Optimized preparation of dithiocarboxylated polyethyleneimine-polyacrylamide and its Cu(Ⅱ) removal performance and mechanism

doi:10.19965/j.cnki.iwt.2023-1157

Abstract

Abstract:

Dithiocarboxylated polyethyleneimine-polyacrylamide〔DT(PEI-PAM)〕 was prepared by using polyacrylamide(PAM),sodium hydroxide(NaOH), sodium hypochlorite(NaClO), and carbon disulfide(CS₂) as raw materials. The Cu(Ⅱ) removal in water samples by DT(PEI-PAM) was investigated as the target, and the optimal preparation conditions of DT(PEI-PAM) were determined by orthogonal experiments. The removal performance of DT(PEI-PAM) for Cu(Ⅱ) was investigated by using flocculation experiments, and the preparation mechanism and the removal mechanism for Cu(Ⅱ) with DT(PEI-PAM) were investigated by characterization means. The results showed that the intermediate polyethylenimide(PEI) was prepared under the optimal conditions as 1% of PAM concentration, 1:1:2 of n(PAM):n(NaClO):n(NaOH), 30 ℃ of reaction temperature, 120 min of reaction time, and 6.5 of pH in reaction medium. The final product DT(PEI-PAM) was prepared under the optimal conditions as 1:2:3 of reactant mass concentration ratio for PEI:CS₂:NaOH, 25 ℃ of pre-reaction temperature, 40 min of pre-reaction time, 60 ℃ of main reaction temperature, and 120 min of main reaction time. The highest removal rate of Cu(Ⅱ) by DT(PEI-PAM) was 96.15% in water sample〔25 mg/L of Cu(Ⅱ) and pH 6.0〕. The infrared characterization and energy spectrum analysis showed that the dithiocarboxyl groups were successfully introduced in DT(PEI-PAM). The mechanism of DT(PEI-PAM) for Cu(Ⅱ) removal was mainly oxidation reduction and chelation precipitation, and the flocculation mechanism was mainly adsorption bridging and net sweep action.

Key words: polyacrylamide, dithiocarboxyl groups, copper-containing wastewater, flocculation

摘要：

以聚丙烯酰胺（PAM）、氢氧化钠（NaOH）、次氯酸钠（NaClO）、二硫化碳（CS₂）为原料，制备了二硫代羧基化聚乙烯亚胺-聚丙烯酰胺〔DT（PEI-PAM）〕。以DT（PEI-PAM）对水样中Cu（Ⅱ）的去除率为考察目标，采用正交实验法确定出DT（PEI-PAM）的最佳制备条件；利用絮凝实验研究了DT（PEI-PAM）对Cu（Ⅱ）的去除性能；通过表征手段探究了DT（PEI-PAM）的制备机理及其除Cu（Ⅱ）机理。结果表明，以PAM质量分数为1%、n（PAM）∶n（NaClO）∶n（NaOH）为1∶1∶2、反应温度为30 ℃、反应时间为120 min、反应介质pH为6.5的最佳条件制备出中间产物聚乙烯亚胺（PEI）；再以PEI、CS₂、NaOH质量浓度比为1∶2∶3、预反应温度为25 ℃、预反应时间为40 min、主反应温度为60 ℃，主反应时间为120 min的最佳条件制备出最终产物DT（PEI-PAM）。DT（PEI-PAM）对含Cu（Ⅱ）水样〔Cu（Ⅱ）初始质量浓度25 mg/L、pH 6.0〕中Cu（Ⅱ）的最高去除率为96.15%。红外表征和能谱分析的结果表明，DT（PEI-PAM）制备过程中成功引入了二硫代羧基，DT（PEI-PAM）对Cu（Ⅱ）的去除机理主要为氧化还原作用和螯合沉淀作用，絮凝作用机理主要为吸附架桥作用，并辅以网捕卷扫作用。

关键词: 聚丙烯酰胺, 二硫代羧基, 含铜废水, 絮凝

CLC Number:

X703.1

Fangjuan SANG, Gang WANG, Xue WANG, Xiaomin YANG. Optimized preparation of dithiocarboxylated polyethyleneimine-polyacrylamide and its Cu(Ⅱ) removal performance and mechanism[J]. Industrial Water Treatment, 2024, 44(12): 67-76.

桑芳娟, 王刚, 王雪, 杨晓敏. 高分子絮凝剂DT（PEI-PAM）的优化制备及其除Cu（Ⅱ）性能与机理[J]. 工业水处理, 2024, 44(12): 67-76.

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Figures/Tables 16

References 24

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实验号	PAM 质量分数/%	反应物比例〔n（PAM）∶ n（NaClO）∶n（NaOH）〕	T ₀/℃	t ₀/min	反应介质 pH	Cu（Ⅱ）去除率/%
实验号	PAM 质量分数/%	反应物比例〔n（PAM）∶ n（NaClO）∶n（NaOH）〕	T ₀/℃	t ₀/min	反应介质 pH	135 mg/L	150 mg/L	165 mg/L
1	1	1∶1∶2	30	30	6.0	84.30	89.91	93.85
2	1	1∶1.5∶2	40	60	6.5	74.47	83.88	90.85
3	1	1∶2∶2	50	90	7.0	82.65	88.58	90.54
4	1	1∶1.5∶2.5	60	120	7.5	77.91	83.70	90.35
5	2	1∶1∶2	40	90	7.5	73.43	82.74	86.83
6	2	1∶1.5∶2	30	120	7.0	72.68	74.16	87.65
7	2	1∶2∶2	60	30	6.5	76.59	87.35	86.26
8	2	1∶1.5∶2.5	50	60	6.0	69.38	77.94	74.97
9	3	1∶1∶2	50	120	6.5	72.70	79.86	88.98
10	3	1∶1.5∶2	60	90	6.0	65.05	71.70	81.38
11	3	1∶2∶2	30	60	7.5	71.20	75.37	81.60
12	3	1∶1.5∶2.5	40	30	7.0	72.65	82.95	83.87
13	4	1∶1∶2	60	60	7.0	68.31	74.32	84.62
14	4	1∶1.5∶2	50	30	7.5	76.44	81.43	81.38
15	4	1∶2∶2	40	120	6.0	72.05	79.78	83.30
16	4	1∶1.5∶2.5	30	90	6.5	81.50	86.41	87.92

实验号	PAM 质量分数/%	反应物比例〔n（PAM）∶ n（NaClO）∶n（NaOH）〕	T ₀/℃	t ₀/min	反应介质 pH	Cu（Ⅱ）去除率/%
实验号	PAM 质量分数/%	反应物比例〔n（PAM）∶ n（NaClO）∶n（NaOH）〕	T ₀/℃	t ₀/min	反应介质 pH	135 mg/L	150 mg/L	165 mg/L
1	1	1∶1∶2	30	30	6.0	84.30	89.91	93.85
2	1	1∶1.5∶2	40	60	6.5	74.47	83.88	90.85
3	1	1∶2∶2	50	90	7.0	82.65	88.58	90.54
4	1	1∶1.5∶2.5	60	120	7.5	77.91	83.70	90.35
5	2	1∶1∶2	40	90	7.5	73.43	82.74	86.83
6	2	1∶1.5∶2	30	120	7.0	72.68	74.16	87.65
7	2	1∶2∶2	60	30	6.5	76.59	87.35	86.26
8	2	1∶1.5∶2.5	50	60	6.0	69.38	77.94	74.97
9	3	1∶1∶2	50	120	6.5	72.70	79.86	88.98
10	3	1∶1.5∶2	60	90	6.0	65.05	71.70	81.38
11	3	1∶2∶2	30	60	7.5	71.20	75.37	81.60
12	3	1∶1.5∶2.5	40	30	7.0	72.65	82.95	83.87
13	4	1∶1∶2	60	60	7.0	68.31	74.32	84.62
14	4	1∶1.5∶2	50	30	7.5	76.44	81.43	81.38
15	4	1∶2∶2	40	120	6.0	72.05	79.78	83.30
16	4	1∶1.5∶2.5	30	90	6.5	81.50	86.41	87.92

DT（PAM-PEI）投加量/（mg·L^-1）		A：PAM质量分数	B：反应物比例	C：T ₀	D：t ₀	E：反应介质pH
135	K ₁	79.83	74.69	77.42	77.49	72.69
	K ₂	73.02	72.16	73.15	70.84	76.32
	K ₃	70.40	75.63	75.29	75.66	74.08
	K ₄	74.58	75.36	71.96	73.84	74.75
	R	9.43	3.47	5.46	6.65	3.62
150	K ₁	86.52	81.71	81.46	85.41	79.83
	K ₂	80.55	77.79	82.34	77.88	84.37
	K ₃	77.47	82.77	81.95	82.36	80.00
	K ₄	80.48	82.75	79.27	79.37	80.81
	R	9.05	4.98	3.07	7.53	4.54
165	K ₁	91.40	88.57	87.75	86.34	83.37
	K ₂	83.93	85.31	86.21	83.01	88.50
	K ₃	83.96	85.42	83.97	86.67	86.67
	K ₄	84.30	84.28	85.65	87.57	85.04
	R	7.47	4.29	3.79	4.56	5.13

DT（PAM-PEI）投加量/（mg·L^-1）		A：PAM质量分数	B：反应物比例	C：T ₀	D：t ₀	E：反应介质pH
135	K ₁	79.83	74.69	77.42	77.49	72.69
	K ₂	73.02	72.16	73.15	70.84	76.32
	K ₃	70.40	75.63	75.29	75.66	74.08
	K ₄	74.58	75.36	71.96	73.84	74.75
	R	9.43	3.47	5.46	6.65	3.62
150	K ₁	86.52	81.71	81.46	85.41	79.83
	K ₂	80.55	77.79	82.34	77.88	84.37
	K ₃	77.47	82.77	81.95	82.36	80.00
	K ₄	80.48	82.75	79.27	79.37	80.81
	R	9.05	4.98	3.07	7.53	4.54
165	K ₁	91.40	88.57	87.75	86.34	83.37
	K ₂	83.93	85.31	86.21	83.01	88.50
	K ₃	83.96	85.42	83.97	86.67	86.67
	K ₄	84.30	84.28	85.65	87.57	85.04
	R	7.47	4.29	3.79	4.56	5.13

实验号	n（PEI）∶n（CS₂）∶n（NaOH）	T ₁/℃	t ₁/min	T ₂/℃	t ₂/min	Cu（Ⅱ）去除率/%
实验号	n（PEI）∶n（CS₂）∶n（NaOH）	T ₁/℃	t ₁/min	T ₂/℃	t ₂/min	135 mg/L	150 mg/L	165 mg/L
1	1∶2∶3	20	10	45	30	53.59	54.65	60.89
2	1∶2∶3	25	20	50	60	79.32	83.67	88.47
3	1∶2∶3	30	30	55	90	92.24	95.36	11.56
4	1∶2∶3	35	40	60	120	95.98	88.74	3.01
5	1∶2∶2	20	20	55	120	59.96	65.38	74.75
6	1∶2∶2	25	10	60	90	68.05	70.48	82.24
7	1∶2∶2	30	40	45	60	55.50	62.55	66.34
8	1∶2∶2	35	30	50	30	52.15	57.27	68.41
9	1∶2∶1	20	30	60	60	26.83	32.49	33.60
10	1∶2∶1	25	40	55	30	29.92	37.61	41.17
11	1∶2∶1	30	10	50	120	31.01	30.18	35.85
12	1∶2∶1	35	20	45	90	25.53	34.08	37.33
13	1∶3∶2.5	20	40	50	90	72.77	80.46	92.34
14	1∶3∶2.5	25	30	45	120	77.48	86.51	92.49
15	1∶3∶2.5	30	20	60	30	72.54	80.68	91.43
16	1∶3∶2.5	35	10	55	60	77.90	83.80	85.84

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