Calculation of the rate of SO2 oxidation to SO3

Approximate equation to calculate the effectiveness factor of catalyst for SO₂ oxidation to SO₃ has been derived. Calculated data agree well with those predicted by a quasi-homogeneous model.

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Mass-spectrometric analysis of SO3 in SO2 oxidation over vanadium catalysts

The detailed composition of the reaction mixture and, in particular, SO₃ concentration, in SO₂ oxidation over vanadium catalysts, have been determined experimentally. Both oxidized and reduced catalysts were shown to absorb a considerable amount of SO₃, the desorption rate of SO₃ being lower than that of its adsorption.

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, , . , , SO₃, .

     

V-Ce/TiO2脱硝催化剂的SO2中毒机理研究

通过表相、体相硫组分的表征分析,结合不同温度下含硫气氛下的活性演变及原位红外研究,获得了VCe(0.1)/TiO2催化剂在180、240和300℃下含硫氛围的NH3-SCR反应中毒机理. 180℃下催化剂上沉积了大量的硫酸氢铵和少量的金属硫酸盐,共同导致在8 h内活性从77.8%降至51.2%,热再生后的活性测试结果表明硫酸氢铵的沉积导致了催化剂活性降低8.3%,金属硫酸盐的沉积导致了催化剂活性降低18.3%.原位红外结果表明中毒后催化剂在180℃下的NH3-SCR反应遵循L-H反应路径.随着温度升高至240、300℃,催化剂上沉积的硫酸氢铵逐渐减少,金属硫酸盐含量增加.不同温度下的抗硫活性结果表明,低温NH3-SCR反应需要较高的氧化还原性能,中高温NH3-SCR反应则需要较高的酸性,金属硫酸盐的生成导致了氧化还原性能降低、酸性增加,因此低温NH3-SCR活性大幅降低,中高温活性则能保持在100%.     

水相法制备Ce-W@TiO_2催化剂的氨选择性催化还原NO(NH_3-SCR)活性和抗SO_2性能研究

采用水相法制备了Ce、W、Ti复合氧化物催化剂并用于氨选择性催化还原NO(NH_3-SCR)过程。TiO_2包裹型Ce-W@TiO_2催化剂表现出最佳的催化活性。205-515℃NO转化率超过90%。SO_2的存在造成所有催化剂低温段NO催化转化率的降低和高温段(425-540℃)NO催化转化率的升高,TiO_2@Ce-W表现出优越的低温抗SO_2性能。通过普通共沉淀法向Ce-W复合氧化物中引入Ti会导致催化剂表面W丰度、酸性位点的减少和低温NO转化率、耐SO_2性能的降低。通过水相法制备的TiO_2包裹型的Ce-W@TiO_2型催化剂,有利于表面W丰度、酸性位点、低温抗SO_2性能和催化活性的提高。     

NH3和SO3对硫酸氢铵和硫酸铵生成的影响

通过建立具有更精确的SO₃组分的实验室模拟烟气系统,同步研究了反应物浓度对硫酸氢铵和硫酸铵生成率和生成进度（生成速率）的影响。在实验浓度范围内,硫酸氢铵的开始生成温度为230-270℃,峰值温度为180-240℃,硫酸铵开始生成温度及峰值温度总体上比硫酸氢铵低40℃左右。硫酸氢铵的生成率明显高于硫酸铵,根据NH₃和SO₃浓度与物质的量比不同,烟温到120℃时,硫酸氢铵的生成率为64%-90%,硫酸铵的生成率为6%-15%,硫酸氢铵的生成率为硫酸铵的6-10倍。反应物浓度的增加会促进硫酸氢铵和硫酸铵的生成,且SO₃较NH₃更有利于硫酸氢铵的生成。硫酸氢铵和硫酸铵生成份额随温度的变化呈单峰状,且随着反应物浓度的增加,其峰值所在的温度区间逐渐升高。     

SO_2对Mn-Ce/TiO_2低温SCR催化剂的毒化作用研究

考察了SO_2对Mn-Ce/TiO_2低温脱硝催化剂活性的影响,利用XRD、BET、SEM和XPS对其毒化作用的原因进行分析。结果表明,SO_2对催化剂活性有明显的抑制作用,使NO_x去除率由84%降至42%左右。主要是SO_2的加入造成催化剂比表面积减小,孔径为5-10 nm的孔数量减少,且催化剂晶相由锐钛矿型转化成金红石型结构,活性组分MnO_x发生晶化现象,破坏了Mn-Ti间的强相互作用。催化剂理化性质的变化造成吸附态氧转化为晶格氧的路径受阻、MnO_2含量减少和CeO_x储氧功能减弱,并且产生氧阻效应而使NO吸附和解吸受阻,造成催化剂活性降低。同时生成的硫酸铵盐在催化剂表面沉积,覆盖了催化剂表面的Lewis酸性位,使其对NH_3吸附能力减弱。     

The mechanism of SO2 oxidation by CH3O2 radicals. Rate coefficients for the reactions of CH3O2 with SO2 and NO

The reactions of CH₃O₂ with SO₂ and NO have been studied by steady state photolysis of azomethane in the presence of O₂SO₂→NO mixtures at 296 K and 1 atm total pressure. The quantum yield of NO oxidation by CH₃O₂ radicals is increased substantially when SO₂ is added to the system indicating an SO₂ induced chain oxidation of NO. The rate law gives k₁/k₂ = (2.5 ± 0.5) × 10^?3 for CH₃O₂ + SO₂ → CH₃O₂SO₂ (1), CH₃O₂ + NO → CH₃O + NO₂ (2). Combining this ratio with the absolute value of k₁ = 8.2 × 10^?15 cm³ s^?1 gives k₂ = 10^{?11.5 ± 02} cm³ s^?1.     

Simultaneous determination of NH3, SO2, NO and NO2 by direct UV-absorption in ambient air

Summary Direct spectroscopic methods are not hampered by wall losses, are highly specific, have a potential for real time detection and offer the possibility to measure several species simultaneously in one experiment. This is demonstrated for the determination of NH₃, NO and SO₂ in ambient air by a differential optical a2bs orption spectroscopy (DOAS) technique in the spectral region 207–221 nm. Detection limits were 1 ng/g or better.     

Spectroscopic properties of guanidinium zinc sulphate [C(NH2)3]2Zn(SO4)2 and ab initio calculations of [C(NH2)3]2 and HC(NH2)3

Raman and FTIR spectra of guanidinium zinc sulphate [C(NH₂)₃]₂Zn(SO₄)₂ are recorded and the spectral bands assignment is carried out in terms of the fundamental modes of vibration of the guanidinium cations and sulphate anions. The analysis of the spectrum reveals distorted SO₄²⁻ tetrahedra with distinct S–O bonds. The distortion of the sulphate tetrahedra is attributed to Zn–O–S–O–Zn bridging in the structure as well as hydrogen bonding. The CN₃ group is planar which is expressed in the twofold symmetry along the C–N (1) vector. Spectral studies also reveal the presence of hydrogen bonds in the sample. The vibrational frequencies of [C(NH₂)₃]₂ and HC(NH₂)₃ are computed using Gaussian 03 with HF/6-31G* as basis set.     

CO oxidation over CuCr/Al2O3 catalysts in presence of SO2

Poisoning of variously prepared CuCr/Al₂O₃ catalysts having different compositions by sulfur dioxide has been studied. Comparative values for a decrease in the catalyst activities have been obtained.

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CO .

     

Vibrational study of hydrogen bonding and structural disorder in Na2H(SO4)2, K3H(SO4)2 and (NH4)3H(SO4)2 crystals

Infrared and Raman spectra on Na₃H(SO₄)₂, K₃ H(SO₄)₂ and (NH₄)₃ H(SO₄)₂ crystals have been investigated at 300 and 100 K in the 4000 to 30 cm⁻¹ region. An assignment of bands in terms of OH group frequencies and more or less distorted tetrahedra of ammonium and sulphate ions is given. The crystallographic and spectroscopic symmetry and/or dissymetry of OHO hydrogen bonds linking sulphate ions into dimers is discussed using OH group frequencies and the splitting of the v₁ (SO₄) Raman bands as criteria. In the particular case of (NH₄)₃H(SO₄)₁ compound containing several solid phases it can be shown that the room temperature phase (II) is strongly disordered, principally because of an orientational disorder of ammonium ions, and that a progressive ordering takes place with temperature lowering.     

SO2存在条件下M/REY催化剂NH3选择性还原NO性能研究

采用浸渍法制备了以REY为载体负载金属氧化物催化剂。采用XRD、NH₃-TPD、NO-TPD、H₂-TPR和XPS对催化剂进行表征,并在固定床微型反应器上评价SO₂存在条件下催化剂在NH₃选择还原NO反应中的活性。实验结果表明,活性组分种类及负载量均影响催化剂性能,Cu(3)/REY催化剂在NH₃选择还原NO反应中表现出较好的低温活性,在SO₂存在条件下,254~390℃时NO的转化率大于95%。催化剂表征结果显示,Cu(3)/REY催化剂的催化活性与其良好的氧化还原性和对NO的吸脱附性能相关。     

Effect of cation-radical activation and catalysis on SO2 oxidation in mild conditions

SO₂ activation by cation-radicals (CR) of tri-p-tolylamine, tri-p-anisylamine and N,N,N,N-tetramethyl-p-phenylenediamine has revealed that stable CR oxidize SO₂ to SO₄ ^2–. The dependence of the reaction rate on the oxidative properties of CR and the reaction medium has been studied. The possibility of SO₂ oxidation by oxygen with CR acting as catalysts is shown.

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- () --, -- N, N, N, N —. , SO₂ SO₂ ^4–. . SO₂ , .

     

SO42-/ZrO2-Al2O3催化剂表面酸性质对正丁烷异构化反应性能的影响研究

采用“沉淀-浸渍”法制备一系列不同硫酸负载量的SO₄^2-/ZrO₂-Al₂O₃催化剂,利用N₂吸附-脱附、Py-FTIR、XRD等手段对催化剂进行表征。在常压、200 ℃、H₂：C₄=2：3和质量空速为3 h^-1的反应条件下,在固定床微型反应评价装置上考察了硫酸负载量对SO₄^2-/ZrO₂-Al₂O₃催化正丁烷异构化反应性能的影响。Py-FTIR结果表明,硫酸化处理为催化剂表面提供了丰富的Brønsted酸性位,其中,强Brønsted酸性位在正丁烷异构化反应中起重要作用,因此,硫酸化处理可显著提高正丁烷异构化活性,而Lewis酸性位与之没有直接关系。     

Zur Bestimmung von SO2 und SO3, in ihren Gemischen

Ohne Zusammenfassung     

Bond function parameter transferability in SO2, SF2 and SO2F2

Ab initio MO studies of the use of gaussian bond functions in the molecules SO₂,SF₂ are presented. It is shown that optimization of bond function exponent and position parameters in the small molecules is a good approximation to the optimum parameter set for SO₂F₂,     

A re-interpretation of the crystal structure of ‘(NH4)2(NH3)[Ni(NH3)2Cl4]’ in terms of (NH4)2−2z[Ni(NH3)2]z[Ni(NH3)2Cl4]

A re-interpretation and re-evaluation of single-crystal X-ray diffraction data of a previously reported ‘(NH₄)₂(NH₃)[Ni(NH₃)₂Cl₄]’ (J. Solid State Chem. 162 (2001) 254) give a new formula (NH₄)_2−2z[Ni(NH₃)₂]_z[Ni(NH₃)₂Cl₄] with z=0.152. This new formula results from defects in an idealized ‘(NH₄)₂[Ni(NH₃)₂Cl₄]’ basic structure, where two adjacent NH₄⁺ cations are replaced by one Ni(NH₃)₂²⁺ unit. Cl⁻ anions from the basic structure complete the coordination sphere of the new Ni²⁺ to [Ni(NH₃)₂Cl₄]²⁻.     

Theoretical study of the oxidation mechanism of NH2

A theoretical prediction of the kinetic parameters of the NH₂ + O₂ [rlhar2] NH₂O₂ reaction was made using the transition-state theory method from the structural, energetic and spectroscopic data calculated using a 4-31G basis set. In the light of this theoretical study this oxidation mechanism is improbable at ordinary temperatures.