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Bonrath, Werner; Bruins, Maaike J.; Mair, Peter; Medlock, Jonathan; Netscher, Thomas; Schütz, Jan; Wüstenberg, Bettina

doi:10.1002/0471238961.2209200101181421.a01.pub2

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“…The process is carried out at industrial scale in pressurised (2-5 bar) batch liquid phase reactors over Pd catalysts. 1 A shift from batch to continuous operation reduces the number of processing steps, which improves environmental performance (E-factor reduction from 23 → 3 kg waste generated kg product -1 ). 2 Alkynols can be classified based on the number of substituents bonded to the hydroxyl C as primary, secondary and tertiary (i.e.…”

Section: Introductionmentioning

confidence: 99%

Zn-Promoted Selective Gas-Phase Hydrogenation of Tertiary and Secondary C4 Alkynols over Supported Pd

González-Fernández

Berenguer-Murcia

Cazorla‐Amorós

et al. 2020

ACS Appl. Mater. Interfaces

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We have investigated the gas phase (P = atm; T = K) hydrogenation of (tertiary alkynol) 2methyl-3-butyn-2-ol (MBY) and (secondary) 3-butyn-2-ol (BY) over a series of carbon (C), nonreducible (Al 2 O 3 and MgO) and reducible (CeO 2 and ZnO) supported mono-(Pd (0.6-1.2% wt.) and Zn (1% wt.)) and bi-metallic Pd-Zn (Pd:Zn mol ratio = 95:5, 70:30 and 30:70) catalysts synthesised by deposition-precipitation and colloidal deposition. The catalysts have been characterised by H 2 chemisorption, hydrogen temperature-programmed desorption (H 2 -TPD), specific surface area (SSA), X-ray photoelectron spectroscopy (XPS) and transmission (TEM) and scanning transmission electron microscopy (STEM) analyses. Reaction over these catalysts generated the target alkenol (2-methyl-3-buten-2-ol (MBE) and 3-buten-2-ol (BE)) through partial hydrogenation and alkanol (2-methyl-butan-2-ol (MBA) and 2-butanol (BA))/ketone (2butanone (BONE)) as a result of full hydrogenation and double bond migration. The catalysts exhibit a similar Pd nanoparticle size (2.7 ± 0.3 nm) but modified electronic character (based on XPS). Hydrogenation activity is linked to surface hydrogen (from H 2 chemisorption and H 2 -TPD). An increase in H 2 :Alkynol (from 1→10) results in enhanced alkynol consumption with greater rate in the transformation of MBY (vs. BY); H 2 :Alkynol had negligible effect on product distribution. Reaction selectivity is insensitive to Pd site electron density with a similar response (S MBE = 65 ± 9% and S BE = 70 ± 8%) over Pd δ-(on Al 2 O 3 and MgO) and Pd δ+ (on C and CeO 2 ).

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Section: Introductionmentioning

confidence: 99%