本文選題：離子交換纖維 + 聚丙烯纖維��； 參考：《鄭州大學(xué)》2015年博士論文

【摘要】：隨著全球工業(yè)化進程快速發(fā)展,重金屬水污染對人類的健康及環(huán)境造成嚴重威脅。其中,六價鉻是一種具有高度致癌性和氧化性的重金屬離子,鉻污染已成為世界各國普遍關(guān)注的環(huán)境問題。目前工業(yè)中對六價鉻廢水的處理方法主要是將六價鉻還原為低毒三價鉻,然后以Cr(OH)3沉淀形式除去。此法產(chǎn)生的固體沉淀容易形成新的污染,并且不能實現(xiàn)鉻離子的資源回收。因此,針對六價鉻廢水的處理開發(fā)一種操作簡單、成本經(jīng)濟的資源化治理工藝具有良好的應(yīng)用價值。離子交換纖維(IEF)是繼離子交換樹脂之后出現(xiàn)的一種新型吸附分離材料,其活性位點包括酸性、堿性以及螯合等化學(xué)官能團。其中,螯合纖維可以利用結(jié)構(gòu)中含孤對電子的原子(N、O、P、S等)與金屬離子形成配位鍵,構(gòu)成與小分子螯合物類似的穩(wěn)定結(jié)構(gòu),具有良好的吸附選擇性。近年來,螯合纖維在深度凈化有害物質(zhì)、痕量元素分離以及有害氣體防護等領(lǐng)域取得了廣泛的應(yīng)用。本文圍繞離子交換纖維資源化治理電鍍含鉻廢水以及新型螯合纖維制備的研究,主要工作內(nèi)容如下:(1)以聚丙烯腈基多胺(PAN-TETA)離子交換纖維為基體,考察了PAN-TETA多胺纖維靜態(tài)吸附六價鉻性能。系統(tǒng)研究了纖維型式、六價鉻濃度、溶液p H等因素對纖維吸附六價鉻性能的影響,采用SEM-EDS等手段分析纖維吸附六價鉻的過程中特征元素(C、N、O、Cr)的含量及分布情況。結(jié)果表明,Cl-型PAN-TETA纖維對六價鉻的吸附量及再生性能均優(yōu)于OH-型纖維,且溶液p H為2~3有利于纖維吸附六價鉻。PAN-TETA纖維對六價鉻的吸附量最高可達425.1mg/g,吸附過程符合準二級動力學(xué)模型(R20.999)。通過表面及斷面SEM-EDS分析,PAN-TETA纖維表面及內(nèi)部的胺基均參與了對六價鉻吸附,且六價鉻分布均勻。PAN-TETA纖維經(jīng)100次靜態(tài)循環(huán)吸附工業(yè)含鉻廢水,鉻離子去除率可達91.0%以上,保持良好的吸附再生性能。(2)在靜態(tài)吸附實驗研究的基礎(chǔ)上,考察了多胺纖維柱吸附六價鉻性能。PAN-TETA纖維對六價鉻的穿透吸附量及飽和吸附量最高分別可達291.2mg/g、426.3mg/g,并且柱吸附過程Thomas模型(R20.9)。硫酸根的存在對PAN-TETA纖維吸附六價鉻造成一定的影響,但隨著吸附時間的延長,纖維上部分的硫酸根可以被溶液中的六價鉻取代,最終達到吸附平衡。氫氧化鈉溶液可快速、有效的洗脫PAN-TETA纖維中的六價鉻,洗脫過程前半段流出液基本呈中性,OH-得到充分利用;后半段流出液呈堿性,含大量可被循環(huán)利用的OH-。PAN-TETA纖維經(jīng)80次再生吸附混合含鉻廢水,其飽和吸附量為230.1mg/g~180.9mg/g,性能較為穩(wěn)定。PAN-TETA纖維經(jīng)5次循環(huán)吸附鍍鉻漂洗廢水,飽和吸附量可達320mg/g以上,并且纖維循環(huán)使用過程中對六價鉻的處理能力無明顯降低。由此可見,該材料可滿足于循環(huán)治理含鉻廢水,尤其適合處理鍍鉻漂洗廢水。(3)在以上研究工作的基礎(chǔ)上,設(shè)計一種多柱串聯(lián)吸附-分步洗脫的工藝對鍍鉻漂洗廢水進行處理。PAN-TETA纖維經(jīng)5次再生吸附鍍鉻漂洗廢水,其飽和吸附量基本在228.4mg/g~324.6mg/g范圍內(nèi)波動。延長吸附時間對PAN-TETA纖維中Cr6+、SO42-、Cl-的離子分布有重要影響,可以使纖維中六價鉻的離子純度得到明顯提高。經(jīng)該工藝洗脫、回收的六價鉻濃度可達30g/L以上,并且可以回用于電鍍行業(yè)。(4)以聚丙烯接枝苯乙烯(PP-St)纖維為骨架,經(jīng)混酸硝化、氯化亞錫還原制得PP-St-NH2功能纖維。硝化反應(yīng)過程中,混酸比例VH2SO4/VHNO3對硝化增重率的影響最大,反應(yīng)時間t次之,混酸體積Vmixed acid影響最小,苯環(huán)上單硝基取代的轉(zhuǎn)化率接近100%。還原反應(yīng)過程中,胺基交換容量最高為5.78mmol/g,硝基還原率可達92%以上。制備得到的PP-St-NH2纖維在300℃以下沒有發(fā)生分解,具有良好的熱穩(wěn)定性。(5)以PP-St-NH2功能纖維為基體,分別與氯乙酸鈉、亞磷酸、水楊醛反應(yīng),得到3種螯合纖維PP-St-IDA、PP-St-PAA、PP-St-SCB,初步考察這三種螯合纖維對Ni2+的選擇性吸附性能。PP-St-NH維分別成功引入亞胺二乙酸、氨基膦酸以及席夫堿螯合結(jié)構(gòu),氨基轉(zhuǎn)化率可達90%以上。PP-St-IDA、PP-St-PAA、PP-St-SCB螯合纖維對鎳離子的靜態(tài)吸附量最高分別為102.6mg/g、51.6mg/g以及44.1mg/g。在鎳離子與鈣離子共存體系中,PP-St-IDA、PP-St-PAA、PP-St-SCB纖維對鎳離子的吸附選擇性為PP-St-IDAPP-St-PAA≈PP-St-SCB。通過對比實驗,PP-St-IDA纖維對鎳離子的吸附量及選擇性明顯優(yōu)于傳統(tǒng)的PAN-COONa纖維,該纖維可望有效用于含鎳廢水處理及回收。
[Abstract]:With the rapid development of the global industrialization process, heavy metal water pollution poses a serious threat to human health and environment. Among them, six valence chromium is a heavy metal ion with high carcinogenicity and oxidation, and chromium pollution has become a widespread environmental problem in the world. At present, the treatment methods of six valent chromium waste water are mainly to be treated in the industry. Six valence chromium is reduced to low toxic trivalent chromium, and then removed in the form of Cr (OH) 3 precipitation. The solid precipitation produced by this method is easy to form new pollution and can not recover the resource of chromium ion. Therefore, a simple operation, cost economical treatment process for the treatment of six valent chromium wastewater is of good application value. Fiber (IEF) is a new type of adsorptive separation material after ion-exchange resin. Its active sites include acidic, alkaline and chelating chemical functional groups. In this, chelating fibers can form coordination bonds with metal ions in the structure of atoms containing isolated electrons (N, O, P, S, etc.) in the structure to form a similar stability to small molecule chelates. In recent years, chelating fibers have been widely used in the fields of deep purification of harmful substances, separation of trace elements and the protection of harmful gases. In this paper, the research on the treatment of electroplated chromium containing wastewater and the preparation of new chelating fiber by ion exchange fiber resources is studied in this paper. The main contents are as follows: (1) The polyacrylonitrile base polyamine (PAN-TETA) ion exchange fiber was used as the matrix to investigate the static adsorption properties of PAN-TETA polyamine fibers for six valent chromium. The effects of fiber type, six valence chromium concentration, P H on the adsorption of six valence chromium on the fiber were systematically studied. SEM-EDS and other means were used to analyze the characteristic elements (C, N, O, C) in the process of adsorption of six valence chromium. The content and distribution of R) showed that the adsorption capacity and regeneration performance of Cl- PAN-TETA fiber for six valence chromium were better than that of OH- fiber, and P H of the solution was 2~3 beneficial to the adsorption of six valence chromium on the adsorption of six valence chromium.PAN-TETA fiber, and the adsorption process conforming to the quasi two class kinetics model (R20.999). Cross section SEM-EDS analysis, the surface of PAN-TETA fiber and the internal amine group are all involved in the adsorption of six valence chromium, and the distribution of six valence chromium is evenly distributed by.PAN-TETA fiber through 100 static cycles to adsorb industrial chromium containing wastewater. The removal rate of chromium ion can reach more than 91%. (2) on the basis of the static adsorption experimental study, a lot of investigation has been made. The absorption of six valence chromium by an amine fiber column, the maximum penetration and saturation adsorption of six valence chromium.PAN-TETA fibers can reach 291.2mg/g, 426.3mg/g, and Thomas model of column adsorption (R20.9). The existence of sulphate root causes a certain effect on the adsorption of six valence chromium on the PAN-TETA fiber, but with the prolongation of the adsorption time, the sulfur on the fiber part of the fiber. The acid root can be replaced by six valence chromium in the solution and finally reach the adsorption equilibrium. Sodium hydroxide solution can quickly and effectively elute six valence chromium in PAN-TETA fiber. The effluent of the first half of the elution process is basically neutral and OH- is fully utilized; the latter half of the effluent is alkaline, and the OH-.PAN-TETA fiber containing a large amount can be recycled for 80 times. The adsorbed mixed chromium containing wastewater has a saturated adsorption capacity of 230.1mg/g~180.9mg/g, and the performance is more stable. The performance of the wastewater is more stable than that of.PAN-TETA. The adsorption capacity of the wastewater is more than 320mg/g by 5 cycles, and the treatment capacity of the six valence chromium in the process of fiber recycling is not obviously reduced. Thus, this material can be satisfied with the recycling treatment. Chromium wastewater, especially suitable for treatment of chromium plating wastewater. (3) on the basis of the above research work, a multi column series adsorption and stepwise elution process was designed for the treatment of chromium plating wastewater. The.PAN-TETA fiber was treated with 5 regenerated adsorption chromium plating wastewater. The saturated adsorption capacity of the wastewater was fluctuated in the range of 228.4mg/g~324.6mg/g. The ion distribution of Cr6+, SO42-, Cl- in PAN-TETA fiber has an important influence on the ion purity of the six valence chromium in the fiber. After the elution process, the concentration of six valence chromium can be above 30g/L and can be reused in the electroplating industry. (4) polypropylene graft styrene (PP-St) fiber as the skeleton, nitrification and chlorination through mixed acid. In the process of nitrification, the effect of the mixed acid ratio VH2SO4/VHNO3 on the nitrification increase rate is the most, the reaction time is t, the mixed acid volume Vmixed acid has the smallest effect. The conversion rate of the mono nitro substitution on the benzene ring is close to the 100%. reduction reaction, and the highest amino exchange capacity is 5.78mmol/g, and the reduction rate of the nitro group is. Up to 92%. The prepared PP-St-NH2 fibers were not decomposed below 300 C and had good thermal stability. (5) PP-St-NH2 functional fibers were used as matrix, respectively, with sodium chloroacetate, phosphoric acid and salicylaldehyde, and 3 kinds of chelating fibers, PP-St-IDA, PP-St-PAA, PP-St-SCB, were obtained, and the selectivity of these three chelate fibers to Ni2+ was preliminarily investigated. The adsorption properties of.PP-St-NH dimension were successfully introduced to imide two acetic acid, amino phosphonic acid and Schiff base chelating structure. The amino conversion rate could reach more than 90%.PP-St-IDA. The highest static adsorption capacity of PP-St-PAA and PP-St-SCB chelating fibers for nickel ions was 102.6mg/g, 51.6mg/g and 44.1mg /g. in the coexistence system of nickel ions and calcium ions, PP-St-IDA, P. P-St-PAA, the adsorption selectivity of PP-St-SCB fiber to nickel ion is PP-St-IDAPP-St-PAA PP-St-SCB. through comparison experiment. The adsorption quantity and selectivity of PP-St-IDA fiber to nickel ion is obviously superior to that of the traditional PAN-COONa fiber. The fiber is expected to be effectively used in the treatment and recovery of nickel containing wastewater.

【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：X781.1

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