WO2011089253A1

WO2011089253A1 - Zirconium-based catalyst compositions and their use for biodiesel production

Info

Publication number: WO2011089253A1
Application number: PCT/EP2011/050918
Authority: WO
Inventors: Melle Koch; Simone Thewissen; Milena Rosso-Vasic; Edwin Nuberg; Hans Van Der Griend; Edgar Evert Steenwinkel
Original assignee: Albemarle Europe Sprl
Priority date: 2010-01-25
Filing date: 2011-01-24
Publication date: 2011-07-28

Abstract

Novel catalysts for producing biodiesel fuels and blending agents for diesel fuels from biological material, and preparation and use of such catalysts are described. To form the catalysts a specified amount of hydrated zirconium sulfate or sulfated zirconia, or both, is impregnated onto particular types of high surface area, high pore volume catalyst support by one or multiple wet impregnations. After drying, the composition is calcined using progressively increasing temperatures at a controlled rate to a specified temperature and held there for a specified period of time. Alternatively, the foregoing procedure is conducted, except that hydrated zirconium sulfate and/or sulfated zirconia and the catalyst support are co-extruded instead of using wet impregnation. The catalysts can effectively convert plants, algae, waste cooking oils, fatty acid distillates, etc., into biodiesel fuel.

Description

ZIRCONIUM-BASED CATALYST COMPOSITIONS AND

THEIR USE FOR BIODIESEL PRODUCTION

BACKGROUND

[0001] In biodiesel fuel production, sulfuric acid is used to convert fatty acids into fatty acid methyl esters (FAMEs). The processing involves use of sulfuric acid and methanol. This type of homogeneous catalysis has various deficiencies. For example, sulfuric acid is a strong acid which has to be used in excess during the esterification reaction, causing numerous safety issues. After reaction the sulfuric acid is typically washed from the end product, a step which requires considerable amount of energy while making the process very time consuming. Moreover, high amounts waste water are produced, which pose disposal and/or purification problems. Because of its pricing volatility and steady price increases, loss of sulfuric acid during the processing can impose economic hardship on the overall process.

[0002] Production of biodiesel fuel and biodiesel fuel blending agents from plants, algae or other biological sources poses still additional problems. Because of the nature and content of these feed stocks, it is desirable, if possible, to use heterogeneous esterification catalysts. However, attempts to make effective use of such catalysts is rendered problematic because the catalytic surfaces can be readily fouled by components in the crude biological feed stocks.

[0003] Various solid acidic catalysts have been found to have activity for particular chemical reactions or types of chemical reactions. However, many such catalysts have been found difficult to produce, especially on a commercial scale, because of relatively complicated processing involved. Other such catalysts have been found to be deficient in use for one or more reasons, including inadequate effectiveness or catalytic life; required use of difficult, expensive, and/or complex processes for producing a given catalyst; need for high processing temperatures in use; and need for use of corrosive substances in catalyst synthesis, such as sulfuric acid, or ammoniated reagents such as ammonia, ammonium salts, or quaternary ammonium salts.

[0004] U.S. Pat. No. 3,032,599 describes preparation of zirconia-based catalysts by use of base promoted precipitation of a zirconyl salt solution in water to form a gel which is then activated at 500°C. However, the acidic activity of these catalysts is low and the gellike structure makes such catalysts difficult to use in industrial operations. U.S. Pat. No. 3,132,110 describes formation of isomerization catalysts by adding an excess of ammonia to an aqueous solution of zirconium sulfate and aluminum sulfate to effect co-precipitation of hydrous sulfated zirconia and hydrous alumina, followed by drying, washing to reduce the sulfate content of the co-precipitated gel to between 0.1% and 15% by weight, and calcining the resultant gel. The handling and processing of gels, together with the complexity of the operation, constitute undesirable features of this process. In a recent paper, Y. Sun, et al., J. Phys. Chem. B 2005, 109, 2567-2572, describe solvent-free preparation of nanosized sulfated zirconia with Bronsted acidic sites by calcination of mixed (NH₄)₂S0₄ and ZrOCl₂-8H₂0. The nanosized sulfated zirconia is reported to exhibit much higher activity than conventional sulfated zirconia in catalytic esterification of cyclohexanol with acetic acid. However, although the nanosized catalysts such as those described by Sun, et al., may have high activity, they are not readily industrially applicable, mainly due to difficult, often incomplete and rather expensive separation from reaction mixture or products. In contrast, the supported catalysts of this invention posses high-activity and are readily industrially applicable. In discussing preparative methods, the authors of this recent paper point out various shortcomings of conventional methods for preparation of conventional sulfated zirconia which generally involve hydrolyzation of zirconium source, drying of zirconium hydroxide, sulfation, activation of the sulfated sample, and calcination of the sample. Process complexity, environmental concerns because of usage of solvents, and less than desirable surface area of the resultant catalysts are also referred to as shortcomings by the authors of this recent paper.

[0005] An underlying problem in the art is that molecules from feed stocks, especially crude feed stocks derived from plants, algae, other biological sources, waste cooking oils, fatty acid distillates, and the like, cannot react easily at active sites of the catalyst to convert the molecules to a desired product in high yield. Therefore, it would be highly advantageous if new materials could be found having improved surface area, improved porosity, and high activity, especially if such new materials could be produced without need for complex processing.

[0006] This invention is deemed to provide solutions to such underlying problem while at the same time achieving some, if not all, of the foregoing advantages while avoiding need for relatively complicated preparative processing.

NON-LIMITING SUMMARY OF THE INVENTION

[0007] This invention provides, among other things, a process for producing a catalyst, which process comprises drying a catalyst precursor which is: (i) a water-wet hydrated zirconium sulfate impregnated onto a support, or a water-wet sulfated zirconia impregnated onto a support, or a water-wet mixture of hydrated zirconia and sulfated zirconia impregnated onto a support; or

(ii) a water-wet co-extruded mixture of catalyst support and zirconium sulfate or sulfated zirconia, or both;

calcining the resultant dried catalyst precursor by subjecting the dried catalyst precursor to progressively increasing temperatures until at least one temperature in the range of about 300 to about 800°C (preferably in the range of about 350 to about 500°C, and especially until a temperature of about 400°C) is reached, and continuing the calcination to form an activated supported catalyst, wherein (i) the support used in forming the catalyst precursor has, prior to use in forming said catalyst precursor, a surface area of at least about 300, preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram, and (ii) said activated supported catalyst has a zirconium content expressed as "Zr" of at least about 14 wt% and a sulfurous content expressed as "S0₄" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst.

[0008] Another aspect of this invention is the provision of new supported catalyst compositions that can exhibit very high activity in acid catalyzed reactions, e.g., esterification, reactions and that are deemed to be suitable for transesterification reactions in producing biodiesel fuels. These catalyst compositions can be in various forms such as for example, pellet, extrudate, or powder form. They are comprised of a calcined supported catalyst in which the support from which such supported catalyst is prepared has, in its original state (i.e., before its use in making such supported catalyst), a surface area of at least about 300, more preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram, such catalyst having a zirconium content expressed as zirconium (Zr) of at least about 14 wt%, and a sulfurous content expressed as "S0₄" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst. Preferred particulate supports used in forming these supported catalysts, are aluminum-containing supports, especially alumina, silica alumina, or boehmite alumina, with surface areas of at least about 300, preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram. The zirconium content expressed as zirconium (Zr) and the sulfurous content expressed as sulfate (S0₄) is typically provided by hydrated zirconium sulfate or sulfated zirconia, or both.

[0009] Further provided by this invention is a process for producing a supported catalyst, which process comprises:

► forming a water-wet catalyst precursor:

(i) by one or multiple wet impregnations of a catalyst support with hydrated zirconium sulfate or sulfated zirconia, or both; or

(ii) by forming an extrudate of a water-wet mixture of catalyst support and zirconium sulfate or sulfated zirconia, or both;

wherein the support used in forming the catalyst precursor has, prior to use in forming said catalyst precursor, a surface area of at least about 300, preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram; and

► drying the water-wet catalyst precursor and then calcining the dried catalyst precursor by subjecting the catalyst precursor to progressively increasing temperatures until at least one temperature in the range of about 300 to about 800°C (preferably in the range of about 350 to about 500°C, and especially until a temperature of about 400°C) is reached, and continuing the calcination to form an activated supported catalyst composition having a zirconium content expressed as "Zr" of at least about 14 wt% and a sulfurous content expressed as "S0₄" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst.

[0010] Also provided by this invention is a process for producing a supported catalyst, which process comprises:

► impregnating a catalyst support by one or multiple wet impregnations with a hydrated zirconium sulfate or sulfated zirconia, or both, to form a water-wet supported catalyst precursor containing an amount of said hydrated zirconium sulfate or sulfated zirconia, or both, in the range of about 10 to about 50 wt% (preferably in the range of about 20 to about 50 wt%, more preferably in the range of about 30 to about 45 wt%, still more preferably in the range of about 35 to about 45 wt%, and especially about 40 wt%) based on the total dry weight of (i) hydrated zirconium sulfate or (ii) sulfated zirconia, or (iii) both of (i) and (ii), and the support used in forming the water-wet supported hydrated zirconium sulfate catalyst precursor, said catalyst support being characterized by having, prior to said impregnation, a surface area of at least about 300, preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram; and

► drying and calcining the initially wet supported hydrated zirconium sulfate catalyst precursor by subjecting said initially wet supported hydrated zirconium sulfate catalyst precursor to progressively increasing temperatures until at least one temperature in the range of about 300 to about 800°C (preferably in the range of about 350 to about 500°C, and especially until a temperature of about 400°C) is reached, and continuing the calcination to form an activated supported catalyst composition having a zirconium content expressed as "Zr" of at least about 14 wt% and a sulfurous content expressed as "SO4" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst.

[0011] Still another process provided by this invention is a process for producing a supported catalyst, which process comprises:

► co-extruding a water-wet mixture of a catalyst support and a hydrated zirconium sulfate or sulfated zirconia, or both, to form a water-wet supported catalyst precursor containing an amount of zirconium sulfate or sulfated zirconia, or both, in the range of about 10 to about 50 wt% (preferably in the range of about 20 to about 50 wt%, more preferably in the range of about 30 to about 45 wt%, still more preferably in the range of about 35 to about 45 wt%, and especially about 40 wt%) based on the total dry weight of (i) hydrated zirconium sulfate or (ii) sulfated zirconia, or (iii) both of (i) and (ii), and the support used in forming the water-wet supported hydrated zirconium sulfate catalyst precursor, said catalyst support being characterized by having, prior to said co-extrusion, a surface area of at least about 300, preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram; and ► drying the water-wet supported catalyst precursor and then subjecting the dried catalyst precursor to progressively increasing temperatures until at least one temperature in the range of about 300 to about 800°C (preferably in the range of about 350 to about 500°C, and especially until a temperature of about 400°C) is reached, and continuing the calcination to form an activated supported catalyst composition having a zirconium content expressed as "Zr" of at least about 14 wt% and a sulfurous content expressed as "S0₄" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst.

[0012] In conducting the processes of this invention, the calcination is typically conducted in the presence of oxygen, e.g., by conducting the calcination under an atmosphere of air desirably as a continuous stream of flowing air. Other suitable free- oxygen containing gaseous mixtures can be used if desired. The drying and calcining steps can be conducted as a single continuing operation or as separate individual operations.

[0013] Preferred catalyst supports for use in the above impregnation and co-extruding processes described above are aluminum-containing supports, especially alumina, silica alumina, or boehmite alumina, with surface areas of at least about 300, preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram. Particularly preferred catalyst supports used in preparing these supported catalysts are silica supports with surface areas of at least about 300 square meters per gram (preferably at least about 350 square meters per gram, still more preferably at least about 400 square meters per gram, and even more preferably at least about 470 square meters per gram) and a pore volume of at least about 1.0 milliliter per gram, preferably at least about 1.1 milliliters per gram, and more preferably at least about 1.2 milliliters per gram.

[0014] This invention can provide processes that avoid recourse to use of strong acids such as sulfuric acid. Likewise, handling and use of basic substances such as ammonia, ammonium salts, or quaternary ammonium salts are not required, but may be used, if desired.

[0015] In addition, this invention also provides nanosized catalysts, that are supported on high pore volume carriers, and that retain high activity. In contrast to conventional unsupported nanosized catalysts, which are not readily industrially applicable mainly due to difficult, often incomplete and rather expensive separation from reaction mixture or products, the supported catalysts of this invention can easily be shaped to a proper particle/extrudate size and can be easily separated from the reaction mixture. However, in order to provide accessibility of catalytically active material, only carriers with proper pore architecture can be and are used in the practice of this invention. Only in this way, retention of activity, enhancement of stability and simplified catalyst separation can be accomplished at the same time.

[0016] Thus, these nanosized supported catalysts of this invention can be formed by utilizing ground, milled, or otherwise suitably pulverized, zirconium sulfate or sulfated zirconia catalysts of this invention in a wet impregnation or a wet co-extrusion process of this invention.

[0017] There is also provided by this invention a new effective way of producing biodiesel fuel from feed stocks originating from biomass such as plants, algae, other natural products, waste cooking oils and fatty acid distillates. This involves use of the above new type of calcined catalyst which is highly effective in esterification and transesterification reactions and deemed resistant to fouling in esterification and transesterification reactions involving feed stocks originating from biomass. The supported catalyst compositions of this invention are also deemed useful for hydrocarbon isomerization and for alkylation reactions, carbonylation, esterification, transesterification as well as other chemical transformations.

[0018] The above and other aspects of this invention will become still further apparent from the ensuing description, accompanying drawings, and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figures 1-6 are graphical presentations of results of esterification runs between oleic acid and methanol, each run being conducted at 130°C with various catalysts of this invention in which the support was a high surface area, high pore volume support of this invention.

[0020] Figures 7-10 are graphical presentations of results of esterification runs between oleic acid and methanol, each run being conducted at 90°C with various catalysts of this invention in which the support was a high surface area, high pore volume support of this invention.

[0021] Figures 11-13 are graphical presentations of results of esterification runs between oleic acid and methanol, each run being conducted at 60°C with various catalysts of this invention in which the support was a high surface area, high pore volume support of this invention.

[0022] Figure 14 is a graphical presentation of comparative esterification runs between oleic acid and methanol conducted at 130°C in which the performance of a catalyst of this invention is compared with that of several commercially-available esterification catalysts.

FURTHER DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF

THE INVENTION

Supported Catalysts and their Production

[0023] Pursuant to this invention, hydrated zirconium sulfate or sulfated zirconia (or a combination of both) is used as a precursor for an active catalyst, and is applied to a suitable particulate support or carrier by wet impregnation or co-extrusion. The application of the hydrated zirconium sulfate or sulfated zirconia to the support is carried out by use of a specified set of operating conditions. The support has, prior to application by wet impregnation of, or co-extrusion with, the hydrated zirconium sulfate solution or sulfated zirconia solution, a high surface area and a very high pore volume, enabling formation of a highly suitable catalyst for use in conducting esterification and transesterification reactions. Supports used in the practice of this invention typically have a surface area of at least about 300 square meters per gram (preferably at least about 350 square meters per gram, still more preferably at least about 400 square meters per gram, and even more preferably at least about 470 square meters per gram) and a pore volume of at least about 1.0 milliliter per gram (preferably at least about 1.1 milliliters per gram, and more preferably at least about 1.2 milliliters per gram). Preferred particulate supports are aluminum-containing supports, especially alumina, silica alumina, or boehmite alumina, with surface areas of at least about 300, more preferably at least about 350, still more preferably at least about 370, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram. Particularly preferred particulate supports are silica supports with surface areas of at least about 300, preferably at least about 350, still more preferably at least about 400 square meters per gram and a pore volume of at least about 1.0 milliliter per gram and preferably at least about 1.1 milliliters per gram.

[0024] A preferred general procedure for preparing a sulfated-zirconia-based catalyst of this invention is as follows: A hydrated zirconium sulfate is added to the carrier or support via one or multiple wet impregnations so that it contains in the range of about 10 to about 50 wt% (preferably in the range of about 20 to about 50 wt%, more preferably in the range of about 30 to about 45 wt%, still more preferably in the range of about 35 to about 45 wt%, and especially an amount of about 40 wt%) of the hydrated zirconium sulfate, based on the total dry weight of the wet supported hydrated zirconium sulfate and the support. The wet supported hydrated aluminum zirconium sulfate product is allowed to age for a period in the range of about 10 minutes to about 2.5 hours (preferably lh). Then, the product is dried at a drying temperature in the range of about 100 to 140°C, preferably at about 120°C. Volatile impurities, intermediates, and/or coproducts are then removed by calcining the product. The calcination is conducted by ramping up the temperature of the dried product 1 to about 100°C per minute (e.g., 40°C per minute), preferably from about 1 to about 20°C per minute, more preferably from about 1 to about 10°C per minute, and most preferably from about 2 to about 8°C per minute and most highly preferably, about 2°C per minute to a temperature in the range of 300-800°C, and holding the product at the calcination temperature for a period of 0.2 to about 4.0 hours and preferably at least 1 to 4 hours. It is possible pursuant to this invention to continue the calcination for a period greater than about 4 hours, but ordinarily there is no particular advantage in doing so. To our surprise it was found that by using specific process conditions in combination with the high surface area and high pore volume carriers used pursuant to this invention, a new material was prepared resulting in a highly active catalyst.

[0025] Without limitation, carriers or supports that can be used in the practice of this invention include alumina-containing carriers (i.e., carriers which comprise alumina such as, for example, high purity alumina, dispersible alumina, precipitated alumina, hydrotalcite, boehmite alumina, gamma alumina, delta alumina, theta alumina, pseudo boehmite alumina, etc.), silica carriers, boehmite carriers, pseudo boehmite carriers, molecular sieves, clays, and modified clays. Boehmite carriers, alumina-containing carriers, and silica-alumina carriers are preferred. Silica carriers are more preferred. The carriers or supports can be in various physical forms such as for example, spheres, beads, and extrudates. Ceramic carriers can be used as supports for catalysts of this invention that were prepared from carriers with small particle sizes.

[0026] A desirable procedure for producing sulfated-zirconia-based catalysts of this invention involves use of a high surface area, high pore volume carrier to enhance surface area and acid activity. For this purpose an alumina-containing or preferably, a silica carrier, is used. The silica carrier typically has a surface area of at least about 300, preferably at least about 350 m²/g and for especially advantageous esterification results, more preferably at least about 400 m²/g and a pore volume of at least about 1.0, and preferably at least about 1.1 mL/g. The alumina-containing carrier typically has a surface area of at least about 300 m²/g, preferably at least about 350 m²/g, more preferably at least about 370 m²/g and for especially advantageous esterification results, at least about 470 m²/g and a pore volume of at least about 1.0 mL/g, preferably at least about 1.1, and more preferably at least about 1.2 mL/g.

[0027] Pore volumes and surface areas are calculated from nitrogen adsorption/desorption isotherms as follows: N₂ adsorption measurements are performed as described in ASTM method D4222-03 (as reapproved 2008), with the following deviations/details: 1) Prior to the measurement, samples are in vacuum degassed at 300°C until the pressure is < 50 milliTorr for at least 1 hour. 2) The measurement is performed on a Micromeritics ASAP 2400 or ASAP 2405 instrument. 3) An isotherm of 41 points is measured. S A-BET (surface area-BET) is abstracted from the data in accordance to ASTM method D3663-03 (as reapproved 2008), with the following details: The standard range used for fitting the SA line is the range: 0.05< P/P0 <0.30. Pore volume is abstracted according to D4641-94 (as reapproved 2006), with the following deviation: The range in nm applied is 2-60 nm. The pore volume reported is the cumulative volume that exists in the range of 2-60 nm.

[0028] Catalysts of this invention formed from silica supports having a surface area of at least about 400 m²/g and a pore volume of at least about 1.1 mL/g are particularly preferred because based on experimental results obtained thus far, they exhibit the highest efficiency in actual esterification runs.

[0029] Without desiring to be bound by theory, it is believed that during the calcination, various chemical species or compounds are formed which may include one or more of zirconia, sulfated zirconia, hydrated sulfated zirconium, and zirconium hydroxide, perhaps along with other double salts or the like.

[0030] The amount of the catalyst precursor hydrated zirconium sulfate, which is applied onto the support by one or multiple wet impregnations is typically in the range of about 10 to about 50 wt%, preferably in the range of about 30 to about 50 wt%, and more preferably in the range of about 35 to about 45 wt%, based on the total dry weight of the wet supported hydrated zirconium sulfate and the support. [0031] Wet impregnations as conducted in the practice of this invention typically result in achieving incipient wetness of the carrier by impregnation from a solution. In other words, impregnation to incipient wetness or incipient wetness impregnation is used.

[0032] After completion of the wet impregnation, which can be carried out as a single operation or as multiple operations in order to achieve the desired extent of impregnation, it is desirable to allow the impregnated catalyst support to age (i. e. , stand) for a period in the range of about 10 minutes to about 2.5 hours (preferably 1 hour). After ageing, the wet impregnated support is then dried at a suitable temperature in the range of about 100 to 140°C, preferably at about 120°C. Thereafter, the dried impregnated support is then calcined. Typically, the calcination is conducted in air, although other free-oxygen- containing gasses can be used or other oxidizing atmosphere, if desired. The calcination is conducted at least at one temperature in the range of 300 to 800°C for at least 0.2 to 4 hours (preferably at least 1 to 4 hours) to form an activated supported sulfated solid catalyst composition of this invention. It is possible pursuant to this invention to continue the calcination for a period greater than about 4 hours, but ordinarily there is no particular advantage in doing so.

[0033] If so desired, the catalyst material or precursors may be shaped. Shaping comprises extrusion, pelletizing, beading and/or spray drying. It must be noted that if the catalyst composition is to be applied in slurry type reactors, fluidized beds, moving beds, expanded beds, generally spray drying or beading is applied. For fixed bed or ebullating bed applications, generally the catalyst composition is extruded, palletized and/or beaded. The shape and size of the catalyst can vary and will typically depend upon the intended application of the catalyst. In the latter case, at any stage prior to or during the shaping step, any additives which are conventionally used to facilitate shaping, can be added. These additives may comprise aluminum stearate, surfactants, graphite, starch, methyl cellulose, bentonite, attapulgite, polyethylene glycols, polyethylene oxides, or mixtures thereof.

[0034] As noted above, the catalyst compositions of this invention can also be prepared by use of a co-extrusion process. A general procedure for conducting such a process involves forming an extrusion solution from water and zirconium sulfate or a hydrated zirconium sulfate. Typically, the solution is formed by adding the zirconium sulfate or sulfated zirconia to water which has been pre-heated and which is maintained at an elevated temperature in the range of about 40°C to about 70°C. During the addition the mixture is agitated, (e.g., by use of stirring). A catalyst support or carrier material having the appropriate surface area and pore volume characteristics described above is added to a suitable mixing device, such as a kneader, followed by adding the extrusion solution while kneading the resultant mixture. The resultant mixture is then extruded into a suitable cylindrical shape followed by drying the extrudate at a suitable temperature in the range of about 100 to 140°C, typically at about 120°C. Thereafter, the dried extrudate is calcined by progressively increasing the temperature of the extrudate at a rate in the range of from about 1 to about 100°C per minute, preferably from about 1 to about 20°C per minute, more preferably from about 1 to about 10°C per minute, and most preferably from about 2 to about 8°C per minute and most highly preferably, about 2°C per minute until at least one temperature in the range of about 300°C to about 800°C, particularly in the range of about 350°C to about 450°C is reached, and continuing the calcination for a period of about 0.2 to about 4 hours (preferably at least 1 to about 4 hours). The proportions used in forming the initial mixture are such as to form an activated supported catalyst composition of this invention having a zirconium content expressed as "Zr" of at least about 14 wt% and a sulfurous content expressed as "S0₄" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst.

[0035] In conducting the calcination, it is very important to utilize a progressively increasing rate of temperature increase (i.e., a rate of ramping up the temperature increase) in the range of from about 1 to about 100°C per minute, preferably from about 1 to about 20°C per minute, more preferably from about 1 to about 10°C per minute, and most preferably from about 2 to about 8°C per minute and most highly preferably, about 2°C per minute and continuing the calcination for a period from at least 0.2 to 4 hours (preferably at least 1 to about 4 hours) to form on said catalyst support an activated supported catalyst composition. Without desiring to be bound by theory, it is believed that the activated catalyst itself may comprise at least one or more of zirconia, sulfated zirconia, hydrated sulfated zirconia, and zirconium hydroxide. Use of the foregoing rates of progressive temperature increase provide carriers with enhanced activities. Heating at a calcination temperature of ca. 400°C for a period of ca. 1-4 hours has been found to be optimal.

[0036] If desired, the support or carrier can be precalcined before use in either the wet impregnation or the co-extrusion process of this invention to ensure that volatile impurities that may be present are removed before use of the support or carrier in the process. [0037] It will be noted that the herein-described process technology of this invention for producing the above novel calcined heterogeneous catalysts of this invention is a direct, economical, straightforward, and facile way of producing such catalysts. For example, this invention involves, among other things, a procedure of impregnating or co-extruding the catalyst supports having the specified surface areas and pore volumes with a specified amount of a wet hydrated zirconium sulfate, and then dry and calcine the impregnated catalyst supports under air or other oxidizing atmosphere at a suitable rate of ramping up to one or more calcination temperatures in the range of ca. 300°C to ca. 800°C, where it is maintained in such temperature range for a period of ca. 0.2-4 hours (preferably at least 1 to about 4 hours) so that an active esterification catalyst is formed. Calcination times of up to 50 or more hours can be used, if desired, but typically shorter times are used in order to minimize operating costs and to maximize productivity.

Preparation of Biodiesel Fuels or a Blending Component for Use in Diesel Fuel

[0038] In accordance with this invention, the activated supported zirconium sulfate or sulfated zirconia catalysts of this invention can be used as catalysts in the preparation of biodiesel fuels or a blending component for use in diesel fuels. The process used typically comprises transesterification and/or esterification of feed stocks originating from biomass (e.g., a natural fat, fatty acids or oil) with a suitable alcoholic reagent such as a lower alkanol, i.e., an alkanol having in the range of 1 to about 6 carbon atoms per molecule, preferably methanol or ethanol.

[0039] Among preferred alcoholic reagents for use in the transesterification and/or esterification reactions to form biodiesel fuels or blending agents for diesel fuels are methanol, ethanol, or both of them, with methanol being preferred.

[0040] Typically, the esterification is conducted using a stoichiometric excess of the alcohol relative to the starting material. Such excess can range from about 3 to about 20 molar ratio excess or even more. The temperature of the esterification reaction will vary to some extent, depending upon the nature of the reactants being used and the particular catalyst of the invention used. Generally speaking, however, the transesterification is carried out at one or more appropriate temperatures in the range of about 50 to about 250°C, and preferably in the range of about 60 to about 130°C. The duration of the transesterification reaction is typically influenced mainly by the temperature(s) at which the transesterification is carried out and the scale of operation. Thus, the time period can be shorter when operating at high temperatures, whereas when operating at lower temperatures, it is desirable to conduct the reaction for longer reaction periods. The esterification reactions can be conducted in periods in the range of about 10 minutes to about 2.5 hours. Inert solvents may be used, if desired. Use of a solvent can be of advantage in cases where the viscosity of the reaction mixture poses difficulties in agitating the reaction mixture.

[0041] In Tables 1-4, a non-limiting overview is provided of natural fats and oils that can be converted with the catalysts of this invention. In Tables 1 -4, the values shown in the tables are weight percentages. Tables 1-4 are illustrative, respectively, of fatty acid contents of (1) vegetable oils, (2) rapeseed oils and canola oils, (3) land animal fats, and (4) fish oils. It will be understood and appreciated that these Tables are not intended to restrict, and should not be interpreted as restricting, the scope of this invention to only the specific compositions set forth in the Tables, as this information is presented for purposes of illustration.

[0042] In Column 1 in each of Tables 1 , 2, and 4, the numeral, if any, following the designation of number of carbon atoms (e.g. , the numeral 0 in "C8:0" for caprylic acid) indicates the number of double bonds in the molecule (i.e., in this case there are no double bonds).

Table 1 - Illustrative Fatt Acid Com onent Contents of Various Vegetable Oils

C₁₈:3 (cis,cis,cis-3,6,9 or

cis,cis,cis-6,9,12), C₁₈H₃₀O2

Other/unknown 0.9 0.4 ~ ~

a) http://en.wikipedia.org/wiki/Palm oil [Reference: Ang, Catharina Y. W.,

Liu, and Yao-Wen Huang, eds. (1999). Asian Foods] .

b) http://www.hort.purdue.edu/newcrop/proceedingsl 990/yl -21 1.html

b) http://www.hort.purdue.edu/newcrop/proceedingsl 990/yl -21 1.html

[0043] As is known in the art, selective breeding rapeseed plants enabled development of low erucic acid varieties of rapeseed. Subsequently, another variety was produced with both a low erucic acid content and a low level of glucosinolates; this was named Canola, from Canadian Oil Low Acid. More recently, a variety developed in 1998 is considered to be the most disease - and drought-resistant variety of Canola to date. Recent varieties such as this have been produced by gene splicing techniques. Oils from any and all such plant varieties can be processed pursuant to this invention.

C₁₆ 23-27 23-26 19-27 (22)

Ci7 1.0-1.4 0.3-0.5 <0.3

C₁₈ 15.5-23 12.8-17.7 5-11 (6)

C₂₀ 0.1-0.2 0-0.3 —

Total Saturated 43-56 37-87 24-40 (28)

Monounsaturated

C₁₄ 0.5-1.0 Traces <0.2

C₁₆ 2.3-4.2 1.4-3.7 5-10 (6)

Ci7 ~ 0.2-0.4 <0.3

C₁₈ 36.5-43 39-45 37-53 (42)

C₂₀ 0.1-0.6 0.5-1.3 ~

Total Monounsaturated 39-45 41-51 42-63 (48)

Polyunsaturated

C₁₈ (2 double bonds) 1.4-3.9 8.5-12 9-25 (18)

C₁₈ (3 double bonds) 0.3-0.8 0.6-1.2 <2 (1)

Total Polyunsaturated 1.5-5 9-13 9-27 (20) c) http://www.iterg.eom/I MG/pdf/CompositionAcidesGrasGraisses] iuiles Animales .pdf

Table 4 - Illusl trative Fatty Acid Component Contents of Fish Oils

e^'icosapentaenoic acid

e) docosahexaenoic acid

Other Reactions in which the Catalysts of this Invention can be Utilized

[0044] The activated supported zirconium sulfate or sulfated zirconia catalysts of this invention can also be used to advantage in conducting transesterification reactions, hydrocarbon isomerizations, alkylation reactions, and many other chemical transformations.

[0045] The following Examples are presented for purposes of illustration. The scope of this invention is not intended to be restricted to only the details presented in these Examples.

EXAMPLE 1

Impregnation of Silica Support, Calcination at 500°C for 1 Hour in a Rotary Oven

[0046] A catalyst composition was prepared by impregnating via incipient wetness impregnation with a H₂0 saturation of 145% at room temperature. 50.2 g of Zr(S0₄)₂-4H₂0 per 60 g of silica carrier with a surface area of 400 m /g and a pore volume of 1.1 mL/g was used, which is 40% of Zr(S0₄)₂ on total impregnated material weight. Zr(S0₄)₂-4H₂0 was dissolved in 120.5 g of water preheated at a stirring hotplate at 50°C. Before impregnation the carrier was precalcined at 450°C for one hour in a static muffle oven under ambient conditions using a temperature ramp of 10°C/min.

[0047] Impregnation was done by dropwise addition of the salt solution to the carrier, which was placed in a rotating pan. Mixture was left for aging in a rotating pan for 1 h. Drying was performed with 100 1/min air with a temperature of 150°C till product temperature reaches 100°C. Then, the dried product was transferred to a static muffle oven and further dried for 24 hours at 120°C .

[0048] This material was calcined at 500 °C for 1 hour in a rotary calcining oven (using a ramp of 7°C/minute). The sample obtained can be used to carry out biodiesel production from fats and/or fatty acids using transesterification or esterification. EXAMPLE 2

Impregnation of Silica Support, Calcination at 400°C for 1 Hour in a Plate Oven

[0049] A catalyst composition was prepared by impregnating via incipient wetness impregnation with a H₂0 saturation of 145%o at room temperature. 50.0 g of Zr(S0₄)₂-4H₂0 per 60 g of silica carrier with a surface area of 400 m /g and a pore volume of 1.1 mL/g was used, which is 40%> of Zr(S0₄)₂ on total impregnated material weight. Zr(S0₄)₂-4H₂0 was dissolved in 120.5 g of water preheated at a stirring hotplate at 50°C.

[0050] Impregnation was done by dropwise addition of the salt solution to the carrier, which was placed in a rotating pan. The mixture was left to age in a rotating pan for 1 hour at room temperature. Drying was performed under an airflow having a temperature of 150°C at a flow of 100 L/min until the product temperature reaches 100°C. Subsequently, the dried product was transferred to a static muffle oven and further dried for 24 hours at 120°C.

[0051] This material was calcined at 400°C for 1 hour in a calcining plate oven (using a ramp of 2°C/minute).

[0052] The sample obtained can be used to carry out biodiesel production from fats and/or fatty acids using transesterification or esterification. EXAMPLE 3

Impregnation of Silica Support, Calcination at 300°C for 1 Hour in a Rotary Oven

[0053] A catalyst composition was prepared by impregnating via incipient wetness impregnation with a demineralized H₂0 saturation of 145% at room temperature. 100 g of Zr(S0₄)₂-4H₂0 per 120 g of silica carrier with a surface area of 400 m²/g and a pore volume of 1.1 mL/g was used, which is 40% of Zr(S0₄)2 on total impregnated material weight. Zr(S0₄)₂-4H₂0 was dissolved in 241 g of water preheated at a stirring hotplate at 50°C.

[0054] Impregnation was done by dropwise addition of the salt solution to the carrier, which was placed in a rotating pan. The mixture was left to age in a rotating pan for 1 hour at room temperature. Drying was performed under an airflow having a temperature of 150°C at a flow of 100 l/min until the product temperature reaches 100°C. Subsequently, the dried product was transferred to a static muffle oven and further dried for 24 hours at 120°C.

[0055] This material was calcined at 300°C for 1 hour in a rotary calcining oven (using a ramp of 10°C/minute).

[0056] The sample obtained can be used to carry out biodiesel production from fats and/or fatty acids using transesterification or esterification.

EXAMPLE 4

Impregnation of Silica Support, Calcination at 300°C for I Hour in a Plate Oven

[0057] A catalyst composition was prepared by impregnating via incipient wetness impregnation with a demineralized H₂0 saturation of 145% at room temperature. 200.0 g of Zr(S0₄)₂-4H₂0 per 240 g of silica carrier with a surface area of 400 m /g and a pore volume of 1.1 mL/g was used, which is 40% of Zr(S0₄)₂ on total impregnated material weight. Zr(S0₄)₂-4H₂0 was dissolved in 482 g of water, preheated at a stirring hotplate at 50°C.

[0058] Impregnation was done by dropwise addition of the salt solution to the carrier, which was placed in a rotating pan. The mixture was left to age in a rotating pan for 1 hour at room temperature. Drying was performed under an airflow having a temperature of 150°C at a flow of 100 1/min until the product temperature reaches 100°C. Subsequently, the dried product was transferred to a static muffle oven and further dried for 24 hours at 120°C.

[0059] This material was calcined at 300°C for 1 hour in a calcining plate oven (using a ramp of 5 °C/minute) .

[0060] The sample obtained can be used to carry out biodiesel production from fats and/or fatty acids using transesterification or esterification.

EXAMPLE 5

Co-extrusion Zirconium Sulfate with Alumina-Containing Support, Calcination at 400°C or 1 Hour in a Rotary Oven

[0061] A catalyst composition was prepared by contacting a 300 grams alumina- containing carrier with a surface area of 470 m /g and a pore volume of 1.2 mL/g, with an extrusion solution. The extrusion solution was prepared by weighing 204.45 gram demineralized water into a beaker while being stirred on a heater to a temperature of 50°C followed by adding 219.50 gram Zr(S0₄)₂-4H₂0. Before extrusion the carrier was precalcined at 450°C for one hour in a static muffle oven under ambient conditions using a temperature ramp of 10°C/min.

[0062] The carrier material was added to a kneader. To this mix the extrusion solution was dosed slowly, while kneading. The mixture that was obtained was extruded in a 1.5mm cylindrical shape. Subsequently the sample was dried for 24 hours at 120°C and calcined in flowing air at 400°C for 1 hour in a rotary oven (using a ramp of 2°C/minute).

EXAMPLE 6

Co-extrusion Sulfated Zirconia with Alumina-Containing Support, Calcination at 400°C or 1 Hour in a Rotary Oven

[0063] A catalyst composition was prepared by contacting a 300 grams alumina- containing carrier with a surface area of 470 m²/g and a pore volume of 1.2 mL/g, with an extrusion solution of sulfated zirconia. The extrusion solution was prepared by weighing 204.45 gram demineralized water into a beaker while being stirred on a heater to a temperature of 50°C followed by adding 219.50 grams sulfated zirconia. The sulfated zirconia was prepared by mixing 140 g of ZrOCl_{3 8}-H₂0 with 350 g NH₄S0₄ with friction in air for 25 minutes and equilibrating overnight. After calcination at 600°C for 5h the material was ready for use. Before extrusion the carrier was precalcined at 450°C for one hour in a static muffle oven under ambient conditions using a temperature ramp of 10°C/min.

[0064] The carrier material was added to a kneader. To this mix the extrusion solution was dosed slowly, while kneading. The mixture that was obtained was extruded in a 1.5mm cylindrical shape. Subsequently the sample was dried for 24 hours at 120°C and calcined in flowing air at 400°C for 1 hour in a rotary oven (using a ramp of 2°C/minute).

EXAMPLE 7

Impregnation of Alumina-Containing Support, Calcination at 400°C for 1 Hour in a Rotary Oven

[0065] A catalyst composition was prepared by impregnating via incipient wetness impregnation with a demineralized H₂0 saturation of 145% at room temperature. 50.2 g of Zr(S0₄)₂-4H₂0 per 60 g of alumina-containing carrier with a surface area of 470 m /g and a pore volume of 1.2 mL/g was used, which is 40%) of Zr(S0₄)₂ on total impregnated material weight. Zr(S0₄)₂-4H₂0 was dissolved in 189.9 g of water preheated at a stirring hotplate at 50°C.

[0066] Impregnation was done by dropwise addition of the salt solution to the carrier, which was placed in a rotating pan. The mixture was left to age in a rotating pan for 1 hour at room temperature. Drying was performed under an airflow having a temperature of 150°C at a flow of 100 1/min until the product temperature reaches 100°C. Subsequently, the dried product was transferred to a static muffle oven and further dried for 24 hours at 120°C.

[0067] This material was calcined at 400°C for 1 hour in a rotary calcining oven (using a ramp of 10°C/minute).

[0068] The sample obtained can be used to carry out biodiesel production from fats and/or fatty acids using transesterification or esterification. EXAMPLE 8

Impregnation of Alumina-Containing Support, Calcination at 300°C for 1 Hour in a Plate Oven

[0069] A catalyst composition was prepared by impregnating via incipient wetness impregnation with a demineralized H₂0 saturation of 145% at room temperature. 100 g of Zr(S0₄)₂-4H₂0 per 240 g of alumina containing carrier with a surface area of 470 m²/g and a pore volume of 1.2 mL/g was used, which is 40% of Zr(S0₄)₂ on total impregnated material weight. Zr(S0₄)₂-4H₂0 was dissolved in 379.8 g of water preheated at a stirring hotplate at 50°C.

[0070] Impregnation was done by dropwise addition of the salt solution to the carrier, which was placed in a rotating pan. The mixture was left to age in a rotating pan for 1 hour at room temperature. Drying was performed under an airflow having a temperature of 150°C at a flow of 100 1/min until the product temperature reaches 100°C. Subsequently, the dried product was transferred to a static muffle oven and further dried for 24 hours at 120°C.

[0071] This material was calcined in a static plate oven with a ramp of 5°C/minute under ambient conditions to 300°C for 1 hour.

[0072] The sample obtained can be used to carry out biodiesel production from fats and/or fatty acids using transesterification or esterification.

EXAMPLES 9-14

Evaluation of Catalysts of This Invention in Esterification at I30°C

[0073] In order to further illustrate the practice and advantages of this invention, sulfated-zirconia-based catalysts of this invention that were produced using high surface, high pore volume silica carriers as described in Examples 1-4 and that were produced using high surface, high pore volume alumina-containing carriers as described in Examples 5-8 were tested for their esterification activity at 130°C, using oleic acid and methanol (MeOH). In each esterification reaction, a mixture of 7.1 grams of oleic acid (technical grade; 90%) and 6.3 grams of methanol was prepared, and to this was added 0.14 gram of the zirconium sulfate catalyst of this invention. The reaction mixture was stirred for 2 hours at 130°C excluding a heating-up period of 20 minutes. The reaction mixture was then filtered and subsequently analyzed by gas chromatography. Determinations were made of the percent conversions to methyl oleate, a typical fatty acid methyl ester (FAME). [0074] Summarized graphically in Figs. 1-6 are the results of the esterification tests of Examples 9-14 respectively. It can be seen from these results that formed acidic high pore volume catalysts of this invention were successful in esterification reactions and that the silica carrier impregnated samples were more efficient under these esterification conditions.

EXAMPLES 15-18

Evaluation of Catalysts of This Invention in Esterification at 90°C

[0075] In a second group of evaluation tests, the sulfated-zirconia-based catalysts of this invention that were produced using high surface, high pore volume silica carriers as described in Examples 1-4 were tested for their esterification activity at even lower esterification temperatures of 90°C, using oleic acid and methanol (MeOH). The amounts of the reaction components and the conditions used for esterification reactions were the same as used in the esterification reactions of Examples 9-14.

[0076] Summarized graphically in Figs. 7-10 are the results of the esterification tests of Examples 15-18 respectively. It can be seen from these results that the high pore volume catalysts of this invention used in these tests were successful in esterification reactions conducted at the lower temperature of 90°C.

EXAMPLES 19-21

Evaluation of Catalysts of This Invention in Esterification at 60°C

[0077] In a third group of evaluation tests, the sulfated-zirconia-based catalysts of this invention that were produced using high surface, high pore volume silica carriers as described in Examples 1-4 were tested for their esterification activity at even lower esterification temperatures of 60°C, using oleic acid and methanol (MeOH). The amounts of the reaction components and the conditions used for esterification reactions were the same as used in the esterification reactions of Examples 9-14.

[0078] Summarized graphically in Figs. 11-13 are the results of the esterification tests of Examples 19-21 respectively. It can be seen from these results that the high pore volume catalysts of this invention used in these tests were successful in esterification reactions conducted at the even lower temperature of 60°C, especially when conducted for at least two hours at the 60°C reaction temperature. COMPARATIVE EXAMPLES A C

Effectiveness of Several Commercially- Available Esteriflcation Catalysts at 130°C

[0079] In order to enable a comparison as between the effectiveness of sulfated-zirconia- based catalysts of this invention and commercially-available esteriflcation catalysts, several solid commercially-available catalysts were tested under the same esteriflcation conditions as used in the 130°C tests of Examples 9-14. Thus, to a mixture of 7.1 grams of oleic acid (technical grade; 90%) and 6.3 grams of methanol was formed, and to this was added 0.14 gram of the commercial catalyst in solid form being evaluated. These commercial catalysts tested were (A) Amberlyst^® 15 (Rohm and Haas Company), a catalytic porous ion exchange resin, (B) Nafion^® SAC- 13 (Sigma Aldrich), a strongly acidic catalyst resin, and (C) niobium pentoxide (Dakram Materials Limited) The reaction mixture was stirred for 2 hours at 130°C excluding a heating-up period of 20 minutes. The reaction mixture was then filtered and subsequently analyzed by gas chromatography. Determinations were made of the percent conversions to methyl oleate, a typical fatty acid methyl ester (FAME).

[0080] Summarized graphically in Fig. 14 are the results of the esteriflcation tests of Comparative Examples A-C. Also, in Fig. 14 are the results of the same esteriflcation runs conducted using a catalyst of this invention, viz. , a catalyst made by impregnating a silica carrier with zirconium sulfate as in Example 1. From the results shown in Fig. 14 it can be seen that the catalyst of this invention was superior to all three of the commercially-available catalyst materials.

[0081] The terms "support" and "carrier" are used interchangeably herein. They are not intended to differentiate one from the other.

[0082] Components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another component, a solvent, or etc.). It matters not what chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution as such changes, transformations, and/or reactions are the natural result of bringing the specified components together under the conditions called for pursuant to this disclosure. Thus the components are identified as ingredients to be brought together in connection with performing a desired operation or in forming a desired composition. Also, even though the claims hereinafter may refer to substances, components and/or ingredients in the present tense ("comprises", "is", etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure. The fact that a substance, component or ingredient may have lost its original identity through a chemical reaction or transformation during the course of contacting, blending or mixing operations, if conducted in accordance with this disclosure and with ordinary skill of a chemist, is thus of no practical concern.

[0083] Each and every patent or publication referred to in any portion of this specification is incorporated in toto into this disclosure by reference, as if fully set forth herein.

[0084] Except as may be expressly otherwise indicated, the article "a" or "an" if and as used herein is not intended to limit, and should not be construed as limiting, a claim to a single element to which the article refers. Rather, the article "a" or "an" if and as used herein is intended to cover one or more such elements, unless the text taken in context clearly indicates otherwise.

[0085] The invention may comprise, consist or consist essentially of the materials and/or procedures recited herein.

[0086] ¹ As used in any claim hereof, the term "consisting essentially of refers to a composition that includes the component(s), substance(s), ingredient(s), method step(s), or process step(s) set forth in the claim and that excludes any component(s), substance(s), ingredient(s), method step(s), or process step(s) that materially affect(s) the basic and novel characteristics of the subject matter of the claim.

[0087] As used herein, the term "at least about X", with respect to a numerical value, is synonymous with the term "about X or more".

[0088] This invention is susceptible to considerable variation in its practice. Therefore the foregoing description is not intended to limit, and should not be construed as limiting, the invention to the particular exemplifications presented hereinabove. The present invention also relates to the following embodiments:

(1) A process for producing a catalyst, which process comprises drying a catalyst precursor which is:

(i) a water-wet hydrated zirconium sulfate impregnated onto a support, or a water-wet sulfated zirconia impregnated onto a support, or a water-wet mixture of hydrated zirconia and sulfated zirconia impregnated onto a support; or

calcining the resultant dried catalyst precursor by subjecting the dried catalyst precursor to progressively increasing temperatures until at least one temperature in the range of from about 300 to about 800°C (preferably in the range of from about 350 to about 500°C, and especially until a temperature of about 400°C) is reached, and continuing the calcination to form an activated supported catalyst, wherein (i) the support used in forming the catalyst precursor has, prior to use in forming said catalyst precursor, a surface area of at least about 300, preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram, and (ii) said activated supported catalyst has a zirconium content expressed as "Zr" of at least about 14 wt% and a sulfurous content expressed as "S0₄" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst.

(2) A process, preferably a process according to item (1), for producing a supported catalyst, which process comprises:

► forming a water-wet catalyst precursor:

(i) by one or multiple wet impregnations of a catalyst support with hydrated zirconium sulfate or sulfated zirconia, or both, or

(ii) by forming an extrudate of a water-wet mixture of a catalyst support and zirconium sulfate or sulfated zirconia, or both;

► drying the water-wet catalyst precursor and then calcining the dried catalyst precursor by subjecting the catalyst precursor to progressively increasing temperatures until at least one temperature in the range of about 300 to about

800°C (preferably in the range of about 350 to about 500°C, and especially until a temperature of about 400°C) is reached, and continuing the calcination to form an activated supported catalyst composition having a zirconium content expressed as "Zr" of at least about 14 wt% and a sulfurous content expressed as "S0₄" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst.

(3) A process as in items (1) or (2), wherein the progressively increasing temperatures increase at a rate of from about 1 to about 100°C per minute, preferably from about 1 to about 20°C per minute, more preferably from about 1 to about 10°C per minute, and most preferably from about 2 to about 8°C per minute and most highly preferably, about 2°C per minute.

(4) A process as in any of items (l)-(3), wherein the calcination period is from about 0.2 to about 4.0 hours.

(5) A process as in item (2), wherein said water-wet catalyst precursor is formed as in (i), preferably wherein in forming said water-wet catalyst precursor as in (i), said water- wet catalyst precursor contains an amount of hydrated zirconium sulfate in the range of about 10 to about 50 wt%, preferably in the range of about 20 to about 50 wt%, more preferably in the range of about 30 to about 45 wt%, still more preferably in the range of about 35 to about 45 wt%, and especially about 40 wt%, based on the total dry weight of the hydrated zirconium sulfate.

(6) A process as in item (2), wherein said water-wet catalyst precursor is formed as in (ii), preferably wherein in forming said water-wet catalyst precursor as in (ii), said water- wet catalyst precursor contains an amount of hydrated zirconium sulfate or sulfated zirconia, or both, in the range of about 10 to about 50 wt%, preferably in the range of about 20 to about 50 wt%, more preferably in the range of about 30 to about 45 wt%, still more preferably in the range of about 35 to about 45 wt%, and especially about 40 wt%, based on the total dry weight of the hydrated zirconium sulfate or sulfated zirconium, or both. (7) A process as in any of items (l)-(6), wherein the catalyst support is at least one aluminum-containing catalyst support, especially alumina, silica alumina, or boehmite alumina, with a surface area prior to use in forming the catalyst precursor of at least about 300, more preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram, particularly preferred the aluminum-containing catalyst support is an alumina- containing support with a surface area of about 470 m²/g and a pore volume of about 1.2 mL/g.

(8) A process as in any of items (l)-(7), wherein the catalyst support is at least one silica catalyst support with a surface area of at least about 300 square meters per gram, preferably at least about 350 square meters per gram, still more preferably at least about 400 square meters per gram, and even more preferably at least about 470 square meters per gram, and a pore volume of at least about 1.0 milliliter per gram, preferably at least about 1.1 milliliters per gram, and more preferably at least about 1.2 milliliters per gram, particularly preferred the silica catalyst support has a surface area of about 400 m /g and a pore volume of about 1.1 mL/g.

(9) A calcined supported catalyst in which the support from which such supported catalyst is prepared has, in its original state, a surface area of at least about 300, more preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram, such catalyst having a zirconium content expressed as zirconium (Zr) of at least about 14 wt%, and a sulfurous content expressed as "S0₄" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst.

(10) A calcined supported catalyst as in item (9), wherein the support is an aluminum- containing support, especially alumina, silica alumina, or boehmite alumina, wherein preferably said support has, prior to its use in forming said catalyst, a surface area of about 470 m²/g and a pore volume of about 1.2 mL/g.

(11) A calcined supported catalyst as in item (9), wherein the support is an silica support. (12) A calcined supported catalyst as in item (9), wherein said support has, prior to its use in forming said catalyst, a surface area of about 400 m²/g and a pore volume of about 1.1 mL/g.

(13) A catalyst precursor composition which comprises, (i) water-wet supported hydrated zirconium sulfate catalyst precursor, or (ii) water-wet mixture of catalyst support and hydrated zirconium sulfate or sulfated zirconia, or (iii) both of (i) and (ii), wherein the support used in forming the catalyst precursor has, prior to use in forming said catalyst precursor, a surface area of at least about 300, preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram.

(14) A catalyst precursor composition as in item (13), wherein said (i) water-wet supported hydrated zirconium sulfate catalyst precursor, or (ii) water-wet mixture of catalyst support and zirconium sulfate or sulfated zirconia, or (iii) both of (i) and (ii) contains an amount of hydrated zirconium sulfate or sulfated zirconia, or both, in the range of about 10 to about 50 wt%, preferably in the range of about 20 to about 50 wt%, more preferably in the range of about 30 to about 45 wt%, still more preferably in the range of about 35 to about 45 wt%, and especially about 40 wt%, based on the total dry weight of the hydrated zirconium sulfate or sulfated zirconium, or both.

(15) A catalyst precursor composition as in items (13) or (14), wherein the support is an aluminum-containing support, especially alumina, silica alumina, or boehmite alumina, or is a silica support, wherein preferably the support prior to its use in forming the catalyst precursor composition is an alumina support having, prior to its use in forming said catalyst, a surface area of about 470 m /g and a pore volume of about 1.2 mL/g or is a silica support having a surface area of about 400 m /g and a pore volume of about 1.1 mL/g.

(16) A catalyst composition formed by calcining a catalyst precursor composition of any of items (13)-(15).

(17) A process for the preparation of a biodiesel fuel or a blending component for use in diesel fuel, which process comprises esterifying a feed stock derived from biological sources comprising plants, algae, natural fat or oil, waste cooking oils, and fatty acid distillates, said process being characterized by conducting the esterification with an alcohol and a catalyst prepared by a process as in any of items (l)-(8) or a catalyst as in any of items (9)-(12) or (16).

Claims

THAT WHICH IS CLAIMED IS:

1. A process for producing a catalyst, which process comprises drying a catalyst precursor which is:

2. A process as in Claim 1, wherein the progressively increasing temperatures increase at a rate of from about 1 to about 100°C per minute, preferably from about 1 to about 20°C per minute, more preferably from about 1 to about 10°C per minute, and most preferably from about 2 to about 8°C per minute and most highly preferably, about 2°C per minute.

3. A process for producing a supported catalyst, which process comprises:

► forming a water-wet catalyst precursor:

► drying the water-wet catalyst precursor and then calcining the dried catalyst precursor by subjecting the catalyst precursor to progressively increasing temperatures until at least one temperature in the range of about 300 to about 800°C (preferably in the range of about 350 to about 500°C, and especially until a temperature of about 400°C) is reached, and continuing the calcination to form an activated supported catalyst composition having a zirconium content expressed as

"Zr" of at least about 14 wt% and a sulfurous content expressed as "SO4" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst.

4. A process as in Claim 3, wherein the progressively increasing temperatures increase at a rate of from about 1 to about 100°C per minute, preferably from about 1 to about 20°C per minute, more preferably from about 1 to about 10°C per minute, and most preferably from about 2 to about 8°C per minute and most highly preferably, about 2°C per minute.

5. A process as in any of Claim 1-4, wherein the calcination period is from about 0.2 to about 4.0 hours.

6. A process as in Claim 3, wherein said water- wet catalyst precursor is formed as in

(i)-

7. A process as in Claim 6, wherein in forming said water- wet catalyst precursor as in

(i) , said water- wet catalyst precursor contains an amount of hydrated zirconium sulfate in the range of about 10 to about 50 wt%, preferably in the range of about 20 to about 50 wt%, more preferably in the range of about 30 to about 45 wt%, still more preferably in the range of about 35 to about 45 wt%, and especially about 40 wt%, based on the total dry weight of the hydrated zirconium sulfate.

8. A process as in Claim 3, wherein said water- wet catalyst precursor is formed as in (ii).

9. A process as in Claim 8, wherein in forming said water-wet catalyst precursor as in

(ii) , said water- wet catalyst precursor contains an amount of hydrated zirconium sulfate or sulfated zirconia, or both, in the range of about 10 to about 50 wt%, preferably in the range of about 20 to about 50 wt%, more preferably in the range of about 30 to about 45 wt%, still more preferably in the range of about 35 to about 45 wt%, and especially about 40 wt%, based on the total dry weight of the hydrated zirconium sulfate or sulfated zirconium, or both.

10. A process as in any of Claims 1-9, wherein the catalyst support is at least one aluminum-containing catalyst support, especially alumina, silica alumina, or boehmite alumina, with a surface area prior to use in forming the catalyst precursor of at least about 300, more preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram.

11. A process as in Claim 10, wherein the aluminum-containing catalyst support is an alumina-containing support with a surface area of about 470 m²/g and a pore volume of about 1.2 mL/g.

12. A process as in any of Claims 1-11, wherein the catalyst support is at least one silica catalyst support with a surface area of at least about 300 square meters per gram, preferably at least about 350 square meters per gram, still more preferably at least about 400 square meters per gram, and even more preferably at least about 470 square meters per gram, and a pore volume of at least about 1.0 milliliter per gram, preferably at least about 1.1 milliliters per gram, and more preferably at least about 1.2 milliliters per gram.

13. A process as in Claim 12, wherein the silica catalyst support has a surface area of about 400 m /g and a pore volume of about 1.1 mL/g.

14. A calcined supported catalyst in which the support from which such supported catalyst is prepared has, in its original state, a surface area of at least about 300, more preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram, such catalyst having a zirconium content expressed as zirconium (Zr) of at least about 14 wt%, and a sulfurous content expressed as "S0₄" of at least about 20 wt%, the foregoing weight percentages being based on the total dry weight of the supported catalyst.

15. A calcined supported catalyst as in Claim 14, wherein the support is an aluminum- containing support, especially alumina, silica alumina, or boehmite alumina.

16. A calcined supported catalyst as in Claim 15, wherein said support has, prior to its use in forming said catalyst, a surface area of about 470 m²/g and a pore volume of about 1.2 mL/g.

17. A calcined supported catalyst as in Claim 14, wherein the support is an silica support.

18. A calcined supported catalyst as in Claim 14, wherein said support has, prior to its use in forming said catalyst, a surface area of about 400 m /g and a pore volume of about

1.1 mL/g.

19. A catalyst precursor composition which comprises, (i) water- wet supported hydrated zirconium sulfate catalyst precursor, or (ii) water- wet mixture of catalyst support and hydrated zirconium sulfate or sulfated zirconia, or (iii) both of (i) and (ii), wherein the support used in forming the catalyst precursor has, prior to use in forming said catalyst precursor, a surface area of at least about 300, preferably at least about 350, still more preferably at least about 400, and even more preferably at least about 470 square meters per gram and a pore volume of at least about 1.0, preferably at least about 1.1, and more preferably at least about 1.2 milliliters per gram.

20. A catalyst precursor composition as in Claim 19, wherein said (i) water-wet supported hydrated zirconium sulfate catalyst precursor, or (ii) water-wet mixture of catalyst support and zirconium sulfate or sulfated zirconia, or (iii) both of (i) and (ii) contains an amount of hydrated zirconium sulfate or sulfated zirconia, or both, in the range of about 10 to about 50 wt%, preferably in the range of about 20 to about 50 wt%, more preferably in the range of about 30 to about 45 wt%, still more preferably in the range of about 35 to about 45 wt%, and especially about 40 wt%, based on the total dry weight of the hydrated zirconium sulfate or sulfated zirconium, or both.

21. A catalyst precursor composition as in Claims 19 or 20, wherein the support is an aluminum-containing support, especially alumina, silica alumina, or boehmite alumina, or is a silica support.

22. A catalyst precursor composition as in Claim 21, wherein the support prior to its use in forming the catalyst precursor composition is an alumina support having, prior to its use in forming said catalyst, a surface area of about 470 m²/g and a pore volume of about

1.2 mL/g or is a silica support having a surface area of about 400 m /g and a pore volume of about 1.1 mL/g.

23. A catalyst composition formed by calcining a catalyst precursor composition of any of Claims 19-22.

24. A process for the preparation of a biodiesel fuel or a blending component for use in diesel fuel, which process comprises esterifying a feed stock derived from biological sources comprising plants, algae, natural fat or oil, waste cooking oils, and fatty acid distillates, said process being characterized by conducting the esterification with an alcohol and a catalyst prepared by a process as in any of Claims 1-10 or a catalyst as in any of Claims 14-18 or 23.