改性活性炭对低浓度二氧化硫吸附动力学模型研究

碱改性活性炭是一种广泛应用于半导体工业和数据中心净化室内吸附二氧化硫的高效材料,但是鲜有针对符合真实建筑环境的低浓度二氧化硫吸附实验及动力学模型进行研究。首先研究了氧化铜-氢氧化钾改性活性炭（CuO-KOH@AC）、氢氧化钾改性活性炭（KOH@AC）、氢氧化镁改性活性炭[Mg（OH）₂@AC]等3种碱改性活性炭在温度为25 ℃、相对湿度（RH）为50%、二氧化硫质量浓度为2 612 mg/L条件下对二氧化硫的吸附性能,结果显示碱改性活性炭对二氧化硫的吸附能力受碱负荷量的影响更多。然后测定了CuO-KOH@AC在二氧化硫质量浓度为522~13 400 mg/L的吸附等温曲线实验值,验证了Langmuir模型、Freundlich模型、Dubin-Radushkevich（D-R）模型的有效性,其中Freundlich模型在低二氧化硫浓度条件（二氧化硫质量浓度为522 mg/L,误差为-12.18%）下拟合效果最好。CuO-KOH@AC在二氧化硫质量浓度为2 612 mg/L、不同RH（1%、50%、75%）条件下的吸附实验表明,RH增加能够促进二氧化硫在吸附剂表面的吸附。傅里叶变换红外光谱对CuO-KOH@AC吸附二氧化硫后的分析表明,吸附剂表面的吸附物种为—SO₃（或SO₄^2-）和—SO₂。X射线光电子能谱对CuO-KOH@AC吸附二氧化硫后的分析结果显示,吸附剂表面S⁶⁺形态占80%~90%,其比例随着RH的增加而增加。CuO-KOH@AC最终以SO₄^2-形式吸附气态二氧化硫,吸附过程以化学吸附为主。     

Reduction of NOx in C3H6/air mixtures over Cu/Al2O3 catalysts

The reduction of nitrogen oxides by propene in the presence of air under net oxidising conditions has been studied for two Cu/alumina catalysts of low (1%) and high (5%) copper loadings in a flow microreactor and by DRIFT. The reaction was studied in the range 473–773 K using mixtures of 2.5% NO, 1% C₃H₆ and 10% O₂ with a balance of nitrogen or helium, using samples which were pretreated in air at 673 K and also over samples which had been pre-exposed to SO₂ at 473 K. The surface species present under reaction conditions have been identified and the sensitivity of their adsorption sites in the two different loaded catalysts to SO₂ pre-treatment has been investigated. SO₂ adsorption enhanced NO adsorption at 473 K in the absence of oxygen and, in reaction, enhanced formation of NCO species leading to increased levels of adsorbed CO as a decomposition product.     

Differential capacitance of the platinum/aqueous-solution interphase

The differential capacitance of polycrystalline platinum in aqueous H₂SO₄ and NaOH solutions has been investigated as a function of bias potential. A capacitance minimum is observed at 0·56 V in H₂SO₄ and − 0·34 V in NaOH solution. There is strong evidence for the irreversible adsorption of oxygen/OH⁻ ions and oxide-film formation. Addition of n-butylamine hinders the adsorption of oxygen/OH⁻ ions and it is itself strongly adsorbed.     

The mechanism of SO2 effect on NO reduction with propene over In2O3/Al2O3 catalyst

An In₂O₃/Al₂O₃ catalyst shows high activity for the selective catalytic reduction of NO with propene in the presence of oxygen. The presence of SO₂ in feed gas suppressed the catalytic activity dramatically at high temperatures; however it was enhanced in the low temperature range of 473–573 K. In TPD and FT-IR studies, the formation of sulfate species on the surface of the catalyst caused an inhibition of NO_X adsorption sites, and the absorbance ability of NO was suppressed by the presence of SO₂, and the amount of ad-NO₃⁻ species decreased obviously. This leads to a decrease of catalytic activity at higher temperatures. However, addition of SO₂ enhanced the formation of carboxylate and formate species, which can explain the promotional effect of SO₂ at low temperature, because active C₃H₆ (partially oxidized C₃H₆) is crucial at low temperature.     

Modifications to the surface chemistry of low-rank coal-based carbon catalysts to improve flue gas nitric oxide removal

The effectiveness of carbons as low-temperature selective catalytic reduction (SCR) catalysts will depend upon their physical and chemical properties. Surface functional groups containing oxygen are closely related to the catalytic activity of carbons. These groups are expected to change the interaction between the carbon surface and the reactants through a variation in adsorption and reaction characteristics. This paper presents a more detailed study of the effects of either gas-phase sulfuric acid or oxygen oxidation treatments on the catalytic NO reduction by low-rank coal-based carbon catalysts. Raw and treated carbons were characterized by N₂ and CO₂ surface areas, TPD and ash content. NO removal capacity of carbons was determined by passing a flow containing NO, H₂O, O₂, NH₃ and N₂ through a fixed bed of carbon at 150°C and 4 s of residence time, the effluent concentration being monitored continuously during the reaction. The effects of varying the type and conditions of the treatment on the physicochemical features of carbons were studied. The gas-phase sulfuric acid treatment (corresponding to a first step SO₂ removal) markedly enhanced carbon activities for NO removal. On the contrary, oxygen oxidation enhanced NO removal capacity of chars to a lower extent. Therefore, the carbons studied could be used in a combined SO₂/NO removal process, because the use and regeneration of the carbon in the first step is beneficial for the performance in the second one.     

Regenerable CaO sorbents for SO2 retention: carbonaceous versus inorganic dispersants

In this study, the behaviour of different activated carbons and some inorganic solids (alumina, silica, titania, magnesia and silicon carbide) as dispersants for Ca(OH)₂-derived CaO under two cycles of SO₂ retention at 300 °C, is analysed. Before performing the second SO₂ adsorption, a regeneration treatment in N₂ at 880 °C is carried out. During the first retention of SO₂, no influence of the dispersant was appreciated, being CaO the only phase responsible of SO₂ capture. However, during the second SO₂ adsorption the nature of the dispersants is important. Thus, comparing the behaviour of the inorganic solids with that exhibited by the activated carbons, it is observed that the activity loss, after the regeneration treatment, was significantly reduced when the activated carbons were used, especially at high dispersant content. The most effective dispersants were found to be those with meso and macroporosity which prevent the CaO (particle size of about 5 nm) sinterisation–agglomeration. This feature was exhibited by the activated carbons chosen.     

Regeneration of a vanadium pentoxide supported activated coke catalyst-sorbent used in simultaneous sulfur dioxide and nitric oxide removal from flue gas: Effect of ammonia

A vanadium pentoxide supported activated coke (V₂O₅/AC) catalyst-sorbent has been reported to be very active for simultaneous removal of SO₂ and NO under dry conditions at temperatures of 200 °C and below. Regeneration of the SO₂-captured catalyst-sorbent is a key step in operation of such a process, which influences the catalyst-sorbent's SO₂ and NO removal activities, lifetime, as well as recovery of sulfur. Due to limited information in this regard, this paper studies thermal regeneration of a V₂O₅/AC catalyst-sorbent with emphases on the effect of atmosphere. The optimum regeneration temperature is found to be 380 °C in an Ar stream and 300 °C in a 5% NH₃/Ar stream. Compared to the fresh V₂O₅/AC, the V₂O₅/ACs regenerated in Ar show lower SO₂ adsorption capacities and higher NO removal activities, while the regenerated V₂O₅/ACs by 5% NH₃/Ar show higher and stable SO₂ adsorption capacities and higher NO removal activities. Two types of reactions occur during the regeneration: reduction of the adsorbed sulfur species by carbon to SO₂ and CO₂, and oxidation of carbon by oxygen in the V₂O₅/AC to CO₂. The carbon consumption of the latter is much more than that of the former in an Ar atmosphere, but fully suppressed by the presence of 5% NH₃. Detailed analysis and characterization of the V₂O₅/AC subjected to the regenerations are presented.     

Promotion of zirconia acidity by addition of sulfate ion

The promotion of zirconia by SO₄²⁻ is studied by percolating of zirconia with aqueous solutions of several sulfur compounds and several concentrations of H₂SO₄ as sources of sulfur. The presence of SO₄²⁻ is necessary to have catalytic activity to isomerize n-butane and produces a great increase in the stability of the physical texture to thermal treatments. The more convenient solution is 1N H₂SO₄·S0₄²⁻/ZrO₂ has the greatest catalytic activity after calcination at 893 K, where the tetragonal phase of ZrO₂ predominates. The catalytic activity was found proportional to the specific surface area and surface SO₄²⁻ concentration.     

Adsorption of SO2 using vanadium and vanadium–copper supported on activated carbon

Activated carbon impregnated with precursor salts of Ba, Co, Cu, Fe, Mg, Mn, Ni, Pb and V and their binary mixtures was used for adsorption of SO₂ at 20 °C. The most promising materials for SO₂ removal are carbons doped with V, Cu and mainly their binary mixtures, which show a synergetic effect. Kinetic curves and isotherms of SO₂ adsorption were obtained at 20 °C. These isotherms are reasonably well fitted by the Langmuir model and the respective parameters were determined. TPD experiments show that adsorption of SO₂ increases the oxygenated groups on the carbon surface. The sample doped with V, after SO₂ adsorption at 20 °C, presents an increase of basic oxygenated groups, which may be responsible for the observed extra adsorption of SO₂.     

A regenerable Fe/AC desulfurizer for SO2 adsorption at low temperatures

A novel regenerable Fe/activated coke (AC) desulfurizer prepared by impregnation of Fe(NO₃)₃ on an activated coke was investigated. Experiment results showed that at 200 °C the SO₂ adsorption capacity of the Fe/AC was higher than that of AC or Fe₂O₃. Temperature-programmed desorption (TPD) revealed that H₂SO₄ and Fe₂(SO₄)₃ were generated on the desulfurizer upon adsorption of SO₂. Effect of desulfurization temperature was also investigated which revealed that with increasing temperature from 150 to 250 °C, the SO₂ removal ability gradually increases. The used Fe/AC can be regenerated by NH₃ at 350 °C to directly form solid ammonium-sulfate salts.     

Influence of CO-evolving groups on the activity of activated carbon fiber for SO2 removal

An investigation was made into the influence of CO-evolving and CO₂-evolving groups on the activities of activated carbon fibers (ACFs) for the oxidative conversion of SO₂ into aq. H₂SO₄ in the presence of O₂ and H₂O. The results indicated that the amount of evolved CO determined the SO₂ removal activity of ACFs, whereas, the amount of evolved CO₂ did not correlate with the ACFs activity for SO₂ removal. A direct proportionality between the amount of evolved CO and the enhanced activity of SO₂ removal was confirmed by using different oxidizing agents for changing the types and amount of oxygen functional groups in ACFs.     

Study of the NOχ reaction with reducing gases on Fe/ZrO2 catalyst

The Fe/ZrO₂ catalyst (1% Fe by weight) shows a strong adsorption capacity toward the nitric oxide (at room temperature the ratio NOFe is ca. 0.5) as a consequence of the formation of a highly dispersed iron phase after reduction at 500–773 K. Nitric oxide is adsorbed mainly as nitrosyl species on the reduced surface where the Fe²⁺ sites are prevailing, but it is easily oxidised by oxygen forming nitrito and nitrato species adsorbed on the support. However, in the presence of a reducing gas such as hydrogen, carbon monoxide, propane and ammonia at 473–573 K the Fe-nitrosyl species react producing nitrogen, nitrous oxide, carbon dioxide and water, as detected by FTIR and mass spectrometers. The results show that nitric oxide reduction is more facile with hydrogen containing molecules than with CO, probably due the co-operation of spillover effects. Experiments carried out with the same gases in the presence of oxygen show, however, a reduced dissociative activity of the surface iron sites toward the species NO_χ formed by NO oxidation and therefore the reactivity is shifted to higher temperatures.     

Activation of monolithic catalysts based on diatomaceous earth for sulfur dioxide oxidation

The formation of the active phases during the activation process of monolithic catalysts based on V₂O₅–K₂SO₄ supported on diatomaceous earth for SO₂ to SO₃ oxidation in flue gases, has been shown to be a crucial factor to achieve satisfactory catalytic performance. As the temperature is increased from room temperature to 470°C, SO₂ and SO₃ are taken up by the green catalyst and the precursors are transformed into the active species. The role of each component of the catalyst during the activation was analyzed by studying the behavior towards SO₂ adsorption of four materials, which contained: diatomaceous earth, diatomaceous earth + V, diatomaceous earth + K, and diatomaceous earth + V + K. The influence of the potassium sulfate accessibility in the green catalyst was studied by using two different preparation methods, which gave rise to differences in the catalysts SO₂ adsorption properties and catalytic performance. Furthermore, the influence of the activation atmosphere was studied using nitrogen, oxygen or a flue gas composition. It was shown that pyrosulfate species should be formed at temperatures below 400°C, to keep the vanadium in the active 5+ oxidation state.     

Effect of V2O5 on the catalytic activity of Pt-based diesel oxidation catalyst

We investigated the suppression of SO₂ oxidation activity by vanadium oxide in Pt-based diesel oxidation catalyst using reaction experiments, temperature programmed desorption (TPD), infrared (IR) and X-ray photoelectron spectroscopy (XPS). There was no interaction between Pt and S indicated by the XPS results. SO₂ was not adsorbed on Pt at room temperature indicated by the absence of peak arising from SO₂ in SO₂ TPD spectra. SO₂ molecules were adsorbed on the hydroxyl groups of TiO₂ and migrated to Pt particles to react with oxygen adsorbed on it. V₂O₅ decreased the adsorption of SO₂ on TiO₂ by the blockage of V₂O₅ on TiO₂.     

燃煤锅炉烟气中Na2SO4生成的化学动力学研究

准东煤燃烧过程中Na₂SO₄的形成会造成锅炉受热面沾污、尾部SCR催化剂失活等问题。烟气中Na₂SO₄形成及转化规律的研究对于预测和控制燃煤烟气中Na₂SO₄的形成有重要意义。发展了烟气中Na/Cl/S/O/H化学动力学模型,研究了烟气中Na₂SO₄的生成过程及转化机理,考察了含氧量、温度、SO₂浓度、H₂O浓度等因素对Na₂SO₄生成的影响。动力学计算结果表明,模型预测结果与实验数据吻合较好,验证了模型的准确性。烟气中的高氧气含量有利于Na₂SO₄的生成。高温加快化学反应的同时,抑制了Na₂SO₄的生成。SO₂和H₂O的影响效果受温度影响较大。反应路径分析表明,Na₂SO₄的生成路径有两个：一是依赖于SO₂直接氧化（NaCl→NaSO₃Cl→NaHSO₄→Na₂SO₄）,二是依赖于SO₂间接氧化（NaCl→NaO₂→NaSO₄→NaHSO₄→Na₂SO₄）。敏感性分析结果表明,Na₂SO₄的生成主要对系统中生成或消耗自由基的反应更为敏感。     

葡萄糖基多孔碳材料对CO2/CH4的分离性能

以淀粉糖（主要成分为葡萄糖）为碳前体,制备了一系列多孔碳材料（C-GLCs-800）,对其进行孔隙结构分析,并应用FT-IR、SEM、TGA对其进行了表征,测定了材料在288、298和308 K下的CO₂和CH₄吸附等温线,根据IAST理论预测了材料对CO₂/CH₄二元体系的吸附选择性。实验结果显示,活化条件对材料的孔隙结构有明显影响,随着KOH/C质量比的增加,所制备的C-GLCs-800比表面积和总孔容先增加后降低。其中C-GLC-800-4的BET比表面积高达3153 m²·g^-1,总孔容为2.056 cm³·g^-1。C-GLC-800-2的窄微孔（V_d<1 nm,孔容0.3538 cm³·g^-1）含量最高,为30.63%。C-GLC-800-2在298 K和10⁵ Pa下对CO₂吸附量高达3.96 mmol·g^-1,明显高于许多传统吸附材料和MOFs材料在相同条件下对CO₂的吸附容量。应用Clausiuse-Clapeyron方程计算了CO₂和CH₄在材料上的吸附热,应用IAST理论计算了CO₂/CH₄的吸附选择性,结果显示C-GLC-800-2对CO₂/CH₄的吸附选择性为8.35。     

Some experimental observations of aerosol formation in the photo-oxidation of sulphur dioxide

The formation of particles in the u.v. photolysis of ppm concentrations of SO₂ in pure nitrogen and in nitrogen-oxygen mixtures has been studied in a flow system. Both the number of particles and the mass of the H₂SO₄ aerosol produced was determined over a range of SO₂ and water vapour concentrations.

In the near u.v. (λ = 290–400nm) the mass conversion of SO₂ to H₂SO₄ was too small to be measured, but particles were detected on a condensation nucleus counter above a threshold SO₂ concentration when the H₂SO₄ formation rate was sufficient to achieve an appreciable nucleation rate. The number of stable particles formed increased with water vapour concentration at a given H₂SO₄ production rate. These experimental data agree reasonably well with recent theoretical calculations of aerosol nucleation and growth rate in the H₂SO₄/H₂O system.

At short wavelengths (λ = 185 nm) a much higher H₂SO₄ formation rate was achieved. Although nucleation occurred at < 1 per cent r.h. the aerosol growth process was slow at low water vapour concentrations. A r.h. of 30 per cent was required for the incorporation of the bulk of the H₂SO₄ into the aerosol phase.     

Investigation of simultaneous adsorption of SO2 and NOx on Na-γ-alumina with transient techniques

The simultaneous adsorption of SO₂ and NO_x on Na-γ-alumina was studied by means of step experiments in a fixed bed plug flow reactor at 387 K and atmospheric pressure. Typically the molar composition of the feed gas was 1.5% SO₂, 1% O₂, 4000 ppm NO, 500 ppm NO₂, and Ar. First the adsorption behavior of the pure components was measured. SO₂ and NO₂ adsorb easily, whereas NO and O₂ do not adsorb. Moreover there is no influence of O₂ on the adsorption behavior of the pure components.

NO and O₂ adsorption require the simultaneous presence of SO₂, NO, and O₂. The NO and O₂ adsorption rate is enhanced by an increasing SO₂/NO ratio. The total amount of SO₂ adsorbed is not affected by the simultaneous adsorption of NO and O₂. However, NO₂ adsorption increases the SO₂ adsorption capacity. In the presence of NO₂ most of the adsorbed NO_x is released as NO.     

Application of TiO2-mounted activated carbon to the removal of phenol from water

TiO₂-mounted activated carbon was prepared through hydrolytic precipitation of TiO₂ from teraisopropyl orthotitanate and following heat treatment at 650–900 °C for 1 h under a flow of nitrogen. The removal of phenol from its aqueous solution under UV irradiation was measured on TiO₂-mounted activated carbons thus prepared. Although BET surface area of TiO₂-mounted activated carbons decreased drastically in comparison with the original activated carbon, the efficiency of phenol removal under UV irradiation was high. The sample heated at 900 °C, which consisted mainly of rutile phase, showed the highest total removal of phenol. Efficiency of phenol degradation is reduced because of phenol adsorption on the catalyst.     

Kinetics and mass transfer effects in the oxidation of ferrous sulfate over doped active carbon catalysts

Ferric sulfate is used in water purification. The oxidation of ferrous sulfate, FeSO₄, to ferric sulfate in acidic aqueous solutions of H₂SO₄ over finely dispersed active carbon particles was studied in a vigorously stirred batch reactor. Molecular oxygen was used as the oxidation agent and two kinds of catalysts were utilized: active carbon, doped active carbon. Both active carbon and doped active carbon catalysts enhanced the oxidation rate considerably.

Systematic kinetic experiments were carried out at the temperature and pressure ranges of 60–100°C and 4–10 bar, respectively. The results revealed that both non-catalytic and catalytic oxidation of Fe²⁺ take place simultaneously. The experimental data were fitted to rate equations, which were based on a plausible reaction mechanism: adsorption of dissolved oxygen on active carbon, electron transfer from Fe²⁺ ions to adsorbed oxygen and formation of surface hydroxyls. A comparison of the Fe²⁺ concentrations predicted by the kinetic model with the experimentally observed concentrations indicated that the mechanistic rate equations were able to describe the intrinsic oxidation kinetics of Fe²⁺ over pure active carbon and doped active carbon catalysts.