制药循环水系统阻垢缓蚀剂的研究
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摘要
在水资源日益短缺今天,国家不断提高水资源和排污费收取标准,就使得每个用水大企业不得不强化循环水装置的运行,提高水的重复利用率,要减少新水补加量,并减少废水排放量。循环冷却水系统是制药水量最大、水质最为复杂的用水系统,系统运行的稳定性对制药安全经济运行具有重要影响。
本论文结合河北某制药企业循环冷却水系统运行特点和水质状况,对目前国内常用的6种单体药剂:2-膦酰基丁烷-1,2,4-三羧酸(PBTCA)、羟基乙叉二膦酸(HEDP)、2-羟基膦酰基乙酸(HPAA)、氨基三甲叉膦酸(ATMP)、丙烯酸/丙烯酸酯共聚物(HB-901)、丙烯酸/丙烯酸酯/AMPS共聚物(HB-903)进行了碳酸钙静态阻垢实验研究和分散氧化铁性能的比较,对PBTCA、HEDP、HPAA、ATMP四种单体药剂进行了缓蚀性能筛选研究,在此基础上,采用正交实验法对筛选出的四种单体药剂PBTCA、HPAA、HB-901和HB-903进行复合配方制备。分别采用极限碳酸盐法和旋转挂片法,对1#～9#复配药剂的阻垢缓蚀性能进行了实验研究,最后优化出适合该制药企业循环冷却水系统的最佳水质稳定配方,并将其应用于实际工程。
实验研究结果表明:
(1)该制药企业补水水质属高碱、高硬型水质,通过水质稳定性判别,该系统随浓缩倍数增加结垢趋势加重,当浓缩倍数超过2.0时,结垢倾向严重。
(2)对6种单体药剂:PBTCA、HB-901、HB-903、HEDP、ATMP、HPAA进行了阻垢实验研究,在相同药剂浓度条件下,对碳酸钙阻垢分散效果:PBTCA>HB-901>HEDP≈ATMP>HPAA>HB903;实验药剂随温度升高阻垢分散效果均出现不同程度降低,其中PBTCA和HB-901耐温性较好;分散氧化铁能力排序为:HB-903>HB-901>PBTCA≈HPAA>HEDP>ATMP。
(3)对4种单体药剂:PBTCA、HEDP、HPAA、ATMP进行了缓蚀实验研究,在不同的实验浓度条件下,4种单体缓蚀率均随使用浓度增加而提高,随温度升高而下降;相同药剂浓度条件下,缓蚀率PBTCA≈HPAA >HEDP≈ATMP。
(4)综合考虑阻垢和缓蚀效果,确定复合配方的主要成分为:PBTCA、HPAA、HB-901和HB-903。
(5)对筛选的四种单体药剂通过正交设计进行复合配方的优化研究,实验结果表明:2#药剂的阻垢缓蚀效果最好,极限浓缩倍数为3.094,腐蚀率为0.0246 mm/a,缓蚀率为93%,各项指标均达到设计规范要求。最终选定的阻垢缓蚀剂配方为:PBTCA:HB-901:HB-903:HPAA之比为10:25:10:10。
Nowadays the water resources are more and more scare. Government is raising the charges on water usage and disposal charge. This trend makes almost every industry company to improve the operation of circulation infrastructure, improving the water recirculation efficiency, in order to reduce the new water supply amount and waste water discharge amount. Water recirculation cooling system is the most complicated water system in medicine production process. The stability of the system has great influence on the safety operation of medicine production.
The most commonly used monomer inhibitors in China are 2 - phosphono butane -1, 2,4 - tricarboxylic acid (PBTCA), Hydroxy ethylidene diphosphonic acid (HEDP), 2 - hydroxy phosphono acetic acid (HPAA), Amino trimethylene phosphonic acid (ATMP) Acrylic acid / Acrylate(HB-901)、Acrylic acid / Acrylate /AMPS Copolymer(HB-903). Based on the Calcium carbonate static scale preventing experiment and comparison with dispersed iron oxide, scale inhibitor ability selection research on PBTCA、HEDP、HPAA、ATMP was carried out. On the bases of this research, Orthogonal Experiment method was adopted to prepare the sample using four selected monomer inhibitors, PBTCA, HEDP, HPAA, ATMP. Using limit carbonate method and rotary coupon method respectively,experiments were carried out feathering on the scale preventing ability of 1#～9# compound pharmacy. At last, the optimized formula of the scale preventing solution for the plant is finally found out. It was applied to real world.
The experimental results show that:
(1) The water supply of this pharmaceutical plant is high alkalinity, high hardness quality. Through the discrimination of water property stability, the scale effect is more severe as the increase of concentration multiple. When the concentration multiple is larger than 2.0, the scale effect tends to be very severe.
(2) Among those 6 monomer inhibitors, PBTCA、HB-901、HB-903、HEDP、ATMP、HPAA, under the same concentration, the scale inhibition abilities of the first selected six monomer inhibitors are: PBTCA>HB-901>HEDP≈ATMP>HPAA>HB903; The scale preventing ability of samples is decreasing with the increase of temperatures. Among all the samples, PBTCA and HB-901 are the best. The ability of disperse iron dioxide of the samples are: PBTCA≈HPAA >HEDP≈ATMP.
(3) Inhibitor ability selection research on PBTCA、HEDP、HPAA、ATMP was carried out. The inhibitor ability of samples is creasing with the increase of concentration. The corrosion prevention effect: PBTCA≈HPAA>HEDP≈ATMP>EDTMP.
(4) Considering the scale preventing effect and the corrosion prevention effect of the inhibitors, the final compound of the inhibitors are composed of PBTCA, HPAA, HB-901 and HB-903.
(5) By the optimization of compound effect research, the test results show that: 2# sample has the best scale and corrosion prevention effect. Its limit concentration multiple is 3.094, the corrosion rate is 0.0246 mm/a, the corrosion prevention rate is 93%.The final ingredients ratio should be PBTCA:HB-901:HB-903:HPAA equals to 10:25:10:10.
本论文结合河北某制药企业循环冷却水系统运行特点和水质状况,对目前国内常用的6种单体药剂:2-膦酰基丁烷-1,2,4-三羧酸(PBTCA)、羟基乙叉二膦酸(HEDP)、2-羟基膦酰基乙酸(HPAA)、氨基三甲叉膦酸(ATMP)、丙烯酸/丙烯酸酯共聚物(HB-901)、丙烯酸/丙烯酸酯/AMPS共聚物(HB-903)进行了碳酸钙静态阻垢实验研究和分散氧化铁性能的比较,对PBTCA、HEDP、HPAA、ATMP四种单体药剂进行了缓蚀性能筛选研究,在此基础上,采用正交实验法对筛选出的四种单体药剂PBTCA、HPAA、HB-901和HB-903进行复合配方制备。分别采用极限碳酸盐法和旋转挂片法,对1#～9#复配药剂的阻垢缓蚀性能进行了实验研究,最后优化出适合该制药企业循环冷却水系统的最佳水质稳定配方,并将其应用于实际工程。
实验研究结果表明:
(1)该制药企业补水水质属高碱、高硬型水质,通过水质稳定性判别,该系统随浓缩倍数增加结垢趋势加重,当浓缩倍数超过2.0时,结垢倾向严重。
(2)对6种单体药剂:PBTCA、HB-901、HB-903、HEDP、ATMP、HPAA进行了阻垢实验研究,在相同药剂浓度条件下,对碳酸钙阻垢分散效果:PBTCA>HB-901>HEDP≈ATMP>HPAA>HB903;实验药剂随温度升高阻垢分散效果均出现不同程度降低,其中PBTCA和HB-901耐温性较好;分散氧化铁能力排序为:HB-903>HB-901>PBTCA≈HPAA>HEDP>ATMP。
(3)对4种单体药剂:PBTCA、HEDP、HPAA、ATMP进行了缓蚀实验研究,在不同的实验浓度条件下,4种单体缓蚀率均随使用浓度增加而提高,随温度升高而下降;相同药剂浓度条件下,缓蚀率PBTCA≈HPAA >HEDP≈ATMP。
(4)综合考虑阻垢和缓蚀效果,确定复合配方的主要成分为:PBTCA、HPAA、HB-901和HB-903。
(5)对筛选的四种单体药剂通过正交设计进行复合配方的优化研究,实验结果表明:2#药剂的阻垢缓蚀效果最好,极限浓缩倍数为3.094,腐蚀率为0.0246 mm/a,缓蚀率为93%,各项指标均达到设计规范要求。最终选定的阻垢缓蚀剂配方为:PBTCA:HB-901:HB-903:HPAA之比为10:25:10:10。
Nowadays the water resources are more and more scare. Government is raising the charges on water usage and disposal charge. This trend makes almost every industry company to improve the operation of circulation infrastructure, improving the water recirculation efficiency, in order to reduce the new water supply amount and waste water discharge amount. Water recirculation cooling system is the most complicated water system in medicine production process. The stability of the system has great influence on the safety operation of medicine production.
The most commonly used monomer inhibitors in China are 2 - phosphono butane -1, 2,4 - tricarboxylic acid (PBTCA), Hydroxy ethylidene diphosphonic acid (HEDP), 2 - hydroxy phosphono acetic acid (HPAA), Amino trimethylene phosphonic acid (ATMP) Acrylic acid / Acrylate(HB-901)、Acrylic acid / Acrylate /AMPS Copolymer(HB-903). Based on the Calcium carbonate static scale preventing experiment and comparison with dispersed iron oxide, scale inhibitor ability selection research on PBTCA、HEDP、HPAA、ATMP was carried out. On the bases of this research, Orthogonal Experiment method was adopted to prepare the sample using four selected monomer inhibitors, PBTCA, HEDP, HPAA, ATMP. Using limit carbonate method and rotary coupon method respectively,experiments were carried out feathering on the scale preventing ability of 1#～9# compound pharmacy. At last, the optimized formula of the scale preventing solution for the plant is finally found out. It was applied to real world.
The experimental results show that:
(1) The water supply of this pharmaceutical plant is high alkalinity, high hardness quality. Through the discrimination of water property stability, the scale effect is more severe as the increase of concentration multiple. When the concentration multiple is larger than 2.0, the scale effect tends to be very severe.
(2) Among those 6 monomer inhibitors, PBTCA、HB-901、HB-903、HEDP、ATMP、HPAA, under the same concentration, the scale inhibition abilities of the first selected six monomer inhibitors are: PBTCA>HB-901>HEDP≈ATMP>HPAA>HB903; The scale preventing ability of samples is decreasing with the increase of temperatures. Among all the samples, PBTCA and HB-901 are the best. The ability of disperse iron dioxide of the samples are: PBTCA≈HPAA >HEDP≈ATMP.
(3) Inhibitor ability selection research on PBTCA、HEDP、HPAA、ATMP was carried out. The inhibitor ability of samples is creasing with the increase of concentration. The corrosion prevention effect: PBTCA≈HPAA>HEDP≈ATMP>EDTMP.
(4) Considering the scale preventing effect and the corrosion prevention effect of the inhibitors, the final compound of the inhibitors are composed of PBTCA, HPAA, HB-901 and HB-903.
(5) By the optimization of compound effect research, the test results show that: 2# sample has the best scale and corrosion prevention effect. Its limit concentration multiple is 3.094, the corrosion rate is 0.0246 mm/a, the corrosion prevention rate is 93%.The final ingredients ratio should be PBTCA:HB-901:HB-903:HPAA equals to 10:25:10:10.
引文
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[7] Persinski Leonard John, Ralston Paul Hotchkiss, Inhibition of scale deposition, US3928196, 1975-12
[8] Gutierrez Elizabeth Charaterizati on of i mmobilize poly - L- as partate as metal chelat or [J] Environmen Science Technology, 1999, 33 (10) : 1664– 1670
[9] Nalco Chemical CO, GB1521440, Method of producing pHospHinico substituted alipHatic carboxylic acids,1978-8
[10] Grigory Y M,Daniel A,Batzel J F.Production of polysuccinimide in cyclic carbonate solvent[P].US:5 756 595.1998-05-26
[11] Masaharu M D,Shinzo Y.Polyaspartic acid.US:6 380 350.2002-04-30
[12] Henkel K.Preparation and use of polyaspartamides[P].DE:19720771,1998
[13] M A Quraishi,Hariom K Sharma.4-Amino-3-butyl-5-mercapto-1,2,4-triazole.a new corrosion inhibitor for mild steel in sulphuric acid[J].Materials Chemistry and Physics.2002(78):18.
[14] Cruz J Garcia-Ochoa,E Castro M.Experimental and theoretical study of the 3-amino-1,2, 4-triazoleand-aminothiazole corrosion inhibitors in carbon steel[J].Journal of the 50Electrochemical Society.2003,150(1):26.
[15] F.Bentiss,M.Bouanis,B.Mernari,etc.Effect of iodide ions on corrosion inhibition of mild steel by 3,5-bis(4-methylthiophenyl)-4H-1,2,4-triazole in sulfuric acid solution[J].Journal of Applied Electrochemistry.2002,(32):671.
[16] K.Fix,L.Seerbo.New corrosion inhibitor technology for use in calcium chloride brine systems[C].54th annual meeting international water conference,1993(62):371-374
[17] Nakato T. Relationship between structure and properties of polyas partic acids [J]. Macromolecules, 1998, 31 ( 7 ) :2 107 - 2 113
[18] Ross Robert J,Low Kim C, Shannon James E. Polyas partatescale inhibitors biod - egradable alternatives to polyacrylates[J].Material Performance, 1997, 36 (4) : 53– 57
[19] Ross K C,Shannon J E.Polyaspartate scale inhibitors biodegradable altern actives to polyacrylates[J].Material performance,1997,(4):52-57
[20]黄娟,徐强,任志峰等.循环冷却水缓蚀剂和阻垢剂的研究进展[J].电镀与精饰,2009,(02)
[21]岳宏,高建村.工业循环冷却水处理缓蚀阻垢剂的应用与发展[J].新疆石油天然气,2009,(04)
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