固定燃烧源排放N2O的采样,分析方法及其监测

烟道气是一含有多种哗合物的复杂体系，除Ｎ２，Ｏ２外，还含有燃烧产物Ｈ２Ｏ，ＣＯ２ＣＯ，ＮＯｘ，ＳＯ２和Ｈ２Ｓ等，烟气样在贮放过程中它们之间相互影响，使各自的浓度发生变化，为了得到烟气中Ｎ２Ｏ含量的准确测定值，分别研究了Ｈ２Ｏ，ＳＯ２和ＮＯ的含量，放置时间对Ｎ２Ｏ生成量的影响，试验结果表明，玻璃注射器不适于贮放烟气样，样品中只有Ｈ２Ｏ，ＳＯ２和ＮＯ三种化合物同时存在时，才会有进一步的Ｎ２Ｏ的生成，其     

喷雾干燥吸收去除烟道气中的SO2

本文报道了处理量为2000m~3/的喷雾干燥法烟气脱硫试验的结果。化学计量比、烟气绝热饱和温度值、喷雾轮切向速度等因素,对脱硫的影响很大。试验表明,以石灰为吸收剂,当趋近绝热饱和温度值为24.5℃,化学计量比为1.2—1.8时,吸收塔的脱硫率为66—79％。而烟气中SO_2浓度增大时,脱硫率略有下降。     

Impact of water on CO2 capture by amino acid ionic liquids

The reversible capture of CO₂ from fossil-fueled industries and the absorption of CO₂ for natural-gas-sweetening purposes are industrial issues closely related to very important environmental, economical, and technological concerns. Biological amino acids can be used for task-specific ionic liquids for reversible CO₂ capture. Several groups have reported efficient and reversible CO₂ capture by such ionic liquids under rigorously dry conditions. However, we have observed that CO₂ capture by amino acid ionic liquids is hugely impacted by the presence of water. In addition, the amino acid anions appear to play only a transitory role in the CO₂ capture in the first minutes of exposure to a wet CO₂ stream. Here, we studied the interaction of two ionic liquids—tetramethylammonium glycinate ([N₁₁₁₁][Gly]) and tetraethylammonium prolinate ([N₂₂₂₂][Pro])—with CO₂ under wet conditions, by ¹³C-NMR. Results show that CO₂ is initially captured in a carbamate form by the amine-functionalized anions of these salts. This capture mode is unambiguously confirmed by a single-crystal X-ray study of the CO₂-ionic liquid complex. However, in solution, as additional CO₂ is added, the carbamate releases the covalently bound CO₂, and the CO₂ remaining in solution shifts in form to an equilibrium mixture of carbonate and bicarbonate. Indeed, when the amount of CO₂ present in the system exceeds about one-half mole per mole of ionic liquid present, the ionic liquid–carbamate complex is detected in only trace amounts, and the neutralized amino acids are readily identifiable by NMR.     

Ionic liquids for the inhibition of gas hydrates. A review

The formation of gas hydrates is a major issue during the operation of oil and gas pipelines, because gas hydrates cause plugging, thereby disrupting the normal oil and gas flows. A solution is to inject gas hydrate inhibitors such as ionic liquids. Contrary to classical inhibitors, ionic liquids act both as thermodynamic inhibitors and hydrate inhibitors, and as anti-agglomerates. Imidazolium-based ionic liquids have been found efficient for the inhibition of CO₂ and CH₄ hydrates. For CO₂ gas hydrates, N-ethyl-N-methylmorpholinium bromide showed an average depression temperature of 1.72 K at 10 wt% concentration. The induction time of 1-ethyl-3-methyl imidazolium bromide is 36.3 h for CO₂ hydrates at 1 wt% concentration. For CH₄ hydrates, 1-ethyl-3-methyl-imidazolium chloride showed average depression temperature of 4.80 K at 40 wt%. For mixed gas hydrates of CO₂ and CH₄, only quaternary ammonium salts have been studied. Tetramethyl ammonium hydroxide shifted the hydrate liquid vapour equilibrium to 1.56 K at 10 wt%, while tetrabutylammonium hydroxide showed an induction time of 0.74 h at 1 wt% concentration.

     

Deep eutectic solvents as green absorbents of volatile organic pollutants

Volatile organic compounds are a major source of air pollutants. Absorption is an effective solution to treat polluted air loaded with volatile organic compounds, but most actual absorbents are often toxic and non-biodegradable. Here, we tested eutectic solvent mixtures for the absorption of volatile organic compounds for the first time. The affinity of solvent mixtures for toluene, acetaldehyde and dichloromethane was determined by measuring vapour–liquid partition coefficients and liquid phase absorption capacities. Results show that the vapour–liquid partition coefficients vary, at 30 °C, from close to zero for acetaldehyde in the mixtures choline chloride:urea, choline chloride:glycerol and tetrabutylphosphonium bromide:glycerol to 0.124 for dichloromethane in the choline chloride:urea eutectic mixture. These values are similar or even superior to those published for ionic liquids and organic solvents. Solvents based on choline chloride, a food additive, and urea, can solubilize up to 500 times more volatile organic compounds compare to water. Moreover, deep eutectic solvents are easier to prepare and more biodegradable than ionic liquids, which are also toxic. Deep eutectic solvents are more biodegradable than silicone oils, which are also expensive. Furthermore, in terms of recycling, the absorption capacities of the tested solvents remained unchanged during five absorption–desorption cycles. These findings are patented.     

MnO2/H2SO4溶液同时脱硫脱硝实验

采用MnO2/H2SO4溶液作为吸收液,以Fe3+作为催化剂在自制的鼓泡反应器内,对模拟烟气进行同时脱硫脱硝的实验研究,主要考察MnO2浓度、Fe3+浓度、pH值、反应温度、NO浓度、SO2浓度、氧含量、烟气流量等因素对SO2和NO脱除效率的影响.实验结果表明,MnO2浓度、Fe3+浓度、烟气流量、反应温度、NO浓度、SO2浓度对脱硝率影响显著,pH值、氧含量对脱硝率影响不大.在整个实验范围内脱硫效率总是保持在98%以上,脱硝效率最高达到70.9%.     

Oxidation of organophosphorus pesticides with chloroperoxidase enzyme in the presence of an ionic liquid as co-solvent

Effects of selected ionic liquids on the efficiency of CPO oxidation of methyl-parathion were studied. In general, the activity of CPO decreases with the increased concentration of ionic liquid. For ionic liquids with the same cation, those with PF₆ ^? exhibit strongest inhibition toward CPO, while those with either BF₄ ^? or metSO₄ ^? show relatively lesser inhibition. It was further demonstrated that even for buffer solutions containing up to 30% concentration of ionic liquids such as EAN, BMIMmetSO₄, and EtPyTFA, CPO still can retain high activity (70–100% compared to that in citrate buffer) for oxidation of methyl-parathion. Photothermal enhancement factors of 3.5 times and corresponding improvements of sensitivity in the determination of organophosphates by the FIA-TLS method are predicted in 30% ionic liquids.     

Carbon dioxide capture under ambient conditions using 2-chloroethylamine

This is the first case applying 2-haloethylamine to CO₂ capture. The prospect of global warming and the urgent need to reduce atmospheric concentration of carbon dioxide has prompted actions at many levels. The conventional capture of carbon dioxide is predominantly based on chemical absorption using ethanolamine. Recent developments of carbon dioxide capture focus on new materials, such as ionic liquids, zeolites, membranes, carbonaceous absorbents, and metal–organic frameworks. However, no unique solution exists currently to solve the problem of carbon dioxide capture. In order to examine the efficiency of 2-chloroethylamine as an absorbent of CO₂, we treated an aqueous solution of 2-chloroethylamine hydrochloride with CO₂ in the presence of an alkali, e.g., NaOH, under ambient conditions. The absorption was complete within 30 min, seemingly following first-order reaction kinetics. Furthermore, we succeeded in capturing CO₂ from ambient air using 2-chloroethanolamine. The efficiency of 2-chloroethylamine as an absorbent of CO₂ could be attributed to the production of stable 2-oxazolidinone, therefore, this reaction is favored thermodynamically. Compared with previously reported absorbents, this novel system is capable of capturing CO₂ with an extremely high efficiency of 1 mol per mol absorbent under ambient conditions, even from the atmosphere. This potential method could be used to capture CO₂ particularly from small, mobile, or low-concentration emission sources.     

噻吩在离子液体中的电化学聚合及其在模拟汽油脱硫中的应用

研究了噻吩在离子液体[HMIM] BF4,[BMIM] BF4和[BMIM] PF6中的电化学聚合,实验证明,噻吩在三种离子液体中均能聚合.将噻吩在离子液体中的电化学聚合应用于模拟汽油脱硫.结果表明:在三种离子液体中都实现了电化学脱除模拟汽油样品中的含硫物质--噻吩.对于不同的离子液体而言,脱硫的最佳电流密度不同,但噻吩的脱除效果均能达到50%-90%.     

Effluents and residues from industrial sites for carbon dioxide capture: a review

The adverse effects of climate change calls for the rapid transformation of manufacturing processes to decrease the emissions of carbon dioxide. In particular, a lower carbon footprint can be achieved by capturing carbon dioxide at the site of emission. Here we review the use of industrial effluents, waste and residues to capture carbon dioxide. Waste include steelmaking slag, municipal solid waste incinerator ashes, combustion fly ash, black liquor, paper mill waste, mining waste, cement waste, construction and demolition waste, waste from the organic industry, and flue gas desulfurization gypsum waste. Capture capacities range from 2 to 800 kg of carbon dioxide per ton of waste, depending on processes, waste type and conditions. Cement waste and flue gas desulfurization gypsum waste show the highest capture capacity per ton of waste.

     

锅炉大气污染物测试

为贯彻国家新标准“锅炉大气污染物排放标准”（ＧＢ５４６８－９１），本文探讨了准确测算烟气流速，干烟气平均分子量等关于锅炉烟尘和ＳＯ２排放浓度测试的技术问题，对不易测试的参数提供经验估算法。     

碳热还原二氧化硫的热力学平衡验证

用煤或焦炭作还原剂，将烟气中的二氧化硫直接还原为元素硫是一种很有应用前景的烟气处理方法。本文采用循环法研究了碳的类型、温度、以及碳用量对反应达到平衡时硫收率和ＳＯ２转化率的影响。实验结果表明，与文献的理论计算结果相比，碳用量对平衡组成的影响基本一致，而温度的影响则不尽相同。     

利用EIA法快速筛查垃圾焚烧飞灰和烟气中的二恶英毒性水平

基于CAPE技术公司的兔子复合克隆抗体的二恶英(PCDD/F)酶免疫分析试剂盒,建立了快速检测垃圾焚烧飞灰和烟气中PCDD/F毒性(TEQ值)的方法.试剂盒的最低检测限为3.3pg·tube-1(即3.3pgTEQ每EIA试管),线性检测范围为10～30pg·tube-1.样品经甲苯索氏抽提后过硅胶柱连接小碳柱净化处理,TCDD/F的回收率大约为50%,与原飞灰PCDD/F分布模式相比净化处理后样品中的TCDD/F含量明显降低.用净化处理后的飞灰溶液作标准溶液,绘制PCDD/F剂量-效应关系曲线,定量分析了2个飞灰样品和2个烟气样品的TEQ浓度,结果表明分析样品的TEQ实测值(HRGC/HRMS分析获得)与预测值(标准曲线计算值)的相对偏差(Rd)均小于15%,说明用该方法定量分析垃圾焚烧飞灰和烟气中PCDD/F毒性是可行的.     

Reaction mechanism of arsenic capture by a calcium-based sorbent during the combustion of arsenic-contaminated biomass: A pilot-scale experience

Pilot-scale combustion is required to treat arsenic-enriched biomass in China. CaO addition to arsenic-enriched biomass reduces arsenic emission. CaO captures arsenic via chemical adsorption to form Ca₃(AsO₄)₂. Large quantities of contaminated biomass due to phytoremediation were disposed through combustion in low-income rural regions of China. This process provided a solution to reduce waste volume and disposal cost. Pilot-scale combustion trials were conducted for in site disposal at phytoremediation sites. The reaction mechanism of arsenic capture during pilot-scale combustion should be determined to control the arsenic emission in flue gas. This study investigated three Pteris vittata L. biomass with a disposal capacity of 600 kg/d and different arsenic concentrations from three sites in China. The arsenic concentration in flue gas was greater than that of the national standard in the trial with no emission control, and the arsenic concentration in biomass was 486 mg/kg. CaO addition notably reduced arsenic emission in flue gas, and absorption was efficient when CaO was mixed with biomass at 10% of the total weight. For the trial with 10% CaO addition, arsenic recovery from ash reached 76%, which is an ~8-fold increase compared with the control. Synchrotron radiation analysis confirmed that calcium arsenate is the dominant reaction product.     

电子束脱除烟道气中硫和氮过程的计算机模拟

电子束干法脱硫脱硝的技术可以同时去除烟道气中的NOx与SO2。根据该处理方法建立脱除NOx和SO2的化学反应机理，并使用计算机模拟的方法，考察体系温度、辐照剂量和氨浓度与去除效率的关系。     

湘南第四纪红壤吸附SO_4~(2-)的机理研究

本文研究了湖南第四纪红粘土及其发育的旱地和水田表层土壤对SO_4~2的吸附.结果表明这三种土壤吸附SO_4~2的顺序为;红粘土>旱地红壤>红壤性水稻土.而且随介质pH的升高,SO_4~2吸附量减少,吸附机理也发生改变:当介质pH6.5以后,解吸占优势.     

“十一五”我国主要工业行业SO2和COD技术减排的效应分析

在分析＂十一五＂期间SO2和COD减排情况的基础上,通过构建体现分行业污染减排的环境效应分解模型,对各主要行业不同减排途径带来的污染技术减排效应进行测算,得到了各行业不同减排途径产生的技术减排效应值以及各行业污染技术减排的贡献度。测算结果显示,＂十一五＂期间火电、钢铁和水泥行业的SO2技术减排效应分别为2080万t、180万t、318万t,其中烟气脱硫工程在工业SO2污染减排中担负了主要贡献作用,贡献率为50.46%,造纸业、化学原料及制品行业、农副食品加工业的COD技术减排效应分别为309万t、103万t、135万t,最终给出了我国主要工业部门的SO2和COD技术减排效应对总减排效应的贡献度,分别为66.05%、51.10%,表明技术减排是＂十一五＂期间顺利实现污染减排的重要保证。     

Decomposition and removal of ionic liquid in aqueous solution by hydrothermal and photocatalytic treatment

We demonstrated a complete decomposition method for ionic liquids (ILs; organic cation part: butyl-methyl or ethyl-methyl imidazolium, and inorganic anion part: PF₆ ⁻, BF₄ ⁻ or Br⁻) in aqueous media by combining a hydrothermal mineralization method with a photocatalytic decomposition (PD) method. As a result, the hydrothermal treatment with Ca(OH)₂ mineralizer could effectively remove the inorganic anion part, such as PF₆ ⁻ or BF₄ ⁻ and the PD could decompose the organic cation part effectively. Therefore, the detoxification of ILs in aqueous media was accomplished by the present method.     

以膨润土为载体的碳酸盐吸收剂对二氧化碳的吸收

采用膨润土为载体,KHCO3为前驱物通过喷雾-干燥法制成固体碳酸钾吸收剂,制成的固体吸收剂粒径大小为0.5—2.0 mm,密度为1.73 g.mL-1.通过K2CO3负载量、吸收温度、吸收时间、床层纵横比等因素考察固体吸收剂对CO2气体的吸收效率及循环反应特性.分析碳酸钾吸收剂对CO2的吸收机理,并与以碳酸氢钠为前驱物制备的吸收剂进行对比,比较两种吸收剂对CO2吸收效果的差异性.通过XRD测试吸收剂吸收反应前后组成的变化,BET多点法测试吸收剂比表面积,扫描电镜观察吸收剂表面形态特征.结果表明,碳酸钾吸收剂和碳酸钠吸收剂对CO2气体均具有较高的吸收量,相比而言碳酸钾吸收剂的碳酸化反应速率较快,而且经过多次循环反应后吸收效果未发生衰减,在60℃—80℃范围内,碳酸钾吸收剂对CO2的吸收能力最佳.     

有害因子胁迫对人支气管上皮细胞SO2生物合成的影响

为了探讨有害因子胁迫与二氧化硫(SO2)细胞生物合成的关系,采用体外培养实验方法研究了不同浓度H2O2(0.1、1、10mmol·L-1)以及不同pH值(6.8、7.2、8.0)培养液对人支气管上皮细胞(BEP2D)SO2产生量(以胞内SO32-含量代表)的影响.结果表明:1)培养液过酸(pH6.8)和过碱(pH8.0)均可使BEP2D细胞SO2产生量显著增加(与对照相比,p<0.05);2)H2O2胁迫也可使BEP2D细胞SO2产生量增加,当H2O2浓度≥1mmol·L-1时,与对照相比,差异达到显著(p<0.05).以上结果提示:人支气管上皮细胞在有害因子的胁迫下可产生内源性SO2;SO2可能是一种生物气体应激分子,能像应激蛋白那样提高生物体对有害因子的抵御能力.