硫氨酯捕收剂的制备及浮选性能

马鑫; 曹占芳; 王帅; 黄小平; 钟宏

doi:10.13374/j.issn2095-9389.2022.04.30.003

硫氨酯捕收剂的制备及浮选性能

doi: 10.13374/j.issn2095-9389.2022.04.30.003

马鑫^{1, 2},
曹占芳^{1, 2},
王帅^{1, 2},
黄小平^{1, 2},
钟宏^{1, 2, ,}

1.
中南大学化学化工学院，长沙 410083
2.
锰资源高效清洁利用湖南省重点实验室，长沙 410083

基金项目: 国家自然科学基金资助项目（52074354）

详细信息

通讯作者:
E-mail: zhongh@csu.edu.cn

中图分类号: TD952
计量
- 文章访问数: 264
- HTML全文浏览量: 105
- PDF下载量: 54
- 被引次数: 0
出版历程
- 收稿日期: 2022-04-30
- 网络出版日期: 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: 为解决硫氨酯捕收剂制备过程中副产品处理困难、存在污染等问题，设计了四种新工艺制备乙硫氨酯（IPETC），分别联产对叔丁基苄基硫醇（BBSH）、苄基三硫代碳酸盐（BTTC）、苄硫基乙基黄药（SBEX）、二苄基二硫醚。在优化的合成工艺条件下，合成IPETC联产BBSH，得到含IPETC和BBSH的复合捕收剂，其中IPETC的质量分数为51%，BBSH的质量分数为41%，IPETC和BBSH的收率达到95%；合成IPETC联产BTTC，IPETC和BTTC的收率分别达到94%和95%，纯度分别为91%和82%；合成IPETC联产SBEX，IPETC的收率和纯度分别达到89%和95%，SBEX的收率和纯度分别为93%和91%；合成IPETC联产二苄基二硫醚，IPETC的收率和纯度分别达到93%和92%，二苄基二硫醚的收率和纯度分别达到95%和94%。考察了制备的复合捕收剂（IPETC与BBSH）对铜钼矿的浮选性能，结果表明，复合捕收剂对铜钼矿表现出良好的捕收性能。联产的新型捕收剂SBEX、BTTC对黄铜矿的捕收力略强于异丁基黄药，对黄铁矿具有较好的选择性，可替代异丁基黄药浮选硫化铜矿。红外光谱和X射线光电子能谱分析结果表明，SBEX、BTTC与黄铜矿作用时，捕收剂分子中的C=S和C—S与矿物表面的金属Cu作用，生成捕收剂与铜的表面络合物吸附在黄铜矿的表面。
- 浮选 /
- 硫氨酯 /
- 三硫代碳酸盐 /
- 硫醇 /
- 二硫醚 /
- 捕收剂
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

HTML全文

图 1 单矿物的XRD图谱. （a）黄铜矿; （b）黄铁矿

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

下载: 全尺寸图片幻灯片

图 2 合成IPETC与BBSH

Figure 2. Synthesis route of IPETC and BBSH

下载: 全尺寸图片幻灯片

图 3 合成IPETC与BTTC

Figure 3. Synthesis route of IPETC and BTTC

下载: 全尺寸图片幻灯片

图 4 合成IPETC与二苄基二硫醚

Figure 4. Synthesis route of IPETC and benzyl disulfide

下载: 全尺寸图片幻灯片

图 5 合成IPETC与SBEX

Figure 5. Synthesis route of IPETC and SBEX

下载: 全尺寸图片幻灯片

图 6 合成产物的质谱图. （a） IPETC; （b） BBSH; （c）二苄基二硫醚; （d） SBEX

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

下载: 全尺寸图片幻灯片

图 7 合成产物的红外光谱图. （a） IPETC; （b） BBSH; （c） BTTC; （d）二苄基二硫醚; （e） SBEX

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

下载: 全尺寸图片幻灯片

图 8 不同矿浆pH和捕收剂用量下的黄铜矿浮选回收率. (a)矿浆pH; (b)捕收剂用量

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

下载: 全尺寸图片幻灯片

图 9 不同矿浆pH和捕收剂用量下的黄铁矿浮选回收率. (a)矿浆pH; (b)捕收剂用量

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

下载: 全尺寸图片幻灯片

图 10 SBEX、黄铜矿、与SBEX作用后的黄铜矿的红外光谱图^[14]

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

下载: 全尺寸图片幻灯片

图 11 BTTC、黄铜矿、与BTTC作用后的黄铜矿的红外光谱图^[13]

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

下载: 全尺寸图片幻灯片

图 12 SBEX、与SBEX作用前后的黄铜矿的XPS精细谱图^[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

下载: 全尺寸图片幻灯片

图 13 BTTC、与BTTC作用前后的黄铜矿XPS精细谱图^[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

下载: 全尺寸图片幻灯片

表 1 捕收剂对内蒙古某铜钼矿的一次粗选实验结果

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

下载: 导出CSV

参考文献(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 戴洪义, 王美君. 乙硫氨酯制备的新工艺: 中国专利, 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 栾和林, 姚文, 武荣成. 一种硫代胺基甲酸酯类化合物的制备方法: 中国专利, 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 徐庆华. 从硫氨酯尾液中回收巯基乙酸萃取工艺的实验研究. 山东化工, 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 万盛辉, 刘广义, 王德庭, 等. 铜抑制剂巯基乙酸的合成工艺. 铜业工程, 2006(4):68
[10]	Li H, Liu G Y. A novel method for the preparation of thionocarbamate. Fine Chem Intermed, 2022, 52(1): 56 李华, 刘广义. 硫代氨基甲酸酯制备新工艺研究. 精细化工中间体, 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 钟宏, 马鑫, 王帅, 等. 一种制备硫氨酯并联产三硫代碳酸盐的方法: 中国专利, 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 钟宏, 马鑫, 王帅, 等. 一种制备硫氨酯并联产二苄基二硫醚的方法: 中国专利, 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 马鑫, 王帅, 钟宏. 苄基三硫代碳酸钠的合成及其对黄铜矿的浮选性能. 中国有色金属学报, 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 钟宏, 黄小平, 王帅, 等. 一种制备硫氨酯并联产2-巯基乙醇或O-烷硫基乙基黄原酸盐的方法: 中国专利, 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, Schaufuß A, Roßbach 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