The influence of ClO− and acidity in the reaction between H2O2 and CuCl2

The potentially explosive reaction of hydrogen peroxide (H₂O₂) and copper chloride (CuCl₂) was investigated. Pressure tests revealed that the reaction was strongly temperature - dependent and can easily undergo runaway reaction. Nevertheless, there was only a slight pressure increase at the low temperatures studied or when using low concentrations of CuCl₂. Under the conditions generating the slight pressure increase, hypochlorite anions (ClO⁻) are generated and the acidity increases. As the reaction reaches completion, ClO⁻ disappears, and the acidity decreases. Interestingly, the addition of phosphate buffer to maintain the weakly acid conditions led to a runaway reaction, and the use of basic ClO⁻ promoted the exothermic reaction. Based on the results, acidity has a strong impact on the reaction behaviour.     

管道截面对氢气/空气预混爆炸影响的实验研究

为研究管道截面对氢气/空气预混火焰形状与传播速度的影响,选用三个长度都为1m而截面尺寸不同的方形管道进行实验。实验结果表明,在截面为80mm×80mm的管道中,四种氢气浓度下预混火焰都发展形成了郁金香火焰。火焰传播速度呈现上升,下降,再上升的波动。在截面为100mm×100mm和150mm×150mm的管道中,只有在氢气浓度20%下形成郁金香火焰,并且传播速度也出现上述的波动。而在氢气浓度25%,30%,40%下,预混火焰都呈指尖形传至管口,未出现郁金香火焰,传播速度都是不断上升。三个管道对比中,截面为100mm×100mm的管道内火焰平均传播速度最快,且压力波第一峰值最大。     

Fe和Fe2+对混合细菌产氢发酵的影响

在研究Fe粉剂量和Fe²⁺浓度对混合细菌产氢发酵的影响基础上,确定Fe和Fe²⁺促进混合细菌产氢能力的最佳阈值,并对乙醇型发酵菌群在不同Fe粉和Fe²⁺浓度下的产氢量和最大比产氢速率进行考察和对比.结果表明,Fe粉和Fe²⁺对乙醇型发酵菌群的产氢能力均有明显的促进作用.以葡萄糖为底物,投加Fe²⁺试验中,Fe²⁺浓度200mg/L获得最大产氢量143.7mL/g,较对照组提高32%;Fe²⁺浓度50mg/L获得单位VSS最大比产氢速率21.2 mL/(h·g),较对照组提高33%.投加单质Fe试验中,Fe粉剂量1000mg/L获得最大产氢量156.1mL/g,较对照组提高44%;Fe粉剂量500mg/L获得单位VSS最大比产氢速率23.5mL/(h·g),较对照组分别提高47%.单质Fe浓度高于50mg/L时,对发酵菌群产氢的促进作用要优于同浓度下的Fe²⁺.同时对混合细菌中铁的全量和形态分布进行了考察.     

Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

阻挡放电联合金属氧化物催化降解H2S的研究

采用介质阻挡放电联合金属氧化物催化降解气态H2S,考察了单组分及复合金属氧化物催化剂、催化剂与低温等离子体结合方式对H2S及副产物O3去除性能的影响,分析了等离子体联合Mn复合金属氧化物催化降解H2S机理。结果表明,金属负载量相同条件下,电压低于22kV时,Mn复合金属氧化物对H2S的催化活性高于单组分Mn金属氧化物,催化活性及对O3的分解能力从大到小依次为:Ag+Mn、Cu+Mn、Fe+Mn、Mn。当电压为18 kV时,Ag+Mn、Cu+Mn、Fe+Mn复合催化剂分别比单组分Mn催化剂对H2S的去除效率提高了近10%、6%、4%。等离子体后催化区域中Mn催化剂催化氧化H2S的效率明显低于等离子体催化区域。Mn催化剂在等离子体后催化区域中能有效催化分解O3。随着电压的升高,Mn金属氧化物在等离子体后催化区域对H2S催化作用逐渐增强。在电压22 kV时,等离子体联合后催化比单独等离子体作用时,H2S去除效率提高了近11%。     

含硫天然气净化厂硫化氢泄漏分析及对策

以川东北某含硫天然气净化厂为对象,通过分析该净化厂的处理工艺及可能造成泄漏的各种原因,确定了硫化氢泄漏危险较高的生产单元。通过工艺压力、流量、物料组分的比对,选取了脱硫单元原料气和硫磺回收单元酸性气作为模拟泄漏物料。对该厂所在地的气象条件和厂区的地形地貌进行了调查,净化厂当地近5年风速、云量统计表明低风速和多云为主导天气,将D1.5m/s作为模拟硫化氢泄漏扩散的典型气象条件。采用了美国石油学会(API)推荐地面粗糙度长度。运用PHAST软件计算了在典型气象条件下通过3种不同孔径泄漏1 min,5min和30min,形成的立即危及生命或健康(IDLH)范围。在典型气象条件下IDLH的下风向边界距离在41m至1190m范围内,以硫磺回收单元的大孔径泄漏为最远。以小孔泄漏为例模拟并讨论了风速、大气稳定度对硫化氢扩散的影响。为降低H2S泄漏风险提出了在线监测及联锁系统设置的要求,对避免和减少硫化氢中毒伤亡事故具有指导意义。     

钻屑法测定煤层H_2S含量

为了测定煤层硫化氢(H2S)含量,防治矿井H2S涌出,提出一种通过钻屑法测定煤层H2S含量的方法。在未受采动影响的新鲜煤壁,采用钻屑法取样,通过测定煤样H2S解吸量、取样过程损失量和H2S残存量确定煤层H2S含量。根据溶于水中H2S的p H值和色谱分析解吸气体中H2S体积分数,确定H2S解吸量;根据煤样解吸规律和气样H2S体积分数,确定H2S损失量;根据色谱分析残存气体中H2S体积分数,确定其残存量。用此方法,对山西某矿H2S涌出煤层进行现场和实验室测定。研究表明,该矿H2S含量为(4.465~6.701)×10-3m3/t。钻屑法测定煤层H2S含量是可行的,可以为矿井H2S治理提供基础数据。     

酸化—吹气—吸收法测定水及废水中的硫化物

本文设计了硫化物测定的酸化－吹气－吸收装置，验证了装置对硫化的回收效果，对硫化物标准溶液的配制及其稳定性进行了研究，对分析条件进行了最佳选择，建立了亚甲基监光度法测定硫化物的分析方法，并对实际样品进行了测定。本方法的检出限为０．００５ｍｇＳ＾２－／ｌ，线性范围为０．００５－０．７００ｍｇＳ＾２－／ｌ，可应用于水和废水样品中微量硫化物的测定。     

Repeated hydrogen peroxide dosing briefly reduces cyanobacterial blooms and microcystin while increasing fecal bacteria indicators in a eutrophic pond

This study explored the effects of H₂O₂ on Cyanobacteria and non-target microbes using fluorometry, microscopy, flow cytometry, and high throughput DNA sequencing of the 16S rRNA gene during a series of mesocosm and whole-ecosystem experiments in a eutrophic pond in NY, USA. The addition of H₂O₂ (8 mg/L) significantly reduced Cyanobacteria concentrations during a majority of experiments (66%; 6 of 9) and significantly increased eukaryotic green and unicellular brown algae in 78% and 45% of experiments, respectively. While heterotrophic bacteria declined significantly following H₂O₂ addition in all experiments, bacteria indicative of potential fecal contamination (Escherichia coli, Enterococcus, fecal coliform bacteria) consistently and significantly increased in response to H₂O₂, evidencing a form of ‘pollution swapping’. H₂O₂ more effectively reduced Cyanobacteria in enclosed mesocosms compared to whole-ecosystem applications. Ten whole-pond H₂O₂ applications over a two-year period temporarily reduced cyanobacterial levels but never reduced concentrations below bloom thresholds and populations always rebounded in two weeks or less. The bacterial phyla of Cyanobacteria, Actinobacteria, and Planctomycetes were the most negatively impacted by H₂O₂. Microcystis was always reduced by H₂O₂, as was the toxin microcystin, but Microcystis remained dominant even after repeated H₂O₂ treatments. Although H₂O₂ favored the growth of eukaryotic algae over potentially harmful Cyanobacteria, the inability of H₂O₂ to end cyanobacterial blooms in this eutrophic waterbody suggests it is a non-ideal mitigation approach in high biomass ecosystems and should be used judiciously due to potential negative impacts on non-target organisms and promotion of bacteria indicative of fecal contamination.