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(12) Patent Application Publication (10) Pub. No.: US 2011/0185625 A1 Singh Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2011/0185625 A1 Singh Et Al US 2011 0185625A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0185625 A1 Singh et al. (43) Pub. Date: Aug. 4, 2011 (54) SOLID, HETEROGENEOUS CATALYSTS AND Publication Classification METHODS OF USE (51) Int. Cl. (75) Inventors: Inder Pal Singh, Edmonton, (CA); CIOL L/9 (2006.01) Shradha Singh, Edmonton (CA); BOI 29/06 (2006.01) Ritesh Patel, Edmonton (CA); BOIJ 29/072 (2006.01) Bharat Mistry, Edmonton (CA); BOI 2/06 (2006.01) Manish Mehta, Edmonton (CA); COB 39/02 (2006.01) Peter Omolo Otieno, Edmonton C07C 67/08 (2006.01) (CA) C07C 27/00 (2006.01) (73) Assignee: SBI Fine Chemicals Inc., (52) U.S. Cl. ................. 44/307: 502/6S: 502/64: 502/73; Edmonton (CA) 502/66; 502/303; 423/700; 560/103:554/170; 568/852 (21) Appl. No.: 13/059,932 (22) PCT Fled: Aug. 20, 2009 (57) ABSTRACT Solid mixed catalysts and methods for use in conversion of (86) PCT NO.: PCTACA2O09/OO1165 triglycerides and free fatty acids to biodiesel are described. A batch or continuous process may be used with the catalysts for S371 (c)(1), transesterification of triglycerides with an alkyl alcohol to (2), (4) Date: Apr. 12, 2011 produce corresponding mono carboxylic acid esters and glyc erol in high yields and purity. Similarly, alkyl and aryl car Related U.S. Application Data boxylic acids and free fatty acids are also converted to corre (60) Provisional application No. 61/090,781, filed on Aug. sponding alkyl esters. The described catalysts are 21, 2008. thermostable, long lasting, and highly active. US 2011/0185625 A1 Aug. 4, 2011 SOLID, HETEROGENEOUS CATALYSTS AND METHODS OF USE -continued Equation-3 CROSS REFERENCE TO RELATED OOCR OH H2O APPLICATIONS OOCR + NaOH -> OH + 3. RCOONa 0001. This application claims the priority of U.S. provi OOCR OH Soap sional patent application Ser. No. 61/090,781 filed on Aug. Triglyceride Glycerol 21, 2008. Equation-4 RCOOCH + H2O NaOH,- RCOONa FIELD OF THE INVENTION Biodiesel Soap 0002 The present invention relates generally to the pro duction of biodiesel from triglycerides and free fatty acids. 0006 Further attempts have been made in the prior art to More particularly, the present invention relates to solid, het replace homogeneous catalysts with Solid catalysts. Such erogeneous catalysts for use in the production of biodiesel. replacement of homogeneous catalysts, for example with Solid metal oxides and double metal cyanides, is perceived to have the advantages of simple retrieval of catalyst, elimina BACKGROUND OF THE INVENTION tion of soap formation and reduction of environmental pol lutants. Further, the use of solid catalysts in place of homo 0003 Biodiesel is a non-toxic fuel that may be used alone geneous catalysts may lead to higher-quality esters and or blended with petroleum diesel at any ratio to create a glycerol, which are more easily separable and without added biodiesel blend. Biodiesel has a high octane number, is essen cost to refine the resulting ester (see for example U.S. Pat. No. tially free of sulfur and aromatics, and is therefore a clean 6,147,196 to Sternet al). In accordance with this expectation, burning fuel, free of NOx and SOX. a number of solid catalysts have now been reported in litera 0004 Biodiesel is commonly produced by transesterifica ture. These are generally based on metal oxides and double tion, the reaction of an alcohol with triglycerides present in metal cyanides to effect the desired transesterification reac animal fat or vegetable oil. Generally, such reactions are tion shown in equation-5 below. catalyzed by homogeneous catalysts such as mineral acids, metal hydroxide, metal alkoxides, and carbonates. As mineral acid catalyzed reactions are slow and therefore economically Equation-5 non-viable, metal hydroxides Such as sodium or potassium hydroxides are more commonly used as they are relatively OOCR Heterogeneous OH Catalyst inexpensive and Suitably effective. One disadvantage to using OOCR + 3 CH-OH Re OH + 3RCOOCH alkaline hydroxides or carbonates in transesterification reac tions is the generation of Soap as a reaction byproduct. The OOCR OH Biodiesel generation of Soap compromises product yields and product Triglyceride Glycerol quality. Glycerol (glycerine) is also produced as a byproduct, however the presence of water and soaps creates an emulsion that complicates the purification of biodiesel and the separa 0007 European patent EP-80-198-243 describes a solid, tion of glycerol from the fatty acid esters. Generally, copious heterogeneous catalyst that is based on a mixture of iron oxide amounts of acids and water are used to neutralize catalyst and with alumina. This catalyst requires a very large catalyst to oil remove Soaps from the desirable reaction products. As a ratio, and extended contact time of more than 6 hours. Reac result, the increased number of steps required to obtain puri tion temperatures of 280°C. to 320°C. are typically required, fied biodiesel and useable quality glycerol add tremendously which results in coloration of the biodiesel and presence of to the cost of production, and also lead to a certain degree of impurities. environmental pollution. 0008 U.S. Pat. No. 5,908,946 describes catalysts prepared 0005. The following equations illustrate the reactions that from mixtures of Zinc oxide, and alumina Zinc aluminate. take place during transesterification to biodiesel by existing While the catalyst does provide complete conversion to methods, using homogeneous catalysts. methyl ester, long reaction times and high temperatures are required. Moreover, the reaction is sensitive to water and free fatty acids. When free fatty acid conversion is desired, an Equation-1 esterification step must be carried out prior to the transesteri fication reaction. OOCR OH 0009 U.S. Pat. No. 7,151,187 describes catalysts made by NaOH OOCR + 3 CH-OH ge OH + 3 RCOOCH combining two or more of titanium isopropoxide, Zinc oxide, alumina, and bismuth salts using nitric acid. Use of nitric acid OOCR OH Biodiesel is not desirable, as it is corrosive, toxic, and has a negative Triglyceride Glycerol impact on the environment. Further, the use of nitric acid also Equation-2 impacts the basicity of the catalyst, which may affect the transesterification reaction. RCOOH + NaOH -- RCOONa + H2O 0010. It has further been shown that exchange of sodium Fatty Acid Soap ions in the 4 A molecular sieves (formula: Na2AlO4)2 (SiO).xH2O), with either K or Cs' leads to a material US 2011/0185625 A1 Aug. 4, 2011 with higher basicity which is essential in heterogeneous 0020. In accordance with a third aspect of the invention, transesterification catalysis. However, testing has shown that there is provided a modified molecular sieve of the general despite enhancement of the basic sites, these ion-exchanged formula K.Nai (AlO4)2(SiO2)2XH2O, KCa,Na, 12 Zeolites failed to achieve complete transformation of triglyc (m+2n)}AlO)2(SiO2).XH2O, Cs,Na2 (AlO4)2 erides to biodiesel. (SiO2)12.xH2O, or Cs, Ca,Na2-2. AlO2)2(SiO2)2. 0011. A double metal cyanide catalyst-FeZn(CN) has XHO. also been shown to transesterify oils at relatively lower tem 0021. In accordance with a fourth aspect of the invention, peratures. However, the slow pace of reaction leads to there is provided a catalyst according to the formula extended reaction time and requires excessive catalyst and a(LaO). X(TiO).y(ZnO).Z(MS), wherein A and X are each reactor Volume. 1;Y is 1-2, Z is 3-4, and wherein MS is a molecular sieve of 0012. A suitable heterogeneous catalyst and method for the general formula K.NaI(AlO4)2(SiO2)2.xH2O, complete transformation of triglycerides to biodiesel and for K.Ca,Na, 12-(2)(AlO2)2(SiO2)12.XH2O, CS,Na, 12-) conversion of free fatty acids to corresponding esters has not (AlO4)2(SiO2)2XH2O, or Cs, Ca,Na2-2 (AlO4)2 been described to date. Further, such reactions do not appear (SiO2).XH2O. to be currently possible under mild temperature and pressure 0022. In accordance with a fifth aspect of the invention, conditions, while minimizing reaction time and product puri there is provided a catalyst according to the formula (AlO). fication steps. (TiO). (ZnO).Z(MS) wherein Z is 10 and wherein MS is a molecular sieve of the general formula K.Na2-2 SUMMARY (AlO4)2(SiO2)2.xH2O, KCa,Na, 12-2 (AlO4)2 (SiO2)2).xH2O, Cs,Na2-((AlO4)2(SiO2)2).xH2O, or 0013. In accordance with a first aspect of the invention, Cs, Ca,Na, 12-2 (AlO4)2(SiO2)2.xH2O. there is provided a solid, heterogeneous catalyst preparation 0023. In accordance with a sixth aspect of the invention, for use in an esterification or transesterification reaction, the there is provided a catalyst according to the formula (Fe,M. mixed catalyst preparation comprising at least one molecular (CN)}. Al-O.TiO.ZnO. MS, wherein M is Cu, Al or La, sieve and at least one catalyst, wherein the catalyst comprises and wherein MS is a molecular sieve of the general formula a metal oxide or double-metal cyanide. KNa2-(AlO2)2(SiO2)12.XH2O, KCa,Na, 12-2} 0014. In an embodiment, the metal oxide is aluminum (AlO)2(SiO2).XHO Cs,Na2-((AIO,(SiO2)2). oxide, calcium oxide, gallium oxide, hafnium oxide, iron XH2O, or Cs, Ca,Na, 12-2 (AlO4)2(SiO2)2XH2O. oxide, lanthanum oxide, silicon oxide, strontium oxide, tita 0024. In accordance with another aspect of the invention, nium oxide, Zinc oxide, or Zirconium oxide. The metal oxide there is provided a method for effectingesterification or trans may be formed by calcination of a metal hydroxide, for esterification of a starting material, comprising reacting the example, aluminum hydroxide, calcium hydroxide, gallium starting material with an alcohol in the presence of a solid, hydroxide, hafnium hydroxide, iron hydroxide, lanthanum heterogeneous catalyst as described above.
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