温度对铜渣和磷矿协同联产制备磷铁影响的实验研究

谢仁齐; 黄润; 刘利; 张金柱

doi:10.3969/j.issn.1000-6532.2022.06.008

温度对铜渣和磷矿协同联产制备磷铁影响的实验研究

贵州大学材料与冶金学院，贵州省冶金工程及过程节能重点实验室，贵州贵阳 550025

详细信息

作者简介: 谢仁齐（1995-），男，硕士，研究方向为矿产资源综合利用

通讯作者: 黄润（1984-），男，教授，研究方向为资源综合利用及炼铁新技术、真空冶金

中图分类号: TD952; TF09

收稿日期: 2020-10-30

修回日期: 2021-10-06

刊出日期: 2022-12-25

Effect of Temperature on the Co-production of Copper Slag and Middle Low-grade Phosphate Rock

School of Materials and Metallurgy, Guizhou University, Laboratory Metallurgical Engineering and Energy Saving Process of Guizhou Province, Guiyang, Guizhou, China

More Information

Corresponding author: Huang Run, rhuang@gzu.edu.cn

Received Date: 30 October 2020

Revised Date: 06 October 2021

Publish Date: 25 December 2022

摘要

摘要:
磷铁是一种重要的工业合金物，在炼钢、化工业及新能源领域和建筑业具有举足轻重的作用，磷铁的开发利用不仅可以为企业带来经济效益，也可为国家经济的发展注入活力。本文在T=1200~1400℃，R（CaO/SiO₂）=1.0，t=60 min，C=12%条件下进行实验。以磷矿和铜渣为原料，石墨作还原剂，在高温节能管式炉中还原焙烧制取磷铁，还原后的试样进行分离、磨矿，采用XRD、SEM和EDS对磷铁及渣进行表征，结果显示：T<1300℃所得磷铁主要物相为Fe₃P，T>1300℃所得磷铁主要物相为Fe₃P、Fe₂P。还原后测得渣的主要成分为硅酸盐类，以偏硅酸钙为主（CaSiO₃）和含有少量的硅酸铝。
- 磷铁 /
- 磷矿 /
- 铜渣 /
- 高温还原
Abstract:
Ferro-phosphorus is an important industrial alloy, which plays a pivotal role in steelmaking, chemical industry, new energy and construction industry. The development and utilization of ferro-phosphorus can not only bring economic benefits to enterprises, but also contribute to the development of national economy. In this paper, the experiment was carried out under the conditions of T=1200℃-1400℃, R(CaO/SiO₂)=1.0, t=60 min and C=12%. Phosphate rock and copper slag were used as raw materials, graphite was used as reducing agent, and ferrophosphorus was produced by reduction and roasting in a high-temperature energy-saving tubular furnace. The reduced samples were separated and ground, XRD, SEM and EDS were used to characterize ferrophosphorus and slag. The results showed that the main phase of ferrophosphorus obtained is Fe₃P at T<1300℃, and the main phase of ferrophosphorus obtained is Fe₃P and Fe₂P at T>1300℃. After reduction, it was measured that the main component of the slag was silicate, mainly calcium metasilicate (CaSiO₃) and a small amount of aluminum silicate.
- Ferro-phosphorus /
- Phosphate rock /
- Copper slag /
- High temperature reduction

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图 1 a：磷矿XRD；b：铜渣XRD

Figure 1.

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图 2 中低品位磷矿与铜渣制备磷铁的工艺流程

Figure 2.

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图 3 a：磷矿可能发生分解反应的吉布斯自由能；b：生成磷铁的吉布斯自由能；c和d：铜渣可能发生分解反应的吉布斯自由能

Figure 3.

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图 4 不同温度下获得到磷铁、金属铁和单质磷

Figure 4.

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图 5 不同温度下试样失重率及生成磷铁

Figure 5.

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图 6 1200℃、1300℃、1350℃、1400℃温度下磷铁的微观形貌与面扫图

Figure 6.

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图 7 还原后生成磷铁XRD

Figure 7.

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图 8 还原后渣相XRD

Figure 8.

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表 1 磷矿和铜渣的化学成分/%

Table 1. Chemical composition of copper slag and phosphate ore

名称	Fe₂O₃	SiO₂	Na₂O	SO₃	MgO	CaO	Al₂O₃	P₂O₅	ZnO	F
磷矿	1.06	9.79	0.43	0.85	1.70	48.94	1.38	32.98	0	2.87
铜渣	56.83	20.62	6.48	4.80	2.63	2.43	2.13	0.29	3.79	0

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表 2 不同温度下点扫描结果/%

Table 2. Spot scan results at different temperatures

	Fe	P	C	O	Ca	Si	Mg	Al
1200(a)	82.02	14.37	2.70	0.79	0.00	0.00	0.05	0.07
1300(a)	83.22	12.91	2.74	0.72	0.00	0.40	0.01	0.00
1350(a)	82.86	13.34	2.52	0.67	0.07	0.52	0.03	0.00
1400(a)	82.89	12.58	2.96	0.93	0.08	0.45	0.03	0.09
1200(b)	93.42	0.91	4.89	0.65	0.00	0.00	0.06	0.08
1300(b)	87.91	0.62	6.49	1.01	0.00	3.84	0.07	0.06
1350(b)	79.04	0.30	13.04	4.84	0.08	2.55	0.15	0.00
1400(b)	82.89	0.31	15.14	0.68	0.09	0.62	0.00	0.01
1200(c)	43.46	0.56	53.29	2.49	0.04	0.00	0.09	0.07
1300(c)	75.90	1.65	19.67	1.26	0.00	1.31	0.17	0.05
1350(c)	6.56	0.06	89.07	4.05	0.11	0.11	0.02	0.02
1400(c)	10.53	0.07	81.32	7.59	0.24	0.22	0.03	0.00
1200(d)	47.87	0.95	15.67	34.56	0.17	0.34	0.24	0.19
1300(d)	40.70	2.36	33.99	19.88	0.00	1.36	1.27	0.45
1350(d)	48.37	12.18	17.33	20.55	0.26	0.53	0.16	0.61
1400(d)	69.72	12.09	13.45	4.07	0.09	0.38	0.05	0.14

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