Forming contact medium

Abstract

The present invention relates to a shaped catalyst body containing copper, aluminum and manganese, a process for producing the shaped catalyst body, and a process for using the shaped catalyst body for hydrogenation, dehydrogenation, hydrocracking or ethynylation.

Description

Technical Field

[0001] The present invention relates to a shaped catalyst body containing copper, aluminum and manganese, a process for producing said shaped catalyst body, and a process for using said shaped catalyst body for hydrogenation, dehydrogenation, hydrocracking or ethynylation.

Background Art

[0002] In recent years, fatty alcohols produced by the hydrocracking of carboxylic acid esters have seen a significant increase in demand due to the hygienic requirements against the coronavirus pandemic. Heterogeneous catalysts containing noble metals, nickel, cobalt and copper are widely used in this reaction. Commercially available catalysts for the hydrocracking of fatty acid esters generally utilize copper-chromium (Cu-Cr) composite materials, which have high performance and mechanical stability. However, due to the environmental problems associated with the disposal of Cr-containing catalysts, their use is expected to be ultimately eliminated in many countries. Therefore, in order to replace the currently used Cu-Cr catalysts in the hydrocracking of carboxylic acid esters, it is more advantageous and sustainable to use Cr-free Cu-containing catalysts with good catalytic activity. As active catalysts for the hydrocracking of carboxylic acid esters, pellet-shaped and extruded CuZn-containing materials, CuMn-containing materials or CuMnAl-containing materials can be used.

[0003] U.S. Patent No. 10,226,760 describes a tablet-shaped Cu-Zn catalyst starting from a heat-treated metal carbonate mixture produced by a precipitation method. It has been found that the carbonate content correlates with the Cu metal surface area of the reduced catalyst. In the examples, these catalysts are used for the hydrocracking of a C12-methyl ester feed at a temperature of 180 °C and a pressure of 280 bar. The catalysts invented here show a significantly increased conversion rate of C12-methyl ester compared to comparative catalysts produced with a lower carbonate content.

[0004] U.S. Patent No. 10,315,188 discloses a CuMnAl tablet-shaped catalyst body obtained by a process of adding a graphite material having a specific particle size of 5.0 μm ≤ D90 ≤ 17.5 μm. The catalyst invented here is used in the hydrogenation of a C12-methyl ester feed at a temperature of 180°C and a pressure of 280 bar in the examples. It has been found that the addition of graphite with a small particle size and a large surface area can lead to an increase in the ester conversion rate and a decrease in the selectivity of paraffin by-products.

[0005] U.S. Patent No. 10,434,500 describes a CuAl tablet-shaped catalyst body obtained by a mixture of calcined and uncalcined carbonates produced by a precipitation method. The catalyst invented here has a specific bimodal porosity, with pores having a pore diameter in the range of 500 - 2500 nm accounting for about 13% of the pore volume, and pores having a pore diameter in the range of 5 - 45 nm accounting for about 75% of the pore volume. However, the pore volume formed by pores having a pore diameter in the range of 45 - 200 nm is less than 10%. It has been found that the pore volume of the catalyst after tablet forming, calcination, and reduction varies as a function of the uncalcined carbonate content. The catalyst invented here is evaluated for the hydrocracking of a C12-methyl ester feed at temperatures of 160°C, 180°C, and 240°C and a pressure of 280 bar in the activity measurement examples. It has been observed that a catalyst with a large pore volume induced by the uncalcined carbonate can result in an increase in the conversion rate of fatty acid esters compared to the comparative catalyst at all three selected temperatures.

[0006] In addition to the above prior art regarding Cr-free Cu catalyst tablets for the hydrocracking of fatty acid esters, for this application, extruded catalysts are also disclosed. Generally, catalyst extrudates have a substantially higher pore volume and a lower bulk density while maintaining at least equivalent mechanical strength compared to catalyst tablets. U.S. Patent No. 10,639,616 describes an extruded catalyst body containing 20 to 43 wt% Cu, 20 to 40 wt% Al, and 1 to 10 wt% Mn based on the total weight of the catalyst, wherein more than 50% of the pore volume is formed by pores having a pore diameter in the range of 7 to 40 nm. However, the pore volume formed by pores having a pore diameter in the range of 45 to 200 nm is less than 10%. The extruded catalyst invented here was observed to have a higher pore volume and a lower bulk density than the comparative catalyst in the form of tablets. The catalyst invented here has been tested for the hydrocracking of a C12-methyl ester feed at temperatures of 160 °C, 180 °C, and 240 °C and a pressure of 280 bar. The data reveals that a significant improvement in the productivity of the target product has been achieved.

[0007] As disclosed in the above prior art, in the commercial use of catalysts in the hydrocracking of methyl esters, it is typically carried out in a gas-phase process operating in a high-pressure range to promote ester conversion and alcohol selectivity. This increases costs, raises requirements regarding reactor design, and also increases the difficulty of control. If the reaction can be carried out at a lower pressure to achieve similar productivity, it would lead to significant cost reduction and risk reduction in plant operation. Furthermore, pressure reduction would be beneficial for a longer catalyst operating life, especially if the catalyst is not sufficiently stable with respect to mechanical strength.

[0008] In view of this background, an object of the present invention is to provide a Cr-free Cu catalyst having improved catalytic performance for hydrogenation, dehydrogenation, hydrocracking, or ethynylation at lower pressures and temperatures.

Prior Art Documents

Patent Documents

[0009] [Patent Document 1] U.S. Patent No. 10226760 [Patent Document 2] U.S. Patent No. 10315188 [Patent Document 3] U.S. Patent No. 10434500 [Patent Document 4] U.S. Patent No. 10639616 [Summary of the Invention] [Problems to be Solved by the Invention]

[0010] Surprisingly, it has been found that this object is achieved by a shaped catalyst body having a substantially low packed bulk density and pore volume within a specific range as compared with conventional shaped catalysts.

[0011] Accordingly, in one aspect, the present invention relates to a shaped catalyst body containing copper, aluminum, and manganese, and having a packed bulk density of 0.87 to 1.43 g / cc. [Means for Solving the Problems]

[0012] In another aspect, the present invention is a) precipitation by combining an aqueous solution of a copper compound, a manganese compound, an aluminum compound, and a precipitant, b) filtering the slurry and washing the precipitate, c) drying and calcining at a temperature in the range of 200 to 1000 °C to form a heat treatment intermediate, d) mixing the heat treatment intermediate, and e) forming into a shaped body relates to a process for producing a shaped catalyst body including.

[0013] In a further aspect, the present invention relates to a process using the shaped catalyst body for hydrogenation, dehydrogenation, hydrocracking or ethynylation.

Brief Description of the Drawings

[0014]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Modes for Carrying Out the Invention

[0015] Before describing some exemplary embodiments of the present invention, it should be understood that the present invention is not limited to the details of the construction or process steps shown in the following description. Other embodiments of the present invention are possible, and the present invention can be implemented or executed in various ways.

[0016] Regarding the terms used in the present disclosure, the following definitions are provided.

[0017] Throughout this description, including the claims, terms such as "comprise", "comprising", etc. may be used interchangeably with terms such as "contain", "containing", etc., and should be interpreted as non-limiting and expandable. That is, for example, additional components or elements may be present. Expressions such as "consists of" or "consists essentially of" or expressions of the same origin may be included within expressions such as "comprises" or expressions of the same origin.

[0018] As used herein, "about" is understood by those skilled in the art and varies to some extent depending on the context in which it is used. When there is a use of this term that is not clear to those skilled in the art even considering the context in which it is used, "about" means plus or minus 10% of that particular term.

[0019] The terms "a", "an", and "the" are used to refer to one or more (i.e., at least one) of the grammatical objects of the article.

[0020] The term "and / or" includes the meanings of "and", "or", and all other possible combinations of the elements associated with this term.

[0021] According to a first aspect, the present invention provides a shaped catalyst carrier containing copper, aluminum, and manganese, the shaped catalyst carrier having a bulk density of 0.87 to 1.43 g / cc, preferably 0.90 to 1.42 g / cc, more preferably 0.95 to 1.35 g / cc. For example, the bulk density may be about 0.87 g / cc, about 0.90 g / cc, about 0.93 g / cc, about 0.95 g / cc, about 1.0 g / cc, about 1.10 g / cc, about 1.20 g / cc, about 1.30 g / cc, about 1.35 g / cc, about 1.40 g / cc, about 1.42 g / cc, about 1.43 g / cc, or any range including and / or between any two of the aforementioned values, but is not limited thereto.

[0022] All references to bulk density in the specification and claims of the present invention are based on measurements using the method described in ASTM-D4164-03.

[0023] In some embodiments of the present invention, the shaped catalyst carrier contains Cu in an amount of 30% to 75% by weight, preferably 40% to 65% by weight, more preferably 45% to 60% by weight, calculated as CuO. For example, the amount of copper oxide can be about 30% by weight, 35% by weight, about 40% by weight, about 45% by weight, about 50% by weight, about 55% by weight, about 60% by weight, about 65% by weight, about 70% by weight, about 75% by weight, or any range including any two of the foregoing values and / or any range therebetween, but is not limited thereto.

[0024] When copper oxide and at least one oxide of another metal (or element) are present, it will be understood that the oxide can be present in the form of each oxide, or a composite oxide of copper and the other metal (or element), or a combination thereof.

[0025] In some embodiments of the present invention, the shaped catalyst carrier contains Al in an amount of 10% to 50% by weight, preferably 20% to 40% by weight, more preferably 25% to 35% by weight, calculated as Al2O3. For example, aluminum oxide can be present in an amount of about 10% by weight, 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 50% by weight, or any range including any two of the foregoing values and / or any range therebetween.

[0026] When aluminum oxide and at least one oxide of another metal (or element) are present, it will be understood that the oxide can be present in the form of each oxide, or a composite oxide of aluminum and the other metal (or element), or a combination thereof.

[0027] In some embodiments of the present invention, the shaped catalyst carrier contains Mn in an amount of 1% to 25% by weight, preferably 5% to 20% by weight, more preferably 7% to 15% by weight, calculated as MnO2. For example, the manganese oxide may be present in an amount of about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, about 10% by weight, about 11% by weight, about 12% by weight, about 13% by weight, about 14% by weight, about 15% by weight, about 16% by weight, about 17% by weight, about 18% by weight, about 19% by weight, about 20% by weight, about 21% by weight, about 22% by weight, about 23% by weight, about 24% by weight, about 25% by weight, or in any range of amounts including and / or between any two of the foregoing values.

[0028] It will be understood that when manganese oxide and at least one oxide of another metal (or element) are present, they may be present in the form of their respective oxides, or a composite oxide of manganese and the other metal (or element), or a combination thereof.

[0029] In some embodiments of the present invention, the shaped catalyst carrier may contain a binder, and the binder includes, but is not limited to, calcium silicate, sodium silicate, silica sol, clay, boehmite, and mixtures thereof.

[0030] In some embodiments of the present invention, the binder contains a zirconium component. In any embodiment of the present invention, the zirconium component may exist in the form of a reduced metal or oxide, or in one or more oxidation states as a precursor to such a form. For example, the zirconium component exists in the form of zirconium oxide. In any embodiment of the present invention, the zirconium component is present in an amount of 3% to 20% by weight of Zr calculated as ZrO₂. Suitable amounts of the zirconium component include, but are not limited to, about 5% to about 15% by weight, about 5% to about 12% by weight, about 5% to about 8% by weight, or any range including and / or between any two of the foregoing values. For example, the zirconium component may be present in an amount of about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, about 10% by weight, about 11% by weight, about 12% by weight, about 13% by weight, about 14% by weight, about 15% by weight, about 16% by weight, about 17% by weight, about 18% by weight, about 19% by weight, about 20% by weight, or any range including and / or between any two of the foregoing values.

[0031] In any embodiment, the shaped catalyst body described herein may further contain an alkali metal component. In any embodiment of the present invention, the alkali metal is selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and combinations thereof. These metals may exist in the form of a reduced metal or oxide, or in one or more oxidation states as a precursor to such a form. For example, the alkali metal component may contain sodium in the form of sodium oxide. In any embodiment of the present invention, the alkali metal may be present in an amount of about 0% to about 1% by weight of the shaped catalyst body. For example, the alkali metal component may be present in an amount of about 0.01% by weight, 0.05% by weight, about 0.1% by weight, about 0.2% by weight, about 0.3% by weight, about 0.4% by weight, about 0.5% by weight, about 0.6% by weight, about 0.7% by weight, about 0.8% by weight, about 0.9% by weight, about 1% by weight, or any range including and / or between any two of the foregoing values.

[0032] In some embodiments of the present invention, the shaped catalyst carrier has a bimodal pore size distribution.

[0033] All references to pore diameter and pore volume in the specification and claims of the present invention are based on measurements using the method described in ASTM-D4284-03.

[0034] In certain embodiments of the present invention, the shaped catalyst carrier exhibits a pore volume of 0.02 to 0.50 ml / g, preferably 0.15 to 0.30 (e.g., the pore volume can be about 0.02 ml / g, about 0.05 ml / g, about 0.10 ml / g, about 0.15 ml / g, about 0.18 ml / g, about 0.20 ml / g, about 0.22 ml / g, about 0.25 ml / g, about 0.27 ml / g, about 0.30 ml / g, or any range including and / or between any two of the foregoing values, but not limited thereto) due to pores having a pore diameter in the range of 45 to 200 nm, and a pore volume of 0.20 to 0.60 ml / g, preferably 0.25 to 0.50 (e.g., the pore volume can be about 0.20 ml / g, about 0.25 ml / g, about 0.30 ml / g, about 0.35 ml / g, about 0.40 ml / g, about 0.45 ml / g, about 0.50 ml / g, about 0.55 ml / g, about 0.60 ml / g, or any range including and / or between any two of the foregoing values, but not limited thereto) due to pores having a pore diameter in the range of 10 to 200 nm.

[0035] In other specific embodiments of the present invention, in the shaped catalyst carrier, 10% to 80%, preferably 35% to 70%, more preferably 45% to 65% of the pore volume is formed by pores having a pore diameter in the range of 45 to 200 nm. For example, the percentages may be about 10%, about 15%, about 20% ml / g, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or any range including and / or between any two of the foregoing values, but are not limited thereto. 70% to 100% of the pore volume is formed by pores having a pore diameter in the range of 10 to 200 nm. For example, the percentages may be about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 100%, or any range including and / or between any two of the foregoing values, but are not limited thereto.

[0036] In some embodiments of the present invention, the shaped catalyst carrier catalyst may have a BET surface area of about 15 m 2 / g to about 70 m 2 / g. For example, the calcined shaped catalyst carrier may have a BET surface area of about 15 m2 / g, about 20 m 2 / g, about 25 m 2 / g, about 30 m 2 / g, about 35 m 2 / g, about 40 m 2 / g, about 45 m 2 / g, about 50 m 2 / g, about 55 m 2 / g, about 60 m 2 / g, about 65 m 2 / g, about 70 m 2 / g, or any range of BET surface area including and / or between any two of the foregoing values. In any embodiment herein, the calcined hydrogenation catalyst has a BET surface area of about 15 m 2 / g to about 70 m 2 / g, about 25 m 2 / g to about 65 m 2 / g, about 45 m 2 / g to about 60 m 2 / g, about 50 m2 / g ~ about 60 m 2 / g, or has a BET surface area in any range including and / or between any two of the aforementioned values.

[0037] According to a second aspect, the present invention a) precipitation by combining an aqueous solution of a copper compound, a manganese compound, an aluminum compound and a precipitant, b) filtering the slurry and washing the precipitate, c) drying and calcining at a temperature in the range of 200 - 1000 °C to form a heat treatment intermediate, d) mixing the heat treatment intermediate, and e) shaping into a shaped body to provide a process for manufacturing a shaped catalyst body.

[0038] The shaped catalyst body can be provided as a tablet or an extrudate. One way of processing the formulation of all components is to extrude it through a shaping orifice to form an extruded catalyst body or extrudate. Other catalyst bodies can be shaped into spheres or any other convenient formation. Another way is to tableting the catalyst. The shaped catalyst has a size of 1 / 32 inch to 8 mm. For example, a hydrocracking catalyst can be extruded or tabletted in sizes such as, but not limited to, 1 / 8 inch × 1 / 8 inch, 3 / 16 inch × 3 / 16 inch, 1 / 4 inch × 1 / 4 inch, 3 / 16 inch × 1 / 4 inch, 1 / 4 inch × 1 / 16 inch, or 1 / 8 inch × 1 / 16 inch.

[0039] In some embodiments of the present invention, the shaped catalyst body can be calcined. In any embodiment of the present invention, the catalyst is a calcined tabletted catalyst.

[0040] This process includes a step of calcining a material mixture at a temperature and for a time sufficient to form a calcined hydrocracking catalyst. In any embodiment of the present invention, the calcination can be carried out at a temperature of about 200°C to about 1000°C. For example, the calcination can be carried out at about 200°C, about 250°C, about 300°C, about 350°C, about 400°C, about 450°C, about 500°C, about 550°C, about 600°C, about 650°C, about 700°C, about 750°C, about 800°C, about 850°C, about 900°C, about 950°C, about 1000°C, or at any temperature within any range including and / or between any two of the foregoing values. In any embodiment of the present invention, the calcination temperature can be about 300°C to about 800°C, about 400°C to about 750°C, or about 500°C to about 700°C. In any embodiment of the present invention, the calcination can be carried out over a period of about 0.5 hours to about 4 hours. In any embodiment, the calcination can be carried out over a period of about 0.5 hours, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, or any range of periods including and / or between any two of the foregoing values.

[0041] According to another aspect, the present invention provides a process using the shaped catalyst body of the present invention for hydrogenation, dehydrogenation, hydrocracking or ethynylation.

[0042] The shaped catalyst body of the present invention is suitable for use in many hydrogenation reactions. Preferably, the shaped catalyst of the present invention is suitable for the liquid-phase hydrocracking of carboxylic acids and esters, preferably a fatty acid methyl ester mixture having 5 to 24 carbon atoms, to form the corresponding fatty alcohol. In particular, the hydrocracking reaction of fatty acid methyl esters is suitable for operation under a specific pressure in the range of 60 to 250 bar, more preferably in the range of 75 to 100 bar.

[0043] Various embodiments are described below. It should be noted that these specific embodiments are neither intended to be an exhaustive description nor intended to be a limitation to the broader aspects discussed herein.

Examples

[0044] Example 1 Weigh 122.2 g of a Cu(NO3)2 solution (15.5 wt% Cu) and mix it with an Mn(NO3)2 solution so that the molar ratio of Cu / Mn is 5.2 / 1.0. Weigh a NaAlO2 solution (12.5 wt% Al) so that the molar ratio of Cu / Al is 1.2 / 1.0 and dilute it with 18.9 g of deionized H2O. Pour 450 ml of deionized H2O into a container. Weigh 90.7 g of Na2CO3 powder, dissolve it in deionized H2O to make 500 ml. Add the Cu(NO3)2, Mn(NO3)2, NaAlO2, and Na2CO3 solutions simultaneously to 450 ml of deionized H2O. Keep the slurry at a constant neutral pH during precipitation. Keep the precipitation temperature constantly at room temperature. Then, filter, wash, and dry the precipitate. Calcinate the dried material in air at 600 °C to obtain a calcined metal carbonate material.

[0045] Mix the above calcined metal carbonate powder with graphite powder. Then, form the mixture into granules by a briquetting step and form a molded body by tableting the granules. Next, calcine the tablet at 750 °C. The described material has a bulk density of 1.4 g / ml, a pore volume of 0.26 ml / g, and a BET surface area of 53 m 2 / g. 93% of the pore volume is formed by pores with pore diameters in the range of 10 - 200 nm. Specifically, 30% of the pore volume is formed by pores with pore diameters in the range of 45 - 200 nm.

[0046] Example 2 Mix the calcined metal carbonate powder material in Example 1 with graphite powder. Then, by a briquetting step, form the mixture into granules having a specific bulk density that is 40% - 50% of the value of the corresponding tablet product. Next, form a molded body by tableting the specific granules. Next, calcine the tablet at 750 °C. The described material has a bulk density of 1.1 g / ml, a pore volume of 0.41 ml / g, and a BET surface area of 50 m 2It has a BET surface area of... / g. 93% of the pore volume is formed by pores with pore diameters in the range of 10 to 200 nm. Specifically, 59% of the pore volume is formed by pores with pore diameters in the range of 45 to 200 nm.

[0047] Example 3 The calcined metal carbonate powder material of Example 1 was mixed with zirconium acetate, alumina, an organic binder, and water, and then kneaded to form a wet mixture having a composition of 52 wt% CuO, 10 wt% MnO2, 30 wt% Al2O3, and 8 wt% ZrO2. Next, the mixture was extruded with an extruder to form a molded body. Then, the extrudate was calcined at 500 °C. The described material has a bulk density of 1.0 g / ml, a pore volume of 0.31 ml / g, and a BET surface area of 50 m 2 / g. 76% of the pore volume is formed by pores with pore diameters in the range of 10 to 200 nm. Specifically, 21% of the pore volume is formed by pores with pore diameters in the range of 45 to 200 nm.

[0048] Comparative Example 1 A metal carbonate powder material was produced by the method described in Example 1. Thereafter, the carbonate material was calcined in air at 800 °C, and then mixed with calcium hydroxide, attapulgite, a plasticizer, silica gel, and water, and then kneaded to form a wet mixture having a composition of 40 wt% CuO, 10 wt% MnO2, 20 wt% Al2O3, 20 wt% SiO2, and 10 wt% CaO. Next, the mixture was extruded with an extruder to form a molded body. Then, the extrudate was calcined at 500 °C. This has a bulk density of 0.8 g / ml, a pore volume of 0.38 ml / g, and a BET surface area of 45 m 2 / g.

[0049] Comparative Example 2 500 g of CuO powder is mixed with calcium hydroxide, a plasticizer, silica gel, hydroxypropyl methylcellulose, and water, and then kneaded to form a wet mixture having a composition of 58 wt% CuO, 21 wt% SiO2, and 14 wt% CaO. Next, the mixture is extruded with an extruder to form a molded body. Next, the extrudate is calcined at 500 °C. The described material has a bulk density of 0.8 g / ml and a BET surface area of 50 m 2 / g.

[0050] Comparative Example 3 591 g of a Cu(NO3)2 (15.5 wt% Cu) solution is weighed and mixed with an Al(NO3)3 solution (4.2 wt% Al) with an Al / Cu molar ratio of 1.56 / 1.0 and 170 g of deionized H2O. 442 g of Na2CO3 powder is weighed and dissolved in 1770 g of deionized H2O. The Cu(NO3)2, Al(NO3)3, and Na2CO3 solutions are simultaneously introduced into a separate container. The slurry is maintained at a pH of about 6.0 during precipitation. The precipitation temperature is constantly maintained at 80 °C. Thereafter, the precipitate is aged, filtered, washed, and dried. 507 g of the described dry powder, 87 g of boehmite, 21 ml of formic acid, and 375 g of water are mixed and kneaded to form a wet mixture. Next, the mixture is extruded to form an extruded material, and then calcined at 600 °C. The described material has a bulk density of 0.85 g / ml and a BET surface area of 21 m 2 / g.

[0051] Comparative Example 4 320 g of Zn(NO3)2·6H2O and 336.4 g of Al(NO3)3·9H2O are weighed into 600 ml of deionized water. 300 g of Na2CO3 powder is weighed and dissolved in 1200 g of deionized water. The two solutions are simultaneously introduced into a separate container while controlling the temperature at 50 °C and the neutral pH. Thereafter, the precipitate is aged, filtered, washed, dried, and calcined at 400 °C.

[0052] The above-mentioned calcined powder is partially redissolved in a mixed solution of HNO3, Cu(NO3)2 and Zn(NO3)2 (atomic ratio of Cu:Zn = 65:13) to form a suspension having a total atomic ratio of Cu:Zn:Al = 65:25:10. This suspension and a 20 wt% Na2CO3 solution are simultaneously introduced into another container while controlling the temperature at 70 °C and the pH at 6.8. Then, the precipitate is aged, filtered, washed, dried, and calcined at 300 °C.

[0053] The tablet is made from the above powder by mixing the powder with graphite powder, slagging, granulating. Next, the granules are compressed into a tablet-shaped catalyst support. The described material has a bulk density of 1.45 g / ml and a pore volume of 0.20 ml / g.

[0054]

Table 1

[0055] From Table 1, it can be seen that the catalyst of the present invention has a higher fraction of pore volume formed by pore diameters in the range of 10 to 200 nm than the comparative example. Specifically, the pore volume formed by pore diameters in the range of 45 to 200 nm is larger for the catalyst of the present invention than the comparative example.

[0056] Hydrocracking of Fatty Acid Methyl Ester (FAME) The activity of the catalyst was tested in a multi-channel fixed-bed reactor as follows. Each catalyst bed was formed from 2.5 ml of catalyst tablets or extrudates in an electric-heater type reactor provided with means for supplying hydrogen gas and nitrogen gas and for supplying a liquid of the C12 - C18 methyl ester feedstock to the upper part of the catalyst bed. First, the catalyst was activated by a method well-known in the art. After the activation procedure was completed, the temperature and pressure were then adjusted to the desired reaction temperature and reaction pressure and equilibrated under hydrogen. The reaction was initiated by starting the supply of methyl ester and hydrogen. After 8 hours of equilibration for each set of reaction conditions, product samples were taken. The conversion rate of the ester and the selectivity to hydrocarbon by-products were evaluated by analyzing samples of the feedstock and the product by gas chromatography. Temperature range: 170 - 250 °C Pressure range: 75 - 250 bar LHSV range: 0.3 - 1.5 h -1 H2 / feedstock molar ratio: (50 - 100) / 1

[0057] Tables 2 to 3 show the values of the ester conversion rate and the selectivity to hydrocarbons obtained under different temperature and pressure conditions.

[0058] The shaped catalyst produced according to the present invention, having a low bulk density, a larger pore volume and a specific pore size distribution, has a higher methyl ester conversion rate compared to the comparative example and the same selectivity to hydrocarbon by-products as the comparative example. This difference in conversion rate is more pronounced at moderately selected reaction pressures such as 75 bar and 100 bar and moderately selected temperatures such as 170 °C and 190 °C. Therefore, it can be said that the plant operation using the catalyst of the present invention will result in significant cost reduction and risk reduction due to the mild operating temperature and operating pressure range.

[0059] [Table 2]

[0060]

Table 3

[0061] Therefore, the catalyst of the present invention has a sufficient ester conversion rate to the target product during plant operation under mild reaction conditions, such as moderate pressure and temperature, which can be said to mean a significant cost reduction and risk reduction.

Claims

1. A shaped catalyst body containing copper, aluminum, and manganese, the shaped catalyst body having a packed bulk density of 0.87 to 1.43 g / cc.

2. The shaped catalyst body according to claim 1, containing 30% to 75% by weight of Cu calculated as CuO.

3. Al 2 O 3 The shaped catalyst carrier according to claim 1 or 2, which is calculated as Al₂O₃ and contains 10% to 50% of Al by weight.

4. The shaped catalyst body according to any one of claims 1 to 3, containing 1% to 25% by weight of Mn calculated as MnO2.

5. The shaped catalyst body according to any one of claims 1 to 4, having a packed bulk density of 0.90 to 1.42 g / cc, preferably 0.95 to 1.35 g / cc.

6. The shaped catalyst body according to any one of claims 1 to 5, having a pore volume of 0.1 to 0.5 ml / g, preferably 0.2 to 0.4 ml / g.

7. The shaped catalyst body according to any one of claims 1 to 6, containing 40% to 65% by weight of Cu calculated as CuO, preferably 45% to 60%.

8. Al 2 O 3 The shaped catalyst carrier according to any one of claims 1 to 7, which is calculated as Al and contains 20% to 40%, preferably 25% to 35% of Al by weight.

9. The shaped catalyst body according to any one of claims 1 to 8, containing 5% to 20% by weight of Mn calculated as MnO2, preferably 7% to 15%.

10. ZrO 2 The shaped catalyst carrier according to any one of claims 1 to 9, further containing 3% to 20% by weight, preferably 5% to 15% by weight of Zr, calculated as

11. The shaped catalyst body according to any one of claims 1 to 10, having a bimodal pore size distribution.

12. A pore volume of 0.02 to 0.50 ml / g, preferably 0.15 to 0.30, due to pores having a pore diameter in the range of 45 to 200 nm, and a pore volume of 0.20 to 0.60 ml / g, preferably 0.25 to 0.50, due to pores having a pore diameter in the range of 10 to 200 nm, exhibited by the shaped catalyst body according to claim 11.

13. The shaped catalyst body according to claim 11 or 12, wherein 10% to 80% of the pore volume is formed by pores having a pore diameter in the range of 45 to 200 nm, and 70% to 100% of the pore volume is formed by pores having a pore diameter in the range of 10 to 200 nm.

14. The shaped catalyst body according to claim 13, wherein 35% to 70%, preferably 45% to 65% of the pore volume is formed by pores having a pore diameter in the range of 45 to 200 nm.

15. a) precipitation by combining an aqueous solution of a copper compound, a manganese compound, an aluminum compound, and a precipitating agent, b) filtering the slurry and washing the precipitate, c) drying and calcining at a temperature in the range of 200 to 1000 °C to form a heat treatment intermediate, d) a step of mixing the heat treatment intermediate, and e) a step of forming into a shaped body A process for producing the shaped catalyst carrier according to any one of claims 1 to 14, comprising:

16. A process of using the shaped catalyst carrier according to any one of claims 1 to 14 for hydrogenation, dehydrogenation, hydrocracking or ethynylation.

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