熔融医药废盐对锆质耐火材料的侵蚀研究

doi:10.16552/j.cnki.issn1001-1625.2025.0284

摘要/Abstract

摘要： 随着医药行业的快速发展,我国医药废盐的年产量与累积量均逐渐增加。电熔融法可高效实现复杂医药废盐的分离提纯,但对耐火材料侵蚀严重,从而影响窑炉使用寿命。本研究根据医药废盐组成,采用SEM、EDS、XRD和热力学计算,研究了熔盐对AZS41#和Z9510两种耐火材料的侵蚀行为与侵蚀机制。结果表明,950 ℃侵蚀48 h后,AZS41#和Z9510两种耐火材料均无变质层,熔盐中的Ca元素主要沿着耐火材料中的玻璃相发生渗透。1 150 ℃侵蚀48 h后,AZS41#样品有约235 μm的变质层,该变质层中无斜锆石相和刚玉相,主要富集元素为Na、Ca、Si,熔盐侵蚀耐火材料后,生成了Na(AlSi₃O₈)物相。Z9510样品有约54 μm的变质层,该变质层有Na元素富集,熔盐侵蚀后生成了CaZrO₃和Na(AlSi₃O₈)两种主要物相。因此,在长期高温的熔盐环境中,Z9510耐火材料的抗侵蚀性更优异。

关键词: 熔融医药废盐, 锆质耐火材料, 侵蚀, 微观结构, 热力学计算, 高温腐蚀

Abstract: With the rapid development of the pharmaceutical industry, the annual production and accumulation of pharmaceutical waste salts in China have steadily increased. While the electrofusion method efficiently separates and purifies complex pharmaceutical waste salts, it causes severe corrosion to refractory materials, significantly affecting furnace longevity. In this study, according to the composition of pharmaceutical waste salt, the corrosion behavior and corrosion mechanism of molten salt on AZS41# and Z9510 refractory materials were studied by means of SEM, EDS, XRD and thermodynamic calculation. The results show that after corrosion at 950 ℃ for 48 h, neither of AZS41# and Z9510 refractory materials show an altered layer, with Ca element from the molten salts predominantly penetrating into the glass phase. After corrosion at 1 150 ℃ for 48 h, AZS41# sample forms an altered layer about 235 μm. There is no zircon phase and corundum phase in the altered layer, and the main enrichment elements are Na, Ca and Si. The Na(AlSi₃O₈) phase is formed after molten salt erosion refractory material. The Z9510 sample has a altered layer of about 54 μm, which is enriched with Na element, and two main phases of CaZrO₃ and Na(AlSi₃O₈) are formed after molten salt erosion. Therefore, in the long-term high-temperature molten salt environment, the corrosion resistance of Z9510 refractory material is more excellent.

Key words: molten pharmaceutical waste salt, zirconia refractory material, corrosion, microstructure, thermodynamic calculation, high-temperature corrosion

中图分类号:

TQ175

程薇薇, 田英良, 杨勤浩, 赵志永, 谢峻林, 何峰. 熔融医药废盐对锆质耐火材料的侵蚀研究[J]. 硅酸盐通报, 2025, 44(9): 3426-3434.

CHENG Weiwei, TIAN Yingliang, YANG Qinhao, ZHAO Zhiyong, XIE Junlin, HE Feng. Corrosion of Zirconia Refractory Materials by Molten Pharmaceutical Waste Salts[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2025, 44(9): 3426-3434.

参考文献

[1] 申桂英, 罗亚敏, 彭孝军. 中国精细化工产品分类和精细化工率[J]. 精细与专用化学品, 2024, 32(8): 1-3.
SHEN G Y, LUO Y M, PENG X J. Classification and rate of fine chemical products in China[J]. Fine and Specialty Chemicals, 2024, 32(8): 1-3 (in Chinese).
[2] 中华人民共和国生态环境部. 危险废物环境管理指南化工废盐[EB/OL]. (2021-12-24)[2025-03-11]. https://www.mee.gov.cn/xxgk2018/xxgk/xxgk01/202112/W020211227380770876616.pdf.
Ministry of Ecology and Environment of the People's Republic of China. Guidelines for environmental management of hazardous waste: chemical waste salts[EB/OL]. (2021-12-24)[2025-03-11]. https://www.mee.gov.cn/xxgk2018/xxgk/xxgk01/202112/W020211227380770876616.pdf (in Chinese).
[3] 李明辉, 许高洁, 宁朋歌. 工业废盐处理及资源化利用进展[J]. 当代化工研究, 2025(1): 10-13.
LI M H, XU G J, NING P G. Progress in industrial waste salt treatment and resource utilization[J]. Modern Chemical Research, 2025(1): 10-13 (in Chinese).
[4] 罗超, 吴凯凯, 邓雅清. 工业废盐资源化处理技术及工程应用[J]. 盐科学与化工, 2024, 53(12): 6-10.
LUO C, WU K K, DENG Y Q. Industrial waste salt resource treatment technology and engineering application[J]. Journal of Salt Science and Chemical Industry, 2024, 53(12): 6-10 (in Chinese).
[5] 李强, 戴世金, 郑怡琳, 等. 工业废盐中有机物脱除和资源化技术进展[J]. 环境工程, 2019, 37(12): 200-206.
LI Q, DAI S J, ZHENG Y L, et al. Discussion on treatment technology and resource recovery of hazardous waste salt containing organics[J]. Environmental Engineering, 2019, 37(12): 200-206 (in Chinese).
[6] 司景. 工业废盐处置及资源化利用现状[J]. 安徽化工, 2021, 47(6): 27-30+36.
SI J. Current situation of industrial salt disposal and resource utilization[J]. Anhui Chemical Industry, 2021, 47(6): 27-30+36 (in Chinese).
[7] 宁文琳, 龚德慧. 呋喃酚醚化废盐渣中有机物回收利用的实验研究[J]. 精细化工中间体, 2010, 40(1): 63-65.
NING W L, GONG D H. Recovery of the organic materials from the wastes formed in the production of benzofuranol[J]. Fine Chemical Intermediates, 2010, 40(1): 63-65 (in Chinese).
[8] WANG J, HONG X T, FANG G M, et al. Deep purification of pesticide waste salt containing high-concentration organic pollutants by ethanol solvents washing and heating treatment[J]. Journal of Environmental Chemical Engineering, 2024, 12(3): 112480.
[9] 薛帅. 膜分离技术DD、ED和BMED处理工业醋酸钠废渣[D]. 合肥: 合肥工业大学, 2016.
XUE S. Membrane separation technologies DD, ED and BMED for treatment of sodium acetate waste residue[D]. Hefei: Hefei University of Technology, 2016 (in Chinese).
[10] 张婧. 制药废水处理中高级氧化技术运用分析[J]. 中国战略新兴产业, 2024 (32): 110-112.
ZHANG J. Analysis of the application of advanced oxidation processes in pharmaceutical wastewater treatment[J]. China Strategic Emerging Industries, 2024 (32): 110-112 (in Chinese).
[11] CATALDO S, IANNÌ A, LODDO V, et al. Combination of advanced oxidation processes and active carbons adsorption for the treatment of simulated saline wastewater[J]. Separation and Purification Technology, 2016, 171: 101-111.
[12] WANG J, LIU H B, GAO Y, et al. Pilot-scale advanced treatment of actual high-salt textile wastewater by a UV/O₃ pressurization process: evaluation of removal kinetics and reverse osmosis desalination process[J]. Science of the Total Environment, 2023, 857: 159725.
[13] LIN C Q, CHI Y, JIN Y Q, et al. Molten salt oxidation of organic hazardous waste with high salt content[J]. Waste Management & Research, 2018, 36(2): 140-148.
[14] 胡卫平, 贺周初, 朱文新, 等. 农药副产废盐渣的无害化处理及利用[J]. 精细化工中间体, 2013, 43(3): 48-50.
HU W P, HE Z C, ZHU W X, et al. Innocuous treatment and recycling of waste salts formed in pesticides production[J]. Fine Chemical Intermediates, 2013, 43(3): 48-50 (in Chinese).
[15] 李鸿源, 张建华. 热解法脱除工业废盐中总有机碳的工艺研究[J]. 无机盐工业, 2024, 56(10): 95-102.
LI H Y, ZHANG J H. Study on removal process of total organic carbon from industrial waste salts by pyrolysis[J]. Inorganic Chemicals Industry, 2024, 56(10): 95-102 (in Chinese).
[16] XIE K, HU H Y, CAO J X, et al. A novel method for salts removal from municipal solid waste incineration fly ash through the molten salt thermal treatment[J]. Chemosphere, 2020, 241: 125107.
[17] XI S B, WEI X L, DING J, et al. The removal of organic contaminants from industrial waste salts by pyrolysis and potential use for energy storage[J]. Journal of Cleaner Production, 2023, 425: 138931.
[18] VILLALBA WEINBERG A, VARONA C, CHAUCHERIE X, et al. Corrosion of Al₂O₃-SiO₂ refractories by sodium and sulfur vapors: a case study on hazardous waste incinerators[J]. Ceramics International, 2017, 43(7): 5743-5750.
[19] 赵燕, 罗华明, 朱宝利, 等. 危废组分中不同钠盐对耐火材料的侵蚀行为[C]//第十八届全国耐火材料青年学术报告会论文集. 长沙, 2022: 321-327.
ZHAO Y, LUO H M, ZHU B L, et al. Corrosion behavior of various sodium salts in hazardous waste components on refractory materials[C]//The 18th National Youth Academic Symposium on Refractory Materials. Changsha, 2022: 321-327 (in Chinese).
[20] ZHAO Y, CAI Y C, LUAN X, et al. Corrosion, permeation and mass transfer mechanisms of alkali metals in corundum refractories[J]. Ceramics International, 2024, 50(18): 33455-33463.
[21] SHI X G, LI B S, LIU H Y, et al. The corrosion resistance mechanisms of the cr-coated SiC in molten Na₂SO₄ salt: strengthened boundaries and protective scales[J]. Corrosion Science, 2021, 185: 109421.
[22] HAN G H, WANG Z X, LIU B B, et al. In-situ improved corrosion resistance of corundum-mullite refractory for the incineration of hazardous spent high-salt organic liquor by Cr₂O₃: Interfacial anti-erosion mechanism[J]. Ceramics International, 2022, 48(9): 12395-12407.
[23] TAKAHASHI J, KAWAI Y, SHIMADA S. Hot corrosion of cordierite/mullite composites by Na-salts[J]. Journal of the European Ceramic Society, 2002, 22(12): 1959-1969.
[24] CHENG G S, ZHAO Y, LONG F, et al. Analysis and prediction of corrosion of refractory materials by sodium salts during waste liquid incineration-thermodynamic study[J]. Materials, 2020, 13(21): 4729.
[25] GEORGE S M, HAYCOCK P W, ORMEROD R M. The mechanism of corrosion of aluminium zirconium silicate (AZS) material in the float glass furnace regenerator[J]. Journal of the European Ceramic Society, 2018, 38(4): 2202-2209.
[26] 李欢. 熔铸锆刚玉耐火材料结构与抗侵蚀性能的研究[D]. 北京: 中国建筑材料科学研究总院, 2023.
LI H. Study on the structure and corrosion resistance of fused cast zirconium-corundum refractories[D]. Beijing: China Building Materials Research Institute, 2023 (in Chinese).
[27] 魏瀚, 毛利民, 王俊涛, 等. 熔铸锆铬刚玉耐火材料抗硼硅酸盐熔体的侵蚀行为[J]. 硅酸盐学报, 2023, 51(12): 3196-3203.
WEI H, MAO L M, WANG J T, et al. Corrosion resistance of fused-cast AZCS refractory by borosilicate melt[J]. Journal of the Chinese Ceramic Society, 2023, 51(12): 3196-3203 (in Chinese).