Catalytic upgrading of waste PET to dimethyl cyclohexane-1,4-dicarboxylate over defective sulfonated UiO-66def-SO3H supported Ru catalyst

doi:10.1016/S1872-2067(24)60242-1

Abstract

Abstract:

Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate) (PETG) possesses excellent properties and stability than traditional poly(ethylene terephthalate) (PET). However, the production and application of PETG are restricted by the expensive monomer (1,4-cyclohexanedimethanol, CHDM). Direct upgrading of waste PET to dimethyl cyclohexane-1,4-dicarboxylate (DMCD) can promote the production of CHDM in large scale. In this work, a bifunctional Ru/UiO-66_def-SO₃H catalyst was synthesized and utilized in coupled methanolysis (of waste PET to dimethyl terephthalate (DMT)) and hydrogenation (of DMT to DMCD) under mild condition. Characterizations revealed that Ru/UiO-66_def-SO₃H possessed mesopores (dominant channels of 2.72 and 3.44 nm), enlarged surface area (998 m²·g^-1), enhanced acidity (580 μmol·g^-1), and Ru nanoparticles (NPs) dispersed highly (45.1%) compared to those of Ru/UiO-66. These combined advantages could accelerate the methanolysis and hydrogenation reactions simultaneously, promoting the performance of direct upgrading of PET to DMCD in one pot. In particular, the conversion of PET and yield of DMCD over Ru/UiO-66_def-SO₃H reached 100% and 97.7% at 170 °C and 3 MPa H₂ within 6 h. Moreover, Ru/UiO-66_def-SO₃H was also capable for the upcycling of waste PET-based products including beverage bottles, textile fiber and packaging film to DMCD.

Key words: Waste plastic refinery, Poly(ethylene terephthalate), Upcycling, Dimethyl cyclohexane-1,4- dicarboxylate, Ru/UiO-66_def-SO₃H

Weitao Ou, Yingdan Ye, Yibin Zhang, Huaiyuan Zhao, Weichen Du, Zhaoyin Hou. Catalytic upgrading of waste PET to dimethyl cyclohexane-1,4-dicarboxylate over defective sulfonated UiO-66_def-SO₃H supported Ru catalyst[J]. Chinese Journal of Catalysis, 2025, 71: 363-374.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60242-1

https://www.cjcatal.com/EN/Y2025/V71/I4/363

Figures/Tables 14

Scheme 1. Different routines for the synthesis of CHDM.

Scheme 2. Schematic illustration for the preparation of UiO-66def-SO3H.

Fig. 1. XRD patterns including enlarged diffractions at 3°-7°, 43°-45° and structural representation of Ru/UiO-66 (a) and Ru/UiO-66def-SO3H (b).

Table 1 The properties of Ru/UiO-66 and Ru/UiO-66def-SO3H.

Catalyst	Lattice parameter ^a	Ru Content (%)		Ru dispersion ^d
Catalyst	(a = b = c, nm)	Bulk ^b	Surface ^c	(%)
Ru/UiO-66	2.07476	4.79	6.13	37.4
Ru/UiO-66_def-SO₃H	2.07404	4.87	4.69	45.1

Table 2 Textural properties of Ru/UiO-66, Ru/UiO-66def-SO3H and their supports.

Sample	A_BET^a (m²·g^-1)	A_ext ^b (m²·g^-1)	A_int ^b (m²·g^-1)	V_micro^b (cm³·g^-1)	V_meso ^c (cm³·g^-1)	V_pore^c (cm³·g^-1)
UiO-66	1012	298	714	0.57	0.15	0.72
Ru/UiO-66	886	276	590	0.48	0.13	0.61
UiO-66_def-SO₃H	1148	517	631	0.43	0.54	0.97
Ru/UiO-66_def-SO₃H	998	453	545	0.39	0.44	0.83

Fig. 2. N2 adsorption-desorption isotherms (a) and pore size distributions (b) of UiO-66def-SO3H and Ru/UiO-66def-SO3H.

Fig. 3. Thermal analysis of Ru/UiO-66 (a) and Ru/UiO-66def-SO3H (b) in N2 flow.

Fig. 4. Pyridine-IR spectra (a) and binding energy of Ru 3p (b) of Ru/UiO-66 and Ru/UiO-66def-SO3H.

Fig. 5. TEM images (a,b,e), distributions of Ru NPs (c), line-scanning EDS (d), and FFT of TEM image with the lattice plane intensity profile (f) of Ru/UiO-66def-SO3H.

Fig. 6. Separated methanolysis of PET under varied reaction temperatures over Ru/UiO-66def-SO3H (a) and Ru/UiO-66 (b). Reaction conditions: 0.1 g catalyst, 2.0 g PET, 20 mL methanol, 2 h.

Fig. 7. Separated hydrogenation of DMT under varied reaction temperatures over Ru/UiO-66def-SO3H (a) and Ru/UiO-66 (b). Reaction conditions: 0.1 g catalyst, 2.0 g DMT, 20 mL methanol, 3 MPa H2, 2 h.

Fig. 8. Time course of direct upgrading of PET over Ru/UiO-66def-SO3H (a) and Ru/UiO-66 (b). Reaction conditions: 0.1 g catalyst, 2.0 g PET, 20 mL methanol, 160 °C, 3 MPa H2.

Fig. 9. Time course (a) and recycle usage (b) of direct upgrading of PET over Ru/UiO-66def-SO3H. Reaction conditions: (a) 0.1 g catalyst, 2.0 g PET, 20 mL methanol, 170 °C, 3 MPa H2; (b) 0.1 g catalyst, 2.0 g PET, 20 mL methanol, 170 °C, 3 MPa H2, 4 h.

Table 3 Direct upgrading of varied PET-based products over Ru/UiO-66def-SO3H.

Entry	Substrate	Conversion of PET (%)	Yield of DMCD (%)
1	beverage bottles	100	95.4
2	textile fiber	100	93.2
3	packaging film	100	92.8

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Catalytic upgrading of waste PET to dimethyl cyclohexane-1,4-dicarboxylate over defective sulfonated UiO-66_def-SO₃H supported Ru catalyst

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