Citation: SONG Hua, ZHANG Yong-Jiang, SONG Hua-Lin, DAI Min. Effect of Citric Acid on the Hydrodesulfurization Performance of Ni₂P/TiO₂-Al₂O₃ Catalyst[J]. Acta Physico-Chimica Sinica, ;2012, 28(03): 661-666. doi: 10.3866/PKU.WHXB201112291 shu

Effect of Citric Acid on the Hydrodesulfurization Performance of Ni₂P/TiO₂-Al₂O₃ Catalyst

1.
1. College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318, Heilongjiang Province, P. R. China;
2. Provincial Key Laboratory of Oil & Gas Chemical Technology, Northeast Petroleum University, Daqing 163318, Heilongjiang Province, P. R. China;
3. Department of Image School, Mudanjiang Medical University, Mudanjiang 157011, Heilongjiang Province, P. R. China

Received Date: 5 August 2011
Available Online: 29 December 2011
Fund Project: 黑龙江省科技厅(2009G0947-00)资助 (2009G0947-00)

A TiO₂-Al₂O₃ complex support was prepared by the sol-gel method. Nickel phosphide catalyst, Ni₂P/TiO₂-Al₂O₃, with citric acid (CA) as a chelating agent, was prepared by impregnation. The catalyst was characterized by X-ray diffraction (XRD), BET specific surface area measurements, H₂-temperature programmed reduction (TPR) and temperature programmed oxidation (TPO), and X-ray photoelectron spectroscopy (XPS). The effects of the molar ratio of CA to Ni on catalyst activity for hydrodesulfurization (HDS) of dibenzothiophene (DBT) were studied. Addition of an appropriate amount of CA into the catalyst can change the pores of the Ni₂P/TiO₂-Al₂O₃ catalyst, increasing the surface area. The specific surface area reached 126.75 m²·g^-1 for n(CA)/n(Ni) of 2/1, an improvement of 57.05 m²·g^-1 compared with the catalyst without CA. Regulating n(CA)/n(Ni) can improve the distribution of the active phase and change the active phase species. Addition of CA decreased the temperature required for reduction of nickel and the phosphorus precursor, as well as promoting the formation of the active phase. CA can limit the deposition of carbon on the catalyst surface to some extent, improving its stability. A molar ratio of n(CA)/n(Ni) of 2/1 was found to be optimal for the catalytic activity of the Ni₂P/TiO₂-Al₂O₃ catalyst prepared with CA as a chelating agent. At a reaction temperature of 360 °C, pressure of 3.0 MPa, hydrogen/oil ratio of 500 (V/V), and liquid hourly space velocity of 2.0 h^-1, the HDS conversion of DBT was 99.5%, which can reduce the sulfur content of a model oil from 2% (w) to 0.01% (w).
- Hydrodesulfurization,
- Nickel phosphide,
- Titanium dioxide,
- Al₂O₃,
- Citric acid,
- Chelating agent
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Effect of Citric Acid on the Hydrodesulfurization Performance of Ni₂P/TiO₂-Al₂O₃ Catalyst