Low-temperature hydrodeoxygenation catalysts, their manufacturing methods and applications

Abstract

This invention relates to low-temperature hydrodeoxygenation catalysts, their manufacturing methods, and their applications. The catalysts of this invention are suitable for the low-temperature removal of alcohols from Fischer-Tropsch synthesis oils, and also for the low-temperature removal of alcohols from other hydrocarbons containing alcohols. The catalysts of this invention use a phosphorus-modified alumina support, nickel as the hydrotreating active component, and lanthanum, cerium, cobalt, and / or zinc (especially cerium) as co-catalyst components. The component loading process employs a stepwise impregnation method to sequentially load the co-catalyst components and the hydrotreating active component onto the support. The catalysts of this invention solve the technical problem of sufficient removal of oxygen-containing compounds at low temperatures.

Description

Technical Field

[0001] This invention relates to a low-temperature hydrodeoxygenation catalyst suitable for the low-temperature hydrodeoxygenation refining process of oxygen-containing compounds in Fischer-Tropsch synthetic oils, particularly for the low-temperature removal of alcohols from Fischer-Tropsch synthetic oils, and also for the low-temperature removal of alcohols from other hydrocarbons containing alcohols. Furthermore, this invention also relates to a method for manufacturing this catalyst. Background Technology

[0002] With the increasing demand for petroleum-based liquid fuels and the dwindling availability of petroleum resources, Fischer-Tropsch synthetic oils, synthesized from syngas using the Fischer-Tropsch synthesis reaction, have attracted attention. Fischer-Tropsch synthetic oils contain a high content of olefins as well as a certain amount of oxygen-containing compounds, such as alcohols, acids, aldehydes, ketones, and esters. Even trace amounts of these oxygen-containing compounds can have numerous adverse effects on subsequent processes, such as corroding equipment and poisoning and deactivating olefin polymerization catalysts (the presence of more than 1% oxygen-containing compounds can cause catalyst poisoning and deactivation). Therefore, thorough removal of oxygen-containing compounds from Fischer-Tropsch synthetic oils is essential.

[0003] The crude products of low-temperature Fischer-Tropsch synthesis mainly consist of light oils, heavy oils, and heavy waxes. Synthetic oils from different fractions undergo olefin saturation and oxygen-containing compound removal reactions in a hydrorefining unit. These products can be used to produce environmentally friendly solvent oils, surfactants, high-grade white oils, drilling fluid base oils, etc., effectively supplementing the petrochemical industry and producing specialized high-end products that are difficult to produce from petroleum-based feedstocks. Hydrodeoxygenation is one of the main methods for removing oxygen-containing compounds from Fischer-Tropsch synthetic oils.

[0004] Traditional petroleum product hydrorefining catalysts typically use metal sulfides as the active phase, with the active metal primarily being non-precious metal systems such as Ni-Mo and Co-Mo. Sulfide catalysts require pre-sulfurization with sulfur-containing compounds before use. Since Fischer-Tropsch synthesis oil is essentially sulfur-free, the sulfur on the catalyst gradually leaches into a metallic state during the reaction, leading to deactivation. Therefore, to maintain catalyst activity, the reaction system needs to be periodically injected with sulfiding agents. However, this results in the presence of sulfur in the processed products, contaminating the Fischer-Tropsch synthesis oil. Metal reduction catalysts, on the other hand, eliminate the need for sulfiding agents, reducing the sulfur injection process and solving the product contamination problem.

[0005] Patent Document 1 discloses a Fischer-Tropsch synthesis oil hydrodeoxygenation catalyst, which consists of one or more main catalytically active metal components selected from Mo, W, and Ni, and a support. Optionally, one or more combinations of B, P, Co, and La may be added as co-catalytic active components. The support is selected from one or more of acid-modified alumina supports, composite supports containing molecular sieves and alumina, and solid acid supports, or any combination of two or more of these. The modified alumina support is a shaped alumina support impregnated with an acid solution of a certain molar concentration (phosphoric acid, oxalic acid, silicotungsten heteropolyacid, or any combination of two or more of these). In Example 2 of Patent Document 1, the reaction temperature was 245°C, and the deoxygenation rate was 98.5%.

[0006] However, the inventors have found that the catalyst in Patent Document 1 has a high reaction temperature (above 240°C) and there is room for improvement in the deoxygenation rate, especially at low temperatures (below 240°C) the deoxygenation rate (i.e., the removal rate of oxygen-containing compounds) is not high enough.

[0007] Patent Document 2 discloses a Fischer-Tropsch synthesis oil hydrogenation catalyst, which mainly consists of hydrogenation active components nickel oxide and tungsten oxide or molybdenum oxide, and a support. The co-catalyst is one or a combination of rare earth metals lanthanum and cerium, and may or may not contain one or any combination of non-metallic elements fluorine, phosphorus, and boron. Patent Document 2 evaluates the phosphorus-containing catalyst at a reaction temperature of 260°C, with a deoxidation rate >99%.

[0008] The inventors discovered that to achieve a deoxygenation rate of over 99%, the catalyst in Patent Document 2 requires a greater variety and complexity of elements (two types of hydrogenation active components). Furthermore, the catalyst in Patent Document 2 operates at a higher reaction temperature and has a lower space velocity. If the catalyst in Patent Document 2 is used at low temperatures, the deoxygenation rate will not be high enough.

[0009] Patent Document 3 discloses a catalyst for the hydrorefining of Fischer-Tropsch synthetic oil. The catalyst primarily consists of a support composed of hydrogenation active components nickel oxide, tungsten oxide, and alumina. One or more of titanium oxide, silicon oxide, zirconium oxide, fluorine, boron, and phosphorus are used as additives to modify the support. The γ-Al₂O₃ support is impregnated with an equal volume of an aqueous or organic solution of one or more of the additive components selected from titanium, silicon, zirconium, fluorine, boron, and phosphorus. The phosphorus-containing catalyst in Patent Document 3 is evaluated at a reaction temperature of 300°C and exhibits a deoxidation rate of 99.76%.

[0010] The inventors have discovered that the catalyst in Patent Document 3 requires a reaction temperature of up to 300°C to achieve a high deoxygenation rate. If the catalyst in Patent Document 3 is used at a low temperature, the deoxygenation rate is not high enough.

[0011] Existing technical documents

[0012] Patent Document 1: CN102794181B

[0013] Patent Document 2: CN101733119B

[0014] Patent Document 3: CN103191754A

[0015] The technical problem to be solved by the present invention

[0016] Achieving a high deoxygenation rate at a relatively low reaction temperature is obviously more economical, especially in terms of reducing energy consumption and CO2 emissions.

[0017] The inventors have discovered that for Fischer-Tropsch synthetic oils, the hydrodeoxygenation reaction is a temperature-sensitive reaction. The deoxygenation rate increases with increasing reaction temperature, and conversely, lower reaction temperatures are less conducive to improving the deoxygenation rate. In actual reaction processes, within a certain temperature range, a 10°C difference in temperature can result in a difference of several percentage points in the deoxygenation rate, or even a difference of ten to twenty percentage points.

[0018] The catalysts in Patent Documents 1 to 3 are all used only at reaction temperatures above 240°C. The inventors have found that once used at lower temperatures (below 240°C), the deoxygenation rate decreases to varying degrees, which is unsatisfactory.

[0019] Furthermore, the fewer elements used in a catalyst, the fewer manufacturing steps and the lower the cost. However, according to the embodiments in Patent Documents 1 to 3, the catalysts in Patent Documents 1 to 3 actually use more elements and have more manufacturing steps.

[0020] Furthermore, patent documents 1 to 3 do not pay particular attention to the removal of alcohols, which constitute a large proportion of the Fischer-Tropsch synthetic oil.

[0021] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a hydrodeoxygenation catalyst for Fischer-Tropsch synthetic oil, which can fully remove oxygen-containing compounds, especially alcohols, at a lower reaction temperature, and the catalyst uses fewer types of elements and has fewer manufacturing steps.

[0022] means of solving technical problems

[0023] Through in-depth research, the inventors have discovered that solving the aforementioned technical problem is a complex process, related not only to the selection of the hydrogenation active component and the co-catalyst component, but also to the properties of the support and the catalyst preparation method / process. These four factors are interrelated.

[0024] Based on this discovery, the inventors conducted extensive research and experiments over a long period and finally found that the above-mentioned technical problems can only be effectively solved when the hydrodeoxygenation catalyst simultaneously meets the following four main characteristics.

[0025] Feature 1: Uses phosphorus-modified alumina as a carrier;

[0026] Feature 2: Nickel is used as the active component for hydrogenation;

[0027] Feature 3: Lanthanum, cerium, cobalt and / or zinc (especially cerium) are used as cocatalyst components;

[0028] Feature 4: The component loading process uses a stepwise impregnation method to sequentially load the co-catalyst component and the hydrogenation active component onto the support.

[0029] Furthermore, when the hydrodeoxygenation catalyst simultaneously satisfies the following four main characteristics, as well as other preferred characteristics described in this application, the effect of the present invention can be further improved. Summary of the Invention

[0030] The present invention includes the following solutions [1] to

[22] :

[0031] [1] A hydrodeoxygenation catalyst, wherein,

[0032] The catalyst comprises a phosphorus-modified alumina support and a hydrogenation active component and a co-catalyst component supported on the phosphorus-modified alumina support.

[0033] The hydrogenation active component is only nickel.

[0034] The co-catalyst component is selected from at least one of lanthanum, cerium, cobalt, and zinc.

[0035] The hydrodeoxygenation catalyst is manufactured by a method comprising the following steps in sequence:

[0036] Step 1: Prepare phosphorus-modified alumina support;

[0037] Step 2, loading the co-catalyst components;

[0038] Step 3, loading the hydrogenated active component,

[0039] In steps 2 and 3, the co-catalyst component and the hydrogenation active component are loaded in steps by impregnation.

[0040] [2] The hydrodeoxygenation catalyst as described in [1], wherein,

[0041] The phosphorus-modified alumina carrier is a γ-Al2O3 carrier.

[0042] [3] The hydrodeoxygenation catalyst as described in [1] or [2], wherein,

[0043] Phosphorus is added to the raw material of the alumina carrier before the alumina carrier is formed.

[0044] In the phosphorus-modified alumina carrier, phosphorus exists in the form of phosphorus pentoxide, and the content of phosphorus pentoxide is 0.5-5% by mass, with the mass of alumina in the phosphorus-modified alumina carrier being 100% by mass.

[0045] [4] The hydrodeoxygenation catalyst as described in [1] or [2], wherein,

[0046] Phosphorus is added to the raw material of the alumina carrier before the alumina carrier is formed.

[0047] In the phosphorus-modified alumina carrier, phosphorus exists in the form of phosphorus pentoxide, and the content of phosphorus pentoxide is 1-3% by mass, with the mass of alumina in the phosphorus-modified alumina carrier being 100% by mass.

[0048] [5] The hydrodeoxygenation catalyst as described in any of [1] to [4], wherein,

[0049] With the catalyst having a mass of 100%, the nickel content, calculated as oxides, is as follows:

[0050] The nickel oxide content is 12-18% by mass.

[0051] [6] The hydrodeoxygenation catalyst as described in any of [1] to [5], wherein,

[0052] With the catalyst having a mass of 100%, the nickel content, calculated as oxides, is as follows:

[0053] The nickel oxide content is 12-16% by mass.

[0054] [7] The hydrodeoxygenation catalyst as described in any of [1] to [6], wherein,

[0055] With the catalyst having a mass of 100%, the content of lanthanum, cerium, cobalt, and / or zinc elements, calculated as oxides, is as follows:

[0056] The content of lanthanum oxide and / or cerium oxide and / or cobalt oxide and / or zinc oxide is 1 to 11% by mass.

[0057] [8] The hydrodeoxygenation catalyst as described in any of [1] to [7], wherein,

[0058] With the catalyst having a mass of 100%, the cerium content, calculated as oxides, is as follows:

[0059] The cerium oxide content is 6-10% by mass.

[0060] [9] The hydrodeoxygenation catalyst as described in any of [1] to [8], wherein,

[0061] The cocatalyst component is cerium only.

[0062]

[10] The hydrodeoxygenation catalyst as described in any of [7] to [9], wherein,

[0063] The rest are phosphorus-modified alumina carriers.

[0064]

[11] The hydrodeoxygenation catalyst as described in any of [1] to

[10] , wherein,

[0065] The catalyst does not contain molybdenum.

[0066]

[12] The hydrodeoxygenation catalyst as described in any of [1] to

[11] , wherein,

[0067] The catalyst was free of silicon, titanium, tungsten, fluorine, and boron.

[0068]

[13] The hydrodeoxygenation catalyst as described in any of [1] to

[12] , wherein,

[0069] Hydrogenated active components are loaded onto a phosphorus-modified alumina support using a complexing agent.

[0070]

[14] The hydrodeoxygenation catalyst as described in

[13] , wherein,

[0071] The complexing agent is citric acid and / or oxalic acid.

[0072] The mass ratio of the complexing agent to nickel oxide is 0.5:1 to 1:1.

[0073]

[15] A method for manufacturing a hydrodeoxygenation catalyst, wherein the method is a method for manufacturing the hydrodeoxygenation catalyst described in any one of [1] to

[14] , wherein,

[0074] The manufacturing method includes the following steps:

[0075] Step 1, obtaining phosphorus-modified alumina support, wherein phosphorus is added by adding a phosphorus-containing precursor to the raw material of the alumina support before the alumina support is formed;

[0076] Step 2: The phosphorus-modified alumina support obtained in Step 1 is first impregnated with a solution containing the co-catalyst components (preferably impregnated in equal volumes), and the impregnated catalyst is dried and calcined to obtain a one-time impregnated catalyst.

[0077] Step 3: Impregnate the primary impregnated catalyst obtained in Step 2 with an aqueous solution of soluble nickel salt (preferably with equal volume impregnation), and then dry and calcine the impregnated catalyst to obtain the hydrodeoxygenation catalyst.

[0078]

[16] The method for manufacturing the hydrodeoxygenation catalyst as described in

[15] , wherein,

[0079] In step 1, 1-5% by mass of extrusion aid guarana powder is added to the pseudoboehmite powder, a precursor of γ-Al2O3, and stirred evenly. An aqueous solution containing 2-5% by mass of nitric acid, 1-5% by mass of citric acid, and phosphorus is added at a water-to-powder ratio of 0.6-1. After mixing, the mixture is extruded on an extruder, dried at 60-120℃, and calcined at 400-750℃ for 3-6 hours to obtain a phosphorus-modified γ-Al2O3 carrier, wherein the concentration of nitric acid is 65-68%.

[0080] In step 2, the phosphorus-modified γ-Al2O3 support obtained in step 1 is first impregnated with an aqueous solution of the metal salt of the co-catalyst component, then dried at 100-140℃ for 8-12 hours, and then calcined at 350-550℃ for 3-6 hours to obtain a one-time impregnated catalyst.

[0081] In step 3, the catalyst obtained from the first impregnation in step 2 is impregnated with an aqueous solution containing soluble nickel salt and complexing agent using the equal volume impregnation method. Then, it is dried at 100-140°C for 8-12 hours and calcined at 350-550°C for 3-6 hours to obtain the hydrodeoxygenation catalyst.

[0082]

[17] A hydrodeoxygenation reaction, wherein the reaction uses a catalyst described in any one of [1] to

[14] , wherein the catalyst is used after being reduced in a reactor, and the reaction is carried out at a reaction temperature of 170°C to 350°C.

[0083]

[18] The hydrogenation deoxygenation reaction as described in

[17] , wherein the reaction temperature is 190°C to 240°C.

[0084]

[19] The hydrogenation deoxygenation reaction as described in

[17] , wherein the reaction temperature is 200℃~230℃.

[0085]

[20] The hydrodeoxygenation reaction as described in

[17] , wherein the reaction is carried out at a pressure of 2-6 MPa, a hydrogen-to-oil ratio of 200-800, and a liquid hourly space velocity of 0.5-4 h⁻¹. -1 It is carried out under the following conditions.

[0086]

[21] The hydrogenation deoxygenation reaction as described in

[17] , wherein the oxide removal rate of the reaction is above 99%.

[0087]

[22] The hydrogenation deoxygenation reaction as described in

[17] , wherein the alcohol removal rate of the reaction is above 99%.

[0088]

[23] The hydrodeoxygenation reaction as described in

[17] , wherein the alcohol removal rate of the reaction is 100%.

[0089] The application of the hydrodeoxygenation catalyst described in any of

[24] [1]~

[14] in the hydrodeoxygenation reaction of Fischer-Tropsch synthetic oil, wherein,

[0090] The reaction was carried out at a reaction temperature of 200℃ to 230℃.

[0091] The application of any of the hydrodeoxygenation catalysts described in

[25] [1] to

[14] in the hydrodeoxygenation reaction of alcohols in hydrocarbons containing alcohols, wherein,

[0092] The reaction was carried out at a reaction temperature of 200℃ to 230℃.

[0093] Invention Effects

[0094] The present invention has the following advantages:

[0095] First, the hydrodeoxygenation catalyst of the present invention (hereinafter sometimes simply referred to as "the catalyst of the present invention") can effectively remove oxygen-containing compounds, especially alcohols, from Fischer-Tropsch synthesis oils at low temperatures. The hydrodeoxygenation catalyst of the present invention can also substantially completely or even completely remove alcohols from hydrocarbons containing alcohols at low temperatures.

[0096] Secondly, although the catalyst of the present invention, which uses nickel as the active hydrogenation component and cerium as the co-catalyst component, uses fewer types of metal elements, it can more fully remove oxygen-containing compounds, especially alcohols, from Fischer-Tropsch synthesis oils at low temperatures, and can also almost completely or even completely remove alcohols from hydrocarbons containing alcohols at even lower temperatures.

[0097] Third, the catalyst of the present invention has fewer manufacturing steps and a simpler manufacturing process.

[0098] In this article, unless otherwise stated, low temperature refers to a reaction temperature of 190℃ to 240℃, and especially to a reaction temperature of 200℃ to 230℃. Detailed Implementation

[0099] In this specification, the numerical range indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits.

[0100] <Hydrodeoxygenation catalyst>

[0101] In Fischer-Tropsch synthetic oils, oxygen-containing compounds typically account for 5% to 15% of the total mass, with the remainder being hydrocarbons.

[0102] The oxygen-containing compounds in Fischer-Tropsch synthetic oils are generally alcohols, acids, aldehydes, esters, and ketones. Among them, the alcohols are n-alcohols, including methanol, ethanol, n-propanol, isobutanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-tetradecyl alcohol, n-pentadecanol, n-hexadecyl alcohol, n-heptadecyl alcohol, n-octadecyl alcohol, and n-nonadecanol, etc.

[0103] The hydrodeoxygenation catalyst of the present invention simultaneously satisfies the following four main characteristics, thereby enabling the low-temperature hydrodeoxygenation reaction using the hydrodeoxygenation catalyst of the present invention to fully remove oxygen-containing compounds, especially alcohols, from Fischer-Tropsch synthetic oils.

[0104] Feature 1: Uses phosphorus-modified alumina carrier;

[0105] Feature 2: Nickel is used as the active component for hydrogenation;

[0106] Feature 3: Lanthanum, cerium, cobalt and / or zinc (especially cerium) are used as cocatalyst components;

[0107] Feature 4: The component loading process uses a stepwise impregnation method to sequentially load the co-catalyst component and the hydrogenation active component onto the support.

[0108] The reasons for achieving this effect are still under investigation, but the inventors believe that the effect is achieved through the interrelation and synergy of the above four characteristics. Even if one characteristic is not satisfied while the other three are satisfied, a sufficiently high deoxygenation rate cannot be achieved at low temperatures.

[0109] The "removal rate of oxygen-containing compounds (deoxygenation rate)" was determined by gas chromatography and / or oxygen elemental analysis. For specific determination methods, please refer to the relevant descriptions in the Examples section.

[0110] <Phosphorus-modified alumina carrier>

[0111] The catalyst of this invention uses a phosphorus-modified alumina support. The alumina support is preferably a γ-Al₂O₃ support. In the phosphorus-modified alumina support, phosphorus exists in the form of phosphorus pentoxide, and with 100% by mass of the alumina support (preferably a γ-Al₂O₃ support) in the phosphorus-modified alumina support, the content of phosphorus pentoxide is 0.5–5% by mass, preferably 1–3% by mass.

[0112] Phosphorus is added to the alumina carrier by adding a phosphorus-containing precursor to the raw material of the alumina carrier before the alumina carrier is formed.

[0113] The phosphorus-modified alumina carrier of the present invention is obtained by adding phosphorus-containing precursors, additives, and acids to the raw materials for preparing the alumina carrier before molding, followed by molding, drying, and calcination. Compared with the method of first molding the alumina carrier and then modifying the molded alumina carrier with phosphorus, this phosphorus modification method of the present invention not only reduces the preparation steps of the modified carrier but also helps to improve the deoxidation rate at low temperatures.

[0114] A complexing agent is preferably added during the manufacturing process of phosphorus-modified alumina support. The complexing agent expands the pores of the support, which helps in the loading of the hydrogenation active component and the co-catalyst component, thus contributing to an increase in the deoxidation rate. Citric acid and / or oxalic acid are preferred complexing agents.

[0115] The inventors have discovered that, with the same feed amount, a higher calcination temperature results in a smaller specific surface area and larger pore size. For catalysts prepared using the impregnation method, the water absorption rate of the support is also a key parameter. The feed amount and calcination temperature also affect the water absorption rate of the support.

[0116] After studying the preparation conditions of the support, the inventors found that as long as the amount of phosphorus precursor fed is such that the content of phosphorus pentoxide in the phosphorus-modified alumina support reaches the content mentioned above, and the following substances, feeding ranges, ratios, drying and calcination temperatures, and calcination times are used, the obtained phosphorus-modified γ-Al2O3 support can be used to prepare the catalyst of the present invention, and the prepared catalyst of the present invention can achieve the target effect of the present invention.

[0117] Specifically, 1-5% by mass of extrusion aid guar gum powder is added to the pseudoboehmite powder, a precursor of γ-Al2O3, and stirred evenly. An aqueous solution containing 2-5% by mass nitric acid (concentration 65-68%), 1-5% by mass citric acid, and phosphorus precursor is added at a water-to-powder ratio of 0.6-1. After kneading, the mixture is extruded on an extruder, dried at 60-120℃, and calcined at 400-750℃ for 3-6 hours to obtain phosphorus-modified γ-Al2O3 support (i.e., phosphorus-modified alumina support).

[0118] It should be noted that if the calcination temperature exceeds 750℃, it will not be conducive to improving the catalytic activity of the final catalyst.

[0119] The phosphorus precursor can be a soluble phosphate such as phosphoric acid, ammonium dihydrogen phosphate, or diammonium phosphate, with phosphoric acid being preferred.

[0120] Furthermore, the phosphorus-modified alumina support of the present invention does not undergo modification with silicon-containing compounds and / or titanium-containing compounds; phosphorus modification is achieved simply by adding a phosphorus-containing precursor to the raw materials for preparing the alumina support before the alumina support is formed. Therefore, the preparation process of the phosphorus-modified alumina support of the present invention is simpler.

[0121] <Hydrogenated Active Components>

[0122] The hydrogenation active component (also referred to as the "main catalytic active component") of this invention is nickel. The nickel is fed in the form of an aqueous solution of a soluble nickel salt. The soluble nickel salt may be nickel nitrate, nickel acetate, nickel carbonate, and / or basic nickel carbonate, preferably nickel nitrate.

[0123] <Catalyst Components>

[0124] Catalyst co-catalyst components (also known as "catalytic promoters") are usually inactive or have very low activity, but when combined with hydrogenation active components, they can significantly improve the activity of the catalyst.

[0125] The co-catalyst components of this invention are lanthanum, cerium, cobalt, and / or zinc, preferably cerium. The inventors have discovered that, in the catalyst of this invention, the combination of the co-catalyst component cerium and the hydrogenation active component nickel exhibits better catalytic activity than lanthanum, cobalt, and zinc, achieving the same or higher deoxygenation rates at lower temperatures.

[0126] The cocatalyst component of the present invention is fed in the form of sulfate, chloride and / or nitrate, preferably nitrate.

[0127] This invention preferably does not add molybdenum as a co-catalyst component. The reasons are as follows:

[0128] Although in Example 1 of Patent Document 1, molybdenum has the highest content among all metal elements (molybdenum oxide accounts for 18% by mass, and nickel and tungsten oxides together account for 8%), the inventors have found that molybdenum only acts as a co-catalyst in the hydrodeoxygenation catalyst, that is, it only acts as an auxiliary agent. Furthermore, during the research, the inventors discovered that for metal reduced-state hydrodeoxygenation catalysts, molybdenum as a co-catalyst component not only does not help improve the hydrodeoxygenation activity of the catalyst, but also reduces the hydrodeoxygenation activity of the catalyst if its content exceeds a certain level. From this perspective, the catalyst of the present invention preferably does not contain molybdenum.

[0129] Incidentally, the inventors discovered that in Example 1 of Patent Document 1, the proportion of molybdenum oxide was too high and the proportion of nickel oxide was too low, making it impossible to achieve a sufficiently high deoxidation rate at low temperatures. In Example 2 of Patent Document 1, although the proportion of molybdenum oxide was reduced and the proportion of nickel oxide was increased, it was still impossible to achieve a sufficiently high deoxidation rate at low temperatures.

[0130] This invention preferably avoids the active or intentional addition of tungsten, silicon, titanium, fluorine, and boron to the catalyst (excluding the possibility of their inclusion as impurities at a content of less than 0.1% by mass). This is because the inventors believe that, for improving deoxidation rates at low temperatures, the catalytic effect of these elements is lower than that of lanthanum, cerium, cobalt, and zinc, especially lower than that of cerium. Sufficient deoxidation can be achieved simply by adding lanthanum, cerium, cobalt, and / or zinc (especially cerium), thus eliminating the need for the addition of tungsten, silicon, titanium, fluorine, and boron.

[0131] <Methods for manufacturing catalysts>

[0132] The method for manufacturing the hydrodeoxygenation catalyst of the present invention comprises the following steps in sequence:

[0133] Step 1: Prepare phosphorus-modified alumina support;

[0134] Step 2, loading the co-catalyst components;

[0135] Step 3, loading the hydrogenated active component,

[0136] In steps 2 and 3, the co-catalyst component and the hydrogenation active component are loaded in steps (i.e., stepwise impregnation) using an impregnation method. Equal-volume impregnation is preferred.

[0137] Preferably, a complexing agent is used to load the hydrogenated active component onto an alumina support. The mass ratio of the complexing agent to nickel oxide is 0.5:1 to 1:1.

[0138] Specifically, the method for manufacturing the hydrodeoxygenation catalyst of the present invention includes the following steps in sequence:

[0139] Step 1, obtaining phosphorus-modified alumina carrier, wherein phosphorus is added to the carrier by adding a phosphorus-containing precursor to the raw materials for preparing the alumina carrier before the alumina carrier is formed;

[0140] Step 2: The phosphorus-modified alumina support obtained in Step 1 is first impregnated with an equal volume of solution containing the co-catalyst component. The impregnated catalyst is then dried and calcined to obtain a one-time impregnated catalyst.

[0141] Step 3: Impregnate the primary impregnated catalyst obtained in Step 2 with an equal volume of aqueous solution of soluble nickel salt, then dry and calcine the impregnated catalyst to obtain the hydrodeoxygenation catalyst.

[0142] More specifically:

[0143] In step 1, 1-5% by mass of extrusion aid guar gum powder is added to the pseudoboehmite powder, a precursor of γ-Al2O3, and stirred evenly. An aqueous solution containing 2-5% by mass of nitric acid (concentration 65-68%), 1-5% by mass of citric acid, and phosphorus is added at a water-to-powder ratio of 0.6-1. After mixing, the mixture is extruded on an extruder, dried at 60-120℃, and calcined at 400-750℃ for 3-6 hours to obtain phosphorus-modified γ-Al2O3 support.

[0144] In step 2, the phosphorus-modified γ-Al2O3 support obtained in step 1 is first impregnated with an aqueous solution of the metal salt of the co-catalyst component, then dried at 100-140℃ for 8-12 hours, and then calcined at 350-550℃ for 3-6 hours to obtain a one-time impregnated catalyst.

[0145] In step 3, the catalyst obtained from the first impregnation in step 2 is impregnated with an aqueous solution containing soluble nickel salt and complexing agent using the equal volume impregnation method. Then, it is dried at 100-140°C for 8-12 hours and calcined at 350-550°C for 3-6 hours to obtain the hydrodeoxygenation catalyst.

[0146] The complexing agent in step 3 is preferably citric acid and / or oxalic acid.

[0147] <Hydrodeoxygenation reaction>

[0148] The catalyst of this invention can effectively catalyze the low-temperature hydrodeoxygenation reaction of oxygen-containing compounds in Fischer-Tropsch synthesis oils, particularly the low-temperature removal of alcohols from Fischer-Tropsch synthesis oils. Furthermore, the catalyst of this invention can effectively catalyze the low-temperature hydrodeoxygenation reaction of alcohols in hydrocarbons containing alcohols.

[0149] The hydrocarbons are petroleum solvent oils and / or pure hydrocarbons, and the alcohols are n-alcohols.

[0150] The reactor used for the hydrodeoxygenation reaction is a fixed-bed reactor.

[0151] The hydrodeoxygenation reaction is carried out using the catalyst of this invention. The catalyst is first reduced in the reactor under a hydrogen atmosphere and then used.

[0152] The hydrodeoxygenation reaction can be carried out at reaction temperatures of 170–350°C. However, for the purposes of this invention, a lower reaction temperature (190–240°C, preferably 200–230°C) is preferred. Because the catalyst of this invention is used, the hydrodeoxygenation reaction can be carried out at low temperatures. Moreover, even at low temperatures, the deoxygenation rate is not lower than, and may even be higher than, that of hydrodeoxygenation reactions carried out at higher temperatures using existing catalysts. Hereinafter, the hydrodeoxygenation reaction carried out at low temperatures will sometimes be referred to as a "low-temperature hydrodeoxygenation reaction."

[0153] Furthermore, for the simulated oils (hydrocarbons containing alcohols) described in the examples, near-complete or even complete deoxygenation can be achieved at relatively low reaction temperatures (e.g., below 210°C). For actual Fischer-Tropsch synthetic oil feedstocks, extremely high deoxygenation rates can also be achieved at slightly higher reaction temperatures (e.g., around 230°C). This is because actual Fischer-Tropsch synthetic oil feedstocks contain a wide variety of oxygen-containing compounds with a broad carbon number distribution, thus requiring a slightly higher reaction temperature to achieve more complete deoxygenation. However, compared to the prior art, reaction temperatures below 240°C (e.g., around 230°C) are still considered low.

[0154] The low-temperature hydrodeoxygenation reaction using the catalyst of this invention has a reaction pressure of 2–6 MPa, a hydrogen-to-oil ratio of 200–800, and a liquid hourly space velocity of 0.5–4 h⁻¹. -1 .

[0155] The "low-temperature hydrodeoxygenation reaction" utilizes the catalyst of this invention, thus enabling the complete removal of oxygen-containing compounds at low temperatures. The deoxygenation rate of oxygen-containing compounds is 99% or higher, with the alcohol removal rate being 99% or higher, preferably 100%.

[0156] Through low-temperature hydrodeoxygenation using the catalyst of the present invention, oxygen-containing compounds in Fischer-Tropsch synthetic oils can be sufficiently removed, and in particular, alcohols in Fischer-Tropsch synthetic oils can be substantially or completely removed. Furthermore, through low-temperature hydrodeoxygenation using the catalyst of the present invention, alcohols in hydrocarbons containing alcohols can be substantially or completely removed.

[0157] <Applications and Uses>

[0158] The catalyst of the present invention is suitable for low-temperature hydrodeoxygenation refining of Fischer-Tropsch synthetic oils and for the low-temperature removal of alcohols from hydrocarbons containing alcohols.

[0159] Example

[0160] Raw material sources: including raw material name, specifications, manufacturers, etc., see Table 1.

[0161] Table 1 Experimental Materials

[0162]

[0163] <Evaluation and Analysis Methods for Oxygen Removal Rate>

[0164] The reaction feedstock used for evaluation was either simulated oil or low-temperature Fischer-Tropsch synthesis oil (i.e., Fischer-Tropsch synthesis oil produced by a low-temperature process). The simulated oil was a heptane solution containing n-butanol, a model compound, as an oxygen-containing compound, wherein the n-butanol content was 15% by mass. The properties of the low-temperature Fischer-Tropsch synthesis oil and its oxygen-containing compound composition are shown in Tables 2 and 3.

[0165] The total oxygen content in low-temperature Fischer-Tropsch synthesis feedstock and deoxygenated products can be analyzed using a PEEA2400 oxygen analyzer. This method can determine the oxygen content in all oxygen-containing organic compounds such as alcohols, acids, aldehydes, ketones, and esters in the oil. Olefin content is analyzed using a bromine index analyzer. Distillation range distribution is determined using gas chromatography-simulated distillation with an Agilent 7890B chromatograph equipped with a flame ionization detector (FID) and a DBHT-SIMD metal capillary column.

[0166] The composition of n-alcohols in simulated oil and low-temperature Fischer-Tropsch synthesis oil was determined by gas chromatography, and the deoxygenation rate was calculated. Specifically, the analysis of reaction (liquid) products included group composition and oxygen-containing compound analysis. An Agilent 7890B gas chromatograph was used for analysis, equipped with an HP-PONA (50m×0.2mm×0.5μm) capillary column and a flame ionization detector (FID).

[0167] Table 2 Properties of the low-temperature Fischer-Tropsch synthesis oil used in the performance evaluation of catalysts for hydrodeoxygenation

[0168]

[0169]

[0170] Note: The total oxygen mass fraction was determined using an oxygen elemental analyzer.

[0171] Table 3. Composition of n-alcohols in low-temperature Fischer-Tropsch synthesis oils

[0172] Name of alcohol mass fraction / % methanol 0.019 ethanol 0.097 n-Propanol 0.154 Isobutanol 0.009 n-Butanol 0.522 n-Pentanol 0.946 n-Hexyl alcohol 1.363 n-Heptane 1.361 Octyl alcohol 1.389 nonyl alcohol 1.242 n-Decanol 1.142 undecyl alcohol 0.841 dodecyl alcohol 0.679 Tridecyl alcohol 0.562 tetradecyl alcohol 0.362 Pentadecyl alcohol 0.299 hexadecyl alcohol 0.238 heptadecanol 0.094 Octadecanol 0.061 nonadecanol 0.025 total 11.405

[0173] <Implementation of Catalyst Performance Evaluation Experiments>

[0174] Catalyst performance evaluation experiments were conducted on a 10mL four-channel fixed-bed oil hydrotreating evaluation device (fixed-bed reactor).

[0175] The catalyst was crushed and sieved to 20-40 mesh, and 10 mL was loaded into a fixed-bed reactor. Before feeding the evaluation reactants, the catalyst was reduced at 420°C for 6 hours under H2 atmosphere, then cooled to the reaction temperatures recorded in Tables 4 to 6 for each example, and then the evaluation reactants were fed. After the feed stabilized, liquid samples were taken for analysis.

[0176] The reaction raw materials used for evaluation were the respective reaction raw materials of each example, comparative example, and reference example listed in Tables 4 to 6 (except for Example 7, which used low-temperature Fischer-Tropsch synthetic oil, all other examples used simulated oil); the reaction temperatures were the respective reaction temperatures of each example, comparative example, and reference example listed in Tables 4 to 6; the reaction pressure was 4 MPa, and the liquid hourly space velocity was 1 h⁻¹. -1The hydrogen / oil volume ratio is 400.

[0177] Carrier Preparation Example 1

[0178] Weigh 300.00g of boehmite powder (225.00g dry basis) and 8.00g of guar gum powder. Add deionized water at a water-to-powder ratio of 0.7:1. Add 11.00g of nitric acid (65-68% concentration), 6.00g of citric acid, and 3.66g of phosphoric acid (85% content) to the deionized water. After mixing, extrude the mixture into strips using a 1.50mm perforated plate on an extruder. Dry the strips at 110℃ and calcine them at 550℃ for 4 hours to obtain the phosphorus-modified γ-Al2O3 carrier.

[0179] Carrier preparation example 2

[0180] Except for changing the amount of phosphoric acid to 5.48 g, the rest of the preparation was carried out in the same manner as in Example 1, and phosphorus-modified γ-Al2O3 support was obtained.

[0181] Carrier preparation example 3

[0182] Except for changing the amount of phosphoric acid to 7.31 g, the rest of the process was carried out in the same manner as in Example 1 of the carrier preparation, and a phosphorus-modified γ-Al2O3 carrier was obtained.

[0183] Carrier preparation example 4

[0184] Except for changing the amount of phosphoric acid to 10.96 g, the rest of the preparation was carried out in the same manner as in Example 1 of the carrier preparation, and phosphorus-modified γ-Al2O3 carrier was obtained.

[0185] Carrier preparation example 5

[0186] Except for changing the amount of phosphoric acid to 5.48 g, the rest of the preparation was carried out in the same manner as in Example 1, and phosphorus-modified γ-Al2O3 support was obtained.

[0187] Carrier preparation example 6

[0188] Except for changing the amount of phosphoric acid to 7.31 g, the rest of the process was carried out in the same manner as in Example 1 of the carrier preparation, and a phosphorus-modified γ-Al2O3 carrier was obtained.

[0189] Carrier Preparation Example 7

[0190] Weigh 300.00g of boehmite powder (225.00g dry basis) and 10.00g of guar gum powder. Add deionized water at a water-to-powder ratio of 0.7:1. Add 6.00g of nitric acid (65-68% concentration), 7.50g of citric acid, and 7.31g of phosphoric acid (85% content) to the deionized water. After mixing, extrude the mixture into strips using a 1.50mm perforated plate on an extruder. Dry the strips at 110℃ and calcine them at 750℃ for 4 hours to obtain the phosphorus-modified γ-Al2O3 carrier.

[0191] Carrier preparation example 8

[0192] Weigh 300.00g of boehmite powder (225.00g dry basis) and 15.00g of guar gum powder. Add deionized water at a water-to-powder ratio of 0.8:1. Add 7.00g of nitric acid (65-68% concentration), 7.50g of citric acid, and 7.31g of phosphoric acid (85% content) to the deionized water. After mixing, extrude the mixture into strips using a 1.50mm perforated plate on an extruder. Dry the strips at 110℃ and calcine them at 550℃ for 4 hours to obtain the phosphorus-modified γ-Al2O3 carrier.

[0193] Carrier preparation example 9

[0194] Weigh 300.00g of boehmite powder (225.00g dry basis) and 12.00g of guar gum powder. Add deionized water at a water-to-powder ratio of 0.8:1. Add 7.00g of nitric acid (65-68% concentration), 14.0g of citric acid, and 7.31g of phosphoric acid (85% content) to the deionized water. After mixing, extrude the mixture into strips using a 1.50mm perforated plate on an extruder. Dry the strips at 110℃ and calcine them at 550℃ for 4 hours to obtain the phosphorus-modified γ-Al2O3 carrier.

[0195] Comparative Example of Carrier Preparation

[0196] Except for changing the amount of phosphoric acid added to 0g (i.e., no phosphoric acid added), the same procedure as in Example 1 was performed to obtain the γ-Al2O3 support.

[0197] Example 1

[0198] Following the preparation example 1, a phosphorus-modified γ-Al2O3 support was prepared.

[0199] Weigh 30.00 g of modified alumina support. Using the equal-volume impregnation method, prepare an aqueous solution of 10.53 g of cobalt nitrate to a certain concentration. Slowly add this solution dropwise onto the alumina support, stir until homogeneous, and impregnate for 6 hours. Dry the impregnated catalyst at 120℃ for 8 hours. Then, place the dried catalyst in a muffle furnace and calcine at 450℃ for 4 hours. This yields the first-impregnated catalyst.

[0200] An equal-volume impregnation method was used. An aqueous solution of 8.58 g nickel carbonate and 4.32 g citric acid was prepared and slowly added dropwise to the catalyst obtained from a single impregnation. After stirring evenly, the solution was impregnated for 6 hours. The impregnated catalyst was then dried at 120℃ for 8 hours. The dried catalyst was then placed in a muffle furnace and calcined at 450℃ for 4 hours to obtain the hydrodeoxygenation catalyst.

[0201] The catalyst performance evaluation was carried out in accordance with the previous section on "Implementation of Catalyst Performance Evaluation Experiment".

[0202] The catalyst composition and performance evaluation results are shown in Table 4.

[0203] Example 2

[0204] Following the preparation example 2, a phosphorus-modified γ-Al2O3 support was prepared.

[0205] Weigh 30.00 g of modified alumina support. Prepare an aqueous solution of 4.79 g of lanthanum nitrate to a certain concentration using the equal-volume impregnation method. Slowly add the aqueous solution dropwise onto the alumina support, stir until homogeneous, and impregnate for 6 h. Dry the impregnated catalyst at 100 °C for 12 h. Then, place the dried catalyst in a muffle furnace and calcine at 500 °C for 3 h. This yields the first-impregnated catalyst.

[0206] An equal-volume impregnation method was used. 21.02 g of nickel nitrate and 4.32 g of oxalic acid were prepared into an aqueous solution of a certain concentration, which was slowly added dropwise to the catalyst obtained from a single impregnation. After stirring evenly, the solution was impregnated for 6 hours. The impregnated catalyst was then dried at 100℃ for 12 hours, and the dried catalyst was placed in a muffle furnace and calcined at 500℃ for 3 hours to obtain the hydrodeoxygenation catalyst.

[0207] The catalyst performance evaluation was carried out in accordance with the previous section on "Implementation of Catalyst Performance Evaluation Experiment".

[0208] The catalyst composition and performance evaluation results are shown in Table 4.

[0209] Example 3

[0210] According to support preparation example 3, a phosphorus-modified γ-Al2O3 support was prepared.

[0211] Weigh 30.00 g of modified alumina support. Prepare an aqueous solution of 7.57 g of cerium nitrate to a certain concentration using the equal-volume impregnation method. Slowly add the solution dropwise onto the alumina support, stir until homogeneous, and impregnate for 6 hours. Dry the impregnated catalyst at 110℃ for 10 hours. Then, place the dried catalyst in a muffle furnace and calcine at 450℃ for 4 hours. This yields a one-time impregnated catalyst.

[0212] An equal-volume impregnation method was used. An aqueous solution of 18.69 g nickel nitrate and 3.36 g citric acid was prepared to a specific concentration and slowly added dropwise to the catalyst obtained from a single impregnation. After stirring thoroughly, the solution was impregnated for 6 hours. The impregnated catalyst was then dried at 110℃ for 10 hours. The dried catalyst was then placed in a muffle furnace and calcined at 450℃ for 4 hours to obtain the hydrodeoxygenation catalyst.

[0213] The catalyst performance evaluation was carried out in accordance with the previous section on "Implementation of Catalyst Performance Evaluation Experiment".

[0214] The catalyst composition and performance evaluation results are shown in Table 4.

[0215] Comparative Example 1

[0216] 30.00 g of the phosphorus-modified alumina support prepared in Example 3 was weighed. Using a co-impregnation component loading process, 18.69 g of nickel nitrate, 3.36 g of citric acid, and 7.57 g of cerium nitrate were prepared into an aqueous solution of a certain concentration according to the equal-volume impregnation method. This solution was slowly added dropwise to the alumina support, stirred evenly, and impregnated for 6 hours. The impregnated catalyst was dried at 110°C for 10 hours, and then placed in a muffle furnace and calcined at 450°C for 4 hours to obtain the hydrodeoxygenation catalyst.

[0217] The catalyst performance evaluation was carried out in accordance with the previous section on "Implementation of Catalyst Performance Evaluation Experiment".

[0218] The catalyst composition and performance evaluation results are shown in Table 4.

[0219] Example 4

[0220] According to support preparation example 4, a phosphorus-modified γ-Al2O3 support was prepared.

[0221] Weigh 30.00 g of modified alumina support. Prepare an aqueous solution of 6.32 g of cobalt nitrate to a certain concentration using the equal-volume impregnation method. Slowly add the solution dropwise onto the alumina support, stir until homogeneous, and impregnate for 6 hours. Dry the impregnated catalyst at 130℃ for 6 hours. Then, place the dried catalyst in a muffle furnace and calcine at 400℃ for 4 hours. This yields the first-impregnated catalyst.

[0222] An equal-volume impregnation method was used. 23.36 g of nickel nitrate, 3.00 g of citric acid, and 3.00 g of oxalic acid were prepared into an aqueous solution of a specific concentration. This solution was slowly added dropwise to the catalyst obtained from a single impregnation. After stirring until homogeneous, the solution was impregnated for 6 hours. The impregnated catalyst was then dried at 130°C for 6 hours. The dried catalyst was then placed in a muffle furnace and calcined at 400°C for 4 hours to obtain the hydrodeoxygenation catalyst.

[0223] The catalyst performance evaluation was carried out in accordance with the previous section on "Implementation of Catalyst Performance Evaluation Experiment".

[0224] The catalyst composition and performance evaluation results are shown in Table 4.

[0225] Example 5

[0226] According to support preparation example 5, a phosphorus-modified γ-Al2O3 support was prepared.

[0227] Weigh 30.00 g of modified alumina support. Using an equal-volume impregnation method, prepare an aqueous solution of 6.81 g cerium nitrate and 2.19 g zinc nitrate to a certain concentration. Slowly add this solution dropwise to the alumina support, stir until homogeneous, and impregnate for 6 hours. Dry the impregnated catalyst at 120℃ for 8 hours. Then, place the dried catalyst in a muffle furnace and calcine at 450℃ for 5 hours. This yields a one-time impregnated catalyst.

[0228] An equal-volume impregnation method was used. 21.02 g of nickel nitrate and 3.24 g of citric acid were prepared into an aqueous solution of a certain concentration, which was slowly added dropwise to the catalyst obtained from a single impregnation. After stirring evenly, the solution was impregnated for 6 hours. The impregnated catalyst was then dried at 120℃ for 8 hours, and the dried catalyst was placed in a muffle furnace and calcined at 450℃ for 5 hours to obtain the hydrodeoxygenation catalyst.

[0229] The catalyst performance evaluation was carried out in accordance with the previous section on "Implementation of Catalyst Performance Evaluation Experiment".

[0230] The catalyst composition and performance evaluation results are shown in Table 4.

[0231] Example 6

[0232] According to support preparation example 6, a phosphorus-modified γ-Al2O3 support was prepared.

[0233] 30.00 g of modified alumina support was weighed. Following an equal-volume impregnation method, 2.39 g of lanthanum nitrate and 6.32 g of cobalt nitrate were prepared into an aqueous solution of a certain concentration. This solution was slowly added dropwise to the alumina support, stirred until homogeneous, and impregnated for 6 hours. The impregnated catalyst was then dried at 120 °C for 8 hours. The dried catalyst was then placed in a muffle furnace and calcined at 450 °C for 5 hours. This yielded the one-time impregnated catalyst.

[0234] An equal-volume impregnation method was used. 21.02 g of nickel nitrate and 3.24 g of citric acid were prepared into an aqueous solution of a certain concentration, which was slowly added dropwise to the catalyst obtained from a single impregnation. After stirring evenly, the solution was impregnated for 6 hours. The impregnated catalyst was then dried at 120℃ for 8 hours, and the dried catalyst was placed in a muffle furnace and calcined at 450℃ for 5 hours to obtain the hydrodeoxygenation catalyst.

[0235] The catalyst performance evaluation was carried out in accordance with the previous section on "Implementation of Catalyst Performance Evaluation Experiment".

[0236] The catalyst composition and performance evaluation results are shown in Table 4.

[0237] Comparative Example 2

[0238] 30.00 g of the phosphorus-modified alumina support prepared in Example 6 was weighed. Using a co-impregnation component loading process, and following an equal-volume impregnation method, 21.02 g of nickel nitrate, 3.24 g of citric acid, 2.39 g of lanthanum nitrate, and 6.32 g of cobalt nitrate were prepared into an aqueous solution of a certain concentration and slowly added dropwise to the alumina support. After stirring evenly, the solution was impregnated for 6 hours. The impregnated catalyst was dried at 120°C for 8 hours, and then placed in a muffle furnace and calcined at 450°C for 5 hours. A one-time impregnated catalyst was obtained.

[0239] The catalyst performance evaluation was carried out in accordance with the previous section on "Implementation of Catalyst Performance Evaluation Experiment".

[0240] The catalyst composition and performance evaluation results are shown in Table 4.

[0241] Comparative Example 3

[0242] According to the comparative example of carrier preparation, γ-Al2O3 carrier was prepared.

[0243] Weigh 30.00 g of the alumina support mentioned above. Using an equal-volume impregnation method, prepare an aqueous solution of 18.69 g of nickel nitrate and 3.36 g of citric acid to a certain concentration. Slowly add this solution dropwise to the catalyst obtained from the first impregnation, stir until homogeneous, and impregnate for 6 hours. Dry the impregnated catalyst at 110℃ for 10 hours. Then, place the dried catalyst in a muffle furnace and calcine at 450℃ for 4 hours to obtain the hydrodeoxygenation catalyst.

[0244] The catalyst performance evaluation was carried out in accordance with the previous section on "Implementation of Catalyst Performance Evaluation Experiment".

[0245] The catalyst composition and performance evaluation results are shown in Table 4.

[0246] Comparative Example 4

[0247] Except that citric acid was not added during the preparation of the phosphorus-modified alumina carrier, the rest of the process was carried out in the same manner as in Example 2.

[0248] The catalyst performance evaluation was carried out in accordance with the previous section on "Implementation of Catalyst Performance Evaluation Experiment".

[0249] The catalyst composition and performance evaluation results are shown in Table 4.

[0250] Example 7

[0251] Except for changing the reaction feedstock for evaluation to low-temperature Fischer-Tropsch synthetic oil (the properties of the synthetic oil and the composition of the n-alcohol are shown in Tables 2 and 3) and changing the reaction temperature to 230°C, the rest of the process was carried out in the same manner as in Example 3 (i.e., using the catalyst of Example 3, but changing the experimental conditions for evaluating the catalyst performance).

[0252] The catalyst composition and performance evaluation results are shown in Table 4.

[0253] Example 8

[0254] Except for replacing the deoxygenation rate with a value calculated using the total oxygen mass fraction measured by an oxygen element analyzer, the rest was carried out in the same manner as in Example 7.

[0255] The catalyst composition and performance evaluation results are shown in Table 5.

[0256]

[0257] Table 5

[0258]

[0259] Note: The total oxygen mass fraction is the result measured by an oxygen elemental analyzer.

[0260] As can be seen from Table 4, the examples that simultaneously use phosphorus-modified alumina support, nickel as the hydrogenation active component, lanthanum, cerium, cobalt and / or zinc as co-catalyst components, and adopt a stepwise impregnation process for component loading (the examples that simultaneously satisfy the aforementioned characteristics 1 to 4) can achieve a deoxidation rate of over 99% even at low temperatures, whether for simulated oil or low-temperature Fischer-Tropsch synthesis feedstock, and can even achieve a deoxidation rate (n-ethanol removal rate).

[0261] In particular, Examples 3 and 7 use only nickel and cerium. For simulated oil, a 100% deoxidation rate can be achieved at a low temperature of 200-210°C. For low-temperature Fischer-Tropsch synthesis oil feedstock, a deoxidation rate of over 99% can be achieved at a low temperature of 230°C.

[0262] According to the oxygen element analyzer, the total oxygen mass fraction of the low-temperature Fischer-Tropsch synthesis oil feedstock was 1.89% (see Table 2). As shown in Table 5, the experimental results of Example 8, measured using an oxygen element analyzer, indicate that the oxygen content is extremely low, even as low as 0 (below the instrument detection limit). This indicates that, based on the oxygen element analyzer results, oxygen-containing compounds in the low-temperature Fischer-Tropsch synthesis oil were sufficiently removed.

[0263] The results above show that the catalyst of the present invention not only has a good removal effect on alcohols, but also has a good removal effect on other oxygen-containing compounds in synthetic oils, and can also fully remove oxygen-containing compounds contained in low-temperature Fischer-Tropsch synthetic oils at low temperatures.

[0264] Comparative Examples 1-3 do not simultaneously satisfy the aforementioned characteristics 1-4, and their deoxygenation rates are significantly lower than those of Examples 1-6.

[0265] Comparative Example 4 was the same as Example 2 except that no complexing agent was added during the preparation of the phosphorus-modified alumina carrier. However, the deoxidation rate was lower than that of Example 2 and did not reach more than 99%.

[0266] It should be noted that since even trace amounts of oxygen-containing compounds can have a significant adverse effect on subsequent processes and equipment (e.g., causing equipment corrosion), the 1% difference between a deoxidation rate of 98% and 99% is also a significant difference.

[0267] Furthermore, according to the inventors' research, existing catalysts, whether for simulated oils or for low-temperature Fischer-Tropsch synthesis feedstocks, cannot achieve the level of deoxygenation rate described in the above embodiments at low temperatures.

[0268] Refer to Examples 1-3 and Example 9

[0269] Except for adjusting the reaction temperature according to the temperatures shown in Table 6, the rest of the procedure was carried out in the same manner as in Example 3.

[0270] The catalyst composition and performance evaluation results are shown in Table 6.

[0271] Table 6

[0272]

[0273] As can be seen from Table 6, the catalyst of the present invention, especially the catalyst of the present invention that satisfies the aforementioned features 1 to 4, can achieve a 100% deoxygenation rate for simulated oil at a low temperature of 200°C.

[0274] Refer to Examples 4 and 5

[0275] Except for replacing cerium nitrate, which is used as a co-catalyst, with ammonium heptamolybdate, adjusting the amounts of nickel nitrate and ammonium heptamolybdate according to the contents shown in Table 7, and adjusting the reaction temperature to 210°C, the rest of the process was carried out in the same manner as in Example 3.

[0276] The catalyst composition and performance evaluation results are shown in Table 7.

[0277] Table 7

[0278]

[0279] As shown in Table 7, at low temperatures, conventional catalysts using nickel as the active hydrogenation component and molybdenum as the co-catalyst component cannot achieve sufficient deoxidation rates. Moreover, increasing the molybdenum content further reduces the deoxidation rate. In other words, molybdenum does not contribute to improving the low-temperature deoxidation rate.

[0280] It should be noted that, according to the inventors' research, even if the carrier prepared by any one of the carrier preparation examples 7 to 9 is used in the above embodiments, the objective effect of the present invention can be achieved in the same way as in the embodiments.

[0281] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil, characterized in that, The hydrodeoxygenation catalyst comprises a phosphorus-modified alumina support and a hydroadditive active component and a co-catalyst component supported on the phosphorus-modified alumina support. The hydrogenation active component is only nickel. The co-catalyst component is selected from at least one of lanthanum, cerium, cobalt, and zinc. In the phosphorus-modified alumina carrier, phosphorus exists in the form of phosphorus pentoxide, and the content of phosphorus pentoxide is 0.5% to 5% by mass, with the mass of alumina in the phosphorus-modified alumina carrier being 100% by mass. With the mass of the aforementioned hydrodeoxygenation catalyst being 100% by mass, the content of each metal element, calculated as oxides, is as follows: The nickel oxide content is 12-18% by mass. The content of lanthanum oxide and / or cerium oxide and / or cobalt oxide and / or zinc oxide is 1-11% by mass. The rest are phosphorus-modified alumina carriers. The hydrodeoxygenation catalyst does not contain molybdenum. The hydrogenation deoxygenation catalyst did not contain silicon, titanium, tungsten, fluorine, or boron. The hydrodeoxygenation catalyst is manufactured by a method comprising the following steps in sequence: Step 1, obtaining phosphorus-modified alumina support, wherein phosphorus is added by adding a phosphorus-containing precursor to the raw material of the alumina support before the alumina support is formed; Step 2: The phosphorus-modified alumina support obtained in Step 1 is first impregnated with a solution containing the co-catalyst components. The impregnated catalyst is then dried and calcined to obtain a primary impregnated catalyst. Step 3: Impregnate the primary impregnated catalyst obtained in Step 2 with an aqueous solution of soluble nickel salt, and then dry and calcine the impregnated catalyst to obtain the hydrodeoxygenation catalyst.

2. The hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil as described in claim 1, characterized in that, The phosphorus-modified alumina carrier is a γ-Al2O3 carrier.

3. The hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil as described in claim 1, characterized in that, In the phosphorus-modified alumina carrier, phosphorus exists in the form of phosphorus pentoxide, and the content of phosphorus pentoxide is 1 to 3% by mass, with the mass of alumina in the phosphorus-modified alumina carrier being 100% by mass.

4. The hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil as described in claim 1, characterized in that, The cocatalyst component is cerium only.

5. The hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil as described in claim 4, characterized in that, With the mass of the aforementioned hydrodeoxygenation catalyst as 100% by mass, the contents of each metal element, calculated as oxides, are as follows: The nickel oxide content is 12-16% by mass. The cerium oxide content is 6-10% by mass. The rest are phosphorus-modified alumina carriers.

6. The hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil as described in claim 1, characterized in that, Hydrogenated active components are loaded onto a phosphorus-modified alumina support using a complexing agent.

7. The hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil as described in claim 6, characterized in that, The complexing agent is citric acid and / or oxalic acid. The mass ratio of the complexing agent to nickel oxide is 0.5:1 to 1:

1.

8. A method for manufacturing a hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil, the method comprising manufacturing the hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil according to any one of claims 1 to 7, characterized in that, The manufacturing method includes the following steps: Step 1, obtaining phosphorus-modified alumina support, wherein phosphorus is added by adding a phosphorus-containing precursor to the raw material of the alumina support before the alumina support is formed; Step 2: The phosphorus-modified alumina support obtained in Step 1 is first impregnated with a solution containing the co-catalyst components. The impregnated catalyst is then dried and calcined to obtain a primary impregnated catalyst. Step 3: Impregnate the primary impregnated catalyst obtained in Step 2 with an aqueous solution of soluble nickel salt, and then dry and calcine the impregnated catalyst to obtain the hydrodeoxygenation catalyst.

9. The method for manufacturing the hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil as described in claim 8, characterized in that, In step 1, 1-5% by mass of extrusion aid guar gum powder is added to the pseudoboehmite powder, a precursor of γ-Al2O3, and stirred evenly. An aqueous solution containing 2-5% by mass of nitric acid, 1-5% by mass of citric acid, and phosphorus is added at a water-to-powder ratio of 0.6-1. After mixing, the mixture is extruded on an extruder, dried at 60-120℃, and calcined at 400-750℃ for 3-6 hours to obtain a phosphorus-modified γ-Al2O3 support, wherein the concentration of nitric acid is 65-68%. In step 2, the phosphorus-modified γ-Al2O3 support obtained in step 1 is first impregnated with an aqueous solution of the metal salt of the co-catalyst component, then dried at 100-140℃ for 8-12 hours, and then calcined at 350-550℃ for 3-6 hours to obtain a one-time impregnated catalyst. In step 3, the primary impregnation catalyst obtained in step 2 is impregnated with an aqueous solution containing soluble nickel salt and complexing agent using an equal volume impregnation method. Then, it is dried at 100-140°C for 8-12 hours and calcined at 350-550°C for 3-6 hours to obtain the hydrodeoxygenation catalyst.

10. A Fischer-Tropsch synthetic oil hydrodeoxygenation reaction, characterized in that, The reaction uses the hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil as described in any one of claims 1 to 7, wherein the hydrodeoxygenation catalyst is used after reduction in the reactor, and the reaction is carried out at a reaction temperature of 170°C to 350°C.

11. The hydrodeoxygenation reaction of Fischer-Tropsch synthetic oil as described in claim 10, characterized in that, The reaction temperature is 190℃~240℃.

12. The hydrodeoxygenation reaction of Fischer-Tropsch synthetic oil as described in claim 10, characterized in that, The reaction temperature is 200℃~230℃.

13. The hydrodeoxygenation reaction of Fischer-Tropsch synthetic oil as described in claim 10, characterized in that, The reaction is carried out at a pressure of 2–6 MPa, a hydrogen-to-oil ratio of 200–800, and a liquid hourly space velocity of 0.5–4 h⁻¹. -1 It is carried out under the following conditions.

14. The hydrodeoxygenation reaction of Fischer-Tropsch synthetic oil as described in claim 10, characterized in that, The oxide removal rate of the reaction is over 99%.

15. The hydrodeoxygenation reaction of Fischer-Tropsch synthetic oil as described in claim 10, characterized in that, The alcohol removal rate of the reaction is over 99%.

16. The hydrodeoxygenation reaction of Fischer-Tropsch synthetic oil as described in claim 10, characterized in that, The alcohol removal rate of the reaction is 100%.

17. The application of the hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil according to any one of claims 1 to 7 in the hydrodeoxygenation reaction of Fischer-Tropsch synthesis oil, characterized in that, The reaction was carried out at a reaction temperature of 200℃ to 230℃.

18. The use of the hydrodeoxygenation catalyst for Fischer-Tropsch synthesis oil according to any one of claims 1 to 7 in the hydrodeoxygenation reaction of alcohols in hydrocarbons containing alcohols, characterized in that, The reaction was carried out at a reaction temperature of 200℃ to 230℃.

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