Selective catalytic hydrogenation of 2-butyne-1,4-diol to cis-2-butene-1,4-diol in mass transfer efficient slurry reactors

Winterbottom, J. M.; Marwan, H.; Viladevall, J.; Sharma, Sathyashankara; Raymahasay, S.

doi:10.1016/s0167-2991(97)80888-9

Cited by 38 publications

(38 citation statements)

References 10 publications

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“…Hydrogen pretreatment of the catalyst was found to enhance the catalyst activity possibly due to the formation of highly active β-Pd _ H sites. The cata lyst was found to retain its activity up to ten recycles giving a total TON of 1.86×10 4 , which is an order of magnitude higher than the literature value. A rate equation has been proposed based on the initial rate data and intrinsic kinetic parameters were evaluated.…”

Section: Discussionmentioning

confidence: 55%

Catalytic Hydrogenation of 2-Butyne-1,4-diol: Activity, Selectivity and Kinetics Studies

Rode

2008

J. Jpn. Petrol. Inst.

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The reaction pathway for hydrogenation of 2-butyne-1,4-diol involves parallel and consecutive isomerization as well as hydrogenation reactions forming other side products along with cis-2-butene-1,4-diol and butane-1,4-diol. Hence, achieving the highest selectivity to butene-and/or butanediol is critical from industrial point of view. Hydrogenation of butynediol is also of fundamental significance, due to its adsorption characteristics leading to the formation of active species and their role in determining the product distribution. Studies on designing various catalyst systems including colloidal as well supported palladium nanoparticles for the hydrogenation of butynediol, role of additives, catalyst pretreatment, kinetic studies carried out in our group has been presented in this review. Interestingly, almost complete selectivity to the intermediate olefinic diol was achieved with 1％ Pd/CaCO3 _ NH3 catalyst system. This could be due to the competitive adsorption of ammonia on the palladium surface along with the substrate 2-butyne-1,4-diol. Studies on catalyst pretreatment and kinetics using palladium catalyst have also been presented here. Nanostructure palladium both colloidal as well as supported catalysts showed a very high catalytic activity (10-40 times more) in the hydrogenation 2-butyne-1,4-diol to cis-2-butene-1,4-diol compared with the corresponding conventional Pd catalysts. For platinum based catalysts, formation of side products was completely eliminated in the hydrogenation of butyne diol. The increase in the basic strength of alkali metal doped Pt catalysts measured by CO2-TPD, led to the increase in electron density of Pt hence, faster desorption and higher selectivity to butenediol. In the case of continuous hydrogenation, the selectivity pattern was completely different from that found in the case of batch slurry reactor and by varying the contact time, the selectivity to both butene-and butanediols could be varied over a wide range of conditions.

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Section: Discussionmentioning

confidence: 55%

Catalytic Hydrogenation of 2-Butyne-1,4-diol: Activity, Selectivity and Kinetics Studies

Rode

2008

J. Jpn. Petrol. Inst.

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“…Pd supported on active carbon ÿl-aments (ACF) in the form of woven fabrics was tested for activity=selectivity in this reaction. Metallic palladium is known to selectively reduce triple bonds (Tedeschi & Clark, 1962) and Pd=C catalysts are known to hydrogenate 2-butyne-1,4-diol to 2-butene-1,4-diol with selectivity up to ¿ 99% (Chaudhari, Gholap, Emig, & Hofmann 1987a;Chaudhari, Jaganathan, Kohle, Emig, & Hofmann, 1987b;Winterbottom et al, 1997). The use of activated carbon in the form of ÿlamentous woven materials as catalytic supports have been already reported in the scientiÿc literature (Jin, Park, Lee, & Ryu, 1996;Mochida et al, 1997;Mochida et al, 1997a,b;Perez et al, 1997;Yoshikawa, Yasutake, & Mochida, 1998;Moon, Park, Kim, & Seo, 1999;Ryu, Kim, Li, & Jaroniec, 1999;Mochida et al, 2000).…”

Section: Introductionmentioning

confidence: 94%

“…The reaction is usually carried out in an aqueous solution at elevated pressures (Hort & Graham, 1962;Ho mann et al, 1974). The reaction network (Winterbottom et al, 1997) is schematically presented in Fig. 1, showing that the target product, cis-2-butene-1,4-diol, is an intermediate and can undergo further hydrogenation.…”

Section: Introductionmentioning

confidence: 99%

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Palladium supported on filamentous active carbon as effective catalyst for liquid-phase hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol

Joannet

Horny

Kiwi‐Minsker

et al. 2002

Chemical Engineering Science

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Structured palladium catalysts suitable for three-phase reactions have been developed based on woven fabrics of active carbon ÿbres (ACF) as the catalytic supports. The Pd=ACF were tested in liquid-phase hydrogenation of 2-butyne-1,4-diol showing a selectivity towards 2-butene-1,4-diol up to 97% at conversions up to 80%. The catalyst multiple reuse with stable activity=selectivity in a batch reactor was also demonstrated. The reaction kinetics was studied and the main kinetic parameters were obtained. Assuming a Langmuir-Hinshelwood kinetics and a weak hydrogen adsorption a suitable kinetic model was developed consistent with the experimental data. ?

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“…The basic g-Al 2 O 3 containing hydroxyl groups [26] is often used as support for the hydrogenation catalysts [21,22,24,27] and therefore was employed by us in this work. The hydrogenation product 2-butene-1,4-diol (B2) is industrially important since it is used as an intermediate in the production of endosulfan, vitamins A and B 6 , as well as in the paper, textile and resin industries [28,29].…”

Section: Introductionmentioning

confidence: 99%

Palladium nanoparticles stabilized in block-copolymer micelles for highly selective 2-butyne-1,4-diol partial hydrogenation

Semagina

Joannet

Parra

et al. 2005

Applied Catalysis A: General

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Pd nanoparticles (2 nm) stabilized in the micelle core of poly(ethylene oxide)-block-poly-2-vinylpyridine were studied in 2-butyne-1,4-diol partial hydrogenation. Both unsupported micelles (0.6 kg Pd /m 3 ) and supported ones on g-Al 2 O 3 (0.042 wt.% Pd) showed nearly 100% selectivity to 2-butene-1,4-diol up to 94% conversion. The only side product observed was 2-butane-1,4-diol. The catalysis was ascribed to Pd nanoparticles' surface modified by pyridine units of micelles and alkali reaction medium (pH of 13.4). TOFs over the unsupported and supported catalysts were found to be 0.56 and 0.91 s À1 (at 323 K, 0.6 MPa H 2 pressure, solvent 2-propanol/water = 7:3), respectively. Reaction kinetics fit the Langmuir-Hinshelwood model assuming weak hydrogen adsorption. The experiments on the catalyst reuse showed that Pd nanoparticles remain inside the micelle core, but the micelles slightly desorbed (less then 5%) during the catalytic run. #

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Selective catalytic hydrogenation of 2-butyne-1,4-diol to cis-2-butene-1,4-diol in mass transfer efficient slurry reactors

Cited by 38 publications

References 10 publications

Catalytic Hydrogenation of 2-Butyne-1,4-diol: Activity, Selectivity and Kinetics Studies

Catalytic Hydrogenation of 2-Butyne-1,4-diol: Activity, Selectivity and Kinetics Studies

Palladium supported on filamentous active carbon as effective catalyst for liquid-phase hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol

Palladium nanoparticles stabilized in block-copolymer micelles for highly selective 2-butyne-1,4-diol partial hydrogenation

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