same time by Fenton reagent (hydrogen peroxide [H2O2] + iron (II) [Fe2+]) in another treatment unit with a smaller volume was also investigated. The efficiency of Fenton oxidation of ARB was compared for the reaction carried out in solution and on magnetite. The magnetic separation method was used to recover magnetite after adsorption or regeneration. The results indicated that the adsorption rate was fast. The capacity was strongly dependent on pH and inorganic anions, and pH 3.8 was optimal for the adsorption of ARB. The adsorption can be described well using the Langmuir model. The oxidation was more efficient for ARB adsorbed on magnetite than in solution. The adsorption capacity of magnetite increased significantly after regeneration, which was the result of an increase in surface area of the adsorbent and change of elemental ratio (oxygen:iron [O:Fe]) on the surface. The maximum adsorption capacity for ARB was 32.4 mg/g adsorbent.     

The removal of hydrogen sulfide in solution by ferric and alum water treatment residuals

This work investigated the characteristics and mechanisms of hydrogen sulfide adsorption by ferric and alum water treatment residuals (FARs) in solution. The results indicated that FARs had a high hydrogen sulfide adsorption capacity. pH 7 rather than higher pH (e.g. pH 8-10) was favorable for hydrogen sulfide removal. The Yan model fitted the breakthrough curves better than the Thomas model under varied pH values and concentrations. The Brunauer-Emmett-Teller surface area and the total pore volume of the FARs decreased after the adsorption of hydrogen sulfide. In particular, the volume of pores with a radius of 3-5 nm decreased, while the volume of pores with a radius of 2 nm increased. Therefore, it was inferred that new adsorption sites were generated during the adsorption process. The pH of the FARs increased greatly after adsorption. Moreover, differential scanning calorimetry analysis indicated that elemental sulfur was present in the FARs, while the derivative thermal gravimetry curves indicated the presence of sulfuric acid and sulfurous acid. These results indicated that both oxidization and ligand exchange contribute to the removal of hydrogen sulfide by FARs. Under anaerobic conditions, the maximum amount of hydrogen sulfide released was approximately 0.026 mg g(-1), which was less than 0.19% of the total amount adsorbed by the FARs. The hydrogen sulfide that was released may be re-adsorbed by the FARs and transformed into more stable mineral forms. Therefore, FARs are an excellent adsorbent for hydrogen sulfide.     

化学改性对活性炭吸附磺胺甲恶唑和布洛芬的影响

以5种化学改性剂(NH3、HCl、H2SO4、HNO3和H2O2)对活性炭进行改性,考察了化学改性对活性炭吸附磺胺甲恶唑(SMX)和布洛芬(IBP)的影响,并结合活性炭改性前后孔结构和表面化学性质的变化特征,利用Pearson相关性分析法,分析了活性炭各项理化指标与其吸附量之间的相关性。结果表明,与原炭相比,各种改性炭对SMX和IBP的吸附能力均有较大幅度提高,24 h时吸附量分别提高了36%~59%和8%~42%。活性炭的比表面积、孔容等物理性质与吸附量的相关系数绝对值均在0.4以内,表现为弱相关。对于SMX,活性炭的羧基官能团与吸附量相关系数r值在0.6~0.8之间;对于IBP,羧基、内酯基分别在吸附的前期和中后期与吸附量表现为强正相关,r达到0.6~0.8以上。本研究中活性炭的表面含氧官能团对其吸附能力表现出更为显著的影响。     

TEPA/TETA改性SBA-15对CO2吸附性能的影响

以非离子表面活性剂P123作为模板剂,正硅酸乙酯为硅源,加入扩孔剂合成SBA-15介孔材料。以三乙烯四胺(TETA)和四乙烯五胺(TEPA)作为改性剂,对所得材料分别进行质量百分比20%、30%、35%和40%的负载量改性,得到CO2的吸附材料。用热重法测定材料的CO2吸附脱附性能,氮气物理吸附-脱附和元素分析法对样品进行表征。结果表明,同样负载条件下,TEPA改性效果显著优于TETA改性,这是由于TEPA比TETA多出一个胺基;在4个附载量中,30%~35%的负载量最优,其中35% TEPA负载量的扩孔SBA-15(SBA-15k)的CO2吸附量最高,达2.86 mmol/g;循环吸附脱附的结果表明经过5次吸附脱附,材料的吸附性能没有明显变化;吸附平衡时间很短,不到10 min,有利于实际应用;氮气物理吸附-脱附和元素分析结果表明,改性剂很好地负载到SBA-15k样品上,SBA-15k对TEPA和TETA的负载改性起到促进作用。     

改性天然生物质材料的吸油性能

为了对木屑这种天然生物质作为吸附材料进行研究,采用碱性双氧水对其进行改性并研究其吸油性能。通过实验,比较了不同改性溶液浓度以及不同改性时间的吸油量,发现经1% H2O2 浸泡改性18 h后,改性木屑(HNCS)的吸附能力大大提高,吸油量达9.4 g·g-1,而改性前仅为6.47 g·g-1,改性使得吸油量提高了45%。同时研究了改性木屑对不同油品的吸油性能的测定,结果显示改性木屑对原油的吸附效果最好。通过扫描电镜(SEM)、热重失重分析以及红外扫描光谱分析研究了改性木屑的物化性能。发现经改性后,木屑的表面更加粗糙,出现了大量的吸附孔隙,且热稳定性提高,表面的亲水基团减少。说明吸油量受到材料内部的孔隙结构,以及表面官能团的影响。     

Biogeochemical analysis of hydrogen sulfide removal by a lava-rock packed biofilter.

Although lava-rock-based biofilters have demonstrated their efficiencies for hydrogen sulfide (H2S) removal found in odorous air emissions, the biogeochemical basis for this removal is unclear. In this study, samples of lava rock and rinse water from biofilters at Cedar Rapids Water Pollution Control Facilities (Iowa) were used to study the structure and chemical composition of lava rock and to identify the predominant microorganism(s) present in lava-rock-based biofilters. It was found that iron, in the form of Fe2+ and Fe3+, was present in lava rock. Although literature suggests that Acidithiobacillus thiooxidans are primarily responsible for gaseous H2S removal in biofilters, our study showed that Acidithiobacillus ferrooxidans was the dominant microorganism in the lava-rock-based biofilters. A novel mechanism for H2S removal in a lava-rock-based biofilter is proposed based on the biogeochemical analysis of lava rock.     

Feasibility study on high-temperature sorption of hydrogen sulfide by natural soils

In this study, seven natural soils were tested for the sorption of hydrogen sulfide from coal gasification gas at high temperature. Results indicate that the LP natural soil has the best performance and the highest sulfur sorption capacity. After extracting free iron oxides, most natural soils have no sorption efficiency. The free iron oxides, therefore, proved to be the major components that react with hydrogen sulfide to form iron sulfides. The sulfur sorption capacity, either determined by EA or breakthrough time, is very close to the theoretical value based on the stoichiometric calculation with the content of free iron oxides. Moreover, the presence of CO is a positive effect while H2 is a negative effect. This can be explained via the water-shift reaction. On the basis of the results of temperature-programmed sulfidation (TPS), the starting temperature for the sorption of hydrogen sulfide is between 623-673 K. From the analyses of temperature-programmed oxidation (TPO) and XPS, the iron polysulfides are the major products and approximately 90% regeneration efficiency can be theoretically achieved while the temperature is controlled higher than 813 K. In the regeneration tests, the results show that the LP natural soil can be regenerated and thus reused after the oxidation process. No significant degeneration occurs on the LP natural soil after five sorption/regeneration cycles. The sulfur sorption capacity of the tenth regenerated soil can be achieved at least 80% compared to the fresh one. The experimental analyzed SO2 concentration from the regeneration process is almost identical to the theoretical calculated equilibrium concentration of the process. Maghemite is the main product after the regeneration process.     

Examination of the influence of phenyltrimethylammonium chloride (PTMA) concentration on acetochlor adsorption by modified montmorillonite

The results presented in this paper show an impact of the concentration of the aromatic organic cation on the adsorption of acetochlor on the surface of the organic-modified montmorillonite. Natural montmorillonite from Bogovina (Boljevac municipality, Serbia) was used for organic modification in this experiment. Cation exchange capacity of this montmorillonite (86 mmol 100 g^?1 of clay) was determined using the methylene blue method. In pretreatment, montmorillonite was modified with NaCl. For the purpose of organic modification, three different concentrations of phenyltrimethylammonium chloride (PTMA) have been selected, based on calculated CEC value: 43 mmol 100 g^?1 of clay (0.5 CEC), 86 mmol 100 g^?1 of clay (1 CEC) and 129 mmol 100 g^?1 of clay (1.5 CEC). The changes in the properties of the inorganic and organic modified montmorillonite were examined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and batch equilibrium method. Freundlich coefficients show higher uptake of the herbicide by montmorillonite modified with PTMA, compared to inorganic-modified montmorillonite. The results also indicate the influence of the organic cation concentration on the adsorption of the selected herbicide.