不同类型清水剂处理油田含聚污水的效果对比

考察了阳离子型CWC-14、非离子型NQS-01和阴离子型AQS-08 3类清水剂对油田含聚污水的处理效果,对比了它们的作用特点和絮体性能。实验结果表明:在清水剂加入量350 mg/L、处理温度65℃、搅拌转速300 r/min、搅拌时间5 min的条件下,CWC-14、NQS-01和AQS-08对含聚污水的除油率分别为98.8%、98.0%和99.4%;NQS-01受处理温度、搅拌条件影响较大;CWC-14受污水中聚合物质量浓度影响最大。清水剂的絮体特点与其作用机理有关,CWC-14的絮凝速率最快,起效时间最短,絮体呈黏性大块状;NQS-01的絮凝速率最慢,起效时间最长,絮体呈浮油状;AQS-08的絮凝速率和起效时间适中,絮体呈松散状、流动性好。对比结果表明,非阳离子型清水剂可有效避免油田含聚污水处理过程中的黏性油泥问题。     

双亲型清水剂处理油田含聚污水

考察了双亲型清水剂QS-03对油田含聚污水处理效果的影响因素,并对其作用机理进行了分析。实验结果表明:当清水剂QS-03的亲水性与亲油性功能基团的摩尔比为2∶1、清水剂加入量大于等于200 mg/L时,处理后污水澄清透明,污水含油量由4 540 mg/L大幅降至26~45 mg/L;在处理温度为50~80℃和污水含油量为3 200~5 800 mg/L的范围内,清水剂QS-03均表现出良好的清水效果,生成的絮体呈松散状,具有良好的流动性。机理分析结果表明,双亲型清水剂QS-03可有效破坏油-水界面双电层、降低界面膜强度,并且与污水中阴离子聚合物的相互作用大幅减弱,因而在高效清水除油的同时可有效避免含聚污水处理中的黏性"含聚油泥"问题。     

电化学脱稳技术处理油田含聚污水

采用"电化学除油器—斜板除油器—核桃壳过滤器"模拟装置处理模拟含聚采油污水,考察了有/无清水剂加入条件下含聚污水的处理效果,并对电化学除油机理进行了分析。实验结果表明:各级处理单元的除油率与电化学处理时间成正比,不加入清水剂、电化学处理40 min时,各级处理单元的除油率均超过92%;在电化学除油器前加入清水剂100 mg/L、电化学处理20 min时,各级处理单元的除油率分别为98.8%~99.4%,处理后污水含油量小于30 mg/L,处理效果优于在斜板除油器前加入清水剂;电化学处理与清水剂处理有良好的协同除油效果,可大幅降低清水剂用量。机理分析结果表明,电化学作用主要使吸附于油-水界面的产出聚合物降解、脱稳,实现了对油-水界面膜强度和界面电荷的有效破坏,除油效果优异且处理后的絮体松散、无黏附性。     

两性聚丙烯酰胺的制备及其絮凝性能

开发了一种对非离子聚丙烯酰胺进行改性制备两性聚丙烯酰胺(APAM)絮凝剂的新方法。以硅藻土悬浮液为絮凝对象,考察了改性反应中影响APAM絮凝效果的因素。结果表明,采用无水乙酸与三甲胺、环氧氯丙烷合成季胺盐型阳离子剂的方法优于采用盐酸的方法;在10mL质量分数为10%、相对分子质量为3×106的非离子型聚丙烯酰胺水溶液中加入8mL浓度为2.6mol/L的阳离子剂,同时控制V(NaOH)∶V(NaClO)为0.44,改性得到的APAM絮凝性能最佳,在pH3～9的较宽范围内对硅藻土悬浮液有较好的絮凝效果。在pH为3、APAM加入量为1.8mg/L时,硅藻土悬浮液的絮凝率可达100%。     

阳离子乳液型清水剂的制备及其在油田污水处理中的应用

以二甲基二烯丙基氯化铵(DMDAAC)为阳离子单体,苯乙烯、丙烯酸丁酯为疏水单体,十六烷基三甲基溴化铵和聚氧乙烯辛基苯酚醚-10(OP-10)为乳化剂,过硫酸铵为引发剂,采用乳液聚合法制备乳液型清水剂。优化了制备清水剂的工艺条件,考察了清水剂对油田污水的处理效果。实验结果表明:在x(DMDAAC)小于20%、n(苯乙烯)∶n(丙烯酸丁酯)为2∶1、乳化剂占单体质量分数为5%、引发剂占单体质量分数为0.5%的优化条件下可制备形成稳定的阳离子乳液清水剂;分子量越大、x(DMDAAC)越大,清水剂的除油效果越好;在x(DMDAAC)为20%、其他最优条件不变的情况下制备的Q20清水剂使用浓度为30 mg/L时可使油田污水含油量从295 mg/L降至13 mg/L。自制清水剂的除油效果好于市售清水剂。     

阳离子型聚丙烯酰胺絮凝剂的开发与煤气化黑水处理

煤气化过程产生的黑水通常采用絮凝处理去除悬浮物及部分有机物后循环使用。以丙烯酰氧乙基三甲基氯化铵为阳离子单体,以氧化还原类和偶氮类引发剂为复合引发剂,采用水溶液自由基共聚法制备了一种适用于黑水絮凝处理的阳离子型聚丙烯酰胺。实验结果表明：引发温度为15~20 ℃时,聚合反应较为平稳,1 h后聚合反应结束,于60~80 ℃干燥,得到产品相对分子质量较高,达（734~1 086）×10⁴;采用该絮凝剂絮凝处理黑水时,絮体大、沉降速率快,絮凝沉降效果佳;在煤气化装置黑水工况温度下,絮凝剂投加量为3 mg/L时,黑水中悬浮物质量浓度可从114 mg/L降至30 mg/L以下,满足现场使用要求。     

TiO2气溶胶快速去除空气中的芥子气模拟剂

在自制反应器内,通过喷射法将纳米TiO_2分散成气溶胶形式,用以降解空气中的芥子气模拟剂二乙基硫醚(DES)。利用自行设计的一套气溶胶沉降行为评价装置,对TiO_2气溶胶的释放条件进行了优化。系统研究了相对湿度、反应温度、光强、催化剂加入量、反应物浓度等因素对DES降解速率和彻底矿化速率的影响。结果表明:TiO_2气溶胶对2.80 mg/L(近似芥子气快速致死浓度)DES降解的半衰期由涂覆型TiO_2的34.5 min缩短至8.5 min;TiO_2气溶胶光催化降解DES的最佳相对湿度为35%,此时CO_2最快生成速率可达34.64μg/(L·min),150 min内彻底矿化比例达66.1%;对于1.5 L反应器,催化剂加入量为30 mg时降解DES的量效比达到最佳状态;TiO_2气溶胶光催化适用于含低浓度DES空气的快速净化。     

采用微絮凝—过滤工艺处理油田采出水

采用微絮凝—过滤工艺处理油田采出水,筛选出最佳絮凝剂并确定了加入量,研究了微絮凝—过滤工艺现场处理油田采出水的效果。实验结果表明:在进水中ρ(油)和SS分别为60 mg/L和25 mg/L的条件下,出水ρ(油)和SS分别为1 mg/L和3 mg/L,去除率分别达到99%和95%;二级过滤出水达到油田回注水标准;应用微絮凝—过滤工艺效果明显。     

废弃饱和盐水钻井液的固液分离

采用化学破胶脱稳和压滤机械分离的化学强化固液分离技术处理江汉油田废弃饱和盐水钻井液(简称废钻井液).最佳固液分离工艺为:调节废钻井液的pH为6.5左右,先加入无机破胶剂(HWJ),HWJ的加入量为15 000 mg/L,以400 r/min的转速搅拌3 min,稀释1倍后,再加入有机破胶剂(HYJ),HYJ的加入量为300 mg/L,以120 r/min的转速搅拌5min.固液分离结果表明,分离后出水率达68.2%,而泥饼湿含量只有55.8%,废钻井液的COD由67 886.8 mg/L降至8 898.9 mg/L.     

改性蒙脱石-壳聚糖絮凝剂处理造纸废水

将改性蒙脱石(MM)和壳聚糖(CTS)制成MM-CTS新型复合絮凝剂,对造纸废水进行絮凝处理.实验结果表明,当MM-CTS的加入量为0.10 mg/L、m(MM):m(CTS):40:1、pH=8.0、搅拌速率为140 r/min、沉降时间为15 min时,絮凝效果最佳,对造纸废水的COD去除率达66.35%,较传统絮凝剂的COD去除率提高了13.7%,药剂成本下降11.1%,具有明显的经济与环境效益.     

Determination of the Burning Characteristics of a Slick of Oil on Water

The burning rate of a slick of oil on a water bed is characterized by three distinct processes, ignition, flame spread and burning rate. Although all three processes are important, ignition and burning rate are critical. The former, because it defines the potential to burn and the latter because of the inherent possibility of boilover. Burning rate is calculated by a simple expression derived from a one-dimensional heat conduction equation. Heat feedback from the flame to the surface is assumed to be a constant fraction of the total energy released by the combustion reaction. The constant fraction (χ) is named the burning efficiency and represents an important tool in assessing the potential of in situ burning as a counter-measure to an oil spill. By matching the characteristic thermal penetration length scale for the fuel/water system and an equivalent single layer system, a combined thermal diffusivity can be calculated and used to obtain an analytical solution for the burning rate. Theoretical expressions were correlated with crude oil and heating oil, for a number of pool diameters and initial fuel layer thickness. Experiments were also conducted with emulsified and weathered crude oil. The simple analytical expression describes well the effects of pool diameter and initial fuel layer thickness permitting a better observation of the effects of weathering, emulsification and net heat feedback to the fuel surface. Experiments showed that only a small fraction of the heat released by the flame is retained by the fuel layer and water bed (of the order of 1%). Ignition has been studied to provide a tool that will serve to assess a fuels ease to ignite under conditions that are representative of oil spills. Two different techniques are used, piloted ignition when the fuel is exposed to a radiant heat flux and flash point as measured by the ASTM D56 Tag Closed Cup Test. Two different crude oils were used for these experiments, ANS and Cook Inlet. Crude oils were tested in their natural state and at different levels of weathering, showing that piloted ignition and flash point are strong functions of weathering level.     

Review of the kinetics of alkaline degradation of cellulose in view of its relevance for safety assessment of radioactive waste repositories

The degradation of cellulose (a substantial component of low- and intermediate-level radioactive waste) under alkaline conditions occurs via two main processes: a peeling-off reaction and a basecatalyzed cleavage of glycosidic bonds (hydrolysis). Both processes show pseudo-first-order kinetics. At ambient temperature, the peeling-off process is the dominant degradation mechanism, resulting in the formation of mainly isosaccharinic acid. The degradation depends strongly on the degree of polymerization (DP) and on the number of reducing end groups present in cellulose. Beyond pH 12.5, the OH^- concentration has only a minor effect on the degradation rate. It was estimated that under repository conditions (alkaline environment, pH 13.3-12.5) about 10% of the cellulosic materials (average DP = 1000-2000) will degrade in the first stage (up to 10⁵ years) by the peeling-off reaction and will cause an ingrowth of isosaccharinic acid in the interstitial cement pore water. In the second stage (10⁵-10⁶ years), alkaline hydrolysis will control the further degradation of the cellulose. The potential role of microorganisms in the degradation of cellulose under alkaline conditions could not be evaluated. Proper assessment of the effect of cellulose degradation on the mobilization of radionuclides basically requires knowing the concentration of isosaccharinic acid in the pore water. This concentration, however, depends on several factors such as the stability of ISA under alkaline conditions, sorption of ISA on cement, formation of sparingly soluble ISA-salts, etc. A discussion of all the relevant processes involved, however, is far beyond the scope of the presented overview.     

Study of Aging Characteristics of Ternary Blends of Polyethylenes—II

Six film samples of low-density polypropylene (LDPE)/linear LDPE (LLDPE)/high-density polypropylene (HDPE) with varying ratios of LDPE (20–45 ... wt%) and LLDPE (25–50 wt%) having a fixed amount of HDPE at 30 wt% were prepared by blown film extrusion technique. The samples were aged at four different temperatures, 55°, 70°, 85°, and 100°C, for four different time periods in the interval of between 150 hours and up to 600 hours. The change in the structure of various constituents and the formation of various oxygenated (peroxy and hydroperoxy) and unsaturated groups during thermo-oxidative degradation was discussed by infrared spectroscopy. The visiosity-average molecular weight was found to have decreased slowly in the initial aging hours and temperatures, whereas it decreased by 10% with its previous value tensile strength that is, 100°C when aged for 600 hours. The tensile strength of the sample first increased by 67% at 55°C and 89% at 70°C up to 450 hours, whereas the values increased by 52.5% at 85°C and 33.9% at 100°C when aged for 150 hours and then decreased. The percentage elongation at break increased by 2.7% at 55°C and 10.7% at 70°C for 150 and 300 hours of aging, respectively, whereas the percentage decreased when aged at 85°C and 100°C for up to 600 hours of aging. The values of gel content (percent) increased and initial degradation temperature decreased with aging time and temperature.     

Calculation of carbon balances for evaluation of the biodegradability of polymers

Establishing carbon balances has been proven to be an applicable and powerful tool in testing biodegradability of polymers. In controlled degradation tests at a 4-L scale with the model polymer poly(-hydroxybutyrate) (PHB), it was shown that the degree of degradation could not be determined with satisfactory accuracy from CO₂ release alone. Instead, the course of degradation was characterized by means of establishing carbon balances for the degradation of PHB withAcidovorax facilis and a mixed culture derived from compost. Different analytical methods for determining the different carbon fractions were adapted to the particular test conditions and compared. Quantitative determination of biomass and residual polymer were the main problems in establishing carbon balances. Amounts of biomass derived from protein measurements depend strongly on assumptions of the protein content of the biomass. Selective oxidation of biomass with hypochlorite was used as alternative, but here problems arose from insoluble metabolic products. Determination of soluble components with the method of chemical oxygen demand (COD) also includes empirical assumptions but seems acceptable if the dissolved carbon fraction is in the range of some 10% total carbon. Results confirm both analytical assays and theoretical approaches, in ending up at values very close to 100%, within an acceptable standard deviation range under test conditions comparable to standard test practice.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

鼓泡式反应器高径比对氨法烟气脱碳性能的影响

以N2和CO2混合气模拟燃烧烟气,研究了鼓泡反应器的高径比以及反应条件对氨法烟气脱碳性能的影响。实验结果表明:在相同高径比的条件下,CO2吸收率随氨水质量分数的增加、反应温度的升高而逐渐增大,随进气CO2体积分数和模拟烟气流量的增加而逐渐减小;CO2吸收率随高径比的增加而增大,在高径比为3.98、氨水质量分数为28%、进气CO2体积分数为10%、模拟烟气流量为1.0L/min、反应温度为40℃的条件下,CO2吸收率最高可达100%。     

Model of technological alternatives of production of sodium chromate (VI) with the use of chromic wastes

This article presents a mathematical model which describes the sodium chromate (VI) production process with the use of chromic waste as a substitution of natural raw materials. This model is a function of selected process parameters common for all of the examined alternatives and based on equations of material balance. Optimization of the elaborated technological alternatives of the production process with use of recycling of chromic waste has been evaluated by determining the extreme value of the quality indicator WJ. This indicator defines the quantity of waste created in the process. Optimization results enabled the selection of the optimal technological solution from all of the alternatives possible for use in industrial practice. Negative values of the indicator prove that there is the possibility of introducing to the process a larger quantity of waste than the one obtained in the process and transported to the storage heaps.     

化学品生物降解性的评价与预测

介绍了有机化学物质生物降解性的测定方法及其预测方法研究概况，并讨论了生物降解性评价的发展前景。     

Mechanism of Microbial Degradation of Slow-Release Fertilizers

Methyleneureas are condensation products of urea and formaldehyde of different molecular mass and solubility; they are used in large amounts both as resins, binders, and insulating materials for industrial applications, as well as a slow-release nitrogen fertilizer for greens, lawns, or in bioremediation processes. In the present study, the microbial breakdown of these products was investigated. The nitrogen was released as ammonia and urea, and the formaldehyde released immediately oxidized via formiate to carbon dioxide. The enzymatic mechanism of metabolization of methyleneureas was studied in microorganisms isolated from soil, which were able to use these compounds as the sole source of nitrogen for growth. A strain of the Gram-negative bacterium Ralstonia paucula (formerly Alcaligenes sp. CDC group IVc-2) completely degraded methylenediurea and dimethylenetriurea to urea, ammonia, formaldehyde, and carbon dioxide. The enzyme initiating this degradation (methylenediurease) was purified and turned out to be different from the previously described enzyme from Ochrobactrum anthropi with regard to its regulation of expression and physicobiochemical properties. Fungal degradation of methyleneureas may occur via the formation of organic acids, thus leading to a nonenzymatic degradation of methyleneureas, which are unstable under acidic conditions.     

Effect of Degree of Substitution of Octenyl Succinate Starch on Enzymatic Degradation

Octenyl succinate starch of degree of substitution (ds) 0.03, 0.07, and 0.11 was synthesized in an aqueous medium. These compounds were then tested for the susceptibility to enzymatic degradation. The multiple-enzyme regime of -amylase, amyloglucosidase, and pullulanase was chosen for the evaluation. This combination of enzymes had been proven to degrade 99.5% of unmodified starch to glucose and hence was chosen for this study. It was found that even small amounts of subsituent caused a considerable decrease in the extent of degradation. The net extent of degradation decreased with increasing ds. Surprisingly, the amount of glucose from all three substituted substrates was quite similar, suggesting the effect small amounts of subtituent had on the enzymatic activity.     

Structure-biodegradation relationships of polymeric materials. 1. Effect of degree of oxidation on biodegradability of carbohydrate polymers

The biodegradability of oxidized starch and inulin has been studied in relation to the degree of periodate oxidation to dialdehyde derivatives, by measuring oxygen consumption and mineralization to carbon dioxide. A higher degree of oxidation of dialdehyde starch and dialdchyde inulin results in a lower rate at which the polymers are biodegraded. It is demonstrated that the biodegradation rate of dialdehyde inulin derivatives decreases more than that of equivalent starch derivatives. The differences in biodegradation behavior between dialdehyde starch and dialdehyde inulin, resulting from comparable modifications, are discussed in terms of conformational structure.