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 , metal alkoxides, and carbonates. As mineral acid catalyzed reactions are slow and therefore economically Equation-5 non-viable, metal 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 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 -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, 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. hydroxide, silicon hydroxide, strontium hydroxide, titanium 0025. The starting material may be an oil, and/or may hydroxide, Zinc hydroxide, or Zirconium hydroxide. comprise triglycerides, free fatty acids, and/or carboxylic 0015. In an embodiment, the double-metal cyanide is of acids. The method may be used to produce biodiesel and/or the general formula Fe,M(CN) wherein M is lanthanum, glycerol as a reaction product. Notably, in Suitable embodi copper or aluminum. ments, soap is not produced as a byproduct of the reaction. 0016. In suitable embodiments, the molecular sieve may 0026. In an embodiment, the reaction is conducted attem be of the type 3 A, 4 A, or 5 A, having the general formula peratures between 150° C. and 250° C. Further, the reaction KNa2AlO4)2(SiO2)2·xH2O, NaI(AlO4)2(SiO2) may be conducted at pressures less than 1000 psi. In various 12.xH2O) or Ca,Na2-((AlO4)2(SiO2)2).xH2O, respec embodiments, the reaction may be conducted in a batch reac tively. The molecular sieve may be, for example, a natural or tor or continuous reactor such as a fixed bed reactor. The synthetic zeolite. Preferably, the molecular sieve is a modified reaction may be conducted in two or more Successive stages. molecular sieve, modified to enhance the basicity of the In a fixed bed reactor, the reaction may be conducted with a molecular sieve. ratio of 0.1-2.0 volumes of injected oil/volume of catalyst per 0017 Suitable modified molecular sieves may have been hour. modified to replace at least one sodium ion within the molecu lar sieve with at least one metal cation. Suitable metal cations DESCRIPTION include K", Cs", and the like, resulting in a general formula of 0027 Generally, the present invention provides solid, het KNa12-(AlO2)2(SiO2)12.l.XH2O, KCa,Na, 12-2} erogeneous catalysts and methods for use in the production of (AlO4)2).XH2O, Cs,Na2 (AlO4)2(SiO2)2.xH2O, or alkyl esters from a starting material containing any one or Cs, Ca,Na, 12-2AiO2)12.xH2O, for example. more of the following: triglycerides, free fatty acids, aromatic 0018. In various embodiments, any of the catalyst prepa carboxylic acids, aliphatic carboxylic acids. rations may be provided in powdered, pelleted, extruded, 0028. The terms “oil”, “feedstock', and “starting mate and/or calcined form. The catalyst remains heterogeneous rial” as used herein refer to a substance having any detectable during the reaction, and is generally recoverable from the triglyceride and/or free fatty acid and/or carboxylic acid reaction products by filtration. (whether aromatic or aliphatic) content, such as animal fats, 0019. In accordance with a second aspect of the invention, Vegetable oils, used cooking oils, and the like. Examples of there is provided a catalyst of the molecular formula: Vegetable oils include, without limitation, canola oil, corn oil, X(LaO).y(La(OH)).Z(TiO) wherein X, y and Z indepen Soybean oil, palm oil, coconut oil, jatropha oil, camolina oil, dently have a value between 1-2. Such catalyst may be pre cottonseed oil, flax oil, Sunflower oil, and rapeseed oil. pared from or lanthanum hydroxide and Examples of animal fats include, without limitation, beef titanium oxide, and these oxides may be prepared in situ. tallow, pork lard, and the like. Other further starting materials US 2011/0185625 A1 Aug. 4, 2011 may also be appropriate. Such as triglycerides present in or isopropyl, butyl and Stearyl alcohol, a monohydric aromatic obtained from certain types of algaes, etc. alcohol such as benzyl or substituted benzyl alcohol or a 0029. The term "heterogeneous” as used herein with dihydric alcohol Such as ethylene glycol, propylene glycol, respect to Solid catalysts, refers to any solid physical form of butane diolora polyhydric alcohol Such as glycerol, Sorbitol, Suitable catalyst, whether a catalyst is calcined or otherwise polyerythritol, polyethylene glycol and poly propylene gly hardened, whether provided in powder, pellet, balled, or col etc. extruded form or anchored to a solid structure Such as a 0033. Further, ROH in equations 6 through 8 represents molecular sieve or natural or synthetic Solid state composi Suitable alcohols, including without limitation: a C to Cs tion. Such catalysts are generally not solubilized during the monohydricaliphatic alcohol Such as methanol, ethanol, pro reaction and the majority of the catalyst is recoverable from panol, isopropanol, butyl alcohol, and Stearyl alcohol; a the reaction products by simple filtration. monohydric aromatic alcohol Such as benzyl alcohol or a substituted benzyl alcohol; a dihydric alcohol such as ethyl Catalyst and Reaction Overview ene glycol, propylene glycol, and butanediol; or a polyhydric 0030 Notably, the catalysts and methods may be used in alcohol Such as glycerol, Sorbitol, polyerythritol, polyethyl the production of high yield, high purity biodiesel. Generally, ene glycol, and polypropylene glycol. Other Suitable alcohols the catalyst may be a metal oxide, or double metal cyanide, or may also be used, as will be apparent to those of skill in the art. mixtures of the foregoing. The catalysts are provided in Solid form, for example in powdered, pelleted, or extruded form, Metal Oxide Catalysts Supported on a solid structure Such as a molecular sieve. The 0034 Inequations 6 through 8, the catalyst may includean resulting catalysts are thermostable. For example, the metal oxide of a metal, for example aluminum, calcium, cerium, oxide based catalysts described below are stable above 600° gallium, hafnium, iron, lanthanum, magnesium, strontium, C., maintain a high level of activity even after prolonged use, titanium, Zirconium, or zinc. Such metal oxides or hydroxides provide excellent selectivity, and are insoluble in triglycer may be used alone or in combination with similar or dissimi ides and alkyl alcohols, preventing elution and Volume loss. lar catalysts, and the catalyst is provided in solid form. For Further, these catalysts are not usually limited by reaction example, the catalyst may be Supported on a molecular sieve temperature and are highly tolerant of free fatty acids and or Zeolite, in which some of the sodium ions have been water content during use. exchanged for potassium or cesium ions. The catalysts may 0031 Equations describing the general reactions are rep be provided as a powder, pellets, balls, or extruded forms, and resented below in Equations 6 through 8. calcined under vacuum or in the presence of a neutral gas

Equation-6 OOCR OH Heterogeneous OOCR" + 3ROH OH + RCOOR + R"COOR + R"COOR

OOCR" OH Biodiesel Triglycerid Glycerol Equation-7 Heterogeneous Catalyst RCOOH + ROH e RCOOR Free Fatty acid Fatty acid ester/Biodiesel Equation-8 Heterogeneous Catalyst RCOOH -- ROH C RCOOR Carboxylic acid Carboxylic acid ester

0032. In the above equations, R', R", and R" may be the (such as argon, nitrogen, or helium) at temperatures between same or different, and each may be a C to C linear or 200° C. to 1200° C., usually between 400° C. to 800° C. Such branched chain alkyl group, which may be further substituted oxides may be obtained commercially or prepared from with hydroxyl, alkoxy or halogens like chloro, bromo or appropriate metal halide, hydroxide, or a metal nitrate. fluoro or an aryl group that can be substituted with chloro, bromo, fluoro, nitro, lower alkoxy or lower alkyl such as Double Metal Cyanide Catalysts methyl, ethyl, propyl, isopropylor butyl which may be further substituted with halogens such as chloro, bromo fluoro or a 0035. In equations 6 through 8, the catalyst may include a phenyl group that can be substituted with chloro, bromo double metal cyanide of the general formula Fe,M(CN), fluoro nitro, lower alkyl or alkoxy group. Further, each may (ROH).XMyHO), where M is a metal, for example lantha represent an alkyl group of a monocarboxyllic acid such as num, strontium, copper, aluminum, magnesium cobalt and acetic, propionic, butyric, caproic, caprilic, capric, lauric, titanium. Values for Xandy may range between 1 and 2. Such myristic, palmitic, oleic, Stearic oradicarboxylic acid such as catalysts may be used alone or in combination with similar adipic acid, which are in an ester form with a C1 to C18 catalysts or with the above-described metal oxide/hydroxide monohydric aliphatic alcohol Such as methyl, ethyl, propyl. catalysts, with the catalyst provided in solid form. For US 2011/0185625 A1 Aug. 4, 2011 example, the catalyst may be Supported on a molecular sieve alcohol to oil, reaction time, temperature, pressure, and or Zeolite, in which some of the sodium ions have been nature and quantity of catalyst. exchanged for potassium or cesium ions. The catalysts may be provided as a powder, pellets, balls, or extruded forms, and Catalysts—Examples calcined in the presence or absence of a neutral gas (such as 0041 All reagents and alcohols used in the following argon, nitrogen, or helium) at temperatures between 100° C. examples were of technical grade. The triglyceride source? to 200° C., usually between 160° C. to 180° C. starting material was food grade canola oil with approxi mately 1% free fatty acids. All metal oxides, molecular Use of Molecular Sieves in Catalyst Preparation sieves, and carboxylic acids were purchased from Aldrich Chemical Co. For free fatty acid reactions, hydrolyzed canola 0036. The mixed catalyst may include a molecular sieve, and safflower oils were used as a source of free fatty acids. for example a natural or synthetic Zeolite. Such substances Reactions were followed by thin layer chromatography and may vary in composition and . The catalyst 400 MHz NMR. GC analyses were performed following may, for example, be a titanium Zeolite prepared by exchange ASTM protocols on HP 6890 gas chromatograph. of silicon atoms with titanium atoms. Further, the molecular sieves may by of types 3 A, 4 A, and 5 A. For example, type Preparation of Catalyst MS-4AK 3A of formula KNa (AlO)2(SiO2).XH2O), or type 4A of formula NaI(AlO·) (SiO).XHO), where n and X 0042 Potassium exchanged molecular sieves were pre are integers. The molecular sieve is first treated to exchange pared by partial ion exchanging molecular sieves of molecu one or more of the existing Sodium ions with potassium and lar formula, NaI(AlO.). (SiO4)2).xH2O (MS-4A). 800 g cesium ions to produce enhanced basic sites. The resulting of MS-4A were suspended in 5000 ml, 0.5 Molar aqueous Substance may be calcined in the presence or absence of a solution of and heated under reflux for 5 neutral gas (such as nitrogen, argon, or helium) and may be hand allowed to cool to room temp. The exchanged molecu used alone as a catalyst or as a solid Support for the metal lar sieves were washed repeatedly to remove excess potas oxide/hydroxide and double metal cyanide catalysts sium hydroxide from the molecular cages of the sieves. described above. Preparation of Catalyst MS-4ACs Reaction Methods 0043 Cesium exchanged molecular sieves were prepared by partial ion exchanging molecular sieves of molecular for 0037. The above-described catalysts may be used with mula, NaI(AlO.). (SiO.).xH2O (MS-4A). MS-4A(100 equal efficiency in a batch, intermittent/semi continuous, or g) was suspended in 700 ml, 0.5 Molar aqueous solution of continuous mode attemperatures between 200° C. and 225° cesium chloride and heated under reflux for 5 hand allowed C. and pressures up to 650 psi, depending on the specific to cool to room temp. The exchanged molecular sieves were catalyst, starting material, and process chosen. washed repeatedly to remove excess cesium chloride from the 0038 Fatty acid esters and glycerol products from the molecular cages of the sieves. reactor are generally of high purity, and the glycerol is color less and high in quality. Quality of the reaction products may Preparation of Catalyst MS-5 AK be further improved by treatment with activated charcoal, 0044 Potassium and cesium exchanged molecular sieves resin, or clay, or by distillation. Any remaining monoglycer were prepared by partial ion exchanging molecular sieves ides in the ester phase may be removed with the glycerol layer molecular formula, Ca,Na (AlO)2(SiO2).XH2O. by partial evaporation of alcohol from the reaction mixture. MS-5A (100 g) was suspended in 7000 ml, 0.5 Molar aque 0039 Batch mode example: Generally, for batch mode ous solution of cesium chloride and heated under reflux for 5 reaction, a mixture of alkyl alcohol, oil, and a catalyst is hand allowed to cool to room temp. The exchanged molecu placed in a sealed autoclave and exposed to temperatures lar sieves were washed repeatedly to remove excess cesium between 150° C. and 300° C., typically between 180° C. and chloride from the molecular cages of the sieves. 230° C. for 30 to 120 minutes. The ratio of catalyst to oil should be 1-10% by weight, and typically 2-6% by weight. Preparation of Catalyst MS-5 ACs The alcohol ratio should be 1-10 volume equivalents, typi cally 3-8 Volume equivalents, most Suitably 6 equivalents 0045 Cesium exchanged molecular sieves were prepared by partial ion exchanging molecular sieves of molecular for with respect to the amount of oil present. After cooling and mula, Ca,Na2-2 (AlO.(SiO2)2XH2O. MS-5 A (100 g) depressurizing, the reaction mixture is recovered from the was suspended in 700 ml, 0.5 Molar aqueous solution of autoclave and filtered to remove the catalyst, which may be cesium chloride and heated under reflux for 5 hand allowed stored for later reuse. Excess alcohol is recovered by distilla to cool to room temp. The exchanged molecular sieves were tion, and the alkyl ester product is recovered from residue by washed repeatedly to remove excess cesium chloride from the decanting the separated glycerol. molecular cages of the sieves. 0040 Continuous/fixed bed example: Generally, oil and alcohol are fed at predetermined fixed rates into a continuous Preparation of Catalyst C-I fixed bed reactor containing the desired mixed solid catalyst. The reactor is maintained at a temperature of 180°C. to 300° 0046 Lanthanum chloride heptahydrate (25 g) was dis C., typically 180° C. to 230° C. depending on the catalyst solved in water (100 ml) at room temperature and a mixture of used. Typical variables should be considered, including type a solution of potassium hydroxide (1 M) and potassium car and quality of feedstock, nature of alcohol, molar ratio of bonate (250 ml) was added over 1 h, whereupon a white US 2011/0185625 A1 Aug. 4, 2011 precipitate was formed. Resulting Suspension was further the resulting white Suspension, a solution of zinc oxide (0.9 g) stirred for 1 hr., the solid was filtered, rinsed with 3x50 ml of in a solution of nitric acid (2.5 g) and water (7.5A ml) was 1:1 methanol water mixture. The resulting solid was dried at added and stirred to get a clear Solution. This clear Solution 100° C. for 24 h and calcined at 600° C. for 3 hours to get was absorbed on 3 molecular sieves of molecular formula, lanthanum oxide (Catalyst C-I). KNaI(AIO.), (SiO.).xH2O, (MS-3 A, 30 g) for one hour and then dried at 100° C. for 5 hours. To this material at Preparation of Catalyst C-II RT was added ammonium hydroxide solution (2 ml) and 0047 Lanthanum chloride heptahydrate (15.2 g) in water dried at 100° C. for 5 hours. The material was calcined at 600° (100 ml) was added to a solution of calcium chloride (30 g) in C. for 3 hours to give catalyst C-XV. water (150 ml) at room temperature under vigorous stirring. A mixture of a solution of potassium hydroxide (1 M, 200 ml) Preparation of Catalyst C-XVI and potassium carbonate (0.5 M, 1000 ml) was added under stirring over one hour, whereby a white precipitate is 0.052 A solution of potassium hexacyanoferrate(II)-trihy obtained. Reaction mixture was further stirred for one hour drate (7.4 g, 17.5 mmol) in 50 ml of water was added to then filtered to recover a white solid, washed with 3x50 ml of lanthanum chloride heptahydrate (65.1 g) dissolved in a mix 1:1 methanol: water mixture. Solid was dried at 100° C. for 24 ture of water (50 ml) and t-butanol (20 ml) at 50° C. over one hand then calcined at 600° C. for 3 hours to obtain lanthanum hour. Reaction mixture was further stirred for additional 18h calcium oxide, X(LaO).y(CaO) (where x=1 and y=3), here and cooled to ambient temperature. Separated solid was fil inafter referred to as catalyst C-II. tered, washed with a 3x40 ml of 1:1 mixture of water and t-butanol. It was dried at RT overnight, then at 60° C. under Preparation of Catalyst C-III reduced pressure for 5 hand finally at 170° C. for another 5h 0.048 Lanthanum aluminum oxide, X(LaO).y(Al2O) to a constant weight. Dried material having molecular for (where X=2 and y=1) hereinafter referred to as catalyst C-III mula FeLa(CN), herein referred to as catalyst C-XVI. was prepared following the procedure described catalyst C-II using aluminum chloride (17 g) and lanthanum chloride (25 Preparation of Catalyst C-XVII g). 0053 DMC catalyst C-XVII having molecular formula FeCu(CN) was prepared using hexacyanoferrate(II)-tri Preparation of Catalyst C-IV hydrate (7.4 g) and copper(II) sulfate (55.9 g) following the 0049 Lanthanum zinc oxide, X(LaO).y(ZnO) (where method described for catalyst C-XVI. X=2 and y=1) hereinafter referred to as catalyst C-IV was prepared following the procedure described catalyst C-II Preparation of Catalyst C-XVIII using Zinc chloride (17 g) and lanthanum chloride (25 g). 0054 DMC catalyst C-XVIII having molecular formula Catalysts C-V to C-XIV FeAl(CN) was prepared using hexacyanoferrate(II)-tri hydrate (7.4 g) and aluminum chloride (23.3 g) following the 0050 Catalysts C-V to C-XIV were prepared by mixing method described for catalyst C-XVI. required metal oxides and exchanged or un-exchanged molecular sieves from Table-1, respectively in water to make Preparation of Catalysts C-XIX to C-XXI a paste. The paste was extruded, dried at 100° C. for 24 hand calcined at 600° C. for 3 hours to obtain Catalysts from C-V 0055 Appropriate calcined metal oxides, a DMC and cal to C-XIV (Table-1). cined Ms-4 AK were mixed together in desired quantities.

TABLE 1. Preparation of mixed metal oxide catalysts:

Ms- Ms Al2O3 ZnO TiO2 LaO3 La OTiO2 FeO. Water 4AK 5AK Yield Catalyst (g) (g) (g) (g) (g) (g) (ml) (g) (g) (g) C-V 6.0 9.8 11.5 — 25.2 C-VI 2.3 4.6 8.O 2.3 8.9 C-VII 8.0 160 16.0 3O.O 3O.O - 65.0 C-VIII 3O.O 300 3O.O 2OO.O 2SO.O - 295 C-IX 30.2 - 29.7 C-X 18O 18.0 40.O 3O.O — 60.0 C-XI 4.5 9.O 2O.O 1O.S — 22.8 C-XII 2O.O – 20.0 C-XIII 3.0 3.0 3.0 6.O 40.O 2S.O 37.5 C-XIV 3.6 8.2 8.2 25 13.4 32.8

Preparation of Catalyst C-XV Water (20 ml) was added to this physical mixture to make a paste. The paste was extruded and dried at 100° C. for 24h 0051. An aqueous solution of ammonium hydroxide (4 and then at 170° C. for 5 h to a constant weight yielding ml) was added drop wise into a stirred solution of 1.3 g of catalysts C-IX to C-XXI, respectively. Compositions of cata aluminum chloride dissolved in 5 ml of deionized water. To lysts C-IX to C-XXI are reported in Table 2. US 2011/0185625 A1 Aug. 4, 2011

TABLE 2 TABLE 3-continued Al2O3. TiO2 Ms-4AK Transesterification of canola oil using batch process Catalyst DMC (g) (g) (g) ZnO(g) (g) Yield (g) % Conversion based on C-XIX C-XVI 0.75 1.5 7.5 11.0 % Catalyst Triglyceride consumption (1.5) C-XX C-XVII 1.5 3.0 1S.O 23.0 (cally (g) X to) (3.0) Catalyst Oil (g) Time (h) 1 Use 2nd Use C-XXI C-XVIII 0.75 1.5 7.5 11.3 (1.5) C-XIII S.O 1.5 1OO 1OO C-XXIII C-XXII 30 S.O S.O 36.0 C-XIII 16.0 1.O 1OO 98.3 C-XIV S.O 1.5 67.8 58.3 (5.0) C-XIV 16.0 1.O 90.2 89.8 C-XV S.O 1.5 40.9 27.0 C-XV 16.0 2.0 1OO 1OO C-XVI S.O 1.5 97.4 1OO Preparation of Catalyst C-XXII C-XVII S.O 1.5 54.8 63.5 C-XVIII S.O 1.5 35.7 36.5 0056 DMC catalyst C-XXII having molecular formula C-XIX S.O 1.5 94.8 81.7 Fe2Zn(CN) was prepared using hexacyanoferrate(II)-tri C-XX S.O 1.5 1OO 81.7 hydrate (7.4 g) and Zinc chloride (23.9 g) following litera C-XXI S.O 1.5 59.1 37.4 ture-described methods. C-XXIII 16.0 1.O 99.0 98.0 C-VIII 10 2.0 99.9 99.8 Reaction—Examples *Single metal oxides were calcined at 600°C. for 3 hrs prior to use Batch Process for Transesterification of Canola Oil to Biodie sel Batch Process for Esterification of Carboxylic Acids or Free 0057 With respect to Table 3 below, a solid, mixed cata Fatty Acids lyst was placed with a mixture of 10 g canola oil and 65 ml 0058. With respect to Table 4 below, a mixture of a car methanol in a 100 ml stainless steel autoclave equipped with boxylic acid or free fatty acids, and appropriate alcohol or a pressure gauge and pressure relief valve. The autoclave was phenol, and a catalyst was placed in a 100 ml stainless Steel sealed and heater in an oil bath at 200° C.10° C. After autoclave equipped with a pressure gauge and pressure relief cooling and release of pressure, the catalyst was recovered valve. The autoclave was then sealed and heated in an oil bath from the reaction products and washed with methanol prior to for the time indicated, then cooled to ambient temperature reuse (and reactivated, if necessary). The filtrate, containing and pressure released. The reaction material was filtered to fatty acid methyl ester (FAME), glycerol, unreacted oil (if recover the catalyst, followed by washing of the catalyst in any) and methanol, was separated by evaporation and layer methanol and reactivation, if necessary. Methanol was separation. Recovered methanol was recycled, glycerol removed by evaporation and the residue was washed with removed, and the remaining oily products were analyzed. The bicarbonate solution to remove unreacted acid. Remaining results are presented in Table 3. solvent was removed by evaporation, and the recovered ester was analyzed by NMR and GC, with results shown in Table 4. TABLE 3 TABLE 4 Transesterification of canola oil using batch process Esterification of carboxylic acids % Catalyst % Conversion based on Triglyceride consumption Sr. Carboxylic Catalyst Time Conversion ( Catalyst (g) x 100 No Acid ROH Catalyst % (h) % Catalyst Oil (g) Time (h) 1 Use 2nd Use 1 Free Fatty Acid Methanol C-VIII 10 1 100 ZnO S.O .5 92.2 prepared Al2O3 S.O .5 90.4 34.O from TiO2 S.O .5 3O4 2O.O Canola oil Ms-4AK S.O .5 94.8 80.0 2 Benzoic Acid Methanol C-X 10 1.5 100 La2O3 S.O .5 OO 1OO 3 Benzoic Acid Methanol C-VIII 10 2 100 La2O3 16.O O OO 1OO 3 2-Iodo Methanol C-X 10 1.5 100 C-II S.O .5 OO 1OO Benzoic Acid C-III S.O .5 OO 1OO 4 2-Iodo Methanol C-VIII 10 1.5 100 C-IV S.O .5 OO 1OO Benzoic Acid C-V S.O .5 97.4 1OO C-VI S.O .5 OO 1OO C-VII S.O .5 95.6 62.6 C-VIII 1O.O .5 OO 1OO Continuous Fixed Bed Reactor Process for Transesterifica C-VIII S.O .5 OO 1OO tion of Canola Oil C-IX S.O .5 98.3 83.5 C-IX 16.O O 90.4 93.8 0059 A tubular stainless steel reactor, equipped with pres C-X S.O .5 OO 1OO C-X 3.0 .5 OO 1OO Sure regulator, back pressure control valve and thermometer, C-X 16.O O OO 1OO was filled with the indicated mixed solid catalyst. Canola oil C-XI S.O .5 OO 98.3 and methanol were introduced at the indicated ratios and flow C-XII S.O .5 71.3 48.7 rates from bottom of the reactor using two high pressure C-XII 16.O O 82.6 82.6 pumps. The reactor was heated externally such that the tem perature inside of the reactor was maintained between 200 US 2011/0185625 A1 Aug. 4, 2011

and 250° C., and internal pressure was maintained between 350 to 1,000 psi, preferably between 400 to 650 psi. Hot TABLE 6-continued effluents exiting from top of the reactor were flashed into an expansion chamber where methanol vapours were separated, Two-Stage Fixed Bed Transesterification of Canola Oil condensed and recycled. Residue liquid was drained into a settling chamber where the lower layer (containing glycerol) VV H VV H Temp Pressure Contact time Conversion% was separated from the product. A series of continuous reac tions were conducted to optimize feed rate, temperature, pres Stage-1 Stage-2 °C. PSI Stage-1 Stage-2 Stage-1 Stage-2 Sure and contact time for maximizing the conversion of oil 1 2OO 6SO 15 30 8O 93.3 into FAME and improving colour and quality of glycerol. The 1 1 2OO 6SO 30 30 82 99.9 separated upper layer containing largely the biodiesel product was analysed using NMR and GC to quantify FAME yield VVH = Volume of oil injectedvolume of catalyst per hr., and remaining oil if any. Results of runs using different cata R is ratio by volume of Oil alcohol. lysts are reported in Table-5.

TABLE 5

Fixed Bed Transesterification of Canola Oil

CONTACT TEMP RHAA PRESSURE TIME CONVERSION CATALYST C. VVH VOLVOL PSI (MIN) (%) C-VII 2OO O.S 1.O 6SO 60 99.8 C-VIII: 2OO O.S 1.O 6SO 60 99.8 C-VII 2OO O.S 2.0 6SO 40 98.0 C-VII 2OO 10 1.O 6SO 30 92.5 C-VII 2OO 10 O.S 6SO 40 95.0 C-VII 200 0.75 O.S 6SO 60 98.3 C-VII 230 O.75 O.S 6SO 60 99.8 C-VII 230 O.75 O.S 700 60 99.9 C-VII 2OO O.3 1.O 6SO 100 99.9 C-VII 200 0.25 1.0 650 120 99.9 C-VII 2OO 1.5 1.O 6SO 40 95.0 C-VII 215 1.5 1.O 6SO 40 97.0 C-VII 200 2.0 1.O 6SO 15 80.0 C-VII 2OO O.S 1.O 6SO 60 99.8 C-VII 200 0.75 O.S 6SO 60 99.7 C-XXIII 2OO O.S 1 6SO 60 97.0 C-II 2OO O.S 1 6SO 60 99.8 VVH = Volume of oil injected volume of catalyst per hr., R is ratio by volume of Oil alcohol. *Recalcined catalyst after several uses

0060. The fixed bed reactor transesterification process 0061 The above-described embodiments of the present may also be completed in two stages. This was carried out in invention are intended to be examples only. Alterations, cases where an incomplete conversion of triglycerides to modifications and variations may be effected to the particular FAME was noticed, or to increase the shift of reaction equi embodiments by those of skill in the art without departing librium, bringing the reaction to completion more quickly. from the scope of the invention, which is defined solely by the The recovered upper layer from the reaction above was claims appended hereto. diluted with the desired quantity of methanol, and introduced into a second reactor system with conditions similar to that 1. A solid, heterogeneous catalyst preparation for use in an described in Table 5. Effluents were concentrated and glyc esterification or transesterification reaction, the mixed cata erol removed. Recovered FAME was analyzed using NMR lyst preparation comprising at least one molecular sieve and and GC, with results reported below in Table 6. Catalyst beds at least one catalyst, wherein the catalyst comprises a metal were regenerated only if required, by heating at 600° C. for oxide or double-metal cyanide. three hours except for catalysts containing DMC, which were 2. The catalyst preparation as in claim 1, wherein the metal heated to 170° C. for five hours. oxide is aluminum oxide, calcium oxide, gallium oxide, hafnium oxide, iron oxide, lanthanum oxide, silicon oxide, TABLE 6 strontium oxide, titanium oxide, Zinc oxide, or Zirconium oxide. Two-Stage Fixed Bed Transesterification of Canola Oil 3. The catalyst preparation as in claim 1, wherein the metal V V H V V H Temp Pressure Contact time Conversion% oxide is formed by calcination of a metal hydroxide. 4. The catalyst preparation as in claim3, wherein the metal Stage-1 Stage-2 °C. PSI Stage-1 Stage-2 Stage-1 Stage-2 hydroxide is aluminum hydroxide, calcium hydroxide, gal 2 2 2OO 6SO 15 15 8O 95.8 lium hydroxide, hafnium hydroxide, iron hydroxide, lantha 1 2 2OO 6SO 30 15 82 95.8 num hydroxide, silicon hydroxide, strontium hydroxide, tita nium hydroxide, Zinc hydroxide, or Zirconium hydroxide. US 2011/0185625 A1 Aug. 4, 2011

5. The catalyst preparation as in claim 1, wherein the 18. A catalyst according to the formula acLa2O3).X(TiO2). double-metal cyanide is of the general formula Fe2M3(CN) y(ZnO).Z(MS), wherein A and Xare each 1;Y is 1-2, Z is 3-4, 10 wherein M is lanthanum, copper or aluminum. and wherein MS is a molecular sieve according to claim 17. 6. The catalyst preparation as in claim 1, wherein the 19. A catalyst according to the formula (Al2O3). (TiO2). molecular sieve is of the type 3 A, 4 A, or 5 A, having the (ZnO).Z(MS) wherein Z is 10 and wherein MS is a molecular general formula KnNa(12-n)(AlO2)12(SiO2)12.xH2O, sieve according to claim 17. NaI(AlO2)12(SiO2)12.xH2O) or CanNa(12-n)(AlO2)12 20. A catalyst according to the formula (Fe2M3 (CN)10}. (SiO2)12.xH2O, respectively. Al2O3. TiO2.ZnO. MS, wherein M is Cu, Al or La, and 7. The catalyst preparation as in claim 1, wherein the wherein MS is a molecular sieve according to claim 17. molecular sieve is a natural or synthetic Zeolite. 21. A method for effecting esterification or transesterifica 8. The catalyst preparation as in claim 1, wherein the tion of a starting material, comprising reacting the starting molecular sieve has been modified to enhance the basicity of material with an alcohol in the presence of a solid, heteroge the molecular sieve. neous catalyst as in claim 1. 22. The method as in claim 21, wherein the starting mate 9. The catalyst preparation as in claim 1, wherein the rial comprises an oil. molecular sieve has been modified to replace at least one 23. The method as in claim 21, wherein the starting mate sodium ion within the molecular sieve with at least one metal rial comprises triglycerides. cation. 24. The method as in claim 21, wherein the starting mate 10. The catalyst preparation as in claim 9, wherein the rial comprises free fatty acids. metal cation is K+ or Cs+, and wherein the modified molecu 25. The method as in claim 21, wherein the starting mate lar sieve has the general formula KnNa(12-n)(AlO2)12 rial comprises carboxylic acid. (SiO2)12.xH2O, KmCanna 12-(m+2n)}(AlO2)12(SiO2) 26. The method as in claim 21, wherein biodiesel is pro 12.xH2O, CsnNa(12-n) (AlO2)12(SiO2)12.xH2O, or duced as a reaction product. CsmCanna 12-(m+2n)}(AlO2)12(SiO2)12.xH2O. 27. The method as in claim 21, wherein the method pro 11. The catalyst preparation as in claim 1, wherein the duces glycerol as a reaction product. catalyst is in powdered, pelleted, or extruded form. 28. The method as in claim 21, wherein soap is not pro 12. The catalyst preparation as in claim 1, wherein catalyst duced as a byproduct of the reaction. is recoverable from the reaction products by filtration. 29. The method as in claim 21, wherein the reaction is 13. The catalyst preparation as in claim 1, wherein the conducted attemperatures between 150° C. and 250° C. catalyst has been calcined. 30. The method as in claim 21, wherein the reaction is 14. A catalyst of the molecular formula: X(La2O3).y(La conducted at pressures less than 1000 psi. (OH)).Z(TiO2) wherein x, y and Z independently have a 31. The method as in claim 21, wherein the reaction is value between 1-2. conducted in a batch reactor. 15. The catalyst as in claim 14 that is prepared from lan 32. The method as in claim 21, wherein the reaction is thanum oxide or lanthanum hydroxide and titanium oxide. conducted continuously using a fixed bed reactor. 16. The catalyst as in claim 15, wherein titanium and lan 33. The method as in claim 21, wherein the reaction is thanum oxide are generated in situ. conducted in two or more Successive stages. 17. A modified molecular sieve of the general formula 34. The method as in either of claim 32, wherein the reac KnNa(12-n) (AlO2)12(SiO2)12.xH2O, KmCanna 12 tion is conducted with a ratio of 0.1-2.0 volumes of injected (m+2n)}(AlO2)12(SiO2)12.xH2O, CsnNa(12-n) (AlO2) oil/volume of catalyst per hour. 12(SiO2)12.xH2O, or CsmCanna 12-(m+2n)}(AlO2)12 (SiO2)12.xH2O. c c c c c