Reconstruction of Cu–ZnO catalyst by organic acid and deactivation mechanism in liquid-phase hydrogenation of dimethyl succinate to 1,4-butanediol

Abstract

A reconstructed Cu–ZnO catalyst with improved stability was fabricated by organic acid treatment method for the liquid-phase hydrogenation of dimethyl succinate to 1,4-butanediol. According to the characterization results of the fresh Cu–ZnO and reconstructed Cu–ZnO, three different forms of ZnO were suggested to be presented on the catalysts: ZnO having strong interaction with Cu species, ZnO that weakly interacted with Cu species and isolated ZnO. The first form of ZnO was believed to be beneficial to the formation of efficient active site Cu⁺, while the latter two forms of ZnO took the main responsibility for the deactivation of Cu–ZnO catalysts in the liquid-phase hydrogenation of diesters. The reconstruction of the Cu–ZnO catalyst by the organic acid treatment method resulted in a new Cu–ZnO catalyst with more Cu⁺ and less ZnO species that leads to deactivation. Furthermore, the deactivation mechanism of Cu–ZnO catalysts in liquid-phase diester hydrogenation in continuous flow system was proposed: the deposition of the polyesters on the catalysts via transesterification catalyzed by weakly interacted ZnO and isolated ZnO leads to the deactivation. These results provided meaningful instructions for designing highly efficient Cu–Zn catalysts for similar ester hydrogenation systems.

Key words： liquid phase; hydrogenation; Cu–ZnO; deactivation mechanism; 1,4-butanediol; diester

Acknowledgements

We are grateful for the financial support from the National Natural Science Foundation of China (Grant Nos. 21878227 and 22278309).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2281-9 and is accessible for authorized users.

References

1 Le S D, Nishimura S. Effect of support on the formation of CuPd alloy nanoparticles for the hydrogenation of succinic acid. Applied Catalysis B: Environmental, 2021, 282: 119619

2 Shang J J, Yao G, Guo R H, Zheng W, Gu L, Lan J W. Synthesis and characterization of biodegradable thermoplastic elastomers derived from N′,N-bis(2-carboxyethyl)-pyromellitimide, poly(butylene succinate) and polyethylene glycol. Frontiers of Chemical Science and Engineering, 2018, 12(3): 457–466

3 Zhou X M. Synthesis and characterization of polyester copolymers based on poly(butylene succinate) and poly(ethylene glycol). Materials Science and Engineering C, 2012, 32(8): 2459–2463

4 Huang Z W, Barnett K J, Chada J P, Brentzel Z J, Xu Z R, Dumesic J A, Huber G W. Hydrogenation of γ-butyrolactone to 1,4-butanediol over CuCo/TiO₂ bimetallic catalysts. ACS Catalysis, 2017, 7(12): 8429–8440

5 Delhomme C, Weuster-Botz D, Kühn F E. Succinic acid from renewable resources as a C4 building-block chemical—a review of the catalytic possibilities in aqueous media. Green Chemistry, 2009, 11(1): 13–26

6 Chen L F, Guo P J, Zhu L J, Qiao M H, Shen W, Xu H L, Fan K N. Preparation of Cu/SBA-15 catalysts by different methods for the hydrogenolysis of dimethyl maleate to 1,4-butanediol. Applied Catalysis A: General, 2009, 356(2): 129–136

7 Ohlinger C, Kraushaar-Czarnetzki B. Improved processing stability in the hydrogenation of dimethyl maleate to γ-butyrolactone, 1,4-butanediol and tetrahydrofuran. Chemical Engineering Science, 2003, 58(8): 1453–1461

8 Ying J T, Han X Q, Ma L, Lu C S, Feng F, Zhang Q F, Li X N. Effects of basic promoters on the catalytic performance of Cu/SiO₂ in the hydrogenation of dimethyl maleate. Catalysts, 2019, 9(9): 704–713

9 Müller S P, Kucher M, Ohlinger C, Kraushaar-Czarnetzki B. Extrusion of Cu/ZnO catalysts for the single-stage gas-phase processing of dimethyl maleate to tetrahydrofuran. Journal of Catalysis, 2003, 218(2): 419–426

10 Li S M, Wang Y, Zhang J, Wang S P, Xu Y, Zhao Y J, Ma X B. Kinetics study of hydrogenation of dimethyl oxalate over Cu/SiO₂ catalyst. Industrial & Engineering Chemistry Research, 2015, 54(4): 1243–1250

11 Wang W C, Wang H, Zhang J W, Kong L X, Huang H J, Liu W, Wang S P, Ma X B, Zhao Y J. Determining roles of Cu⁰ in the chemosynthesis of diols via condensed diester hydrogenation on Cu/SiO₂ catalyst. ChemCatChem, 2020, 12(15): 3849–3852

12 Zhao Y J, Guo Z Y, Zhang H J, Peng B, Xu Y X, Wang Y, Zhang J, Xu Y, Wang S P, Ma X B. Hydrogenation of diesters on copper catalyst anchored on ordered hierarchical porous silica: pore size effect. Journal of Catalysis, 2018, 357: 223–237

13 Schlander J H, Turek T. Gas-phase hydrogenolysis of dimethyl maleate to 1,4-butanediol and γ-butyrolactone over copper/zinc oxide catalysts. Industrial & Engineering Chemistry Research, 1999, 38(4): 1264–1270

14 Küksal A, Klemm E, Emig G. Single-stage liquid phase hydrogenation of maleic anhydride to γ-butyrolactone, 1,4-butanediol and tetrahydrofurane on Cu/ZnO/Al₂O₃ catalysts. Studies in Surface Science and Catalysis, 2000, 130: 2111–2116

15 Aubrecht J, Pospelova V, Kikhtyanin O, Lhotka M, Kubička D. Understanding of the key properties of supported Cu-based catalysts and their influence on ester hydrogenolysis. Catalysis Today, 2022, 397–399: 173–181

16 Ding G Q, Zhu Y L, Zheng H Y, Zhang W, Li Y W. Study on the reaction pathway in the vapor-phase hydrogenation of biomass-derived diethyl succinate over CuO/ZnO catalyst. Catalysis Communications, 2010, 11(14): 1120–1124

17 Besson M, Gallezot P. Deactivation of metal catalysts in liquid phase organic reactions. Catalysis Today, 2003, 81(4): 547–559

18 Wan X Y, Ren D Z, Liu Y J, Fu J, Song Z Y, Jin F M, Huo Z B. Facile synthesis of dimethyl succinate via esterification of succinic anhydride over ZnO in methanol. ACS Sustainable Chemistry & Engineering, 2018, 6(3): 2969–2975

19 Karanwal N, Sibi M G, Khan M K, Myint A A, Chan Ryu B, Kang J W, Kim J. Trimetallic Cu–Ni–Zn/H-ZSM-5 catalyst for the one-pot conversion of levulinic acid to high-yield 1,4-pentanediol under mild conditions in an aqueous medium. ACS Catalysis, 2021, 11(5): 2846–2864

20 Zhang L, Mao J B, Li S M, Yin J M, Sun X D, Guo X W, Song C S, Zhou J X. Hydrogenation of levulinic acid into gamma-valerolactone over in situ reduced CuAg bimetallic catalyst: strategy and mechanism of preventing Cu leaching. Applied Catalysis B: Environmental, 2018, 232: 1–10

21 Zhao Y J, Zhang Y Q, Wang Y, Zhang J, Xu Y, Wang S P, Ma X B. Structure evolution of mesoporous silica supported copper catalyst for dimethyl oxalate hydrogenation. Applied Catalysis A: General, 2017, 539: 59–69

22 Yao Y Q, Wu X Q, Gutierrez O Y, Ji J, Jin P, Wang S P, Xu Y, Zhao Y J, Wang S P, Ma X B, Lercher J A. Roles of Cu⁺ and Cu⁰ sites in liquid-phase hydrogenation of esters on core-shell CuZn_x@C catalysts. Applied Catalysis B: Environmental, 2020, 267: 118698

23 Zhang B, Chen Y, Li J W, Pippel E, Yang H M, Gao Z, Qin Y. High efficiency Cu–ZnO hydrogenation catalyst: the tailoring of Cu–ZnO interface sites by molecular layer deposition. ACS Catalysis, 2015, 5(9): 5567–5573

24 Dong X Q, Lei J W, Chen Y F, Jiang H X, Zhang M H. Selective hydrogenation of acetic acid to ethanol on Cu-In catalyst supported by SBA-15. Applied Catalysis B: Environmental, 2019, 244: 448–458

25 Zhang J W, Kong L X, Chen Y, Huang H J, Zhang H H, Yao Y Q, Xu Y X, Xu Y, Wang S P, Ma X B, Zhao Y. Enhanced synergy between Cu⁰ and Cu⁺ on nickel doped copper catalyst for gaseous acetic acid hydrogenation. Frontiers of Chemical Science and Engineering, 2021, 15(3): 666–678

26 Westen T V, Groot R D. Effect of temperature cycling on ostwald ripening. Crystal Growth & Design, 2018, 18(9): 4952–4962

27 Yan S, Salley S O, Simon Ng K Y. Simultaneous transesterification and esterification of unrefined or waste oils over ZnO-La₂O₃ catalysts. Applied Catalysis A: General, 2009, 353(2): 203–212

28 Yan S, Mohan S, DiMaggio C, Kim M, Ng K Y S, Salley S O. Long term activity of modified ZnO nanoparticles for transesterification. Fuel, 2010, 89(10): 2844–2852

29 Istadi I, Prasetyo S A, Nugroho T S. Characterization of K₂O/CaO-ZnO catalyst for transesterification of soybean oil to biodiesel. Procedia Environmental Sciences, 2015, 23: 394–399

30 Babu N S, Sree R, Prasad P S S, Lingaiah N. Room temperature transesterification of edible and nonedible oils using a heterogeneous strong basic Mg/La catalyst. Energy & Fuels, 2008, 22(3): 1965–1971

31 Wu X M, Zhu F F, Qi J J, Zhao L Y, Yan F W, Li C H. Challenge of biodiesel production from sewage sludge catalyzed by KOH, KOH/activated carbon, and KOH/CaO. Frontiers of Environmental Science & Engineering, 2017, 11(2): 3–13

32 Kikhtyanin O, Aubrecht J, Pospelova V, Kubička D. On the origin of the transesterification reaction route during dimethyl adipate hydrogenolysis. Applied Catalysis A: General, 2020, 606: 117825