Efficient Absorptive Oxidation of H_(2)S Using a Fe(Ⅲ)-Cu(Ⅱ) Coupled DES (ChCl/EG) Desulfurizer

In this experiment,an EG/ChCl deep eutectic solvent(DES)was synthesized using choline chloride(ChCl)and ethylene glycol(EG)as the raw materials.The synthesized DES was characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis.The results demonstrate the successful synthesis of DES.A certain amount of FeCl_(3) and CuSO_(4) was added to the DES to promote the absorption of H_(2)S;thus,a Fe(Ⅲ)-Cu(Ⅱ)coupled DES desulfurization system was obtained.The effects of DES raw materials’ratio,FeCl_(3) concentration,water content,CuSO_(4) concentration,and reaction temperature on the desulfurization efficiency and the regeneration conditions were studied.The results show that ChCl/EG DES with a molar ratio of 1:2 has a better desulfurization effect,and the addition of an appropriate amount of water can effectively promote the dissolution of CuSO_(4) and the absorption of H_(2)S.An appropriate increase in reaction temperature and CuSO_(4) concentration would also promote the absorption of H_(2)S.When the concentration of CuSO_(4) in DES desulfurizer was 0.15 mol/L,the gas speed was 20 mL/min,and the sulfur capacity could reach 10.23 g/L.The desulfurizer could be regenerated by passing O_(2),and the desulfurization efficiency did not change much after repeated use of desulfurization-regeneration many times.The desulfurization product was characterized by XRD as rhombohedral sulfur.

脱除工业废气中微量COS杂质的研究进展

羰基硫(COS)主要是石油加工和有机物合成等生产过程中产生的,是常见的有机物中间体,对人体有毒害作用。介绍了COS的危害、来源及制备等和各种脱除方法包括还原法、吸收法、水解法、吸附法、光解法等方法。归纳了脱除COS方法的反应机理和动力学研究。展望了脱除COS方法的研究前景。

脱除工业废气中微量COS杂质的研究进展

氧硫化碳(COS)主要是石油加工和有机物合成等生产中产生的,是有机中常见的有机物中间体,对人体有毒害作用。介绍了COS的危害、来源及制备等和各种脱除方法包括还原法、吸收法、水解法、吸附法、光解法等方法。归纳了脱除COS方法的反应机理和动力学研究。展望了脱除COS方法的研究前景。

Study on Industrial Application of Hydrogen Sulfide Removal by Wet Oxidation Method with High Gravity Technology

The removal of hydrogen sulfide from gas plays an important role in rational utilization of resources and environ- mental protection. In this paper, the process of hydrogen sulfide removal by wet oxidation method in a rotating packed bed was investigated in a scale for treating 10 000 Nm3/h of gas. On the basis of studying the influence of the species and con- centration of alkali source, the liquid/gas volume ratio, the high gravity factor, and the hydrogen sulfide content in feed gas on the desulfurization effect, the suitable technological conditions were obtained. The hydrogen sulfide removal efficiency could reach 98.0% under these conditions. The results of continuous operation of process facilities showed that the high gravity method has many merits including higher desulfurization rate, good stability in operation, lower liquid/gas volume ratio, greater operation elasticity, and apparent energy saving effects.

高温脱除H_2S/COS热力学可行性分析

利用自由焓极值法基本原理和ＭＡＴＬＡＢ计算语言，对高温脱除Ｈ２Ｓ／ＣＯＳ 的可行性金属组分进行热力学分析和计算。结果表明Ｍｎ 、Ｆｅ、Ｃｕ、Ｍｏ 适合在７００Ｋ～１０００Ｋ 温区内进行脱硫反应；Ｚｎ适合在４００ ～８００Ｋ 温区内脱硫；Ｃａ、Ｂａ 到１０００Ｋ 时才具有明显的脱硫性能。结合ＩＧＣＣ 技术及经济分析，Ｍｎ 、Ｆｅ 是较为理想的脱硫组分。

Environmental Properties of Minerals and Contaminants Purified by the Mineralogical Method

The investigation of the environmental properties of minerals, i.e., environmental mineralogy, is a branch of science dealing with interactions between natural minerals and spheres of the Earth surface as well as a reflection of global change, prevention of ecological destruction, participation in biomineralogy, and remediation of environmental pollution. Pollutant treatment by natural minerals is based on the natural law and reflects natural self-purification functions in the inorganic world, similar to that of the organic world - a biological treatment. A series of case studies related to natural self-purification, which were mostly completed by our group, are discussed in this paper. In natural cryptomelane there is a larger pseudotetragonal tunnel than that formed by [MnO6] octahedral double chains, with an aperture of 0.462-0.466 nm2, filled with K cations. Cryptomelane might be a real naturally-occurring mineral of the active octahedral molecular sieve (OMS-2). CrⅥ-bearing wastewater can be treated by natural pyrrhotite, which is used as a reductant to reduce CrⅥ and as a precipitant to precipitate CrⅢ simultaneously. Batch experiments were conducted using the CTMAB-Montmorillonite as an adsorbent for aromatic contaminants (phenol, aniline, benzene, toluene and xylenes), which are detected frequently in the leaching water from municipal waste deposits around China. The CTMAB modification has proved very effective to enhance the adsorption capacity of the sorbent. Expansion of vermiculite develops loose interior structures, such as pores or cracks, inside briquettes, and thus brings enough oxygen for combustion and the sulfation reaction. Effective combustion of the original carbon reduces the amount of dust in the fly ash.

基于Test Method 1311法重结晶α-半水石膏重金属元素的浸出特性研究

以脱硫石膏及其常压盐溶液法重结晶得到的α-半水石膏为研究对象,采用改进的Tessier流程和Test Method 1311法研究两种石膏晶体重金属元素的赋存形态和浸出特性,并对其进行环境效应评价。结果表明:重结晶过程能够释放脱硫石膏中的重金属元素并使其赋存形态改变;重结晶后石膏晶体中的重金属组分短期内可达到释放平衡,其中Cr、Pb、Ni元素的最大浸出量明显低于对应的脱硫石膏,As元素的浸出量几乎不变;α-半水石膏的环境友好性优于脱硫石膏,但仍具有污染环境的潜在风险。

煤层H_(2)S与煤脱硫协同治理研究

为研究煤层H_(2)S与煤脱硫的协同治理,自制装置对复配碱液进行H_(2)S吸收和煤脱硫试验。采用离子色谱法、X射线光电子能谱、形态硫测试对吸收液和煤样进行表征,分析协同治理机理,利用响应面法分析各因素对H_(2)S吸收和煤脱硫的影响程度。结果显示:单一碱液均可吸收H_(2)S,但脱硫效果微弱;添加NaClO后,协同治理效果显著且能避免H_(2)S二次逸散,其中NaOH+NaClO协同治理效果最优。在反应后,H_(2)S及煤中低价态硫噻吩、硫醇和硫醚减少,吸收液中SO_(4)^(2-)及煤中高价态硫(亚)砜增加,表明NaOH为元素硫歧化提供碱性条件,元素硫继而被NaClO氧化。NaOH质量浓度对H_(2)S吸收影响最大,NaClO质量浓度对煤脱硫影响最大,NaOH和NaClO交互对煤脱硫与H_(2)S吸收影响显著。利用Design-Expert软件确定最佳参数:NaOH质量浓度为54 g/L、NaClO质量浓度为54 g/L、温度为21.4℃。

高硫石油焦脱硫方法研究现状与展望

介绍了石油焦中硫的存在形态及分布,详细叙述了化学氧化脱硫、高温煅烧脱硫、微生物脱硫和溶剂萃取法脱硫方法的优缺点,对比了脱硫机理,总结了高硫石油焦脱硫的研究进展,对于石油焦脱硫的未来发展方向提出了展望。

气化渣基脱硫活性焦制备工艺与性能评价

煤气化过程中产生的气化渣的处置问题日趋严重。气化渣中的残余炭具有较发达的孔隙结构和较大的比表面积,具有制备活性炭和其他高附加值碳材料的潜质。通过水介重力分选方法得到高品质气化渣分离炭后,采用配煤法制备脱硫活性焦,可实现气化渣的高附加值利用。通过单因素试验法及正交试验法考察在气化渣分离炭高掺比条件下配煤种类、比例及炭化、活化工艺条件对脱硫活性焦结构和性能影响。研究表明,气化渣分离炭在掺入比例为50%时,活性焦的最佳配煤组成为:焦煤29%、长焰煤8%、煤沥青13%;最佳炭化条件为:升温速率5℃/min、炭化温度700℃、炭化时间30 min;最佳活化条件为:活化温度900℃、升温速率8℃/min、活化时间120 min、活化水量1.0 mL/(g·h)。利用固定床反应装置对气化渣基脱硫活性焦进行脱硫和再生性能评价,在最佳配方和工艺条件下,公斤级试验制备的脱硫活性焦耐磨强度为97.26%,耐压强度为696.3 N(实测值),灰分为11.66%,碘吸附值为378.78 mg/g,脱硫值为28.5 mg/g,满足脱硫用煤质颗粒活性炭指标A型优级品的技术指标且再生性能良好。以气化渣分离炭作为碳源制备脱硫活性焦在大幅降低活性焦生产成本的同时,也为气化渣的高值化利用提供了一条可行途径,对气化渣的减量化、资源化、高值化利用具有重要意义。

Simultaneous removal of SO2 and NO using a spray dryer absorption(SDA) method combined with O3 oxidation for sintering/pelleting flue gas

Based on the demand of sintering/pelleting flue gas ultra-low emission,a semi-dry method using a spray dryer absorber (SDA) combined with O3 oxidation was proposed for simultaneous removal of SO2 and NO.Effects of O3 injection site,O3/NO molar ratio,and spray tower temperature on the removal efficiencies were investigated.It was revealed that both desulfurization and denitrification efficiencies could reach to 85%under the conditions of setting O3 injection site inside of tower,O3/NO molar ratio 1.8,spray tower temperature 85°C,Ca/(S+2N) molar ratio 2.5 and slurry flow rate 300 m L/hr.CaSO3/Ca(OH)2 mixture slurry was used as absorbent to simulate operating conditions in iron and steel industry.The result shows that the addition of CaSO3 weakens both removal efficiencies.In addition,the reaction mechanism of simultaneous removal of SO2 and NO using SDA combined with O3 oxidation was proposed.

O_(3)oxidation combined with semi-dry method for simultaneous desulfurization and denitrification of sintering/pelletizing flue gas

With the vigorous development of China's iron and steel industry and the introduction of ultra-low emission policies,the emission of pollutants such as SO_(2)and NO x has received unprecedented attention.Considering the increase of the proportion of semi-dry desulfurization technology in the desulfurization process,several semi-dry desulphurization technologies such as flue gas circulating fluidized bed(CFB),dense flow absorber(DFA)and spray drying absorption(SDA)are briefly summarized.Moreover,a method for simultaneous treatment of SO_(2)and NOx in sintering/pelletizing flue gas by O_(3)oxidation combined with semidry method is introduced.Meantime,the effects of key parameters such as O_(3)/NO molar ratio,Ca SO_(3),SO_(2),reaction temperature,Ca/(S+2 N)molar ratio,droplet size and approach to adiabatic saturation temperature(AAST)on denitrification and desulfurization are analyzed.Furthermore,the reaction mechanism of denitrification and desulfurization is further elucidated.Finally,the advantages and development prospects of the new technology are proposed.

基于异质堆叠集成学习的脱硫剂加入量预测

KR搅拌法是铁水预脱硫的重要工艺之一,但在脱硫过程中脱硫剂的加入量主要依赖于人工经验控制,导致一次脱硫命中率较低,铸坯质量不稳定。为准确控制脱硫剂加入量,提高一次脱硫命中率,提出一种基于异质堆叠集成学习的脱硫剂加入量预测方法。首先,进行数据清洗,采用LOF算法结合专家经验剔除异常值。其次,采用最大信息系数结合斯皮尔曼秩相关系数进行特征筛选。最后,引入堆叠集成算法,基于评价指标和误差相关性分析优选模型的不同基学习器,并采用Optuna算法为基学习器寻找最优参数组合,建立异质堆叠集成预测模型。以现场采集的脱硫数据作为样本进行实例分析,结果表明,模型的决定系数(R^(2))为91.6%,均方根误差(RMSE)为197.79,平均绝对误差(MAE)为117.14,平均绝对百分比误差(MAPE)为6.95%。

基于RSM的工业副产品改性硫铝酸钙水泥性能分析

为研究工业副产品烟气脱硫石膏(FGDG)、粉煤灰(FA)和石灰石(LS)对硫铝酸盐水泥(SAC)熟料无侧限抗压强度(UCS)和pH的影响规律,采用FGDG,FA和LS改性SAC熟料,并在7 d和28 d龄期进行UCS和pH测试.采用响应面方法(RSM),建立UCS和pH的回归模型,分析各因素交互对其影响.研究结果表明:UCS和pH均受到FGDG,FA和LS单因素和各因素交互作用影响.FGDG和LS,LS和FA的交互作用对浆体7 d和28 d的UCS影响显著,LS和FA,FGDG和FA的交互作用对浆体pH 7 d影响显著,但对浆体pH 28 d影响并不显著.利用RSM-BBD多目标优化法进行优化各工业副产品,建立的回归模型具有较高的可信度和精确度,得到改性硫铝酸钙水泥满足高UCS低pH时各工业副产品的合适添加比,其试验值和预测值误差较小.

脱硫建筑石膏制备石膏晶须及其应用研究

以脱硫建筑石膏为原料,采用水热法制备石膏晶须,可以实现脱硫石膏的高效利用。文章研究了工艺条件对石膏晶须形貌的影响,通过扫描电子显微镜和X射线衍射等测试手段表征晶须形貌及物相,并研究了自制的石膏晶须对水泥基体材料力学性能的影响。结果表明:以脱硫建筑石膏制备的石膏晶须不用预处理原料,操作较简单;溶液的质量分数5%、反应温度140℃、反应时间2.5 h、反应pH值5、媒晶剂用量2%是最理想的工艺条件,可制备出形貌优良、长径比约为100的石膏晶须;掺入1.5%的石膏晶须时,水泥材料的抗折、抗压强度分别提高了30.5%和28.4%。

熔融制样-X射线荧光光谱法测定KR脱硫剂中氧化钙、氧化镁和二氧化硅含量的研究

目前对于KR脱硫剂中氧化钙、氧化镁和二氧化硅含量的测定采用络合滴定法和分光光度法进行分析。上述方法存在周期较长、操作繁琐、检测过程须接触危险化学品、产生废液等缺点。采用灼烧减量、熔融制样,X射线荧光光谱法测定KR脱硫剂中氧化钙、氧化镁和二氧化硅含量简单快速、具有较好的精密度、准确度,缩短了检验周期,大幅提高了检验效率。

化工企业脱硫石膏盐溶液法制备硫酸钙晶须的工艺研究

采用湿法脱硫工艺处理化工厂的废气时,会产生一种固体废弃物即脱硫石膏。与传统石膏相比,化工厂脱硫石膏中含有大量的有机杂质,综合利用难度更大。通过实验探索以化工厂脱硫石膏为原料制备硫酸钙晶须的生产工艺,分别采用盐溶液法制备晶须,探索盐溶液法中不同种类、不同浓度的盐溶液对产品的晶型形貌的影响。结果表明,采取盐溶液法制备晶须时,共对比5种不同盐溶液的效果,发现质量分数为10%的氯化钙中制备的晶须形貌最好,长径比为20~40,满足国标要求,且转化率较高。

Preparation and selection of Fe-Cu sorbent for COS removal in syngas

A series of iron-based sorbents prepared with iron trioxide hydrate,cupric oxide by a novel method was studied in a fixed-bed reactor for COS removal from syngas at moderate temperature.In addition,the sorbents mixed with various additives in different ratios were tested.The effects of additive type and ratio on the breakthrough capacity and desulfurization performance,as well as the influence of operating conditions on sulfidation behavior of the sorbent,were investigated.The simulate gas contained 1%COS,5%CO_(2),20%-30%CO and 60%-70%H_(2).The outlet gases from the fixed-bed reactor were automatically analyzed by on-line mass spectrometry,and the COS concentration before breakthrough can be kept steady at 1 ppmv.The result shows that the breakthrough sulfur capacity of the sorbent is as high as 25 g-S/100 g.At 700 K and space velocity of 1000 h^(-1),the efficiency of sulfur removal and breakthrough sulfur capacity of the sorbent increase with the increase of copper oxide with an optimum value.The result shows that the species and content of additives also affect desulfurization performance of the sorbent.

不同施用模式下脱硫石膏对苏打型盐碱地改良效果研究

以玉米为指示作物,开展了脱硫石膏不同施用量及施用方式改良盐碱地研究。设窄垄间平铺旋耕(PS)、窄垄间沟施(GS)、窄垄两侧沟施(CS)等3种施用方式,22.50、15.00、7.50、5.25和3.00 t/hm^(2)共5个施用梯度。结果表明,土壤含盐量以GS处理7.50 t/hm^(2)的梯度降低效果最好,降低了46.2%,其次是15.00 t/hm^(2)梯度,降低了45.9%,2种处理与其他处理间差异显著;土壤pH、碱化度改良效果均以GS处理22.50 t/hm^(2)梯度最好,与15.00、7.50 t/hm^(2)梯度无显著差异;土壤容重以GS处理22.50 t/hm^(2)梯度下降幅度最大,降幅达到26.7%;在出苗率上,5.25 t/hm^(2)梯度表现为CS>GS>PS,其余梯度均表现为GS>CS>PS,梯度间以22.50 t/hm^(2)出苗率最高,GS处理22.50、15.00、7.50 t/hm^(2)梯度间出苗率均无显著差异,与其他2个梯度差异显著;产量表现为GS处理7.50 t/hm^(2)梯度最高,达到11572.5 kg/hm^(2),与其他梯度产量差异显著。综合其耕层土壤指标、玉米出苗率及产量表现,脱硫石膏最佳施用方法及施用量为窄垄沟施7.50 t/hm^(2)。

Multistage desulfurization mechanism to reduce sulfur content of high ferrotitanium prepared using thermite method

High ferrotitanium is used as a deoxidizer and alloying agent in steelmaking processes and is mainly produced using high-cost remelting processes.The thermite method is a simple and low-cost method for preparing low ferrotitanium.However,the high levels of S,Al,and O residues in the product severely restrict its applicability in the low-cost preparation of good-quality high ferrotitanium.In this study,a novel multistage deep reduction method for preparing high-quality high ferrotitanium is proposed,and the multistage desulfurization mechanism is systematically investigated.The results indicate that multistage desulfurization is an effective method for reducing the S content of high ferrotitanium prepared via the thermite method.During the strong desulfurization stage,Ti_(2)S reacts with CaO at the slag-metal interface and produces CaS.The S content decreases,while the O content increases,with the increase of CaO in the CaO-Al_(2)O_(3)-based slag.During the deep desulfurization,Ti_(2)S is deeply reduced by the Ca and produces CaS,thus further reducing the S content.The S content decreases with the incremental addition of Ca and can be reduced to 0.035 wt%after multistage desulfurization.