锅炉受热面复合陶瓷涂层抗高温SO_2腐蚀性能

针对燃煤锅炉受热面存在的高温腐蚀问题,采用料浆法在20G钢材表面制备复合陶瓷涂层,烧结后的复合陶瓷涂层表面较为致密,涂层与基材具有良好的结合状态。对喷涂及未喷涂陶瓷涂层钢片在SO_2腐蚀气氛环境下的抗高温腐蚀性能进行试验,并采用热分析动力学方法对试验数据进行处理,结果表明,在400~500℃温度范围内,两种试样的腐蚀过程均符合一维扩散反应动力学模式,计算求得喷涂涂层钢片腐蚀反应活化能低于未喷涂涂层钢片,涂层具有较好的抗高温腐蚀性能。对腐蚀试验后试样的形貌、成分和物相分析结果显示,涂层在SO_2气氛下腐蚀后,表面生成K_2SO_4晶粒,但由于涂层较为致密,阻止了S的扩散,内部基本没有检测到K2SO4的存在。     

石墨表面Si-SiC-TaB2抗烧蚀复合涂层的制备及性能研究

为了提高碳材料的抗烧蚀性能，以石墨块作为基体，SiC(d₅₀=10μm)、B₄C(d₅₀=50μm)、TaC(d₅₀=3μm)为主要原料，采用料浆法结合反应熔渗Si在石墨材料表面制备了Si-SiC和Si-SiC-TaB₂涂层，研究了涂层的物相组成、显微结构和元素分布，考察了Si-SiC-TaB₂复合涂层在室温至1 600℃的抗热震性能，并通过等离子火焰烧蚀试验(2 350℃分别烧蚀120和1 980 s)测试了涂层对石墨材料高温下的抗烧蚀防护性能。结果表明：Si-SiC-TaB₂复合涂层结构致密，涂层中SiC和TaB₂陶瓷颗粒与Si无明显界面；在1 600℃热震循环20次后，涂层试样的质量基本逐渐增加，具有良好的抗热震性能；Si-SiC-TaB₂复合涂层试样烧蚀1 980 s后质量增加，表面覆盖了含有Ta₂O₅和SiO₂的Ta...     

抗粘附氟碳复合涂层在烟囱中的应用

为提高湿法脱硫后烟囱内壁防护涂层的防腐性能,以氟碳树脂(PEVE)和聚四氟乙烯(PTFE)粒子为原料,采用喷涂工艺及室温固化制备出具有抗粘附性能的防腐蚀氟碳复合涂层。利用硫酸腐蚀实验、抗粘附冷凝实验、耐温实验、耐磨性实验,分别评价涂层的耐酸性、抗粘性、耐温性、耐磨性,并通过扫描电子显微镜对腐蚀前后涂层的形貌变化进行分析。结果表明,当PTFE∶PEVE的质量比为1∶2时,制备的PTFE/PEVE复合涂层在竖直倾角小于5°且酸气温度小于60℃时,表面未出现酸性冷凝液附着,具有优异的抗粘附特性;且分别经室温20%H₂SO₄浸泡90 d和低温(50℃)10%H₂SO₄的浸泡7 d,涂层表现出较强的耐酸性能;涂层表面能承受200℃的高温而不发生脱落、鼓包、开裂等现象,具有良好的耐温性能。此外,受力氟碳复合涂层在砂纸上拖行200 cm后,表面疏水角度降为150.2°,依旧保持超疏水状态,具有良好的耐磨性。     

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。     

四元体系Na+,K+//Br-,SO42——H2O373K相平衡

采用等温溶解平衡法研究了四元体系Na⁺,K⁺//Br^-,SO₄^2--H₂O在373 K条件下的相平衡关系,测定了平衡溶液的溶解度和密度,并根据实验数据绘制相应的相图、水图和密度图。研究发现:交互四元体系Na⁺,K⁺//Br^-,SO₄^2--H₂O在373 K温度下,有复盐钾芒硝Na₂SO₄·3K₂SO₄生成,相图由3个共饱和点、7条单变量曲线和5个结晶区组成。其中,5个结晶区分别对应单盐:K₂SO₄,KBr,NaBr,Na₂SO₄和复盐Na₂SO₄·3K₂SO₄(Gla)。     

碱金属化合物对V2O5/AC催化剂低温脱硝的影响

研究了碱金属化合物(K₂SO₄)对活性炭(AC)担载五氧化二钒(V₂O₅)组成的V₂O₅/AC催化剂的低温脱硝活性的影响。发现在V₂O₅/AC催化剂表面负载碱金属化合物(K₂SO₄)后其脱硝活性大大降低。用等体积浸渍法制备了V₂O₅/AC催化剂和K_x-V₂/AC(x=0.5,1,2)催化剂。采用5种模型对动力学实验数据进行关联。结果显示,无论V₂O₅/AC催化剂是否负载K₂SO₄,Eley-Rideal模型均比其他模型可更好地描述SCR脱硝反应,碱金属化合物(K₂SO₄)的存在提高了反应活化能,但并不改变反应机理。     

金属表面Ni/Al-13wt%TiO2/Al2O3梯度复合陶瓷涂层的腐蚀行为

为了解决陶瓷涂层中的通孔问题，把复合材料与梯度材料的主应用到陶瓷涂层，采用等离子喷涂技术在Q235钢表面形成Ni/Al-13wt％TiO2/Al2O3梯度复合陶瓷涂层，对其在沸腾的5％HCl溶液中的腐蚀行为进行了研究。结果表明，Ni/Al-13wt%TiO2/Al2O3梯度复合陶瓷涂层中的通孔率较单一层Al2O3陶瓷涂层显著降低，带有该梯度复合陶瓷涂层试样的耐蚀性明显提高，该涂层腐蚀14天仍未出现鼓泡削落现象。     

搪瓷封孔处理对45CT涂层热腐蚀行为的影响

采用超音速电弧喷涂在Super304H不锈钢表面制备了45CT涂层,然后用含SiO₂和硅酸盐的搪瓷粉对其进行封孔,研究了有无封孔的涂层表面涂覆75%(质量分数)Na₂SO₄+25%(质量分数)NaCl盐膜后在700°C下的热腐蚀行为。通过X射线衍射仪、扫描电镜和能谱仪分析了高温腐蚀产物的成分、结构和形貌。结果发现45CT涂层在腐蚀过程中出现明显质量损失,表面生成了以富铁氧化物为外层,富铬氧化物为内层的双层氧化膜,腐蚀产物剥落严重。涂层/基体界面有明显裂纹,基体一侧发生了晶间腐蚀。搪瓷封孔层具有较高的热稳定性和较低的腐蚀速率,因此在熔盐中仅发生了轻微溶解,有效地提高了45CT涂层的抗热腐蚀性。     

轻质碳酸镁纤维的制备

以MgSO₄·7H₂O和K₂CO₃为原料、PEG为结构导向剂,采用共沉淀法合成出轻质碳酸镁纤维,其废液为K₂SO₄/K₂Mg(SO₄)₂溶液。通过XRD、SEM和TG-DTA对样品进行表征,探究了影响轻质碳酸镁组成和形貌的因素及活性碳酸镁纤维形成机理。结果表明：在室温,搅拌速率为300 rad·min^-1、Mg SO₄浓度为1.0 mol·L^-1、Mg SO₄与K₂CO₃摩尔比为1∶1.1、PEG添加量为MgSO₄·7H₂O质量的30%的条件下,可制备分散性良好、晶须平均长度约为15.89μm、直径0.97μm、长径比为16.38的轻质碳酸镁纤维。     

K2CO3和CaCO3对低温制备SiC多孔陶瓷性能的影响

采用固相反应法制备SiC多孔陶瓷,通过添加二元复合烧结助剂K₂CO₃和CaCO₃与SiC在空气气氛下氧化生成的SiO₂在较低温度下生成低共融相,促进SiC多孔陶瓷在1100℃-1200℃温度下烧成。研究烧成温度、K₂CO₃和CaCO₃添加量对SiC多孔陶瓷的抗弯强度、显气孔率、气体渗透率、相组成和显微结构的影响。结果表明：当K₂CO₃和CaCO₃添加量分别为1wt%和1wt%,在空气气氛下1100℃保温3h制备的样品综合性能较佳,抗弯强度为33.6MPa,显气孔率为36.3%,气体渗透率为728m³/(m²·h·KPa)。     

Fluxing reactions of sulphate and carbonates in cement clinkering. I. Systems CaSO4-K2SO4 and K2SO4-CaCO3

Phase equilibria and thermodynamics have been used to determine compatabilities in the systems CaSO₄-K₂SO₄ and K₂SO₄-CaCO₃. In the CaSO₄-K₂SO₄ system, a polymorphic inversion at 200°C is encountered in K₂Ca₂(SO₄)₃. Thermodynamic calculation of the reciprocal salt system K₂SO₄-CaCO₃-CaSO₄-K₂CO₃ discloses that the join K₂SO₄-CaCO₃ constitutes a stable binary: experiments in flowing CO₂ at 1 bar pressure confirm this. A noteworthy feature of the system is the solid solution of CaCO₃ in K₂SO₄, reaching 20% mol % CaCO₃. The eutectic, located at 880°C and 43 mol % CaCO₃, is attainable without significant decomposition. The possible consequences to clinkering reactions are discussed.     

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.     

EIS study of the effect of high levels of SO2 on the corrosion of polyester-coated galvanised steel at different relative humidities

The effect of SO₂ on the degradation of polyester-coated galvanised steel at different relative humidities was investigated using electrochemical impedance spectroscopy. Measurements were performed on specimens which had been tested in an accelerated gaseous corrosion test. For this purpose the samples were subjected to SO₂ gas for 16 days in atmospheric test cells with adjusted relative humidity (RH) from 60 to 100%. Subsequently, the impedance response of the coated material was measured and evaluated. The results indicated that the coating performance varies with RH. Thus, under condensing conditions, the organic coating and galvanised layer was totally removed, the impedance response being interpreted as the formation of an iron sulphide film on the surface. At lower RH, remarkably, the coating remained effectively intact with the coating resistance varying inversely with RH. This work is relevant to the application of such organic-coated products adjacent to combustion flues where high levels of SO₂ occur in association with high humidity.     

Synthesis,characterization and electrochemical evaluation of anticorrosion property of a tetrapolymer for carbon steel in strong acid media

A novel tetrapolymer(TP) consisting of carboxylate, sulphonate, phosphonate and sulfur dioxide based comonomers was synthesized using Butler cyclopoymerization technique. The synthesized tetrapolymer was characterized using FTIR,1 H-NMR,~(13)CNMR and elemental analysis. The performance of the tetrapolymer as a corrosion inhibitor for St37 carbon steel in 15% HCl and 15% H_2SO_4 acid media was assessed using electrochemical impedance spectroscopy(EIS), linear polarization resistance(LPR), potentiodynamic polarization(PDP) and electrochemical frequency modulation(EFM) techniques. The influence of addition of a small amount of KI on the corrosion inhibition efficiency of TP was also assessed. Results obtained showed that the tetrapolymer moderately inhibited the corrosion of St37 steel in the acid media with protection efficiency of 79.5% and 61.1% at the optimum concentration of 1000 mg·L~(-1) studied in HCl and H_2SO_4 media respectively. On addition of 5 mmol·L~(-1) KI to the optimum tetrapolymer concentration, the protection efficiency was upgraded to 90.6% and 93.5% in HCl and H_2SO_4 environment, respectively. The enhanced performance of the polymer in the presence of KI is due to synergistic action deduced from synergism parameter(S1) which was found to be greater than unity.The tetrapolymer afforded the corrosion inhibition of St37 steel in the acid media by virtue of adsorption of the polymer molecules on the steel surface which was confirmed by ATR-FTIR analysis of the adsorbed film extracted from the steel surface. TP + KI formed complex with St37 steel surface in H_2SO_4 solution but not in HCl solution.     

Molecular structure–reactivity relationships for the oxidation of sulfur dioxide over supported metal oxide catalysts

The catalytic oxidation of sulfur dioxide to sulfur trioxide over several binary (M_xO_y/TiO₂) and ternary (V₂O₅/M_XO_Y/TiO₂) supported metal oxide catalysts was systematically investigated. The supported metal oxide components were essentially 100% dispersed as surface metal oxide species, as confirmed by Raman spectroscopy characterization. The sulfur dioxide oxidation turnover frequencies of the binary catalysts were all within an order of magnitude (V₂O₅/TiO₂>Fe₂O₃/TiO₂>Re₂O₇/TiO₂  CrO₃/TiO₂  Nb₂O₅/TiO₂>MoO₃/TiO₂  WO₃/TiO₂). An exception was the K₂O/TiO₂ catalysts, which is essentially inactive for sulfur dioxide oxidation. With the exception of K₂O, all of the surface metal oxide species present in the ternary catalysts (i.e., oxides of V, Fe, Re, Cr, Nb, Mo and W) can undergo redox cycles and oxidize SO₂ to SO₃. The turnover frequency for sulfur dioxide oxidation over all of these catalysts is approximately the same at both low and high surface coverages. This indicates that the mechanism of sulfur dioxide oxidation is not sensitive to the coordination of the surface metal oxide species. A comparison of the activities of the ternary catalysts with the corresponding binary catalysts suggests that the surface vanadium oxide and the additive surface metal oxide redox sites act independently without synergistic interactions. The V₂O₅/K₂O/TiO₂ catalyst showed a dramatic reduction in the catalytic activity in comparison to the unpromoted V₂O₅/TiO₂ catalyst. The ability of K₂O to significantly retard the redox potential of the surface vanadia species is primarily responsible for the lower catalytic activity of the ternary catalytic system. The fundamental insights generated from this research can potentially assist in the molecular design of the air pollution control catalysts: (1) the development of catalysts for low temperature oxidation of SO₂ to SO₃ during sulfuric acid manufacture (2) the design of efficient SCR DeNO_x catalysts with minimal SO₂ oxidation activity and (3) improvements in additives for the simultaneous oxidation/sorption of sulfur oxides in petroleum refinery operations.     

府谷煤CO2催化气化反应性的研究

加入适宜的催化剂可以提高气化反应速率,降低起始气化温度。为了研究不同阴离子（SO₄^2-、CO₃^2-、Cl^-）盐对府谷煤热失重过程的影响,利用热重分析仪对负载了8种催化剂（K₂CO₃、K₂SO₄、KCl;Na₂CO₃、Na₂SO₄、NaCl;FeSO₄、FeCl₂）的煤样进行了CO₂气化实验,其中每克府谷煤的K⁺、Na⁺、Fe²⁺负载量分别为0.001mol。同时采用升温动力学模型进行了数据拟合。实验结果表明：催化剂对煤与CO₂的低温热解并无明显的催化作用,而在高温气化阶段催化效果显著。对于钾盐和钠盐催化剂,当阳离子相同时,其催化活性顺序为：CO₃^2->SO₄^2->Cl^-。对于铁盐催化剂,FeSO₄的催化活性优于FeCl₂。动力学结果发现：负载催化剂煤样的活化能大小符合上述实验规律,分布在169～232.6kJ/mol之间,相比原煤（267.9kJ/mol）都有一定程度的降低。     

板式换热器Ni-P-TiO2复合纳米镀层微生物污垢特性

换热器微生物污垢问题普遍存在于能源化工领域,污垢的聚集会导致设备的流动阻力、燃料消耗和维护成本支出大幅度增加。本文采用复合纳米镀层来抑制和减轻换热表面的微生物污垢的附着和沉积。首先采用化学镀的方式,在板式换热器的不锈钢316板上镀覆 Ni-P-TiO₂复合纳米镀层和对照性的Ni-P 镀层。基于板式换热器的微生物污垢在线监测实验系统,研究了镀覆Ni-P-TiO₂复合纳米镀层的板式换热器微生物污垢特性。结果表明,清洁状态下,镀覆两种镀层的板式换热器其摩擦系数（f）和Nusselt数（Nu）相较未镀覆板式换热器均略有增加;微生物污垢实验后,相比较未镀覆的板式换热器,镀覆Ni-P镀层的板式换热器污垢热阻减少了8.36%~23.07%,而镀覆Ni-P-TiO₂复合纳米镀层的板式换热器污垢热阻减少了16.6%~30.96%;在相同微生物污垢实验工况下,镀覆Ni-P-TiO₂复合纳米镀层的板式换热器的摩擦系数（f）相比Ni-P镀层的低2.54%~11.82%,但Nu却明显高于Ni-P镀层达8.47%~9.45%,并且污垢热阻明显小于Ni-P镀层达10.66%~18.18%,镀覆Ni-P-TiO₂复合纳米镀层的板式换热器展现了优异的强化传热性能和抑垢性能。     

Manganese leaching in high concentration flue gas desulfurization process with semi-oxidized manganese ore

Manganese leaching during high concentration flue gas desulfurization process with semi-oxidized manganese ore was studied in this paper. It was found that there were different reaction pathways among which MnO_2,Mn_2O_3 and MnCO_3 in semi-oxidized manganese ore during flue gas desulphurization and manganese leaching.High SO_2 concentration facilitated redox reaction between MnO_2 and SO_2, and high concentration of H_2SO_4 accelerated MnCO_3/Mn_2O_3 leaching from semi-oxidized ore. Kinetics study showed that manganese leaching in flue gas desulfurization process with semi-oxidized ore was controlled by a mixed-control model, that is the surface chemical reaction and mass diffusion dominated both the oxidation of SO_2 and manganese leaching process. The apparent activation energy was 13.05 k J·mol~(-1) and the reaction orders with respect to SO_2 and H_2SO_4 concentration were 1.38 and 0.10, respectively. Finally, a semi-empirical rate equation based on shrinking core model was derived to describe the process.