廢覆銅板分選殘渣生物脫毒工藝優化及機理

仉麗娟; 李雨欣; 范越; 任凌霄; 王慧雅; 王藝; 丁克強; 周洪波

doi:10.13374/j.issn2095-9389.2021.12.03.005

廢覆銅板分選殘渣生物脫毒工藝優化及機理

doi: 10.13374/j.issn2095-9389.2021.12.03.005

仉麗娟^{1, 2},
李雨欣¹,
范越¹,
任凌霄¹,
王慧雅¹,
王藝¹,
丁克強¹,
周洪波^2, ,

1.
南京工程學院環境工程學院，南京 211167
2.
中南大學資源加工與生物工程學院，長沙 410083

基金項目: 江蘇省科技廳青年基金資助項目（BK20210934）；南京工程學院高層次引進人才科研啟動基金資助項目（YKJ202001）；江蘇省大學生創新訓練計劃重點資助項目（202111276014Z，202211276023Z）；江蘇省雙創博士人才計劃資助項目（JSSCBS20210595）

詳細信息

通訊作者:
E-mail: zhouhb@csu.edu.cn

中圖分類號: TG142.71
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出版歷程
- 收稿日期: 2021-12-03
- 網絡出版日期: 2022-05-05
- 刊出日期: 2023-02-01

Cu extraction from waste copper clad laminate sorting residue in a two-stage bioleaching process: Process optimization and mechanism

1.
School of Environmental Engineering, Nanjing Institute of Technology, Nanjing 211167, China
2.
Key Laboratory of Biometallurgy, School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China

More Information

Corresponding author: E-mail: zhouhb@csu.edu.cn

摘要

摘要: 廢覆銅板分選殘渣量大，殘留銅質量分數約為1%，潛在利用價值高。為了獲得廢覆銅板分選殘渣生物浸出脫毒工藝最優條件及探明其生物浸出相關機理，首先采用Box?Behnken響應曲面法設計三因素（參數因子包括初始pH值、固形物含量和Fe²⁺濃度；響應值為銅浸出率）三水平共計17個實驗的優化實驗方案。響應面多項回歸擬合分析指出：銅浸出率回歸模型與實際試驗擬合性較好，實驗誤差較小，對廢覆銅板分選殘渣中銅生物浸出過程優化具有一定參考性。在最優化條件下(初始pH值為 1.65、廢覆銅板分選殘渣投加量300 g·L^?1和Fe²⁺質量濃度為6.13 g·L^?1)經過4 h生物浸出獲得(92.2±0.27)%的銅浸出率。其次，廢覆銅板殘渣生物浸出脫毒放大改進實驗中（100 L攪拌槽）：增加曝氣和攪拌，同時外加酸調控體系pH值<2.5，延長浸出至6 h，銅最大浸出率>98%，浸出渣中銅殘留質量分數≤0.02%。未反應縮核動力學模型顯示殘渣中銅生物浸出過程受界面傳質和固體膜層內擴散混合控制。綜上所述，廢覆銅板分選殘渣中的銅主要通過Fe³⁺氧化和H⁺攻擊溶出；嗜酸氧化亞鐵微生物持續氧化Fe²⁺→Fe³⁺，不僅降低了總鐵消耗量，也促進了殘渣中銅的釋放。研究結果將為廢舊電子電器綠色資源化再生利用提供理論支撐。
- 廢覆銅板分選殘渣 /
- 生物浸出 /
- 響應面設計 /
- 機理 /
- 資源化
Abstract: Much waste copper clad laminate sorting residue is generated from the flotation process of recovering copper resources from waste printed circuit boards. The improper treatment and disposal of waste copper clad laminate sorting residue harms the environment and human health. According to the National Hazardous Waste List (2021 edition) of China, this waste belongs to HW13 (900-451-13) hazardous waste. The sorting residue contains approximately 1% copper, which is similar to the average copper grade of 0.8% in China. Therefore, this residue is an important copper renewable resource and has a high potential for copper recycling. To optimize the effective factors, including the Fe²⁺ concentration, initial solution pH value, and pulp density, and clarify the mechanism during the bioleaching process of waste copper clad laminate sorting residue, a Box–Behnken design of response surface methodology was first used, and a scheme consisting of 17 experiments was designed in the present study. Through the multiple regression fitting analysis of experimental results, a quadratic polynomial regression model was established. The regression model showed high reliability and simulation accuracy and was then used to optimize the bioleaching process. Under the optimal conditions (6.13 g·L^?1 Fe²⁺, initial leaching solution pH value of 1.65, and pulp density of 30%), 92.2% maximum Cu extraction was obtained. Then, a modified scale-up bioleaching experiment in a 100-L stirred tank was performed. The results indicated that the maximum copper recovery reached 98%, and less than 0.02% of copper was detected in the bioleaching residue after 6 h of bioleaching because of the improved bioleaching operating conditions in the 100-L stirred tank, including slowly adding the sorting residue, additional stirring (200 r·min^?1), aerating (20 L·h^?1), and controlling the bulk pH value (solution pH value <2.5 adjusted with 50% (v/v) H₂SO₄). Leaching kinetic data described by a modi?ed shrinking core model indicated that interfacial transfer and diffusion across the solid ?lm layer controlled the copper dissolution kinetics. In conclusion, copper in the sorting residue was dissolved primarily by Fe³⁺ oxidation and secondarily by H⁺ attack throughout the bioleaching process. Notably, the continuous regeneration of Fe³⁺ by an iron-oxidation microbial consortium led to more Fe³⁺ distributed across the solid film layer of residual iron/calcium compounds and accumulated on the reacted core, which not only reduced total iron consumption (particularly Fe³⁺) but also substantially improved copper extraction from waste copper clad laminate sorting residue. These findings should have important implications for the green recycling and reuse of waste printed circuit boards and other waste electronic appliances.
- waste copper clad laminate sorting residue /
- bioleaching /
- Box–Behnken design /
- mechanism /
- resource recycling

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圖 1 廢覆銅板分選殘渣XRD分析

Figure 1. XRD analysis of dry waste copper clad laminate sorting residue

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圖 2 100 L攪拌槽反應裝置示意圖

Figure 2. Schematic diagram of the 100 L stirred tank

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圖 3 實際銅浸出率與Box?Behnken響應面數學模型預測值對照圖

Figure 3. Comparison between an actual copper extraction and the predicted value of the Box?Behnken response surface model

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圖 4 不同因素之間交互作用對銅浸出率的影響.（a）初始pH與固形物含量；（b）初始pH與Fe²⁺質量濃度；（c）固形物含量與Fe²⁺質量濃度

Figure 4. Effects of interactions between different factors on copper recovery: (a) initial pH and Fe²⁺ concentration; (b) initial pH and pulp density; (c) Fe²⁺ concentration and pulp density

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圖 5 100 L攪拌體系中不同理化參數隨時間的變化情況. （a）銅浸出率；（b）pH和氧化還原電位；（c）Fe³⁺和Fe²⁺質量濃度；（d）菌濃

Figure 5. Variations in different physical and chemical parameters with time in the 100 L stirred tank: (a) copper extraction; (b) pH value and redox potential; (c) concentration of Fe³⁺ and Fe²⁺; (d) cell density

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圖 6 100 L攪拌體系中，銅浸出隨時間變化不同浸出動力學模型擬合結果. (a) 固體膜層內擴散控制；(b) 化學反應控制；(c) 界面傳質和固體膜層擴散混合控制

Figure 6. Bioleaching kinetics of Cu recovery during bioleaching in the stirred tank: (a) diffusion model；(b) reaction model; (c) mixed-control model

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圖 7 廢覆銅板分選殘渣中銅生物浸出機理

Figure 7. Mechanisms of Cu extraction from waste copper clad laminate sorting residue by bioleaching with a ferrous-energy enriched microbial consortium

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表 1 廢覆銅板分選殘渣主要成分分析

Table 1. Main components of dry waste copper clad laminate sorting residue

Sn	Fe	Ca	Na	Al	Zn	Mg	Mn	Cr	Au	Cu	Ni	Co	Ag
0.050	0.410	6.510	0.140	3.530	0.025	0.230	0.010	0.007	<0.010	0.750	0.004	0.002	0.002

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表 2 Box?Behnken Design響應面實驗因素及水平值設置

Table 2. Factor codes and levels of Box?Behnken design

Value	pH	Pulp density/(g·L^?1)	Fe²⁺ concentration/(g·L^?1)
Low value	1.5	250	3
High value	2.1	350	7

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表 3 Box?Behnken實驗設計及銅浸出率

Table 3. Experimental design and copper recovery of Box?Behnken design

Run	pH	Pulp density/ ( g·L^?1)	Fe²⁺ concentration/ (g·L^?1)	Cu recovery/%
1	1.8	300	5	91.57
2	1.5	300	3	89.32
3	2.1	300	7	88.19
4	2.1	300	3	82.00
5	1.5	300	7	91.29
6	1.8	350	7	89.34
7	1.8	300	5	90.44
8	1.8	300	5	90.44
9	1.5	350	5	91.03
10	1.5	250	5	88.95
11	2.1	350	5	86.20
12	1.8	300	5	91.01
13	1.8	250	7	91.65
14	2.1	250	5	86.93
15	1.8	300	5	89.32
16	1.8	350	3	84.76
17	1.8	250	3	88.28
Note: In the software calculation of Design-Expert 8.0, the value of pulp density used the percentage of waste copper clad laminate sorting residue dosage/leaching solution volume.

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表 4 回歸模型方差分析

Table 4. Analysis of variance for the regression model

Source	Sum of squares	Degrees of freedom	Mean square	P value	Significance
Model	100.64	9	11.18	0.0081	**
A?pH	37.28	1	37.28	0.0017	**
B?pulp density	2.51	1	2.51	0.2436
C?Fe²⁺ concentration	32.44	1	32.44	0.0025	**
AB	1.97	1	1.97	0.2959
AC	4.45	1	4.45	0.1337
BC	0.37	1	0.37	0.6416
A²	10.02	1	10.02	0.0384	*
B²	2.28	1	2.28	0.2644
C²	7.26	1	7.26	0.067
Residual	10.83	7	1.55
Lack of Fit	8.04	3	2.68	0.1131
Pure Error	2.79	4	0.7
Cor Total	111.47	16
Notes:* represents that difference is significant at the 0.05 level (P<0.05); ** represents that difference is significant at the 0.01 level (P<0.01).

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表 5 浸出渣浸出毒性鑒定

Table 5. Identi?cation of the leaching toxicity of the leached residue

Metal	Test value by HJ/T 300/(mg·L^?1)	Limited value in GB16889—2008/ (mg·L^?1)	Test value by HJ/T 299/ (mg·L^?1)	Limited value in GB 5085.3—2007/ (mg·L^?1)
Cu	14.76	40	0.174	100
Zn	5.51	100	0.00167	100
Ni	0.157	0.5	0.103	15
Cr	0.0616	4.5	0.304	12
Ag	—	—	0.00691	5
Pb	0.001	0.25	0.300	5
Sn	0.001	0.3	0.001	2.5
Hg	0.001	0.05	0.00099	0.25
Cd	0.00162	0.15	0.03	0.5
Ba	0.43	25	1.7	150

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