【作者】 张伟娟；

【导师】 廖隆理； 但卫华；

【作者基本信息】 四川大学 ， 皮革化学与工程， 2003， 硕士

【摘要】 本文首次将一套正规的二氧化碳超临界流体设备应用到制革中的铬鞣工序，既简化了工序又不降低成革质量和不增加成本，同时真正做到无污染制革，实现了制革行业中提倡的“零排放”。 实验表明二氧化碳超临界流体代替水做介质条件下的铬鞣因素和传统工艺有所不同。在二氧化碳超临界流体条件下的铬鞣影响因素有：工作温度、工作压力、工作时间、机械作用、起始pH值、夹带剂的用量和铬鞣剂用量等，通过对各实验条件下坯革的收缩温度、Cr含量、粒面细致度和革面颜色等比较，寻求出了铬鞣工序的优化条件。 实验还发现二氧化碳超临界流体作为一种新型的无污染制革技术，有其独特的优点，比如坯革的孔隙率、面积、厚度和脱脂作用与传统的水相铬鞣均有所不同，特别是成革面积和厚度比传统铬鞣革大和厚的特征，为其工业化的应用展现了极为光明的前景。 研究还表明该铬鞣新法的成革，其物理性能和感官质量均达到和优于常规鞣法。 本论文借用了传统铬鞣机理的研究方法，以坯革的Ts和Cr含量等理化指标作为判定依据，研究了酯化皮块和去氨基皮块在水和二氧化碳超临界流体两种介质中铬鞣时胶原羧基和氨基对铬鞣的影响。结果表明，在二氧化碳超临界流体作介质铬盛时，胶原的验基仍是与铬凝剂结合的主要基团，氨基是次要基团。得出了二氧化碳超临界流体代替水作介质，铬鞍用酯化胶原想基和去氨基方法来研究其铬燥机理等是可行的结论。 本论文为二氧化碳超临界流体代替水做介质在制革铬躁中的实际应用，特别是为进一步更好地研究二氧化碳超临界流体制革以及铬燥机理提供了有借鉴意义的研究方法和与重要参考。更多还原

【Abstract】 A new supercritical carbon dioxide fluid equipment was developed first time for chrome tanning process of leather manufacture. The experiment results showed that using this equipment the chrome tanning process was simplified without decreasing the quality of leather, the environment pollution was minimized and "zero release" which was promoted continuously was really achieved.The factors affecting chrome tanning in supercritical carbon dioxide fluid were temperature, pressure, mechanical action, time, initial pH, entrainer and chrome dosage, which had some difference from traditional methods. The chrome tanning behavior in supercritical carbon dioxide fluid was determined by the shrinkage temperature, chrome content in wet blue, the color of the leather and the grain state etc, and then sought the optimum conditions in chrome tanning in supercritical carbon dioxide fluid.In addition, as a new non-waste method the supercritical carbon dioxide fluid has its great potential properties on leather manufacturing, for example, fiber’s porosity, area, thickness and degreases effects which are different from traditional methods, especially the characteristics of area yield and thickness were better than traditional methods.Physical properties and sense performances of the finished leather which chrome tanned by supercritical carbon dioxide were match or overmatch the properties of the traditional tanning.The mechanism of chrome tanning in supercritical carbon dioxide fluid medium also discussed primarily. The reactive groups involved has been studiedusing modified collagen such as methylated collagen and deaminated collagen, then these pretreated pickled hides were chrome tanned under water and supercritical carbon dioxide fluid mediums and determined the shrinkage temperature and chrome content of the chromed tanned leather. The results showed that the carboxyl groups rather than amino groups of the collagen fibers were the main reactive centers for chrome tanning in supercritical carbon dioxide fluid, which also approving that the method can put into practice.The present study has made a practical application of supercritical carbon dioxide fluid to chromium tanning and especially established a foundation for further understand of supercritical carbon dioxide fluid on leather making, and that the chemical theory of chromium tanning might be better acquired.更多还原