含硫纤维素衍生物的制备及性能研究

VIP免费

3.0 牛悦 2024-11-19 4 4 2.93MB 94 页 15积分

侵权投诉

摘要

含硫纤维素主要有巯基纤维素（SC）、纤维素磺原酸酯（CCX）和聚硫醚型纤

维素（PTCC）三种衍生物。这些含硫纤维素衍生物作为功能高分子材料，主要应

用于分析化学、环境科学与工程、化学化工、冶金等领域。本论文对这三种含硫

纤维素衍生物的制备、材料性能、吸附性能、解吸再生性能、吸附机理及其应用

进行了系统性研究。

SC 的制备方法：棉花先经过冰醋酸润胀，然后按 15g 棉花－100mL 巯基乙酸

－浓硫酸 1.0mL 的比例，在 40°C 条件下，反应 48 小时。制备的巯基纤维素色泽

洁白、机械强度较好，碘量法测定巯基含量在 1.70%左右。

CCX 的制备方法：将脱脂棉撕成小片，在常温下浸入 10％～20％的 NaOH 溶

液中制备碱纤维。10 分钟后取出碱纤维，将分拨好的碱纤维放入烧杯中，倒入 CS2

将其全部淹没，约十分钟，待棉纤维呈现浅黄色，立即将其取出，迅速用蒸馏水

洗至洗液呈中性。得到的纤维素磺原酸酯可以立即使用，也可以在 50°C～70°C 以

下烘干，备用。碘量法测定 CCX 中含硫量在 2.1％左右。

PTCC 的制备方法：将 5g 脱脂棉置于 250mL 三角瓶中，加入 17.5%的NaOH

溶液 25mL，搅匀，使脱脂棉完全湿润，并使脱脂棉反应 4小时，使纤维活化，然

后在棉花中加入环硫氯丙烷 15g，并且搅拌均匀。然后放入烘箱在 47℃下反应 20

小时再在 60℃下反应 4小时后取出。在试样中加入 40mL 95%乙醇，并在 60℃下

搅拌半小时。搅拌完毕后分别过滤，所得棉纤维用蒸馏水洗涤多次，然后用丙酮

抽提，再用蒸馏水洗涤至无氯离子，随后在 60℃烘干至恒重。烘干后 PTCC 重量

为：11.617g。按本方法制备聚硫醚纤维素工艺简单且含硫量高，氧瓶燃烧法测定

其含硫量在 21.3％左右。

对材料的稳定性和使用性能进行了考察。溶液酸度和温度对 SC、CCX 和PTCC

的水解影响很小，日常阳光照射和大气中的氧气对 SC、

CCX 和PTCC 的的影响也

甚微，总体性能来说稳定性 PTCC>SC>CCX。SC 和CCX 抗强氧化剂的能力较差，

因此巯基纤维素和纤维素磺原酸酯应避免与强氧化剂直接接触，否则将严重影响

其饱和吸附容量。PTCC 相对于 SC 和CCX 来说，抗强氧化剂、抗紫外光照射能

力明显高于 SC 和CCX，在 1% H2O2, 1% HNO3和0.5％的 KMnO4溶液中浸泡

80min，其相对含硫量仍旧很高，分别为 94％、96％和 91％，在 300 瓦的紫外灯

下照射 80min，含硫量下降幅度不大，且其饱和吸附容量变化不大，并不影响其实

际应用。

SC 对Hg2+、Cu2+、Pb2+、Cd2+和Zn2+均具有较好的吸附性能，其吸附饱和容

量分别为：58、17、55、29、10(mg/g)。CCX 对Hg2+、Cu2+、Pb2+、Cd2+和Zn2+

的饱和吸附容量要高一些分别为：82、26、77、49、24(mg/g)。PTCC 对Hg2+ 、

Ag+、维多利亚艳兰 BO、阳离子红 X－GRL、氯化十六烷基吡啶的饱和吸附容

量非常高，分别为： 161、256、98、70、219(mg /g)。用 2mol/L 盐酸溶液对已饱

和的 SC 进行洗脱再生试验。Pb2+、Cd2+、Cu2+、等重金属离子都能被洗脱液完全

洗脱（汞的洗脱需要 NaCl 饱和的 5mol/L 盐酸），且洗脱率高达 98％以上。NaCl

饱和的 1:1浓盐酸对 CCX 进行洗脱再生试验，Cd2+、Cu2+、Zn2+等重金属离子能

被完全被洗脱，洗脱率高达 95％以上，但对于与 CCX 结合力较大的 Pb2+、Hg2+

等离子，则较难洗脱。用 12％的氨水溶液对吸附饱和的 PTCC 进行洗脱，洗脱效

果良好，重复 5次后的 PTCC 仍具有较高的吸附容量，且其饱和吸附量趋向于稳

定。

研究了PTCC的吸附平衡和吸附动力学。实验结果表明氯化十六烷基吡啶的吸

附等温数据符合Langmuir吸附等温式，其相关系数R2为0.9491, 而对于Freundlich

吸附等温式，其相关系数R2为0.8574，小于L方程的相关系数，说明PTCC对此类污

染物的吸附更符合Langmuir方程，该吸附体系兼有化学吸附和物理吸附。研究了

PTCC对维多利亚艳兰 BO、阳离子红X-GRL和氯化十六烷基吡啶的吸附动力学。

在室温下，维多利亚艳兰 BO、阳离子红X-GRL和氯化十六烷基吡啶的一级吸附

相关系数R2分别为0.9716、0.9870、0.9916，二级吸附相关系数R2为0.9988、0.9995、

0.9971，从实验所得数据看，三种污染物的吸附速率数据当用Lagergren一级动力学

方程拟合时，R2值显示其存在较好的相关性，但其R2值均小于用二级动力学吸附的

相关系数，因此，维多利亚艳兰 BO、阳离子红X-GRL和氯化十六烷基吡啶在PTCC

上的吸附行为遵循二级动力学模型。

研究了 SC、CCX 和PTCC 用于处理重金属工业废水的工艺流程及工艺条件等。

工艺路线为：前期使用化学沉淀法，去除部分重金属离子；调节 pH6.0～8.0，然

后用 SC、

CCX 或PTCC 吸附柱对废水中重金属离子进行吸附。实验结果表明该工

艺具有去除率高、操作简单、投资成本低、管理方便等诸多优点。与其它传统工

艺相比，优势明显。研究表明，SC、CCX 和PTCC 对水溶液中的重金属离子具有

良好的吸附性能。

SC、CCX 和PTCC 不仅仅适用于环境分析检测领域，还适用于对重金属离子

的废水进行深度处理，应用前景广阔。随着对 SC、CCX 和PTCC 的进一步研究，

它们将在今后的环境检测、分析化学、化工、冶金、机械加工等行业的废水治理

发挥更为重要的作用。

关键词：巯基纤维素纤维素磺原酸酯聚硫醚型纤维素制备性能吸

附重金属废水治理

ABSTRACT

Sulfur-containing cellulose derivatives include sulfhydryl cellulose (SC), cotton

cellulose xanthate (CCX) and polythioehter type cotton cellulose (PTCC), and as

functional polymer material, they are mainly used in the fields of analytical chemistry,

environmental science, metallurgy, and so on. In this paper, the preparation process,

properties, adsorption and regeneration properties, adsorption mechanisms and

application of them were systematically studied.

The preparation of SC: 15g Cotton was swelled in acetic acid solution, then 100ml

thioglycolic acid and 10ml concentrated sulfuric acid was added. The sulphydryl

cellulose in white color with fine mechanical strength was obtained after reacting 48

hours in the temperature of 40°C. And its sulfur content was 1.70% which was

determined by iodimetry.

The preparation of CCX: The alkali cellulose was made of adsorbent cotton by

soaking in sodium hydroxide (10%~20%) for 10 min. Then taken out and put into

Buchner funnel, it was filtrated in order to remove the redundant alkali solution. And

then the alkali cellulose was xanthated with carbon disulfide for almost 40 min. The

product was washed and dried at the temperature between 50°C and 70°C for spare use.

And its sulfur content was 2.1％determined by iodimetry.

The preparation of PTCC: Polythioehter type cotton cellulose (PTCC) with fine

properties was synthesized by etherification of cotton cellulose with

chloromethylthiirane (CMT). The results show that the concentration of sodium

hydroxide and the reactant ratio between cotton fiber and chloromethylthiirane will

affect the yield and sulfur containing of the product. The better polythioether type

cotton cellulose with high sulfur containing will be made when the concentration of

alkali is 20% and the molar ratio between the glucose unit of cellulose and

chloromethylthiirane is between 1:3.7 and 1:5. The preparation process is simple here

and this new kind of material can be used to adsorb mercury, silver, cationic dries and

cationic surfactants. And its sulfur content was 21.3 ％determined by oxygen flask

combustion method.

The stabilities and properties of sulfur-containing cellulose derivatives were

studied. The acidity and temperature of solution had little effect on SC, CCX and PTCC,

while the light of sunshine and oxygen in air also affected little on them. According to

their total-property, PTCC is better than SC which is better than CCX. SC and CCX

have low resistance on strong oxidants, so in their application they should avoid

direct-contact on strong oxidants. But compared with SC and CCX, PTCC has much

better resistance on strong oxidants and direct ultraviolet irradiation. In the water

solution of 1% hydrogen peroxide, 1% nitric acid and 0.5% potassium permanganate for

80 min, the sulfur containing of PTCC was decreased a little with the drop of 6%, 4%

and 9% respectively. And under the direct irradiation of 300w ultraviolet lamp for 80

min, the sulfur content of PTCC has slight decrease and its saturated adsorption

capacity has a little drop which would not affect its application.

With fine adsorption capacities on Hg2+, Cu2+, Pb2+, Cd2+ and Zn2+, the saturated

adsorption capacities of SC on them is 35, 8, 30, 20, 10(mg/g) respectively. CCX has

greater adsorption capacities on Hg2+, Cu2+, Pb2+, Cd2+ and Zn2+, which is 82, 26, 77,

49, 24(mg/g) respectively. While PTCC has impressive adsorption capacities on Hg2+,

Ag+, Victoria pure blue BO, cationic red X-GRL and cetylpyridnium chloride, which

is 161, 256, 98, 70, 219(mg/g)respectively. Furthermore, the washed and regenerated

test of saturated SC was done with 2 mol/L hydrochloric acid solution. It revealed that

most heavy metal ions such as Pb2+, Cd2+, Cu2+, Hg2+ etc, can be removed from SC and

the removal ratio was up to 98%. And repeat this test on saturated CCX with 1:1

concentrated hydrochloric acid which was saturated by sodium chloride. It was proved

that most heavy metal ions such as Cd2+, Cu2+, Zn2+ etc, could be easily removed from

CCX, but some ions, for example Pb2+ and Hg2+, which were combined intensively

with CCX, were slight harder to be removed. And then the washed and regenerated test

of saturated PTCC was done with 12% ammonia solution with fine regenerated results.

Its adsorption capacities are still huge and tend to be stable after regenerating for 5

times.

The adsorption equilibrium and kinetic were studied. The results indicated that the

adsorption isotherm of cetylpyridnium chloride fited Langmuir equation with the

correlation coefficient of 0.9491 which is larger than that of Freundlich equation, 0.8574.

It proved that this adsorption isotherm fits L equation better, and this adsorption system

has both chemical and physical adsorption. Furthermore, the kinetic adsorptions of VPB

BO, Cationic Red X-GRL and cetylpyridium chloride on PTCC were also studied. The

correlation coefficient of their first-order lagergren equation was 0.9716, 0.9870, 0.9916

respectively, while their second-order correlation coefficient was 0.9988, 0.9995 and

0.9917 respectively. The experiments’ results showed that their coefficient R2had fine

correlation when described by first-order equation, which were less than R2of

second-order adsorption. Therefore ，the uptake process of VPB BO, Cationic Red

X-GRL and cetylpytidium chloride followed second-order kinetic model.

The process flow and conditions of treating wastewater containing heavy metal

ions by SC, CCX and PTCC were studied. In the former phase of this process, some of

heavy metal ions were removed by chemical precipitation. And then the pH value

adjusted between 6.0 and 8.0, SC, CCX or PTCC was used to adsorb remanent heavy

metal ions in wastewater. The results demonstrate that this process compared to

conventional process has many significant advantages, such as high removal ratio,

simple operation, low investment, easy management, etc. And the results show that SC,

CCX and PTCC have great adsorption properties on heavy metal ions in aqueous

solution.

SC, CCX and PTCC can not only be used in the field of environmental analysis

and testing, but also in the deep treatment of wastewater contaminated by heavy metal

ions. So they have wide application prospects. As the deeper studies on SC, CCX and

PTCC, they will play an more important role in the treatment of wastewater which

comes from the fields of environmental testing, analytical chemistry, chemical industry,

metallurgy, mechanical processing and so on.

Keywords: sulfhydryl cellulose, cotton cellulose xanthate, polythioether

type cotton cellulose, preparation, properties, adsorption, heavy metal

ions, wastewater treatment

中文摘要

ABSTRACT

第一章绪论 ......................................................... 1

1.1 纤维素简介.........................................................................................................1

1.1.1 自然界中的纤维素..........................................................................................1

1.1.2 纤维素的化学结构..........................................................................................2

1.1.3 纤维素的结晶度和可及度...............................................................................2

1.1.4 纤维素的物理性质...........................................................................................3

1.1.5 纤维素的化学性质...........................................................................................3

1.2 废水处理的主要方法 ............................................................................................. 6

1.3 吸附剂的研究概况 ................................................................................................. 8

1.4 吸附的种类和影响吸附的因素 ............................................................................ 9

1.4.1 吸附机理及分类..............................................................................................9

1.4.2 影响吸附的因素............................................................................................10

1.5 含硫纤维素衍生物简介及国内外的研究现状 .................................................. 12

1.5.1 常见的含硫纤维衍生物.................................................................................12

1.5.2 含硫纤维素衍生物的应用及其特点............................................................14

1.6 本论文的指导思想和研究目的 ........................................................................15

1.7 本论文的主要研究内容 ....................................................................................17

第二章实验部分 .................................................... 19

2.1 仪器与材料 .......................................................................................................... 19

2.1.1 主要实验仪器................................................................................................19

2.1.2 实验材料与试剂..........................................................................................19

2.2 实验方法 ............................................................................................................. 20

2.2.1 材料的制备..................................................................................................20

2.2.2 含硫纤维素衍生物材料的含硫量测定方法...............................................21

2.2.3 含硫纤维素衍生物饱和吸附容量的测定..................................................24

2.2.4 含硫纤维素衍生物的动态吸附穿透点的测定..........................................24

2.2.5 等温吸附线的测定......................................................................................25

2.2.6 红外光谱分析..............................................................................................26

第三章实验结果与讨论 .............................................. 27

文档加载中……请稍候！
如果长时间未打开，您也可以点击刷新试试。

下载文档到电脑，查找使用更方便

15 积分 4人已下载

立即下载 VIP免费下载

摘要：

摘要含硫纤维素主要有巯基纤维素（SC）、纤维素磺原酸酯（CCX）和聚硫醚型纤维素（PTCC）三种衍生物。这些含硫纤维素衍生物作为功能高分子材料，主要应用于分析化学、环境科学与工程、化学化工、冶金等领域。本论文对这三种含硫纤维素衍生物的制备、材料性能、吸附性能、解吸再生性能、吸附机理及其应用进行了系统性研究。SC的制备方法：棉花先经过冰醋酸润胀，然后按15g棉花－100mL巯基乙酸－浓硫酸1.0mL的比例，在40°C条件下，反应48小时。制备的巯基纤维素色泽洁白、机械强度较好，碘量法测定巯基含量在1.70%左右。CCX的制备方法：将脱脂棉撕成小片，在常温下浸入10％～20％的NaOH溶液中制备碱...

展开>> 收起<<

含硫纤维素衍生物的制备及性能研究.pdf

共94页,预览10页

还剩页未读，继续阅读

含硫纤维素衍生物的制备及性能研究

相关推荐

开通VIP享超值会员特权

作者详情

相关内容

推荐作者

热门标签

举报选择: