无磷水处理阻垢剂的合成与应用研究
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摘要
工业循环水中大量使用的含磷阻垢缓蚀剂,对水资源和环境的破坏日益引起了人们的高度重视,我国部分省市在禁止使用含磷洗涤剂的基础上已开始限制含磷阻垢剂的使用,开发推广无磷阻垢剂是水处理技术的发展方向。
本文研究开发了两种无磷阻垢剂,一是以L-天冬氨酸为主要原料合成的聚天冬氨酸;二是利用水溶液聚合工艺合成的丙烯酸—马来酸酐—丙烯酸甲酯三元共聚物,并表征了其结构。依据火电厂循环水阻垢剂性能测试规范,完成了模拟水样和国内五个大型火电厂水样静态阻垢性能的测试,结果表明,这两种阻垢剂的组合使用,可以对碳酸钙的阻垢率达到或接近100%,且用量小于含磷系列,为进一步的工业推广奠定了基础。
合成聚天冬氨酸的条件:反应温度为180～220℃、反应时间2h、催化剂量5%;水解5克聚琥珀酰亚胺需要2mol/L的NaOH溶液30ml、水解温度50～60℃、时间1h、用0.008molHCl中和;将水解液缓慢滴入高速搅拌的甲醇中,甲醇用量为水解液质量的3～6倍。在此工艺下得到聚天冬氨酸钠粉末,外观为白色的轻质粉末,堆积密度0.35g/ml,不用进行脱色和粉碎。
合成丙烯酸三元共聚物的条件为:在氧化还原引发体系下单体配比为丙烯酸甲酯:丙烯酸:顺酐=3∶2.5∶4.5、混合引发剂用量8%、反应温度60～70℃、时间5小时。
Amount of organic and inorganic phosphorus scale inhibitor used in industrial recycling water damaged water resources and polluted environment. This attracts people attention increasingly. On the basis of prohibition of phosphorus-containing detergent, many cities in China started restricting the use of phosphorus-containing scale inhibitor. Developing and applying phosphate-free scale water treatment technology is the direction of water treatment industry.
In this paper, two kinds of phosphate-free scale water treatments was researched and developed. One is polyaspartic acid synthesized using L-aspartic acid as the main raw material; the other is AA/MA/MAc copolymers synthesized by aqueous solution polymerization process, meanwhile their structures were characterized and the molecular weight distribution was tested. We finished the scales of static water samples testing in simulation water and in five domestic large-scale thermal power recycling water basing on scale of standardized test performance. The results showed that both using these two scale inhibitors, the inhibition rate of CaCO3 is at or near 100%, and the amount is less than phosphorus-containing. The research pave the way to promote the industrialization.
The optimum reaction conditions of polyaspartic acid were found as follows: Reaction temperature ranges from 180～220℃.Reaction time duration is about 2 hs. Consumption amount of catalyzer is 5 % of the amount of L-aspartic acid,it need 30ml 2mol / L NaOH solution to hydrolyze 5g polysuccinimide. The temperature of hydrolyzable reaction ranges from 50～60℃and the reaction time is 1.0 h. The Consumption amount of HC1 to neutralize the remanent NaOH is about 0.08mol/L. the white low-density powder of the the sodium salt of polyaspartic acid are got by dropping the hydrolyzable solution to carbinol that its Consumption amount is 3～6 times to the amount of solution. the powder's density is about 0.35g/ml.
The optimum reaction conditions of acrylic copolymers were found as follows:In oxidation - reduction system, MA/AA/MAc = 3:2.5:4.5. Consumption amount of initiator is 8%.Reaction temperature ranges from 60～70℃, and reaction time duration is about 5 hs.
本文研究开发了两种无磷阻垢剂,一是以L-天冬氨酸为主要原料合成的聚天冬氨酸;二是利用水溶液聚合工艺合成的丙烯酸—马来酸酐—丙烯酸甲酯三元共聚物,并表征了其结构。依据火电厂循环水阻垢剂性能测试规范,完成了模拟水样和国内五个大型火电厂水样静态阻垢性能的测试,结果表明,这两种阻垢剂的组合使用,可以对碳酸钙的阻垢率达到或接近100%,且用量小于含磷系列,为进一步的工业推广奠定了基础。
合成聚天冬氨酸的条件:反应温度为180～220℃、反应时间2h、催化剂量5%;水解5克聚琥珀酰亚胺需要2mol/L的NaOH溶液30ml、水解温度50～60℃、时间1h、用0.008molHCl中和;将水解液缓慢滴入高速搅拌的甲醇中,甲醇用量为水解液质量的3～6倍。在此工艺下得到聚天冬氨酸钠粉末,外观为白色的轻质粉末,堆积密度0.35g/ml,不用进行脱色和粉碎。
合成丙烯酸三元共聚物的条件为:在氧化还原引发体系下单体配比为丙烯酸甲酯:丙烯酸:顺酐=3∶2.5∶4.5、混合引发剂用量8%、反应温度60～70℃、时间5小时。
Amount of organic and inorganic phosphorus scale inhibitor used in industrial recycling water damaged water resources and polluted environment. This attracts people attention increasingly. On the basis of prohibition of phosphorus-containing detergent, many cities in China started restricting the use of phosphorus-containing scale inhibitor. Developing and applying phosphate-free scale water treatment technology is the direction of water treatment industry.
In this paper, two kinds of phosphate-free scale water treatments was researched and developed. One is polyaspartic acid synthesized using L-aspartic acid as the main raw material; the other is AA/MA/MAc copolymers synthesized by aqueous solution polymerization process, meanwhile their structures were characterized and the molecular weight distribution was tested. We finished the scales of static water samples testing in simulation water and in five domestic large-scale thermal power recycling water basing on scale of standardized test performance. The results showed that both using these two scale inhibitors, the inhibition rate of CaCO3 is at or near 100%, and the amount is less than phosphorus-containing. The research pave the way to promote the industrialization.
The optimum reaction conditions of polyaspartic acid were found as follows: Reaction temperature ranges from 180～220℃.Reaction time duration is about 2 hs. Consumption amount of catalyzer is 5 % of the amount of L-aspartic acid,it need 30ml 2mol / L NaOH solution to hydrolyze 5g polysuccinimide. The temperature of hydrolyzable reaction ranges from 50～60℃and the reaction time is 1.0 h. The Consumption amount of HC1 to neutralize the remanent NaOH is about 0.08mol/L. the white low-density powder of the the sodium salt of polyaspartic acid are got by dropping the hydrolyzable solution to carbinol that its Consumption amount is 3～6 times to the amount of solution. the powder's density is about 0.35g/ml.
The optimum reaction conditions of acrylic copolymers were found as follows:In oxidation - reduction system, MA/AA/MAc = 3:2.5:4.5. Consumption amount of initiator is 8%.Reaction temperature ranges from 60～70℃, and reaction time duration is about 5 hs.
引文
[1]汪祖模.水质稳定剂.北京华东化工学院出版社,1996
[2]李瑞华.工业阻垢剂的最新发展.北京化工,1990.20(3):41-46
[3]李瑞华.阻垢剂的最新进展.化工时刊,1989,(5):2-9
[4]周本省.工业水处理技术.第一版.北京:化学工业出版社,1997
[5]尤秀兰.绿色阻垢剂的研究进展.化学清洗,2000,16(2):25-26
[6]艾仕云.有机膦酸盐缓蚀阻垢剂的研究和发展.化学清洗,1997,1(1):27-30
[7]路长青,韩应琳,马迎军等.阻垢剂的性能及其协同效应.应用化学,1996,13(1):83-85
[8]鲍其鼎,何高荣.我国冷却水处理剂的研究与开发.水处理技术研讨会论文集
[9]傅承碧EDTMP和HDTMP的合成及缓蚀阻垢性能的研究.沈阳化工,1996,(1):1-4
[10]项成林.有机膦羧酸盐缓蚀阻垢剂的研究与应用.工业水处理,1993,(3):3-7
[11]徐晓东.绿色水处理剂的研究及应用进展.工业水处理,2001,18(3):47-49
[12]马政生.无磷洗涤助剂.第一版.北京:化学工业出版社,2005
[13]高秀山,张渡.火电厂循环冷却水处理.第一版.中国电力出版社,2002
[14]Gregory J.McGiffney..Method of Controlling Scale Formation in Brine Concentration and Evaporation System.U.S.Patent 5866011
[15]熊蓉春,魏刚,周娣等.绿色阻垢剂环氧琥珀酸的合成.工业水处理.1999(3):11-13
[16]吕志芳,董伟,夏明珠等.聚环氧琥珀酸的阻垢缓蚀性能研究.工业水理.2001(3):23-25
[17]谢荣禄.天冬氨酸镁钾对伴有心衰的心律失常的影响.广东药学院学报[J],1999,5(1):9-60.
[18]杨士林,黄君礼,陶虎春等.阻垢剂-聚天冬氨酸的致突变性,健康与环境杂志[J],2004,21(6):398-400.
[19]Koweton S,Huang S J,Swift G.Polyaspartic acid:synthesis,biodegradation and current application[J],Environ.Polym.Degrad.,1997,5(3):175-181.
[20]Groth,et al.Process for preparing polysuccinimide and polyaspartic acid[P],US,5610255,1997.
[21]Sikes C S,Weeler A P.Inhibition of inorganic or biological CaCO_3 deposition by polyamino acid derivatives[P],US,4534881,1985.
[22]Koskan L P,Low K C.Polyaspartic acid as a calcium carbonate and a calcium phosphate inhibitor[P],WO:92-16462,1992,09,15.
[23]Koskan L P,Low K C.Polyaspartic acid as calcium sulfate and a barium sulfate inhibitor [P],US,5116513,1992.
[24]张冰如,风亭.生物可降解聚天冬氨酸阻垢性能的研究[J],工业水处理,2004,2:46-48.
[25]洋式林,黄君礼等.聚天冬氨酸制造工艺进展[J].环境污染治理技术与设备,2002,9(3):38-41.
[26]徐寿昌.工业冷却水处理技术[A],北京化学工业出版社,1984.8,87-89
[27]Compton R G,Daly P J.The dissolution/precipition kinetics of calcium carbonate:an assessment of various kinetics equations using a rotating disk electrode[J].Journal of Colloid and Interface Science,1987:115,493.
[28]Morgenthaler L N,Khaib Z I,French R N i,Cox K R.Chemical simulate for scale problems in Oil and gasproduction.Material Performance,1991:37.
[29]Geiger G E.Improve corrosion and deposition control in alkaline cooling water systems.Hydrocarbon Processing.1996:93,
[30]Patel S,N icol A J.Developing a cooling water inhibitor with multifunctional deposit control properties.Material Performance,1996:41.
[31]Suitor J W,MarnerW J,Ritter R B.The history and status of research in fouling of heat exchanger in cooling water service[J].Can J Chem.Eng,1977,55:374.
[32]郑邦乾,清泉,分子阻垢剂及其阻垢机理[J].油田化学,1984,(2):81.
[33]Gill,J S,Anderson.C D,Varsanik.R G.Mechanism of scale inhibition by phosphonstes [A].Proc 44th Int.Water Conf[C].Pittaburgy:Pa(USA),1983,4:6.
[34]汪祖模,蔡兰坤.有机膦酸羧酸型水质稳定剂的研究[J].华东化工学院学报,1989(5):05.
[35]Carter P W,Hillier A C,Ward M D.Nano scale surface topotraphy growth of molecule crystals:the role of an isotropic inter-molecule by bonding[J].Am.Chem.Soc.1994,116:944.
[36]雷武,冷却水系统中阻垢剂性能的评定方法[J].化工进展,2002,21(4):275.
[37]安钢,孙波,魏荣宝,董迎.聚天门冬氨酸阻垢作用的研究,天津理工学院学报[J],2002,18(3):34-36
[38]Ian Ralph Collins.Surface Electrical Properties of Barium Sulfate Modified by Adsorption of Poly α,βAspartic Acid,Journal of Colloid and Interface Science[J],212,535-544(1999)
[39]孙波,魏荣宝,安钢,米镇涛.类蛋白质阻垢剂聚天门冬氨酸的合成研究,南开大学[J],2002,35(2):90-96
[40]徐耀军,杨文中,等.聚天冬氨酸的阻垢缓蚀性能[J].南京工业大学学报,2002,24(1):87-89.
[41]中村亦夫.增溶水溶性高分子[M].东京:化学工业社,1984.
[42]GB-16632-1996碳酸钙沉淀法测定阻垢剂的阻垢率
[43]霍宇凝.环保型水处理剂聚天冬氨酸及其复配物的研制与阻垢缓蚀性能的研究[D].华东理工大学,2001,41
[44]冷一欣.聚天冬氨酸的合成与应用[D].南京工业大学,2005,22
[45]黄家董,宋华烈,宋景尧.辽宁化工,1986,(6):8-14
[46]徐群杰,单贞华,周国定.复配聚天冬氨酸对3%NaCl溶液中白铜(B30)的缓蚀作用[J].华东电力,2006,34(5):16-18
[2]李瑞华.工业阻垢剂的最新发展.北京化工,1990.20(3):41-46
[3]李瑞华.阻垢剂的最新进展.化工时刊,1989,(5):2-9
[4]周本省.工业水处理技术.第一版.北京:化学工业出版社,1997
[5]尤秀兰.绿色阻垢剂的研究进展.化学清洗,2000,16(2):25-26
[6]艾仕云.有机膦酸盐缓蚀阻垢剂的研究和发展.化学清洗,1997,1(1):27-30
[7]路长青,韩应琳,马迎军等.阻垢剂的性能及其协同效应.应用化学,1996,13(1):83-85
[8]鲍其鼎,何高荣.我国冷却水处理剂的研究与开发.水处理技术研讨会论文集
[9]傅承碧EDTMP和HDTMP的合成及缓蚀阻垢性能的研究.沈阳化工,1996,(1):1-4
[10]项成林.有机膦羧酸盐缓蚀阻垢剂的研究与应用.工业水处理,1993,(3):3-7
[11]徐晓东.绿色水处理剂的研究及应用进展.工业水处理,2001,18(3):47-49
[12]马政生.无磷洗涤助剂.第一版.北京:化学工业出版社,2005
[13]高秀山,张渡.火电厂循环冷却水处理.第一版.中国电力出版社,2002
[14]Gregory J.McGiffney..Method of Controlling Scale Formation in Brine Concentration and Evaporation System.U.S.Patent 5866011
[15]熊蓉春,魏刚,周娣等.绿色阻垢剂环氧琥珀酸的合成.工业水处理.1999(3):11-13
[16]吕志芳,董伟,夏明珠等.聚环氧琥珀酸的阻垢缓蚀性能研究.工业水理.2001(3):23-25
[17]谢荣禄.天冬氨酸镁钾对伴有心衰的心律失常的影响.广东药学院学报[J],1999,5(1):9-60.
[18]杨士林,黄君礼,陶虎春等.阻垢剂-聚天冬氨酸的致突变性,健康与环境杂志[J],2004,21(6):398-400.
[19]Koweton S,Huang S J,Swift G.Polyaspartic acid:synthesis,biodegradation and current application[J],Environ.Polym.Degrad.,1997,5(3):175-181.
[20]Groth,et al.Process for preparing polysuccinimide and polyaspartic acid[P],US,5610255,1997.
[21]Sikes C S,Weeler A P.Inhibition of inorganic or biological CaCO_3 deposition by polyamino acid derivatives[P],US,4534881,1985.
[22]Koskan L P,Low K C.Polyaspartic acid as a calcium carbonate and a calcium phosphate inhibitor[P],WO:92-16462,1992,09,15.
[23]Koskan L P,Low K C.Polyaspartic acid as calcium sulfate and a barium sulfate inhibitor [P],US,5116513,1992.
[24]张冰如,风亭.生物可降解聚天冬氨酸阻垢性能的研究[J],工业水处理,2004,2:46-48.
[25]洋式林,黄君礼等.聚天冬氨酸制造工艺进展[J].环境污染治理技术与设备,2002,9(3):38-41.
[26]徐寿昌.工业冷却水处理技术[A],北京化学工业出版社,1984.8,87-89
[27]Compton R G,Daly P J.The dissolution/precipition kinetics of calcium carbonate:an assessment of various kinetics equations using a rotating disk electrode[J].Journal of Colloid and Interface Science,1987:115,493.
[28]Morgenthaler L N,Khaib Z I,French R N i,Cox K R.Chemical simulate for scale problems in Oil and gasproduction.Material Performance,1991:37.
[29]Geiger G E.Improve corrosion and deposition control in alkaline cooling water systems.Hydrocarbon Processing.1996:93,
[30]Patel S,N icol A J.Developing a cooling water inhibitor with multifunctional deposit control properties.Material Performance,1996:41.
[31]Suitor J W,MarnerW J,Ritter R B.The history and status of research in fouling of heat exchanger in cooling water service[J].Can J Chem.Eng,1977,55:374.
[32]郑邦乾,清泉,分子阻垢剂及其阻垢机理[J].油田化学,1984,(2):81.
[33]Gill,J S,Anderson.C D,Varsanik.R G.Mechanism of scale inhibition by phosphonstes [A].Proc 44th Int.Water Conf[C].Pittaburgy:Pa(USA),1983,4:6.
[34]汪祖模,蔡兰坤.有机膦酸羧酸型水质稳定剂的研究[J].华东化工学院学报,1989(5):05.
[35]Carter P W,Hillier A C,Ward M D.Nano scale surface topotraphy growth of molecule crystals:the role of an isotropic inter-molecule by bonding[J].Am.Chem.Soc.1994,116:944.
[36]雷武,冷却水系统中阻垢剂性能的评定方法[J].化工进展,2002,21(4):275.
[37]安钢,孙波,魏荣宝,董迎.聚天门冬氨酸阻垢作用的研究,天津理工学院学报[J],2002,18(3):34-36
[38]Ian Ralph Collins.Surface Electrical Properties of Barium Sulfate Modified by Adsorption of Poly α,βAspartic Acid,Journal of Colloid and Interface Science[J],212,535-544(1999)
[39]孙波,魏荣宝,安钢,米镇涛.类蛋白质阻垢剂聚天门冬氨酸的合成研究,南开大学[J],2002,35(2):90-96
[40]徐耀军,杨文中,等.聚天冬氨酸的阻垢缓蚀性能[J].南京工业大学学报,2002,24(1):87-89.
[41]中村亦夫.增溶水溶性高分子[M].东京:化学工业社,1984.
[42]GB-16632-1996碳酸钙沉淀法测定阻垢剂的阻垢率
[43]霍宇凝.环保型水处理剂聚天冬氨酸及其复配物的研制与阻垢缓蚀性能的研究[D].华东理工大学,2001,41
[44]冷一欣.聚天冬氨酸的合成与应用[D].南京工业大学,2005,22
[45]黄家董,宋华烈,宋景尧.辽宁化工,1986,(6):8-14
[46]徐群杰,单贞华,周国定.复配聚天冬氨酸对3%NaCl溶液中白铜(B30)的缓蚀作用[J].华东电力,2006,34(5):16-18