{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T03:53:45Z","timestamp":1790740425110,"version":"4.1.0"},"reference-count":40,"publisher":"Wiley","issue":"52","license":[{"start":{"date-parts":[[2017,8,16]],"date-time":"2017-08-16T00:00:00Z","timestamp":1502841600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001665","name":"Agence Nationale de la Recherche","doi-asserted-by":"publisher","award":["ANR-12-CD2I-0002"],"award-info":[{"award-number":["ANR-12-CD2I-0002"]}],"id":[{"id":"10.13039\/501100001665","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2017,9,18]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A practical and cost\u2010effective ruthenium\u2010catalyzed self\u2010metathesis of non\u2010refined methyl oleate (85\u2009%) derived from very high oleic sunflower oils was demonstrated at pilot scale using a robust and kg\u2010scale commercially available SIPr\u2010M71 pre\u2010catalyst. The simple addition of 1\u2005wt\u2009% bleaching earths (Tonsil 110FF) to a thermally pretreated oil could efficiently prevent catalyst deactivation. Remarkably, without the need for filtration, the catalytic system was able to achieve a turnover number (TON) of more than 744\u2009000 at a catalyst loading of only 1\u2005ppm. At large scale (up to 200\u2005kg), the equilibrium of the self\u2010metathesis reaction was reached within 1\u2005hour at 50\u2009\u00b0C under neat conditions at a very low 5\u2005ppm catalyst loading to produce the expected primary metathesis products (PMP), that is, 9\u2010octadecene and dimethyl\u20109\u2010octadecenoate, with a productive TON of 94900.<\/jats:p>","DOI":"10.1002\/chem.201703049","type":"journal-article","created":{"date-parts":[[2017,7,3]],"date-time":"2017-07-03T12:17:09Z","timestamp":1499084229000},"page":"12729-12734","source":"Crossref","is-referenced-by-count":15,"title":["Bleaching Earths as Powerful Additives for Ru\u2010Catalyzed Self\u2010Metathesis of Non\u2010Refined Methyl Oleate at Pilot Scale"],"prefix":"10.1002","volume":"23","author":[{"given":"Jessica","family":"Allard","sequence":"first","affiliation":[{"name":"Ecole Nationale Sup\u00e9rieure de Chimie de Rennes UMR CNRS 6226  11 All\u00e9e de Beaulieu, CS 50837 35708 Rennes Cedex 7 France"},{"name":"OLEON SAS, Venette BP 20609  60206 Compi\u00e8gne Cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Idriss","family":"Curbet","sequence":"additional","affiliation":[{"name":"Ecole Nationale Sup\u00e9rieure de Chimie de Rennes UMR CNRS 6226  11 All\u00e9e de Beaulieu, CS 50837 35708 Rennes Cedex 7 France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guillaume","family":"Chollet","sequence":"additional","affiliation":[{"name":"ITERG  11 rue Monge-Parc industrie Bersol 2 33600 Pessac France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fabien","family":"Tripoteau","sequence":"additional","affiliation":[{"name":"DEMETA SAS  6 rue Pierre-Joseph Colin 35000 Rennes France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sophie","family":"Sambou","sequence":"additional","affiliation":[{"name":"OLEON SAS, Venette BP 20609  60206 Compi\u00e8gne Cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fr\u00e9d\u00e9ric","family":"Caijo","sequence":"additional","affiliation":[{"name":"DEMETA SAS  6 rue Pierre-Joseph Colin 35000 Rennes France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yann","family":"Raoul","sequence":"additional","affiliation":[{"name":"OLEON SAS, Venette BP 20609  60206 Compi\u00e8gne Cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5145-1600","authenticated-orcid":false,"given":"Christophe","family":"Cr\u00e9visy","sequence":"additional","affiliation":[{"name":"Ecole Nationale Sup\u00e9rieure de Chimie de Rennes UMR CNRS 6226  11 All\u00e9e de Beaulieu, CS 50837 35708 Rennes Cedex 7 France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4551-473X","authenticated-orcid":false,"given":"Olivier","family":"Basl\u00e9","sequence":"additional","affiliation":[{"name":"Ecole Nationale Sup\u00e9rieure de Chimie de Rennes UMR CNRS 6226  11 All\u00e9e de Beaulieu, CS 50837 35708 Rennes Cedex 7 France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7080-9708","authenticated-orcid":false,"given":"Marc","family":"Mauduit","sequence":"additional","affiliation":[{"name":"Ecole Nationale Sup\u00e9rieure de Chimie de Rennes UMR CNRS 6226  11 All\u00e9e de Beaulieu, CS 50837 35708 Rennes Cedex 7 France"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2017,8,16]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"Report of the United Nations Conference on Environmental Development Rio de\u2005Janeiro (Brazil) http:\/\/www.un.org\/esa\/sustdev accessed June 3\u201314 1992."},{"key":"e_1_2_2_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.201601256"},{"key":"e_1_2_2_3_1","unstructured":"Selected comprehensive books on olefin metathesis:"},{"key":"e_1_2_2_4_2","volume-title":"Handbook of Metathesis","year":"2015"},{"key":"e_1_2_2_5_2","volume-title":"Olefin Metathesis: Theory and Pratice","year":"2014"},{"key":"e_1_2_2_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejlt.200800027"},{"key":"e_1_2_2_7_1","unstructured":"\u00a0"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF02523427"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201305308"},{"key":"e_1_2_2_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201305308"},{"key":"e_1_2_2_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/b703294c"},{"key":"e_1_2_2_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/1615-4169(200208)344:6\/7<671::AID-ADSC671>3.0.CO;2-G"},{"key":"e_1_2_2_12_1","doi-asserted-by":"publisher","DOI":"10.1007\/s11244-012-9832-0"},{"key":"e_1_2_2_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b01428"},{"key":"e_1_2_2_14_1","unstructured":"Extra-pure methyl oleate (>99\u2009%) is commercialized by Aldrich 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W.Lemke K. D.Uptain F.Amore T.Abraham PCT Int. Appl. WO2009\/020667;"},{"key":"e_1_2_2_18_2","unstructured":"Z.Lysenko B. R.Maughon J.Bicerano K. A.Burdett C. P.Christenson C. H.Cummins M. L.Dettloff J. M.Maher A. K.Schrock P. J.Thomas R. D.Varjian J. E.White PCT Int. Appl. WO2003\/093215;"},{"key":"e_1_2_2_19_2","unstructured":"S. A.Cohen D. R.Anderson Z.Wang T. M.Champagne T. A.Ung US Pat. 2014\/0275681;"},{"key":"e_1_2_2_20_2","unstructured":"K. D.Uptain C.Tanger H.Kaido PCT Int. Appl. WO2009\/020665."},{"key":"e_1_2_2_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200900407"},{"key":"e_1_2_2_22_1","unstructured":"The other compounds were identified as saturated and mono- or poly- unsaturated fatty methyl esters: C14:0 (0.02\u2005wt.%); C14:1 (0.01\u2005wt.%); C16:0 (2.7\u2005wt.%); C16:1 (0.03\u2005wt.%); C18:0 (1.3\u2005wt.%); C18:2 (1.6\u2005wt.%); C22:0 (0.06\u2005wt.%) and C22:1 (0.2\u2005wt.%)."},{"key":"e_1_2_2_23_1","unstructured":"The kinetic profile of the reaction showed that the equilibrium was reached within 4\u2005min (see Supporting Information for details)."},{"key":"e_1_2_2_24_1","unstructured":"\u00a0"},{"key":"e_1_2_2_25_2","first-page":"26","volume":"32","author":"Hales R.","year":"2016","journal-title":"Oils Fats Int."},{"key":"e_1_2_2_26_2","unstructured":"Tonsil\u00ae bleaching earths are commercialized by Clariant."},{"key":"e_1_2_2_27_1","unstructured":"Radia 7072\u00ae is commercialized by Oleon company. The other compounds were identified as saturated and mono- or poly-unsaturated fatty methyl esters: C16:0 (3.4\u2005wt.%); C16:1 (0.1\u2005wt.%); C18:0 (1.8\u2005wt.%); C18:2 (3.1\u2005wt.%); C18:3 (1.8\u2005wt.%); C20:0 (0.2\u2005wt.%) C22:0 (0.3\u2005wt.%) and C22:1 (0.7\u2005wt.%)."},{"key":"e_1_2_2_28_1","unstructured":"The recrystallization process leading to a better quality of raw material (i.e. 94\u2009%) appeared too costly and inappropriate at industrial scale."},{"key":"e_1_2_2_29_1","unstructured":"The peroxide value is defined as the amount of peroxide oxygen per 1\u2005kg of oil and is determined by measuring the amount of iodine which is formed by the reaction of peroxides with iodide ion."},{"key":"e_1_2_2_30_1","unstructured":"Composition of the crude after filtration: (Z\/E)-2(15.7\u2005wt.%) (Z\/E)-3(27.2\u2005wt.%) (E)-1(26.6\u2005wt.%) (Z)-1(8.2\u2005wt.%)."},{"key":"e_1_2_2_31_1","unstructured":"Composition of Tonsil Supreme 110FF\u00ae (average values): SiO2(75.5\u2009%) Al2O3(12\u2009%) Fe2O3(2.4\u2009%) CaO (0.4\u2009%) MgO (1.4\u2009%) Na2O (0.3\u2009%) K2O (1\u2009%)."},{"key":"e_1_2_2_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201500261"},{"key":"e_1_2_2_33_1","unstructured":"\u00a0"},{"key":"e_1_2_2_34_2","unstructured":"Additional experiments were done showing the detrimental effect of a mixture of metallic oxides (Fe2O3 CaO and MgO) towards the Ru-catalyst (see Supporting Information for details). For previous studies reporting the catalyst decomposition by oxidation see:"},{"key":"e_1_2_2_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2009.11.092"},{"key":"e_1_2_2_36_2","unstructured":"M.Mauduit F.Caijo C.Cr\u00e9visy PCT Int. Appl. 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