Polyethylene hydrogenolysis over bimetallic catalyst with suppression of methane formation

doi:10.1007/s11705-024-2461-x

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (10) : 110 https://doi.org/10.1007/s11705-024-2461-x

Polyethylene hydrogenolysis over bimetallic catalyst with suppression of methane formation

Xiangkun Zhang, Bingyan Sun, Zhigang Zhao, Tan Li, Marc Mate, Kaige Wang(

)

State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

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Abstract

Hydrogenolysis has been explored as a promising approach for plastic chemical recycling. Noble metals, such as Ru and Pt, are considered effective catalysts for plastic hydrogenolysis, however, they result in a high yield of low-value gaseous products. In this research, an efficient bimetallic catalyst was developed by separate impregnation of Ni and Ru on SiO₂ support resulting in liquid products yield of up to 83.1 C % under mild reaction conditions, compared to the 65.5 C % yield for the sole noble metal catalyst. The carbon distribution of the liquid products from low density polyethylene hydrogenolysis with Ni-modified catalyst also shifted to a heavier fraction, compared to that with Ru catalyst. Meanwhile, the NiRu catalyst exhibited excellent performance in suppressing the cleavage of the end-chain C–C bond, leading to a methane yield of only 10.4 C %, which was 69% lower than that of the Ru/SiO₂ catalyst. Temperature programmed reduction and desorption of hydrogen and propane were further conducted to reveal the detailed mechanism of low density polyethylene hydrogenolysis over the bimetallic catalyst. The results suggested that the Ni-Ru alloy exhibited stronger H adsorption properties indicating improved hydrogen coverage on the catalyst surface thus enhancing the desorption of reaction intermediates. The carbon number distribution was ultimately skewed toward heavier liquid products.

Keywords hydrogenolysis polyethylene bimetallic catalyst depolymerization mechanism

Corresponding Author(s): Kaige Wang

Just Accepted Date: 10 May 2024 Issue Date: 28 June 2024

Cite this article:

Xiangkun Zhang,Bingyan Sun,Zhigang Zhao, et al. Polyethylene hydrogenolysis over bimetallic catalyst with suppression of methane formation[J]. Front. Chem. Sci. Eng., 2024, 18(10): 110.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2461-x
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I10/110

Fig.1 XRD patterns of 5Ru/SiO₂ (black), 0.5Ni5Ru/SiO₂ (red), 1Ni5Ru/SiO₂ (blue), 2Ni5Ru/SiO₂ (green), and 3Ni5Ru/SiO₂ (purple) catalysts with an expanded view of the (101) peaks.

Fig.2 Structural characterization of Ru/SiO₂ catalyst and Ni-modified Ru/SiO₂ catalyst. (a) TEM image of Ru/SiO₂ catalyst with specific lattice structure of Ru (101) crystal plane. (b) Morphology of the Ru/SiO₂ catalyst with particle size distribution statistics. (c) High magnification image of the 1Ni5Ru/SiO₂ catalyst showing a lattice spacing of 0.203 nm, consistent with Ni (111), and a lattice spacing of 0.206, consistent with Ru (101), indicating a Ni-Ru alloy structure. (d) Morphology of the 1Ni5Ru/SiO₂ catalyst with partical size distribution statistics. (e) Correspinding EDS elemental mapping images of Si, O, Ru, and Ni in 1Ni5Ru/SiO₂ catalyst.

Fig.3 XPS pattern of (a) Ru and (b) Ni in the catalyst.

Fig.4 Effect of (a, b) temperature, (c, d) initial hydrogen pressure, and (e, f) reaction time on LDPE hydrogenolysis over Ru/SiO₂ catalyst. The three graphs (a, c, and e) on the first line show yields of non-solid products, which consist of liquid (solid bars) and gaseous (faded bars) products, under different conditions. The left three graphs (b, d, and f) on the second line present the carbon distributions of the gas products. Reactions of (a, b) were conducted under 3 MPa H₂ for 4 h. Reactions of (c, d) were conducted under 250 °C for 4 h. Reactions of (e, f) were conducted under 250 °C and 3 MPa H₂. All reactions were performed with 1.5 g LDPE and 50 mg catalyst.

Fig.5 Effect of Ni loadings in NiRu/SiO₂ catalyst on LDPE hydrogenolysis. Yields and selectivities for hydrogenolysis over 5Ru/SiO₂ (pink), 0.5Ni5Ru/SiO₂ (blue), 1Ni5Ru/SiO₂ (green), 2Ni5Ru/SiO₂ (purple), and 3Ni5Ru/SiO₂ (yellow) catalyst. (a) Yields of non-solid products, which consist of liquid (solid bars) and gaseous (faded bars) products. (b) Yields to non-gas products by fuel range: light liquids, C4–C22; wax, C23–C45; solid residue, above C45. (c) Carbon distributions of the gas product. (d) Carbon distributions of the liquid products. Reactions were performed at 250 °C and 3 MPa H₂ with 1.5 g LDPE and 50 mg catalyst for 4 h.

Fig.6 (a) H₂-TPR and (b) H₂-TPD results of 1Ni5Ru/SiO₂ and 5Ru/SiO₂ catalysts.

Fig.7 Mass selective detector signal graphs for nuclei with m/z ratios of (a) 28 and (b) 44.

Fig.8 Schematic of the proposed reaction mechanisms. (a) Conversion process from LDPE to desired liquid hydrocarbons over 1Ni5Ru/SiO₂ catalyst. (b) Cascade hydrogenolysis converts LDPE to methane and light hydrocarbons over a 5Ru/SiO₂ catalyst.

Fig.9 Carbon distribution of the reaction products of the model compound.

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