废弃PET化学升级为DMCD的缺陷型磺酸化Ru/UiO-66def-SO3H催化剂

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

催化学报 ›› 2025, Vol. 71: 363-374.DOI: 10.1016/S1872-2067(24)60242-1

废弃PET化学升级为DMCD的缺陷型磺酸化Ru/UiO-66_def-SO₃H催化剂

区维韬^a, 叶莹丹^a, 张艺濒^a, 赵怀远^a^,^b^,^*(), 杜玮辰^a^,^b, 侯昭胤^a^,^b^,^*()

^a浙江大学化学系, 生物质化工教育部重点实验室, 浙江杭州 310028
^b浙江恒逸石化研究院有限公司, 浙江杭州 311200

收稿日期:2024-11-20 接受日期:2025-01-20 出版日期:2025-04-18 发布日期:2025-04-13
通讯作者: * 电子信箱: zyhou@zju.edu.cn (侯昭胤), huaiyuanzhao@zju.edu.cn (赵怀远).
基金资助:
浙江省“尖兵”-“领雁”科技发展计划(2024C01045);国家自然科学基金(21773206);中央高校基本科研业务费专项基金(226-2022-00055)

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

Weitao Ou^a, Yingdan Ye^a, Yibin Zhang^a, Huaiyuan Zhao^a^,^b^,^*(), Weichen Du^a^,^b, Zhaoyin Hou^a^,^b^,^*()

^aKey Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China
^bZhejiang Hengyi Petrochemical Research Institute Co., Ltd., Hangzhou 311200, Zhejiang, China

Received:2024-11-20 Accepted:2025-01-20 Online:2025-04-18 Published:2025-04-13
Contact: * E-mail: zyhou@zju.edu.cn (Z. Hou), huaiyuanzhao@zju.edu.cn (H. Zhao).
Supported by:
“Pioneer” and “Leading Goose” R&D Program of Zhejiang(2024C01045);National Natural Science Foundation of China(21773206);Fundamental Research Funds for the Central Universities(226-2022-00055)

摘要/Abstract

摘要：

对苯二甲酸-乙二醇-1,4-环己烷二甲醇共聚酯(PCT/PETG)以及对苯二甲酸-四甲基环丁二醇-环己二醇共聚酯(PCTG)具有耐热性高、韧性好、抗冲击、透明和可回收等优势, 广泛用于婴儿制品、儿童玩具、高端显示材料和高性能粉末涂料等领域. 然而, 合成上述共聚酯的关键单体1,4-环己烷二甲醇(CHDM)严重依赖进口, 价格昂贵, 传统的对苯二甲酸二甲酯(DMT)两步加氢制备CHDM需要使用贵金属(Pd)催化剂, 工艺条件苛刻. 直接采用废弃聚对苯二甲酸乙二醇酯(PET)为原料化学升级制备CHDM及其关键中间体1,4-环己烷二甲酸二甲酯(DMCD)可以取代昂贵的DMT原料, 研制可以实现这个过程的催化剂和反应机理具有十分重要的意义和应用前景, 这也是目前废弃聚酯转化方向的研究热点.
针对PET的链状结构、中间产物(DMT)的分子体积大(1.32-1.37nm)、“一锅”法化学升级制备DMCD需要醇解活性中心和加氢活性中心的协同作用以及适宜的孔径和表界面特性等. 本文制备了缺陷型磺酸化UiO-66_def-SO₃H负载的Ru基催化剂(Ru/UiO-66_def-SO₃H), 成功地利用该催化剂实现了废弃PET “一锅”法化学升级制备DMCD的新工艺. 表征结果显示, 与传统的微孔型Ru/UiO-66催化剂相比, Ru/UiO-66_def-SO₃H中生成了规则的介孔孔道(2.72和3.44 nm), 具有较大的比表面积和孔体积(分别为998 m²·g^-1和0.83 cm³·g^-1), 酸量大(580 μmol·g^-1), 亲/疏水性(接触角为22.9°)适宜, Ru与载体(Zr-O)相互作用较强, Ru分散度高(45.1%)等优势. Ru/UiO-66_def-SO₃H催化剂在单独的PET醇解到DMT, 以及DMT加氢到DMCD过程中都具有较好的活性, 这主要归因于配位不饱和Zr-O节点的暴露以及-SO₃H的引入可以增加酸性位点(PET醇解活性位点)的数量, 介孔孔道有利于DMT/DMCD等的扩散, 亲水性能提升能够增强带有末端羟基的PET及其低聚物的吸附, 而且Ru的分散度高, 与载体的强相互作用, 催化剂的酸性等也可以进一步促进DMT加氢反应的进行. 上述特征也是废弃PET “一锅”法化学升级制备DMCD的关键. 然后, 直接以PET为原料, 发现在m(cat.)/m(PET) = 0.05 g·g^-1, 170 °C, 3 MPa H₂条件下反应6 h, PET完全转化(100%), DMCD产率高达97.7%. 并且, Ru/UiO-66_def-SO₃H在PET基废弃产品(饮料瓶, 纺织纤维, 包装膜)直接化学升级为DMCD反应中也具有较好的性能. 最后, 通过详细表征反应液中的可溶产物和残余固体的组成, 并结合理论计算, 分析了PET醇解以及DMT加氢的反应路径和机理, 发现PET “一锅”法化学升级制备DMCD首先需要在催化剂的酸性中心作用下醇解解聚成中间体DMT, 然后DMT再进一步加氢. 可以实现上述步骤有效衔接的关键是催化剂的酸性、加氢活性、介孔结构和表面亲疏水性的高效协同.
综上, 本工作中研制的缺陷型磺酸化Ru/UiO-66_def-SO₃H催化剂可以将酸性中心、加氢活性中心和介孔结构和表面亲疏水性等高效地组合在一起, 这些特性的协同作用弥补了各自的不足. 该催化剂在单独的PET醇解、DMT加氢以及废弃PET “一锅”法化学升级制备DMCD反应中都具有优异的活性. 本文为设计和合成高效催化剂以及废弃PET的化学升级转化提供了新思路.

关键词: 废弃聚对苯二甲酸乙二醇酯, 化学升级, 1,4-环己烷二甲酸二甲酯, Ru/UiO-66_def-SO₃H

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

区维韬, 叶莹丹, 张艺濒, 赵怀远, 杜玮辰, 侯昭胤. 废弃PET化学升级为DMCD的缺陷型磺酸化Ru/UiO-66_def-SO₃H催化剂[J]. 催化学报, 2025, 71: 363-374.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60242-1

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图/表 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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废弃PET化学升级为DMCD的缺陷型磺酸化Ru/UiO-66_def-SO₃H催化剂

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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