Hydrodeoxygenation catalyst

Abstract

The present specification describes a catalyst for the hydrodeoxygenation of an alcohol, the catalyst comprising: from 0.1 wt% to 1.5 wt% palladium on a zirconia support; from 1.0 wt% to 5.0 wt% of molybdenum; and from 0.05 wt% to 0.5 wt% of tin. A method for making the catalyst and a hydrodeoxygenation process using the catalyst are also described.

Description

[0001] Invention Field This invention relates to catalysts for hydrodeoxygenation of feed streams, particularly catalysts for converting sugars, sugar alcohols and other carbohydrates into lower molecular weight oxygenated compounds.

[0002] background There is an urgent need for alternatives to fossil fuels. Biomass (materials derived from living or recently living biological materials) is a potential renewable alternative. A key challenge in promoting and sustaining the use of biomass is the need to develop efficient and environmentally friendly technologies for converting biomass into useful products.

[0003] One such commercial process for converting biomass into fuel is developed by Virent Inc. under the name BioForming. TM Sales. This process involves the extraction of soluble carbohydrates from biomass, converting the biomass into reactive intermediates via a combination of aqueous reforming (APR) and / or hydrodeoxygenation (HDO), followed by further reactions to produce hydrocarbons. This process is described in US9314778B2 (Virent, Inc) and the references cited therein.

[0004] A key requirement of the HDO process is the efficient removal of oxygen from carbohydrates without significantly damaging the corresponding carbon backbone. US9314778B2 compares the performance of monometallic, bimetallic, and trimetallic catalysts in the HDO reaction. The described trimetallic catalysts include 2% Pd-2% Mo-0.5% Sn on zirconia tungstate (Examples 24, 35) or 2% Pd-5% Mo-1% Sn on zirconia tungstate (Example 26), in each case using zirconia tungstate from Norpro as the support. The performance of these catalysts in converting food-grade corn syrup feedstock into monooxygenates was tested. When compared to a 3% Pd catalyst on zirconia tungstate, these trimetallic catalysts gave similar yields of monooxygenates, but the yields of undesirable C7+ condensation products were much lower (see Table 9 in the references). Monometallic, bimetallic, and trimetallic catalysts for the HDO reaction are also described in US10131602B2.

[0005] While the Pd-Mo-Sn catalyst on tungstate zirconium oxide has shown good performance in the HDO reaction, there is room for further improvement. It would be advantageous if the amount of palladium could be reduced without sacrificing activity.

[0006] This invention solves these problems. Invention Overview By carefully selecting the amounts of Pd, Mo, and Sn, the inventors have surprisingly managed to provide a catalyst with comparable or better activity in the HDO reaction while having a lower palladium content than previous HDO catalysts. Furthermore, the inventors have managed to simplify the catalyst preparation route, making it involve only a single impregnation step and thus easier to implement on a large scale.

[0008] In a first aspect, the present invention relates to a catalyst for the hydrodeoxygenation of alcohols, the catalyst comprising: on a zirconium oxide support 0.1 wt% to 1.5 wt% palladium; 1.0 wt% to 5.0 wt% molybdenum; and Tin, ranging from 0.05 wt% to 0.5 wt%.

[0009] In a second aspect, the present invention relates to a method for manufacturing a hydrodeoxygenation catalyst, the method comprising the following steps: (i) Dissolve palladium salt, molybdenum salt, tin salt and chelating agent together to produce an impregnation solution; (ii) Add the impregnation solution to the zirconium oxide support to provide the impregnated support; (iii) The dried impregnated carrier; and (iv) Calcining the impregnated support to produce a hydrodeoxygenation catalyst; The hydrodeoxygenation catalyst is defined in the first aspect.

[0010] In a third aspect, the present invention relates to a hydrodeoxygenation process comprising the step of treating a feed stream containing carbohydrate feedstock with a catalyst to produce oxygenated compounds of lower molecular weight, wherein the catalyst is as defined in the first aspect.

[0011] Attached Figure Description Figure 1 The relationship between basic sites / BET surface area and activity is shown.

[0012] Figure 2 The relationship between acidic site / BET surface area and activity is shown.

[0013] Figure 3 This shows how to measure the average diameter of a trilobe; the trilobe shown has an average diameter of 1.4 mm.

[0014] Detailed Explanation Any subheadings are included for convenience only and should not be construed as limiting the content of this disclosure in any way.

[0015] catalyst The present invention also relates to a catalyst for the hydrodeoxygenation of alcohols, the catalyst comprising: on a zirconium oxide support 0.1 wt% to 1.5 wt% palladium; 1.0 wt% to 5.0 wt% molybdenum; Tin, ranging from 0.05 wt% to 0.5 wt%.

[0016] To avoid ambiguity, wt% of metal refers to the amount of metal relative to the total weight of the catalyst.

[0017] The inventors' research has shown that increasing the palladium and / or molybdenum content is associated with improved catalyst performance. While some tin is required to achieve sufficient performance, increasing the tin content above 0.5 wt% negatively impacts performance. Therefore, the inventors have discovered that if the tin content remains low, the palladium content can also remain low. This is surprising, and the palladium and tin loadings presented herein are significantly different from the loadings of the trimetallic examples comprising 2 wt% palladium and 0.5 wt% or 1 wt% tin described in US9314778B2 (Examples 24, 26, and 35).

[0018] Palladium is currently a very expensive metal, and therefore the palladium loading should be as low as possible without negatively impacting performance. Preferably, the catalyst contains 0.1 wt% to 1.5 wt% palladium, such as 0.1 wt% to 1.2 wt% palladium or 0.1 wt% to 1.0 wt% palladium. In some embodiments, the palladium loading is 0.3 wt% to 1.5 wt% palladium, such as 0.3 wt% to 1.2 wt% palladium or 0.3 wt% to 1.0 wt% palladium.

[0019] While increasing the Mo content appears to improve catalyst performance, excessive Mo should be avoided for cost reasons. Preferably, the catalyst contains 1.0 wt% to 5.0 wt% molybdenum, such as 1.0 wt% to 3.0 wt%, or 1.0 wt% to 2.5 wt%.

[0020] While some tin is required to achieve sufficient performance, increasing the tin content above 0.5 wt% negatively impacts performance. Therefore, the catalyst contains 0.05 wt% to 0.5 wt% tin. Preferably, the catalyst contains 0.05 wt% to 0.3 wt% tin, such as 0.1 wt% to 0.3 wt% tin.

[0021] Preferably, the content of metals other than palladium, molybdenum, tin, and zirconium in the catalyst is ≤ 0.1 wt% based on the total weight of the catalyst, if any such metal is present. Preferably, the content of such other metals is ≤ 0.05 wt%, such as ≤ 0.01 wt%.

[0022] Preferred catalysts include: 0.1 wt% to 1.5 wt% palladium; 1.0 wt% to 3.0 wt% molybdenum; and Tin, ranging from 0.05 wt% to 0.3 wt%.

[0023] The inventors' research has shown that the catalytic activity in the HDO reaction is also related to the metal surface area. Preferably, the catalyst has a surface area ≥ 1.0 m² when measured by CO chemisorption according to the procedure reported in the Examples section. 2 / g 催化剂 The surface area of ​​the metal. A typical surface area is 1.0 m². 2 / g 催化剂 Up to 5.5 m 2 / g 催化剂 Such as 1.0 m 2 / g 催化剂 Up to 3.0 m 2 / g 催化剂 Such as 1.0 m 2 / g 催化剂 Up to 2.5 m 2 / g 催化剂 .

[0024] Catalyst manufacturing The catalyst described herein can be prepared by a sequential impregnation process or by a co-impregnation process. The advantage of the co-impregnation process is that it is easier to scale up than the sequential impregnation process. When using a co-impregnation process, it is preferable to include a chelating agent to stabilize the metal in solution. A preferred chelating agent is citric acid.

[0025] The palladium salt can be a palladium(II) salt or a palladium(IV) salt, preferably a palladium(II) salt. Palladium(II) nitrate is particularly preferred.

[0026] Any suitable molybdenum salt can be used. The preferred salt is ammonium molybdate ((NH4)6Mo7O). 24 Ammonium molybdate is readily available commercially.

[0027] The procedure described in US9314778 uses tin(IV) chloride as a tin salt. While various tin(IV) salts can be used in this invention, tin(IV) oxalate is preferred because it poses less health hazard.

[0028] The zirconium oxide support used in step (ii) is preferably as defined in the “Support” section.

[0029] carrier The support preferably contains ≥ 95 wt% ZrO2 based on the total weight of the support. The amount of metal oxides other than ZrO2 is preferably ≤ 5 wt% (support contains ≥ 95 wt% ZrO2), preferably ≤ 4 wt% (support contains ≥ 96 wt% ZrO2), ≤ 3 wt% (support contains ≥ 97 wt% ZrO2), ≤ 2 wt% (support contains ≥ 98 wt% ZrO2), or ≤ 1 wt% (support contains ≥ 99 wt% ZrO2).

[0030] When measured using the procedures reported in the examples, the carrier preferably has a total pore volume of 0.10 mL / g to 0.40 mL / g. A typical total pore volume is 0.12 mL / g to 0.30 mL / g.

[0031] The carrier preferably has 0.006 wt% / m³ as measured by the MBOH test reported in the examples. 2 Up to 0.015wt% / m 2 Preferably 0.0075 wt% / m 2 Up to 0.014 wt% / m 2 The density of basic sites. When impregnated with Pd, Mo, and Sn, supports with basic site densities within these ranges exhibit optimal performance as HDO catalysts, such as... Figure 1 As shown in the image.

[0032] When measured using the procedure reported in the examples, the carrier preferably has 15 µL. NH3 / m 2 Up to 30 µL NH3 / m 2 Preferably 19 µL NH3 / m 2 Up to 28 µL NH3 / m 2 The density of acidic sites. When impregnated with Pd, Mo, and Sn, supports with acidic site densities within these ranges exhibit optimal performance as HDO catalysts, such as... Figure 2 As shown in the image.

[0033] Preferably, the carrier has a crushing strength of 20 N to 140 N when measured using the procedures reported in the examples. Typical crushing strengths are 20 N to 80 N, such as 20 N to 60 N.

[0034] In one embodiment, the support is a tungstate catalyst comprising ≥ 95 wt% ZrO2 and ≤ 5 wt% WO3. These supports can be used to prepare HDO catalysts, as described in US9314778B2.

[0035] In one embodiment, the support is substantially free of tungsten (W), for example containing ≤ 0.1 wt% W, such as ≤ 0.05 wt% W.

[0036] In one embodiment, the carrier has a spherical cross-section.

[0037] In a preferred embodiment, the carrier has a trilobal or tetralobal cross-section. Particularly preferred carriers have a trilobal cross-section with an average diameter of 1.0 mm to 4.0 mm, such as 1.0 mm to 2.0 mm.

[0038] Carrier manufacturing The inventors investigated the use of zirconium oxide (ZrO2) or Zr(OH)4 as a raw material in step (i). Regardless of the raw material used, a carrier with good radial crushing strength can be produced.

[0039] Any suitable lubricant can be used in step (i). Preferred lubricants include microcrystalline cellulose, hydroxymethyl cellulose, or metal stearates. Typically, the lubricant and ZrO2 or Zr(OH)4 are dried and blended in step (i).

[0040] Step (ii) involves forming an extrudate or tablet. In the case of extrusion, an additive is first added to the product mixture from step (i). The additive is typically provided as an aqueous solution. The primary function of the additive is to act as a binder for the ZrO2 or Zr(OH)4 raw materials. It is not intended to be bound by any theory that the additive can cause crosslinking (in the case of zirconium acetate or zirconium nitrate) or peptization (in the case of nitric acid or ammonium hydroxide). The inventors have found that the choice of additive affects the acid / base properties of the resulting zirconia support, which can influence the suitability of the support for the catalyst in question.

[0041] In some implementations, the additive is ammonia or an acid, such as nitric acid. In both cases, the support has acceptable strength and performs well as an HDO catalyst.

[0042] While adding ammonia or acids as additives produces supports with good strength and good to excellent performance as HDO catalysts, the use of ammonia or acids may be incompatible with manufacturing equipment. Therefore, in some embodiments, zirconium salts are used. Preferred zirconium salts include zirconium nitrate, zirconium acetate, and ammonium zirconium carbonate. Surprisingly, the use of zirconium salts as additives results in supports with higher strengths than those achievable with ammonia or nitric acid. Therefore, the use of zirconium salts may be preferred when a high-strength zirconia support is required. The use of zirconium salts, particularly zirconium acetate, is generally also more compatible with manufacturing equipment than ammonia or acids, and for this reason, zirconium salts may be preferred.

[0043] In the case of tableting, it is not necessary to add additives to the product of step (i) before tableting.

[0044] Step (ii) also involves forming a shaped article by extrusion (“extrudate”) or by tableting (“tablet”). In each case, the cross-section of the shaped article may be spherical (e.g., cylindrical) or shaped. Preferably, the shaped article has a trilobal or tetralobal cross-section, as this provides a catalyst with a high geometrical surface area beneficial to activity. Extrusion and tableting conditions will be well known to those skilled in the art.

[0045] Typically, the shaped article (“extrudate”) formed by extrusion will have an elongated shape. The cross-section of the extrudate can be spherical (i.e., cylindrical extrudate) or shaped. Multi-lobed shapes such as trefoil or tetralobes are preferred, especially trefoil. Particularly suitable shapes are trefoil shapes with an average diameter of 1.0 mm to 4.0 mm, such as 1.0 mm to 2.0 mm. Figure 3 It shows how to measure the average diameter of a trefoil.

[0046] Step (iii) involves drying the molded article to remove excess water. The drying conditions will be readily determined by those skilled in the art.

[0047] Step (iv) involves calcining the product of step (iii). The inventors have found that while calcination temperature does not appear to have a significant effect on support strength, it does affect its performance as an HDO catalyst. When the support is used as an HDO catalyst, a calcination temperature in step (iv) is preferably between 300°C and 800°C, such as between 300°C and 500°C or between 350°C and 450°C. A calcination time of 2–6 hours is generally sufficient, although this can vary depending on scale.

[0048] Example raw materials SGN SZ31164 is a commercial zirconia extrusion (1.2 mm diameter) from Saint Gobain.

[0049] ZOH-85 is a commercial Zr(OH)4 from Zircomet.

[0050] Z-3186 is a commercial ZrO2 product from Daiichi Kigenso Kagaku Kogyo Co. Ltd.

[0051] RC-100 is a commercial ZrO2 product from Daiichi Kigenso Kagaku Kogyo Co. Ltd.

[0052] XZO 631 / 01 is a commercial Zr(OH)4 from MEL Chemicals.

[0053] General procedures for manufacturing carriers The raw material (ZrO2 or Zr(OH)4) is dried and mixed with a lubricant (microcrystalline cellulose, hydroxymethyl cellulose, or magnesium stearate). In the case of an extruded catalyst, an additive solution (5% ammonia, 5% nitric acid, zirconium nitrate solution, or zirconium acetate solution) is added, and the mixture is extruded into lobes with an average diameter of 1.3 mm or cylinders with a diameter of 1.6 mm. In the case of a granular catalyst, the mixture of raw material and lubricant is granulated into flakes with a diameter of 3.3 mm. The material is dried (120°C) and then calcined under specified conditions.

[0054] Program for measuring crushing strength Radial crushing strength was measured using an Engineering Systems CT6 instrument. A crushing rate of 22 mm / min and a 50 kg force sensor were used. Twenty individual particles were analyzed and averaged.

[0055] Program for measuring total orifice volume and BET surface area Surface area was measured using a Micromeritics 2420 ASAP physical adsorption analyzer by applying the BET method according to ASTM Method D 3663-03, "Standard Tests for Surface Area". Nitrogen gas was used as the adsorbate, and measurements were taken at liquid nitrogen temperature. The cross-sectional area of ​​nitrogen molecules was taken as 16.2 Å. 2 Prior to analysis, the sample was degassed by purging with dry nitrogen at the optimal temperature for at least 1 hour. (At 0.05 P / P) o Up to 0.20 P / P o (including 0.05 P / P) o and 0.20 P / P oFive relative pressure / volume data pairs were obtained within a relative pressure range. The equilibration time for each point was 10 seconds. Surface area was reported based on the weight of the degassed sample. Complete adsorption / desorption isotherms were measured within a relative pressure range of 0.05 to 0.995 and back to 0.05. The final point on the adsorption isotherm (0.995 P / P) was used. o The total pore volume is determined at point ().

[0056] Program for measuring acidic site density The particles were ground into powder and loaded into a Micromeritics AutoChem 2950HP thermal analyzer. A helium flow of 40 mL / min was passed through the particles at atmospheric pressure while heating to 400°C at a rate of 20°C / min. The temperature of 400°C was maintained for 10 minutes, followed by cooling to 120°C. After reaching 120°C, a helium flow of 40 mL / min and a helium flow of 5% v / v ammonia were passed through the particles for 30 minutes. Physically adsorbed ammonia was purged with a helium flow of 40 mL / min for 30 minutes. The particle temperature was then increased to 700°C at a rate of 5°C / min and maintained for 30 minutes, during which time the desorption of ammonia from the particles was monitored using a TCD detector. The total amount of desorbed ammonia was calculated by integrating the desorption profile, which had been calibrated using a known amount of ammonia-containing helium. This value was then normalized to the sample BET surface area (measured according to the BET surface area procedure) to obtain the total amount of ammonia in µL. NH3 / m 2 The density of acidic sites was calculated.

[0057] Program for measuring the density of basic sites The program is based on the article " Evaluation of Surface Acid-Basic Properties of Inorganic-Based Solids by Model Catalytic Alcohol Reaction Networks ( Catalyst Reviews , 48:315-362, 2006) and " Synthesis and Characterization of ZrO 2 as Acid-Basic Catalysts: Reactivity of 2-Methyl-3-butyn-2-ol ” ( Journal of Catalysis The procedure described in 183, 240-250 (1999)).

[0058] Six g of granules, along with 15 mL of 2-methyl-3-butyn-2-ol (MBOH) and a single drop of water, were loaded into a static 45 mL autoclave. The autoclave was placed in an oven at 200 °C for 18 hours, then cooled to room temperature. The concentrations of 2-methyl-1-buten-3-yne (Mbyne), isopropylidene acetone (MO), 2-methyl-3-butyn-2-ol (MBOH), 3-methyl-2-butenal (Prenal), 3-hydroxy-3-methyl-2-butanone (HMB), and 4-hydroxy-4-hydroxy-4-methyl-2-pentanone (DAA) in the reaction liquid were analyzed by gas chromatography using external standard. A certain amount of acetone and 4-hydroxy-4-hydroxy-4-methyl-2-pentanone (DAA) were added, and the result was divided by the BET surface area of ​​the granules (6 g) to obtain the wt.% 碱性产物 / m 2 The density of basic sites was calculated.

[0059] Program for measuring the surface area of ​​metal The area of ​​palladium metal was measured on a Micromeritics HTP 6 Station chemisorption analyzer using a static (gas pressure) method.

[0060] Use approximately 1 g to 2 g of sample. First, heat the sample to 140 °C at 10 °C / min in 100% helium flowing at 50 SCCM and maintain at 140 °C for 30 min. Then, turn off the helium and allow the sample to cool to 35 °C under vacuum. Next, heat the sample to 100 °C at 10 °C / min in 100% hydrogen flowing at 50 SCCM and maintain at 100 °C for 120 min to reduce Pd. After the reduction phase is complete, turn off the hydrogen and evacuate the sample to less than 10 µmHg at 100 °C for 60 min. Then, cool the sample to 35 °C under vacuum and continue evacuation at less than 10 μmHg for another 10 min. A leak test is then performed before analysis. An acceptable leak rate is less than 5 μmHg / min. If the leak rate exceeds this value, the integrity of the sample may be compromised, and a lower metal area may result due to the re-oxidation of palladium by air leaking into the system. Metal area analysis was performed at 35 °C, with 100% carbon monoxide added to the sample within a pressure range between 100 mmHg and 760 mmHg. At each pressure, chemisorbed carbon monoxide was allowed to reach equilibrium, and the volume of gas absorbed was automatically measured and recorded. The pressure / absorption pair constituted the chemisorption isotherm. At the end of the analysis, the sample was drained, and the weight reduction was recorded.

[0061] This analysis requires the measurement of two isotherms. The first is a measure of the “total” carbon monoxide absorbed by the sample, which includes both chemisorbed and physisorbed carbon monoxide. The sample is then evacuated to remove the physisorbed (“weak”) component, and the isotherm is repeated to quantify the amount of physisorbed carbon monoxide back on the sample. The isotherms are checked to ensure that only the linear portion is used in data simplification. The instrument software calculates the Pd surface area based on the total hydrogen absorption and the difference between the “total” and “weak” (i.e., “strong”) components, and reports the palladium surface area based on these values ​​by extrapolating the data back to zero pressure. These are typically referred to as the Pd area (0tot) and Pd area (0str) (str = strong), respectively. The reduced weight is used to represent the catalyst reduction in m 2 g -1 The calculated area of ​​Pd.

[0062] General co-impregnation process for manufacturing HDO catalysts The supports S1 and S3 to S7 described in Table 1 were converted into HDO catalysts C1 and C3 to C7 using the following procedure. Zirconia extrudate was loaded into a rotary drum. An impregnation solution was prepared by dissolving ammonium molybdate, palladium nitrate solution, tin oxalate, and citric acid in deionized water up to the absorbance volume of the extrudate. The impregnation solution was added to the rotary drum mixer over approximately 2 minutes with gentle rotation (approximately 2 rpm), and the mixture was allowed to tumble for an additional 15 minutes (approximately 2 rpm). The impregnated flakes were transferred to an oven and dried overnight at 105 °C, and then calcined in air at an incline rate of 2 °C / min for 4 hours. The resulting catalyst contained 1 wt% Pd, 2 wt% Mo, and 0.25 wt% Sn, except for S2, which contained 1 wt% Pd, 1 wt% Mo, and 0.25 wt% Sn.

[0063] General sequential impregnation process for manufacturing HDO catalysts The carrier S2 described in Table 1 was converted into HDO catalyst S2 using the following procedure: Zirconia extrudate was loaded into a drum. An impregnation solution was prepared by dissolving ammonium molybdate, tin oxalate, and citric acid in deionized water up to the absorbance volume of the extrudate. The impregnation solution was added to the drum mixer over approximately 2 minutes with gentle rotation (approximately 2 rpm), allowing the mixture to tumble for an additional 15 minutes (approximately 2 rpm). The impregnated extrudate was transferred to an oven and dried overnight at 105°C, and then calcined in air at an incline rate of 2°C / min for 4 hours. The catalyst intermediate was then removed from the oven and loaded into the drum. The palladium nitrate impregnation solution was replenished to the absorbance volume with deionized water. The impregnation solution was added to the drum mixer over approximately 2 minutes with gentle rotation (approximately 2 rpm), allowing the mixture to tumble for an additional 15 minutes (approximately 2 rpm). The impregnated extrudate was transferred to an oven and dried at 105°C overnight, and then calcined in air at 400°C at an incline rate of 2°C / min for 4 hours. The analysis of the data in Table 1 indicates the following: • Good crushing strength can be achieved when Zr(OH)4 or ZrO2 is used as raw material; • The addition of zirconium nitrate (S6) or zirconium acetate (S7) is beneficial to strength, especially zirconium nitrate; Figure 1 The relationship between basic site / BET area and activity is shown. The activity peak of C5 is based on support S5, which has a concentration of 0.0119 wt% / m² from MBOH testing. 2 The density of basic sites.

[0064] Figure 2 The relationship between acidic site / BET area and activity is shown. This relationship is less pronounced compared to the basic site density.

[0065] Changes in metal loading Various catalysts were prepared using the general procedure reported above. The amounts of ammonium molybdate, palladium nitrate, and tin oxalate were varied to investigate the effect of metal loading. The support was varied to investigate its effect. Statistical models were applied to the data to find the correlation between performance and catalyst activity. The model found a statistically significant correlation between catalyst activity and (1) Mo content and (2) metal surface area. The selected data are reported in Tables 2 and 3. The results in Table 2 compare a range of catalysts with approximately the same Pd, Mo, and Sn contents (target 1 wt% Pd, 2 wt% Mo, and 0.25 wt% Sn) but using different supports. Changing the support can be used to influence the metal surface area and, consequently, the activity. Surprisingly, by selecting appropriate Pd, Mo, and Sn contents and by choosing a suitable support, it is possible to match and even outperform catalysts with much higher Pd contents (C8). The results in Table 3 compare a series of catalysts with the same support and approximately the same metal surface area. Because metal surface area is a parameter influenced by many factors, including the loading of the metals (Pd, Mo, and Sn) and the characteristics of the support, it is impossible to systematically change the contents of Pd, Mo, and Sn at a constant metal surface area. However, statistical models show a positive correlation between Mo content and catalyst activity, as can be seen by comparing C14 and C15. Surprisingly, by selecting appropriate contents of Pd, Mo, and Sn, catalyst C8, with a much higher Pd content, can be matched and even outperformed.

[0066] Analysis of the data from Examples C1 to C15 indicates the following relationships: • H2 consumption can be improved by increasing the Mo content; • H2 consumption can be improved by increasing the surface area of ​​the metal.

[0067] By carefully selecting the support and the contents of Pd, Mo and Sn, it has been demonstrated that the Pd content can be reduced from 2 wt% (C8) to 0.4 wt% (C15) without sacrificing catalyst activity.

Claims

1. A catalyst for the hydrodeoxygenation of alcohols, comprising: a catalyst on a zirconium oxide support. 0.1 wt% to 1.5 wt% palladium; 1.0 wt% to 5.0 wt% molybdenum; and Tin, ranging from 0.05 wt% to 0.5 wt%.

2. The catalyst according to claim 1, wherein the catalyst comprises 0.1 wt% to 1.0 wt% palladium.

3. The catalyst according to claim 1 or claim 2, wherein the catalyst comprises 1.0 wt% to 3.0 wt% molybdenum.

4. The catalyst according to any one of claims 1 to 3, wherein the catalyst comprises 0.05 wt% to 0.3 wt% tin.

5. The catalyst according to any one of claims 1 to 4, wherein, when measured by CO chemisorption, the catalyst has ≥ 1.0 m 2 / g 催化剂 The metal surface area.

6. The catalyst according to any one of claims 1 to 5, wherein the catalyst has a concentration of 1.0 m when measured by CO chemisorption. 2 / g 催化剂 Up to 3.0 m 2 / g 催化剂 The metal surface area.

7. The catalyst according to any one of claims 1-6, wherein the catalyst is in the form of a shaped body.

8. The catalyst according to claim 7, wherein the shaped body has a spherical cross-section.

9. The catalyst according to claim 7, wherein the shaped body has a trilobal cross-section.

10. The catalyst according to claim 9, wherein the shaped body has a trilobal cross-section with an average diameter of 1.0 mm to 4.0 mm.

11. The catalyst according to any one of claims 1 to 10, wherein the content of metals present in the catalyst other than palladium, molybdenum, tin and zirconium is ≤ 0.1 wt% based on the total weight of the catalyst, if any such metal is present.

12. The catalyst according to any one of claims 1 to 11, wherein the support has a total pore volume of 0.10 mL / g to 0.40 mL / g when measured by N2 physisorption.

13. The catalyst according to any one of claims 1 to 12, wherein the support has a density of 15 µL. NH3 / m 2 Up to 30 µL NH3 / m 2 The density of acidic sites.

14. The catalyst according to any one of claims 1 to 13, wherein the support has a density of 19 µL. NH3 / m 2 Up to 28 µL NH3 / m 2 The density of acidic sites.

15. The catalyst according to any one of claims 1 to 14, wherein the support has a molecular weight of 0.006 wt% / m² as measured by MBOH test. 2 Up to 0.015 wt% / m 2 The density of basic sites.

16. The catalyst according to any one of claims 1 to 15, wherein the support has a molecular weight of 0.0075 wt% / m² as measured by MBOH test. 2 Up to 0.014 wt% / m 2 The density of basic sites.

17. A method for manufacturing a hydrodeoxygenation catalyst, comprising the following steps: (i) Dissolve palladium salt, molybdenum salt, tin salt and chelating agent together to produce an impregnation solution; (ii) Add the impregnation solution to the zirconium oxide support to provide an impregnated support; (iii) Dry the impregnated carrier; as well as (iv) Calcining the impregnated support to produce the hydrodeoxygenation catalyst; The hydrodeoxygenation catalyst described herein is as defined in any one of claims 1 to 16.

18. The method of claim 17, wherein the chelating agent is citric acid.

19. The method according to claim 17 or claim 18, wherein the carrier has a total pore volume of 0.10 mL / g to 0.40 mL / g when measured by N2 physisorption.

20. The method according to any one of claims 17 to 19, wherein the carrier has a density of 15 µL. NH3 / m 2 Up to 30 µL NH3 / m 2 The density of acidic sites.

21. The method according to any one of claims 17 to 19, wherein the carrier has a density of 19 µL. NH3 / m 2 Up to 28 µL NH3 / m 2 The density of acidic sites.

22. The method according to any one of claims 17 to 21, wherein the carrier has a content of 0.006 wt% / m² as measured by the MBOH test. 2 Up to 0.015 wt% / m 2 The density of basic sites.

23. The method according to any one of claims 17 to 21, wherein the carrier has a content of 0.0075 wt% / m² as measured by the MBOH test. 2 Up to 0.014 wt% / m 2 The density of basic sites.

24. The method according to any one of claims 17 to 23, wherein the palladium salt is palladium nitrate.

25. The method according to any one of claims 17 to 24, wherein the molybdenum salt is ammonium molybdate.

26. The method according to any one of claims 17 to 25, wherein the tin salt is tin oxalate.

27. The method according to any one of claims 17 to 26, wherein the calcination in step (iv) is carried out at 350°C-450°C.

28. A hydrodeoxygenation process comprising the step of treating a feed stream containing carbohydrate feedstock with a catalyst to produce an oxygenated compound of lower molecular weight, wherein the catalyst is as defined in any one of claims 1 to 16.

29. The hydrodeoxygenation process according to claim 28, wherein the feed stream comprises sugar and / or sugar alcohol.

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