有机絮凝剂对铁矿相沉降性能影响及其吸附机理

doi:10.11949/0438-1157.20220405

化工学报 ›› 2022, Vol. 73 ›› Issue (9): 4122-4132.DOI: 10.11949/0438-1157.20220405

有机絮凝剂对铁矿相沉降性能影响及其吸附机理

鲁统鹏¹^,²^,³(), 潘晓林¹^,²^,³(), 吴鸿飞¹^,²^,³, 李煜¹^,²^,³, 于海燕¹^,²^,³()

^1.东北大学多金属共生矿生态化冶金教育部重点实验室，辽宁沈阳 110819
^2.东北大学冶金学院，辽宁沈阳 110819
^3.沈阳市有色金属资源循环利用重点实验室，辽宁沈阳 110819

收稿日期:2022-03-22 修回日期:2022-06-28 出版日期:2022-09-05 发布日期:2022-10-09
通讯作者: 潘晓林,于海燕
作者简介:鲁统鹏（1995—），男，硕士研究生，danubeblue@foxmail.com
基金资助:
国家自然科学基金项目(22078055);中央高校基本科研业务费专项资金项目(N2225002)

Effect of organic flocculant on settling performance of iron-bearing minerals and its adsorption mechanism

Tongpeng LU¹^,²^,³(), Xiaolin PAN¹^,²^,³(), Hongfei WU¹^,²^,³, Yu LI¹^,²^,³, Haiyan YU¹^,²^,³()

^1.Laboratory for Ecological Metallurgy of Multimetallic Mineral (Ministry of Education), Northeastern University, Shenyang 110819, Liaoning, China
^2.School of Metallurgy, Northeastern University, Shenyang 110819, Liaoning, China
^3.Key Laboratory for Recycling of Nonferrous Metal Resources (Shenyang), Shenyang 110819, Liaoning, China

Received:2022-03-22 Revised:2022-06-28 Online:2022-09-05 Published:2022-10-09
Contact: Xiaolin PAN, Haiyan YU

摘要/Abstract

摘要：

通过模拟拜耳法赤泥沉降过程研究了聚丙烯酸铵(PAAA)、阴离子聚丙烯酰胺(APAM)和氧肟酸絮凝剂(HPAM/HCPAM)对赤铁矿和针铁矿沉降性能的影响规律和絮凝后絮体的粒径分布及分形维数，并利用傅里叶变换红外光谱探讨了絮凝剂与铁矿相的吸附机理。在不同类型絮凝剂中，添加氧肟酸絮凝剂铁矿相沉降速度最快，且氧肟酸含量越高，沉降性能越好；聚丙烯酸铵和阴离子聚丙烯酰胺絮凝剂对铁矿相沉降性能影响较小；同等条件下赤铁矿沉降速度要远高于针铁矿，增加絮凝剂添加量有助于提高针铁矿沉降速度。在赤铁矿絮体中，添加PAAA絮体粒径最大，HPAM絮体分形维数最大、致密性最好；在针铁矿絮体中，添加APAM絮体粒径最大，HCPAM絮体分形维数最大、致密性最好。氧肟酸絮凝剂与铁矿相形成结构稳定、吸附能力强的五元环状螯合物，增强了赤铁矿和针铁矿的絮凝效果；PAAA通过双齿桥接配位与赤铁矿表面发生吸附，通过单齿配位与针铁矿表面发生吸附，其吸附能力弱于五元环；APAM与赤铁矿和针铁矿表面发生化学吸附，沉降性能差。

关键词: 沉降, 吸附, 絮凝, 粒度分布, 赤铁矿, 针铁矿

Abstract:

The effect of ammonium polyacrylate (PAAA), anionic polyacrylamide (APAM) and hydroxamic acid flocculant (HPAM/HCPAM) on the settling performance of hematite and goethite by simulating the Bayer red mud settlement was studied, and the particle size distribution and fractal dimension of flocs as well as the flocculation mechanism were analyzed by Fourier transform infrared spectroscopy. Among the different types of flocculants, the iron ore phase sedimentation rate is the fastest with the addition of hydroxamic acid flocculant, and the higher the hydroxamic acid content, the better the sedimentation performance; the ammonium polyacrylate and anionic polyacrylamide flocculants have little effect on the settling performance of iron-bearing minerals; under the same conditions, the settling velocity of hematite is much higher than that of goethite, and increasing the amount of flocculant helps to improve the settling velocity of goethite. Among the hematite flocs, the PAAA flocs have the largest particle size, while the HPAM flocs have the largest fractal dimension and the best compactness; among the goethite flocs, the APAM flocs have the largest particle size, while the HCPAM flocs have the largest fractal dimension and the best compactness. The hydroxamic acid flocculant forms a five membered ring chelate with a stable structure and strong adsorption capacity with hematite and goethite, which enhances the flocculation performance of hematite and goethite; PAAA is adsorbed with hematite through bidentate bridging, and adsorbed with goethite through monodentate coordination, the adsorption capacity of which is weaker than five-membered ring; APAM adopts the chemical adsorption with hematite and goethite with a poor settling performance.

Key words: sedimentation, adsorption, flocculation, particle size distribution, hematite, goethite

中图分类号:

TF 803.23

鲁统鹏, 潘晓林, 吴鸿飞, 李煜, 于海燕. 有机絮凝剂对铁矿相沉降性能影响及其吸附机理[J]. 化工学报, 2022, 73(9): 4122-4132.

Tongpeng LU, Xiaolin PAN, Hongfei WU, Yu LI, Haiyan YU. Effect of organic flocculant on settling performance of iron-bearing minerals and its adsorption mechanism[J]. CIESC Journal, 2022, 73(9): 4122-4132.

图/表 13

表1 不同絮凝剂的类型及官能团

Table 1 Types of different flocculants and functional groups

Flocculant type	Functional group
ammonium polyacrylate (PAAA)	—COO^-
anionic polyacrylamide (APAM)	—CONH₂，—COO^-
mixed hydroxamic acid (HPAM)	—CONHOH，—CONH₂，—COO^-
high content hydroxamic acid (HCPAM)	—CONHOH

图1 赤铁矿和针铁矿的XRD谱图

Fig.1 XRD patterns of hematite and goethite

表2 赤铁矿、针铁矿与不同絮凝剂作用下的沉降性能

Table 2 Settling performance of different flocculants with hematite and goethite

Iron-bearing mineral	Flocculant	v₁/(m·h^-1)	v₅/(m·h^-1)	Compression ratio/%	Supernatant turbidity/NTU
hematite	no flocculant	0.621	0.738	24.88	70.71
	PAAA	0.771	0.842	25.71	136.59
	APAM	0.481	0.718	26.83	114.53
	HPAM	4.434	1.716	21.46	327.76
	HCPAM	7.397	1.759	19.51	292.47
goethite	no flocculant	0.046	0.029	89.50	221.00
	PAAA	0.068	0.041	88.00	160.71
	APAM	0.025	0.026	92.00	88.94
	HPAM	0.246	0.211	62.50	32.47
	HCPAM	0.305	0.508	53.00	30.41

图2 赤铁矿（a）、针铁矿（b）与不同絮凝剂作用下的沉降曲线

Fig.2 Settling curves of different flocculants with hematite (a) and goethite (b)

图3 赤铁矿在不同絮凝剂添加量作用下的沉降曲线

Fig.3 Settling curves of hematite with different flocculants additions

图4 针铁矿在不同絮凝剂添加量作用下的沉降曲线

Fig.4 Settling curves of goethite with different flocculants additions

表3 赤铁矿、针铁矿与不同絮凝剂形成絮体的粒度参数

Table 3 Particle size of hematite and goethite flocs formed with different flocculants

Iron-bearing mineral	Flocculant	D_(0.1)/μm	D_(0.5)/μm	D_(0.9)/μm	Specific surface area/(m²‧kg^-1)
hematite	no flocculant	0.06	3.91	11.80	32390
	PAAA	14.33	63.07	186.33	182.13
	APAM	11.40	42.38	186.00	223.73
	HPAM	13.00	36.63	80.87	236.47
	HCPAM	15.40	59.40	135.33	181.17
goethite	no flocculant	0.11	6.25	29.73	12230
	PAAA	13.10	43.60	125.00	83.27
	APAM	14.60	46.10	99.50	80.23
	HPAM	10.80	26.40	71.50	132.90
	HCPAM	12.40	33.50	106.00	87.70

图5 赤铁矿（a）、针铁矿（b）与不同絮凝剂形成絮体的粒度分布

Fig.5 Particle size distributions of hematite (a) and goethite (b) flocs formed with different flocculants

表4 赤铁矿和针铁矿的分形维数

Table 4 Fractal dimension of hematite and goethite

Iron-bearing mineral	Flocculant	D_f
Iron-bearing mineral	Flocculant	1	2	3	Average
hematite	PAAA	2.493	2.488	2.492	2.491
	APAM	2.436	2.443	2.447	2.442
	HPAM	2.537	2.541	2.547	2.542
	HCPAM	2.373	2.377	2.381	2.377
goethite	PAAA	2.224	2.238	2.248	2.237
	APAM	2.157	2.156	2.155	2.156
	HPAM	2.324	2.331	2.338	2.331
	HCPAM	2.433	2.434	2.433	2.433

图6 赤铁矿、絮凝剂和絮凝后的赤铁矿絮体的FT-IR图(Ⅰ—絮凝剂;Ⅱ—赤铁矿;Ⅲ—絮凝后的赤铁矿)

Fig.6 FT-IR spectra of flocculants, hematite and flocculant-treated hematite(Ⅰ—flocculant;Ⅱ—hematite;Ⅲ—flocculant-treated hematite)

图7 赤铁矿与不同絮凝剂官能团的吸附机理示意图

Fig.7 Schematic diagram of adsorption mechanism between hematite and different flocculant functional groups

图8 针铁矿、絮凝剂和絮凝后的针铁矿絮体的FT-IR图(Ⅰ—絮凝剂;Ⅱ—针铁矿;Ⅲ—絮凝后的针铁矿)

Fig.8 FT-IR spectra of flocculants, goethite and flocculant-treated goethite(Ⅰ—flocculant;Ⅱ—goethite;Ⅲ—flocculant-treated goethite)

图9 针铁矿与不同絮凝剂官能团的吸附机理示意图

Fig.9 Schematic diagram of adsorption mechanism between goethite and different flocculant functional groups

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有机絮凝剂对铁矿相沉降性能影响及其吸附机理

Effect of organic flocculant on settling performance of iron-bearing minerals and its adsorption mechanism

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