我国石化行业温室气体排放源识别

依据《2006年IPCC（政府间气候变化专门委员会）国家温室气体清单指南》及《温室气体协议》,对我国石化行业温室气体排放源进行了识别。结合温室气体排放源范围的两种划分方法,为石化行业的主要生产部门--油气开采、原油炼制与加工、石化原料与制品制造编制了初步的温室气体排放源清单,并简要介绍了石化行业温室气体排放量的核算方法,为石化行业温室气体排放量核算体系的构建奠定基础。     

油品储运行业挥发性有机物排放控制技术评估

分析了我国油品储运行业的VOCs排放环节和特点。选取燃烧法、吸收法、吸附法、冷凝法、膜分离法等VOCs排放末端控制技术作为研究对象,介绍了各方法的原理和适用条件。建立了包括环境性能、技术性能、经济性能3方面共10项指标的综合评价指标体系。采用模糊评价方法分析了油品储运行业VOCs排放末端控制备选技术的综合性能。结果表明,冷凝法和膜分离法具有良好的综合性能,是油品储运行业VOCs排放的最佳末端控制技术。     

石化企业挥发性有机物排放量核算常见问题分析

石化行业是我国工业源挥发性有机物（VOCs）排放管控的重点行业,也是VOCs排放量核算最为复杂的行业。本文梳理了石化行业12类排放源项VOCs排放核算方法的适用条件,依据广东省重点石化企业VOCs治理实施情况评估所掌握的情况,以实例对比分析的方式,总结了企业在实际VOCs排放量核算方面存在的问题,并就如何提高VOCs排放量核算的真实性和准确性提出了相关建议。     

试点VOCs排污收费对于大气污染防治工作有何意义？

财政部、国家发展改革委、环境保护部前不久印发了《挥发性有机物排污收费试点办法》（以下简称《办法》）,提出从今年10月1日起对石油化工行业和包装印刷行业征收挥发性有机物（以下简称VOCs）排污费。此次VOCs试点收费对于大气污染防治工作有何意义？华南理工大学环境与能源学院院长叶代启教授认为《办法》的实施完善了VOCs防控体系,填补了多年来未能从国家层面利用经济手段控制VOCs的空白。目前,我国VOCs排放量已位居世界第一位。我国VOCs的排放源主要有工业源、民用源、交通源和农业源。     

石化行业的VOCs排放控制管理

概述了我国挥发性有机化合物（VOCs）的排放情况。介绍了国内外VOCs的管理现状。分析了国内石化行业VOCs排放控制管理中存在的主要问题以及污染物排放过程的类别。提出了明确定义、制定相关标准、完善分类管理体系、研究最佳的可行性控制技术等加强VOCs排放控制管理的对策和建议。     

焦化生产中VOCs排放特征分析及精准治污建议

选取我国北方某焦化生产集中区内两家典型焦化企业进行了VOCs采样分析,利用最大增量反应活性法计算了臭氧生成潜势(OFP)贡献占比,并据此提出针对性治理建议.有组织排放口、无组织排放单元及区域环境测得的VOCs组分依次为55、27、21种,分为单环芳烃、含氧VOCs、多环芳烃、烷烃、烯烃、卤代烃及其他共7大类别,以萘、茚...     

石化企业内浮顶罐挥发性有机物排放量核算与影响因素分析

以某石化企业内浮顶罐为实例,根据AP-42公式,从浮顶罐结构、油品性质、周转量及环境因素4个方面对内浮顶储罐的VOCs排放进行研究。计算结果表明：浮盘缝隙损耗和挂壁损耗是内浮顶储罐VOCs排放的主要来源;浮盘构造、周转量、罐壁锈蚀程度及边缘密封形式是内浮顶罐VOCs损耗的主要影响因素;罐漆颜色、储罐直径、油品种类及储液温度为次要影响因素;固定顶支撑柱数量、环境湿度及环境风速对储罐挥发损耗的影响较小。针对分析结果,提出降低储罐VOCs挥发损耗的措施。     

现代煤化工行业挥发性有机物管控问题分析

分析了现代煤化工行业存在的VOCs管控相关产业政策、标准要求与产业发展不匹配,泄漏检测与修复(LDAR)工作推进缓慢、VOCs排放量核算不准确和VOCs治理工作难开展等问题。提出如下建议:在LDAR工作方面,重新认识LDAR工作、源头控制和增加泄漏情况数据统计环节;在VOCs排放量核算方面,全面识别企业VOCs排放源项、准确收集VOCs核算所需参数和控制采样分析误差;在VOCs治理方面,尽快制定VOCs排放有关标准、识别VOCs管控重点和开发VOCs过程及末端治理技术。     

油田污油池VOCs源强核算

以油田两处污油池为研究对象开展VOCs浓度监测,结合社会科学统计软件包（Statistical Package for the Social Science,SPSS）的Pearson相关分析对监测数据进行了分析;并利用地面浓度反推法核算污油池的VOCs排放源强,将结果与排放系数法计算值进行对比;最后对下风向不同距离采样线监测数据反推源强逐渐减小的原因进行了讨论。结果表明：污油池B各采样线监测数据间的相关性好,反推出的源强较为准确,VOCs年排放量为17.6 t/a;而污油池A监测数据间的相关性不佳,可能是由于其他无组织排放源相距较近影响所致,不适合直接应用地面浓度反推法计算其源强,需要结合其他排放源的情况进行修正。     

我国电石法生产聚氯乙烯行业汞排放清单

提出了我国电石法聚氯乙烯(PVC)生产全生命周期汞排放清单的计算方法。采用低汞触媒有盐酸脱吸工艺、高汞触媒有盐酸脱吸工艺、高汞触媒无盐酸脱吸工艺的汞输入因子分别为0.045 g/kt、0.091 g/kt和0.122 g/kt,回收产品的汞输出分布因子分别为95.37%、81.97%和97.18%。估算得到:2010年我国电石法PVC生产汞输入量792.8~814.8 t;回收的产品汞705.9~724.4 t,通过大气无组织排放、管道残留以及其他未知途径汞排放79.6~82.8 t;废水汞排放1.3 t;固体废物汞排放3.6~3.7 t;废酸汞排放2.5~2.6 t。回收的产品汞是汞输出的主要途径。     

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.     

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.     

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.     

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.     

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%。     

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。     

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.     

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.