粗苯酐与杂醇油综合利用制备增塑剂的研究.pdf

经 验 交 流 粗苯酐与杂醇油综合利用制备增塑剂的研究 石顺存 万圣明 王 珏 唐春然 湖南科技大学化学化工学院, 湘潭 411201 摘要 在固体酸催化下, 粗苯酐与杂醇油直接酯化再经减压蒸馏制备邻苯二甲酸 C4～ C5混合酯增塑剂, 经中试生产 表明 , 该工艺技术是可行的, 苯酐及 C4～ C5醇回收利用率均可达 90以上, 且废水排放量很少。 其最佳工艺条件为 1 酯化反应 C4～ C5醇 ∶ 苯酐2 . 6∶ 1. 0, 催化剂用量为反应物总质量的 1. 5, 温度 110～ 160 ℃, 时间 5 h, 反应 在搅拌下进行; 2 减压蒸馏 蒸馏压力2. 0 kPa。 关键词 粗苯酐 杂醇油 综合利用 邻苯二甲酸 C4～ C5混合酯 增塑剂 1 引言 粗苯酐主要来自萘氧化或邻二甲苯氧化制苯酐 的副产物, 其回收利用, 国外主要采用焚烧法处理。 国内已有一部分开发作 DIBP 邻苯二甲酸二异丁 酯 [ 1] 增塑剂 ,但大多数仍采用直接升华法或重结晶 法予以回收利用 。直接升华法回收粗苯酐中苯酐 ,产 品质量难以达到合格品要求, 且生产安全性较差; 重 结晶回收法 ,苯酐回收率仅为 70左右, 且存在严重 的下水污染。 杂醇油为酒精法生产丁二烯或发酵法生产酒精 精馏时的副产物 ,可用以制取增塑剂及油漆的溶剂或 从中提取异戊醇 [ 2] 等 。杂醇油开发作邻苯二甲酸 C4～ C5混合酯 ,已有一些报道 [ 3～ 6] 。但它们均系采用 纯苯酐与已精制的杂醇油酯化 、中和、水洗及蒸馏的 工艺路线 ,其工艺流程长 ,酸碱耗量大, 且产生大量的 废水污染 。 本研究采用了固体酸催化粗苯酐及杂醇油为原 料直接制备邻苯二甲酸 C4～ C5混合酯的工艺技术。 该工艺由粗苯酐与杂醇油直接酯化回收苯酐及 C4～ C5醇 ,不但解决了经典的无机强酸作催化剂所带来 的诸如反应中副产物多、产物后处理工艺复杂 、 产品 色泽深 、 设备腐蚀严重 、酸碱耗量大以及污水排放量 大等缺点 ,而且苯酐及 C4～ C5醇回收利用率均高达 90以上。邻苯二甲酸 C4～ C5混合酯产品, 分子量 及其沸程均较 DIBP 及 DBP 邻苯二甲酸二丁酯 的 大,且由于酯基长短大小不等 ,性能互补 ,其相应性能 优于 DIBP 及 DBP [ 6] , 可用作纤维素树脂和聚氯乙烯 塑料等的增塑剂 。 2 试验 2. 1 酯化基本原理 酯化反应过程中, 在固体酸催化下 ,主要是苯酐 与杂醇油中 C4～ C5醇发生酯化反应。 酯化反应是可逆反应 ,利用化学平衡移动的原理 及C4～ C5醇与水共沸的特点, 采用过量的 C4～ C5醇 将酯化反应产生的水不断带离酯化反应釜。 2. 2 制备流程 粗苯酐与杂醇油制备邻苯二甲酸 C4～ C5混合酯 工艺流程见附图 。 附图 粗苯酐与杂醇油制备邻苯二甲酸 C4～ C5混合酯工艺流程 粗苯酐 苯酐含量 ≥80, 以 CaCO3计的碱性化 合物含量≤0. 5 经粉碎预处理后 ,在固体酸催化剂 作用下与杂醇油发生酯化反应。反应结束并分离催 化剂后减压蒸馏 ,分别回收过量的 C4～ C5醇、低沸物 如单酯 和酯化反应生成的邻苯二甲酸 C4～ C5混合 酯。被分离的催化剂和回收的 C4～ C5醇及低沸物 等,可参与下一釜的酯化反应 。 其中,酯化小试在装有回流冷凝管及分水器的 500 mL 三口瓶中进行 ; 中试生产试验系以 100 L 不锈 钢酯化反应釜及其配套装置进行。 采用该工艺制备邻苯二甲酸C4～ C5混合酯,可达 到 如下 指标要求 色度 Pt-Co≤60 号, 酯含量 ≥ 99. 0,酸度 以苯二甲酸计 ≤0. 030, 加热减量 ≤ 0. 7,闪点 ≥ 160 ℃。显然,其产品质量不低于由杂醇 油和工业级纯苯酐制得的相应混合酯 [ 7] ,而且,所采用 77 环 境 工 程 2005年 2 月第23 卷第1 期 固体酸催化剂易于与粗酯分离,废水排放量很少。 3 结果与讨论 3. 1 小试结果 3. 1. 1 原料配比对酯化反应的影响 不同醇酐配比对酯化反应的影响结果如表 1。 表 1 不同醇酐配比对酯化反应的影响 项目 C4～ C5醇 ∶ 苯酐 2. 2∶ 1 . 0 2 . 4∶ 1 . 0 2 . 6∶ 1. 0 2. 8 ∶ 1. 0 3. 0∶ 1 . 0 反应时间 h10 6 5 6 6 粗酯产物酸值 mgg- 1 9 . 756 . 545 . 034. 965. 18 由表 1 看出 ,当 C4～ C5醇 ∶ 苯酐 2. 6∶ 1. 0, 酯化反应时间较短 , 酯化反应较完全 粗酯酸值较 低 。故杂醇油的投量以此为宜。 3. 1. 2 催化剂用量对酯化反应的影响 在其他反应条件相同的情况下 ,催化剂用量其对 酯化反应的影响如表 2 所示 。 表 2 催化剂用量对酯化反应的影响 项目 催化剂用量 反应物总质量 0. 51. 01. 52 . 02. 5 反应时间 h9 7 5 5 5 粗酯产物酸值 mgg- 117. 508 . 825 . 505. 034. 74 由表 2 看出, 随着催化剂用量增加, 反应时间缩 短,粗酯产物酸值降低 。但当催化剂用量达到 1. 5 以上时 ,继续加大催化剂用量, 粗酯产物酸值降低不 多。综合催化剂成本 ,故确定适宜催化剂用量为反应 物总质量的1. 5。 3. 1. 3 反应温度及时间对酯化反应的影响 酯化反应过程中 ,C4～ C5醇游离的量逐渐减少, 故在一定给热量下 ,酯化温度逐渐提高 , 这也有利于 酯化反应的完成。但酯化温度不宜超过 160 ℃, 否 则,势必影响产品色度。所以, 酯化反应温度一般控 制为 110～ 160 ℃。 由表 1及表 2 看出, 反应时间进一步延长, 酸值 降低很少。这是因为, 随着酯化反应的深入 ,未反应 羟基减少,C4～ C5醇与水共沸带水量逐渐减少。故 酯化反应时间以控制 5 h 左右为宜 。 3. 1. 4 蒸馏压力对产品的影响 减压蒸馏过程中 , 经回收 C4～ C5醇及脱除低沸 物后 ,系统蒸馏压力对产品的影响结果如表 3。 表 3 蒸馏压力对产品的影响 蒸馏 压力 kPa 终点 釜温 ℃ 产品有关指标 色度 Pt-Co 号酸度 以苯二甲酸计 苯酐回收 率 5 . 52651500. 10180. 2 4 . 02561000. 04585. 1 2 . 0236600. 02890. 5 1 . 0215400. 02393. 0 表 3 结果表明 ,为防止氧化分解 、 保证产品色度 及苯酐收率 ,达到本文 2. 2 中产品指标要求, 系统蒸 馏压力宜 2. 0 kPa 。经进一步实验测得 , 邻苯二甲 酸C4～ C5混合酯热分解温度为235 ℃ 左右。 3. 2 中试结果 3. 2. 1 技术可行性 粗苯酐与杂醇油制备邻苯二甲酸 C4～ C5混合 酯,其中试生产结果如表 4 所示 。 表 4 粗苯酐与杂醇油制备邻苯二甲酸 C4～ C5混合酯中试生产结果 粗苯酐及苯酐规格混合酯产品有关指标 外观苯酐 碱性化合物 以CaCO3计 色度 Pt -Co 号酸度 以苯二甲酸计 酯 苯酐 C4～ C5醇 回收率 备注 纯白99. 00150 . 00799. 898 . 0 97. 0产品合格＊ 灰白94. 60 . 17300 . 02099. 496 . 0 94. 8产品合格＊ 灰白86. 80 . 21450 . 02599. 293 . 2 92. 7 产品合格＊ 灰色80. 60 . 46600 . 02899. 191 . 5 91. 1 产品合格＊ 黑色72. 31 . 294001 . 41090. 281 . 4 88. 3产品不合格 注 ＊指达到上述“2. 2”中指标要求。 由表 4看出, 与工业级 99. 0苯酐相比 ,采用粗 苯酐为原料制备邻苯二甲酸 C4～ C5混合酯, 产品色 度及酸度均有所升高而苯酐回收率均有所降低。而 且,随着粗苯酐原料外观色度加深、苯酐含量降低及 碱性化合物含量升高 ,混合酯产品色度及酸度依次增 高而其酯含量及苯酐回收率依次降低。但是 ,当采用 符合本文“2. 2”中规格要求的粗苯酐时, 该工艺可以 获得酯含量 99. 0 以上的邻苯二甲酸C4～ C5混合酯 产品 ,粗苯酐中苯酐及杂醇油中 C4～ C5醇的回收率 均可达到 90以上。而且, 所生产的中试产品 ,经现 78 环 境 工 程 2005年 2 月第23 卷第1 期 场试用表明,能够良好地应用于塑料制鞋行业 。 因此 ,粗苯酐与杂醇油直接酯化再减压蒸馏制备 邻苯二甲酸C4～ C5混合酯,技术上是可行的 。 3. 2. 2 搅拌对酯化反应的影响 中试 生 产 结 果 表 明, 搅 拌 时 的 出 水 速 度 0. 54 kg h 是接近不搅拌时 0. 29 kg h 的 2 倍。这 是因为 ,在酯化反应过程中 ,前期搅拌促进苯酐的溶 解,后期搅拌有利于增加羟基与醇的碰撞几率而提高 反应速度 。 3. 2. 3 减压蒸馏系统蒸馏压力进一步降低 如上所述, 减压蒸馏脱除低沸物后 ,系统蒸馏压 力对苯酐及C4～ C5醇的回收利用率和产品质量等均 产生重要影响。进一步降低系统蒸馏压力,具有重要 意义 。 对于中试装置减压蒸馏系统, 除配置合适的真空 泵、 进行合理配管外 , 还预先模拟工业化生产装置进 行了管道系统试验 。在强度试验、气密性试验合格 后,还进行了严格的真空度检验 [ 8] 。结果, 系统蒸馏 压力可稳定在 1. 0～ 2. 0 kPa 以下 。 4 结论 粗苯酐与杂醇油 ,在固体酸催化下直接酯化并减 压蒸馏制备邻苯二甲酸 C4～ C5混合酯 ,中试生产表 明技术上是可行的。该工艺“以废治废” ,不但使粗苯 酐中苯酐及杂醇油中 C4～ C5醇回收率均可达到90 以上 、 废水排放量少 ,而且 ,在满足塑料制鞋等行业用 户使用要求的同时, 相应增塑剂产品的生产成本大大 降低 。 参考文献 1 CN1065859A . 粗苯酐回收利用的方法. 2 张嫦. 杂醇油的利用及其深加工. 西南民族学院学报, 2001. 27 4 440～ 442. 3 朱宪, 周忠华, 许斌. 用杂醇油制备邻苯二甲酸C4～ C5混合酯增塑 剂的研究. 精细化工,1994. 11 3 52～ 55. 4 孙学军, 田君濂, 王善田. 邻苯二甲酸混合酯的制备杂醇油的开 发利用. 山东化工,1994. 2 7～ 9. 5 张慧玲, 覃元秋, 陆彬凯. 强酸树酯催化合成邻苯二甲酸混合酯增 塑剂. 广西大学学报,1996. 21 4 377～ 382. 6 汪多仁. 邻苯二甲酸 C4～ C5混合酯. 现代涂料与涂装. 1999. 2 36～ 37. 7 汪多仁. 增塑剂化学品生产配方和合成工艺. 北京 科学技术文献 出版社, 1999. 55～ 59. 8 GBJ5023597. 工业金属管道工程施工及验收规范. 作者通讯处 石顺存 411201 湖南湘潭市 湖南科技大学化学化 工学院 2004- 04-26 收稿 上接第 44页 参考文献 1 张益, 陶华主编. 垃圾处理处置技术及工程实例. 北京 化学工业出 版, 2002, 217～ 218. 2 高亮, 周立, 吴树桐等. 赴欧洲垃圾焚烧厂考察报告. 环境卫生工 程, 2001. 9 2 84～ 88. 3 张盛, 高亮. 考察日本垃圾焚烧发电设备的报告. 环境卫生工程, 2002. 10 4 204～ 206. 4 Renbi Bai. Mardina Sutanto . The practice and challenges of solid waste management in Singapore[ J] . Waste Management, 2002. 22 557～ 567. 5 He Dewen, Chai Liyuan. Progress on Energy and Pollution Control of Municipal Solid Waste by Incineration Technology[ C] . In Proceedings of International Symposium on Solid Waste Incineration and Flue Gas Cleaning Technologies. The Chinese Society of Environmental Sciences, Fuzhou, China , 2002. 39～ 43. 6 王建勇, 施耀新, 郝福民. 上海城市生活垃圾和发电技术分析. 锅炉 技术, 2002. 33 11 29～ 32. 7 金鑫, 张少盾. 太原垃圾焚烧发电工程设计路线. 中国环保产业, 2002. 9 32～ 33. 8 林福成. 南海环保电厂垃圾焚烧系统特点及调试. 四川电力技术, 2002. 3 48～ 49. 9 安丽. 稳定化 固化废物中重金属的渗漏行为, 环境污染与防治, 1994. 18～ 22. 作者通讯处 仲兆平 210096 东南大学动力系 热能所 2004- 05-24 收稿 79 环 境 工 程 2005年 2 月第23 卷第1 期 Abstract The goalwas to recycle secondary alloys raw material from solid waste of high-speed-steel tool swarf by electrothermal process. The techniques and the factors affecting the quality of products were analyzed. For getting pure high-speed-steel tool grinding swarf, the pre - treatment was needed. The multi -alkaline slag could not only meet the need of high heat value, low oxidation andgoodfluidity , but also increase the recovery ratio of alloys andwipe out impurity. The compound reducing reagent was about 98～ 100 of its theoretical consumption. The results showed that the quality of the secondary alloy raw material recycled from waste solid of high -speed -steel tool could meet the need of steel -making. From which remarkable social and economic benefits are achieved. Keywords high speed steel, solid waste, grinding swarf, secondary alloy raw material and electrothermal process DETERMINATION OF TOTAL CHROMIUM INWASTE -WATERBY FLAME ATOMIC ABSOPTION SPECTROPHOTOMETRYYe Jun 61 Abstract A determination of total chromium in environmental samples by flame atomic absorption spectrophotometry was studied. The optimal analytical conditions were ascertained through different experimental conditions. Analytical precision and accuracy were also validated by means of analysis of standard samples and realistic samples. The experimental results showed that this was easy to operate. The anylytical efficiency was promoted, analytical precision and accuracy were good as well, so this could be applied and popularized. Keywords flame atomic absorption spectrophotometry, tatal chromium and determination MODIFIED LOGISTIC CURVEMODEL OF OVERALLUATION OFATMOSPHERE ENVIRONMENTAL QUALITYJinKaizheng 62 Abstract In order to test the grade criteria of atmosphere environmental quality , to resolve the non -uni problem of uation results of atmosphere environmental quality inds, and to raise the grade resolution of uation, a new model a modified Logistic curve model is suggested, whose atmosphere environmental quality grade is a real number. The calculation example shows that the scheme is practical, effective and general,which can be applied to uating other environmental quality. Keywords Atmosphere environemntal quality , overall uation and modified Logistic curve model APPRAISEMENT OF ENVIRONMENTAL QUALITY OF WATER BODIES BY TENDENCY WEIGHT POLLUTION INDEXYang Shijian et al 65 Abstract It was suggested that the of tendency weight pollution index should be used to assess the environmental quality of water bodies in the light of shortcomings of the of average pollution index, which was also compared to the average pollution index through examples. The results showed that the of tendency weight pollution index is accurate and convenient for the assessment on water bodies. Keywords environmental quality of water, uation, average pollution index and tendency weight pollution index DETERMINATION OFCOPPER,ZINC,LEADAND CADMIUM IN SOIL BY ATOMIC ABSORPTION SPECTROMETRYPan Haiyan et al 68 Abstract Through comparison of several counteraction systems, HNO3-HF -H2O2system is selected for Pb and Cd, while HNO3-HF -HClO4 system is selected for Cu and Zn. It has been showed through determinations of standard samples that the measured values are in the range of guaranteed oneswith a relative standard error of 2. 2～ 7. 2 and a recovery of 83～ 116for Pb and Cd; whereas a relative standard error of 2. 6～ 4. 5 and a recovery of 92～ 103 belong to Cu and Zn. Keywords atomic absorption spectrometry, soil, Cu, Zn, Pb and Cd ASSESSMENT OF WORKING ENVIRONMENT AMENITY BASED ON GREY RELEVANCY ANALYSISZhang Dongfang et al 70 Abstract In working environment amenity assessment, there are lots of influencing factor with different attributes. For the purpose of reflecting the attributes in the assessment and avoiding the trouble of distributing weight to every index, which is difficult generally, according to the principle of grey relevancy analysis, we take the amenity standard asa zone and discuss the coefficient ρto avoidthe random; according to the principle of maximum relevancy , the degree of the working environment amenity is ascertained. The analysis by practical example shows that this has a preferable applicability in the amenity assessment of working environment. Keywords grey relevancy analysis, hierarchy analysis, working environment and amenity ANALYSIS OF ACID VOLATILE SULFIDE AND SIMULTANEOUSLY EXTRACTED METALS IN SEDIMENTS OF GUILINLi Zhenping et al 73 Abstract It was measured that the acid volatile sulfide AVSand simultaneously extracted metals SEMin aquatic sedimentsof Guilin, and the character of AVS changing with depth was also studied. A preliminary prediction of biological toxicity of the heavy metals to aquatic sediments of Guilin was conducted by means of [ SEM] [ AVS] . Keywords acid volatile sulfide, simultaneously extracted metals, sediments and biological toxicity STUDY ON PREPARING PLASTICIZER BY COMPREHENSIVE UTILIZATION OF CRUDE 5 ENVIRONMENTAL ENGINEERING Vol. 23, No. 1,Feb. , 2005 PHTHALIC ANHYDRIDE AND FUSEL OILShi Shuncun et al 77 Abstract The preparation of qualified phthalic C4～ C5mixed ester plasticizer involves direct esterification of crude phthalic anhydride with fuseloil catalyzed by solid acid and distillation of the ester under reduced pressure. It was indicated by trial production that the technique is feasible. Both rate of recovery of phthalic anhydride and C4～ C5alcohol can exceed 90, and the discharge of waste water is very little. Factors such as the ratio of feedings and catalyst, reaction temperature and time, agitation and the distilling pressure were studied in the test. The optimal technological conditions are as follows. 1For esterification, n C4～ C5alcohol ∶n C8H4O32. 6∶ 1. 0, amount of catalyst is 1. 5 of the total mass of reactants, and the reaction is carried out at 110～ 160℃ for 5 h with agitation. 2 The ester is distilled under reduced pressure 2. 0 kPa. The exploitation of technology will inaugurate a new approach to the comprehensive utilization of crude phthalic anhydride and fusel oil. Keywords crude phthalic anhydride, fusel oil, comprehensive utilization, phthalic C4～ C5mixed ester and plasticizer STUDY ON ADSORPTION OF CADMIUM ⅡIN WASTEWATERWITH MODIFIED BENTONITE Luo Tai′ an et al 80 Abstract The abilities in treating Cadmium Ⅱof original and modified bentonite had been compared in this study. The results show that the adsorption of CdⅡby modified bentonite is better than that of the original bentonite.The pH value of wastewater and the amounts of modifiedbentonite will greatly influence the adsorption of CdⅡ .The adsorptive percentage reached 96 in treating 40 mg L CdⅡ wastewater at pH8～ 9 by 4 g L modified bentonite. The curves of isothermal adsorption of original and modified bentnite in treating CdⅡare in line with the equation of Freundlich. Keywords modified bentonite, cadmiumⅡand adsorption RESEARCH ON THE VISCOSITY OF THE LEACHATE FROM MUNICIPAL SOLID WASTE LANDFILLSQu Xian et al 82 Abstract The viscosity of leachatewith different CODCrconcentrations from 1 000 to 75 000 mg L from laboratory experimentswas tested in different temperature from 5 to 70 centigrade . The experimental results showed that the viscosity of leachate at similar temperatures is linear with CODCrconcentration. The different specific viscosities of leachate with different concentrations were ascribed to the solute in leachate. It is acceptable to omit the influence of viscosity when studying the moisture movement in the landfills. Keywords municipal solid waste landfill, viscosity of leachate and specific viscosity RESEARCH ON CALCIUM CARBONATE INHIBITION BEHAVIOR OF POLYEPOXY SODIUM SUCCINATEYu Yuxin et al 85 Abstract The effect of several factors on calcium carbonate inhibition behavior of polyepoxy sodium succinate is studied. The experimental results indicate that the polyepoxy sodium succinate is an excellent water treatment agent. It can be used in water system with high calcium concentration and at high temperature for a long time remaining significant scale inhibition. Keywords polyepoxy sodium succinate, scale inhibitor and calcium carbonate STUDYONMODIFIEDCLAY-LINERPERANCEANDTHEANALYSISOFITS INFLUENCING FACTORSDong Jun et al 87 Abstract Hexadecyltrimethylammonium bromide HDTMABand polyaluminium cations were used as denaturant to per organic, inorganic, and organic -inorganic modification on the natural clay respectively. Investigations were conducted into availability and feasibility of the modified -liners to contanminants removal and leachate penetration control. Various influencing factors on the perance of the modified -liners were also analyzed. Experimental results indicated