Chromium-free copper-calcium silicate catalyst for fatty ester hydrogenation / hydrogenation

Abstract

The hydrocracking / hydrogenation catalyst comprises copper oxide, calcium oxide, silicon dioxide, and sodium oxide, the hydrocracking / hydrogenation catalyst is a powder, tablet, or extrudate, the hydrocracking / hydrogenation catalyst is substantially free of chromium, and the hydrocracking / hydrogenation catalyst comprises a crystallite phase of CuO and a crystallite phase of cubic SiO2, rhombohedral calcium carbonate CaCO3, triclinic calcium silicate CaSiO3, calcium silicate hydroxide hydrate (Ca 14 Si 24 O 58 (OH)₈·2H₂O), calcium silicate hydrate 4CaO·5SiO₂·5H₂O, alumina, and combinations of two or more thereof.

Description

[[Technical Field]]

[0001] Cross-Reference to Related Applications This application claims the priority benefit of U.S. Provisional Application No. 63 / 109,591, filed on November 4, 2020, the entire content of which is incorporated herein by reference in its entirety.

[0002] The present technology generally relates to the field of catalysts for hydrocracking / hydrogenation. More specifically, it relates to a slurry-phase copper-calcium silicate-based catalyst in powder form for fatty acid ester hydrocracking / hydrogenation. [[Background Art]]

[0003] Commercial slurry processes for producing fatty alcohols typically use copper-chromium (CuCr) catalysts. [[Summary of the Invention]] [[Problem to be Solved by the Invention]]

[0004] As environmental regulations on chromium-containing chemical substances or catalysts become stricter, it is important to develop catalysts that do not contain chromium and instead utilize other materials as both chemical and mechanical stability promoters and supports. [[Means for Solving the Problem]]

[0005] In one aspect, the hydrocracking catalyst / hydrogenation catalyst comprises copper oxide, calcium oxide, silicon dioxide, and sodium oxide, wherein the hydrocracking catalyst / hydrogenation catalyst is in powder form and is substantially free of chromium. In various embodiments, the calcined hydrocracking catalyst / hydrogenation catalyst comprises from about 35 wt% to about 85 wt% of CuO, from about 8 wt% to about 20 wt% of CaO, from about 10 wt% to about 30 wt% of SiO2, and from about 0.1 wt% to about 5 wt% of Na2O.

[0006] In another aspect, there is provided a method for preparing a calcined hydrocracking catalyst / hydrogenation catalyst, the method comprising the steps of: mixing a copper-containing material and a silicate-containing material in a solution; adding a caustic material to form an aqueous slurry comprising a precipitate; collecting the precipitate; drying the precipitate to form a dried precipitate; and calcining the dried precipitate to form the calcined hydrocracking catalyst / hydrogenation catalyst, wherein the calcined hydrocracking catalyst / hydrogenation catalyst is a powder, and the calcined hydrocracking catalyst / hydrogenation catalyst is substantially free of chromium. A calcined hydrocracking catalyst / hydrogenation catalyst prepared according to the method is also provided.

[0007] In a further aspect, there is provided a method of hydrogenating a carbonyl-containing organic compound, the method comprising contacting the carbonyl-containing organic compound with a hydrocracking catalyst / hydrogenation catalyst, wherein the hydrocracking catalyst / hydrogenation catalyst is a catalyst comprising copper oxide, calcium oxide, silicon dioxide and sodium oxide, the hydrocracking catalyst / hydrogenation catalyst is a powder, and the hydrocracking catalyst / hydrogenation catalyst is substantially free of chromium. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] [Figure 1] Fig. 1 is a graph of particle size formation as a function of precipitation time based on "volume In" according to Example 1. Each plot shows the cumulative volume percent (vol%) distribution of particles detected via laser diffraction within the particle size range. [Figure 2] Fig. 2 is a graph of particle size formation as a function of precipitation time based on "pass rate" according to Example 1. Each plot shows a normal distribution curve in which the majority of the sample volume is occupied by mid-range size particles (i.e., volume percent). [Figure 3] Fig. 3 is a diagram showing X-ray diffraction (XRRD) patterns of catalysts of the present invention having calcination temperatures of 500°C, 650°C, 750°C and 800°C according to Examples 2, 5, 7 and 8, respectively. [Figure 4] Fig. 4 is a schematic diagram of an autoclave reactor used for catalyst performance testing according to various embodiments. [Figure 5]This is a graphical comparison of the methyl ester conversion rate (percentage) as a function of time for CuO on a standard CuCr catalyst, a CuAl catalyst, and the calcium silicate catalyst described (Example 1) under various embodiments. [Figure 6] This is a graphical comparison of the fat alcohol selectivity (percentage) as a function of time for CuO on a standard CuCr catalyst, a CuAl catalyst, and the described calcium silicate catalyst (Example 1) under various embodiments. [Figure 7] This is a graphical comparison of the fatty alcohol yield (percentage) as a function of time for CuO on a standard CuCr catalyst, a CuAl catalyst, and the described calcium silicate catalyst (Example 1) under various embodiments. [Figure 8A] This is a graphical comparison of the methyl ester conversion rate (percentage) as a function of time, based on the examples. [Figure 8B] This is a comparison of the methyl ester conversion rate (percentage) as a function of time, focusing on the high conversion rate portion, based on the examples. [Figure 9A] This is a graphical comparison of the selectivity (percentage) of fatty alcohols as a function of time, based on the examples. [Figure 9B] This is a comparison of fatty alcohol selectivity (percentage) as a function of time, focusing on the highly selective portion, based on the examples. [Figure 10A] This is a graphical comparison of the fatty alcohol yield (percentage) as a function of time, based on the examples. [Figure 10B] This is a comparison of the fatty alcohol yield (percentage) as a function of time, focusing on the high-yield portion, based on the examples. [Figure 11] This is a graph comparing the methyl ester conversion rate (percentage) as a function of time for examples with different Na content. [Figure 12] This is a graphical comparison of the selectivity (percentage) of fatty alcohols as a function of time for examples with different Na content. [Figure 13]This is a graph comparing the fatty alcohol yield (percentage) as a function of time for examples with different Na content. [Figure 14] This graph shows the catalytic performance of CuO in a wax ester slurry process (feeds injected at times 0, 1, 2, and 3) on a standard CuCr catalyst, a CuAl catalyst, and the calcium silicate catalyst described (Example 3), according to the examples. A higher SAP value indicates a lower conversion rate. [Figure 15] This graph shows the cumulative wax ester conversion rates for CuO on a standard CuCr catalyst, a CuAl catalyst, and the described calcium silicate catalyst (Example 3) in various embodiments. [Figure 16] This graph shows the results of filterability tests for samples using CuCr-based catalysts, CuAl-based catalysts, and CuO on the described calcium silicate catalyst (Example 1) in a methyl ester slurry process. [Modes for carrying out the invention]

[0009] Various embodiments are described below. It should be noted that specific embodiments are not intended as exhaustive descriptions or as limitations to broader embodiments described herein. One embodiment described in relation to a particular embodiment is not necessarily limited to that embodiment and can be implemented in any other embodiment.

[0010] Where used herein, “about” is to be understood by those skilled in the art and varies to some extent depending on the context in which it is used. Where there is a use of this term that is not clear to those skilled in the art, “about” means up to plus or minus 10% of the particular term, given the context in which it is used.

[0011] The use of the terms “a,” “an,” and “the,” as well as similar referents, in the context of describing elements (particularly in the context of the claims below), should be interpreted as encompassing both singular and plural, unless otherwise specifically indicated herein or unless it is clearly inconsistent with the context. The enumeration of ranges of values ​​herein is intended merely as a convenient way of referring individually to each distinct value contained within the range, unless otherwise indicated herein, and each distinct value is incorporated herein as if it were individually enumerated herein. All methods described herein may be performed in any suitable order unless otherwise indicated herein or unless it is clearly inconsistent with the context. The use of any example or illustrative language provided herein (e.g., “etc.”) is intended merely to better illustrate embodiments and does not limit the claims unless otherwise specified. No language herein should be interpreted as indicating that an element not claimed is essential.

[0012] As used herein, the term "hydrocracking / hydrogenation" refers, in a particular application, to a catalyst capable of catalyzing either or both of a hydrocracking and / or hydrogenation reaction.

[0013] As used herein, the terms “baked,” “baked,” or “baked” refer to heating the catalyst precursor precipitate in an oven under an air or controlled oxygen atmosphere, as a dry filtered cake in some embodiments.

[0014] Where used herein, “substantially chromium-free” is intended to indicate that, to the greatest extent possible, the materials described are excluded from the formulation. However, trace amounts may be carried over due to contamination of the starting reagents. For example, where the term used is “substantially chromium-free,” it is intended that all chromium is ideally excluded, but trace amounts of chromium may be carried over due to contamination by chromium in other starting reagents, such as copper, manganese, and aluminum source materials. For example, in some embodiments, “substantially chromium-free” may contain less than 1000 ppm of chromium, such as less than 750 ppm, less than 500 ppm, or less than 100 ppm. Where appropriate, substantially chromium-free means that the catalyst does not contain any detectable chromium (0.0 wt% chromium). Similarly, in some embodiments, this term also applies to manganese.

[0015] Chromium-free calcium copper silicate powder catalysts can be prepared for slurry phase hydrocracking applications, and in many respects, these catalysts have proven superior to state-of-the-art copper-chromium catalysts currently in use in commercial settings. For example, the powder catalysts described herein exhibit superior catalytic performance in terms of activity and selectivity, reduced metal leaching, and comparable stability under reaction conditions compared to state-of-the-art Cu-chromium catalysts.

[0016] In one embodiment, a hydrocracking catalyst / hydrogenation catalyst containing copper(II) oxide ("CuO") is provided on calcium silicate powder (i.e., the catalyst is a copper calcium silicate material). The catalyst is active for the hydrogenation or hydrocracking of compounds having a carbonyl component, particularly for the hydrocracking reactions of methyl esters and wax esters. The hydrocracking catalyst / hydrogenation catalyst contains about 35% to about 85% by weight of CuO, about 8% to about 20% by weight of CaO, about 10% to about 30% by weight of SiO2, about 0.1% to about 5% by weight of Na2O, about 0% to about 1.5% by weight of Al2O3, and about 0% to about 1% by weight of K2O. In some embodiments, the hydrocracking catalyst / hydrogenation catalyst comprises about 35% to about 70% by weight of CuO, about 8% to about 16% by weight of CaO, about 15% to about 22% by weight of SiO2, about 0.1% to about 0.75% by weight of Na2O, 0 to about 1.5% by weight of Al2O3, and 0 to about 0.75% by weight of K2O. The hydrocracking catalyst / hydrogenation catalyst is substantially chromium-free. In some embodiments, the calcium silicate catalyst may contain manganese, but in other embodiments, the catalyst is substantially manganese-free.

[0017] The catalyst consists of a crystalline phase of CuO and CaCO3, SiO2, CaSiO3, Ca 14 Si 24 O 58 The crystalline phases exhibit one or more from the list of (OH)8·2H2O (trascottite or calcium silicate hydroxyhydrate), 4CaO·5SiO2·5H2O (torbelmorite or calcium silicate hydrate), and Al2O3. In some embodiments, the calcined hydrocracking catalyst / hydrogenation catalyst is CuO and cubic SiO2, rhombohedral calcium carbonate CaCO3, triclinic calcium silicate CaSiO3, calcium silicate hydroxide hydrate (Ca 14 Si 24 O 58 It exhibits additional crystallite phases selected from the group consisting of (OH)8·2H2O), calcium silicate hydrate 4CaO·5SiO2·5H2O, alumina, and two or more combinations thereof. The Brunauer-Emmett Teller surface area (BET SA) is approximately 20 m²2 / g to about 100 m 2 / g. In some embodiments, the BET SA is about 5 m 2 / g to about 85 m 2 / g.

[0018] The copper calcium silicate catalyst may be in the form of a powder. The average particle size of the powder may be described according to the following particle size distribution ("PSD"), that is, D 10 from about 1 μm to about 10 μm, D 50 from about 10 μm to about 25 μm, and D 90 from about 30 μm to about 45 μm. It may comprise a PSD of D 10 from about 1 μm to about 1.5 μm, D 50 from about 16 μm to about 20 μm, and D 90 from about 30 μm to about 35 μm. The loosely packed bulk density of the copper calcium silicate powder catalyst is from about 0.25 g / ml to about 0.6 g / ml, and the CuO crystallite size is from about 50 Å to about 250 Å. In some embodiments, the CuO crystallite size is from about 50 Å to less than 240 Å. Methods for preparing the copper calcium silicate catalysts and their use in hydrocracking / hydrogenation reactions are also described.

[0019] It is also worth noting that since the catalyst needs to be separated from the reactor slurry for reuse, filtration characteristics are important in fatty alcohol production when using a slurry phase process to enable a pure fatty alcohol product. The copper calcium silicate powder catalysts described herein exhibit good filtration characteristics similar to those of state-of-the-art Cu-chromium materials. Catalysts with good filtration / separation characteristics enable high production throughput in fatty alcohol production plants.

[0020] In another embodiment, a method for preparing a calcined hydrocracking catalyst / hydrogenation catalyst is provided. This method includes the steps of mixing a copper-containing material and a silicate-containing material in solution, adding a caustic material to form an aqueous slurry containing a precipitate, collecting the precipitate, drying the precipitate to form a dry powder, and calcining the dry powder to form a calcined hydrocracking catalyst / hydrogenation catalyst. In various embodiments, the calcined hydrocracking catalyst / hydrogenation catalyst may be a powder. In any of the above embodiments, the calcined hydrocracking catalyst / hydrogenation catalyst may be substantially chromium-free.

[0021] According to this method, the aqueous slurry has a pH of approximately 6.0 to approximately 9.0. This includes a pH of approximately 7 to 7.5.

[0022] In this method, collection may involve removing the precipitate via filtration of the aqueous slurry, and collecting the precipitate as a filtration cake. The precipitate may be washed with water to remove some of the sodium from the filtration cake. Washing may be carried out with a large amount of water and may be repeated (two, three, four or more washes).

[0023] In the preparation method, drying of the precipitate may be carried out in an oven in a heated atmosphere. The heating may be about 40°C to about 200°C, about 75°C to about 150°C, or about 100°C to about 125°C. Drying may be carried out for a period of time to ensure that a dry powder is obtained. According to various embodiments, the period may be 1 hour to 24 hours or longer. This includes about 5 hours to about 15 hours, or about 8 hours to about 12 hours. In some embodiments, drying is overnight.

[0024] In any of the embodiments described above, the firing may be carried out at a temperature of about 400°C to about 800°C. This may include about 500°C to about 800°C, about 500°C to about 750°C, or about 600°C to about 750°C. The firing may be carried out over a period of time to complete the firing of the dried powder. According to various embodiments, the period may be about 10 minutes to about 10 hours. This includes about 0.5 hours to about 3 hours.

[0025] In any of the embodiments of the above method, the copper-containing material may be a copper salt comprising copper nitrate, copper sulfate, copper chloride, copper bromide, copper acetate, or any two or more combinations thereof. Similarly, the silicate-containing material may be a silicate comprising calcium silicate.

[0026] In any of the above embodiments of this method, the caustic material may be any caustic material. Exemplary corrosive agents include, but are not limited to, Na2CO3, NaOH, K2CO3, KOH, or any two or more combinations thereof.

[0027] The calcium copper silicate catalyst may also be in powder form. The average particle size of the powder is given by the following particle size distribution ("PSD"), i.e., D 10 Approximately 1μm~approximately 10μm, D 50 Approximately 10 μm to approximately 25 μm microns, and D 90 It may be described according to approximately 30 μm to approximately 45 μm. If the catalyst is in powder form, the average particle size is given by the following particle size distribution ("PSD"), i.e., D 10 Approximately 1μm~approximately 10μm, D 50 Approximately 10 μm to approximately 25 μm microns, and D 90 This can be explained according to approximately 30 μm to approximately 45 μm. 10 Approx. 1μm~Approx. 1.5μm, D 50 Approximately 16 μm to approximately 20 μm, and D 90 It may contain PSDs of approximately 30 μm to 35 μm. In some embodiments, D 10 This can be approximately 1 μm to approximately 2 μm, or approximately 4 μm to approximately 9 μm. In some embodiments, D 50This can be approximately 10 μm to approximately 25 μm, or approximately 16 μm to approximately 20 μm. In some embodiments, D 90 The size can be approximately 30 μm to 45 μm, or approximately 35 μm to 40 μm. The loosely packed bulk density of the copper-calcium silicate powder catalyst is approximately 0.25 g / ml to 0.6 g / ml, and the CuO crystallite size is approximately 50 Å to 250 Å. In some embodiments, the CuO crystallite size is approximately 50 Å to less than 240 Å. Methods for producing the copper-calcium silicate catalyst and their use in hydrocracking / hydrogenation reactions are also described.

[0028] Prior to activation, the hydrocracking catalyst / hydrogenation catalyst may contain about 35% to about 85% by weight of CuO, about 8% to about 20% by weight of CaO, about 10% to about 30% by weight of SiO2, and about 0.1% to about 5% by weight of Na2O. In other embodiments, prior to activation, the calcined hydrocracking catalyst / hydrogenation catalyst may contain about 60% to about 70% by weight of CuO, about 10% to about 15% by weight of CaO, about 15% to about 25% by weight of SiO2, and about 0.5% to about 2% by weight of Na2O. In further embodiments, prior to activation, the calcined hydrocracking catalyst / hydrogenation catalyst contains about 35% to about 70% by weight of CuO, about 8% to about 16% by weight of CaO, about 15% to about 22% by weight of SiO2, about 0.1% to about 0.75% by weight of Na2O, about 0.5% to about 1.5% by weight of Al2O3, and about 0.1% to about 0.75% by weight of K2O. In some embodiments, prior to activation, the calcined hydrocracking catalyst / hydrogenation catalyst may contain about 0.5% to about 1% by weight of Na2O, or less than about 0.5% to about 1% by weight of Na2O.

[0029] In this method, the hydrocracking catalyst / hydrogenation catalyst is substantially chromium-free. In some embodiments, the calcium silicate catalyst may contain manganese, but in other embodiments, the catalyst is substantially manganese-free.

[0030] In this method, the Brunauer-Emmett Teller surface area (BET SA) of the catalyst powder is approximately 20 m². 2 / g~approx. 100 m2 It may be / g. In some embodiments, BET SA is about 5 m 2 / g ~ approx. 85 m 2 / g, or approximately 10 m 2 / g ~ approx. 85 m 2 / g, or approximately 15 m 2 / g ~ approx. 80 m 2 It is / g.

[0031] Similar to the catalyst materials described above, the calcined hydrocracking catalyst / hydrogenation catalyst produced by this method exhibits an XRD pattern showing CuO, and also contains cubic SiO2, rhombohedral calcium carbonate CaCO3, triclinic calcium silicate CaSiO3, and calcium silicate hydroxide hydrate (Ca 14 Si 24 O 58 The catalyst exhibits additional crystallite phases selected from the group consisting of (OH)8·2H2O), calcium silicate hydrate (4CaO·5SiO2·5H2O), alumina, and two or more combinations thereof. Furthermore, the calcined hydrocracking catalyst / hydrogenation catalyst may exhibit a CuO crystallite size of approximately 50 Å to less than approximately 240 Å, or a CuO crystallite size of approximately 50 Å to approximately 175 Å. In addition, the calcined hydrocracking catalyst / hydrogenation catalyst may exhibit a calcium silicate hydrate crystallite size of approximately 550 Å to less than approximately 673 Å, or approximately 550 Å to approximately 650 Å.

[0032] In another embodiment, a method for hydrogenation / hydrocracking of a carbonyl-containing organic compound is provided. This method comprises contacting the carbonyl-containing organic compound with an activated catalyst, which is one of the calcination hydrocracking catalysts / hydrogenation catalysts described herein. In various embodiments, the carbonyl-containing organic compound may include ketones, aldehydes, and / or esters. In some embodiments, it is a fatty acid ester. More specifically, in any embodiment disclosed herein, the carbonyl-containing organic compound is a fatty acid methyl ester (e.g., C8-C 20 Carbon chain), fatty acid wax ester (e.g., C 18 -C 40This may include, but is not limited to, carbon chains, furfural, methyl phenyl ketone, dimethyl or diethyl ester, or any two or more mixtures thereof. Hydrogenation / hydrocracking may be carried out in a slurry phase reactor, which may be a batch reactor, a continuously stirred tank reactor, a column reactor, or a column reactor.

[0033] According to some embodiments, the method may further include the step of reducing the calcined hydrocracking catalyst / hydrogenation catalyst in a hydrogen atmosphere to obtain a pre-reduced (activated) calcined hydrocracking catalyst / hydrogenation catalyst. In some embodiments, the reduction may be carried out in the presence of a solvent for a time and temperature sufficient to reduce the calcined hydrocracking catalyst / hydrogenation catalyst.

[0034] The present invention, as generally described herein, will be more readily understood by referring to the following examples, which are provided as illustrations and are not intended to limit the invention.

[0035] Examples Comparative Example: A commercial catalyst containing copper and chromium (Cu-Cr) was supplied by BASF (Cu1950P (copper chromite catalyst having 36 wt% Cu and 32 wt% Cr)).

[0036] A Cu-Al-O catalyst (comparative example) was prepared according to U.S. Patent No. 6,455,464. Copper nitrate solution (1640 g; 15.48% Cu) was diluted to 2500 ml with deionized water. Sodium aluminate (815.6 g, 25% Al2O3) was dissolved and diluted to 2500 ml with deionized water. The copper nitrate and sodium aluminate solutions were then simultaneously added to a 12-liter reactor containing 2500 ml of deionized water at a rate of approximately 33 ml / min. Sodium carbonate powder (318 g dissolved in 1500 ml of deionized water) was added to maintain the reactor at a pH of approximately 7.4. The catalyst then precipitated from the solution at room temperature, and the precipitate was collected by filtration as a filtration cake. The cake was then washed at least three times with 3000 ml of deionized water. After washing the cake and drying it overnight at 120°C, CuAl powder was baked at 700°C to 800°C for 2 hours. Next, the excellent performance of the catalyst of the present invention when applied to the hydrocracking of fatty esters using a reference catalyst was explained.

[0037] Example 1: Preparation of CuOCaSiO3 catalyst. A Cu(NO3)2 solution (1756 g, 16.2 wt% Cu) was diluted to a total volume of 1800 ml with deionized water in a reactor equipped with a mixing paddle, and the mixing speed was set to 800 RPM (revolutions per minute). Calcium silicate (237.5 g; LOI = 16% "MicroCel E®" (synthetic calcium silicate hydrate available from Imerys)) was slowly added to the Cu(NO3)2 solution. Stirring was continued until the calcium silicate was completely dispersed. Sodium carbonate (700 g; "soda ash") was dissolved in deionized water (3 liters) to form a solution, which was then added to the Cu(NO3)2 and calcium silicate slurry to maintain a pH of approximately 7 at room temperature. A precipitate formed over approximately 1 hour and was collected by filtration as a filtration cake. The cake was then washed with deionized water, subsequently dried, and baked at 500°C for 2 hours to form the catalyst. The catalyst contains approximately 60 wt% CuO, with the remainder being CaSiO3 and other trace amounts. Chemical analysis: CuO 63.1 wt%, CaO 13.9 wt%, SiO2 21.8 wt%, and Na2O 1.4 wt%. Loose ABD (apparent bulk density): 0.2 g / ml, tightly packed ABD (apparent bulk density): 0.3 g / ml. Table 1 shows the particle size distribution (PSD) with and without sonication.

[0038] [Table 1]

[0039] Example 2: Pilot plant procedure for CuOCaSiO3 catalyst. Cu(NO3)2 solution (31.6 kg; 16.2 wt% Cu) was diluted to 25 L with deionized water in a reactor equipped with a mixer set to approximately 800 RPM. Calcium silicate (4.275 kg; LOI = 16%; "MicroCel E®") was slowly added to the Cu(NO3)2 solution. Stirring was continued until the calcium silicate was completely dispersed. Sodium carbonate (10.8 kg; "soda ash") was dissolved in deionized water (40 L) containing NaOH (3.6 kg) to form a solution. The soda ash and NaOH solution was then added to the Cu(NO3)2 and calcium silicate slurry, maintaining a pH of approximately 7 at room temperature. A precipitate formed over approximately 1 hour and was collected by filtration as a filtration cake. The cake was then washed with deionized water and subsequently dried (120°C). The PSD of the material is D 10 9.7 μm, D 50 26.6 μm, and D 90 It is 66.4 μm.

[0040] Examples 3-8 The powder from Example 2 was subjected to different firing temperatures according to Table 2. In each example, the powder from Example 2 was fired by heating it to the indicated temperature in a muffle furnace for 1 hour, and then held at that temperature for 2 hours before cooling to room temperature.

[0041] [Table 2]

[0042] Examples 9-12 The catalyst from Example 1 was prepared with different sodium content. These catalysts had almost the same composition after calcination at approximately 500°C for 12 hours: 63.1% by weight CuO, 13.9% by weight CaO, and 21.8% by weight SiO2. The only difference was the Na2O content in the catalyst due to differences in washing with varying amounts of deionized water. The results are shown in Table 3.

[0043] [Table 3]

[0044] Figures 1 and 2 show how catalyst particle size is formed and changes during precipitation in Example 1. Each plot in Figure 1 shows the cumulative volume % (vol%) distribution of particles detected by laser diffraction within the particle size range. Each plot in Figure 2 shows a normal distribution curve in which the majority of the sample volume is occupied by medium-range sized particles (i.e., volume %, vol%). According to the plots, the catalyst is D 10 7.7 μm, D 50 19.1 μm, and D 90 It should have a PSD of 37.5 μm. However, it is clear that the average particle size distribution depends on the precipitation conditions.

[0045] BET Surface Area Measurement: BET (Brunauer-Emmett-Teller) surface area measurements were performed according to ASTM method D3663-03, the standard test method for surface area of ​​catalysts and catalyst supports. A portion of the catalyst BET surface area is summarized in Table 4.

[0046] [Table 4]

[0047] Table 4 clearly shows that higher firing temperatures result in lower BET surface area. 14.3 to 82 m 2 All copper silicate catalysts with a BET SA of 3.4 / g exhibit good fatty alcohol yields from hydrocracked methyl esters. Further calcination at higher temperatures, e.g., 800°C, yields very low BET SA, 3.4 m 2 / g results in lower activity.

[0048] XRD analysis of catalysts selected from Examples 3-8. XRD analysis was performed on Examples 3-8 (calcined at 500°C-800°C) to identify the crystallite phase and crystallite size. XRD analysis was performed according to the procedure described herein. An empyrean diffraction system with a copper anode was operated at a generator setting of 45 kV and 40 mA to generate XRD analysis data at a wavelength of 1.54060 Å for Cu K α1 Radiation was generated. The optical path consisted of a primary solar slit of 0.04 rad, a 15 mm beam mask, a divergent slit of 1°, a 2° anti-scattering slit, a sample, a monochromator, a secondary solar slit of 0.02 rad, and an X'Celerator position-sensitive detector.

[0049] The sample catalyst was ground into a fine powder using a mortar and pestle, and then packed back into a circular mount sample holder. The sample holder was mounted on a sample spinner during data acquisition to improve particle count statistics. Data acquisition from the circular mount covered the range of 15° to 90°²θ using continuous scans with a step size of 0.017°²θ and a time of 400 seconds per step. A graphite monochromator was used to measure Cu K β Unwanted radiation, including radioactive material, was removed. Phase identification analysis was performed using Panalytical HighScore version 4.5 software and the ICDD PDF 4+2020 version powder diffraction file database. HighScore was also used for profile fitting to determine the d-interval, FWHM, and peak positions used to calculate crystallite size estimates using Scherrer's formula. Details of the XRD patterns and crystallite sizes of the samples in each example are shown below.

[0050] Example 3, calcined at 500°C, exhibited a major peak that closely matches monoclinic copper oxide (CuO). Several smaller remaining peaks closely match rhombohedral calcium carbonate (CaCO3). Candidates for the remaining few peaks are calcium silicate hydrate (4CaO·5SiO2·5H2O), cubic silica (SiO2), and / or alumina phase (Al2O3). The crystallite size of copper oxide was estimated based on the (111) reflectance at approximately 58 Å.

[0051] Example 5, calcined at 650°C, exhibited a main peak that closely matched monoclinic copper oxide (CuO). A small remaining peak candidate was rhombohedral calcium carbonate (CaCO3). 3) These are calcium silicate hydrate (4CaO·5SiO2·5H2O), calcium silicate hydrate (Ca2SiO4·H2O), and / or cubic silica (SiO2). The crystallite size of copper oxide was estimated based on (111) reflection at approximately 80 Å.

[0052] Example 7, calcined at 750°C, exhibited major peaks that closely matched monoclinic copper oxide (CuO) and triclinic calcium silicate (CaSiO3). Hydrogen oxide calcium silicate (Ca2SiO4·0.3H2O) could fit into several very small trace peaks. The crystallite size of copper oxide was estimated based on the (111) reflection at approximately 149 Å. The crystallite size of calcium silicate was estimated based on the (220) reflection at 573 Å.

[0053] Example 8, calcined at 800°C, exhibited major peaks that closely matched monoclinic copper oxide (CuO) and triclinic calcium silicate (CaSiO3). Hydrogen oxide calcium silicate (Ca2SiO4·0.3H2O) could fit into several very small trace peaks. The crystallite size of copper oxide was estimated based on the (111) reflection at approximately 240 Å. The crystallite size of calcium silicate was estimated based on the (220) reflection at 673 Å.

[0054] XRD analysis of these catalysts revealed that the catalysts are composed of CuO and the following crystalline phases: cubic SiO2, rhombohedral calcium carbonate (CaCO3), triclinic calcium silicate (CaSiO3), and truscottite (calcium silicate hydrate; Ca 14 Si 24 O 58 This indicates the presence of one or more of the following: (OH)8·2H2O), tobermorite (calcium silicate hydrate; 4CaO·5SiO2·5H2O), and alumina. These are shown in Figure 3.

[0055] Furthermore, it has been shown that the crystallite phase changes with variations in firing temperature. Increasing the firing temperature increases the CuO crystallite size from approximately 58 Å to approximately 240 Å. Table 5 shows the effect of firing temperature on CuO crystallite size. CuO crystallite size was estimated based on (111) reflection. Calcium silicate hydrate also begins to dehydrate as the temperature increases, eventually forming triclinic calcium silicate CaSiO3. The crystallite size of calcium silicate increases from 573 to 673 Å as the firing temperature changes from 750°C to 800°C.

[0056] [Table 5]

[0057] Catalytic performance. Test procedure. Catalytic activity and catalyst selectivity were evaluated by slurry phase hydrogenolysis of methyl esters to fatty alcohols. Catalytic performance was evaluated for both methyl ester hydrogenolysis and wax ester hydrogenolysis in a 1-liter autoclave (exemplified in Figure 4).

[0058] [Table 6]

[0059] [Table 7]

[0060] Procedure for methyl ester hydrocracking: The catalyst (0.8 wt%) was loaded into the reactor through the opening of the top screw on the reactor head. 452 g of C12-C14 fatty acid methyl ester was loaded through a funnel located on the gas line used for pressurization and hydrogen gas supply. The autoclave system was purged several times with N2 to remove air, and then purged several times with hydrogen. The stirring speed was set to 2000 rpm, the furnace temperature was increased to 280°C, and the autoclave was covered with a jacket (a typical ramping rate was 3°C / min). At 280°C, the autoclave was pressurized with H2 to 2500 psi, indicated by a start time of "0". Every 5 hours, 5 ml of liquid sample was collected through an inlet / outlet with frit at the tip inside the autoclave. The sample was then analyzed by GC. The total fatty alcohol yield was calculated by summing the fatty alcohol concentrations from the GC analysis.

[0061] Procedure for wax ester hydrocracking:

[0062] [Table 8]

[0063] The catalyst is loaded by opening the top screw of the reactor head. 454 g of C 12 -C 14 The fatty alcohol is loaded through a funnel placed on the gas line used for pressurization and hydrogen gas supply. The autoclave was purged several times with N2 to remove air, then purged several times with hydrogen. Stirring was started at 1500 rpm and the furnace was raised to temperature in the jacketed autoclave (typical ramping rate 3°C / min). At 300°C, the autoclave was pressurized to 4350 psi with hydrogen and 55 g of C2 was added. 16 -C 18 The fatty acid was injected through a pump. This was designated as the start time "0". 5 ml of the liquid sample was collected at 1 hour through an inlet with frit at the tip inside the autoclave. Then, 55 g of C was added. 16 -C 18Fatty acids were injected. This sampling and injection of fatty acids was continued at the 2nd and 3rd hours. After 3 HOS (time in contact with vapor), the experiment was continued for 6 hours without further injection of fatty acids. Each sample (a total of 6 samples) was analyzed by gas chromatography ("GC").

[0064] The SAP (saponification) value of each sample was calculated by wet titration, and the fatty acid conversion rate was calculated based on the SAP decrease percentage: conversion rate (%) = (SAP value in the obtained feed mixture - SAP value in the product) × 100 / SAP value. For each experiment, the sample from the last hour was also analyzed by GC FID to measure the concentrations of fatty alcohols and by-products.

[0065] Comparison of Catalytic Performance of Commercial CuCr and CuAl vs. CuO-CaSiO3 Catalysts Under the described test conditions, the CuAl powder catalyst performed worse than the commercial CuCr powder catalyst in methyl ester hydrocracking. However, the CuO-CaSiO3 catalyst described herein exhibited significantly superior performance, as shown in Figures 5-7. As the reaction time progressed, the desired product fatty alcohol of CuO-CaSiO3 was consistently higher than that of the CuCr-based catalyst throughout the test period. These results demonstrate that the CuO-CaSiO3 powder catalyst is suitable as a replacement for the CuCr powder catalyst for fatty methyl ester hydrocracking applications.

[0066] Effect of BET surface area on catalytic performance: Lower calcination temperatures result in a larger BET surface area, and therefore higher hydrogenation / hydrodecomposition activity. However, high BET SA powder catalysts are more susceptible to chemical attack, particularly from acids in the feedstock, leading to greater metal leaching into the hydrodecomposition products. When the catalyst is calcined at a sufficiently high temperature, the catalyst's BET surface area decreases, forming a more stable catalyst that is stable under reaction conditions, i.e., stable to feedstocks containing some acid. Catalyst powders were calcined at different temperatures in Examples 3-8, which produced powders with different BET SA values. These samples were tested for methyl ester hydrodecomposition catalytic performance. The results are shown in Figures 8-10. The product alcohol yield curves show that all catalysts produced at calcination temperatures in the range of 500°C to 750°C exhibit good alcohol yields. These results are for 14 to 80 m 2 This indicates that catalysts with a wide range of BET surface area (BET) per g provide good catalytic performance. However, calcination at 800°C results in a significantly lower BET surface area (3.4 m²). 2 This resulted in a larger CuO crystallite size (240 Å) and consequently, poor catalytic performance with low alcohol yields. Therefore, it is clear that the CuO-CaSiO3 catalyst has higher activity than the current CuCr catalyst.

[0067] Effect of Sodium Oxide Content on Catalytic Performance A series of catalysts with different sodium oxide content from Examples 9-12 were evaluated for slurry phase methyl ester hydrocracking. As shown in Figures 11-13, the catalyst of Example 9, which contains 1.4 wt% Na2O, exhibits lower activity and selectivity than the commercial CuCr standard. Further washing to remove residual sodium improves catalytic performance. The catalyst of Example 12 has the highest activity and yields the highest rate of fatty alcohol products throughout the test period.

[0068] Comparison of Wax Ester Hydrocracking Performance To compare catalyst performance, liquid products during the reaction were collected for SAP (saponification) value analysis. The SAP value is the hydrolysis of the ester by KOH (or NaOH) to form an alcohol and a potassium or sodium salt of the corresponding acid. A higher SAP value indicates a higher ester content. In this case, a higher SAP value means that a smaller amount of ester is converted to alcohol, i.e., lower catalytic activity. The performance of the CuO-CaSiO3 catalyst for wax ester hydrocracking was compared with that of a state-of-the-art CuCr catalyst. In this series of tests, the hydrocracking product was drawn every hour for analysis, followed by the injection of fresh fatty acids as feed during the first four hours.

[0069] The results are summarized in Figures 14 and 15. The figures show that after the fourth injection and as the reaction time continues, the residual wax ester decreases, and the ester conversion rate also decreases as the system approaches equilibrium. The catalyst of Example 3 (calcined at 500°C) consistently shows a higher wax ester conversion rate than the CuCr-based catalyst, starting from the second hour of the test (Figure 14 and Table 9). The higher conversion rate of the CuCr catalyst during the first hour may be due to a more easily reduced process by that catalyst. Overall, the CuO-CaSiO3 catalyst exhibits significantly higher activity and alcohol yield.

[0070] [Table 9]

[0071] Another advantage of the CuO-CaSiO3 catalyst is its better selectivity for fatty alcohols and the lower generation of hydrocarbon byproduct impurities in the slurry phase wax ester process. As shown in Table 10, the new CuO-CaSiO3 catalyst produces less dodecane, tetradecane, hexadecane, and octadecane compared to the CuCr catalyst. All of these alkanes are excess hydrogenation byproducts that reduce the purity and yield of the product.

[0072] [Table 10]

[0073] Catalytic Filtration Characteristics: Catalytic separation experiments (both centrifugation and filtration) were conducted on spent slurry in a slurry phase methyl ester process to compare catalytic filterability. The results show that the CuO-CaSiO3 catalyst has separation characteristics equivalent to those of state-of-the-art catalysts.

[0074] This is a qualitative estimate of sedimentation and separation by centrifugation at 11,000 rpm for 5 minutes, with photographs taken for visual comparison. First, the spent catalyst slurry was stirred with the liquid product and unreacted fatty acid methyl ester (0.8 wt% catalyst packing) for 5 minutes. Then, the top 35 mL of liquid was collected and photographs were taken to confirm whether any particles were suspended. Separation efficiency is qualitatively measured based on the color and particulate matter suspended in the collected liquid.

[0075] Centrifugal separation tests showed that both the CuO-CaSiO3 catalyst and the CuCr catalyst produced a clear liquid product. To further confirm this, the liquid product was analyzed for metal leaching from the catalyst. As shown below, both the CuO-CaSiO3 catalyst and the CuCr catalyst exhibited low metal leaching (Table 11). This indicates that the CuO-CaSiO3 catalyst has good chemical stability under reaction conditions.

[0076] [Table 11]

[0077] Filtration Procedure: A used catalyst slurry (12 ml; well mixed) was loaded into a syringe. A syringe filter (0.45 μm) was attached to the tip of the syringe, and the timer was started when the syringe plunger was first activated. If the filtrate did not come out at maximum hand pressure, filtration was stopped and the filter was replaced. After filtering 12 mL of slurry, the timer was stopped. This test qualitatively estimates the ease of filtration (time required to produce the same volume of filtrate) using a 0.45 μm filter. Some results are shown in Figure 16, demonstrating that the CuO-CaSiO3 catalyst has a filtration time similar to that of state-of-the-art catalysts.

[0078] While specific embodiments have been illustrated and described, it should be understood that modifications and changes can be made by those skilled in the art without departing from the broader aspects of the art as defined in the following claims.

[0079] The embodiments described herein as exemplary can be adequately implemented without any one or more elements or limitations not specifically disclosed herein. Therefore, terms such as “comprising,” “including,” and “containing” should be read broadly and without limitation. Furthermore, the terms and expressions used herein are for illustrative purposes only, not limitation, and in the use of such terms and expressions, there is no intention to exclude any equivalents of the exhibited and described features or any part thereof, although it should be recognized that various modifications are possible within the scope of the claimed technology. Furthermore, the phrase “essentially consisting of” should be understood to include the specifically enumerated elements and any additional elements that do not substantially affect the fundamental and novel features of the claimed technology. The phrase “consisting of” excludes elements not specified.

[0080] This disclosure should not be limited to the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from its spirit and scope. In addition to those enumerated herein, functionally equivalent methods and compositions within the scope of this disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to be included in the appended claims. This disclosure should be limited only by the terminology of the appended claims, encompassing the entire scope of equivalents to which such claims are granted. It should be understood that this disclosure is not limited to specific methods, reagents, compounds, or compositions, and that they may, of course, vary. It should also be understood that the terminology used herein is intended solely to describe specific embodiments and is not intended to limit them.

[0081] Furthermore, where any feature or aspect of the present disclosure is described in relation to the Markush group, a person skilled in the art will recognize that the present disclosure also describes any individual element or subgroup of elements of the Markush group.

[0082] As will be understood by those skilled in the art, for all purposes, and especially with regard to providing written explanations, all scopes disclosed herein also encompass all possible subscopes and combinations thereof. Any scope enumerated can be readily recognized as sufficiently explainable and enabling the division of the same scope into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope discussed herein can readily be divided into lower thirds, middle thirds, upper thirds, etc. Also, as will be understood by those skilled in the art, all phrases such as “at most,” “at least,” “greater than,” and “less than” include the numbers enumerated and refer to scopes that can later be divided into subscopes as discussed above. Finally, as will be understood by those skilled in the art, a scope includes individual elements.

[0083] All publications, patent applications, issued patents, and other documents referenced herein are incorporated herein by reference as if each individual publication, patent application, issued patent, or other document were specifically and individually indicated to be incorporated by reference in whole. Definitions contained in the text incorporated by reference are excluded insofar as they conflict with the definitions in this disclosure.

[0084] Other embodiments are described in the following claims.

Claims

1. copper oxide, Calcium oxide, Silicon dioxide, and sodium oxide A hydrocracking catalyst / hydrogenation catalyst that includes, The aforementioned hydrocracking catalyst / hydrogenation catalyst is in powder form. The aforementioned hydrocracking catalyst / hydrogenation catalyst does not contain chromium. Said hydrocracking catalyst / hydrogenation catalyst comprises a CuO crystallite phase and cubic SiO ２ , rhombohedral calcium carbonate CaCO ３ , triclinic calcium silicate CaSiO ３ , calcium silicate hydroxide hydrate (Ca １４ Si ２４ O ５８ (OH) ８ ·2H ２ O), calcium silicate hydrate 4CaO·5SiO ２ ·5H ２ O, alumina, and an additional crystallite phase selected from the group consisting of a combination of two or more thereof. Prior to activation, the hydrocracking catalyst / hydrogenation catalyst contains 0.5% to 1% by weight of Na₂O, and the activation represents a preliminary reduction before using the hydrocracking catalyst / hydrogenation catalyst.

2. The aforementioned powder has d particles ranging from 1 μm to 10 μm. １０ A hydrocracking catalyst / hydrogenation catalyst according to claim 1, having a % particle size.

3. The aforementioned powder has particles ranging from 10 μm to 25 μm. ５０ A hydrocracking catalyst / hydrogenation catalyst according to claim 1 or claim 2, having a % particle size.

4. The aforementioned powder has d particles of 30 μm to 45 μm. ９０ A hydrocracking catalyst / hydrogenation catalyst according to any one of claims 1 to 3, having a % particle size.

5. Before activation, the hydrocracking catalyst / hydrogenation catalyst comprises 35% to 85% by weight of CuO, 8% to 20% by weight of CaO, and 10% to 30% by weight of SiO ２ , and 0.5% to 1% by weight of Na ２ A hydrocracking catalyst / hydrogenation catalyst according to any one of claims 1 to 4, comprising O.

6. The hydrocracking catalyst / hydrogenation catalyst according to any one of claims 1 to 5, wherein the hydrocracking catalyst / hydrogenation catalyst does not contain manganese before activation.

7. The aforementioned hydrocracking catalyst / hydrogen catalyst is 5m ２ / g to 85m ２ A hydrocracking catalyst / hydrogenation catalyst according to any one of claims 1 to 6, exhibiting a Brunauer-Emmett Teller ("BET") surface area per gram.

8. The hydrogenocrack catalyst / hydrogenation catalyst according to any one of claims 1 to 7, wherein the hydrogenocrack catalyst / hydrogenation catalyst exhibits a CuO crystallite size of 50 Å to less than 240 Å.

9. A method for preparing a hydrocracking catalyst / hydrogenation catalyst, wherein the method is: The steps include mixing a copper-containing material and a silicate-containing material in a solution, The steps include adding a caustic material to form an aqueous slurry containing a precipitate, The steps include collecting the aforementioned precipitate, The steps include drying the aforementioned precipitate to form a dried precipitate, The steps include: calcining the dried precipitate to form a calcined hydrocracking catalyst / hydrogenation catalyst; Includes, The aforementioned calcined hydrogenolysis catalyst / hydrogenation catalyst is in powder form. The aforementioned calcined hydrogenolysis catalyst / hydrogenation catalyst does not contain chromium. The firing step is carried out at a temperature of 500°C to 750°C. Prior to activation, the calcined hydrocracking catalyst / hydrogenation catalyst contains 0.5% to 1% by weight of Na₂O, and the activation represents a preliminary reduction before using the calcined hydrocracking catalyst / hydrogenation catalyst.

10. The method according to claim 9, wherein the aqueous slurry has a pH of 6.0 to 9.

0.

11. The method according to claim 9 or 10, wherein the step of collecting includes filtering the aqueous slurry to remove the precipitate.

12. The method according to any one of claims 9 to 11, wherein the firing step is performed for 10 minutes to 10 hours.

13. The method according to claim 12, wherein the firing step is performed for 0.5 to 3 hours.

14. The method according to any one of claims 9 to 13, wherein the copper-containing material is a copper salt comprising copper nitrate, copper sulfate, copper chloride, copper bromide, copper acetate, or any two or more combinations thereof.

15. The method according to any one of claims 9 to 14, wherein the silicate-containing material comprises a silicate containing calcium silicate.

16. The aforementioned caustic material is Na ２ CO ３ NaOH, K ２ CO ３ The method according to any one of claims 9 to 15, wherein the material is KOH, or any two or more combinations thereof.

17. The aforementioned powder has d particles ranging from 1 μm to 10 μm. １０ The method according to any one of claims 9 to 16, having a % particle size.

18. The aforementioned powder has d particles of 1 μm to 2 μm. １０ The method according to claim 17, having a % particle size.

19. The aforementioned powder has d particles ranging from 4 μm to 9 μm. １０ The method according to claim 17, having a % particle size.

20. The aforementioned powder has particles ranging from 10 μm to 25 μm. ５０ The method according to any one of claims 9 to 19, having a % particle size.

21. The aforementioned powder has a particle size of 16 μm to 20 μm. ５０ The method according to claim 20, having a % particle size.

22. The aforementioned powder has d particles of 30 μm to 45 μm. ９０ The method according to any one of claims 9 to 21, having a % particle size.

23. The aforementioned powder has a particle size of 35 μm to 40 μm. ９０ The method according to claim 22, having a % particle size.

24. Before activation, the calcined hydrocracking catalyst / hydrogenation catalyst contains 35% to 85% by weight of CuO, 8% to 20% by weight of CaO, and 10% to 30% by weight of SiO ２ , and 0.5% to 1% by weight of Na ２ The method according to any one of claims 9 to 23, comprising O.

25. Before activation, the calcined hydrocracking catalyst / hydrogenation catalyst contains 60% to 70% by weight of CuO, 10% to 15% by weight of CaO, and 15% to 25% by weight of SiO ２ , and 0.5% to 1% by weight of Na ２ The method according to any one of claims 9 to 24, comprising O.

26. Prior to activation, the calcined hydrocracking catalyst / hydrogenation catalyst contains 0.5% to less than 1% by weight of Na. ２ The method according to any one of claims 9 to 25, comprising O.

27. The method according to any one of claims 9 to 26, wherein, prior to activation, the calcined hydrocracking catalyst / hydrogenation catalyst does not contain manganese.

28. The aforementioned calcined hydrogenolysis catalyst / hydrogenation catalyst is 5m ２ / g ~ 85m ２ The method according to any one of claims 9 to 27, relating to a Brunauer-Emmett Teller ("BET") surface area per g.

29. The BET surface area is 10 m². ２ / g ~ 85m ２ The method according to claim 28, wherein the amount is / g.

30. The BET surface area is 15 m². ２ / g to 80m ２ The method according to claim 28 or claim 29, wherein the amount is / g.

31. The aforementioned calcined hydrogenolysis catalyst / hydrogenation catalyst is composed of CuO and cubic SiO ２ , rhombohedral calcium carbonate CaCO ３ Triclinic calcium silicate CaSiO ３ , calcium silicate hydroxide hydrate (Ca １４ Si ２４ O ５８ (OH) ８ ・2H ２ O), calcium silicate hydrate (4CaO・5SiO ２ ・5H ２ The method according to any one of claims 9 to 30, wherein the crystallite phase is selected from the group consisting of 0), alumina, and two or more combinations thereof.

32. The method according to any one of claims 9 to 31, wherein the calcined hydrogenolysis catalyst / hydrogenation catalyst exhibits a CuO crystallite size of 50 Å to less than 240 Å.

33. The method according to claim 32, wherein the calcined hydrogenolysis catalyst / hydrogenation catalyst exhibits a CuO crystallite size of 50 Å to 175 Å.

34. The method according to any one of claims 9 to 33, wherein the calcined hydrocracking catalyst / hydrogenation catalyst exhibits a calcium silicate hydrate crystallite size of 550 Å to less than 673 Å.

35. The method according to claim 34, wherein the calcined hydrocracking catalyst / hydrogenation catalyst exhibits a calcium silicate hydrate crystallite size of 550 Å to 650 Å.

36. A method for hydrogenating a carbonyl-containing organic compound, comprising the step of contacting the carbonyl-containing organic compound with a hydrocracking catalyst / hydrogenation catalyst obtained by the method described in any one of claims 9 to 35.

37. The method according to claim 36, carried out in a slurry phase reactor.

38. The method according to claim 37, wherein the slurry phase reactor is selected from a continuously stirred tank reactor, a tower reactor, or a column reactor.

39. The method according to any one of claims 36 to 38, wherein the carbonyl-containing organic compound includes a fatty methyl ester, a wax ester, or a combination thereof.

40. The aforementioned fatty methyl ester is C ８ -C ２０ The method according to claim 39, comprising a methyl ester.

41. The aforementioned wax ester is C ８ -C １８ The method according to claim 39 or 40, comprising a wax ester.

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