磷化工副产物磷铁渣绿色循环真空脱硅

白倩; 荆碧; 李秋霞

doi:10.3969/j.issn.1000-6532.2024.02.020

磷化工副产物磷铁渣绿色循环真空脱硅

云南师范大学化学化工学院，云南　昆明　650500

详细信息

作者简介: 白倩（1990-），女，硕士，研究方向为冶金化学

通讯作者: 李秋霞（1971-），女，博士，教授，研究方向为冶金化学

中图分类号: TD91

收稿日期: 2022-06-28

刊出日期: 2024-04-25

Desilicification Reclying Ferrophosphorus Slag under Vacuum

Faculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, Yunnan, China

More Information

Corresponding author: LI Qiuxia, qiuxiali03@163.com

Received Date: 28 June 2022

Publish Date: 25 April 2024

摘要

摘要:
这是一篇冶金工程领域的论文。为了绿色利用磷化工副产物磷铁渣，本文对磷化工副产物磷铁添加CaO进行脱硅热力学计算并开展实验研究。在温度为900～1700 K范围内，SiO₂和CaO的摩尔比为1∶1～3时，反应生成CaO·SiO₂、2CaO·SiO₂、3CaO·SiO₂和3CaO·2SiO₂的$ \Delta {G_T} $值均小于0，说明添加适量的CaO可以脱除磷化工副产磷铁中的SiO₂。进一步实验研究表明：压力为10～40 Pa，温度为1573 K时，加入适量氧化钙，使原料磷铁中的二氧化硅和氧化钙的摩尔比为1∶1，得到的上层产物主要是以硅酸盐Ca₂SiO₄、Ca₃SiO₅的形式存在，下层产物主要以Fe₂P存在，脱硅磷铁经检测ω（Si）<0.07%，可以作为过渡金属磷化物的前驱体，为磷铁绿色循环与利用提供了新思路。
- 冶金工程 /
- 磷铁渣 /
- 脱硅 /
- 金属磷化物 /
- 真空
Abstract:
This is an article in the field of metallurgical engineering. For recycling theferrophosphorus slag which a by-products of phosphorus chemical industry,the thermodynamic calculations and experimentally investigations of the removal of SiO₂ by added CaO were carried out. The results of thermodynamic calculations of the reaction between SiO₂ and CaO show that: the Gibbs free energy values of generating CaO·SiO₂, 2CaO·SiO₂, 3CaO·SiO₂ and 3CaO·2SiO₂ are less than zero, when the temperature in 900～1700 K range and molar ratio of(SiO₂∶CaO)= 1∶1～3. It is feasible to generate calcium silicate by adding CaO, which can be used as a method of desilicification for ferrophosphorus slag. The experimental results show that:there are two layers of the products,i.e. Ca₂SiO₄, Ca₃SiO₅in the upper layer and Fe₂P in the lower layer when the pressure between 10～40 Pa and the temperature 1573 K and molar ratio of SiO₂∶CaO = 1∶1. The final products were testified to be ω（Si）<0.07%, which can be served as the precursor of transition metal phosphide and the potential feasibility of ferrophosphorus recycling.
- Metallurgical engineering /
- Ferrophosphorus /
- Desilicification /
- Metal phosphide /
- Vacuum

HTML全文

图 1 反应（1）～（4）的ΔG_T-T关系

Figure 1.

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图 2 1573 K反应60 min上层渣样的XRD

Figure 2.

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图 3 1573 K保温60 min的下层产品XRD

Figure 3.

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表 1 磷铁渣的XRF分析结果/ %

Table 1. XRF result of ferrophosphorus slag

Fe P O Si Mn C Ca V Cr Cu Ni Al Mg

73.8 16.3 4.35 1.53 1.24 0.821 0.860 0.249 0.218 0.180 0.167 0.162 0.0971

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参考文献(13)

[1]	史艳梅, 张兵. 过渡金属磷化物作为高效电解水析氢及加氢催化剂[J]. 科学观察, 2020, 15(6):59-61.SHI Y M, ZHANG B. Transition metal phosphides as efficient catalysts for hydrogen precipitation and hydrogenation in electrolytic water[J]. Scientific Observation, 2020, 15(6):59-61. SHI Y M, ZHANG B. Transition metal phosphides as efficient catalysts for hydrogen precipitation and hydrogenation in electrolytic water[J]. Scientific Observation, 2020, 15(6):59-61.
[2]	张红星. 汽柴油品质量标准与清洁燃料生产技术手段[J]. 中国石油和化工标准与质量, 2007(8):41-43.ZHANG H X. Quality standards for diesel fuel and technical means for cleaner fuel production[J]. China Petroleum and Chemical Standards and Quality, 2007(8):41-43. doi: 10.3969/j.issn.1673-4076.2007.08.011 ZHANG H X. Quality standards for diesel fuel and technical means for cleaner fuel production[J]. China Petroleum and Chemical Standards and Quality, 2007(8):41-43. doi: 10.3969/j.issn.1673-4076.2007.08.011
[3]	Z J Zhao, Z X Zhu, X B Bao, et al. Facile construction of metal phosphides (MP, M = Co, Ni, Fe, and Cu) wrapped in three-dimensional N, P-codoped carbon skeleton toward highly efficient hydrogen evolution catalysis and lithium-ion storage[J]. ACS Applied Materials & Interfaces, 2021, 13(8):30-41.
[4]	侯朝霞, 李思瑶, 王凯, 等. 磷化物及磷基复合材料在二次电池中的研究进展[J]. 功能材料, 2021, 52(2): 2025-2033.HOU C X, LI S Y, WANG K , et al. Research progress of phosphides and phosphorus-based composites in secondary batteries[J]. Functional Materials, 2021, 52(2): 2025-2033. HOU C X, LI S Y, WANG K , et al. Research progress of phosphides and phosphorus-based composites in secondary batteries[J]. Functional Materials, 2021, 52(2): 2025-2033.
[5]	白倩. 磷铁真空热分解及磷铁加镍制备金属磷化物[D]. 昆明: 云南师范大学, 2016: 6-8.BAI Q. Vacuum thermal decomposition of ferrophosphorus and preparation of metal phosphides by adding nickel to ferrophosphorus[D]. Kunming: Yunnan Normal University, 2016. BAI Q. Vacuum thermal decomposition of ferrophosphorus and preparation of metal phosphides by adding nickel to ferrophosphorus[D]. Kunming: Yunnan Normal University, 2016.
[6]	肖洁琼, 吴小宁, 王倩, 等. 过渡金属磷化物的制备及其催化性能研究进展[J]. 化学通报, 2021, 84(3):215-224.XIAO J Q, WU X N, WANG Q, et al. Progress in the preparation of transition metal phosphides and their catalytic properties[J]. Chemistry Bulletin, 2021, 84(3):215-224. XIAO J Q, WU X N, WANG Q, et al. Progress in the preparation of transition metal phosphides and their catalytic properties[J]. Chemistry Bulletin, 2021, 84(3):215-224.
[7]	朱对虎, 李平. 过渡金属磷化物催化剂综述[J]. 工业催化, 2019, 27(7):7-10.ZHU D H, LI P. A review of transition metal phosphide catalysts[J]. Industrial Catalysis, 2019, 27(7):7-10. doi: 10.3969/j.issn.1008-1143.2019.07.002 ZHU D H, LI P. A review of transition metal phosphide catalysts[J]. Industrial Catalysis, 2019, 27(7):7-10. doi: 10.3969/j.issn.1008-1143.2019.07.002
[8]	朱晓辉, 邱臻哲, 白倩, 等. 磷化工副产磷铁的利用研究进展[J]. 无机盐工业, 2015, 47(2):6-8.ZHU X H, QIU Z Z, BAI Q, et al. Research progress on the utilization of phosphorus chemical by-product ferrophosphorus[J]. Inorganic Salt Industry, 2015, 47(2):6-8. ZHU X H, QIU Z Z, BAI Q, et al. Research progress on the utilization of phosphorus chemical by-product ferrophosphorus[J]. Inorganic Salt Industry, 2015, 47(2):6-8.
[9]	付克明, 朱虹, 张勤善, 等. 湿法加碱-燃烧粉煤灰合成P沸石的研究[J]. 武汉理工大学学报, 2010, 32(6):32-34.FU K M, ZHU H, ZHANG Q S, et al. Synthesis of P zeolite by wet addition of alkali and combustion of fly ash[J]. Journal of Wuhan University of Technology, 2010, 32(6):32-34. doi: 10.3963/j.issn.1671-4431.2010.06.008 FU K M, ZHU H, ZHANG Q S, et al. Synthesis of P zeolite by wet addition of alkali and combustion of fly ash[J]. Journal of Wuhan University of Technology, 2010, 32(6):32-34. doi: 10.3963/j.issn.1671-4431.2010.06.008
[10]	童军武, 孙培梅. 粉煤灰和氧化钙烧结过程的热力学分析[J]. 新技术新工艺, 2010(2):78-81TONG J W, SUN P M. Thermodynamic analysis of sintering process of fly ash and calcium oxide[J]. New Technology and New Process, 2010(2):78-81 doi: 10.3969/j.issn.1003-5311.2010.02.028 TONG J W, SUN P M. Thermodynamic analysis of sintering process of fly ash and calcium oxide[J]. New Technology and New Process, 2010(2):78-81 doi: 10.3969/j.issn.1003-5311.2010.02.028
[11]	袁海滨, 李秋霞, 朱富龙, 等. 二氧化硅在真空碳热-氯化法炼铝过程中的行为[J]. 中南大学学报:自然科学版, 2012(3):803-808.YUAN H B, LI Q X, ZHU F L, et al. Behavior of silicon dioxide in vacuum carbothermal-chlorination alumina refining[J]. Journal of Central South University:Natural Science Edition, 2012(3):803-808. YUAN H B, LI Q X, ZHU F L, et al. Behavior of silicon dioxide in vacuum carbothermal-chlorination alumina refining[J]. Journal of Central South University:Natural Science Edition, 2012(3):803-808.
[12]	刘予成, 李秋霞, 邱臻哲, 等. SiO₂对氟磷酸钙真空碳热还原反应的影响[J]. 真空科学与技术学报, 2013, 3:293-296.LIU Y C, LI Q X, QIU Z Z, et al. Effect of SiO₂ on the vacuum carbothermal reduction reaction of calcium fluorophosphate[J]. Journal of Vacuum Science and Technology, 2013, 3:293-296. doi: 10.3969/j.issn.1672-7126.2013.03.20 LIU Y C, LI Q X, QIU Z Z, et al. Effect of SiO₂ on the vacuum carbothermal reduction reaction of calcium fluorophosphate[J]. Journal of Vacuum Science and Technology, 2013, 3:293-296. doi: 10.3969/j.issn.1672-7126.2013.03.20
[13]	傅献彩, 沈文霞, 姚天扬, 等. 物理化学[M]. 北京: 高等教育出版社, 2005.FU X C, SHEN W X, YAO T Y, et al. Physical Chemistry [M]. Beijing: Higher Education Press, 2005. FU X C, SHEN W X, YAO T Y, et al. Physical Chemistry [M]. Beijing: Higher Education Press, 2005.