本文選題：浸酸 + 少鹽浸酸　； 參考：《陜西科技大學》2017年碩士論文

【摘要】：傳統(tǒng)的浸酸鉻鞣會產(chǎn)生大量高濃度的含鹽含鉻廢水,不僅造成環(huán)境污染,鉻資源的浪費,同時增加廢水治理的難度與成本,不利于制革工業(yè)的可持續(xù)發(fā)展�；谥聘锝岬哪z原電荷排斥理論,合成了以磺酸基為主功能基的系列浸酸鉻鞣助劑,并將其應(yīng)用于浸酸鉻鞣過程,能夠有效降低廢液中的中性鹽及Cr(III)含量,以期實現(xiàn)制革過程的少鹽浸酸清潔鉻鞣。以丙烯酸(AA)和對苯乙烯基磺酸鈉(SSS)為原料,在(NH_4)_2S_2O_8-NaHSO_3的反應(yīng)體系中合成低分子量的AA-SSS共聚物(簡稱AS低聚物)。利用三因素三水平正交試驗確定最佳抑制酸皮膨脹AS低聚物的合成條件為:n(AA):n(SSS)=1.5:1,(NH_4)_2S_2O_8和NaHSO_3用量分別為單體總質(zhì)量的5%和3%。通過傅里葉紅外光譜(FT-IR)證明了聚合反應(yīng)的發(fā)生;凝膠滲透色譜(GPC)圖譜表明該低聚物的Mn為2069,分布系數(shù)為1.05;將在優(yōu)化條件下制備的AS低聚物單獨用于無鹽浸酸,在用量3%(灰皮質(zhì)量計,下同)時皮膨脹度為11.51%,當配合使用3.2%的食鹽時便可以實現(xiàn)少鹽浸酸,廢液中Cl-含量從常規(guī)的345.06 mmol/L顯著下降至145.26 mmol/L;SEM對比圖譜表明:AS少鹽浸酸鉻鞣藍濕革粒面更加清潔,毛孔清晰,DSC分析顯示:少鹽浸酸鞣革的熱分解積分面積小,交聯(lián)程度較常規(guī)浸酸鞣革低。XRD分析表明:酸皮、正常浸酸鉻鞣藍濕革、AS少鹽浸酸藍濕革結(jié)晶度分別為68.21%、13.49%、3.23%,可見AS少鹽浸酸鉻鞣工藝對酸皮內(nèi)部結(jié)晶性結(jié)構(gòu)影響更大。選取5-磺基水楊酸、對甲基苯磺酸、牛磺酸、十二烷基磺酸、氨基磺酸、2-氨基-1,4-苯二磺酸應(yīng)用于輔助浸酸,都可以不同程度的實施少鹽浸酸。當采用灰皮重的2.1%的2-氨基-1,4-苯二磺酸與3%的AS低聚物配合應(yīng)用于浸酸時,可以完全實現(xiàn)無鹽浸酸;與傳統(tǒng)浸酸鉻鞣相比,這種無鹽浸酸鉻鞣方法的廢液中Cr_2O_3含量從3.945 g/L降低至3.522 g/L,Cl-從345.06 mmol/L減少至幾乎為零;但坯革物理力學性能稍差;其DSC曲線顯示:常規(guī)浸酸鉻鞣藍濕革的積分面積、峰型寬度均較大,其熱穩(wěn)定較佳。將2-氨基-1,4-苯二磺酸用乙醛酸進行化學反應(yīng)改性,合成一種含磺酸基與羧基的Schiff堿結(jié)構(gòu)的化合物(簡稱GA)。利用FTIR和1HNMR證明了化學反應(yīng)的發(fā)生;對軟化皮進行浸酸時,當GA添加量為2%時,配合1%食鹽就可以實現(xiàn)少鹽浸酸,且生皮基本不發(fā)生酸膨脹;基于此,采用4.5%的鉻粉進行鞣制,所得藍濕革Ts便可達到105.5℃;與常規(guī)浸酸鉻鞣相比,少鹽浸酸少鉻鞣體系廢液中Cr2O3從3.305 g/L降低至1.546 g/L,Cl-含量從374.2 mmol/L下降至59.6 mmol/L;SEM觀察顯示其縱切面纖維分散程度相似,粒面更加清潔。EDS顯示鉻元素在縱切面分布均勻,藍濕革物理力學性能優(yōu)異。以苯酚、濃硫酸、甲醛、尿素、雙酚S等為原料,合成了一種含磺酸基與酚羥基的合成鞣劑,GPC圖譜顯示其Mn為1961,分布系數(shù)為1.01;將3.0%AS低聚物、2.0%合成鞣劑、1.6%食鹽結(jié)合共同應(yīng)用于浸酸時,可以實施少鹽浸酸;浸酸鉻鞣實驗發(fā)現(xiàn):與傳統(tǒng)浸酸鉻鞣相比,這種少鹽浸酸工藝可以將鉻鞣廢液中Cr_2O_3含量從3.945 g/L降低至2.654 g/L,Cl-從345.06mmol/L降低至50.43 mmol/L;由DSC曲線可知:常規(guī)浸酸鉻鞣藍濕革的積分面積大于少鹽浸酸鉻鞣,其熱穩(wěn)定較高;XRD分析可知:傳統(tǒng)浸酸鉻鞣藍濕革與少鹽浸酸藍濕革的結(jié)晶度分別為13.49%、5.64%�？梢娚冫}浸酸工藝對酸皮內(nèi)部結(jié)構(gòu)影響更大。
[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.
【學位授予單位】：陜西科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TS529.2;TQ944

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