Renewable Alkanes

Recently, extensive efforts have been made to synthesize liquid hydrocarbons from biomass feedstocks. In 2004, Dumesic and co-workers reported that a clean stream of alkanes could be produced by aqueous phase reforming of sorbitol over a bifunctional catalyst. The sugar is repeatedly dehydrated using a solid acid catalyst and then hydrogenated using a precious metal catalyst such 

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Huber GW, Cortright RD, Dumesic JA (2004) Renewable alkanes by aqueous-phase reforming of biomass-derived oxygenates. Angew Chem Int Ed 43 1549-1551... 

Chen, L.G., Li, H.W., et al., 2016. Catal3ftic hydroprocessing of fatty acid methyl esters to renewable alkane fuels over Ni/HZSM-5 catalyst. Catalysis Today 259, 266—276. 

Alkanesulfonates are the petrochemically derived sulfur analogs of soaps, which are alkane carboxylates based on renewable resources. The main difference between alkanesulfonates and soaps is, however, that alkanesulfonates consist of a rather complex mixture of homologs with different carbon chain lengths and isomers with an almost statistical distribution of the functional group along the hydrophobic carbon chain (Fig. 1), whereas soap is a mixture of homologs of alkane 1-carboxylates with an even number of carbon atoms. 

Davda, R. R. Shabaker, J. W. Huber, G. W. Cortright, R. D. Dumesic, J. A., A review of catalytic issues and process conditions for renewable hydrogen and alkanes by aqueous-phase reforming of oxygenated hydrocarbons over supported metal catalysts. Applied Catalysis B 2005,56,171. 

It is now superflous to point out the renewed interest for the Fischer-Tropsch (F-T) synthesis (j) i. . the conversion of CO+H2 mixtures into a broad range of products including alkanes, alkenes, alcohols. Recent reviews (292.9k ) emphasized the central problem in F-T synthesis1 selectivity or more precisely chain-length control. 

Considerable attention has been paid to the application of CNTs as the catalyst support for Fischer Tropsch synthesis (FTS), mainly driven by utilization of the confinement effect (Section 15.2.3). In general, this process is a potential alternative to synthesize fuel (alkanes) or basic chemicals like alkenes or alcohols from syngas, which can be derived from coal or biomass. The broad product spectrum, which can be controlled only to a limited extent by the catalyst, prohibited its industrial realization so far, however, it is considered an important building block for future energy and chemical resource management based on renewables. 

Advances in petroleum characterization at the molecular structure level by GC-MS methods renewed interest in OSC. Within the past few years, at least one-thousand new and novel OSC that previously were not known to be present in petroleum and bitumens have been reported. Tentative molecular structures inferred from GC-MS and other techniques have been confirmed in many cases by synthesis of authentic reference-compounds. The difficult and time-consuming synthetic work has been crucial in validating many of the novel structures. Another key finding has been that immature bitumens and crude oils (samples that have not received significant thermal stress) differ markedly from the previously known OSC in that they have carbon-skeletons resembling ubiquitous biomarker hydrocarbons (e.g., n-alkanes, isoprenoid alkanes, steranes, and hopanes). This similarity, of course, suggests that the hydrocarbons and OSC have common biogenic precursors. 

In recent years, the production of simple hydrocarbrnis from biomass has attracted strong interest in the renewables community, due to the fact that the products are considered drop-in substitutes for petroleum-derived alkanes, with evident applications to fuels and chemical production. HMF has received much attention in this regard as a platform for extended carbon chain products, the hydrodeoxygenation (HDO) of which gives products which are essentially diesel or aviation fuels, depending on their hydrocarbon distribution. Aldol-type condensation reactions can take place in aqueous solution between HMF (or its derivatives) and biogenic ketones... 

The metal-catalysed C-H bond dual activation and functionalisation have brought in the last two decades a revolution for the direct synthesis of complex molecules and molecular materials. Now the functionalisation of sp C-H bond for cross-coupled C-C or C-heteroatom bond formation presents advantages to replace, with better atom economy, the classical catalytic cross-coupling reactions involving a stoichiometric amount of an organometallic. In parallel the sp C-H bond activation, besides a faster access to natural products, is offering the possibility to functionalise alkanes in connection with renewable energy. 

The three major sources of alkanes throughout the world are the fossil fuels, namely natural gas, petroleum, and coal. Fossil fuels accoimt for approximately 85% of the total energy consumed in the United States. Nuclear electric power, hydroelectric power, and renewable energy sources such as solar and wind power make up most of the remaining 15%. In addition, fossil fuels provide the bulk of the raw materials used to make organic chemicals. 

Davda, R., Shabaker, W., Huber, W., Cortright, D. Dumesic, A. (2005). A Review of Catalytic Issues and Process Conditions for Renewable Hydrogen and Alkanes by Aqueous-phase Reforming of Oxygenated Hydrocarbons over Supported Metal Catalysts. Applied Catalysis B Environmental, Vol. 56, No. 1-2, (March 2005), pp. 171-186, ISSN 09263373... 

Bond JQ, Upadhye AA, Olcay H, Tompsett GA, Jae J, Xing R, et al. Production of renewable jet fuel range alkanes and commodity chemicals from integrated catalytic processing of biomass. Energy Environ Sci 2014 7 1500-23. 

In the other paper, a completely renewed potential energy function for alkanes and cycloalkanes was optimised. In form it is a GVPP with Morse functions for C-C and C-H bond deformations, and with numerous cross terms. Por non-bonded interactions, Lennard-Jones 9-6 plus Coulomb terms were transferred from previous work d... 

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