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: 347
- 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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參考文獻(31)

[1]	Bu Y J, Hu Y H, Sun W, et al. Fundamental flotation behaviors of chalcopyrite and galena using O-isopropyl-N-ethyl thionocarbamate as a collector. Minerals, 2018, 8(3): 115 doi: 10.3390/min8030115
[2]	Fischback B C, Harris G H. Process for the Manufacture of Dialkyl Thionocarbamates: US Patent, 2691635. 1954-10-12
[3]	Hamm P C. Destroying Vegetation with Haloalkenyl Disubstituted Thionocarbamates: US Patent, 3224864. 1965-12-21
[4]	Bishop M D, Gray L A. Catalytic Synthesis of Thionocarbamates from Xanthates and Amines: US Patent, 5041599. 1991-08-20
[5]	Dai H Y, Wang M J. Process of Preparing Ethyl Ammonia Sulfate: China Patent, 96110154. 1998-01-14 戴洪義, 王美君. 乙硫氨酯制備的新工藝: 中國專利, 96110154. 1998-01-14
[6]	Lewellyn M E. Process for the Preparation of N-Allyl-O-Alkyl Thionocarbamates: US Patent, 4482500. 1984-11-13
[7]	Luan H L, Yao W, Wu R C. Prepn of Thioamino-Formates Compounds: China Patent, 96106463. 1997-07-09 欒和林, 姚文, 武榮成. 一種硫代胺基甲酸酯類化合物的制備方法: 中國專利, 96106463. 1997-07-09
[8]	Xu Q H. Experimental study on extraction process of recovery of thioglycolic acid from the sulfur ammonia ester solution. Shandong Chem Ind, 2015, 44(12): 10 徐慶華. 從硫氨酯尾液中回收巰基乙酸萃取工藝的實驗研究. 山東化工, 2015, 44(12):10
[9]	Wan S H, Liu G Y, Wang D T, et al. Compounding process of thioglycolic acid using as depressant against copper sulfides. Copp Eng, 2006(4): 68 萬盛輝, 劉廣義, 王德庭, 等. 銅抑制劑巰基乙酸的合成工藝. 銅業工程, 2006(4):68
[10]	Li H, Liu G Y. A novel method for the preparation of thionocarbamate. Fine Chem Intermed, 2022, 52(1): 56 李華, 劉廣義. 硫代氨基甲酸酯制備新工藝研究. 精細化工中間體, 2022, 52(1):56
[11]	Zhong H, Ma X, Wang S, et al. Method for Preparing Thionocarbamate and Trithiocarbonate: China Patent, 201610801951. 2017-02-08 鐘宏, 馬鑫, 王帥, 等. 一種制備硫氨酯并聯產三硫代碳酸鹽的方法: 中國專利, 201610801951. 2017-02-08
[12]	Zhong H, Ma X, Wang S, et al. Method for Producing Thionocarbamate and Dibenzyl Disulfide: China Patent, 201610801983. 2017-02-08 鐘宏, 馬鑫, 王帥, 等. 一種制備硫氨酯并聯產二芐基二硫醚的方法: 中國專利, 201610801983. 2017-02-08
[13]	Ma X, Wang S, Zhong H. Sodium benzyl trithiocarbonate synthesis and flotation performance to chalcopyrite. Chin J Nonferrous Met, 2018, 28(5): 1067 馬鑫, 王帥, 鐘宏. 芐基三硫代碳酸鈉的合成及其對黃銅礦的浮選性能. 中國有色金屬學報, 2018, 28(5):1067
[14]	Huang X P, Jia Y, Wang S, et al. Novel sodium O-benzythioethyl xanthate surfactant: Synthesis, DFT calculation and adsorption mechanism on chalcopyrite surface. Langmuir, 2019, 35(47): 15106 doi: 10.1021/acs.langmuir.9b03118
[15]	Zhong H, Huang X P, Wang S, et al. Method for Preparing Thionocarbamates and Co-producing 2-mercaptoethanol or O-alkylthioethyl Xanthogenate: China Patent, 201810519232. 2018-09-25 鐘宏, 黃小平, 王帥, 等. 一種制備硫氨酯并聯產2-巰基乙醇或O-烷硫基乙基黃原酸鹽的方法: 中國專利, 201810519232. 2018-09-25
[16]	Xiao J J, Liu G Y, Zhong H. The adsorption mechanism of N-butoxypropyl-S-[2-(hydroxyimino) propyl] dithiocarbamate ester to copper minerals flotation. Int J Miner Process, 2017, 166: 53 doi: 10.1016/j.minpro.2017.07.003
[17]	Andrew F P, Ajibade P A. Synthesis, characterization and anticancer studies of bis-(N-methyl-1-phenyldithiocarbamato) Cu(II), Zn(II), and Pt(II) complexes: Single crystal X-ray structure of the copper complex. J Coord Chem, 2018, 71(16-18): 2776 doi: 10.1080/00958972.2018.1489537
[18]	Suyantara G P W, Hirajima T, Miki H, et al. Selective flotation of chalcopyrite and molybdenite using H₂O₂ oxidation method with the addition of ferrous sulfate. Miner Eng, 2018, 122: 312 doi: 10.1016/j.mineng.2018.02.005
[19]	Du M M, Zhang Y Q, Hussain I, et al. Effect of pyrite on enhancement of zero-valent iron corrosion for arsenic removal in water: A mechanistic study. Chemosphere, 2019, 233: 744 doi: 10.1016/j.chemosphere.2019.05.197
[20]	Makhlouf M M, Radwan A S, Ghazal B. Experimental and DFT insights into molecular structure and optical properties of new chalcones as promising photosensitizers towards solar cell applications. Appl Surf Sci, 2018, 452: 337 doi: 10.1016/j.apsusc.2018.05.007
[21]	Liu S, Xie L, Liu G Y, et al. Hetero-difunctional reagent with superior flotation performance to chalcopyrite and the associated surface interaction mechanism. Langmuir, 2019, 35(12): 4353 doi: 10.1021/acs.langmuir.9b00156
[22]	Yin Z G, Hu Y H, Sun W, et al. Adsorption mechanism of 4-amino-5-mercapto-1, 2, 4-triazole as flotation reagent on chalcopyrite. Langmuir, 2018, 34(13): 4071 doi: 10.1021/acs.langmuir.7b03975
[23]	Liu S, Zhong H, Liu G Y, et al. Cu(I)/Cu(II) mixed-valence surface complexes of S-[(2-hydroxyamino)-2-oxoethyl]-N, N-dibutyldithiocarbamate: Hydrophobic mechanism to malachite flotation. J Colloid Interface Sci, 2018, 512: 701 doi: 10.1016/j.jcis.2017.10.063
[24]	Deng T, Yu S, Lotter N O, et al. Laboratory testwork of mixed xanthates for the raglan ore // Proceedings of Canadian Mineral Processors. Ottawa, 2010, 1: 253
[25]	Liu G Y, Qiu Z H, Wang J Y, et al. Study of N-isopropoxypropyl-N’-ethoxycarbonyl thiourea adsorption on chalcopyrite using in situ SECM, ToF-SIMS and XPS. J Colloid Interface Sci, 2015, 437: 42 doi: 10.1016/j.jcis.2014.08.069
[26]	Smart R S C. Surface layers in base metal sulphide flotation. Miner Eng, 1991, 4(7-11): 891 doi: 10.1016/0892-6875(91)90072-4
[27]	McIntyre N S, Cook M G. X-ray photoelectron studies on some oxides and hydroxides of cobalt, nickel, and copper. Anal Chem, 1975, 47(13): 2208 doi: 10.1021/ac60363a034
[28]	Szargan R, Schaufu? A, Ro?bach P. XPS investigation of chemical states in monolayers: Recent progress in adsorbate redox chemistry on sulphides. J Electron Spectrosc Relat Phenom, 1999, 100(1-3): 357 doi: 10.1016/S0368-2048(99)00055-9
[29]	Beattie D A, Kempson I M, Fan L J, et al. Synchrotron XPS studies of collector adsorption and co-adsorption on gold and gold: Silver alloy surfaces. Int J Miner Process, 2009, 92(3-4): 162 doi: 10.1016/j.minpro.2009.03.009
[30]	Acres R G, Harmer S L, Beattie D A. Synchrotron XPS, NEXAFS, and ToF-SIMS studies of solution exposed chalcopyrite and heterogeneous chalcopyrite with pyrite. Miner Eng, 2010, 23(11-13): 928 doi: 10.1016/j.mineng.2010.03.007
[31]	Fairthorne G, Fornasiero D, Ralston J. Effect of oxidation on the collectorless flotation of chalcopyrite. Int J Miner Process, 1997, 49(1-2): 31 doi: 10.1016/S0301-7516(96)00039-7