有机膦羧酸型水质稳定剂的合成及其缓蚀阻垢性能研究
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摘要
膦羧酸型水质稳定剂，缓蚀阻垢性能的优异和污染少而在工业冷却水处理系统中应用越来越普遍。本学位论文以膦羧酸型化合物2-膦酸丁烷-1，2，4-三羧酸(简称PBTCA)和聚合膦羧酸型化合物膦酸化水解聚马来酸酐(简称PHPMA)为研究对象，实验研究了合成两种产品的新工艺条件，并对合成产品的组成结构进行了分析。在缓蚀阻垢性能方面对合成产品进行了实验研究。合成的两种产品为开发精细磷化工产品开辟了一条新的途径。
以亚磷酸二乙脂、反丁烯二酸二乙脂、丙烯酸乙脂等为反应原料，在碱性催化剂(乙二胺)的作用下经三步反应得到2-膦酸丁烷-1，2，4-三羧酸(简称PBTCA)。在水为溶剂、H_2O_2为引发剂、FeCl_3为催化剂的条件下，以顺丁烯二酸酐和亚磷酸为原料经两步反应合成制得膦酸化水解聚马来酸酐(简称PHPMA)。用红外光谱、质谱和高效液相色谱对合成产品的组成结构进行了分析。
以旋转挂片失重法分别考察了合成产品在单独使用、预膜处理和以金属离子复配的情况下的缓蚀性能。结果表明：合成的PBTCA产品在20mg/l的药剂用量时就可达到明显的缓蚀效果；在预膜处理时，只需加入4mg/l的用量就可达到缓蚀要求；在复配时与Zn~(2+)的协同性较好。合成的PHPMA产品在50mg/l的药剂用量下其缓蚀率可达90%以上；预膜处理，只需10mg/l就能达到缓蚀要求；在复配时与Ni~(2+)的协同性较为明显。
以动态鼓泡法研究了合成产品的阻垢性能。实验验证了合成产品在低浓度下，CaCO_3晶体生长动力学属于Langmuir吸附模型。考察了合成的PHPMA产品在不同的药剂用量、PH值、钙离子浓度等条件下的阻垢性能。
研究结果表明，合成产品缓蚀阻垢性能较高，适合应用于工业冷却水处理系统。
The organic phosphoncarboxylic acid water stabilizing agents are widely used in industrial cooling water system, for their excellent anticorrosion and antiscaling properties.
Phosphonocarboxylic acid compound 2-phosphonobutane-1,2,4梩ricarboxylic acid(PBTCA), and poly-phosphonocarboxylic acid compound-phosphonated hydrolytic polymaleic anhydride(PHPMA) was synthesized with a new synthetic technique. These two products have been studied with experimental methods. The systematically experimental study of synthetic products in corrosion and scale inhibition properties has been done.
The 2-phosphonobutane-l,2,4-tricarboxylic acid(PBTCA) was synthesized through 3 reactive steps by using fumaric diethylester, ethyl phosphite, and ethyl acrylate as raw material and using ethylenediamine as catalyzer. The synthesis of phosphonoanted hydrolytic polymaleic anhydride(PHPMA) can be completed with 2 steps by using water as solvent, maleic anhydride and phosphorous acid as raw material, F^C^ as causer, FeCl? as catalyzer, at temperature about llO'C.The molecular structure and composition were analyzed by using IR spectrum, mass spectrum and high performance liquid chromatography(HPLC).
A rotary hanged weight losing method was used to measure the anti corrosion properties of the synthetic products in different dosages. The result indicate: 20mg/l of PBTCA shows significant effect of anticorrosion. If it is used in pretreatment, 4mg/l of PBTCA was enpugh to reach the same effect. Furthermore, Zn2+ greatly enhanced the anticorrosion effect of anticorrosion of PBTCA. 50mg/l of PHPMA shows great effect of anticorrosion. When it is used in pretreatment film, 10mg/l of was enough to get the same effect. Especially, Ni2+ can enhance the anticorrosion of PHPMA.
The antiscaling property of synthetic products was studied by using method of
dynamic bubble. Especially, the kinetic study of inhibition mechanism of PBTCA on CaCO3 scale was made through experiment. It is found that the absorption of PBTCA on the crystal surface accords with the characters of Langmuir model, which is a kind of single molecule layer sorption. For synthesis PHPMA product, its scale inhibition properties was experimentally investigated in different dosage of agent, value of PH , and concentration of calcium ion.
The studied results show: the synthetic two products have excellent anticorrosion and antiscaling properties, so these two products can be used in industrial cooling water treatment system.
以亚磷酸二乙脂、反丁烯二酸二乙脂、丙烯酸乙脂等为反应原料，在碱性催化剂(乙二胺)的作用下经三步反应得到2-膦酸丁烷-1，2，4-三羧酸(简称PBTCA)。在水为溶剂、H_2O_2为引发剂、FeCl_3为催化剂的条件下，以顺丁烯二酸酐和亚磷酸为原料经两步反应合成制得膦酸化水解聚马来酸酐(简称PHPMA)。用红外光谱、质谱和高效液相色谱对合成产品的组成结构进行了分析。
以旋转挂片失重法分别考察了合成产品在单独使用、预膜处理和以金属离子复配的情况下的缓蚀性能。结果表明：合成的PBTCA产品在20mg/l的药剂用量时就可达到明显的缓蚀效果；在预膜处理时，只需加入4mg/l的用量就可达到缓蚀要求；在复配时与Zn~(2+)的协同性较好。合成的PHPMA产品在50mg/l的药剂用量下其缓蚀率可达90%以上；预膜处理，只需10mg/l就能达到缓蚀要求；在复配时与Ni~(2+)的协同性较为明显。
以动态鼓泡法研究了合成产品的阻垢性能。实验验证了合成产品在低浓度下，CaCO_3晶体生长动力学属于Langmuir吸附模型。考察了合成的PHPMA产品在不同的药剂用量、PH值、钙离子浓度等条件下的阻垢性能。
研究结果表明，合成产品缓蚀阻垢性能较高，适合应用于工业冷却水处理系统。
The organic phosphoncarboxylic acid water stabilizing agents are widely used in industrial cooling water system, for their excellent anticorrosion and antiscaling properties.
Phosphonocarboxylic acid compound 2-phosphonobutane-1,2,4梩ricarboxylic acid(PBTCA), and poly-phosphonocarboxylic acid compound-phosphonated hydrolytic polymaleic anhydride(PHPMA) was synthesized with a new synthetic technique. These two products have been studied with experimental methods. The systematically experimental study of synthetic products in corrosion and scale inhibition properties has been done.
The 2-phosphonobutane-l,2,4-tricarboxylic acid(PBTCA) was synthesized through 3 reactive steps by using fumaric diethylester, ethyl phosphite, and ethyl acrylate as raw material and using ethylenediamine as catalyzer. The synthesis of phosphonoanted hydrolytic polymaleic anhydride(PHPMA) can be completed with 2 steps by using water as solvent, maleic anhydride and phosphorous acid as raw material, F^C^ as causer, FeCl? as catalyzer, at temperature about llO'C.The molecular structure and composition were analyzed by using IR spectrum, mass spectrum and high performance liquid chromatography(HPLC).
A rotary hanged weight losing method was used to measure the anti corrosion properties of the synthetic products in different dosages. The result indicate: 20mg/l of PBTCA shows significant effect of anticorrosion. If it is used in pretreatment, 4mg/l of PBTCA was enpugh to reach the same effect. Furthermore, Zn2+ greatly enhanced the anticorrosion effect of anticorrosion of PBTCA. 50mg/l of PHPMA shows great effect of anticorrosion. When it is used in pretreatment film, 10mg/l of was enough to get the same effect. Especially, Ni2+ can enhance the anticorrosion of PHPMA.
The antiscaling property of synthetic products was studied by using method of
dynamic bubble. Especially, the kinetic study of inhibition mechanism of PBTCA on CaCO3 scale was made through experiment. It is found that the absorption of PBTCA on the crystal surface accords with the characters of Langmuir model, which is a kind of single molecule layer sorption. For synthesis PHPMA product, its scale inhibition properties was experimentally investigated in different dosage of agent, value of PH , and concentration of calcium ion.
The studied results show: the synthetic two products have excellent anticorrosion and antiscaling properties, so these two products can be used in industrial cooling water treatment system.
引文
1．马梅生，我国水污染状况及控制对策，水处理技术，1995，21(6)，11-14。
2．徐寿吕，工业冷却水处理技术，化学工业出版社，1984。
3．李仲先，循环冷却水的水质稳定与处理，冶金出版社，1987。
4．龙荷云，循环冷却水处理，江苏科学技术出版社，1991。
5．纪永亮、林明鹤，工业循环冷却水处理技术进展，工业水处理，1990，10(1)，3-7。
6. Journal of the cooling tower institute, 1985,6(1),18-23
7．天津化工研究院503组，磷系配方用于循环冷却水时的适用条件，工业水处理，1981，2，10-13
8. Herbert H. Uhling, Corrosion and Corrosion Control, John Wiley & Sons Inc., New York, 1971
9．铃木静夫、加藤健司，工业用水处理，东京内田老鹤圃新社，1971
10. C. C. Nathan, Corrosion Inhibitors, National Association of Corrosion Engineers, Houston Taxas, 1973
11. Betz Laboratories, Inc., Betz Handbook of Industrial water Conditioning (Seventh edition), Trevose. Pennsylvania, 1986
12．许建华，水的特种处理，上海，同济大学出版社，1989
13．黄伯芬、王刚，化学世界，1996，2，89
14. Edward D. Schroeder, Water and wastewater Treatment, McGraw-Hill Book Company. USA, 1977
15. Ruta Rakutis, Water Management Chemicals, Special Chemicals, 1987,32(4),71-79
16．李慰庭，有机膦酸及其在水处理技术中的多方面应用，工业水处理，1989，4，1-12
17．汪祖模、徐玉佩，有机多元膦酸的制备及其在水处理等方面的应用，华东化工学院学报，1987，3，14-20
18. w. James, Mccop, The Chemical Treatment of Cooling Water, Chemical Publishing Company, New York, 1974
19. Arthur, J. Freedman, Materials Performance, 1974,13(12),114-118
20. G. Bohnsack, Mechanisms of Organic Inhibitors Used in Cooling Water corrosion control, Materials Performance, 1986,25(5),277-280
21. T. Imai and T. Uchida, A newly Developed Polymer to Inhibit Scale in Cooling Water Systems, Material performance, 1992,49(5),1203-1208
22．徐北妮，我国水处理剂现状与发展，化学工程师，1998，6(3)，43-45
23．汪祖模、蔡兰坤，有机膦羧酸型水质稳定剂的研究，华东化工学院学报，1989，15(6)，699-704
24．李裕芳，我国冷却水处理技术的现状与展望，工业水处理，1988，4，25-29
25．熊家林、刘钊杰、贡长生，磷化工概论，化学工业出版社，1994，224-226
26．Ger Offen，2061838 1971
27．韩应琳、刁月民，2-膦酸丁烷-1，2，4-三羧酸的合成，工业水处理，1993，13(6)，16-19
28．汪祖模、徐丽英，聚合膦羧酸型水质稳定剂的合成与缓蚀阻垢性能的评定，华东化工学院学报，1986，12(1)，69-77
29. USP 4931586 1971
30. A. N. Pudovik, IV Konovalova, Synthesis, 1979,2,81
31. Shizunobu Hayashimoto, Doshisha Diaigaku Keukyu Hokoku, 1967,7(4),193-202
32. A. Marshall, An Investigation into the Mechanism of Syneyistic Dimodic Corrosion Inhibitor, Corrosion, 1981,37(4),214-216
33．桑希勤，水为溶剂膦羧酸型水质稳定剂的合成及性能测定，化学工程师，1998，6(3)，43-45
34．中华人民共和国国国家标准，GB/T 10535-1997——“水处理剂 水解聚马来酸酐”
35．化工行业标准HG/T 2159-91，水处理剂缓蚀性能测定—旋转挂片法
36．化工行业标准HG/T 5-1526—83，冷却水化学处理标准腐蚀片技术条件
37. A Catalogue from CIBA-GEIGY(UK) Limited 1983: "A New, advanced, versatile building block for use in water treatment"
38．项成林，有机膦羧酸缓蚀阻垢剂的研究与应用，工业水处理，1993，13(6)，3-7
39．[美]J．W．麦科伊，冷却水的化学处理，化工部化工设计院译，化学工业出版社，1979年
40. E. Barbara, Surface Studies of Corrosion Inhibitors in Cooling Water
systems, Materials Performance, 1990,29(1),158-162
41．于令弟，磷系水处理复合配方的研究，化工进展，1997，2，47-50
42．检索查新报告书，云南省科技情报研究所查新中心，编号：2001-390
43．化工行业标准HG/T 2024-91水处理药剂阻垢性能测定方法—鼓泡法
44．闵乃本，晶体生长的物理基础，上海科学技术出版社，1980
45．天津大学物理化学教研室，物理化学，北京，高等教育出版社，1979
46. G. H. Nancollas, M. M. Reedy, The Kinetics of Crystallization of Scale Forming Minerals, Petrol. Eng. J., 1974,(4),117-126
47. G. H. Nancollas, M. M. Reedy, The Crystallization of Calcium Carbonate Ⅱ, Calcite Growth Mechanism, J. Coll. And Interface. Sci., 1971,(37),824-830
48. M. M. Reedy, G. H. Nancollas, The Crystallization of Calcium Carbonate Ⅰ, Isotopic Exchange and Kinetics, J. Coll. And Interface. Sci., 1971,(36),166-172
49．汪祖模，水质稳定剂，上海，华东化工学院出版社，1991，245-268
2．徐寿吕，工业冷却水处理技术，化学工业出版社，1984。
3．李仲先，循环冷却水的水质稳定与处理，冶金出版社，1987。
4．龙荷云，循环冷却水处理，江苏科学技术出版社，1991。
5．纪永亮、林明鹤，工业循环冷却水处理技术进展，工业水处理，1990，10(1)，3-7。
6. Journal of the cooling tower institute, 1985,6(1),18-23
7．天津化工研究院503组，磷系配方用于循环冷却水时的适用条件，工业水处理，1981，2，10-13
8. Herbert H. Uhling, Corrosion and Corrosion Control, John Wiley & Sons Inc., New York, 1971
9．铃木静夫、加藤健司，工业用水处理，东京内田老鹤圃新社，1971
10. C. C. Nathan, Corrosion Inhibitors, National Association of Corrosion Engineers, Houston Taxas, 1973
11. Betz Laboratories, Inc., Betz Handbook of Industrial water Conditioning (Seventh edition), Trevose. Pennsylvania, 1986
12．许建华，水的特种处理，上海，同济大学出版社，1989
13．黄伯芬、王刚，化学世界，1996，2，89
14. Edward D. Schroeder, Water and wastewater Treatment, McGraw-Hill Book Company. USA, 1977
15. Ruta Rakutis, Water Management Chemicals, Special Chemicals, 1987,32(4),71-79
16．李慰庭，有机膦酸及其在水处理技术中的多方面应用，工业水处理，1989，4，1-12
17．汪祖模、徐玉佩，有机多元膦酸的制备及其在水处理等方面的应用，华东化工学院学报，1987，3，14-20
18. w. James, Mccop, The Chemical Treatment of Cooling Water, Chemical Publishing Company, New York, 1974
19. Arthur, J. Freedman, Materials Performance, 1974,13(12),114-118
20. G. Bohnsack, Mechanisms of Organic Inhibitors Used in Cooling Water corrosion control, Materials Performance, 1986,25(5),277-280
21. T. Imai and T. Uchida, A newly Developed Polymer to Inhibit Scale in Cooling Water Systems, Material performance, 1992,49(5),1203-1208
22．徐北妮，我国水处理剂现状与发展，化学工程师，1998，6(3)，43-45
23．汪祖模、蔡兰坤，有机膦羧酸型水质稳定剂的研究，华东化工学院学报，1989，15(6)，699-704
24．李裕芳，我国冷却水处理技术的现状与展望，工业水处理，1988，4，25-29
25．熊家林、刘钊杰、贡长生，磷化工概论，化学工业出版社，1994，224-226
26．Ger Offen，2061838 1971
27．韩应琳、刁月民，2-膦酸丁烷-1，2，4-三羧酸的合成，工业水处理，1993，13(6)，16-19
28．汪祖模、徐丽英，聚合膦羧酸型水质稳定剂的合成与缓蚀阻垢性能的评定，华东化工学院学报，1986，12(1)，69-77
29. USP 4931586 1971
30. A. N. Pudovik, IV Konovalova, Synthesis, 1979,2,81
31. Shizunobu Hayashimoto, Doshisha Diaigaku Keukyu Hokoku, 1967,7(4),193-202
32. A. Marshall, An Investigation into the Mechanism of Syneyistic Dimodic Corrosion Inhibitor, Corrosion, 1981,37(4),214-216
33．桑希勤，水为溶剂膦羧酸型水质稳定剂的合成及性能测定，化学工程师，1998，6(3)，43-45
34．中华人民共和国国国家标准，GB/T 10535-1997——“水处理剂 水解聚马来酸酐”
35．化工行业标准HG/T 2159-91，水处理剂缓蚀性能测定—旋转挂片法
36．化工行业标准HG/T 5-1526—83，冷却水化学处理标准腐蚀片技术条件
37. A Catalogue from CIBA-GEIGY(UK) Limited 1983: "A New, advanced, versatile building block for use in water treatment"
38．项成林，有机膦羧酸缓蚀阻垢剂的研究与应用，工业水处理，1993，13(6)，3-7
39．[美]J．W．麦科伊，冷却水的化学处理，化工部化工设计院译，化学工业出版社，1979年
40. E. Barbara, Surface Studies of Corrosion Inhibitors in Cooling Water
systems, Materials Performance, 1990,29(1),158-162
41．于令弟，磷系水处理复合配方的研究，化工进展，1997，2，47-50
42．检索查新报告书，云南省科技情报研究所查新中心，编号：2001-390
43．化工行业标准HG/T 2024-91水处理药剂阻垢性能测定方法—鼓泡法
44．闵乃本，晶体生长的物理基础，上海科学技术出版社，1980
45．天津大学物理化学教研室，物理化学，北京，高等教育出版社，1979
46. G. H. Nancollas, M. M. Reedy, The Kinetics of Crystallization of Scale Forming Minerals, Petrol. Eng. J., 1974,(4),117-126
47. G. H. Nancollas, M. M. Reedy, The Crystallization of Calcium Carbonate Ⅱ, Calcite Growth Mechanism, J. Coll. And Interface. Sci., 1971,(37),824-830
48. M. M. Reedy, G. H. Nancollas, The Crystallization of Calcium Carbonate Ⅰ, Isotopic Exchange and Kinetics, J. Coll. And Interface. Sci., 1971,(36),166-172
49．汪祖模，水质稳定剂，上海，华东化工学院出版社，1991，245-268