500t/a聚丙烯酸钠絮凝剂生产工艺设计
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摘要
随着我国丙烯酸工业的迅速发展，亟需发展其下游产品。高分子量聚丙烯酸钠是一类广泛用于烧碱和纯碱行业盐水精制、氧化铝生产的赤泥沉降分离、味精厂废水中蛋白质回收和制糖等行业的高分子材料。也是丙烯酸使用量很大的一类产品。在我国市场需求量很大但生产能力很小，产品性能欠佳。因此建设能够生产产品性能好、具有一定规模的高分子量聚丙烯酸钠生产厂，对于促进我国丙烯酸产业的发展，和提高我国高分子量聚丙烯酸钠的生产、质量水平都具有重要的意义。
本设计是针对我国高分子量聚丙烯酸钠在性能上存在分子量上不去、水溶解性能差、溶解时间长和生产上存在设备投资大、生产操作复杂、能耗较高的问题。经过多年来的研究和在生产性试验的基础上，遵循技术上先进、工艺上可靠、经济上合理、系统上最优的原则完成。生产所用的主要原料是丙烯酸和氢氧化钠，生产方法是盘式水溶液聚合法，即使用氢氧化钠中和的丙烯酸水溶液，在复合引发剂存在下，加入有助于提高分子量和水溶解性能的有机胺等聚合助剂，在自行设计的反应盘中进行常温聚合，湿胶体产物经肉类绞碎机造粒，干燥，压散，粉碎而制得分子量高达2500万以上、水溶解性能好(无凝胶物)、溶解速度快(＜30min)、使用效果好的聚丙烯酸钠商品。所采用工艺的特点是：丙烯酸钠溶液采用能高效脱除阻聚剂的方法去除阻聚剂，在聚合过程使用复合引发剂、加入具有提高分子量、促进水溶解性能的聚合助剂，在常温下进行反应；反应在专门设计的带条形格涂有不粘涂料的反应盘中进行；胶体产物采用肉类绞碎机造粒；生产工艺简单、设备投资小、能耗较低。
本设计的主要内容包括：对高分子量聚丙烯酸钠的国内外研究状况、应用领域和应用现状、生产概况、市场需求情况和应用前景的综述；通过试验对工艺流程中聚合方法、阻聚剂脱除方法、造粒方法、干燥和粉碎方法进行选择和论证；对生产的物料及能量进行了衡算；详细介绍了生产工艺流程及控制；并简要说明了主要设备选型和工艺尺寸的计算、设备投资估算、车间的设备布置、原料的消耗和定额；对建设工程、技术经济指标进行了简单分析。
With the rapid development of acrylic acid industry in our country, it is in urgent need to develop products from acrylic acid. Polymeric sodium polyacrylate is not only a kind of macrolecule material widely practiced in purification of salt solution in industries of caustic soda and soda, red soil sedimentation separation in producing alumina, recovery of protein in waste water from monosodium glutamate factory, and refining sugar industry, but also a kind of product consuming a great deal of acrylic acid. It is in great demand of domestic market, but less in production capacity and bad in properties of product. So a certain size of polymeric sodium polyacrylate factory is to be built to supply better properties of goods which is of important sense on promoting development of acrylic acid industry and improving the level of production and quality.
This design is focussed on the problems on difficulty to increase molecular weight, bad water solubility and large equipment investment, complicated operation and wasted energy in production of polymeric sodium polyacrylate. Based on the study on polymeric sodium polyacrylate and experiments in production for many years, and according to the principles of advanced technology, credible technics, reasonable economics and optimized system, the design is completed. The 籱ain raw materials are acrylic acid and sodium hydroxide, which are made reaction by pan polymerization in water. That is, the acrylic acid solution neutralized by sodium hydroxide is being polymerized at normal temperature in the designed reaction tray, with the composite initiator and polymerization promoter, such as organic amine to increase molecular weight and to improve water solubility. The product in wet colloided state is made into grains by disintegrator, dried by desiccator, and smashed into the fine of sodium polyacrylate with molecular weight over 25 million, better water solubility (without gel left ), and fast solution (within 30 min ). The characteristic of this technology are as follows: (1) the sodium polyacrylate solution that the inhibitor can be eliminated by the efficient method, with the composite initiator and polymerization promoter able to increase molecular weight and improve water solubility on polymerization, can be made reaction at normal temperature; (2) the reactor is a kind of ingotal grid tray coated with non-sticking coating,; (3) The product is made into grains by disintegrator; (4) It is simple in technology, less equipment investment and saving on energy.
The main contents of this design included: Summerization on the Status of Research on Polymeric Sodium Polyacrylate in Domestic and Abroad, Field and Current Status of Applications, the Situation of Production, the Need of Market and Applying in the Future; Selection and Demonstration on Polymerization Method, Eliminating Inhibitor, Granulation, Drying and Smashing in the Technological Process; The Calculation of Raw Materials and Energy; Technological Process and Controlling; The Design of Main Equipments; The Calculation of Investment; The Arrangement of Equipments in Workgroup; Consumption and Quota of Raw Materials; Illustration on Construction Engineering; Economic Analysis.
本设计是针对我国高分子量聚丙烯酸钠在性能上存在分子量上不去、水溶解性能差、溶解时间长和生产上存在设备投资大、生产操作复杂、能耗较高的问题。经过多年来的研究和在生产性试验的基础上，遵循技术上先进、工艺上可靠、经济上合理、系统上最优的原则完成。生产所用的主要原料是丙烯酸和氢氧化钠，生产方法是盘式水溶液聚合法，即使用氢氧化钠中和的丙烯酸水溶液，在复合引发剂存在下，加入有助于提高分子量和水溶解性能的有机胺等聚合助剂，在自行设计的反应盘中进行常温聚合，湿胶体产物经肉类绞碎机造粒，干燥，压散，粉碎而制得分子量高达2500万以上、水溶解性能好(无凝胶物)、溶解速度快(＜30min)、使用效果好的聚丙烯酸钠商品。所采用工艺的特点是：丙烯酸钠溶液采用能高效脱除阻聚剂的方法去除阻聚剂，在聚合过程使用复合引发剂、加入具有提高分子量、促进水溶解性能的聚合助剂，在常温下进行反应；反应在专门设计的带条形格涂有不粘涂料的反应盘中进行；胶体产物采用肉类绞碎机造粒；生产工艺简单、设备投资小、能耗较低。
本设计的主要内容包括：对高分子量聚丙烯酸钠的国内外研究状况、应用领域和应用现状、生产概况、市场需求情况和应用前景的综述；通过试验对工艺流程中聚合方法、阻聚剂脱除方法、造粒方法、干燥和粉碎方法进行选择和论证；对生产的物料及能量进行了衡算；详细介绍了生产工艺流程及控制；并简要说明了主要设备选型和工艺尺寸的计算、设备投资估算、车间的设备布置、原料的消耗和定额；对建设工程、技术经济指标进行了简单分析。
With the rapid development of acrylic acid industry in our country, it is in urgent need to develop products from acrylic acid. Polymeric sodium polyacrylate is not only a kind of macrolecule material widely practiced in purification of salt solution in industries of caustic soda and soda, red soil sedimentation separation in producing alumina, recovery of protein in waste water from monosodium glutamate factory, and refining sugar industry, but also a kind of product consuming a great deal of acrylic acid. It is in great demand of domestic market, but less in production capacity and bad in properties of product. So a certain size of polymeric sodium polyacrylate factory is to be built to supply better properties of goods which is of important sense on promoting development of acrylic acid industry and improving the level of production and quality.
This design is focussed on the problems on difficulty to increase molecular weight, bad water solubility and large equipment investment, complicated operation and wasted energy in production of polymeric sodium polyacrylate. Based on the study on polymeric sodium polyacrylate and experiments in production for many years, and according to the principles of advanced technology, credible technics, reasonable economics and optimized system, the design is completed. The 籱ain raw materials are acrylic acid and sodium hydroxide, which are made reaction by pan polymerization in water. That is, the acrylic acid solution neutralized by sodium hydroxide is being polymerized at normal temperature in the designed reaction tray, with the composite initiator and polymerization promoter, such as organic amine to increase molecular weight and to improve water solubility. The product in wet colloided state is made into grains by disintegrator, dried by desiccator, and smashed into the fine of sodium polyacrylate with molecular weight over 25 million, better water solubility (without gel left ), and fast solution (within 30 min ). The characteristic of this technology are as follows: (1) the sodium polyacrylate solution that the inhibitor can be eliminated by the efficient method, with the composite initiator and polymerization promoter able to increase molecular weight and improve water solubility on polymerization, can be made reaction at normal temperature; (2) the reactor is a kind of ingotal grid tray coated with non-sticking coating,; (3) The product is made into grains by disintegrator; (4) It is simple in technology, less equipment investment and saving on energy.
The main contents of this design included: Summerization on the Status of Research on Polymeric Sodium Polyacrylate in Domestic and Abroad, Field and Current Status of Applications, the Situation of Production, the Need of Market and Applying in the Future; Selection and Demonstration on Polymerization Method, Eliminating Inhibitor, Granulation, Drying and Smashing in the Technological Process; The Calculation of Raw Materials and Energy; Technological Process and Controlling; The Design of Main Equipments; The Calculation of Investment; The Arrangement of Equipments in Workgroup; Consumption and Quota of Raw Materials; Illustration on Construction Engineering; Economic Analysis.
引文
[1] 大森英三(日)．丙烯酸酯及其聚合物[M]．北京：化学工业出版社，1995．
[2] 曾之平，赵红坤，白永康，等．聚丙烯酸盐的制备及应用[J]．河南化工，1997，(5)：8～9．
[3] 严瑞瑄．水溶性高分子[M]．北京：化学工业出版社，1998，196～222．
[4] G. F. Fanta, R. C. Burr, C. R. Russell, et, al. Graft copolymers of starch. Ⅰ Copolymerization of gelatinized wheat starch with acrylonitrile. Formation of copolymer and effect of solvent on copolymer composition. [J] Appl. Polymer Sci. 1966,10(5): 929～937
[5] G. F. Fanta, R. C. Burr, C. R. Russell, et, al. Graft copolymers of starch. Ⅱ Copolymerization of gelatinized wheat starch with acrylonitrile. Influence of reaction conditions on copolymer compounds [J] Polymer Sci. Pt B 1966,10:765～769
[6] G F Fanta, R C Burr, C R Russell,et al. Graft copolymers of starch. Ⅲ Copolymerization of gelatinized wheat starch with acrylonitrile. Influence of reaction conditions on copolymer compounds [J] Polymer Sci. Pt B J Appl Polym [J], 1967,11(3):457
[7] L Gugliemelli,M O Weaver, C R Russell. Base-hydrolyzed starch-polyacrylonitrile (S-PAN)graft copolymer. J Appl Polymer Sci, 1969,13(6)2007～201
[8] 黄伯芬，王刚．ZG—93丙烯酸共聚物阻垢分散剂的研制及阻垢机理探讨[J]．化学世界，1996，(2)：88～94．
[9] 秦增全．马来酸酐—丙烯酸共聚物的制备方法[J]．CN：1099764A，1995．
[10] 许观藩，方天如，高林，等．低分子量水溶性聚合物的制备[J]．CN：1085568A，1994．
[11] BASF G. Muenster A.Rohmann M. U.S.P4301266,1981.
[12] Hughes K.A Kine B.B Swift G. U.S.P4314044,1982.
[14] Nagarajan M.K. Journal of the American Oil Chemist's Society 1985,62(5):949～955.
[15] Robert. L. Davidson. Handbook of Water-Soluble Gum and Resins.New york, 1980.
[16] Laurence GD. Polyacrylate thickening: agents[p].US:4 338 239,1982.
[17] Boisvert J P, Persello J, Castding J C, et al. Dispersion of alumina coated TiO_2 Particles by adsorption of sodium polyacxylate. Colloids and Surfaces, 2001,178(1): 187—198
[18] Hua F, Qian M. Synthesis of self-crosslinking sodium polyacrylate hydrogel and woter-absorbing mechanism. Journal of Materials Socience,2001,36(3):731～738
[19]余学军，徐丹，刘明，等．速溶高分子量聚丙烯酸钠的合成研究[J]．化学世界，1999，(6)：310～312．
[20](日)山口繁，坪井启史，入江好夫．马来酸基共聚物及其制备方法和应用[P]．JP：94190523．3，1995-11-29．
[21]万福忠，陈昌镜，朱艳梅．常温合成高分子量聚丙烯酸钠及其分子量的测定[J]．湖北化工 1994，(3)：28～30．
[22]康正，崔英德，郭建维，等．年产120吨聚丙烯酸钠絮凝剂的工艺设计与投产[J]．广州化工，2000，28(4)：151～153．
[23]戚银城，刘宝龙．高分子量聚丙烯酸钠的合成及应用研究[J]．北京化工学院学报(自然科学版)，1990，17(1)：19～24．
[24]韩淑珍．反相悬浮聚合法新工艺合成聚丙烯酸钠高分子絮凝剂工业化开发研究[J]．精细与专用化学品，2000，(17)：15～17．
[25]徐湘凌，张志成，费宾，等．丙烯酸钠反相乳液聚合[J]．高分子学报，1998，(2)：134～138．
[26]卢万明．固体聚丙烯酸钠在我厂的使用效果[J]．氯碱工业，1997，(12)：4～5．
[27]李泽洁．聚丙烯酸钠助沉剂在精制盐水中的应用[J]．福建化工，1998，(4)：20～21．
[28]王德怀．速溶型固体聚丙烯酸钠用于盐水助沉的试验[J]．氯碱工业，1995，(11)：16～19．
[29](日)山田、兴一．赤泥的絮凝与沉降[J]．轻金属[J]，1980，(3)：20～21．
[30]江新民，桂康．聚丙烯酸钠在赤泥分离中的应用[J]．轻金属，1999，(6)：17～20．
[31]黄民生，朱莉．味精废水的絮凝—吸附法预处理试验研究[J]．水处理技术，1998，24(5)：299～302．
[32]买文宁，黄普选．味精发酵母液提取蛋白饲料[J]．给水排水，2002，28(11)：43～44
[33]张轶东，曾心苗，李朝顺，等．高效蛋白质浓缩剂的制备及浓缩作用的研究[J]．离子交换与吸附，1997，(6)．
[34]张国民．氯碱行业现状分析和2002年发展展望．中国经济展望：产业卷，2002(1)；266～276
[35]无．2001年纯碱市场回顾与2002年纯碱市场预测．中国石油和化工分析报告，2002，(3)：50～51
[36]郭铨，刘淑娟．流程计算-化学平衡、物料和热量平衡．第一版．北京：科学出版社．1985．5～10
[37]上海医药管理局上海医药设计院．化工工艺设计手册(下册)．第一版．北京：化学工业出版社．1986．733～737
[38]穆赫列诺夫(苏)．化学工艺过程计算．第一版．大连工学院化工系 译．北京：化学工业出版社．1985．79～93
[39]李应麟，尹其光．化工过程的物料衡算和能量衡算．第一版．北京：高等教育出版社．1987．88～107
[40]国家医药管理局上海医药设计院．化工工艺设计手册(下册)．第一版．北京：化学工业出版社．1986638
[41]刘道德．化工厂的设计与改造—典型例选及其解析．第一版．湖南：中南工业大学出版社．1995．270～276
[2] 曾之平，赵红坤，白永康，等．聚丙烯酸盐的制备及应用[J]．河南化工，1997，(5)：8～9．
[3] 严瑞瑄．水溶性高分子[M]．北京：化学工业出版社，1998，196～222．
[4] G. F. Fanta, R. C. Burr, C. R. Russell, et, al. Graft copolymers of starch. Ⅰ Copolymerization of gelatinized wheat starch with acrylonitrile. Formation of copolymer and effect of solvent on copolymer composition. [J] Appl. Polymer Sci. 1966,10(5): 929～937
[5] G. F. Fanta, R. C. Burr, C. R. Russell, et, al. Graft copolymers of starch. Ⅱ Copolymerization of gelatinized wheat starch with acrylonitrile. Influence of reaction conditions on copolymer compounds [J] Polymer Sci. Pt B 1966,10:765～769
[6] G F Fanta, R C Burr, C R Russell,et al. Graft copolymers of starch. Ⅲ Copolymerization of gelatinized wheat starch with acrylonitrile. Influence of reaction conditions on copolymer compounds [J] Polymer Sci. Pt B J Appl Polym [J], 1967,11(3):457
[7] L Gugliemelli,M O Weaver, C R Russell. Base-hydrolyzed starch-polyacrylonitrile (S-PAN)graft copolymer. J Appl Polymer Sci, 1969,13(6)2007～201
[8] 黄伯芬，王刚．ZG—93丙烯酸共聚物阻垢分散剂的研制及阻垢机理探讨[J]．化学世界，1996，(2)：88～94．
[9] 秦增全．马来酸酐—丙烯酸共聚物的制备方法[J]．CN：1099764A，1995．
[10] 许观藩，方天如，高林，等．低分子量水溶性聚合物的制备[J]．CN：1085568A，1994．
[11] BASF G. Muenster A.Rohmann M. U.S.P4301266,1981.
[12] Hughes K.A Kine B.B Swift G. U.S.P4314044,1982.
[14] Nagarajan M.K. Journal of the American Oil Chemist's Society 1985,62(5):949～955.
[15] Robert. L. Davidson. Handbook of Water-Soluble Gum and Resins.New york, 1980.
[16] Laurence GD. Polyacrylate thickening: agents[p].US:4 338 239,1982.
[17] Boisvert J P, Persello J, Castding J C, et al. Dispersion of alumina coated TiO_2 Particles by adsorption of sodium polyacxylate. Colloids and Surfaces, 2001,178(1): 187—198
[18] Hua F, Qian M. Synthesis of self-crosslinking sodium polyacrylate hydrogel and woter-absorbing mechanism. Journal of Materials Socience,2001,36(3):731～738
[19]余学军，徐丹，刘明，等．速溶高分子量聚丙烯酸钠的合成研究[J]．化学世界，1999，(6)：310～312．
[20](日)山口繁，坪井启史，入江好夫．马来酸基共聚物及其制备方法和应用[P]．JP：94190523．3，1995-11-29．
[21]万福忠，陈昌镜，朱艳梅．常温合成高分子量聚丙烯酸钠及其分子量的测定[J]．湖北化工 1994，(3)：28～30．
[22]康正，崔英德，郭建维，等．年产120吨聚丙烯酸钠絮凝剂的工艺设计与投产[J]．广州化工，2000，28(4)：151～153．
[23]戚银城，刘宝龙．高分子量聚丙烯酸钠的合成及应用研究[J]．北京化工学院学报(自然科学版)，1990，17(1)：19～24．
[24]韩淑珍．反相悬浮聚合法新工艺合成聚丙烯酸钠高分子絮凝剂工业化开发研究[J]．精细与专用化学品，2000，(17)：15～17．
[25]徐湘凌，张志成，费宾，等．丙烯酸钠反相乳液聚合[J]．高分子学报，1998，(2)：134～138．
[26]卢万明．固体聚丙烯酸钠在我厂的使用效果[J]．氯碱工业，1997，(12)：4～5．
[27]李泽洁．聚丙烯酸钠助沉剂在精制盐水中的应用[J]．福建化工，1998，(4)：20～21．
[28]王德怀．速溶型固体聚丙烯酸钠用于盐水助沉的试验[J]．氯碱工业，1995，(11)：16～19．
[29](日)山田、兴一．赤泥的絮凝与沉降[J]．轻金属[J]，1980，(3)：20～21．
[30]江新民，桂康．聚丙烯酸钠在赤泥分离中的应用[J]．轻金属，1999，(6)：17～20．
[31]黄民生，朱莉．味精废水的絮凝—吸附法预处理试验研究[J]．水处理技术，1998，24(5)：299～302．
[32]买文宁，黄普选．味精发酵母液提取蛋白饲料[J]．给水排水，2002，28(11)：43～44
[33]张轶东，曾心苗，李朝顺，等．高效蛋白质浓缩剂的制备及浓缩作用的研究[J]．离子交换与吸附，1997，(6)．
[34]张国民．氯碱行业现状分析和2002年发展展望．中国经济展望：产业卷，2002(1)；266～276
[35]无．2001年纯碱市场回顾与2002年纯碱市场预测．中国石油和化工分析报告，2002，(3)：50～51
[36]郭铨，刘淑娟．流程计算-化学平衡、物料和热量平衡．第一版．北京：科学出版社．1985．5～10
[37]上海医药管理局上海医药设计院．化工工艺设计手册(下册)．第一版．北京：化学工业出版社．1986．733～737
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