The influence of degree of substitution on blend miscibility and biodegradation of cellulose acetate blends

In this account, we report our findings on blends of cellulose acetate having a degree of substitution (DS) of 2.49 (CA2.5) with a cellulose acetate having a DS of 2.06 (CA2.0). This blend system was examined over the composition range of 0–100% CA2.0 employing both solvent casting of films (no plasticizer) and thermal processing (melt-compressed films and injection molding) using poly(ethylene glycol) as a common plasticizer. All thermally processed blends were optically clear and showed no loss in optical quality after storage for several months. Thermal analysis and measurement of physical properties indicate that blends in the middle composition range are partially miscible, while those at the ends of the composition range are miscible. We suggest that the miscibility of these cellulose acetate blends is influenced primarily by the monomer composition of the copolymers. Bench-scale simulated municipal composting confirmed the biodestructability of these blends and indicated that incorporation of a plasticizer accelerated the composting rates of the blends.In vitro aerobic biodegradation testing involving radiochemical labeling conclusively demonstrated that both the lower DS CA2.0 and the plasticizer significantly enhanced the biodegradation of the more highly substituted CA2.5.While this work was in progress, Robert Gardner was struck with cancer and died on June 6, 1995. This paper is dedicated to his memory and to his contributions as a friend and colleague.     

Production of hydrogen by steam gasification of dehydrochlorinated poly(vinyl chloride) or activated carbon in the presence of various alkali compounds

Steam gasification of dehydrochlorinated poly(vinyl chloride) (PVC) or activated carbon was carried out in the presence of various alkali compounds at 3.0 MPa and 560°C–660°C in a batch reactor or in a semi-batch reactor with a flow of nitrogen and steam. Hydrogen and sodium carbonate were the main products, and methane and carbon dioxide were the minor products. Yields of hydrogen were high in the presence of sodium hydroxide and potassium hydroxide. The acceleration effect of the alkali compounds on the gasification reaction was as follows: KOH > NaOH > Ca(OH)₂ > Na₂CO₃. The rate of gasification increased with increasing partial steam pressure and NaOH/C molar ratio. However, the rate became saturated at a molar ratio of NaOH/C greater than 2.0.     

Effect of environmental parameters on the degradability of polymer films in laboratory-scale composting reactors

Previous research in our laboratory reported a convenient laboratory-scale composting test method to study the weight loss of polymer films in aerobic thermophilic (53°C) reactors maintained at a 60% moisture content. The laboratory-scale compost reactors contained the following synthetic compost mixture (percentage on dry-weight basis): tree leaves (45.0), shredded paper (16.5), food (6.7), meat (5.8), cow manure (17.5), sawdust (1.9), aluminum and steel shavings (2.4), glass beads (1.3), urea (1.9), and a compost seed (1.0) which is designated Mix-1 in this work. To simplify the laboratory-scale compost weight loss test method and better understand how compost mixture compositions and environmental parameters affect the rate of plastic degradation, a systematic variation of the synthetic mixture composition as well as the moisture content was carried out. Cellulose acetate (CA) with a degree of substitution (DS) value of 1.7 and cellophane films were chosen as test polymer substrates for this work. The extent of CA DS-1.7 and cellophane weight loss as a function of the exposure time remained unchanged when the metal and glass components of the mixture were excluded in Mix-2. Further study showed that large variations in the mixture composition such as the replacement of tree leaves, food, meat, and sawdust with steam-exploded wood and alfalfa (forming Mix-C) could be made with little or no change in the time dependence of CA DS-1.7 film weight loss. In contrast, substituting tree leaves, food, meat, cow manure, and sawdust with steam-exploded wood in combination with either Rabbit Choice (Mix-D) or starch and urea (Mix-E) resulted in a significant time increase (from 7 to 12 days) for the complete disappearance of CA DS-1.7 films. Interestingly, in this work no direct correlation was observed between the C/N ratio (which ranged from 13.9 to 61.4) and the CA DS-1.7 film weight loss. Decreasing moisture contents of the compost Mix-2 from 60 and 50 and 40% resulted in dramatic changes in polymer degradation such that CA DS-1.7 showed an increase in the time period for a complete disappearance of polymer films from 6 to 16 and 30 days, respectively.Guest Editor: Dr. Graham Swift, Rohm & Haas.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

降水中甲酸、乙酸和草酸的离子色谱法测定及样品保存研究

甲酸、乙酸和草酸是降水中有机酸的主要成分。研究选用离子色谱法同时测定降水中的甲酸、乙酸和草酸,并对降水样品中3种有机酸的保存条件进行了研究。优化后的色谱条件为4. 0 mmol/L Na_2CO_3和1. 2 mmol/L NaHCO_3混合淋洗液,淋洗液流速为1. 0 m L/min,进样体积为200μL,电导池温度为30℃,柱温为室温。甲酸、乙酸和草酸的检出限分别为0. 002、0. 005、0. 005 mg/L,实际降水样品测定时平行样的相对标准偏差为1. 4%～12%,加标回收率为95%～118%。样品采集后需尽快用0. 45μm聚醚砜微孔滤膜过滤,4℃以下冷藏密封保存,2 d内测定。若用氢氧化钠溶液调节p H至8～10,样品可保存7 d。     

Oxidation inhibition of sulfite in dual alkali FGD system

A laboratory-scale well-mixed thermostatic reactor with continuously blasting air was used to investigate the oxidation inhibition of sulfite in dual alkali flue gas desulfurization （FGD） system. The effects of operating parameters such as pH value and catalyst concentration on the oxidation were studied. Sodium thiosulfate was used in the system, and was found that it significantly inhabited the sulfite oxidation. In the absence of catalyst, sodium thiosulfate at 12.67 mmol/L had an inhibition efficiency of approximately 98%. While in the presence of catalyst, sodium thiosulfate at 26.72 mmol/L had an inhibition efficiency less than 85.0%. The oxidation reaction order of sulfite in the sodium thiosulfate was determined to be -1.90 and 4）.55 in the absence and presence of the catalyst, respectively. Apparent activation energy of oxidation inhibition was calculated to be 53.9 kJ/mol. Pilot tests showed that the consumption rate of thiosulfate agreed well with the laboratory-scale experimental results.     

Polymer Mineralization in Soils: Effects of Cold Storage on Microbial Populations and Biodegradation Potential

Soil retrieval, processing and storage procedures can have a profound effect on soil microorganisms. In particular, changes in soil microbial populations may adversely affect the biological activity of a soil and drastically alter the soil's potential to mineralize added substrates. The effects of cold storage on the biodegradation of a series of test polymers was investigated using two soils—a synthetic soil mix (SM-L8) and a field soil (Bridgehampton silt loam) from Rhode Island (RI-1). Biodegradation tests were conducted using freshly prepared/collected soil and again following storage at 4°C for 3 to 8 months. Prior to each biodegradation test, the soils were incubated at 60% water-holding capacity (WHC) and 25°C to rejuvenate the microbial populations; the soils were incubated for periods of 48 h (freshly collected soil) or 25 days (soils stored at 4°C). Soil microbial populations were assessed by enumerating different segments of the population on agar plates containing different selective media. Mineralization of the test polymers (cellulose, poly-3-hydroxybutyrate, and starch acetate, d.s. 1.5) was monitored using standard respirometric techniques. Our results demonstrated that cold storage had a generally negative effect on the soil microbial populations themselves but that its effect on the capacity of the soil microorganisms to degrade the test polymers varied between soils and polymer type. Whereas cold storage resulted in dramatic shifts in the community structure of the soil microbial populations, substantial restoration of these populations was possible by first conditioning the soils at 60% WHC and ambient temperatures for 25 days. Likewise, although the effects of cold storage on polymer mineralization varied with the test polymer and soil, these effects could be largely offset by including an initial 25-day stabilization period in the test.     

三油酸甘油酯-醋酸纤维素复合膜萃取水体中痕量有机氯农药的研究

以三油酸甘油酯-醋酸纤维素复合膜(TECAM)萃取作为监测水体中痕量有机氯农药的方法．探讨分析过程中的影响因素和优化条件,结果表明,膜萃取分析方法对17种有机氯农药的平均加标回收率为53％-111％,对强疏水性污染物表现出较高的回收率．利用该方法在南方某自来水厂各工艺段水体中检测出了滴滴涕及其代谢产物、六六六等五种有机氯农药．     

COD组分分析的实验条件及结果可靠性分析

本研究尝试用SF(OURmax/OURen)代替S(0)/X(0)来作为呼吸法确定COD组分最优实验条件的参数,从而简化测量过程且可实现自动化操作.另外由生长消耗COD与生物量的比值来判断测量结果的可靠性.结果表明,获得可靠的RBCOD组分分析结果的实验条件为:1对于易生物降解含量较高的水质(如由乙酸钠配制的污水),SF在2.8~5.3范围内,生长消耗COD与生物量比值在30%以内;2对于易生物降解和难生物降解物质适中的水质(如典型生活污水),SF应在5.8~6.4左右,生长消耗COD与生物量比值在30%以内;3而对于含有大量难生物降解物质的工业废水(垃圾渗滤液),SF在15以下,且生长消耗COD与生物量的比值在40%以内.由此可见,采用呼吸法确定COD组分,其最优条件SF范围随碳源的复杂程度的上升而上升.     

氯化钠/纳米疏水二氧化硅超细干粉制备及灭火性能研究

选用氯化钠为基体制备金属火灾超细干粉灭火剂。应用反溶剂法对其改性,使纳米疏水二氧化硅吸附在氯化钠晶体表面,其中分散剂为PEG-1000。结果表明,纳米疏水二氧化硅的添加有利于细化氯化钠颗粒,但过量的添加会起反作用,最佳用量为3 wt%左右,平均粒径为2.18μm。镁片灭火实验证明超细复合干粉的灭火性能明显好于传统氯化钠灭火剂(商用D类灭火剂),纳米疏水二氧化硅最佳添加量为3 wt%,此时灭火时间仅需传统灭火剂的一半。最后利用FDS5.0模拟干粉颗粒与燃烧火焰作用过程,模拟结果表明干粉覆盖对火焰具有一定的抑制效果,并分析了复合干粉灭火机理。     

电子供体对地下水中高氯酸盐生物去除的影响研究

通过静态实验,考察了电子供体类型及用量对厌氧条件下微生物去除地下水中高氯酸盐的影响.结果表明,电子供体醋酸盐和H₂的加入,可以明显提高ClO₄^-的去除率,驯化后的微生物去除ClO₄^-的速率比未加入电子供体时提高约1.4~3倍.Monod动态模型能很好地拟合两种电子供体环境下ClO₄^-的微生物去除过程,分别以醋酸盐和H₂作为电子供体时,基质半饱和常数K_s为12.6 mg·L^-1和2.2 mg·L^-1,最大比基质消耗速率V_m为0.45 d^-1和0.08 d^-1.动力学参数表明,本实验条件下,异养型混合菌去除ClO₄^-的效果明显优于自养型混合菌;在少数受高浓度ClO₄^-污染的地下水环境中,为了提高ClO₄^-的去除速率只有通过增加菌体浓度或提高微生物酶的活性来实现.随着电子供体醋酸盐用量增加,ClO₄^-的(比)消耗速率逐渐增大.当初始CH₃COO^-与ClO₄^-的比例为3.80 mg(COD)/mg(ClO₄^-)时,比消耗速率v最大(0.27 d^-1).