环保型循环冷却水处理剂的合成.pdf

环保型循环冷却水处理剂的合成 * 张彦河 张利辉 田彩莉 郭茹辉 杨维之 刘振法 河北省能源研究所, 石家庄 050081 摘要 以柠檬酸为原料, 分子内脱水生成乌头酸, 与少量丙烯酸合成了乌头酸 -丙烯酸共聚物 AA -AA , 对反应的相关 条件及共聚物的生物降解性进行了一系列研究。结果表明, 反应的链转移剂质量分数 10 时, 产物性能最佳。共聚 物AA -AA 具有优良的阻垢性能及生物降解性, 30 d 的生物降解率可达 6013 。 关键词 乌头酸 共聚物 生物降解性 * 河北省科技攻关计划项目 1 引言 为了减少水处理剂对环境的影响, 人们开始着眼 于绿色水处理的研究开发, 一些有关无磷非氮和可生 物降解的水处理剂研究结果相继报导 [ 1, 2] , 这些研究 推动了循环冷却水处理技术的发展。 乌头酸又称丙烯三羧酸, 是乌头菌在一定条件下 的代谢产物。乌头酸可以在微生物作用下进一步降 解并最终转化成二氧化碳。本实验是关于以柠檬酸 为原料合成乌头酸 -丙烯酸水处理剂的方法及反应条 件的研究结果。 2 实验部分 211 主要仪器及原料 仪器 电热套 搅拌器 恒温水浴锅 四口反应 瓶 恒温摇床; 原料 柠檬酸 硫酸 丙烯酸 异丙醇 过硫酸 铵均为分析纯。 212 乌头酸 -丙烯酸共聚物的合成 在装有温度计及搅拌器的四口反应瓶中加入规 定剂量的柠檬酸及硫酸, 加热、 熔化、 搅拌、 控温, 在 130 140 e 下反应 115 h, 产物即是乌头酸, 分离提纯 后备用。 在装有温度计、 滴液漏斗及回流冷凝器的反应瓶 中, 加入合成的乌头酸、 一定量的异丙醇及水, 控制温 度, 同时滴加过硫酸铵水溶液及少量的丙烯酸。滴加 完毕, 继续搅拌反应 2 h 即可得乌头酸 -丙烯酸共聚 物。产品外观为黄色粘稠状液体, 有效物质含量 30 。 213 静态阻垢率的测定 [ 3] 阻碳酸钙垢性能测定试验条件为 Ca 2 250 mgP L, HCO - 3250 mgP L, 均以CaCO3计 , 浓缩 倍数 115, 水浴温度 80 e 。 214 生物降解性能的测定 [ 1] 在锥形瓶中加入含有乌头酸 -丙烯酸共聚物的营 养液900mL, 接种物 015 mL, 将瓶盖好, 放入20 1 e 的摇床上振荡, 在试验的第 1、 10、 15、 20、 25、 30 d 分别 测定样品的 COD 值。接种物的制备方法是将 100 g 菜园土悬浮于1 000 mL蒸馏水中, 搅拌后沉淀 30min, 用粗滤纸过滤, 弃去最初 200 mL 滤液, 其余备用。样 品的降解率按下式计算 降解率1- Ct- Cct Co- Cco 100 式中 Co 含受试物质的接种反应液中实测的 COD初始浓度的平均值; Ct t 时刻含有受试物质的反应液中的 COD浓度的平均值; Cco 空白对照中实测的 COD 初始浓度的 平均值; Cct t 时刻空白对照中实测的 COD 浓度的 平均值。 3 实验结果与讨论 311 聚合反应温度对阻垢率的影响 反应温度对阻垢率的影响见表 1。 表 1 反应温度对阻垢率的影响 反应温度 Pe阻垢率 857312 908111 958813 1009412 从表 1 结果可知, 随着聚合温度的上升, 合成产 75 环 境 工 程 2005年 4 月第23 卷第2 期 物的阻垢率明显提高。由于在反应体系中含有异丙 醇, 当温度超过 100 e 时开始回流, 温度不能再提高。 适当提高反应温度, 有利于提高共聚物的阻垢率。 312 异丙醇用量对阻垢率的影响 异丙醇用量对阻垢率的影响见表 2。 表 2 异丙醇用量对阻垢率的影响 异丙醇质量分数阻垢率 35 107 56211 77812 109516 139611 159611 异丙醇作为聚合反应的链转移剂, 对产物的阻垢 率起着很大的影响, 异丙醇用量越大, 产物阻垢率越 高。但异丙醇用量超过 10 时, 链转移达到平衡, 产 物阻垢率提高已不再明显, 相反过量的使用链转移 剂, 产物浑浊和其它药剂的复配能力降低。 313 过硫酸铵对阻垢率的影响 引发剂过硫酸铵用量对阻垢率的影响见表 3。 表 3 过硫酸铵用量对阻垢率的影响 过硫酸铵质量分数阻垢率 37012 48416 59416 69510 过硫酸铵作为引发剂对聚合反应起着催化作用。 由表 3可知, 过硫酸铵质量分数 5 时, 既是反应适 宜的量。 314 丙烯酸用量对阻垢率的影响 丙烯酸用量对阻垢率的影响见表 4。 表 4 丙烯酸用量对阻垢率的影响 丙烯酸质量分数阻垢率 58015 109517 159612 丙烯酸属石化产品, 生物降解特别困难, 为了提 高产物的生物降解性, 应尽量减少丙烯酸的质量分 数。由于丙烯酸是活性较高的单体, 它能与乌头酸共 聚, 增加共聚链接能力, 提高阻垢率, 所以丙烯酸用量 又不能太少。由表 4 可知, 丙烯酸质量分数达 10 时, 即能满足两方面的要求。 315 可生物降解性的测定 按照 214 的试验方法, 测定了乌头酸 -丙烯酸水 处理剂在微生物作用下的降解性能, 结果见表 5。 表 5 乌头酸 -丙烯酸共聚物生物降解率 时间 P d阻垢率 101017 152312 204011 255116 306013 由表 5 可知, 乌头酸 -丙烯酸共聚物具有可生物 降解性, 随着时间的增加, 降解率提高, 30 d生物降解 率达到6013。 4 结论 以柠檬酸为原料, 在硫酸作用下分子内脱水转化 为乌头酸, 然后和少量丙烯酸共聚, 异丙醇作为共聚 反应的链转移剂, 可以制得乌头酸 -丙烯酸的共聚物。 异丙醇作为此聚合反应的链转移剂, 对产物的阻 垢性能起着很大的作用。异丙醇的最佳使用量是反 应物总量的 10 。 乌头酸 -丙烯酸共聚物具有优良可生物降解性, 30 d 的生物降解率达到 6013 , 因此共聚物是一种环 保型的循环冷却水处理剂。 参考文献 1 熊蓉春, 董雪玲, 魏刚. 绿色生物高分子聚天冬氨酸的合成及其阻 垢性能研究. 工业水处理,2001. 21 1 17 20. 2 熊蓉春, 魏刚, 周娣等.绿色阻垢剂聚环阳琥珀酸的合成. 工业水处 理, 1999. 19 3 11 13. 3 唐文伟, 曾新平, 李义元等. 水质稳定剂TJ -302 的合成及其阻垢性 能研究. 工业水处理,2003. 23 10 52 56. 作者通讯处 张彦河 050081 河北省石家庄市友谊南大街 46 号 河北省能源研究所 电话 03113053046 2004- 04- 02 收稿 76 环 境 工 程 2005年 4 月第23 卷第2 期 and abroad.The fly ash of CFB is not utilized effectuarlly at the present time.This paper introduces the s of exciting the activity of CFB fly ash and experimental study on producing masonry cement by CFB fly ash. Keywords CFB flyash, alkali excitation, activity and masonry cement UATION ON POTENTIAL ECOLOGICAL RISK OF HEAVY METAL POLLUTION OF SEDIMENTS IN HAIHE RIVERWang Shengqiang et al 62 ,,,,,,,,,,,,,,,,, ,,,,,, Abstract Through analyzing the contents of typical heavy metal pollutants Cu, Pb, Zn, Cd and Cr in sediments of Haihe River, adopting the index number techniques of single factor andHakanson ecological risk, the quality statusof these sedimentswere uated; the pollution of the sediments by heavy metals and the potential ecological risk of Haihe River were determined quantitatively. Keywords Haihe River, sediment, heavy metals and ecological risk RESEARCH ON MODEL OF RELATION BETWEEN THE UTILIZATION OF COAL RESOURCES AND SO2POLLUTION OF ATMOSPHERE IN THE URBAN AREA OF JIAOZUO CITY Wang Hailin et al 64 ,,,,, ,,,,,,,,,,,,,,,,,,,, ,,,,,,,,,,,,,,,,,,,,,, Abstract Firstly the relation between the utilization of coal resources and SO2pollution of the urban area atmosphere of Jiaozuo City was researched.The diffusing model of SO2pollution applying to the urban area atmosphere of Jiaozuo City was set up. In the model the contribution from area pollution sources was calculated by transing it to the background concentration, so the model was greatly simplified. By which SO2 concentrations from 1996 to 2000were also calculated and compared withthe monitoring data, it is found that the model is suitable for the actual conditions of the test zone. Based on which, SO2concentrations in this area were forecasted. Keywords pollution sources of coal utilization, SO2pollution, diffusing model of atmosphere pollution and prediction of atmosphere pollution MODEL DEVELOPMENT AND IDENTIFICATION OF RAPID FILTRATION PROCESSES Tong Qingyuan et al 67 ,,,, ,, ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Abstract This paper is part of a national framework for systematically assessing water safety risks, yet with focus only on the simulation of the rapid filtration process.The filtration process is described by a dynamic and conceptual model, represented by partial differential equations, and the simulated components include CODMn, NH3-N,turbidity and microorganisms.The simulated sub -processes included diffusion, biodegradation, sediment, adsorption, desorption and backwash. The model is calibrated by a set of field data from a large waterworks in the south of China,where contamination of drinking water resources is notable. The results reveal that the model fits the observed data quite well and is satisfactory for its future application. Keywords simulation, rapid filtration process, CODMn, turbidity and NH3-N A NEW BIOLOGICAL PROCESS STUDY ON NITROGEN REMOVAL MECHANISM OF BI - CYCLIC TWO -PHASE BICT PROCESSPan Yang et al 69,,,,, ,,,,,,,,,,,,,,,, Abstract Under the operational condition, synthetic wastewater was used in the experiments to investigate the perance of nitrogen removal by the BICT of the reactor. The results of the experimental study can be concluded as follows. The nitrogen removal mechanism of BICTP is sequential nitrification and denitrification. A separte attached -growth reactor was adoptedto enhance the function of nitrification and increase the efficiency and the stability of nitrogenremoval process. Under suitable conditions, the removal rate of TNtotal nitrogen can reachover 80 , and the effluent concentration of TN can be controlled below 15 mgP L. Keywords activated sludge, nitrification, denitrification and nitrogen removal NUMERICAL SIMULATIONANDCOAGULATIONEFFICIENCYOFFLOWFIELDFOR RECIPROCATING BAFFLED FLOCCULATION TANKZhu Jiaolin et al 72,,,,,,,,,,,,, Abstract In this paper, the numerical simulation is applied to the flow field for a reciprocating baffled flocculation tank. Based on the characteristic of flocculation tank an analysis of the influence of the flow field on flocculation is carried out.The conclusion indicates the optimum value of A1PA2is from 1. 2 to 1. 5,where A1is the area of the wetted cross -section in the corner and A2is the area of the wetted cross -section in the gallery. The coagulation efficiency in the tank is relatively perfect if designed it according to the optimum value of A1PA2. Keywords reciprocating baffled flocculation, flow field, A1PA2andANSYS SYNTHESIS OF CIRCULATING COOLING WATER TREATMENT AGENT FIT FOR FRIENDLY ENVIRONMENTZhang Yanhe et al 75,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Abstract A newly biodegradable copolymer was synthesized by aconitic acid and a small quantity of acrylic acid, and citric acid was 5 ENVIRONMENTAL ENGINEERING Vol123, No12,Apr. ,2005 converted to aconitic acid by inner -dehydration. The synthetic conditions and biodegradability of the copolymer were studied andthe results showed that production had optimal perance when the qualitative amount of chain transfer agent was 10 . AA -AA had better scale inhibition perance and good biodegradability, which could be biodegraded to 60. 3 in 30 days. Keywords aconitic acid, copolymer and biodegradability ELEMENTARYINTRODUCAITONTONEWDREDGINGPROCESSFORRIVERAND RESERVOIRXiang Wenying et al 77,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Abstract Several traditional dredging s for river and resevoir have been analysed and compared. Then, a new process has been presented, that is air -lift assisted with sel- f excited oscillation pulse water jet for dredging. The authors analyse the theory of the new process, demonstrate the mechanism of continuedprocess while crushing and pumpping the solid accumulation under thewater. At last, the relation between the pressure of air compressor and the dredging amount has been analysed. Keywords dredging, air -lift, sel- f excited oscillation pulse water jet and crushing EFFECT OF ADDITIVE ON COMBUSTION CHARACTERISTICS OF COALQiang Feng et al 79, Abstract For studying the effect of additive onthe combustion characteristics of a coal, five metal oxides and salts were chosen as potential additive components, and by employing the cross -cut experimental , their effects on the combustion characteristics of char particles were examined. Based on the analysis of range and variance, the optimum composition of additive was then derived. Further experiments revealedthat the additive with composition as proposed by this research could effectively reduce the ignition temperature of the coal and increase its calorific value during combustion. Finally, on the basis of the experiments, the mechanism of the promotion of coal combustion was discussed. Keywords coal, additive and combustion characteristics APPLICATION OF SPRAYING TECHNOLOGY FOR SGLZ - SLAG TANK IN SHOUGANG GROUPWang Cunzheng et al 81,,,,,,, ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Abstract The spraying technology for SGLZ - slag tank has been applied to No. 3 stee- l making plant of Shougang Group successfully.The application results proved that this technology can eliminate effectively dust pollution which caused by the slags padded under slag tanks, increase the rate of the first emptying slag tanks and decrease the loss of slag tanks. It has notable environmental, social and economical benefits. Keywords slag tanks, spraying and rate of first emptying slag tanks ENGINEERING TEST OF / ZERO DISCHARGE0 OF RESIDUAL ORGANIC SLUDGE Ruan Zhihua 83 ,,,,, ,,,,, ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Abstract It is generally difficult to treat the residual sludge produced by treatment of organic wastewater through activated sludge process. Based on the successful laboratory tests and through the examination of field running for one year, a new process of normal temperature aerobic hydrolytic acidification -biological reaction was used to eliminate the residual sludge produced during treating organic wastewater and realized/ zero discharge 0 of the sludge. The new process features convenient operation andmanagement, which can also increase the qualified rate of CODCrof the original system by 5 15 .Therefore it can be applied especially to the system of treating organic wastewater containing nitrogen. Keywords residual sludge, water treatment system, amount of sludge -discharging and organic wastewater STUDYTHINKINGOFENERGY -CONSERVINGOXIOATION DITCH TECHNOLOGYOF SEWAGE DISPOSAL IN CHINALiu Zuwen et al 85,,,,,,,,,,,,,,, ,,,,,,,,,,, Abstract It is expounded that the technical development of oxidation ditch andthe superiority in the choice of technology of sewage disposal in the small and medium -sized cities. According to the current situation of sewage disposal in small and medium -sized cities in China and the application characteristics of the technology of oxidation ditch, it is put forward that the study thinking of the energy -conserving technology of sewage disposal, which fits for the current situation of sewage disposal in small and medium -sized cities in China. Keywords municipal sewage, oxidation ditch and energy -conserving technology Manager Central Research Institute of Building and Construction of MCC Group Editor The Editorial Department of Environmental Engineering Publisher Industrial Construction Magazine Agency 33, Xitucheng Road, Haidian District, Beijing 100088, China Telephone 010 82227637、 82227638 Fax 010 82227637 Chief EditorWeng Zhongying Domestic All Local Posts DistributorChina International Book Trading Corporation P. O. Box 399, Beijing China Journalistic Code ISSN1000- 8942 CN11- 2097 PX E- mail Addresshjgc hjgc. com. cn WWW AddresshttpP P www. hjgc. com. cn 6 ENVIRONMENTAL ENGINEERING Vol123, No12,Apr. ,2005