超临界流体染色工艺特征参数及影响因素研究
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摘要
超临界染色技术的应用可显著减少染色用水、用能及废水处理量。染色中各操作参数对染色效果的影响及实验参数的优化一直是学者们研究的重点。目前,对超临界染色的研究主要有实验及模拟两种方法。本文综合应用以上两种方法,通过对超临界染色工艺中各操作参数的研究,得出各参数的影响特性及合适的操作条件,为超临界染色的实际应用提供设计依据。
本文研究的主要内容有：
(1)基于有限元原理建立了筒状加料条件下的二维染色传质模型,运用该模型计算了纤维材料沿径向及轴向的染色效果。
(2)通过改变模型中的特征参数,本文综合考察了染色时间、纤维厚度、流体流量、反应釜尺寸等参数对染色效果的影响。结果表明：染色时间及流体流量的增加不仅会提高染料吸收量,还会降低纤维材料的染色不均匀性。
(3)建立了一套带有循环设备的超临界染色装置。以超临界二氧化碳为介质,应用乙醇作为助溶剂,对PET纤维进行了染色研究。测试了实验压力、温度、助溶剂、纤维厚度等条件对染色深度K/S值及纤维摩擦色牢固度的影响。结果表明：实验温度及压力的升高均会提高染料吸收量及染色均匀度。将乙醇作为助溶剂后,纤维材料表层的染色效果提高显著,但影响效果会随厚度的增加而迅速减弱。实验压力的增加虽可以提高染料吸收量,但却不能保证高吸收量条件下的摩擦色牢固度。在本实验条件下,温度的升高在提高染色效果的同时并未对材料的摩擦色牢固度产生显著影响。
(4)利用本文实验装置,以棉布为染色对象,对天然纤维的染色性能进行了研究。通过改变实验温度、压力、染料种类、助溶剂种类等参数,考察棉布在超临界流体中的染色效果。结果表明：染料种类的选择对染色效果具有显著影响。本文中,在添加水作为助溶剂的条件下碱性染料及分散染料的染色效果较好,循环装置的加入可显著改善染料的扩散效果,提高染色均匀度。
The technology of supercritical dyeing can significantly reduce the need of water, energy and the wastewater which is needed to deal with. The influence of operation parameters to dyeing effect and the confirming about the proper operation parameters have been the focus of research to the scholars. At present, the research method about supercritical dyeing is divided into two kinds which are experiment and simulation. This paper using both experiment and simulation methods, through the study about the operation parameters in supercritical dyeing, we can get the influence about operation condition and the proper value about them, all of them can provide design reference to the practical application of supercritical dyeing.
The main contents of this paper are as follows:
(1) Based on the theory of finite element and tubular charging condition this paper established a2D dyeing mass transfer model, Using this model to calculate the dyeing effect of fiber materials along the radial and axial direction.
(2) By changing the characteristic parameters of the model, this paper has investigated the influence of dyeing time, fiber thickness, fluid flow and the size of reaction kettle to the dyeing effect. The result is found that:the increase of dyeing time and fluid flow can not only improve the dye absorption, but also reduce the dyeing heterogeneity of the fiber materials.
(3)The supercritical dyeing device with cycle system has been set up. The supercritical carbon dioxide is used as medium, ethanol is used as cosolvent, the dyeing effect of PET has been investigated. This paper has studied the influence of pressure, temperature, cosolvent, fiber thickness to the dyeing depth of K/S and friction color firmness. The results are indicated that:the increase of temperature and pressure can improve the dye absorption and reduce the dyeing heterogeneity of the fiber materials. When use ethanol as cosolvent, the dyeing effect at the surface of fiber is observably increased. But the impact of it is declined rapidly when the thickness is increased. Though the increase of pressure can improve the dye absorption, but it can not ensure the friction color firmness, in this condition, the rise of temperature can improve the dyeing effect and at the same time make the friction color firmness stay steadily.
(4) To study the natural fiber dyeing properties, the experiment device which established in this paper is used and using the cotton as dyeing object. Through the change of temperature, pressure, dyes, cosolvent, the dyeing effect of cotton in the supercritical fluid is studied. It is found that:the choice of the dyes has observably influence to the dyeing effect. In this paper, when add water as cosolvent the alkaline dyes and disperse dyes are showed good dyeing effect, the dye diffusion effect can be observably improved when the cycle system is added, and the dyeing uniformity can be also improved.
本文研究的主要内容有：
(1)基于有限元原理建立了筒状加料条件下的二维染色传质模型,运用该模型计算了纤维材料沿径向及轴向的染色效果。
(2)通过改变模型中的特征参数,本文综合考察了染色时间、纤维厚度、流体流量、反应釜尺寸等参数对染色效果的影响。结果表明：染色时间及流体流量的增加不仅会提高染料吸收量,还会降低纤维材料的染色不均匀性。
(3)建立了一套带有循环设备的超临界染色装置。以超临界二氧化碳为介质,应用乙醇作为助溶剂,对PET纤维进行了染色研究。测试了实验压力、温度、助溶剂、纤维厚度等条件对染色深度K/S值及纤维摩擦色牢固度的影响。结果表明：实验温度及压力的升高均会提高染料吸收量及染色均匀度。将乙醇作为助溶剂后,纤维材料表层的染色效果提高显著,但影响效果会随厚度的增加而迅速减弱。实验压力的增加虽可以提高染料吸收量,但却不能保证高吸收量条件下的摩擦色牢固度。在本实验条件下,温度的升高在提高染色效果的同时并未对材料的摩擦色牢固度产生显著影响。
(4)利用本文实验装置,以棉布为染色对象,对天然纤维的染色性能进行了研究。通过改变实验温度、压力、染料种类、助溶剂种类等参数,考察棉布在超临界流体中的染色效果。结果表明：染料种类的选择对染色效果具有显著影响。本文中,在添加水作为助溶剂的条件下碱性染料及分散染料的染色效果较好,循环装置的加入可显著改善染料的扩散效果,提高染色均匀度。
The technology of supercritical dyeing can significantly reduce the need of water, energy and the wastewater which is needed to deal with. The influence of operation parameters to dyeing effect and the confirming about the proper operation parameters have been the focus of research to the scholars. At present, the research method about supercritical dyeing is divided into two kinds which are experiment and simulation. This paper using both experiment and simulation methods, through the study about the operation parameters in supercritical dyeing, we can get the influence about operation condition and the proper value about them, all of them can provide design reference to the practical application of supercritical dyeing.
The main contents of this paper are as follows:
(1) Based on the theory of finite element and tubular charging condition this paper established a2D dyeing mass transfer model, Using this model to calculate the dyeing effect of fiber materials along the radial and axial direction.
(2) By changing the characteristic parameters of the model, this paper has investigated the influence of dyeing time, fiber thickness, fluid flow and the size of reaction kettle to the dyeing effect. The result is found that:the increase of dyeing time and fluid flow can not only improve the dye absorption, but also reduce the dyeing heterogeneity of the fiber materials.
(3)The supercritical dyeing device with cycle system has been set up. The supercritical carbon dioxide is used as medium, ethanol is used as cosolvent, the dyeing effect of PET has been investigated. This paper has studied the influence of pressure, temperature, cosolvent, fiber thickness to the dyeing depth of K/S and friction color firmness. The results are indicated that:the increase of temperature and pressure can improve the dye absorption and reduce the dyeing heterogeneity of the fiber materials. When use ethanol as cosolvent, the dyeing effect at the surface of fiber is observably increased. But the impact of it is declined rapidly when the thickness is increased. Though the increase of pressure can improve the dye absorption, but it can not ensure the friction color firmness, in this condition, the rise of temperature can improve the dyeing effect and at the same time make the friction color firmness stay steadily.
(4) To study the natural fiber dyeing properties, the experiment device which established in this paper is used and using the cotton as dyeing object. Through the change of temperature, pressure, dyes, cosolvent, the dyeing effect of cotton in the supercritical fluid is studied. It is found that:the choice of the dyes has observably influence to the dyeing effect. In this paper, when add water as cosolvent the alkaline dyes and disperse dyes are showed good dyeing effect, the dye diffusion effect can be observably improved when the cycle system is added, and the dyeing uniformity can be also improved.
引文
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[2]是伟元.对印染企业清洁生产的思考和实践[J].印染,2000,26(6):5-7.
[3]白晓慧.印染废水处理技术及其进展[J].印染,2000,26(12):44-50.
[4]Saus D, Knitlle D, Schollmeyer E. Dyeing of textiles in supercritical carbon Dioxide [J].Textile Res,1993,63(3):135.
[5]A.Ferri, M.Banchero, L.Manna, et al. Dye uptake and partition ratio of disperse dyes between a PET yarn and supercritical carbon dioxide [J].Supercritical Fluids,2006, 37:107-114.
[6]A. Ferri, M.Banchero, L. Manna, et al. An experimental technique for measuring high solubilities of dyes in supercritical carbon dioxide[J].Supercritical Fluids,2004,30:41-49.
[7]陆同庆,龙家杰,程安康,等.超临界二氧化碳流体中分散染料的溶解性研究[J].印染,2005,05:21-24.
[8]陆同庆,龙家杰,张培群,等.涤纶织物超临界二氧化碳染色研究[J].染料与染色,2004,41(6)：346-347.
[9]廖隆理,冯豫川,陈敏,等.CO2超临界流体介质中无污染制革技术研究(Ⅲ):CO2超临界流体介质中的皮革染色研究[J].皮革科学与工程,1999,9(4):6-12.
[10]李志义,孟庭宇,张晓冬,等.利用分散蓝60对涤纶进行超临界流体染色的实验研究[J].高校化学工程学报,2006,20(2):203-207.
[11]李志义,胡大鹏,张晓冬,等.关于超临界流体染色的工艺基础研究[J].现代化工2003,23(5):5-8.
[12]祁亚玲,崔波.绿色超临界流体的应用研究[J].化工新型材料,2004,4(32):29-32.
[13]邢彦军,黄钢,沈丽,等.超临界CO2流体染色设备的研发进展[J].纺织导报,2011,8:79-86.
[14]Sunghd, Shimj. Solubility of C.I.disperse red 60 and C.I.disperse blue 60 in supercritical carbon dioxide [J].Chem Eng Data,1999,44:985-989.
[15]Anna Tarasova, Frank Burden. Johann Gasteiger Robust modelling of solubility in supercritical carbon dioxide using Bayesian methods [J].Journal of Molecular Graphics and Modelling,2010, 28:593-597.
[16]Homu Lin, Chihyung Liu, Chenghsi Cheng, et al. Solubilities of disperse dyes of blue 79, red 153, and yellow 119 in supercritical carbon dioxide [J].Journal of Supercritical Fluids,2001,21:1-9.
[17]Tsaicc, Linhm, Leemj. Solubilit y of disperse yellow 54 in supercritical carbon dioxide with or without cosolvent [J].Fluid Phase Equilibria,2007,260(2):287-294.
[18]Shinodat, Tamurak. Solubilities of C. I. disperse red 1 and C. I. disperse red 13 in supercritical carbon dioxide [J].Fluid Phase Equilibria,2003,213:115-123.
[19]Tamurak, Shinodat. Binary and ternary solubilities of disperse dyes and their blend in supercritical carbon dioxide [J].Fluid Phase Equilibria,2004,219:25-32.
[20]K. Tamura, T. Shinoda. Binary and ternary solubilities of disperse dyes and their blend in supercritical carbon dioxide[J]. Fluid Phase Equilibr,2004,219:25-32.
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