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Le Touquet – Paris-Plage, France

Patent
French Institute of Petroleum, Axens, Total S.A., Sofiproteol, ThyssenKrupp and Bionext | Date: 2013-10-30

The present invention concerns an integrated process for the production of liquid hydrocarbons starting from a feed containing at least one fraction of biomass and optionally at least one fraction of another feed, said process comprising at least one pre-treatment step, a gasification step, a step for conditioning synthesis gas, a water scrubbing step, a step for eliminating acid gases, a final purification step, and a catalytic Fischer-Tropsch synthesis reaction step.


Process chains of thermo chemical conversion of lignocellulosic biomass through gasification and Fischer-Tropsch synthesis (known as BTL) represent promising alternatives for biofu-els production. Since biomass is heterogeneous and not homogeneously spread over territories, one of the major technological stakes of the project is to develop a flexible industrial chain capable of co-treating the widest possible range of biomass and fossil fuel feedstock. The present study aims at characterizing biomass diversity (availability and potentials by area, cost and mineral composition) by carrying out a state of the art, as a preliminary step in order to define a series of biomasses to be tested in the demonstration plant and therefore define specifications for the process. Fifty different biomasses were considered for their bioenergy application potential and were finally classified into four categories: agricultural by-products, dedicated energy crops, (Very) Short Rotation Coppice ((V)SRC) and forestry biomasses. Biomass availability and potentials were investigated by the mean of a literature review of past and current projects (e.g. RENEW project, Biomass Energy Europe Project, etc.) and scientific articles. Most collected data are technical potentials, meaning that they take into account biophysical limits of crops and forests, technological possibilities, competition with other land uses and ecological constraints (e.g. natural reserves). Results show various emerging markets: North and South America have considerable amounts of agricultural by-products, forest residues, and large land areas which could be dedicated to energy crops; Africa shows relevant possibilities to grow Short Rotation Forestry (SRF) and energy crops; Russia has large available quantities of agricultural by-products and forest residues, as well as little valuable land where energy crops and SRC could be grown, and Asia shows relevant amounts of forest residues and possibilities of growing SRC, as well as relevant quantities of agricultural residues (notably from palm oil cropping systems). To a lesser extent, Europe also presents significant amounts of agricultural co-products and forestry residues which could be available for bio-energy. Nevertheless an improvement of biomass supply structure is necessary to be in the position to answer the demand for BtL (Biomass to Liquid) industry. Mineral composition is also a relevant parameter to be considered for the thermochemical conversion process, since the Fischer-Tropsch catalysis - last step of the conversion process - is very sensitive to mineral elements of biomass. Concerning mineral composition of biomasses, five public databases were analysed to collect relevant characteristics and the information was aggregated in one large database dedicated to the project. Nitrogen, chlorine, phosphorus, sulphur, ash and energy contents are the major parameters collected. By analysing these data, we observe that fast-growing plants (typically agricultural co-products) contain much more minerals than low-growing crops (typically forest residues). This is mostly due to the fertilizers spread in the fields for the growth of agricultural crops. Consequently, agricultural by-products appear as the most constraining biomasses in terms of mineral contents. Regarding costs, a literature review was also carried out, with a special focus on the French case. Most data come from REGIX Programme and French organisms (FCBA, Association AILE, etc.). This allowed us to observe that agricultural by-products are the cheapest biomasses (10 to 15 €/MWh, equivalent to 50 to 75 €/TDM), as they are still considered as sub-products of grains. Their price is only driven by conditioning and transport costs. (Very) short rotation forestry bio-masses are slightly more expensive (13 to 17 €/MWh, equivalent to 70 to 90 €/TDM), due to harvest costs, but they remain cheaper than energy crops (20 to 22 €/MWh, equivalent to 95 to 110 €/TDM), whose crop management practices (basically phytosanitary treatments and fertilization) increase costs. Finally, forestry wood chips show very variable prices (11 to 25 €/MWh, equivalent to 60 to 130 €/TDM), depending on the costs attributed to wood material, technology used, access to the plots, and the use of storage platform or not. © 2013, IFP Energies nouvelles.


Sutter M.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry | Pehlivan L.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry | Lafon R.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry | Dayoub W.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry | And 3 more authors.
Green Chemistry | Year: 2013

1,2,3-Trimethoxypropane (1,2,3-TMP) was prepared from glycerol in one step in good yield and selectivity by phase transfer catalysis. According to OECD guidelines, a toxicity study was realized for this compound. It revealed that 1,2,3-TMP has a low acute toxicity, no skin sensitization, no mutagenicity and no ecotoxicity in an aquatic environment. This compound was also used as a solvent for the reduction of organic functions using either aluminium hydride or 1,1,3,3-tetramethyldisiloxane (TMDS) as a benign hydride source. In particular, a new process for the reduction of nitriles to amines in 2-MeTHF and in 1,2,3-TMP was developed, using TMDS in combination with copper triflate (Cu(OTf)2). © 2013 The Royal Society of Chemistry.


Sutter M.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry | Dayoub W.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry | Metay E.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry | Raoul Y.,Sofiproteol | Lemaire M.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry
Green Chemistry | Year: 2013

From available and bio-sourced methyl esters, monoglycerides or oleic sunflower refined oil, the corresponding 1-O-alkyl (di)glycerol ethers were obtained in both high yields and selectivity by two different pathways. With methyl esters, a reductive alkylation with (di)glycerol was realized under 50 bar hydrogen pressure in the presence of 1 mol% of Pd/C and an acid co-catalyst. A second two step procedure was evaluated from methyl esters or triolein and consisted of a first transesterification to the corresponding monoglyceride with a BaO/Al2O3 catalyst, then its reduction to the desired glycerol monoether with a recyclable heterogeneous catalytic system Pd/C and Amberlyst 35 under H2 pressure. In addition, a mechanism for the reaction was also proposed. This journal is © 2013 The Royal Society of Chemistry.


Da Silva E.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry | Dayoub W.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry | Mignani G.,Rhodia | Raoul Y.,Sofiproteol | Lemaire M.,CNRS Institute of Molecular and Supramolecular Chemistry and Biochemistry
Catalysis Communications | Year: 2012

The synthesis of propylene carbonate from propylene glycol and carbon dioxide in the presence of various catalysts has been reported. Benzonitrile has been used as both solvent and dehydrating agent. Under optimal conditions, the best results were obtained in the presence of alkali carbonate catalysts. The propylene carbonate yield could reach up to 20% with a propylene-1,2-glycol conversion of 44%. © 2012 Elsevier B.V.

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