Hydrogenation of Dicyclopentadiene Resin and Its Monomer over High Efficient CuNi Alloy Catalysts

Abstract

Dicyclopentadiene (DCPD) resin polymerized by DCPD contains a large number of unsaturated bonds, hydrogenation plays an important role in enhancing its thermal stability and decoloring. Herein, a series of supported Cu−Ni‐Al catalysts with high distribution and large surface areas derived from direct reduction of hydrotalcite‐like compounds have been synthesized. The hydrogenation properties of supported Cu−Ni‐Al catalysts for the DCPD resin and its monomer have been investigated. The Cu1Ni3‐Al2O3 catalyst shows the highest DCPD conversion (>99%) and selectivity to tetrahydrodicyclopentadiene (THDCPD) (>98%) under mild conditions (40 °C, 2 MPa H2) compared with the corresponding catalysts prepared by impregnation and mechanically mixed method. Due to the high particle dispersion of active‐sites and the synergistic effect between metallic Cu and Ni, the optimal catalyst (Cu1Ni3‐Al2O3) also presents an expected catalytic activity in the hydrogenation of DCPD resin.

Structure Evolution of Ni–Cu Bimetallic Catalysts Derived from Layered Double Hydroxides for Selective Hydrogenation of Furfural to Tetrahydrofurfuryl Alcohol

“…Various Cu x Ni y /MgAl-LDH hydrotalcite precursors with different Cu/Ni molar ratios (M 2+ /M 3+ = 2, x / y = 3:1, 1:1, 1:3) were fabricated by a coprecipitation method . To get a better process of precipitation, in this typical experiment, 60 mL of aqueous solution of corresponding 50 mmol of metal nitrates including Cu­(NO 3 ) 2 ·H 2 O, Ni­(NO 3 ) 2 ·6H 2 O, Mg­(NO 3 ) 2 ·6H 2 O, and Al­(NO 3 ) 3 ·9H 2 O (the detail was shown in Table S1) and 120 mL of sodium hydroxide solution (1 mol/L) were dropped quite slowly and simultaneously into 8.5 mL of sodium carbonate solution (1 mol/L) by controlling the dropping rate of metal nitrates and sodium hydroxide solution at 1:2.…”

Rationally Constructing A Nano MOF-Derived Ni and CQD Embedded N-Doped Carbon Nanosphere for the Hydrogenation of Petroleum Resin at Low Temperature

“…Hence, transition metals, especially Ni, have been put forward as alternatives because of their abundant reserves and low cost. But suffering from the inferior intrinsic activities, PR hydrogenation over Ni-based catalysts is performed at a higher temperature (250–270 °C) up to now. − Such a rigorous reaction condition might lead to the depolymerization of PR, which vitally decreases its stability. In short, whether for the noble or non-noble catalyst, there has been no report on the highly effective PR hydrogenation below 200 °C so far.…”

Hierarchical Flower-Like NiCu/SiO2 Bimetallic Catalysts with Enhanced Catalytic Activity and Stability for Petroleum Resin Hydrogenation

“…To date, the catalysts for the hydrogenation of PR to produce high-quality HPR mainly include the palladium-based catalysts, − metal sulfide catalysts, ,, and nickel-based catalysts. − Bai et al reported the hydrogenation of dicyclopentadiene resin over supported palladium catalysts with high dispersity derived from the direct reduction of hydrotalcite-like compounds. Satisfactorily, the hydrogenation degree (HD) could be reached up to 96.5% after hydrogenation.…”

“…In addition, to maintain the sulfide state of the catalyst, a sulfur-containing agent should be added to the raw material, which will contaminate the product. In recent years, much effort has been made to develop nickel-based catalysts for the hydrogenation of PR. ,, Wei et al reported a small eggshell-type Ni-based catalyst over a fluid catalytic cracking catalyst residue for C 5 PR hydrogenation, and the results showed excellent catalytic activity, with the bromine value decreasing from 27 to 0.98 g Br/100 g after a two-stage hydrogenation process. Chen et al reported the preparation of Ni-PVP/PFC3R catalyst, with polyvinyl pyrrolidone (PVP) as a dispersant for C 9 PR hydrogenation, and the bromine value was reduced from 48.50 to 1.25 g Br/100 g. In order to further improve the activity of the Ni-based catalyst, Bai et al proposed highly dispersed Cu 1 Ni 3 –Al 2 O 3 catalysts by directly reducing hydrotalcite-like compounds for the hydrogenation of dicyclopentadiene, and the excellent catalytic performance with the conversion of 99% and selectivity to tetrahydrodicyclopentadiene of 98% could be reached due to the highly dispersed active sites and the synergistic effect between Cu and Ni.…”

“…However, it is well known that Pd is highly susceptible to irreversible deactivation by the poisoning of impurities such as S or Cl in the raw materials, which greatly shortens the service life of the catalysts. 10 Supported sulfide catalysts show high resistance to sulfur poisoning and good catalytic hydrogenation performance; 23 unfortunately, it can easily give rise to the degradation of PR, resulting in the decrease of the softening point of the products. In addition, to maintain the sulfide state of the catalyst, a sulfur-containing agent should be added to the raw material, which will contaminate the product.…”