熔融-固相缩聚法中固相聚合对聚乳酸合成的影响

以L 乳酸单体为原料 ,熔融 -固相缩聚法合成了聚乳酸 ,重点研究了固相聚合的工艺条件。结果表明 ,绝对压力 60Pa ,氯化亚锡为催化剂 ,分段控温 ,可使聚乳酸的粘均分子量提高到固相聚合反应前的 5 3倍。通过对固相聚合产物的结晶度和熔点的分析 ,探讨了固相聚合的机理。     

用硫酸铁铵容量法测定钛精矿中二氧化钛含量

样品在过氧化钠熔融、水浸取及盐酸酸化后，在盐酸和硫酸介质中，隔绝空气，用金属铝将钛(Ⅳ)还原至钛(Ⅲ)，以硫氰酸盐为指示剂，用硫酸铁铵标准溶液滴定。     

Synthesis and characterization of new thermally stable poly(ester‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic dihydroxy compounds

A series of new alternating aromatic poly(ester‐imide)s were prepared by the polycondensation of the preformed imide ring‐containing diacids, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A model compound (3) was also prepared by the reaction of 2b with phenol, its synthesis permitting an optimization of polymerization conditions. Poly(ester‐imides) were fully characterized by FTIR, UV‐vis and NMR spectroscopy. Both biphenylene‐ and binaphthylene‐based poly(ester‐imide)s exhibited excellent solubility in common organic solvents such as tetrahydrofuran, m‐cresol, pyridine and dichloromethane. However, binaphthylene‐based poly(ester‐imide)s were more soluble than those of biphenylene‐based polymers in highly polar organic solvents, including N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 261 and 315 °C. Thermal behaviour of the polymers obtained was characterized by thermogravimetric analysis, and the 10 % weight loss temperatures of the poly(ester‐imide)s was in the range 449–491 °C in nitrogen. Furthermore, crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resultant poly(ester‐imide)s exhibited nearly an amorphous nature, except poly(ester‐imide)s derived from hydroquinone and 4,4′‐dihydroxybiphenyl. In general, polymers containing binaphthyl units showed higher thermal stability but lower crystallinity than polymers containing biphenyl units. Copyright © 2005 Society of Chemical Industry     

生物除铬(VI)效果及机理探讨

以特定污泥挂膜的自制厌氧生物滤床系统具有良好的去铬(VI)能力。恒流泵最佳流量为47mL/min,外加碳源使废水COD约140mg/L,铬(VI)的浓度由60mg/L左右降到0.5mg/L以下(一级排放标准),需要4h,而对照组(未加碳源)需要14h。铬(VI)浓度由64.66mg/L提高到75.53mg/L时,对系统负面影响甚微,提高到95.47mg/L时,系统出水达标所需时间延长到7.5h。添加微量金属离子与未添加微量金属离子的情况相比,处理效率提高21.26%。分析试验表明:铬(VI)的去除途径可能是由生物还原作用将六价铬还原为三价铬,形成氢氧化铬沉积于微生物表面。     

Comparison of Lactic Acid Productivities at High Substrate Conversions in a Continuous Two-stage Fermenter With Cell Recycle Using Different Kinetic Models

The steady-state performance of a two-stage recycle fermenter with two different types (I and II) of configurations for staging was investigated numerically for the continuous production of lactic acid. In Type I the bleed broth withdrawn from the first stage is supplied to the second fermenter, and in Type II both filtrate and bleed broth from the first stage are introduced to the second stage. Using four different kinetic models taken from the literature, the effects of operating parameters on the overall lactic acid productivities and the overall substrate conversions are examined. At moderate conversions, productivities for Type I operation are found to be higher than those for Type II and for the single-stage system. In the case of high conversions close to complete consumption, Type II operation is more efficient than the Type I and single-stage systems. For 99% conversion and 40 kg m^-3 substrate feed concentration, productivities for Type II are predicted to be 14-74% higher compared to those for the single-stage system at the same bleed ratios.     

Continuous precipitation of calcium sulfate dihydrate from waste sulfuric acid and lime

Precipitation of calcium sulfate dihydrate, gypsum, from (i) a pure sulfuric acid/lime suspension and (ii) a waste sulfuric acid/lime suspension in a continuous pilot plant in the temperature range from 40 °C to 80 °C was studied. It was observed that in the case of waste sulfuric acid with a high content of Mg²⁺ and Fe²⁺ ions, several hours after the beginning of the precipitation, partial dissolution of the product and modification of the crystals from needle‐ and plate‐like to agglomerated structures occurred. It is suggested that the secondary changes occur due to the increased concentration of Mg²⁺ and Fe²⁺ ions in the reactor. Below 60 °C, and above 70 °C plate‐like and needle‐like single crystals respectively were formed. The mean size (d₅₀) of the crystals was found to increase with increasing temperature and decrease with the initial concentration of lime. Gypsum produced between 70 °C and 80 °C is suitable for further processing for construction plaster. In a precipitation process with pure sulfuric acid only single perfect needle‐like crystals occurred. Copyright © 2005 Society of Chemical Industry     

Rate of ammonia oxidation in a synthetic saline wastewater by a nitrifying mixed‐culture

Most of the kinetic studies on nitrification have been performed in diluted salts medium. In this work, the ammonia oxidation rate (AOR) was determined by respirometry at different ammonia (0.01 and 33.5 mg N‐NH₃ L^?1), nitrite (0–450 mg N‐NO₂^? L^?1) and nitrate (0 and 275 mg N‐NO₃^? L^?1) concentrations in a saline medium at 30 °C and pH 7.5. Sodium azide was used to uncouple the ammonia and nitrite oxidation, so as to measure independently the AOR. It was determined that ammonia causes substrate inhibition and that nitrite and nitrate exhibit product inhibition upon the AOR. The effects of ammonia, nitrite and nitrate were represented by the Andrews equation (maximal ammonia oxidation rate, r_AOMAX, = 43.2 [mg N‐NH₃ (g VSS_AO h)^?1]; half saturation constant, K_SAO, = 0.11 mg N‐NH₃ L^?1; inhibition constant K_IAO, = 7.65 mg N‐NH₃ L^?1), by the non‐competitive inhibition model (inhibition constant, K_INI, = 176 mg N‐NO₂^? L^?1) and by the partially competitive inhibition model (inhibition constant, K_INA, = 3.3 mg N‐NO₃^? L^?1; α factor = 0.24), respectively. The r_AOMAX value is smaller, and the K_SAO value larger, than the values reported in diluted salts medium; the K_IAO value is comparable to those reported. Process simulations with the kinetic model in batch nitrifying reactors showed that the inhibitory effects of nitrite and nitrate are significant for initial ammonia concentrations larger than 100 mg N‐NH₄⁺ L^?1. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of an interpenetrating polymer network composed of poly(methacrylic acid) and poly(vinyl alcohol)

Temperature and pH‐responsive interpenetrating polymer network (IPN) hydrogels, constructed with poly(methacrylic acid) (PMAA) and poly(vinyl alcohol) (PVA), by a sequential IPN method, were studied. The characterization of IPN hydrogels was investigated by Fourier‐transform infrared spectroscopy, differential scanning calorimetry (DSC) and swelling under various conditions. The IPN hydrogels exhibited relatively high swelling ratios, in the range 230–380 %, at 25 °C. The swelling ratios of the PMAA/PVA IPN hydrogels were pH and temperature dependent. DSC was used for the quantitative determination of the amounts of freezing and non‐freezing water. The amount of free water increased with increasing PMAA content in the IPN hydrogels. Copyright © 2004 Society of Chemical Industry     

高压脉冲放电处理含氰废水的影响因素探讨

焦化废水中含有大量的氰化物,必须采取有效措施进行去除,传统去除方法运行成本高、操作复杂。提出了用高压毫微秒脉冲产生的非平衡等离子体处理含氰废水的方法,对其影响因素pH值、放电时间、气流量、放电条件等进行了大量的实验研究,结果表明:溶液初始pH值为9.09,放电2 h,放电电压46 kV时氰化物的去除率最高可达93.2%,氰化物质量浓度可降至0.26 mg/L。实验对比了放电与不放电氰化物的去除效果:相同条件下放电后氰化物的去除率大大提高,为焦化废水中氰化物的去除提出了一种新的方法。