硫氨酯捕收劑的制備及浮選性能

馬鑫; 曹占芳; 王帥; 黃小平; 鐘宏

doi:10.13374/j.issn2095-9389.2022.04.30.003

硫氨酯捕收劑的制備及浮選性能

doi: 10.13374/j.issn2095-9389.2022.04.30.003

馬鑫^{1, 2},
曹占芳^{1, 2},
王帥^{1, 2},
黃小平^{1, 2},
鐘宏^{1, 2, ,}

1.
中南大學化學化工學院，長沙 410083
2.
錳資源高效清潔利用湖南省重點實驗室，長沙 410083

基金項目: 國家自然科學基金資助項目（52074354）

詳細信息

通訊作者:
E-mail: zhongh@csu.edu.cn

中圖分類號: TD952
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- 文章訪問數: 348
- HTML全文瀏覽量: 153
- PDF下載量: 56
- 被引次數: 0
出版歷程
- 收稿日期: 2022-04-30
- 網絡出版日期: 2022-10-10
- 刊出日期: 2023-08-25

Preparation and flotation performance of thionocarbamates

MA Xin^{1, 2},
CAO Zhan-fang^{1, 2},
WANG Shuai^{1, 2},
HUANG Xiao-ping^{1, 2},
ZHONG Hong^{1, 2
, ,}

1.
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
2.
Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources, Changsha 410083, China

More Information

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

摘要

摘要: 為解決硫氨酯捕收劑制備過程中副產品處理困難、存在污染等問題，設計了四種新工藝制備乙硫氨酯（IPETC），分別聯產對叔丁基芐基硫醇（BBSH）、芐基三硫代碳酸鹽（BTTC）、芐硫基乙基黃藥（SBEX）、二芐基二硫醚。在優化的合成工藝條件下，合成IPETC聯產BBSH，得到含IPETC和BBSH的復合捕收劑，其中IPETC的質量分數為51%，BBSH的質量分數為41%，IPETC和BBSH的收率達到95%；合成IPETC聯產BTTC，IPETC和BTTC的收率分別達到94%和95%，純度分別為91%和82%；合成IPETC聯產SBEX，IPETC的收率和純度分別達到89%和95%，SBEX的收率和純度分別為93%和91%；合成IPETC聯產二芐基二硫醚，IPETC的收率和純度分別達到93%和92%，二芐基二硫醚的收率和純度分別達到95%和94%。考察了制備的復合捕收劑（IPETC與BBSH）對銅鉬礦的浮選性能，結果表明，復合捕收劑對銅鉬礦表現出良好的捕收性能。聯產的新型捕收劑SBEX、BTTC對黃銅礦的捕收力略強于異丁基黃藥，對黃鐵礦具有較好的選擇性，可替代異丁基黃藥浮選硫化銅礦。紅外光譜和X射線光電子能譜分析結果表明，SBEX、BTTC與黃銅礦作用時，捕收劑分子中的C=S和C—S與礦物表面的金屬Cu作用，生成捕收劑與銅的表面絡合物吸附在黃銅礦的表面。
- 浮選 /
- 硫氨酯 /
- 三硫代碳酸鹽 /
- 硫醇 /
- 二硫醚 /
- 捕收劑
Abstract: To address the problems of byproduct treatment and pollution in thionocarbamate preparation, four novel processes for preparing O-isopropyl-N-ethyl thionocarbamate (IPETC) were designed, which can coproduce 4-(tert-butyl)benzyl mercaptan (BBSH), sodium benzyl trithiocarbonate (BTTC), sodium O-benzylthioethyl xanthate (SBEX), and benzyl disulfide, respectively. All the products were confirmed via FTIR and mass spectrometry. The composite collector (IPETC and BBSH mass contents were 51% and 41%, respectively) was synthesized via one-pot reaction of sodium isopropyl xanthate, 4-tert-butylbenzylchloride, and ethylamine using tert-butyl alcohol as solvent. The yield of IPETC and BBSH was 95% in the process of coproducing IPETC and BBSH. Specifically, BTTC and IPETC were synthesized via a reaction of sodium isopropyl xanthate, benzyl chloride, ethylamine, carbon disulfide, and sodium hydroxide. The IPETC and BTTC yields were 94% and 95% with a purity of 91% and 82% in the process of coproducing IPETC and BTTC, respectively. Meanwhile, SBEX and IPETC were synthesized via reaction of sodium isopropyl xanthate, 2-chloroethanol, ethylamine, benzyl chloride, carbon disulfide, and sodium hydroxide. The IPETC and SBEX yields were 89% and 93% with a purity of 95% and 91% in the process of coproducing IPETC and SBEX, respectively. Benzyl disulfide and IPETC were synthesized via a reaction of sodium isopropyl xanthate, benzyl chloride, ethylamine, and hydrogen peroxide. The IPETC and benzyl disulfide yields were 93% and 95% with a purity of 92% and 94% in the processof coproducing IPETC and benzyl disulfide, respectively. The flotation response of copper-molybdenum ore independent with IPETC and BBSH collectors and with their mixture was assessed. The flotation results indicate that the composite collector displays a superior collecting capability for copper sulfide ore. Further, the combination of IPETC and BBSH could give rise to a synergistic effect, significantly enhancing the overall flotation performance. The flotation performance of SBEX and BTTC on chalcopyrite and pyrite was also investigated. The flotation results indicate that SBEX and BTTC exhibited better collecting performance than sodium isobutyl xanthate (SIBX), which can replace SIBX for the flotation separation of copper sulfide. FTIR spectra and X-ray photoelectron spectroscopy analyses were conducted. The results indicate that when all three sulfur atoms in BTTC bond to the mineral surface, the hydrophobicity increases when compared to xanthates, wherein oxygen does not bond to the surface. Further, the thioether structure can increase the hydrophobicity of SBEX on the chalcopyrite surface, and SBEX features a higher collecting recovery toward chalcopyrite than SIBX. The results indicate that BTTC and SBEX might bond with copper atoms on the chalcopyrite surface through their sulfur atoms to form BTTC-Cu and SBEX-Cu surface complexes.
- flotation /
- thionocarbamates /
- trithiocarbonates /
- mercaptans /
- disulfides /
- collector

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圖 1 單礦物的XRD圖譜. （a）黃銅礦; （b）黃鐵礦

Figure 1. XRD patterns of single minerals: (a) chalcopyrite; (b) pyrite

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圖 2 合成IPETC與BBSH

Figure 2. Synthesis route of IPETC and BBSH

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圖 3 合成IPETC與BTTC

Figure 3. Synthesis route of IPETC and BTTC

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圖 4 合成IPETC與二芐基二硫醚

Figure 4. Synthesis route of IPETC and benzyl disulfide

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圖 5 合成IPETC與SBEX

Figure 5. Synthesis route of IPETC and SBEX

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圖 6 合成產物的質譜圖. （a） IPETC; （b） BBSH; （c）二芐基二硫醚; （d） SBEX

Figure 6. Mass spectra of the synthesized products: (a) IPETC; (b) BBSH; (c) benzyl disulfide; (d) SBEX

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圖 7 合成產物的紅外光譜圖. （a） IPETC; （b） BBSH; （c） BTTC; （d）二芐基二硫醚; （e） SBEX

Figure 7. FTIR spectra of the synthesized products: (a) IPETC; (b) BBSH; (c) BTTC; (d) benzyl disulfide; (e) SBEX

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圖 8 不同礦漿pH和捕收劑用量下的黃銅礦浮選回收率. (a)礦漿pH; (b)捕收劑用量

Figure 8. Recovery of chalcopyrite flotation under different pulp pH and collector concentration: (a) pulp pH; (b) collector concentration

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圖 9 不同礦漿pH和捕收劑用量下的黃鐵礦浮選回收率. (a)礦漿pH; (b)捕收劑用量

Figure 9. Recovery of pyrite flotation under different pulp pH and collector concentration: (a) pulp pH; (b) collector concentration

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圖 10 SBEX、黃銅礦、與SBEX作用后的黃銅礦的紅外光譜圖^[14]

Figure 10. FTIR spectra of SBEX and chalcopyrite before and after interaction with SBEX^[14]

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圖 11 BTTC、黃銅礦、與BTTC作用后的黃銅礦的紅外光譜圖^[13]

Figure 11. FTIR spectra of BTTC and chalcopyrite before and after interaction with BTTC^[13]

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圖 12 SBEX、與SBEX作用前后的黃銅礦的XPS精細譜圖^[14]. （a） Cu 2p; （b） S 2p

Figure 12. High-resolution XPS spectra^[14]: (a) Cu 2p; (b) S 2p

①—chalcopyrite; ②—SBEX; ③—SBEX treated chalcopyrite

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圖 13 BTTC、與BTTC作用前后的黃銅礦XPS精細譜圖^[13]. （a） Cu 2p; （b） S 2p

Figure 13. High-resolution XPS spectra^[13]: (a) Cu 2p; (b) S 2p

①—BTTC treated chalcopyrite; ②—chalcopyrite; ③—BTTC

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表 1 捕收劑對內蒙古某銅鉬礦的一次粗選實驗結果

Table 1. Flotation conditions and results of copper-molybdenum ore from Inner Mongolia Copper-Molybdenum Mine

Entry	Reagents and their dosages/(g·t^?1)	Products	Yield/%	Grade/%		Recovery/%
Entry	Reagents and their dosages/(g·t^?1)	Products	Yield/%	Cu	Mo	Cu	Mo
1	Composite collector, 24 Pine oil, 24	Concentrates	5.64	3.99	0.44	76.08	70.90
		Tailings	94.36	0.075	0.011	23.92	29.10
		Feed	100.00	0.296	0.035	100.00	100.00
2	IPETC 24 Pine oil, 24	Concentrates	6.07	3.69	0.29	74.91	60.70
		Tailings	93.93	0.08	0.012	25.09	39.30
		Feed	100.00	0.299	0.029	100.00	100.00
3	BBSH, 24 Pine oil, 24	Concentrates	6.98	3.11	0.31	72.11	69.80
		Tailings	93.02	0.09	0.010	27.89	30.20
		Feed	100.00	0.301	0.031	100.00	100.00

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