廢汽車催化劑鐵捕集熔煉渣一步法制備微晶玻璃研究

鄭環東; 丁云集; 何學峰; 史志勝; 菅金鑫; 張深根

doi:10.13374/j.issn2095-9389.2022.02.17.001

廢汽車催化劑鐵捕集熔煉渣一步法制備微晶玻璃研究

doi: 10.13374/j.issn2095-9389.2022.02.17.001

1.
北京科技大學新材料技術研究院金屬材料循環利用研究中心，北京 100083
2.
北京科技大學順德創新學院，佛山 528399

基金項目: 國家自然科學基金重點資助項目（U2002212，52204412）；國家重點研發專項資助項目（2021YFC1910504，2019YFC1907101）；廣東省基礎與應用基礎研究基金資助項目（2020A1515110408）；佛山市人民政府科技創新專項資金資助項目（BK21BE002）；中央高校基本科研業務費資助項目（FRF-TP-20-031A1）

詳細信息

通訊作者:
E-mail: dingyunji@ustb.edu.cn

中圖分類號: TG142.71
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出版歷程
- 收稿日期: 2022-02-17
- 網絡出版日期: 2022-04-02
- 刊出日期: 2022-12-01

One-step glass-ceramics production process using iron smelting slags of spent automotive catalysts

1.
Research Center for Metal Materials Recycling, Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China
2.
Shunde Graduate School, University of Science and Technology Beijing, Foshan 528399, China

More Information

Corresponding author: E-mail: dingyunji@ustb.edu.cn

摘要

摘要: 低溫鐵捕集技術是回收廢汽車催化劑中鉑族金屬最有前途的技術之一。鐵捕集熔煉渣以硅鋁酸鹽為主，同時含有少量有毒重金屬（如Cr、Ba、Ni、Mn等），其處置與資源化利用是當前行業的難題。本文致力于鐵捕集熔煉渣的重金屬固化和資源化利用，充分利用硅鋁酸鹽為網絡形成體，以重金屬和酸洗污泥中CaF₂為形核劑，通過一步法制備微晶玻璃。差示掃描量熱分析結果表明，隨著酸洗污泥用量（質量分數）從7%增至28%，樣品的玻璃化轉變溫度與析晶溫度間隙由211 ℃降低到150 ℃，基礎玻璃的析晶活化能從321.8 kJ·mol^?1降低到303.5 kJ·mol^?1，Avrami指數由1.7增至3.7。表明酸洗污泥可以降低成核與析晶的溫差，有利于實現一步法工藝。酸洗污泥添加量（質量分數）為21%時，在900 ℃下熱處理1.2 h制備的微晶玻璃具有較佳性能，即密度3.04 g·cm^?3，吸水率（質量分數）0.11%，維氏硬度和抗彎強度分別為742.72 HV和119.32 MPa。浸出毒性試驗表明重金屬Cr、Ba、Ni等均滿足美國環保局提出的毒性浸出實驗（TCLP）標準。玻璃結構分析表明酸洗污泥有利于增加基礎玻璃中的非橋氧含量，降低玻璃網絡聚合度，增強結晶趨勢。
- 廢催化劑 /
- 酸洗污泥 /
- 微晶玻璃 /
- 一步法 /
- 結晶
Abstract: The most important secondary resources of platinum group metals (PGMs) are spent automotive exhaust catalysts, which are called “mobile PGM mines.” Low-temperature iron-capture technology is a promising technology for recovering PGMs due to its high efficiency and low pollution. Because of the content of aluminosilicates and toxic heavy metals (Cr, Ba, Ni, and Mn), the disposal of iron-capture smelting slag is necessary. This paper is devoted to the solidification of heavy metals and the resource utilization of iron-capture smelting slag. Glass-ceramics were made by a one-step method using aluminosilicates as network formers. Heavy metals and CaF₂ are employed as nucleating agents in pickling sludge. According to the analysis of differential scanning calorimetry, the glass transition temperature and crystallization temperature of samples are in the range of 650 ℃–700 ℃ and 800 ℃–920 ℃, respectively. The gap between the glass transition temperature and crystallization temperature of samples decreased from 211 ℃ to 150 ℃ when increasing the amount of pickling sludge from 7% to 28% (mass fraction). The devitrification activation energy decreased from 321.8 to 303.5 kJ·mol^?1, while the Avrami index increased from 1.7 to 3.7. It demonstrates that pickling sludge can reduce the temperature difference between nucleation and crystallization, which is beneficial in realizing the one-step process. The effects of pickling sludge and heat treatment systems on glass-ceramics were investigated. The diopside phase is the main crystalline phase of glass-ceramics. Nepheline and Magnetite phases were detected when the amount of pickling sludge (mass fraction) reached 28%. The physical properties of the glass-ceramics were improved with the increase in heat treatment temperature and time. When the addition amount of pickling sludge (mass fraction) was 21%, the glass-ceramics prepared by heat treatment at 900 ℃ for 1.2 h had the best properties; namely, the density was 3.04 g·cm^?3, the water absorption (mass fraction) was 0.11%, and the Vickers hardness and flexural strength were 742.72 HV and 119.32 MPa, respectively. The Toxicity Characteristic Leaching Procedure (TCLP) leaching standard was met by heavy metals such as Cr, Ba, and Ni in the toxicity test. Glass structure analysis revealed that the pickling sludge increased the nonbridging oxygen content in the base glass while reducing the degree of glass network polymerization, resulting in an enhanced crystallization tendency. The pickling sludge proved to have potential as an inexpensive nucleating agent in the preparation of glass-ceramics with excellent performance. The glass-ceramics with these unique properties are promising to be applied as building materials.
- spent catalysts /
- pickling sludge /
- glass-ceramics /
- one-step process /
- crystallization

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圖 1 冶煉渣和酸洗污泥XRD圖譜

Figure 1. XRD patterns of smelting slag and pickling sludge

下載: 全尺寸圖片幻燈片

圖 2 不同酸洗污泥用量基礎玻璃的DSC圖譜

Figure 2. DSC of parent glass with different pickling sludge mass fraction

下載: 全尺寸圖片幻燈片

圖 3 基礎玻璃ln(T_p²/α)與1000T_p^?1關系圖

Figure 3. Variation of ln(T_p²/α) and 1000T_p^?1

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圖 4 不同酸洗污泥用量制備的微晶玻璃XRD圖譜

Figure 4. XRD of glass-ceramics with different mass fraction of pickling sludge

下載: 全尺寸圖片幻燈片

圖 5 不同用量酸洗污泥制備的微晶玻璃SEM圖. (a) 7%; (b) 14%; (c) 21%; (d) 28%

Figure 5. SEM of glass-ceramics with different mass fraction of pickling sludge: (a) 7%; (b) 14%; (c) 21%; (d) 28%

下載: 全尺寸圖片幻燈片

圖 6 不同酸洗污泥用量對微晶玻璃性能的影響. (a) 密度和吸水率; (b) 維氏硬度和抗彎強度

Figure 6. Physical and chemical properties of the samples: (a) density and water adsorption; (b) Vickers hardness and bending strength

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圖 7 不同酸洗污泥用量下微晶玻璃斷口形貌圖. (a) 7%; (b) 14%; (c) 21%; (d) 28%

Figure 7. Fracture morphology of samples with different mass fraction of pickling sludge: (a) 7%; (b) 14%; (c) 21%; (d) 28%

下載: 全尺寸圖片幻燈片

圖 8 不同熱處理制度下GC-3的微觀形貌圖. (a) 800 ℃，0.5 h; (b) 850 ℃，0.5 h; (c) 900 ℃，0.5 h; (d) 900 ℃， 0.4 h; (e) 900 ℃，0.8 h; (f) 900 ℃，1.2 h

Figure 8. Micromorphology of samples under varying heat treatment systems: (a) 800 ℃，0.5 h; (b) 850 ℃，0.5 h; (c) 900 ℃，0.5 h; (d) 900 ℃，0.4 h; (e) 900 ℃，0.8 h; (f) 900 ℃，1.2 h

下載: 全尺寸圖片幻燈片

圖 9 不同酸洗污泥用量下基礎玻璃的紅外分析

Figure 9. DSC of parent glass with different content of pickling sludge

下載: 全尺寸圖片幻燈片

圖 10 不同酸洗污泥用量基礎玻璃的拉曼分峰擬合. (a) 7%; (b)14% ; (c)21% : (d)28%

Figure 10. DSC of parent glass with different content pickling sludge: (a) 7%; (b)14% ; (c)21% : (d)28%

下載: 全尺寸圖片幻燈片

表 1 原料的化學成分（質量分數）

Table 1. Main chemical composition of different materials %

Materials	CaO	SiO₂	Al₂O₃	Na₂O	ZrO₂	CeO₂	Fe₂O₃	CaF₂	Cr₂O₃	Others
Smelting slag	22.09	38.69	8.20	6.46	6.89	4.53	4.28	2.32	0	6.54
Pickling sludge	30.67	7.89	2.57	1.48	0	0	20.85	22.86	5.32	8.36

下載: 導出CSV

表 2 不同酸洗污泥制備基礎玻璃析晶活化能(E)和Avrami指數(n)

Table 2. Crystallization activation energy (E) and Avrami index (n) of base glasses prepared from pickling sludges with different content

Pickling sludge (mass fraction)/%	Slope	Intercept	R-squared	ΔT	E/ (kJ·mol^?1)	v /min^?1	n
7	38.7	?23.5	0.99	211	321.8	6.2 × 10¹¹	1.7
14	38.6	?24.5	0.98	204	320.9	1.7 × 10¹²	2.4
21	37.9	?23.9	0.99	157	315.1	9.1 × 10¹¹	3.1
28	36.5	?22.6	0.99	150	303.5	2.4 × 10¹¹	3.7

下載: 導出CSV

表 3 微晶玻璃的耐酸/堿性及重金屬固化效果對比

Table 3. Comparison of acid/alkaline resistance and leaching toxicity of glass-ceramic

Samples	Acid resistance /%	Alkali resistance /%	Leaching concentrations of heavy metals/ (mg·L^?1)
Samples	Acid resistance /%	Alkali resistance /%	Cr	Ba	Ni	Mn
GC-1	99.27	99.95	0.36	0.62	0.01	0.97
GC-2	98.83	99.95	0.42	0.59	0	0.82
GC-3	98.67	99.97	0.61	0.51	0	0.69
GC-4	98.35	99.93	0.67	0.39	0	0.67
TCLP limits			5	100	5

下載: 導出CSV

表 4 樣品GC-3性能檢測結果

Table 4. Performance test results of the samples GC-3

Heat treating regime		Vickers hardness, HV	Bending strength /MPa	Density/ (g·cm^?3)	Water adsorption/ %	Corrosion resistance/ %
Temperature /℃	Time /h	Vickers hardness, HV	Bending strength /MPa	Density/ (g·cm^?3)	Water adsorption/ %	H₂SO₄	NaOH
800	1	697.53	87.73	2.96	0.13	98.44	99.93
850	1	707.85	109.15	3.03	0.12	98.67	99.97
900	1	723.48	116.79	3.04	0.09	99.10	99.96
900	0.4	678.92	80.82	2.89	0.08	98.96	99.98
900	0.8	691.98	94.28	2.93	0.10	99.05	99.86
900	1.2	742.72	119.32	3.04	0.11	99.16	99.79

下載: 導出CSV

表 5 不同酸洗污泥用量基礎玻璃的基礎結構單元面積及非橋氧含量

Table 5. Deconvoluted spectra and unbridged oxygen content in the glasses

Samples	Q⁰ /%	Q¹ /%	Q² /%	Q³ /%	R-squared	NBO/T
GC-1	6.83	18.31	32.86	42.00	0.9991	1.90
GC-2	6.61	18.48	36.36	38.55	0.9995	1.93
GC-3	6.88	18.70	38.23	36.19	0.9994	1.96
GC-4	5.49	16.32	32.31	45.88	0.9997	1.81

下載: 導出CSV

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