页岩气压裂返排液处理技术的研究进展

页岩气是一种重要的天然气资源,在其水力压裂开采过程中加入了多种有机添加剂,产生了大量具有高黏度、高COD、高含盐量特性的压裂返排液,常规处理技术难以实现其达标排放或回用。分析了页岩气压裂返排液的组分和特点,归纳总结了成熟的传统处理技术和新型处理技术的特点,提出了优化压裂返排液处理工艺、加强环境信息公开、研发节能环保的新型页岩气压裂技术的未来发展方向,为页岩气压裂返排液无害化、资源化处理技术的研发提供了思路和参考。     

压裂返排液循环使用技术综述

综述了传统处理方法和深度处理方法两大类压裂返排液处理方法的特点和处理效率。介绍了对氧化破胶的压裂返排液和非氧化破胶的压裂返排液进行处理的方法和机理,以及返排液循环使用效果和性能检测的标准。指出研发含有高分子聚合物稠化剂的返排液循环使用工艺、高效便捷的压裂返排液循环使用工艺和新型可循环使用的压裂液体系等将是未来压裂返排液循环使用的发展方向。     

页岩气压裂返排液回用影响因素及回用技术研究

针对压裂返排液中的特征污染物，开展了单因素实验，确定了处理目标；以两口页岩气井的压裂返排液为研究对象开展了单元处理工艺的研究，并进行了现场实验。单因素实验结果表明，影响压裂返排液回用的特征污染物为高价金属离子和SS。采用絮凝—化学澄清工艺处理压裂返排液，对浊度、钙离子、铁离子的去除率分别达到98%、71%、96%以上。压裂返排液经现场处理后，SS从2 400.0 mg/L降至3.4 mg/L，总硬度从1 160 mg/L降至125 mg/L，总铁从35.60 mg/L降至0.28 mg/L，满足NB/T 14003.1—2015要求；用处理出水配制的滑溜水压裂液的性能指标与地表水配制的相当，满足DB61/T 575—2013要求。     

油田压裂返排液处理技术研究进展

分析了油田压裂返排液的组分和特点,归纳总结了成熟的传统压裂返排液处理技术和新型处理技术的优缺点,提出了压裂返排液处理应朝着优化工艺组合、开发高级氧化和电絮凝等新技术、研制撬装处理设备使处理工艺模块化和有效成分回收利用等未来方向发展,为油田压裂返排液无害化、资源化处理技术的研发提供了思路和参考。     

压裂返排液的处理及回用

制备了沸石负载纳米TiO_2催化剂和蒙脱土负载纳米零价铁吸附剂,结合传统处理技术,构建了"絮凝—预氧化(Fenton氧化)—沸石负载纳米TiO_2催化臭氧氧化—蒙脱土载负纳米零价铁吸附"组合工艺,处理压裂返排液,考察了影响COD去除效果的因素。实验结果表明:在催化剂投加量1.0 g/L、臭氧通入时间5 min、吸附剂投加量5.0 g/L、吸附时间4 h的最佳条件下,COD从原水的4 032.60 mg/L降至37.03 mg/L,处理后出水各项指标均达到GB 8978—1996《污水综合排放标准》中的一级标准;80℃下,出水回用配制的压裂液黏度为4.4 mPa·s,高于自来水配制和压裂返排液配制的压裂液,耐温性有一定提升。     

新型三维电化学氧化体系处理压裂返排液

采用不锈钢作阴极、镀钌铱的钛板作阳极、铁碳材料作粒子电极,构建新型三维电化学氧化体系,处理压裂返排液,并通过响应曲面法考察COD去除率和除油率的影响因素。实验结果表明:回归方程的相关系数及校正相关系数均大于0.9,回归方程的线性关系显著;返排液COD去除率和除油率影响因素的大小顺序均为电流电解时间粒子填充比,其中关键因素是电流,电解时间和粒子填充比之间的交互作用具有较大影响;在电解时间为31.8 min、电流为4.4 A、粒子填充比为61.2%的条件下,COD从606.4 mg/L降至68.5 mg/L,含油量从153.7 mg/L降至9.1 mg/L,达到GB 8978—1996《污水综合排放标准》中的一级标准。     

由氨碱法废液直接生产氯化钙的方法

该发明涉及一种由氨碱法废液直接生产氯化钙的方法。该方法是：氨碱法废液经露天蒸发后由二效预热器预热到70℃左右，送入二效加热器，与来自一效分离器的二次蒸汽换热，钙液经二效分离器分离，二次蒸汽进入三效加热器，增浓的钙液进入三效加热器继续蒸发提浓；钙液在三效分离器中汽液分离，产生更高浓度的钙液，二次蒸汽由真空系统抽走，更高浓度的钙液经三效出料泵送至离心机分离盐；除去盐后的钙液通过一效给液泵进入一效加热器，与外供的生蒸汽换热，再经一效分离器进行汽液分离，使钙液浓缩成成品，二次蒸汽进入二效加热器作为其热源。     

苏里格气田压裂返排液的处理及循环利用技术

针对苏里格气田压裂返排液的特点,形成一套以"微生物降解—化学氧化"、"屏蔽-沉淀"、"混凝-沉降"、"交联抑制"为特色的返排液处理技术,处理后水质清澈透明、无异味,满足重复配液需求。开发了一套模块化多功能处理装置,可满足不同的返排液处理需求,灵活方便、可靠性强、效率高,处理能力最高达300m~3/d。该技术已在苏里格区域全面推广应用,取得了良好的社会经济效益。     

国外动态

蒸发—焚烧法降低废水处理费用Chemical Engineering,2 0 0 1,10 8( 6 ) :2 3　　在 2 0 0 1年 5月德国 Düsseldorf举办的环境技术展览会上 ,韩国 Key Engineering公司展出了一种焚烧系统 ,用于处理含低沸点有机化合物或形成共沸点混合物的废水。这类废水的焚烧需要消耗大量的能量 ,因为废水中的化合物不易浓缩。该新方法可将能耗降低 70 %～ 75 %。在该新工艺中 ,废水先用低压蒸汽进行蒸发 ,与1 0 0℃空气混合后进入一个再生式热氧化 ( RTO)装置。有机化合物在 1 2 0 0℃被氧化成二氧化碳和水。由蒸发器排出的非挥发性物质被喷入一个…     

蒸发-焚烧法降低废水处理费用

在2001年5月德国Düsseldorf举办的环境技术展览会上,韩国Key Engineering公司展出了一种焚烧系统,用于处理含低沸点有机化合物或形成共沸点混合物的废水.这类废水的焚烧需要消耗大量的能量,因为废水中的化合物不易浓缩.该新方法可将能耗降低70%～75%. 在该新工艺中,废水先用低压蒸汽进行蒸发,与100℃空气混合后进入一个再生式热氧化( RTO) 装置.有机化合物在1200℃被氧化成二氧化碳和水.由蒸发器排出的非挥发性物质被喷入一个小型焚烧炉,由RTO装置来的热燃烧气燃烧.在RTO装置中,燃烧开始时先由电加热器启动 ,以后整个系统的能量需求就由有机物的燃烧热来提供.废物的分解效率在99%以上. 该法的投资约为常规焚烧炉的一半.第一座处理能力为4 m.t./a的工业装置已在韩国Yosu 运转了2年,处理辛戊二醇生产废水.     

Distribution of Cd,Ck, Pb and Zn in Soil and Vegetation Compartments in Stands of Five Boreal Tree Species in N.E. Sweden

Concentrations and total quantity of cadmium (Cd), cupper (Cu),lead (Pb) and zink (Zn) were determined in biomass and soil compartments in a replicated tree species experiment with 27-yr-old stands growing on former farmland in N.E. Sweden. Sequentialextractions of soil samples were performed in order to estimate the exchangeable and an organically bound fraction of each element. The tree species included were Picea abies (L.)H. Karst., Pinus sylvestris L., Pinus contorta Dougl., Larix sibirica Ledeb., and Betula pendula Roth.Tree species influenced the rate of removal of Cu, Pb and Zn incase of stemwood harvesting, and of Cd, Cu and Zn in the case ofwhole-tree harvesting. B. pendula and P. abies had higher quantities and average concentrations of Zn in the biomass. For all species, >50% of the Zn in the stems was found in the bark. P. abies and L. sibirica had higher quantities of Cu in the biomass than the other species.P. abies and P. contorta had high quantities of Cd inthe biomass in relation to the other species. Branches and stembark contained high concentrations of Cd and Pb in relation to foliage and stemwood. Dead branches had especially high concentrations of Pb. The high accumulation rate of Zn in thebiomass of B. pendula was related to a low exchangeable amount of Zn in the A horizon. In the superficial centimeters ofthe A horizon, a depletion similar to that found for Zn was detected for Cu, whereas for Cd and Pb, no correlations were found between quantities of elements in the trees and element pools in the soil.     

Programs assessing implementation and effectiveness of state forest practice rules and BMPs in the West

The major forest nonpoint source control programs in the West are largely regulatory, either under forest practices acts (California, Idaho, New Mexico, Nevada, Oregon, and Washington) or a streamside management act (Montana). These programs and the specific rules they enforce continue to undergo intensive scrutiny. Still, the questions are the same for these regulatory programs as for states that base nonpoint source control on voluntary BMPs (Arizona, Colorado, Utah, Wyoming). Are the rules or BMPs being applied, and are they effective in reducing nonpoint source pollution to levels that protect beneficial uses of water? The level of debate about forestry in the West has resulted in detailed monitoring and research to answer these questions. In the past, state agencies have assumed levels of BMP compliance based on the percent of operations without enforcement actions. These estimates are being replaced by statistically valid and reproducible monitoring of forest practices rules and BMP compliance levels. BMP effectiveness is being assessed using both qualitative and quantitative methods. This can involve field assessments, process-based research, and control watershed studies. Some trend monitoring is also beginning. With the regional implementation rate for forestry BMPs at about 94% and rising, it is likely that effectiveness testing will continue to be a priority and consume the majority of assessment resources for this region.     

Hysteresis in Reversal of Central European Mountain Lakes from Atmospheric Acidification

Extremely high emissions of S and N compounds in Central Europe (both 280 mmol m^-2 yr^-1) declined by 70and 35%, respectively, during the last decade. Decreaseddeposition rates of SO₄ ^-2, NO₃ ^-, and NH₄ ⁺ in the region paralleled emission declines. The reduction in atmospheric inputs of S and N to mountain ecosystemshas resulted in a pronounced reversal of acidification in the Tatra Mountains and Bohemian Forest lakes. Between the 1987–1990and 1997–1999 periods, concentrations of SO₄ ^-2 and NO₃ ^- decreased (average ± standard deviation) by 22±7 and 12±7 mol L^-1, respectively, in theTatra Mountains, and by 19±7 and 15±10 mol L^-1, respectively, in the Bohemian Forest. Their decrease was compensated in part (1) by a decrease in Ca²⁺ + Mg²⁺ (17±7 mol L^-1) and H⁺ (4±6 mol L^-1), and an increase in HCO₃ ^-(10±10 mol L^-1) in the Tatra Mountains lakes, and (2) by a decrease in Al (7±4 mol L^-1), Ca²⁺ + Mg²⁺ (9±6 mol L^-1), and H⁺ (6±5 mol L^-1), in Bohemian Forest lakes. Despite the rapid decline in lake water concentrations of SO₄ ^-2 and NO₃ ^- in response to reduced S and N emissions, their present concentrations in some lakes are higher than predictionsbased on observed concentrations at comparable emission rates during development of acidification. This hysteresis in chemical reversal from acidification has delayed biological recovery of the lakes. The only unequivocal sign of biological recovery hasbeen observed in erné Lake (Bohemian Forest) where a cladoceran species Ceriodaphnia quadrangular has recentlyreached its pre-acidification abundance.     

Reconstruction of Long-Term Changes in Lake water Chemistry,Zooplankton and Benthos of a Small,Acidified High-Mountain Lake: Magic Modelling and Palaeolimnogical Analysis

Starolesnianske pleso is a small and shallow acid lake in the High Tatra Mountains, situated at 2000 m above sea level, on granitic bedrock, with sparse and thin soil cover. When detailed measurements began in the 1980s Starolesnianske pleso had pH below 5 and only one species of cladoceran zooplankton, the ubiquitous Chydorus sphaericusPalaeolimnological investigations show changes in cladoceran zooplankton and chironomid zoobenthic assemblages since about 1920 and a major change in 1970–1980. The dynamic acidification model MAGIC was used to reconstruct changes in water chemistry over the past 150 years. The results from MAGIC agree well with the sediment record; pH levels gradually decreased from 6.5 in the mid-1800s to about 5.6 in 1920 (first response in biota) to below 5.0 by 1970, and concentrations of inorganic aluminium rose dramatically beginning about 1960. In the 1990s the lake water chemistry showed clear signs of reversal in acidification brought about by a major decline in S deposition.     

Heavy Metals Removal by Biosorption and Flotation

The removal of a mixture of heavy (toxic) metal cations (copper, nickeland zinc) from liquid effluents was investigated in this study at pilotscale, using counter-current contact mode. The innovative processinvolved the abstraction of metal ions onto fungal biosorbents, followedby the application of flotation for the subsequent solid/liquid separationof biomass particles. The ability of microorganisms to remove metal ionsfrom aqueous solutions is a well-known phenomenon. Nevertheless,engineering considerations are very important in decisions, concerningthe commercial future of biosorption and practical solutions are neededfor certain problems, such as the efficient post-separation ofmetal-loaded biomass. The two processes (flotation and biosorption) caneffectively operate in combination, in what it was termed biosorptiveflotation process. The sorbents may be recycled, after appropriate elutionof metals, as well as the treated (clean) water.     

Starch-plastic materials—Preparation,physical properties,and biodegradability (a review of recent USDA research)

Recent starch-plastic research at the National Center for Agricultural Utilization Research is reviewed and related worldwide efforts are noted. Properties of starch that influence its formulation and performance in plastics are discussed. Methods are given for preparation of starch-poly(methyl acrylate) graft copolymer, starch-poly(ethylene-co-acrylic acid), and starch-poly(ethylene-co-acrylic acid)-polyethylene plastics. Their physical properties are discussed, as is degradability by enzymes or amylolytic organisms from soil, ponds, and streams.The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

四氮唑废水处理工艺设计

高浓度、高盐分的四氮唑生产废水通过三效蒸发浓缩，馏出液经铁炭氧微电解和混凝预处理，再采用水解酸化一接触氧化一反应二沉主体组合工艺进行处理。研究了该工艺所需构筑物和设备的设计与选型。该工艺在正常运行条件下，处理后出水pH6～9，COD 302mg／L，BOD5 108mg／L，SS30mg／L，色度36倍，水质达到GB8978--1996（污水综合排放标准》三级标准。     

Application of Cellulose Microfibrils in Polymer Nanocomposites

Cellulose microfibrils obtained by the acid hydrolysis of cellulose fibers were added at low concentrations (2–10% w/w) to polymer gels and films as reinforcing agents. Significant changes in mechanical properties, especially maximum load and tensile strength, were obtained for fibrils derived from several cellulosic sources, including cotton, softwood, and bacterial cellulose. For extruded starch plastics, the addition of cotton-derived microfibrils at 10.3% (w/w) concentration increased Young’s modulus by 5-fold relative to a control sample with no cellulose reinforcement. Preliminary data suggests that shear alignment significantly improves tensile strength. Addition of microfibrils does not always change mechanical properties in a predictable direction. Whereas tensile strength and modulus were shown to increase during addition of microfibrils to an extruded starch thermoplastic and a cast latex film, these parameters decreased when microfibrils were added to a starch–pectin blend, implying that complex interactions are involved in the application of these reinforcing agents.     

High Immobilization of NH4+ in Danish Heath Soil Related to Succession,Soil and Nutrients: Implications for Critical Loads of N

During recent decades heathlands havechanged into grasslands in regions with high atmosphericnitrogen deposition. In regions with intermediatedeposition level (e.g., Denmark) changes have been lesspronounced which may be due to delay or decrease inresponse of the ecosystem. The mor layer (O horizon) mayplay an important role for this delay due to high sinkstrength for N. In this study, the capacity for netNH₄ ⁺ immobilization and mineralization wasstudied during short- and long-term incubations (2–36 days)of mor samples from Danish dry inland heaths. High short-term capacity for net NH₄ ⁺ immobilization wasfound to be a general characteristic of Danish heath morlayers both under heather (Calluna vulgaris) andcrowberry (Empetrum nigrum ssp nigrum), the latterdominating late stages in heathland succession. The netNH₄ ⁺ immobilization was higher under youngcompared to old or dead vegetation, and higher on lessnutrient poor soils than on extremely nutrient poor soils.The addition of N, P and C stimulated CO₂ productionand net NH₄ ⁺ immobilization, but not net Nmineralization. The immobilization of ¹⁵NH₄ ⁺caused release of dissolved organic N, increased N anddecreased C/N ratio in the microbial biomass, and indicatedgrowth of microorganisms with other metabolic abilitiesthan the indigenous population. No evidence was obtained ofstabilization of immobilized ¹⁵NH₄ ⁺ intosoil organic matter during the experiment. On background ofthe results and current knowledge it was concluded that therecognition of the high capacity for net NH₄ ⁺immobilization in mor layers does not allow for a raiseof critical loads for N for northern dry inland heaths.     

Does Soil Acidification Affect Spruce Needle Chemical Composition and Tree Growth?

In 1994, a large survey of soil chemistry was undertaken in thecounty of Värmland in central Sweden (Lundström et al., 1998).The southern part of the county was affected by soilacidification whereas there were no such indications in thenorthern part. To investigate the influence of soil chemistryon the trees at the specific sites, the survey was continued byan analysis of needle chemistry (Norway spruce) which wasundertaken at 150 of the 180 sites, and of tree growth at 65 ofthe 180 sites. Growth was expressed as a ratio between expectedgrowth, estimated with a national, empirical growth model, andthe growth observed in the field. In statistical analyses,using rank correlation, PCA and PLS, there were only weakindications of an influence of soil chemistry on needlechemistry and on tree growth. A moderate correlation betweennitrogen and sulphur in needles was found, which wasinterpreted as an effect of deposition and of processes in thetree canopy. No obvious regional pattern of the growth ratiowas found, in contrast to the clear pattern of soilacidification. The statistical analysis could not with anycertainty point out any of the soil chemistry variables asespecially important for the tree growth ratio.