少盐浸酸铬鞣助剂的合成与应用性能

发布时间：2018-05-31 19:07

本文选题：浸酸 + 少盐浸酸　；参考：《陕西科技大学》2017年硕士论文

【摘要】：传统的浸酸铬鞣会产生大量高浓度的含盐含铬废水,不仅造成环境污染,铬资源的浪费,同时增加废水治理的难度与成本,不利于制革工业的可持续发展。基于制革浸酸的胶原电荷排斥理论,合成了以磺酸基为主功能基的系列浸酸铬鞣助剂,并将其应用于浸酸铬鞣过程,能够有效降低废液中的中性盐及Cr(III)含量,以期实现制革过程的少盐浸酸清洁铬鞣。以丙烯酸(AA)和对苯乙烯基磺酸钠(SSS)为原料,在(NH_4)_2S_2O_8-NaHSO_3的反应体系中合成低分子量的AA-SSS共聚物(简称AS低聚物)。利用三因素三水平正交试验确定最佳抑制酸皮膨胀AS低聚物的合成条件为:n(AA):n(SSS)=1.5:1,(NH_4)_2S_2O_8和NaHSO_3用量分别为单体总质量的5%和3%。通过傅里叶红外光谱(FT-IR)证明了聚合反应的发生;凝胶渗透色谱(GPC)图谱表明该低聚物的Mn为2069,分布系数为1.05;将在优化条件下制备的AS低聚物单独用于无盐浸酸,在用量3%(灰皮质量计,下同)时皮膨胀度为11.51%,当配合使用3.2%的食盐时便可以实现少盐浸酸,废液中Cl-含量从常规的345.06 mmol/L显著下降至145.26 mmol/L;SEM对比图谱表明:AS少盐浸酸铬鞣蓝湿革粒面更加清洁,毛孔清晰,DSC分析显示:少盐浸酸鞣革的热分解积分面积小,交联程度较常规浸酸鞣革低。XRD分析表明:酸皮、正常浸酸铬鞣蓝湿革、AS少盐浸酸蓝湿革结晶度分别为68.21%、13.49%、3.23%,可见AS少盐浸酸铬鞣工艺对酸皮内部结晶性结构影响更大。选取5-磺基水杨酸、对甲基苯磺酸、牛磺酸、十二烷基磺酸、氨基磺酸、2-氨基-1,4-苯二磺酸应用于辅助浸酸,都可以不同程度的实施少盐浸酸。当采用灰皮重的2.1%的2-氨基-1,4-苯二磺酸与3%的AS低聚物配合应用于浸酸时,可以完全实现无盐浸酸;与传统浸酸铬鞣相比,这种无盐浸酸铬鞣方法的废液中Cr_2O_3含量从3.945 g/L降低至3.522 g/L,Cl-从345.06 mmol/L减少至几乎为零;但坯革物理力学性能稍差;其DSC曲线显示:常规浸酸铬鞣蓝湿革的积分面积、峰型宽度均较大,其热稳定较佳。将2-氨基-1,4-苯二磺酸用乙醛酸进行化学反应改性,合成一种含磺酸基与羧基的Schiff碱结构的化合物(简称GA)。利用FTIR和1HNMR证明了化学反应的发生;对软化皮进行浸酸时,当GA添加量为2%时,配合1%食盐就可以实现少盐浸酸,且生皮基本不发生酸膨胀;基于此,采用4.5%的铬粉进行鞣制,所得蓝湿革Ts便可达到105.5℃;与常规浸酸铬鞣相比,少盐浸酸少铬鞣体系废液中Cr2O3从3.305 g/L降低至1.546 g/L,Cl-含量从374.2 mmol/L下降至59.6 mmol/L;SEM观察显示其纵切面纤维分散程度相似,粒面更加清洁。EDS显示铬元素在纵切面分布均匀,蓝湿革物理力学性能优异。以苯酚、浓硫酸、甲醛、尿素、双酚S等为原料,合成了一种含磺酸基与酚羟基的合成鞣剂,GPC图谱显示其Mn为1961,分布系数为1.01;将3.0%AS低聚物、2.0%合成鞣剂、1.6%食盐结合共同应用于浸酸时,可以实施少盐浸酸;浸酸铬鞣实验发现:与传统浸酸铬鞣相比,这种少盐浸酸工艺可以将铬鞣废液中Cr_2O_3含量从3.945 g/L降低至2.654 g/L,Cl-从345.06mmol/L降低至50.43 mmol/L;由DSC曲线可知:常规浸酸铬鞣蓝湿革的积分面积大于少盐浸酸铬鞣,其热稳定较高;XRD分析可知:传统浸酸铬鞣蓝湿革与少盐浸酸蓝湿革的结晶度分别为13.49%、5.64%。可见少盐浸酸工艺对酸皮内部结构影响更大。
[Abstract]:A large amount of high concentration of chromium containing chromium containing wastewater will be produced by traditional chrome tanning, which not only causes environmental pollution, waste of chromium resources, but also increases the difficulty and cost of wastewater treatment, which is not conducive to the sustainable development of tannery industry. The additive, which is used in chrome tanning process, can effectively reduce the neutral salt and Cr (III) content in the waste liquid, so as to realize the clean chrome tanning in the process of tanning. With acrylic acid (AA) and sodium styrene sulfonate (SSS) as raw materials, a low molecular weight AA-SSS copolymer (called AS) is synthesized in the reaction system of (NH_4) _2S_2O_8-NaHSO_3. The synthesis conditions of AS oligomers with the best inhibition of acid skin expansion by the three factor three horizontal orthogonal test are as follows: n (AA): n (SSS) =1.5:1, (NH_4) _2S_2O_8 and NaHSO_3 are 5% of the total mass of monomers and 3%. through Fourier infrared spectroscopy (FT-IR) to demonstrate the occurrence of polymerization; gel osmotic chromatography (GPC) atlas shows that this low The Mn of the polymer is 2069 and the distribution coefficient is 1.05. The AS oligomer prepared under the optimized condition is used for salt free acid leaching alone. The expansion degree of the skin is 11.51% when the dosage is 3% (gray skin quality meter, the same below). The content of Cl- in the waste liquid can be reduced to 145.26 mmol/L from the conventional 345.06 mmol/L to 145.26 mmol/L; SEM in the waste liquid. The contrast atlas shows that the grain surface of AS chrome tanning wet leather is cleaner and the pores are clear. DSC analysis shows that the thermal decomposition integral area of the tanned leather with less salt leaching is smaller than that of the conventional pickled tanning leather, and the low.XRD analysis shows that the crystallinity of the acid skin, the normal leach chrome tanning blue wet leather and the AS less salt soaking wet blue wet leather are 68.21%, 13.49%, 3.23%, respectively, AS, respectively. 5- sulfonylsalicylic acid, methyl benzsulfonic acid, taurine, twelve alkyl sulfonic sulfonic acid, amino sulfonic acid, and 2- amino -1,4- benzene two sulfonic acid can be used in the aid of acid leaching, which can be used in different degrees of salt leaching. When 2.1% of 2- amino -1,4- benzene two sulfonic acid and 3 are used. % AS oligomer combined with acid leaching can fully realize salt free acid leaching. Compared with traditional chrome tanning, the content of Cr_2O_3 in this salt free chrome tanning method is reduced from 3.945 g/L to 3.522 g/L, and Cl- is reduced from 345.06 mmol/L to almost zero; but the physical properties of the billet leather are poor; the DSC curve shows that conventional chrome tanning is used for tanning. The integral area and peak width of the blue wet leather are all large and their thermal stability is better. The chemical reaction of 2- amino -1,4- benzene two sulfonic acid is modified by glyoxylic acid to synthesize a compound containing Schiff base structure containing sulfonic and carboxyl groups (GA). The chemical reaction is proved by FTIR and 1HNMR; when the softening skin is dipped in acid, the amount of GA is added as GA At 2%, less salt can be achieved with 1% salt, and the skin basically does not have acid expansion; based on this, the Ts of blue wet leather can reach 105.5 C by tanning 4.5% chromium powder. Compared with conventional chrome tanning, the Cr2O3 from 3.305 g /L decreases from 3.305 to 1.546 g/L, and Cl- content decreases from 374.2 mmol/L to 59.6 compared with conventional chrome tanning. Mmol/L, SEM observation showed that the dispersion of the fiber in the longitudinal section was similar, the grain surface was more clean and.EDS showed that the chromium element was evenly distributed in the longitudinal section, and the physical and mechanical properties of the blue wet leather were excellent. A synthetic tanning agent containing sulfonic and phenol hydroxyl was synthesized with phenol, concentrated sulfuric acid, formaldehyde, urea, bisphenol S and so on. The GPC atlas showed that its Mn was 1961. The coefficient is 1.01; the 3.0%AS oligomer, the 2% synthetic tanning agent, and the 1.6% salt combination can be applied to the acid leaching. The chrome tanning experiment shows that the Cr_2O_3 content in the chrome tanning waste solution can be reduced from 3.945 g/ L to 2.654 g/L, and Cl- from 345.06mmol/L to 50.43 mmol/ compared with the traditional chrome tanning process. L; it is known from the DSC curve that the integral area of the conventional chrome tanned wet blue wet leather is greater than that of the less salt leaching chrome tanning, and its thermal stability is higher. The XRD analysis shows that the crystallinity of the traditional chrome tanning wet leather and the less salt soaked wet blue wet leather is 13.49%, and the 5.64%. can see that the less salt leaching process has a greater impact on the internal structure of the acid skin.
【学位授予单位】：陕西科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TS529.2;TQ944

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