納米微晶纖維素的氨基化改性及其吸附性能研究
發(fā)布時間：2018-11-28 20:23
【摘要】：近年來,紡織、塑料、造紙、印刷及食品等化學(xué)工業(yè)所排放的廢水中含有的染料及重金屬離子日益增加,不僅造成了環(huán)境污染,而且給人類的健康帶來了巨大危害。因此,開發(fā)高效廉價的染料和重金屬離子去除方法成為亟待解決的問題。由于具備低成本、對毒性污染物不敏感、流程簡單靈活等優(yōu)勢,吸附法成為去除染料和重金屬離子最常用的方法。最近,具有較大比表面積及眾多吸附位點的納米吸附劑受到越來越多的關(guān)注。本論文以納米微晶纖維素(NCC)為原料,首先對其進(jìn)行高碘酸鹽氧化,制得二醛納米纖維素(DANC)。然后,利用席夫堿反應(yīng)將乙二胺接枝到DANC上,得到具有游離氨基的氨基納米纖維素(ANCC)。最后,將ANCC用作陰離子染料及鉻離子的吸附劑,并研究其吸附性能及機(jī)理。首先,采用硫酸水解法將漂白闊葉木硫酸鹽漿(BHKP)水解,得到初始原料NCC。利用NaIO4氧化NCC,生成DANC,探討了NaIO4用量、反應(yīng)時間和反應(yīng)溫度對DANC醛基含量、Zeta電位、結(jié)晶指數(shù)及晶粒尺寸的影響,并通過FT-IR、XRD和TGA對產(chǎn)物性能進(jìn)行表征。結(jié)果表明,隨著NaIO4用量的增加,DANC的醛基含量逐漸增加；延長反應(yīng)時間可以提高產(chǎn)物的醛基含量；在溫度為40℃以下時,提高溫度會促進(jìn)氧化反應(yīng)的進(jìn)行,而當(dāng)溫度超過40℃,提高溫度反而會抑制反應(yīng)的進(jìn)行。在NaIO4用量為6 mmol/g、反應(yīng)時間為48 h、反應(yīng)溫度為40℃時,經(jīng)過氧化改性所得的產(chǎn)物DANC的醛基含量為105.1%、Zeta電位為-19.5 mV。FT-IR分析表明,NCC經(jīng)NaIO4氧化后,在其表面成功地引入了醛基。XRD分析表明,DANC的晶型沒發(fā)生變化,仍保持纖維素-Ⅰ晶型。但與NCC相比,其結(jié)晶指數(shù)有所降低,且隨著NaIO4用量的增加,結(jié)晶指數(shù)逐漸下降。熱重分析結(jié)果顯示,經(jīng)NaIO4氧化后,DANC的熱穩(wěn)定性降低。隨著NaIO4用量的增加,其初始降解溫度逐漸降低。然后,利用乙二胺通過席夫堿反應(yīng)對DANC進(jìn)行氨基化改性,獲得具有游離氨基的氨基納米纖維素(ANCC)。探討了乙二胺用量對產(chǎn)物得率、氨基含量和Zeta電位的影響,并通過FT-IR、XRD、TGA、AFM和元素分析對產(chǎn)物性能進(jìn)行表征。結(jié)果表明,隨著乙二胺用量的增加,ANCC的氨基含量和Zeta電位亦逐漸增加。FT-IR分析表明,DANC經(jīng)氨基化改性后,成功地引入了氨基。標(biāo)準(zhǔn)茚三酮顯色檢測驗證了產(chǎn)物中游離氨基的存在。XRD分析表明,ANCC的晶型沒發(fā)生變化,仍保持纖維素-Ⅰ晶型。AFM圖片顯示,由于樣品表面親水性氨基的引入,ANCC的分散性有所提高。但與NCC相比,其粒徑有所降低。最后,將ANCC用作陰離子染料和鉻離子的吸附劑,探討了ANCC用量、吸附時間及反應(yīng)體系pH對吸附效果的影響,并對吸附等溫線和吸附動力學(xué)進(jìn)行了分析。結(jié)果表明,較大的ANCC用量、較長的吸附時間及酸性條件下,ANCC對酸性大紅GR具有較好的吸附效果。當(dāng)ANCC用量從0.5 g/L增加到1.0g/L時,脫色率由62%增長至100%；pH為4.7時,ANCC對酸性大紅GR的脫色率為67.3%。ANCC對酸性大紅GR的吸附符合Langmiur吸附等溫模型；比較了ANCC對酸性大紅GR(酸性染料)、剛果紅4BS(直接染料)和活性嫩黃K-4G(活性染料)的吸附,發(fā)現(xiàn)ANCC對剛果紅4BS的吸附能力最強(qiáng)。ANCC對三種陰離子染料的吸附動力學(xué)都遵循準(zhǔn)二階動力學(xué)模型。在pH為2的條件下,ANCC對鉻離子具有較高的去除能力。ANCC對鉻離子的吸附符合準(zhǔn)二階動力學(xué)模型和BET吸附等溫模型。
[Abstract]:In recent years, the increasing of the dye and heavy metal ions contained in the waste water discharged from the chemical industries such as textile, plastics, paper making, printing and food, not only caused the environmental pollution, but also brought great harm to the human health. Therefore, the method of developing high-efficiency and cheap dye and heavy metal ion is a problem to be solved urgently. The method has the advantages of low cost, no sensitivity to toxic pollutants, simple and flexible flow, and the like, and the adsorption method is the most common method for removing the dye and heavy metal ions. Recently, nano-adsorbents with a large specific surface area and a large number of adsorption sites are attracting more and more attention. In this paper, the nano-microcrystalline cellulose (NCC) was used as the raw material, and then the periodate was oxidized to obtain the dialdehydes nano-cellulose (DANC). The ethylenediamine was then grafted onto the DANC using a schiff base reaction to give an amino nano-cellulose (ANCC) with a free amino group. Finally, ANCC was used as an adsorbent for anionic dye and chromium ion, and its adsorption properties and mechanism were studied. First, the bleached broad-leaved wood kraft pulp (BHKP) is hydrolyzed by a sulfuric acid hydrolysis method to obtain the initial raw material NCC. The effects of NaIO4 dosage, reaction time and reaction temperature on the content of DANC, Zeta potential, crystallization index and grain size were discussed by using NaIO4 to oxidize NCC, and the product properties were characterized by FT-IR, XRD and TGA. The results show that, with the increase of the amount of NaIO4, the aldehyde group content of the DANC is increased gradually, the reaction time can be prolonged, the aldehyde group content of the product can be increased, and when the temperature is lower than 40 DEG C, the oxidation reaction can be carried out, and when the temperature is more than 40 DEG C, Increasing the temperature will instead inhibit the reaction. The aldehyde group content of the product DANC obtained after the oxidation modification was 105.1% and the Zeta potential was-19.5mV. FT-IR analysis showed that the NCC was successfully introduced into the aldehyde group after NaIO4 oxidation. The XRD analysis shows that the crystal type of the DANC is not changed, and the cellulose-I-crystal is still maintained. However, compared with NCC, the crystallization index decreased, and the crystallization index decreased with the increase of the amount of NaIO4. The results of the thermal re-analysis show that the thermal stability of the DANC decreases after NaIO4 oxidation. As the amount of NaIO4 increases, its initial degradation temperature is gradually reduced. The DANC was then amino-modified with ethylenediamine by a schiff base reaction to obtain an amino nano-cellulose (ANCC) having a free amino group. The effects of the amount of ethylenediamine on the product yield, the amino content and the Zeta potential were discussed, and the product properties were characterized by FT-IR, XRD, TGA, AFM and elemental analysis. The results showed that the amino content and Zeta potential of ANCC were also increased with the increase of the amount of ethylenediamine. The FT-IR analysis showed that the amino group was successfully introduced after the modification of the DANC. The presence of free amino groups in the product is verified by the development of standard triketone. The XRD analysis shows that the crystal type of ANCC is not changed, and the cellulose-I-crystal is still maintained. The AFM picture shows that the dispersibility of ANCC is improved due to the introduction of hydrophilic amino groups on the surface of the sample. but its particle size is reduced as compared to NCC. In the end, ANCC was used as an adsorbent of anionic dye and chromium ion, and the influence of ANCC dosage, adsorption time and pH of reaction system on the adsorption effect was discussed, and the adsorption isotherm and adsorption kinetics were analyzed. The results show that ANCC has a good adsorption effect on the acid big red GR under the condition of long adsorption time and acid condition. When the amount of ANCC was increased from 0.5 g/ L to 1. 0g/ L, the decoloration rate was increased from 62% to 100%, and the decoloration rate of the ANCC to the acid red GR was 67.3% when the pH was 4.7. The adsorption of the ANCC on the acid large red GR was in accordance with the Langmuir adsorption isotherm model, and the ANCC was compared with the acid large red GR (acid dye). The adsorption of red 4BS (direct dye) and active light yellow K-4G (reactive dye) showed that the adsorption capacity of ANCC to the red 4BS was the strongest. The adsorption kinetics of the ANCC to the three anionic dyes follow the quasi-second-order kinetic model. and under the condition of pH 2, the ANCC has higher removal capacity for chromium ions. The adsorption of chromium ions by ANCC is in accordance with the quasi-second-order kinetic model and the BET adsorption isotherm model.
【學(xué)位授予單位】：齊魯工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：O647.33;X703
本文編號：2364160
[Abstract]:In recent years, the increasing of the dye and heavy metal ions contained in the waste water discharged from the chemical industries such as textile, plastics, paper making, printing and food, not only caused the environmental pollution, but also brought great harm to the human health. Therefore, the method of developing high-efficiency and cheap dye and heavy metal ion is a problem to be solved urgently. The method has the advantages of low cost, no sensitivity to toxic pollutants, simple and flexible flow, and the like, and the adsorption method is the most common method for removing the dye and heavy metal ions. Recently, nano-adsorbents with a large specific surface area and a large number of adsorption sites are attracting more and more attention. In this paper, the nano-microcrystalline cellulose (NCC) was used as the raw material, and then the periodate was oxidized to obtain the dialdehydes nano-cellulose (DANC). The ethylenediamine was then grafted onto the DANC using a schiff base reaction to give an amino nano-cellulose (ANCC) with a free amino group. Finally, ANCC was used as an adsorbent for anionic dye and chromium ion, and its adsorption properties and mechanism were studied. First, the bleached broad-leaved wood kraft pulp (BHKP) is hydrolyzed by a sulfuric acid hydrolysis method to obtain the initial raw material NCC. The effects of NaIO4 dosage, reaction time and reaction temperature on the content of DANC, Zeta potential, crystallization index and grain size were discussed by using NaIO4 to oxidize NCC, and the product properties were characterized by FT-IR, XRD and TGA. The results show that, with the increase of the amount of NaIO4, the aldehyde group content of the DANC is increased gradually, the reaction time can be prolonged, the aldehyde group content of the product can be increased, and when the temperature is lower than 40 DEG C, the oxidation reaction can be carried out, and when the temperature is more than 40 DEG C, Increasing the temperature will instead inhibit the reaction. The aldehyde group content of the product DANC obtained after the oxidation modification was 105.1% and the Zeta potential was-19.5mV. FT-IR analysis showed that the NCC was successfully introduced into the aldehyde group after NaIO4 oxidation. The XRD analysis shows that the crystal type of the DANC is not changed, and the cellulose-I-crystal is still maintained. However, compared with NCC, the crystallization index decreased, and the crystallization index decreased with the increase of the amount of NaIO4. The results of the thermal re-analysis show that the thermal stability of the DANC decreases after NaIO4 oxidation. As the amount of NaIO4 increases, its initial degradation temperature is gradually reduced. The DANC was then amino-modified with ethylenediamine by a schiff base reaction to obtain an amino nano-cellulose (ANCC) having a free amino group. The effects of the amount of ethylenediamine on the product yield, the amino content and the Zeta potential were discussed, and the product properties were characterized by FT-IR, XRD, TGA, AFM and elemental analysis. The results showed that the amino content and Zeta potential of ANCC were also increased with the increase of the amount of ethylenediamine. The FT-IR analysis showed that the amino group was successfully introduced after the modification of the DANC. The presence of free amino groups in the product is verified by the development of standard triketone. The XRD analysis shows that the crystal type of ANCC is not changed, and the cellulose-I-crystal is still maintained. The AFM picture shows that the dispersibility of ANCC is improved due to the introduction of hydrophilic amino groups on the surface of the sample. but its particle size is reduced as compared to NCC. In the end, ANCC was used as an adsorbent of anionic dye and chromium ion, and the influence of ANCC dosage, adsorption time and pH of reaction system on the adsorption effect was discussed, and the adsorption isotherm and adsorption kinetics were analyzed. The results show that ANCC has a good adsorption effect on the acid big red GR under the condition of long adsorption time and acid condition. When the amount of ANCC was increased from 0.5 g/ L to 1. 0g/ L, the decoloration rate was increased from 62% to 100%, and the decoloration rate of the ANCC to the acid red GR was 67.3% when the pH was 4.7. The adsorption of the ANCC on the acid large red GR was in accordance with the Langmuir adsorption isotherm model, and the ANCC was compared with the acid large red GR (acid dye). The adsorption of red 4BS (direct dye) and active light yellow K-4G (reactive dye) showed that the adsorption capacity of ANCC to the red 4BS was the strongest. The adsorption kinetics of the ANCC to the three anionic dyes follow the quasi-second-order kinetic model. and under the condition of pH 2, the ANCC has higher removal capacity for chromium ions. The adsorption of chromium ions by ANCC is in accordance with the quasi-second-order kinetic model and the BET adsorption isotherm model.
【學(xué)位授予單位】：齊魯工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：O647.33;X703
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