铁强化电解锰阳极液体系中氧化锰矿烟气脱硫和锰浸出工艺

结合电解锰生产工艺,以氧化锰矿为原料,以电解锰生产过程产生的电解阳极液废水配置烟气脱硫浆液,在其中添加FeSO₄强化电解锰阳极液体系下氧化锰矿烟气脱硫及浸锰能力,探讨铁强化氧化锰矿烟气脱硫和浸锰的工艺条件对烟气SO₂脱除和锰浸出的影响机制。研究发现FeSO₄的加入,通过FeSO₄与MnO₂之间的氧化还原反应以及产物三价铁离子和二价锰离子的协同催化作用,可同时提高锰矿烟气脱硫效率和锰的浸出率。锰矿粒径越小,脱硫及浸锰效率越高。温度升高,氧化锰矿浆液烟气脱硫率逐渐下降,浸锰率则先升高后下降,并在60℃时达到最大。浆液液固比和烟气流量的增大均会导致烟气脱硫率的下降,但会提高氧化锰矿浸锰率。进口SO₂浓度过高会导致脱硫率下降,但更有利于浸锰。采用5级逆流吸收对7%的烟气进行铁离子强化氧化锰浆脱硫,得到最终SO₂出口浓度293μL/L,溶液Mn²⁺浓度为44.72g/L,满足电解要求。铁强化电解锰阳极液体系有效回收利用了电解锰生产废水,不仅集脱硫浸锰工艺为一体,且可实现脱硫和浸锰效率的同时提升,为电解锰行业的清洁生产和资源综合利用提供理论依据和技术参考。     

Sulfur resource recovery based on electrolytic manganese residue calcination and manganese oxide ore desulfurization for the clean production of electrolytic manganese

An environmentally friendly and resource-conserving route to the clean production of electrolytic manganese was developed, in which the electrolytic manganese residue(EMR) was initially calcined for cement buffering;then the generated SO_2-containing flue gas was managed using manganese oxide ore and anolyte(MOOA) desulfurization; at last, the desulfurized slurry was introduced to the electrolytic manganese production(EMP). Results showed that 4.0 wt% coke addition reduced the sulfur of calcined EMR to 0.9%, thereby satisfying the cement-buffer requirement. Pilot-scale desulfurization showed that about 7.5 vol% of high SO_2 containing flue gas can be cleaned to less than 0.1 vol% through a five-stage countercurrent MOOA desulfurization. The desulfurized slurry had 42.44 g·L~(-) Mn~(2+) and 1.92 g·L~(-1) S_2 O_6~(2-), which was suitable for electrowinning after purification, and the purity of manganese product was 99.93%, satisfy the National Standard of China YB/T051-2015.This new integrated technology fulfilled 99.7% of sulfur reutilization from the EMR and 94.1% was effectively used to the EMP. The MOOA desulfurization linked the EMP a closed cycle without any pollutant discharge, which promoted the cleaner production of EMP industry.     

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.     

Studies on sulphatization—I. Sulphatization of manganese ore with pyrite

The sulphatization of low grade manganese ore with iron pyrites has been studied. The effect of reaction period, temperature, ratio of manganese to sulphur, particle size, surface area and packing density was investigated and the extent of sulphatization was reported as recovery of manganese sulphate. Under optimum heating time of 2 h at 600°C with finely powdered (?150±200 mesh BSS pyrite and ?300±325 mesh manganese ore) reactants, the conversion to manganese sulphate was 82%.     

锰泥中二氧化锰富集方法的研究

锰泥为两步氧化法生产高锰酸钾后的残渣，其中含有质量分数约20％的二氧化锰。以低热固相反应法为主，使锰泥中的二氧化锰得到富集，纯度达到82％以上，回收率接近100％。与其它锰泥处理方法相比，本方法的特点是工艺得到了大大的简化，为锰泥的综合利用和环境的改善提供了理论依据和切实可行的方法。     

Cu-Zn-Ni/Al_2O_3及Ni含量对天然气超深度脱硫性能影响的实验研究

用共沉淀法加浸渍法制成Ni质量分数分别为0,5%,10%的Cu-Zn-Ni/Al2O3复合三元脱硫剂,通过天然气脱硫实验,研究了它们的脱硫性能。实验结果表明,合适的Ni含量会增强Cu-Zn-Ni/Al2O3脱硫剂的超深度脱硫性能(小于10×10-9 m3/m3),并且随着温度的升高,脱硫性能逐渐增强,最终会趋于稳定。空速(SV)为400,1 200,2 400h-1时,Ni质量分数5%的Cu-Zn-Ni/Al2O3脱硫剂性能最优,在280℃分别达到5×10-9,5×10-9,6×10-9 m3/m3的脱硫深度;SV为400,1 200h-1时,0Ni脱硫剂脱硫性能优于10%Ni脱硫剂;SV为2 400h-1时,10%Ni脱硫剂脱硫性能优于0Ni脱硫剂。     

中温锰系黑色磷化膜组织结构和性能

研究了一种中温锰系黑色磷化工艺。介绍了预黑处理液配方和中温锰系磷化液配方。对通过预黑处理后的磷化工艺和普通磷化工艺的膜重随磷化时间的变化以及耐蚀性进行了比较。通过电子探针研究了2种工艺所得磷化膜的表面形貌及其膜的组成。结果表明,新工艺所得的磷化膜较厚,其晶粒堆积紧密,组成中的铁含量较高、并含有黑化剂A,硫酸铜点滴腐蚀时间是普通工艺的4倍,盐雾试验时间达到72h。该工艺已经应用于生产中。     

Simultaneous SO x /NO x removal in a fluidized bed reactor using natural manganese ore

In this experiment, the simultaneous removal of SO₂ and NO from flue gases was investigated through the use of natural manganese ore as a sorbent‐catalyst in a fluidized bed reactor. Selective catalytic reduction behavior was determined as a function of the sulfation degree within the temperature range from 100 °C to 500 °C. The natural manganese ore showed a high activity in the production of nitrogen and water by the reaction of nitric oxide with ammonia and oxygen up to around 200 °C. At higher temperatures, the nitric oxide removal efficiency decreased due to the oxidation of ammonia by oxygen. With the increase of sulfation degree, the temperature at which the maximum selective catalytic reduction of nitric oxide appears gradually increased, however the maximum nitric oxide removal efficiency decreased. Additionally, we investigated the removal efficiency of sulfur dioxide and nitric oxide with reaction time in a batch fluidized bed reactor within a temperature range of 350 °C to 500 °C. As the reaction temperature increased, the adsorption capacity of sulfur dioxide increased, but the nitric oxide removal efficiency decreased. © 2001 Society of Chemical Industry     

中、小型电厂烟气湿法脱硫后塔顶直排的研究

对湿法脱硫系统中不同烟气排放方式的环境影响和投资运行进行了分析。结果表明,在环境影响方面,塔顶直排方式对环境影响不明显;在投资运行方面,投资运行费用顺序为增设GGH〉不设GGH的原烟囱排放〉塔顶直排。因此,中、小型电厂烟气排放采用塔顶直排的方式是可行的。     

Effect of water on extractive desulfurization of fuel oils using ionic liquids:A COSMO-RS and experimental study

When evaluating ionic liquids(ILs) for extractive desulfurization(EDS) of fuel oils, the inevitable presence of water in the system may have a significant and in many cases strongly negative effect. However, few studies have considered this particular issue and a promoted water effect on EDS is scarcely reported. In this work,COSMO-RS was firstly employed to calculate the capacity and selectivity for EDS of various IL/H_2 O mixtures,which cover different IL characters and a wide water concentration range. Experiments were then conducted with a representative IL [C_4MIM][H_2PO_4], whose stable and even promoted extraction performance with a small amount of water was suggested by COSMO-RS. Through analyses of the desulfurization ratio, the crosssolubility and the water content in the desulfurized fuel, the promoted effect of water within a certain range(b 10 wt%) was experimentally demonstrated. Moreover, such effect of water was explained combining the viscosity, the solvent–solute interactions and the COSMO-RS based analysis.     

电解锰渣替代工业石膏用作水泥缓凝剂的试验研究

电解锰渣是电解锰加工行业中常见的一种工业固废,目前的处置方式主要为地下填埋或者露天堆存,其大量无序堆放带来了严重的环保问题。随着新环保法的实施,地方政府和电解锰加工企业面临的环保形势更加严峻,电解锰渣的合理处置成为地方经济社会发展所面临的重要核心问题。采用德国布鲁克元素分析仪等仪器设备对电解锰渣的特性进行了分析和研究,通过将电解锰渣与工业石膏搭配用作水泥缓凝剂,探索了在水泥生产过程中资源化利用电解锰渣的可行性,具有良好的环保效应和经济效益,对于电解锰渣的有效处置具有一定的参考价值。     

Experimental study on SO2 recovery using a sodium-zinc sorbent based flue gas desulfurization technology

A sodium–zinc sorbent based flue gas desulfurization technology (Na–Zn-FGD) was proposed based on the experiments and analyses of the thermal decomposition characteristics of CaSO3 and ZnSO3·2.5H2O, the waste products of calcium-based semi-dry and zinc-based flue gas desulfurization (Ca–SD-FGD and Zn–SD-FGD) tech-nologies, respectively. It was found that ZnSO3·2.5H2O first lost crystal H2O at 100 °C and then decomposed into SO2 and solid ZnO at 260 °C in the air, while CaSO3 is oxidized at 450 °C before it decomposed in the air. The ex-perimental results confirm that Zn–SD-FGD technology is good for SO2 removal and recycling, but with problem in clogging and high operational cost. The proposed Na–Zn-FGD is clogging proof, and more cost-effective. In the new process, Na2CO3 is used to generate Na2SO3 for SO2 absorption, and the intermediate product NaHSO3 reacts with ZnO powders, producing ZnSO3·2.5H2O precipitate and Na2SO3 solution. The Na2SO3 solution is clogging proof, which is re-used for SO2 absorption. By thermal decomposition of ZnSO3·2.5H2O, ZnO is re-generated and SO2 with high purity is co-produced as well. The cycle consumes some amount of raw material Na2CO3 and a small amount of ZnO only. The newly proposed FGD technology could be a substitute of the traditional semi-dry FGD technologies.     

温度对生物净化滤柱中氨氮、铁、锰去除效果的影响

温度是生物净化滤柱运行的一个重要参数,采用生物净化滤柱处理模拟含氨氮、铁、锰地下水,考察水温从约25℃降到约6℃过程中氨氮、铁、锰的去除效果。结果表明,出水氨氮、总铁、锰的浓度分别低于0.15mg/L、0.1mg/L、0.05mg/L,均低于国家标准。出水总铁、锰均未受到水温下降的影响,但是出水氨氮浓度逐渐从约0.02mg/L升高到约0.12mg/L。进一步分析发现,铁主要在滤层的0~0.4m段去除,去除效果没有受到水温变化的影响。氨氮、锰主要在滤层的0~0.8m段去除,其沿程浓度均随水温降低而明显升高。氨氮、锰的生物去除符合一级动力学反应,水温为24.6℃、15.3℃、6.7℃时,两者的动力学常数k分别为0.154min^-1、0.186min^-1,0.143min^-1、0.175min^-1,0.103min^-1、0.163min^-1;半反应时间t_1/2分别为4.51min、3.72min,4.83min、3.96min,6.72min、4.24min。随着试验水温的降低,氨氮、锰的去除效果明显受到影响。     

电解锰渣－废玻璃低温烧结制备陶瓷砖的研究

以电解锰渣和废玻璃为主要原料,采用低温烧结法制备陶瓷砖,探讨了烧结温度、电解锰渣及废玻璃的含量对陶瓷砖基本性能的影响。结果表明,随着烧结温度的升高,陶瓷砖吸水率先减小后增大,体积密度先增大后减小;随着锰渣含量的增加,陶瓷砖的吸水率逐渐增大,体积密度逐渐减小;随着玻璃含量的增加,陶瓷砖的吸水率逐渐减小,体积密度逐渐增大。40 g陶 瓷原料,当锰渣的添加量为32%（质量分数）、玻璃的添加量为10 g、烧结温度为900 ℃时,得到的陶瓷砖的吸水率最低、体积密度最大。     

湍球塔钠碱法烟气脱硫特性研究

以SO_2和空气混合模拟工业烟道气,在矩形湍球塔中进行烟气脱硫实验研究,考察了多种操作参数对脱硫率的影响。实验结果表明,增加碱液浓度、喷淋量和颗粒静床高度可以提高湍球塔脱硫效率；湍球塔脱硫效率随烟气进口温度升高而下降。     

开孔导流管喷动床烟气脱硫技术实验研究

研究了一种新型的半干法脱硫开孔导流管喷动床。在相同静床层高度下,研究了其最小喷动速度、最大喷动压降、喷动高度;在相同钙硫摩尔比、入口SO2质量浓度、进气温度、绝热饱和温差条件下,以消石灰为脱硫剂,研究了其脱硫性能。实验结果表明,与传统柱锥型喷动床相比,开孔导流管喷动床具有更好的流体力学性能和脱硫效率。实验条件下最适宜的操作条件为:钙硫摩尔比为0.9—2.5,进气温度为120—130℃,绝热饱和温差为10℃。     

Effect of processing parameters on the vulcanisation of natural rubber using glutaraldehyde

The process ability of vulcanising natural rubber using glutaraldehyde at low temperature has been studied. The main objective of this work is to improve the properties and stability of natural rubber (NR) using glutaraldehyde as a curing agent. In this study, the vulcanised samples were prepared systematically and compared with sulphur cured natural rubber vulcanisates. The influence of mole ratio of ammonia and glutaraldehyde, and the processing parameters (i.e. curing time and temperature) was investigated. The cured NR based on glutaraldehyde exhibited better hardness and thermal properties than that of the NR cured from conventional sulphur system. The experimental results reveal that the properties of glutaraldehyde cured NR can be developed with the proper additives combination and conditions adopted in the preparation. This cured system is very interesting due to it can be used for high temperature industrial applications. Moreover, it eases of processing at low temperature and cost.     

Ambient temperature CO oxidation using copper manganese oxide catalysts prepared by coprecipitation: effect of ageing on catalyst performance

Copper manganese oxides are prepared using a coprecipitation procedure and studied for the oxidation of CO at ambient temperature. In particular, the effect of the ageing tune, i.e. the time that the precipitate remains in contact with the precipitating medium, is investigated. It is shown that this parameter is of crucial importance in controlling the catalytic performance and that catalysts which are aged for 30 min or 300 min give the best performance. Preliminary characterisation using powder X-ray diffraction indicates that a combination between CuO and copper manganese oxide may be responsible for the enhanced activity observed with these samples.     

基于中温烟气多污染物控制的烟气脱硫实验

中温（200～400℃）烟气多污染物一体化脱除方法能够实现烟尘、NO_x、SO₂一体化脱除,在当前环境问题日趋严峻的背景下具有一定的发展前景。氢氧化钙作为该方法的一种潜力脱硫剂,在中温条件下进行烟气中SO₂脱除的实验研究较少,针对该情况,在自制实验系统上探究了不同因素对SO₂脱除效果的影响,研究表明,在实验室自制的固定床实验系统下,烟气成分中水蒸气、CO₂、NO_x、O₂等的存在会对脱硫产生抑制,升高温度对SO₂脱除有一定促进作用。对吸附产物进行了XRD、SEM等表征,验证了化学吸附机理,氢氧化钙在该温度区间会逐渐分解形成氧化钙,促进SO₂的吸附与内扩散,使得脱硫效果提高。研究结果为进一步提高脱硫效果,提高氢氧化钙活性,并为下一步实现中温下烟气多污染物一体化脱除奠定基础。