廢均相催化劑氧化?絡合浸出銠工藝及其動力學

丁云集; 李佳怡; 鄭環東; 崔言杰; 劉波; 張深根

doi:10.13374/j.issn2095-9389.2021.10.20.005

廢均相催化劑氧化?絡合浸出銠工藝及其動力學

doi: 10.13374/j.issn2095-9389.2021.10.20.005

丁云集^{1, 2},
李佳怡^{1, 3},
鄭環東¹,
崔言杰¹,
劉波¹,
張深根^1, ,

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
3.
有研資源環境技術研究院（北京）有限公司生物冶金國家工程實驗室，北京 101407

基金項目: 國家重點研發專項資助項目（2021YFC1910504，2019YFC1907101）；國家自然科學基金資助項目（U2002212，52204412）；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: zhangshengen@mater.ustb.edu.cn

中圖分類號: TF837
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出版歷程
- 收稿日期: 2021-10-21
- 網絡出版日期: 2022-10-18
- 刊出日期: 2023-02-01

Oxidation–complexation leaching and kinetic study of rhodium from spent homogeneous 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 Innovation Institute, University of Science and Technology Beijing, Foshan 528399, China
3.
National Engineering Laboratory of Biohydrometallurgy, GRINM Resources and Environment Tech. Co., Ltd., Beijing 101407, China

More Information

Corresponding author: E-mail: zhangshengen@mater.ustb.edu.cn

摘要

摘要: 基于Rh在廢均相催化劑中的賦存狀態，研發出綠色解離Rh–P化學鍵及Rh的絡合浸出新技術，實現了Rh的綠色高效浸出，杜絕了傳統廢均相催化劑焚燒–碎化–酸浸工藝流程長、污染嚴重、回收率低等問題。首先通過蒸餾將低熔點有機物去除，然后采用H₂O₂將均相銠膦絡合物中的Rh⁺氧化成Rh³⁺，減少有機配體對Rh的束縛；同時Rh³⁺與Cl^–絡合形成水溶性的RhCl₆^3–進入溶液中。研究了蒸餾溫度、Cl^–濃度、H₂O₂用量、H⁺濃度、反應時間等對Rh的回收率影響，并采用響應曲面法優化了Cl^–濃度、H₂O₂用量和反應時間等工藝參數。結果表明：各參數對Rh回收率的影響大小為：H₂O₂用量>Cl^–濃度>反應時間，優化的工藝參數為：蒸餾溫度260 ℃、Cl^–濃度3.0 mol?L^–1、H₂O₂用量為廢均相催化劑的37%（體積分數）、H⁺濃度1.0 mol?L^–1、反應時間4.5 h，Rh的回收率達到98.22%。最后，采用分光光度法研究了Rh的氧化–絡合動力學行為，表明該反應的活化能為39.24 kJ?mol^–1，屬于化學反應控速。
- 銠 /
- 廢均相催化劑 /
- 蒸餾 /
- 響應曲面法 /
- 動力學
Abstract: Rhodium-containing homogeneous catalysts are the most active catalysts for homogeneous hydrogenation. Spent homogeneous catalysts contain 100–2000 g?t^–1 of rhodium (Rh) and plenty of hazardous organic components, making them an essential resource of Rh. The recovery of Rh from homogeneous catalysts has excellent economic and environmental benefits. Based on Rh in the spent homogeneous catalysts, a new technology for green dissociation of the Rh–P chemical bond and complexation leaching of Rh was developed, allowing the green and efficient recovery of Rh. Compared with traditional incineration-fragmentation and acid leaching methods, the proposed technology eliminated issues such as long process times, severe environmental pollution, and a low recovery rate of Rh. In this study, first, the low-melting-point organics were removed using distillation. Then, the Rh⁺ in the homogeneous rhodium–phosphine complex was oxidized as Rh³⁺ through H₂O₂, which reduced the binding of organic ligands to Rh. Meanwhile, the RhCl₆^3? formed by Rh³⁺ and Cl^– dissolved into the aqueous solution. The effects of distillation temperature, the concentration of Cl^–, the dosage of H₂O₂, the concentration of H⁺, and reaction time on the recovery efficiency of Rh were studied. The parameters listed above were optimized using response surface methodology. The results showed that the influence of each parameter on the recovery efficiency of Rh was as follows: H₂O₂ dosage > Cl^– concentration > reaction time. The recovery efficiency of Rh reached 98.22% after 4 h of distillation at 260 °C, leaching Rh in the mixture solution of 3.0 mol?L^–1 Cl^–, 37% (volume fraction) of the spent homogeneous catalyst dosage of H₂O₂, 1.0 mol?L^–1 H⁺, and at 90 °C for 4.5 h. Finally, the oxidation–complexation kinetic behavior of Rh was studied using spectrophotometry. The activation energy of the leaching reaction was 39.24 kJ?mol^–1, indicating that the rate-controlling step of this process was a surface chemical reaction.
- rhodium /
- spent homogeneous catalysts /
- distillation /
- response surface method /
- kinetics

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圖 1 廢銠均相催化劑的回收工藝流程圖

Figure 1. Schematic of the recovery process of spent Rh homogeneous catalysts

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圖 2 蒸餾過程示意圖

Figure 2. Diagram of the distillation process

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圖 3 紅外分析光譜.（a）廢均相催化劑；（b）蒸餾產物

Figure 3. Infrared absorption spectrum recorded: (a) spent RCHC; (b) distillate

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圖 4 240~320 ℃下蒸餾產物的體積及Rh濃度

Figure 4. Volume of distillate and concentration of Rh at temperatures ranging from 240–320 ℃

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圖 5 氯離子濃度(a)、雙氧水用量(b)、反應時間(c)、H⁺濃度(d)對Rh浸出率的影響

Figure 5. Effects of Cl^– concentration (a), H₂O₂ dosage (b), leaching time (c), and H⁺ concentration (d) on Rh leaching efficiency

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圖 6 不同因素相互作用對Rh浸出率影響的三維響應圖. (a) C, time=4 h; (b) B, c(Cl^–) = 5 mol?L^–1; (c) A, H₂O₂用量為30%

Figure 6. Response surface plots for the interaction effects on the Rh leaching rate: (a) C, time = 4 h; (b) (b) B, c(Cl^–) = 5 mol?L^–1; (c) A, H₂O₂ dosage of 30%

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圖 7 廢均相催化劑氧化浸出Rh的反應示意圖

Figure 7. Diagram of oxidation leaching of Rh using spent homogeneous catalysts

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圖 8 不同濃度的RhCl₆^3–溶液的紫外吸收光譜

Figure 8. Ultraviolet absorption spectra of RhCl₆^3?solution at different concentrations

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圖 9 ln(A_∞? A_t)與反應時間的關系

Figure 9. Relationship between ln(A_∞? A_t) and reaction time

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圖 10 40~90 ℃反應條件下Rh氧化浸出的Arrhenius圖

Figure 10. Arrhenius plot for oxidation leaching of Rh at temperatures of 40–90 ℃

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表 1 Rh氧化浸出回歸方程的方差分析

Table 1. ANOVA results of the reduced quadratic model for the Rh leaching efficiency

Source	Sum of squares	Mean square	F value	p-value Prob>F
Model	10550.87	1172.32	12.38	0.0003
A	3690.05	3690.05	38.97	< 0.0001
B	2460.03	2460.03	25.98	0.0005
C	341.94	341.94	3.61	0.0866
AB	5.41	5.41	0.057	0.8159
AC	484.85	484.85	5.12	0.0471
BC	307.27	307.27	3.25	0.1018
A²	2254.83	2254.83	23.82	0.0006
B²	410.16	410.16	4.33	0.0641
C²	1121.33	1121.33	11.84	0.0063
Residual	946.80	94.68	—	—
Lack of fit	941.00	188.20	162.32	< 0.0001
Pure error	5.80	1.16	—	—
Cor total	11497.66	—	—	—

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表 2 響應曲面模型的相關性分析

Table 2. Correlation analysis of response surface method

Category	Value	Category	Value
Standard deviation	9.73	R²	0.9177
Mean	63.47	R_adj²	0.8435
Coefficient of fariance	15.33	Pred R²	0.3791
PRESS	7139.13	Adeq precision	10.702

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表 3 不同溫度下Rh氧化絡合浸出動力學參數

Table 3. Kinetic parameters of the chemical reaction control model for Rh leaching at different temperatures

T/℃	k	R²
45	0.00146	0.9818
60	0.0014	0.9864
75	0.00467	0.9821
90	0.00762	0.9663

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