The gas-phase deoxydehydration of 2,3-butanediol to butene was investigated in aplug flow reactor over SiO 2 -supported vanadium oxide, g-alumina, P/ZSM-5, andM gO catalysts with acid/bases ites of varying strengths. 5wt% vanadium on SiO 2 (i.e.,5V/SiO 2 )s howedt he best performance with 100 %conversion and up to 45.2 %b utene selectivity.T he combination of weak acid sites and polymericV O x surfaces peciesp rovided the 5V/SiO 2 catalystw ith bifunctional capabilities to achieve both dehydration and transfer hydrogenation, which allowed it to catalyze the deoxydehydration of 2,3-butanediol to butene even in the absence of H 2 .A s2 ,3-butanediol is ac ommon yet underutilized biomassp roduct, this reactionm ay provide av iable route for ab iomass-to-chemicals application for 2,3butanediol.Upgrading of biomass to fuels and chemicals is important for sustainable human development, and intense studiesa re being undertaken to find new technologiest oc onvert the large amount of availablebioderived oxygenates into fuels and chemicals. [1] The vicinal diol 2,3-butanediol (2,3-BDO) is ac ommon biomass product that is synthesized by using bacteria sugars derived from biomass feedstock such as corn starch. [1c] It has great potentialt or eplaces ynthetic 2,3-BDO in the market owing to its cost effectiveness relative to the chemical hydrolysis of 2,3-butene oxide. Whereas its other isomers such as 1,4-butanediola nd 1,3-butanediol have been widely studied for their conversion into other chemicals such as tetrahydrofuran and butyrolactone, [2] these cyclization reactions are not availablef or 2,3-BDO owing to the vicinal positiono fi ts OH groups.T hus, 2,3-BDO is much less studied than 1,4-and 1,3-butanediol, although it could follow multiple oxidation, reduction, and dehydration pathways. [1c,d] The dehydration of 2,3-BDO mainly produces butanone (also knowna sm ethyl ethyl ketone, MEK) and 2-methylpropanal (MPA) through aE 1/E2 mechanism followed by 1,2-rearrangement by hydride and methyl shifts, respectively. [2a] This is readily achieved on acid sites, such as those availablei np hosphate catalysts or zeolites. [3] However,t he doubled ehydration of 2,3-BDO to butadiene is more challenging than that of 1,4-butanediol because the carbonyl compounds MEK and MPAf ormed from 2,3-BDOa re more difficult to dehydrate further than enol compounds such as 3-buten-1-ol, whicha re typically formed from 1,4-butanediol. [4] Alternatively,Z heng et al. recently reported aC u/ZSM5 catalyst that could convert2 ,3-BDOi nto butene in the presence of an excess amount H 2 withoutf urther hydrogenation to butane. [5] In this study,t he gas-phase conversion of 2,3-BDO was performed over SiO 2 -supported vanadium oxide, g-alumina, P/ ZSM-5, and MgO catalysts with acid/base sites of varying strengths. We show that ad eoxydehydration pathway of 2,3-BDO to butene in the absence of H 2 exists that proceeds through ah ydrogen-donor mechanism from 2,3-BDO to MEK over vanadium oxide (VO x )s urfaces ites.The ammonia temperature-programmed d...
A low-olefin production process was developed with natural gas as the feedstock. The proposed process directly generates low olefins based on the Fischer−Tropsch synthesis reaction. Techno-economic assessments were conducted to evaluate the economic aspects of the developed process, whereby data were compared to that of the counterpart gas-to-liquid process. Results showed that the Fischer−Tropsch to olefins process has good economic prospects. This work provides a feasible approach for a low-olefin production process through process synthesis and optimization. Input chilling utilities could be reduced by 45% compared to that before the exergy recuperation and heat integration, while the heating utilities could be reduced to 0 MMBtu/h. Effects of catalyst's selectivity to low olefins on the economic performance of the proposed process were also analyzed.
The Cover shows the green Supertree Grove from the authors’ country, symbolizing the artificial processing of biomass‐derived 2,3‐butanediol, which is catalytically converted to butene, methyl ethyl ketone, acetaldehyde and other industrial chemicals. It represents the harmony between biotechnology and the chemical industry realized by a biomass‐to‐chemicals application.In their Communication, K. M. Kwok et al. demonstrate that 2,3‐butanediol, a product of bacteria fermentation, can be catalytically converted to butene on vanadium oxide catalysts through deoxydehydration without external H2, involving a transfer hydrogenation mechanism supported by studies of the intermediates and surface spectroscopic analysis. More information can be found in the Communication by K. M. Kwok et al. on page 2443 in Issue 13, 2017 (DOI: 10.1002/cctc.201700301).
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