Synergistic catalysis of the N-hydroxyphthalimide on flower-like bimetallic metal-organic frameworks for boosting oxidative desulfurization

Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.

Mathematical simulation of hot metal desulfurization during KR process coupled with an unreacted core model

A three-dimensional mathematical model was established to predict the multiphase flow,motion and dispersion of desulfurizer particles,and desulfurization of hot metal during the Kanbara reactor(KR)process.The turbulent kinetic energy-turbulent dissipation rate(k-ε)turbulence model,volume-of-fluid multiphase model,discrete-phase model,and unreacted core model for the reaction between the hot metal and particles were coupled.The measured sulfur content of the hot metal with time during the actual KR process was employed to validate the current mathematical model.The distance from the lowest point of the liquid level to the bottom of the ladle decreased from 3170 to2191 mm when the rotation speed increased from 30 to 110 r/min,which had a great effect on the dispersion of desulfurizer particles.The critical rotation speed for the vortex to reach the upper edge of the stirring impeller was 70 r/min when the immersion depth was 1500 mm.The desulfurization rate increased with the increase in the impeller rotation speed,whereas the influence of the immersion depth was relatively small.Formulas for different rotation parameters on the desulfurization rate constant and turbulent energy dissipation rate were proposed to evaluate the variation in sulfur content over time.

Process design for gas condensate desulfurization and synthesis of nano-13X zeolite adsorbent: equilibrium and dynamic studies

This paper summarizes the results of a study of adsorption of sulfur compounds from a high-sulfur feed on improved spherical-shaped nano-AgX zeolite. For this purpose, the nano-AgX zeolite was initially synthesized and improved with silver compounds such as silver nitrate, and then it was utilized in the adsorption process. In order to investigate the equilibrium and dynamics of the adsorption process, adsorptive desulfurization of real feed(i.e., sour gas condensate from the South Pars gas field) was carried out in batch and continuous processes under several operating conditions; a temperature-dependent Langmuir isotherm model was used to fit the equilibrium data. The value of monolayer adsorption capacity(q_m) and adsorption enthalpy(ΔH) were calculated to be 1.044 mmol/g and 16.8 kJ/mol, respectively. Furthermore, a detailed theoretical model was employed in order to model the breakthrough experiments. The results revealed that an increase in the feed flow rate and 1/T values will cause linear and exponential increase in the total mass transfer coefficient(ks). Isotherm and dynamic breakthrough models were found to be in agreement with the experimental data.

Wet flue gas desulfurization performance of 330 MW coal-fired power unit based on computational fluid dynamics region identification of flow pattern and transfer process

Wet Flue Gas Desulfurization(WFGD)unit based upon spray scrubber has beenwidely employed to control SO_(2) emissions from flue gas in coal-fired power plant.To clarify the dependence of desulfurization performance on inter-phase transfer behaviors with non-ideal contacting patterns of flue gas and slurry droplets,three regions in spray scrubber are distinguished in terms of gas-slurry flow structures using CFD method in the Eulerian-Lagrangian framework.A comprehensive model is established by involving the transfer process between two phases and chemical reactions in aqueous phase,which is validatedwith the measured data froma WFGD scrubber of 330 MW coal-fired power unit.Numerical results show that the overall uniformity degree of flue gas in whole scrubber is largely determined by the force-balanced droplets in the middle part of scrubber,which is dominated by counter-current mode.Both momentum transfer behavior and SO_(2) chemical absorption process present the synchronicity with the evolution of gas-slurry flow pattern,whilst the heat transfer together with H_(2)O evaporation has little effect on overall absorption process.Three regions are firstly defined as Gas Inlet Region(GIR),Dominant Absorption Region(DAR)and Slurry Dispersed Region(SDR)from the bottom to top of scrubber.SO_(2) is mainly scrubbed in DAR,which provides much more intensive interaction between two phases compared to GIR or SDR.A better understanding of the desulfurization process is obtained from the fundamental relationship between transport phenomena and chemical reactions based upon the complicated hydrodynamics of gas-slurry two-phase flow,which should be useful for designing and optimizing the scrubber in coal-fired power unit.

AN ADVANCED COAL DESULFURIZATION PROCESS──SELECTIVE FLOCCULATION

Selective flocculation is an idea separation method to separate ultrafine pyrite from coal. A number of selective flocculation separation tests under different conditions have been done and the results are very encouraging. The results also show that desulfurization and deashing can be finished simultaneously in selective fIocculation process. It is an advanced coal desulfurization process.

DEVELOPMENT OF SMOVEN PROCESS FOR HOT GAS DESULFURIZATION

The Beijing Research lnstitute of Coal Chemistry (BRICC) is developing the SMOVEN process for hot gas desulfurization. The SMOVEN process features sulfidation in an entrained bed,regeneration in a low velocity fluid bed or a moving bed with oxygen and sorbent circuIation con-trolled by gas stream. A series of tests on the bench scale unit and the continuous process devel-opment unit were carried out. The regenerable metal oxide sorbents were adopted for the sulfur-related components removing from coal gas at the temperature of 550-650℃. A fluidized bed gasifier of 100 mm (id) generated coal gas for tests. The principle of SMOVEN process has been positively verified.

Feasibility of an innovative integrated process of simultaneous desulfurization and denitrification for high strength wastewater

An anaerobic expanding-bed reactor was adopted to investigate the feasibility of an innovative integrated process of simultaneous desulfurization and denitrification (SDD) for high strength wastewater. In the reactor, heterotrophic bacteria (including sulfate reducing bacterium and denitrifying bacteria) and autotrophic bacteria (including Thiobacillus denitrificans) cooperated together by incubating and enriching functional bacteria on different carriers in the anaerobic activated sludge. Synthetic wastewater with high concentrations of sulfate and nitrate was employed. The experimental results showed that the removal efficiency of sulfate and nitrate was above 85%, elemental sulfur was observed while nitrate was absent in effluent. The balance of sulfur, nitrogen and electron was discussed respectively, which indicated that the integrated SDD process could be actualized. These results might provide a guidance to further investigate the key factors affecting the integrated SDD process and to improve the efficiency of desulfurization and denitrification in wastewater treatment.

Leaching calcium from phosphogypsum desulfurization slag by using ammonium chloride solution: Thermodynamics and kinetics study

Phosphogypsum(PG) desulfurization slag is a calcium-rich residue from reductive decomposition of PG using sulfur as the reductant. We proposed a technology of preparation light calcium carbonate with PG desulfurization slag, which mainly contains two steps: leaching and carbonizing. In this work, we concentrated on the former, in which ammonium chloride aqueous solution was utilized as leaching agent to extract calcium from the slag, and conducted thermodynamics and kinetics study on it. Fact Sage software was employed to do thermodynamic and phase equilibrium diagram calculations. The influence of leaching conditions including agitation speed, initial concentration of leaching solution, reaction temperature, and liquid/solid ratio on the calcium leaching rate was discussed in detail by means of experiment optimal design. A kinetic model developed from the shrinking core model was given to describe the leaching process. The apparent kinetic activation energy(Ea) of the leaching reaction was calculated to be 10.58 kJ·mol^-1.

Trail of sulfur during the desulfurization via reactive adsorption on Ni/ZnO

The reactive adsorption behavior of thiophene on the reduced Ni/ZnO sample was investigated by a combination of theoretical and experimental study.It is widely accepted that Ni is responsible for the sulfur-removal of thiophene to release S-free hydrocarbons.Such surface reaction was simulated by DFT method.It is demonstrated that thiophene is mainly adsorbed as p-complexation mode over metallic Ni.During desulfurization,the Se Ni bond is formed and the Ce S bond is thus split without pre-hydrogenation,resulting in the formation of Ni_(3)S_(2)phase and S-free C4 olefin which can be further saturated in the presence of H_(2).The S-transfer between Ni_(3)S_(2)and ZnO was monitored by in-situ XRD and STEM with EDS mapping.Two essential features were identified for efficient S-transfer,namely,1)the H_(2)atmosphere,and 2)the two phases are presented with close contact.Based on the acquired information,a general scenario of sulfur trail has been proposed for the desulfurization of thiophene on Ni/ZnO.

脱硫石膏制备α-半水石膏研究进展及应用

随着中国工业的不断发展,产生了大量的脱硫石膏,目前脱硫石膏的综合利用量虽在逐年增加,但其利用率却在降低,探寻脱硫石膏的高值化利用途径迫在眉睫,其中脱硫石膏资源化利用途径之一是将其脱水转化成α-半水石膏。利用脱硫石膏来制备高性能、高附加值的α-半水石膏,不仅能减轻石膏堆积对环境的污染,减少天然石膏的开采,还能带来新的经济效益。基于此,系统地综述了国内外脱硫石膏制备α-半水石膏的研究现状及影响因素,总结了其生产工艺路径及应用,并对推进脱硫石膏的减量化、资源化利用提出了展望,旨在提高固废利用率,促进“碳中和、碳减排”。

采用自主研发的在线前处理系统同时分析脱硫废水中阴阳离子

电厂专用的全自动脱硫废水分析仪可以实现对超高浓度脱硫废水的自动化前处理以及分析,样品通过自动二步稀释,并与双系统离子色谱仪联用,对脱硫废水中的阴、阳离子同时进行检测。脱硫废水中阳离子主要有Na+、NH4+、K+、Mg2+、Ca2+,阴离子主要有F-、Cl-、NO3-、SO42-。本研究对仪器相关参数进行了验证,测试结果为,4种阴离子和5种阳离子的混合标准溶液在其线性关系内相关系数均大于0.999;4种阴离子的峰高和峰面积重复性RSD小于2.29%,5种阳离子的峰高和峰面积重复性RSD小于1.78%,实际样品中4种加标阴离子回收率在93.5%~100.2%之间;5种阳离子加标回收率在95.4%~103.8%之间。结果证明,该系统大大提高了分析效率,节省了人工成本,填补了市场空白。

双螺杆挤出机胶粉脱硫工艺条件的研究

研究同向双螺杆挤出机的螺杆结构、脱硫温度和螺杆转速对胶粉脱硫的影响。结果表明:螺杆结构越有利于提高螺杆的混合和剪切能力,胶粉的溶胶含量越大,交联密度越小;当脱硫温度从170℃升高至190℃时,胶粉的脱硫效果有一定改善;当螺杆转速从50 r·min^(-1)增至90 r·min^(-1)时,胶粉的脱硫效果明显改善;当脱硫温度为180~190℃、螺杆转速为50~70 r·min^(-1)时,中等混合和剪切能力螺杆脱硫的胶粉的脱硫效果较好,脱硫胶粉胶料的拉伸性能较优。

基于深度AttLSTM网络的脱硫过程建模

脱硫过程是具有高度动态非线性和较大延迟时间的复杂工业过程,为了解决烟气脱硫过程的建模问题,设计了注意力机制下的深度长短期记忆(attention mechanism-based long short-term memory,AttLSTM)网络,并基于该网络设计自动编码器,完成脱硫过程异常点的检测。该文首次提出使用AttLSTM网络自编码器对脱硫过程进行离群点检测,并且该网络模型同样首次应用于脱硫过程的辨识任务中。从更深的意义上讲,该文尝试使用深度学习模型对复杂系统进行辨识,所建立的AttLSTM网络之前未出现在系统辨识领域,该网络的出现可以丰富辨识模型的选择,同时为人工智能技术在系统辨识领域和控制领域的应用与推广提供参考。实验结果表明,相比于之前文献出现的脱硫过程建模方法,所提方法在不同性能指标上均具有更好的表现,由此可以证明深度AttLSTM网络在脱硫场景下的有效性。

不同脱硫钢的钢包炉精炼工艺优化

针对目前某钢厂1#钢包精炼炉(LF)精炼工艺存在的不合理问题,以Q355ND钢(成品中w(S)≤0.005%)为深脱硫钢、Q235B钢(成品中w(S)≤0.020%)为低脱硫钢进行生产试验。基于罗氏线圈测量交流电原理,计算LF炉电耗,通过对弧流、相电压以及主要工艺参数的分析,研究了氩气流量、造渣料对脱硫效果的影响,并提出适应不同程度脱硫钢种生产的合理工艺。结果表明,Q355ND钢中石灰、化渣剂、合金用量分别为8.50~10.00 kg/t、1.26 kg/t、1.92 kg/t,Q235B钢中石灰、化渣剂、合金用量分别为4.74~5.00 kg/t、1.20 kg/t、1.71 kg/t时,精炼工艺较合理。当钢包透气性较好时,供电期间氩气流量约为380~400 L/min,未通电期间氩气流量约为100 L/min时精炼效果较好。采用两次供电模式,生产效果更佳。

渣油加氢装置催化剂全蜡油硫化技术应用总结

分析了固定床渣油加氢装置开工全部使用蜡油硫化方案的可行性。某公司首次采用全蜡油硫化对新鲜催化剂进行预硫化,全蜡油硫化可节省装置开工时间16 h,减少装置开工柴油使用量,减少产生不合格蜡油720 t,在低温硫化阶段蜡油硫化的上硫率更高,硫化更均匀。对比分析了全蜡油硫化与分阶段硫化的催化剂性能,在工艺条件、原料性质基本相同的条件下,两种不同方式硫化后的催化剂杂质脱除率同样高,活性相当。使用全蜡油硫化的催化剂运行周期相对较长,说明全蜡油硫化催化剂的稳定性较高。全蜡油硫化具有操作简单、节约资源、还原活性好等优点,对于其他同类装置具有借鉴意义,为今后同类装置开工优化预硫化操作提供了宝贵经验。

脱硫塔圆锥体断裂原因分析

利用金相、扫描电镜和X射线衍射等分析手段,对原料烧结厂脱硫塔圆锥体脱落的原因进行了分析,结果表明,由于脱硫灰附着在脱硫塔圆锥体内壁上,烟气中的水汽在圆锥体内壁形成冷凝水,烟气中或烟气经ClO_(2)气体氧化后反应生成的腐蚀成分溶入冷凝水,形成电解质,渗入脱硫灰中,使脱硫塔圆锥体钢板内壁产生电化学腐蚀;由于脱硫塔圆锥体材质为Q235普碳钢,不具有耐蚀性,导致在钢板内壁形成较厚的腐蚀产物,与脱硫灰附着物在脱硫塔内壁形成结垢,进一步发生缝隙腐蚀,烟气与氧化剂ClO_(2)气体反应生成的Cl^(-),与烟气中自带的Cl^(-)一起,加速了脱硫塔腐蚀进程。最终使得圆锥体钢板不断腐蚀减薄,导致其承重能力下降,当承重能力低于圆锥体自身重量时,圆锥体断裂并脱落。

低温三效蒸发工艺中脱硫废水蒸发特性研究

脱硫废水蒸发特性是低温三效蒸发工艺参数确定的重要指标,通过蒸发实验,研究了脱硫废水蒸发速率与废水悬浮固、含盐浓度、密度间的关系,确定了系统最佳运行状态下的出料浓度。实验结果表明:脱硫废水悬浮固低利于废水蒸发,废水中固体颗粒可为盐分结晶提供晶种,颗粒冲刷作用降低了列管结垢风险,综合考虑蒸发效率和降低列管结垢风险,进水悬浮固建议为4%;脱硫废水蒸发速率随着含盐浓度的增加而降低,且含盐浓度越大蒸发速率降低得越快,可能与溶液黏度、溶液表面张力以及离子水合数有关;脱硫废水蒸发速率与溶液密度负相关,当溶液密度超过1400 kg/m^(3)时,蒸发速率显著下降,能耗明显增加,综合考虑系统高效运行和压滤机压滤效果,建议出料密度为1400 kg/m^(3)。浓缩倍率是低温三效蒸发系统工艺设计的重要指标,浓缩倍率与原水悬浮固负相关,应根据原水悬浮固及出料密度确定浓缩倍率进而完成三效蒸发系统总体设计。

干法脱硫工艺在煤层气田的应用——以沁水盆地潘河区块为例

本文以沁水盆地潘河区块15号煤产出气中硫化氢的脱除工艺为例,结合煤层气田的集输工艺和生产情况,阐述了如何进行脱硫工艺选择、脱硫药剂选择、安装位置选择、工艺设计,并对煤层气区块的伴生硫化氢处理提出合理建议。

复合法脱硫脱氰在焦化厂的应用探究

本文针对山西焦化脱硫脱氰装置运行不稳定、脱硫效果差、运行成本高等问题,分析影响复合法脱硫脱氰效率的制约因素,在此基础上对脱硫方案中的碱源、脱硫位置等方面进行了优化调整;继而对影响脱硫的诸多因素进行了研究,得到了较优的工艺参数:脱硫液温度35~38℃、煤气温度28~32℃、脱硫液PDS质量分数30×10^(-6)~40×10^(-6)、对苯二酚质量浓度0.2~0.4 g/L以及液气比为35~40 L/m^(3)。应用效果良好,不但使脱硫后煤气脱硫效率满足了环保要求,并且也有效地降低了运行成本。

工业废气处理用VOC光催化装置及工作方法探究

工业生产过程中产生的废气主要有:有机溶剂类、化工类、涂料类等。本文主要介绍了工业废气处理中常用的光催化法,分析了其技术原理,该方法具有设备结构简单、净化效率高、能耗低、无二次污染等优点。目前,该方法已应用于工业生产过程中的废气处理中。