Thermal hazard assessment for synthesis of 3-methylpyridine-N-oxide

The exothermic oxidation of 3-methylpyridine with hydrogen peroxide was analyzed by Reaction Calorimeter (RC1e) in semi-batch operation. Heat releasing rate and heat conversion were studied at different operating conditions, such as reaction temperature, feeding rate, the amount of catalyst and so on. The thermal hazard assessment of the oxidation was derived from the calorimetric data, such as adiabatic temperature rise (ΔT_ad) and the maximum temperature of synthesis reaction (MTSR) in out of control conditions. Along with thermal decomposition of the product, the possibility of secondary decomposition under runaway conditions was analyzed by time to maximum rate (TMR_ad). Also, risk matrix was used to assess the risk of the reaction. Results indicated that with the increase of the reaction temperature, the reaction heat release rate increased, while reaction time and exotherm decreased. With the increase of feeding time, heat releasing rate decreased, but reaction time and exotherm increased. With the amount of the catalyst increased, heat releasing rate increased, reaction time decreased and exothermic heat increased. The risk matrix showed that when the reaction temperature was 70 °C, feeding time was 1 h, and the amount of catalyst was 10 g and 15 g, respectively, the reaction risk was high and must be reduced.     

Water treatment sludge for phosphate removal from the effluent of UASB reactor treating municipal wastewater

Aluminium-based water treatment sludge was used as a coagulant for removing/recovering phosphate from the effluent of upflow anaerobic sludge blanket (UASB) reactor treating municipal wastewater. The effect of three variables, namely sludge dose, initial pH and fresh coagulant (poly-aluminium chloride, PACl) dose was studied using response surface methodology. About 87% phosphate removal could be obtained at the optimum conditions of sludge dose 13.8 g/L, initial pH 6, and fresh PACl dose 5.8 mg Al/L. In order to achieve a similar phosphate removal, a dose in the range of 30–40 mg Al/L of fresh PACl was required. The results suggest that water treatment sludge can be reused as a coagulant for post-treatment of UASB reactor effluent treating municipal wastewater and can be considered as a promising alternative for removing phosphate which can substantially reduce the consumption of fresh PACl. The sludge generated during this process could potentially be used in land application which results in recycling of phosphate.     

Steel slag carbonation in a flow-through reactor system: The role of fluid-flux

Steel production is currently the largest industrial source of atmospheric CO₂. As annual steel production continues to grow, the need for effective methods of reducing its carbon footprint increases correspondingly. The carbonation of the calcium-bearing phases in steel slag generated during basic oxygen furnace (BOF) steel production, in particular its major constituent, larnite {Ca₂SiO₄}, which is a structural analogue of olivine {(MgFe)₂SiO₄}, the main mineral subjected to natural carbonation in peridotites, offers the potential to offset some of these emissions. However, the controls on the nature and efficiency of steel slag carbonation are yet to be completely understood. Experiments were conducted exposing steel slag grains to a CO₂-H₂O mixture in both batch and flow-through reactors to investigate the impact of temperature, fluid flux, and reaction gradient on the dissolution and carbonation of steel slag. The results of these experiments show that dissolution and carbonation of BOF steel slag are more efficient in a flow-through reactor than in the batch reactors used in most previous studies. Moreover, they show that fluid flux needs to be optimized in addition to grain size, pressure, and temperature, in order to maximize the efficiency of carbonation. Based on these results, a two-stage reactor consisting of a high and a low fluid-flux chamber is proposed for CO₂ sequestration by steel slag carbonation, allowing dissolution of the slag and precipitation of calcium carbonate to occur within a single flow-through system.     

SBBR处理腈纶生产废水的实验研究

二甲基乙酰胺湿纺腈纶废水是含有难降解物质的化工废水,碳氮比低,水质波动大。采用序批式生物膜反应器对二甲基乙酰胺湿纺腈纶废水进行实验研究,结果表明:在工艺参数为曝气时间3 h,溶解氧4.5~5.5 mg/L,补充无机碳源碳酸氢钠0.5 mg/L,缺氧停留时间2 h的工况下,COD去处理率为75%,BOD为98%,TOC为70%,NH4+-N为94%,TN为80%,DMAC达到99%。     

上推流厌氧反应器连续干发酵猪粪产沼气试验研究

为解决猪粪连续干发酵存在的氨抑制和出料难等难题,在温度(25±2)℃、有机负荷为干物质(TS)4.44 g.(L.d)-1的条件下,采用上推流式厌氧反应器(UPAR)对猪粪进行连续干式发酵试验,研究了猪粪干发酵过程的产气情况、氨抑制现象和出料流动性,并考察了上推流厌氧反应器进行猪粪干发酵的可行性.试验采用4种不同TS质量分数(20%、25%、30%、35%)的猪粪作为原料,经160 d的运行.结果表明,进料TS质量分数对发酵过程有很大的影响,4种不同进料TS质量分数稳定的池容产气率分别为2.40、1.73、0.89、0.62 L.(L.d)-1,进料TS质量分数为20%、25%和30%的产气效率明显优于进料TS=35%的产气效率.随着进料TS质量分数从20%增加到35%,氨氮质量浓度>2 300 mg.L-1会出现明显的产气抑制.在进料TS=35%时,氨氮质量浓度能达到3 800 mg.L-1,产气速率相对于进料TS=20%递减74.1%.当进料TS达到35%、出料TS质量分数达到17.1%、流速<0.002 m.s-1时,UPAR不能顺利出料.     

Reaction mechanism and process safety assessment of acid-catalyzed synthesis of tert-butyl peracetate

Esterification during the synthesis of tert-butyl peracetate (TBPA) is highly exothermic. Since peroxides (tert-butyl hydroperoxide TBHP and TBPA) are intrinsically thermosensitive, this synthesis process is potentially dangerous. In this work, the exothermic process and mechanism of TBPA synthesis using acetic anhydride (Ac₂O) and TBHP under the catalysis of sulphuric acid (H₂SO₄) were clarified by calorimetry, infrared spectroscopy, and high-performance liquid chromatography. To substantially alleviate the thermal risk of the reaction, and to feasibly select appropriate synthesis conditions for ensuring the process safety of the synthesized products, several sets of isothermal and isoperibol experiments were performed using calorimetry. The intermediates formed and concentration changes during the reaction were monitored using in-situ Fourier-transform infrared spectroscopy. Differential scanning calorimetry and adiabatic calorimetry were used to assess the thermal hazard of the materials during the synthesis process. The reaction mechanism was verified using density functional theory calculations. The results revealed that a controlled increase in exothermicity could be achieved by adding aqueous TBHP to Ac₂O in semi-batch experiments in isothermal mode, and accordingly, the highest yield was 95.71%. Experiments combined with theoretical calculations revealed that the primary exothermic event was the TBPA formation reaction, and the removal of a large amount of water from TBHP prior to this is favourable for the reaction. The criticality classes of this reaction were of Grade 2.     

SBR双颗粒污泥系统脱氮除磷性能研究

以模拟废水为研究对象,对SBR双颗粒污泥系统的脱氮除磷性能进行了考察.试验结果表明,A₂N双颗粒污泥系统能使硝化菌和聚磷菌分别在各自最佳的环境中生长,有利于系统脱氮除磷的稳定和高效运行,可控制性也得到了提高.在COD为300 mg·L^-1条件下,系统对COD的平均去除率达到78.8%,大部分COD被聚磷菌用来合成PHA;当溶解氧控制在3.55~4.90 mg·L^-1和5.60~6.60 mg·L^-1之间时,硝化SBR对氨氮的去除率分别为87.0%和94.5%.除磷SBR仅设置缺氧段时,磷去除率为72%;增设后曝气段后,磷去除率增至85%.NO_x^--N(NO₂^--N+ NO₃^--N)的去除主要发生在缺氧段,在反硝化除磷时作为电子受体被去除,平均去除率为90.6%.     

A novel method to synthesize polyaluminum chloride with a membrane reactor

Al13 or Alb is usually regarded as the most efficient species of polyaluminum chloride(PAC), the performance flocculant for water treatment. This paper was intended to report a new method to synthesize PAC with high content Alb, by using the membrane reactor. NaOH solutions were managed to permeate slowly through the micropores of ultrafiltration membrane into AlCl3 solutions under the suitable transmembrane pressure(TMP). Meanwhile NaOH drops size was limited to nano-scale, resulting in dramatical reduction of the characteristic diffusion time and great increment of contact interface between the strong base and AI ions in solution to favor the formation of Al(OH)4^-, the precursor of AI,3, so few precipitates and much Alb are produced. When the initial concentration of AlCl3/NaOH is 0.40/2.0 (mol/L), MWCO = 10000, TMP = 0.0085 MPa, T= 305 K and B(molar ratio of OH^-/Al^3 ) = 2.25, the quantity of Alb attains about 80%. The results of ^27Al-NMR determination showed that the Al13 content is equal to Alb content. And our PAC product has shown better flocculation effects than the commercial product.     

UASB反应器处理淀粉废水的效果及影响因素

介绍了UASB反应器处理玉米淀粉废水的效果,分析了主要因素对处理效果的影响。淀粉废水处理实际工程的运行数据表明,UASB反应器处理玉米淀粉废水具有稳定的处理效果,COD去除率在83%以上,BOD5去除率在90%以上,出水满足后续好氧处理工艺的要求;有机负荷、pH值、碱度、出水循环、SO42-和悬浮物等是影响处理效果和颗粒污泥形成及其性质的几个关键因素。     

UASB反应器处理维生素B12淀粉混合废水的研究

为考察厌氧技术处理维生素Ｂ１２淀粉混合废水的可行性,进行了采用ＵＡＳＢ反应器处理废水研究,结果表明,在中温条件下,当进水ＣＯＤ浓度为１００００－１２０００ｍｇ／Ｌ时,ＣＯＤ容积负荷可达到３０ｋｇ／（ｍ＾３．ｄ）,ＣＯＤ去除率为８０％,容积产气率为１６．８０ｍ＾３／（ｍ＾３．ｄ）。