Process for hydrogenating a hydrocarbon resin using a catalyst with a protective coating

Abstract

The invention relates to a process for the hydrogenation of an unsaturated hydrocarbon feedstock comprising: (1) preparing a particulate material, wherein the particles of the particulate material comprise a hydrogenation catalyst or a precursor thereof, and one or more organic compounds, wherein the one or more organic compounds comprise one or more carboxylic acids and / or one or more esters and / or one or more ether moieties; (2) providing an unsaturated hydrocarbon feedstock; (3) preparing a mixture comprising the particulate material obtained in (1), the unsaturated hydrocarbon feedstock provided in (2), hydrogen and optionally a solvent system; (4) heating the mixture prepared in (3) to a temperature in the range of 210-360 °C for hydrogenation of the hydrocarbon feedstock.

Description

Technical Field

[0001] This invention relates to a method for hydrogenating unsaturated hydrocarbon feedstock. Background Technology

[0002] The market for hydrogenated petroleum resins as adhesives, for example, in packaging and nonwoven fabrics, is booming. Hydrogenation of these resins improves thermal stability and produces the desired water-white product. For example, WO 2015 / 008247 A2 relates to a nickel / silicon / aluminum mixed oxide and its use in the hydrogenation of hydrocarbon resins.

[0003] Currently, resin-based nickel hydride powder catalysts are mainly produced using precipitation, reduction, and stabilization methods. However, these production methods have drawbacks. The risk of dust formation, especially carcinogenic, mutagenic, and reproductively toxic substances (in this case, nickel), is a significant concern, particularly as regulations become increasingly stringent. Furthermore, due to the material's flammable nature, extreme care must be taken when exposed to air, necessitating a lengthy and costly stabilization step. Nickel reduced with a compatible medium coating can overcome these drawbacks. However, this medium is invisible to the resin feed. Therefore, the material should be highly similar to, or even identical to, the corresponding resin.

[0004] Therefore, polystyrene with a molecular weight of approximately 2800 g / mol is chemically very similar to C9 hydrocarbon resin feedstocks, for example. In this regard, WO 2017 / 208164 A1 relates to a metal catalyst protected by a molten polymer coating and its use in the hydrogenation of hydrocarbon resin feedstocks. Similarly, this reduced nickel coating is applied with fats and oils to provide a protected catalyst as droplets for the hydrogenation of oleochemical feedstocks, such as vegetable oils. Thus, WO 2004 / 035204 A1 relates to a nickel / silicon / aluminum mixed oxide coated as a protective coating with hardened soybean fat, which is subsequently dissolved in a feedstock of unsaturated fatty compounds. On the other hand, US 9,045,410 B2 relates to nickel supported on silica as a catalyst for the hydrogenation of unsaturated fatty materials, wherein the catalyst can be coated in fatty substances (e.g., hardened soybean or palm oil fat) such that the catalyst is suspended in droplets, forming a protective layer.

[0005] US 2008 / 161588 A1 relates to a method for hydrogenating fats or oils using a nickel silicate catalyst. The catalyst is provided in the form of solid “droplets” coated with a protective hydrogenated vegetable oil, which has been hydrogenated to the point that the material is solid at room temperature, with soybean oil used as the feedstock.

[0006] US 2005 / 027136 A1 relates to a method for hydrogenating an unsaturated feedstock using nickel on an alumina-supported catalyst dispersed in a fatty component, said fatty component being solid at room temperature.

[0007] US 2014 / 336287 A1 relates to the use of coated nickel catalysts in particulate form for the hydrogenation of unsaturated aliphatic, oil, and / or hydrocarbon resins. The nickel catalysts may be coated with C10-C13 aliphatic hydrocarbon liquids, hydrogenated desulfurized heavy naphtha, petroleum solvent oils, and tetrahydronaphthalene, aromatics, esters, and ethers.

[0008] However, there remains a need for new methods to protect hydrogenation catalysts used for the hydrogenation of resin feedstocks, particularly resin feedstocks that are liquid at room temperature or have low melting or softening points, so that they cannot be used as protective materials themselves. In particular, there remains a need for methods to protect hydrogenation catalysts for the hydrogenation of liquid resin feedstocks or resin feedstocks with low melting or softening points, methods that are more time- and / or cost-effective and / or more environmentally friendly than methods known in the art. Detailed Implementation

[0009] The object of this invention is to provide an alternative method for protecting hydrogenation catalysts used in the hydrogenation of hydrocarbon resin feedstocks, a method that is more time- and cost-effective. Specifically, the object of this invention is to provide a method for protecting hydrogenation catalysts used in the hydrogenation of hydrocarbon resin feedstocks, involving the use of readily available, particularly natural products or their derivatives. Surprisingly, it has been found that hydrogenation catalysts used in the hydrogenation of hydrocarbon feedstocks can be effectively protected by coating them with one or more organic compounds containing one or more carboxylic acids and / or one or more ester moieties, wherein said compounds undergo in-situ deoxygenation under the conditions of hydrocarbon feedstock hydrogenation, thus converting them into water, CO and / or CO2 and hydrocarbons. Indeed, given the technical biases in the art, this is quite unexpected, where protective coatings of hardened vegetable oils or fats would lead to contamination of the hydrogenated hydrocarbon end products if used in the hydrogenation process of hydrocarbon feedstocks (see, for example, WO 2017 / 208164A1: page 2, first complete paragraph). As a result, it was found quite unexpectedly that protective coatings containing compounds comprising one or more carboxylic acids and / or one or more ester moieties, especially protective coatings containing natural fats, can be used for the hydrogenation of hydrocarbon feedstocks without contaminating the hydrocarbon feedstocks, but instead provide hydrocarbons that can be easily separated from the hydrogenated hydrocarbon products by distillation or similar methods.

[0010] Therefore, the present invention relates to a method for hydrogenating unsaturated hydrocarbon feedstock, comprising:

[0011] (1) Prepare particulate material, wherein the particles of the particulate material contain a hydrogenation catalyst or its precursor, and one or more organic compounds, wherein the one or more organic compounds contain one or more carboxylic acids and / or one or more esters, and / or one or more ether moieties, preferably one or more carboxylic acids and / or one or more ester moieties, more preferably one or more ester moieties.

[0012] (2) Provide unsaturated hydrocarbon feedstock;

[0013] (3) Prepare a mixture comprising the particulate material obtained in (1), the unsaturated hydrocarbon feedstock provided in (2), hydrogen and an optional solvent system;

[0014] (4) The mixture prepared in (3) is heated to a temperature of 210 to 360°C to hydrogenate the hydrocarbon feedstock, preferably in the range of 220 to 340°C, more preferably in the range of 230 to 320°C, more preferably in the range of 240 to 300°C, more preferably in the range of 250 to 290°C, more preferably in the range of 260 to 280°C and more preferably in the range of 265 to 275°C.

[0015] This method may include further method steps. Furthermore, any of the defined method steps may include further method steps, particularly steps related to the preparation of the particulate material. Preferably, for preparing the particulate material in (1), the method includes:

[0016] (1.a) Provide a hydrogenation catalyst or a precursor thereof;

[0017] (1.b) Provides one or more organic compounds comprising one or more carboxylic acids and / or one or more esters and / or one or more ether moieties, preferably one or more carboxylic acids and / or one or more ester moieties, more preferably one or more ester moieties;

[0018] (1.c) Optionally, one or more organic compounds provided in (1.b) are heated to a temperature above the melting point of one or more organic compounds;

[0019] (1.d) Disperse the hydrogenation catalyst provided in (1.a) in one or more organic compounds provided in (1.b) and optionally heat it in (1.c);

[0020] (1.e) The dispersion obtained in (1.d) is shaped into particles, preferably.

[0021] (1.f.) Cool the shaped dispersion obtained in (1.e) to a temperature below the melting point of one or more organic compounds;

[0022] Preferably, in (1), one or more organic compounds comprise one or more alkyl moieties, more preferably one or more C10-C24 alkyl moieties, more preferably one or more C12-C22 alkyl moieties, more preferably one or more C14-C20 alkyl moieties, and more preferably one or more C16-C18 alkyl moieties.

[0023] Preferably, in (1), one or more organic compounds contain one or more alkylene moieties, more preferably one or more C1-C6 alkylene moieties, more preferably one or more C2-C4 alkylene moieties, and more preferably one or more C3 alkylene moieties.

[0024] Preferably, in (1), one or more organic compounds include one or more compounds selected from triglycerides, fatty acids and mixtures of two or more thereof, preferably selected from one or more vegetable oils and mixtures of both, more preferably selected from palm oil, soybean oil, rapeseed oil, sunflower oil, peanut oil, cottonseed oil, palm kernel oil, coconut oil, olive oil and mixtures of two or more thereof, more preferably selected from the group consisting of palm oil, soybean oil, cottonseed oil and mixtures of two or more thereof, more preferably selected from palm oil, soybean oil and mixtures of two or more thereof, wherein more preferably one or more organic compounds include palm and / or soybean oil, preferably palm oil, wherein more preferably one or more organic compounds are composed of palm and / or soybean oil, preferably palm oil.

[0025] In the case where one or more organic compounds in (1) contain triglycerides and / or fatty acids, the triglycerides and / or fatty acids are preferably hydrogenated triglycerides and / or fatty acids.

[0026] Preferably, in (1), one or more organic compounds comprise one or more ether moieties, more preferably two or more ether moieties, and one or more alkylene moieties, preferably two or more alkylene moieties, more preferably two or more C1-C3 alkylene moieties, more preferably two or more C1-C2 alkylene moieties, more preferably two or more C1 alkylene moieties, wherein one or more organic compounds more preferably comprise one or more polyoxyalkylene moieties, more preferably one or more polyoxyalkyl(C1-C3) alkylene moieties, more preferably one or more polyoxyalkyl(C1-C2) alkylene moieties, more preferably one or more polyoxyalkyl(C1) alkylene moieties, wherein one or more organic compounds more preferably include polyoxymethylene moieties.

[0027] Preferably, in (1), the melting point of one or more organic compounds is in the range of 30 to 100°C, more preferably 35 to 90°C, more preferably 40 to 80°C, more preferably 45 to 75°C, more preferably 50 to 70°C, and more preferably 55 to 65°C.

[0028] The preferred unsaturated hydrocarbon feedstock comprises one or more alkanes, more preferably one or more C5 to C17 alkanes, more preferably one or more C5 to C15 alkanes, more preferably one or more C5 to C13 alkanes, more preferably one or more C5 to C11 alkanes, more preferably one or more C5 to C9 alkanes, more preferably one or more C5 and / or C9 alkanes, and more preferably one or more C9 alkanes.

[0029] Preferably, the unsaturated hydrocarbon feedstock comprises one or more compounds selected from C5 resin, C9 resin, C5 / C9 copolymer resin, dicyclopentadiene resin, and mixtures of two or more thereof, more preferably selected from C5 resin, C9 resin, C5 / C9 copolymer resin, and mixtures of two or more thereof, even more preferably selected from C5 resin, C9 resin, and mixtures of two or more thereof, wherein the unsaturated hydrocarbon feedstock more preferably comprises C9 resin, and more preferably, the hydrocarbon feedstock is composed of C5 and / or C9 resin, preferably composed of C9 resin.

[0030] The preferred unsaturated hydrocarbon feedstock contains 800 wppm or less sulfur by element, more preferably 500 wppm or less, more preferably 300 wppm or less, more preferably 250 wppm or less, more preferably 200 wppm or less, more preferably 180 wppm or less, more preferably 150 wppm or less, more preferably 130 wppm or less, more preferably 100 wppm or less, more preferably 80 wppm or less, more preferably 60 wppm or less, more preferably 40 wppm or less, more preferably 20 wppm or less, more preferably 10 wppm or less, more preferably 5 wppm or less.

[0031] The preferred solvent system contains one or more hydrocarbons, more preferably one or more alkanes, more preferably one or more C5-C18 alkanes, more preferably one or more C5-C16 alkanes, more preferably one or more C5-C14 alkanes, more preferably one or more C6-C13 alkanes, more preferably one or more C7-C12 alkanes, more preferably one or more C8-C11 alkanes, and more preferably one or more C9-C10 alkanes.

[0032] Preferably, the weight ratio of the hydrogenation catalyst to one or more organic compounds in the particulate material particles in (1) is 5:95 to 75:25, more preferably 10:90 to 60:40, more preferably 15:85 to 50:50, more preferably 20:80 to 45:55, more preferably 23:77 to 40:60, more preferably 25:75 to 34:66, and most preferably from 27:73 to 32:68.

[0033] Preferably, the hydrogenation catalyst in (1) comprises nickel, wherein preferably, the amount of nickel in the hydrogenation catalyst is calculated as an element and is in the range of 5 to 95 wt% of the catalyst based on 100 wt% hydrogenation, preferably 10 to 90 wt%, more preferably 20 to 80 wt%, more preferably 30 to 70 wt%, more preferably 35 to 65 wt%, more preferably 40 to 60 wt%, more preferably 45 to 55 wt%.

[0034] When the hydrogenation catalyst in (1) contains nickel, it is preferred that the nickel is present in elemental form, preferably in an amount of 10 to 99 wt% of the nickel contained in 100 wt% of the hydrogenation catalyst, preferably in an amount of 30 to 98 wt%, more preferably 50 to 95 wt%, more preferably 60 to 90 wt%, more preferably 70 to 85 wt%, more preferably 75 to 82 wt%, more preferably 78 to 80 wt%.

[0035] Further, preferably, the hydrogenation catalyst in (1) comprises one or more transition metals selected from rhodium, iridium, ruthenium, platinum, palladium, and combinations of two or more of them, wherein more preferably, the hydrogenation catalyst in (1) comprises platinum and / or palladium, more preferably platinum.

[0036] When the hydrogenation catalyst contains one or more transition metals selected from rhodium, iridium, ruthenium, platinum, palladium, and combinations thereof, it is preferred that the amount of one or more transition metals is based on 100 wt% of the hydrogenation catalyst, and the metal in the hydrogenation catalyst is calculated as 0.01 to 10 wt%, more preferably 0.05 to 7 wt%, more preferably 0.1 to 5 wt%, more preferably 0.5 to 3 wt%, more preferably 0.7 to 2 wt%, more preferably 0.8 to 1.5 wt%, more preferably 0.9 to 1 wt%.

[0037] Furthermore, when the hydrogenation catalyst in (1) contains one or more transition metals selected from rhodium, iridium, ruthenium, platinum, palladium, and combinations thereof, it is preferred that one or more transition metals are present in an amount of 100 wt% or more as elements, more preferably 50 wt% or more of more transition metals present in an amount of 80 wt% or more as elements, more preferably 90 wt% or more, more preferably 95 wt% or more, more preferably 98 wt% or more, more preferably 99 wt% or more, more preferably 99.9 wt% or more.

[0038] (1) The hydrogenation catalyst preferably comprises one or more oxides selected from refractory metal oxides and mixtures thereof, more preferably selected from silicon dioxide, alumina, magnesium oxide and mixtures of two or more thereof, wherein more preferably the hydrogenation catalyst comprises silicon dioxide and / or alumina, preferably silicon dioxide or silicon dioxide and alumina, more preferably silicon dioxide.

[0039] (1) In the case where the hydrogenation catalyst comprises one or more oxides selected from the group consisting of refractory metal oxides and mixtures thereof, the amount of one or more oxides in the hydrogenation catalyst is preferably in the following range based on 100 wt% of the hydrogenation catalyst, 5 to 95 wt% as oxides, more preferably 8 to 90 wt%, more preferably 10 to 80 wt%, more preferably 13 to 70 wt% wt%, more preferably 15 to 65 wt%, more preferably 18 to 60 wt%, more preferably 20 to 55 wt%.

[0040] According to the invention, the preferred hydrogenation catalyst further comprises a component capable of trapping sulfides to prevent poisoning of the catalytically active component in the hydrogenation catalyst, particularly comprising one or more transition metals selected from the group consisting of rhodium, iridium, ruthenium, platinum, palladium, and combinations of two or more thereof, and particularly comprising platinum and / or palladium, especially platinum in specific and preferred embodiments. Therefore, in this respect, it is preferred that the hydrogenation catalyst in (1) further comprises oxides selected from silver, lanthanum, antimony, nickel, bismuth, cadmium, lead, tin, vanadium, calcium, strontium, barium, cobalt, copper, tungsten, zinc, molybdenum, manganese, and iron, including mixed oxides of two or more thereof, wherein preferably, the hydrogenation catalyst in (1) further comprises metal oxides of zinc and / or iron, preferably zinc oxide.

[0041] (1) The pore volume of the hydrogenation catalyst is preferably 0.1 to 1.5 ml / g, wherein the pore volume refers to the hydrogenation catalyst in which there are no compounds in the pores, more preferably 0.2 to 1.2 ml / g, more preferably 0.3 to 1 ml / g, more preferably 0.4 to 0.8 ml / g, more preferably 0.5 to 0.7 ml / g, more preferably 0.55 to 0.6 ml / g, wherein the pore volume is preferably determined according to ISO 15901-3:2007.

[0042] Preferably, the average pore size of the hydrogenation catalyst in (1) is within Within a certain range, where the average pore size specifically refers to the absence of any compounds in the pores of the hydrogenation catalyst, more preferably 30 to... More preferably 50 to More preferably 60 to More preferably 70 to More preferably 80 to More preferably 90 to More preferably 95 to The average aperture is preferably determined according to ISO 15901-1:2016.

[0043] (1) The preferred BET surface area of ​​the hydrogenation catalyst is 100-600 m². 2 / g, where the BET surface area specifically refers to the hydrogenation catalyst in which no compound is present in its pores, more preferably 120 to 500 m². 2 / g, more preferably 140 to 450m 2 / g, more preferably 160 to 400m 2 / g, more preferably 180 to 350 mg 2 / g, more preferably 200 to 300m 2 / g, more preferably 220 to 280m 2 / g, more preferably 240 to 260m 2 / g, wherein the BET surface area is preferably determined according to ISO 9277:2010.

[0044] The average particle size D50 of the preferred hydrogenation catalyst is in the range of 1 to 50 μm, more preferably 3 to 25 μm, more preferably 4 to 15 μm, more preferably 5 to 10 μm, more preferably 6-8 μm, and more preferably 6.5-7 μm, wherein the average particle size D50 is preferably determined according to ISO 13320:2009.

[0045] (3) The weight ratio of particulate material to unsaturated hydrocarbon feedstock in the mixture is preferably 1:99 to 40:60, more preferably 3:97 to 35:65, more preferably 5:95 to 30:70, more preferably 7:93 to 25:75, more preferably 9:91 to 23:77, more preferably 11:89 to 21:79, more preferably 13:87 to 19:81, and more preferably 15:85 to 17:83.

[0046] (3) The weight ratio of unsaturated hydrocarbon feedstock to solvent system in the mixture is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, more preferably 20:80 to 80:20, more preferably 25:75 to 75:25, more preferably 30:70 to 70:30, more preferably 35:65 to 65:35, more preferably 40:60 to 60:40, more preferably 45:55 to 55:45.

[0047] Preferably (4) the pressure is 10 to 250 bar, more preferably 20 to 200 bar, more preferably 30 to 180 bar, more preferably 40 to 150 bar, more preferably 50 to 120 bar, more preferably 60 to 100 bar, more preferably 70 to 90 bar, more preferably 75 to 85 bar.

[0048] When (4) is carried out at a pressure of 10-120 bar, it is preferable that the gas phase of the mixture prepared in (3) and heated in (4) contains 50% or more hydrogen, more preferably 80% or more, more preferably 90% or more, more preferably 95% or more, more preferably 98% or more, more preferably 99% or more, and more preferably 99.9% or more.

[0049] Preferably (4) the time is within the range of 0.1 hours to 20 hours, more preferably 0.25 hours to 10 hours, more preferably 0.5 hours to 5 hours, more preferably 1 hour to 3 hours, and more preferably 1.5 hours to 2.5 hours.

[0050] As described above, the process may include further method steps. Furthermore, any defined method step may include additional method steps, particularly those related to the preparation of the hydrogenation catalyst.

[0051] According to the first alternative, preferably, in order to provide the hydrogenation catalyst precursor in (1), the method includes:

[0052] (i) Provide an aqueous solution containing one or more salts of one or more transition metals;

[0053] (ii) Provide an aqueous solution containing one or more bases;

[0054] (iii) Providing an aqueous dispersion containing one or more refractory metal oxides in water;

[0055] (iv) Add the aqueous solutions provided in (i) and (ii) to the aqueous dispersion provided in (iii) to precipitate the hydrogenation catalyst precursor;

[0056] (v) Separation of the hydrogenation catalyst precursor obtained in (iv); and

[0057] (vi) Optionally wash and / or dry and / or calcine the hydrogenation catalyst precursor separated in (v).

[0058] Preferably, the hydrogenation catalyst in (1) is prepared by a method according to the first alternative comprising (i), (ii), (iii), (iv), (v) and (vi), as described above, wherein the method further comprises:

[0059] (vii) The hydrogenation catalyst precursor obtained in (v) or (vi) is reduced in a hydrogen atmosphere to obtain the hydrogenation catalyst.

[0060] Preferably, the hydrogenation catalyst in (1) is prepared by a method according to the first alternative comprising (i), (ii), (iii), (iv), (v), (vi) and (vii), as disclosed above, wherein the method further comprises:

[0061] (viii) In an atmosphere containing air, preferably in an atmosphere composed of air, the hydrogenation catalyst obtained in (vii) is passivated.

[0062] In the case where the method further includes (i) according to the first alternative described above, preferably, in (i), one or more transition metals are selected from nickel, rhodium, iridium, ruthenium, platinum, palladium and combinations of two or more thereof, more preferably selected from nickel, platinum, palladium and combinations of two or more thereof, wherein more preferably the one or more transition metals include nickel and / or platinum, preferably nickel, wherein more preferably, one or more transition metals are nickel and / or platinum, preferably nickel.

[0063] In the case where the method further includes (ii) according to the first alternative disclosed above, preferably, in (ii), one or more bases comprise one or more compounds selected from inorganic and organic bases, more preferably selected from inorganic bases, wherein one or more bases are preferably selected from hydroxides, carbonates, aluminates and mixtures of two or more thereof, more preferably selected from alkali metal hydroxides, alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof, more preferably selected from alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof, wherein more preferably the one or more bases comprise one or more alkali metal carbonates, wherein the alkali metal is preferably selected from lithium, sodium, potassium, rubidium, cesium and mixtures of two or more thereof, more preferably selected from the group consisting of lithium, sodium, potassium and mixtures of two or more thereof, wherein more preferably the alkali metal is sodium and / or potassium, preferably sodium.

[0064] In the case where the method further includes (iii) according to the first alternative described above, preferably, in (iii), one or more refractory metal oxides are selected from silicon dioxide, alumina, magnesium oxide and mixtures thereof, wherein more preferably the one or more refractory metal oxides include silicon dioxide and / or alumina, preferably silicon dioxide or silicon dioxide and alumina, more preferably silicon dioxide, wherein more preferably the one or more refractory metal oxides are composed of silicon dioxide and / or alumina, preferably silicon dioxide or silicon dioxide and alumina, more preferably silicon dioxide.

[0065] Furthermore, in the case where the method further includes (iii) according to the first alternative described above, it is preferred that, in (iii), the pore volume of one or more refractory metal oxides is 0.3 to 5 ml / g, more preferably 0.5 to 4 ml / g, more preferably 0.8 to 3.5 ml / g, more preferably 1 to 3 ml / g, more preferably 1.3 to 2.5 ml / g, more preferably from 1.5 to 2 ml / g, more preferably 1.6 to 1.8 ml / g, more preferably 1.7 to 1.75 ml / g, wherein the pore volume is preferably determined according to ISO 15901-3:2007.

[0066] In cases where the method further includes (i), (ii), (iii) and (iv) according to the first alternative described above, it is preferable to add the aqueous solution provided in (i) and (ii) to the aqueous dispersion provided in (iii) sequentially or simultaneously, preferably simultaneously, in (iv).

[0067] Furthermore, where the method further includes (i), (ii), (iii) and (iv) according to the first alternative described above, it is preferable that (iv) be performed at a temperature range of 25 to 95°C, more preferably 30 to 90°C, more preferably 35 to 85°C, more preferably 40 to 80°C, more preferably 45 to 75°C, more preferably 50 to 70°C, and more preferably 55 to 65°C.

[0068] Furthermore, in cases where the method further includes (i), (ii), (iii) and (iv) according to the first alternative described above, preferably, in (iv), the pH is maintained in the range of 5 to 10, more preferably 5.5 to 9.5, more preferably 6 to 9, more preferably 6.5 to 8.5, and more preferably 7 to 8 during the precipitation of the mixed oxides.

[0069] In the case where the method further includes (vii), preferably, the reduction in (vii) according to the first alternative described above is carried out in a temperature range of 200 to 500°C, more preferably 250°C up to 470°C, more preferably 300 to 440°C, more preferably 350 to 420°C, and more preferably 380 to 400°C.

[0070] In the case where the method further includes a reduction (vii) according to the first alternative described above, it is preferred that the reduction (vii) is carried out for 0.25 to 5 hours, more preferably for 0.5 hours to 4 hours, more preferably for 1 to 3.5 hours, more preferably for 1.25 to 3 hours, more preferably for 1.5 to 2.5 hours, and more preferably for 1.75 to 2.25 hours.

[0071] In the case where the method further includes passivation according to the first alternative (viii) described above, the passivation in (viii) is preferably carried out in a temperature range of 75 to 150°C, more preferably from 80 to 130°C, more preferably from 85 to 120°C, more preferably from 90 to 110°C, and more preferably from 95 to 105°C.

[0072] In cases where the method further includes passivation according to the first alternative (viii) described above, the passivation in (viii) is preferably carried out for 0.25 to 4 hours, more preferably for 0.5 hours to 3 hours, more preferably for 0.75 to 2.5 hours, more preferably for 1 to 2 hours, and more preferably for 1.25 to 1.75 hours.

[0073] According to the second alternative, preferably, in order to provide the hydrogenation catalyst in (1), the method comprises:

[0074] (i) Provide an aqueous solution containing one or more salts of one or more transition metals;

[0075] (ii) Provide an aqueous solution containing one or more silica precursor salts;

[0076] (iii) Provide an aqueous solution containing one or more alumina precursor salts;

[0077] (iv) Add the aqueous solutions provided in (i) and (ii) to the aqueous solution provided in (iii) to precipitate the hydrogenation catalyst precursor;

[0078] (v) Separation of the hydrogenation catalyst precursor obtained in (iv);

[0079] (vi) Optionally wash and / or dry and / or calcine the hydrogenation catalyst precursor separated in (v).

[0080] Preferably, the hydrogenation catalyst in (1) is prepared by a method according to the second alternative comprising (i), (ii), (iii), (iv), (v) and (vi), as disclosed above, wherein the method further comprises:

[0081] (vii) The hydrogenation catalyst precursor obtained in (v) or (vi) is reduced in a hydrogen atmosphere to obtain the hydrogenation catalyst.

[0082] Preferably, the hydrogenation catalyst in (1) is prepared by a method according to the second alternative comprising (i), (ii), (iii), (iv), (v), (vi) and (vii), as disclosed above, wherein the method further comprises:

[0083] (viii) In an atmosphere containing air, preferably in an atmosphere composed of air, the hydrogenation catalyst obtained in (vii) is passivated.

[0084] In the case where the method further includes (i) according to the second alternative described above, preferably in (i) one or more transition metals are selected from nickel, rhodium, iridium, ruthenium, platinum, palladium and combinations of two or more thereof, more preferably selected from nickel, platinum, palladium and combinations of two or more thereof, wherein more preferably the one or more transition metals include nickel and / or platinum, preferably nickel, wherein more preferably, one or more transition metals are nickel and / or platinum, preferably nickel.

[0085] In cases where the method further includes (i), (ii), (iii) and (iv) according to the second alternative described above, it is preferable to add the aqueous solution provided in (i) and (ii) to the aqueous solution provided in (iii) sequentially or simultaneously, preferably simultaneously, in (iv).

[0086] When the method further includes (iv) according to the second alternative described above, it is preferred that (iv) be carried out in a temperature range of 35 to 100°C, more preferably 50 to 99°C, more preferably 70 to 98°C, more preferably 80 to 97°C, more preferably 85 to 96°C, and more preferably 90 to 95°C.

[0087] Furthermore, in the case where the method further includes (iv) according to the second alternative described above, it is preferred that, in (iv), the pH is maintained in the range of 6 to 10 during the precipitation of the mixed oxides, more preferably 6.5 to 9.5, more preferably 7 to 9, and even more preferably 7.5 to 8.5.

[0088] In cases where the method further includes (vi) according to the second alternative described above, the calcination in (vi) is preferably carried out at a temperature range of 200 to 700°C, more preferably 250 to 600°C, more preferably 300 to 500°C, more preferably 325 to 450°C, and more preferably 350 to 400°C.

[0089] In the case where the method further includes (vii) according to the second alternative described above, the reduction in (vii) is preferably carried out in a temperature range of 200 to 500°C, more preferably 300 to 470°C, more preferably 350 to 450°C, more preferably 400 to 440°C, and more preferably 420 to 430°C.

[0090] When the method further includes (vii) according to the second alternative described above, it is preferred that (vii) be performed within the range of 0.25 to 5 hours, more preferably 0.5 to 4 hours, more preferably 1 to 3.5 hours, more preferably 1.25 to 3 hours, more preferably 1.5 to 2.5 hours, and more preferably 1.75 to 2.25 hours.

[0091] In cases where the method further includes (viii) according to the second alternative described above, the passivation in (viii) is preferably carried out in a temperature range of 75 to 150°C, more preferably 80 to 130°C, more preferably 85 to 120°C, more preferably 90 to 110°C, and more preferably 95 to 105°C.

[0092] In the case where the method further includes (viii) according to the second alternative described above, the passivation in (viii) is preferably carried out in the range of 0.25 to 4 hours, more preferably 0.5 to 3 hours, more preferably 0.75 to 2.5 hours, more preferably 1 to 2 hours, and more preferably 1.25 to 1.75 hours.

[0093] The preferred form of particulate material is in the form of tablets, flakes, or droplets.

[0094] The preferred particulate material has an average particle size of 1 to 25 mm, more preferably 2 to 15 mm, more preferably 3 to 10 mm, more preferably 4 to 8 mm, and more preferably 5 to 6 mm.

[0095] The unit bar (abs) refers to 10 5 Pa is an absolute pressure, and the unit Angstrom refers to 10⁻⁶ Pa. -10 The length of m.

[0096] The invention is further illustrated by the following set of embodiments and combinations of embodiments derived from indicated dependencies and reverse references. In particular, it should be noted that in each instance of reference to the scope of embodiments, such as in the context of the term "method as described in any one of embodiments 1 to 4," each embodiment within that scope is intended to be clearly disclosed by a person skilled in the art, i.e., the wording of the term should be understood by a person skilled in the art to be synonymous with "the method as described in any one of embodiments 1, 2, 3, and 4." Furthermore, it should be clearly pointed out that the following set of embodiments is not a set of claims defining the scope of protection, but rather an appropriate structural portion of the description of the general and preferred aspects of the invention.

[0097] 1. A method for hydrogenating an unsaturated hydrocarbon feedstock, comprising: (1) preparing a particulate material, wherein the particles of the particulate material comprise a hydrogenation catalyst or a precursor thereof, and one or more organic compounds, wherein the one or more organic compounds comprise one or more carboxylic acids and / or one or more esters, and / or one or more ether portions, preferably one or more carboxylic acids and / or one or more ester portions, more preferably one or more ester portions; (2) providing an unsaturated hydrocarbon feedstock; (3) preparing a mixture comprising the particulate material obtained in (1), the unsaturated hydrocarbon feedstock provided in (2), hydrogen, and optionally a solvent system; and (4) heating the mixture prepared in (3) to 210 to 360°C for hydrogenating the hydrocarbon feedstock, preferably 220 to 340°C, more preferably 230 to 320°C, more preferably 240 to 300°C, more preferably 250 to 290°C, more preferably 260 to 280°C, more preferably within a temperature range of 265 to 275°C.

[0098] 2. The method according to embodiment 1, wherein the particulate material in (1) is prepared, the method comprising: (1.a) providing a hydrogenation catalyst or a precursor thereof; (1.b) providing one or more organic compounds comprising one or more carboxylic acids and / or one or more esters and / or one or more ether moieties, preferably one or more carboxylic acids and / or one or more ester moieties, more preferably one or more ester moieties; (1.c) optionally heating one or more organic compounds provided in (1.b) to a temperature above the melting point of one or more organic compounds; (1.d) dispersing the hydrogenation catalyst provided in (1.a) in one or more organic compounds provided in (1.b) and optionally heating in (1.c); (1.e) shaping the dispersion obtained in (1.d), preferably shaping it into particles; (1.f.) cooling the shaped dispersion obtained in (1.e) to a temperature below the melting point of one or more organic compounds.

[0099] 3. The method according to embodiment 1 or 2, wherein in (1), one or more organic compounds comprise one or more alkyl moieties, preferably one or more C10-C24 alkyl moieties, more preferably one or more C12-C22 alkyl moieties, more preferably one or more C14-C20 alkyl moieties, and more preferably one or more C16-C18 alkyl moieties.

[0100] 4. The method according to any one of embodiments 1 to 3, wherein in (1), the one or more organic compounds comprise one or more alkylene moieties, preferably one or more C1-C6 alkylene moieties, more preferably one or more C2-C4 alkylene moieties, and more preferably one or more C3 alkylene moieties.

[0101] 5. The method according to any one of embodiments 1 to 4, wherein in (1), the one or more organic compounds comprise one or more compounds selected from triglycerides, fatty acids and mixtures of two or more thereof, preferably selected from the group consisting of vegetable oils and mixtures of two or more thereof, more preferably selected from palm oil, soybean oil, rapeseed oil, sunflower oil, peanut oil, cottonseed oil, palm kernel oil, coconut oil, olive oil and mixtures thereof, more preferably selected from palm oil, soybean oil, cottonseed oil and mixtures of two or more thereof, more preferably selected from palm oil, soybean oil and mixtures of two or more thereof, more preferably selected from palm oil, soybean oil and mixtures of two or more thereof, more preferably, the one or more organic compounds comprise palm and / or soybean oil, preferably palm oil, more preferably, the one or more organic compounds consist of palm and / or soybean oil, preferably palm oil.

[0102] 6. The method according to embodiment 5, wherein the triglycerides and / or fatty acids are hydrogenated triglycerides and / or fatty acids.

[0103] 7. The method according to any one of embodiments 1 to 6, wherein in (1), one or more organic compounds comprise one or more ether moieties, preferably two or more ether moieties, and one or more alkylene moieties, preferably two or more alkylene moieties, more preferably two or more C1-C3 alkylene moieties, more preferably two or more C1-C2 alkylene moieties, more preferably two or more C1 alkylene moieties, wherein one or more organic compounds more preferably comprise one or more polyoxyalkylene moieties, more preferably one or more polyoxy(C1-C3) alkylene moieties, more preferably one or more polyoxy(C1-C2) alkylene moieties, more preferably one or more polyoxy(C1) alkylene moieties, wherein one or more organic compounds more preferably include polyoxymethylene moieties.

[0104] 8. The method according to any one of embodiments 1 to 7, wherein in (1), the melting point of one or more organic compounds is 30 to 100°C, preferably 35 to 90°C, more preferably 40 to 80°C, more preferably 45 to 75°C, more preferably 50 to 70°C, and more preferably 55 to 65°C.

[0105] 9. The method according to any one of embodiments 1 to 8, wherein the unsaturated hydrocarbon feedstock comprises one or more alkanes, preferably one or more C5 to C17 alkanes, more preferably one or more C5 to C15 alkanes, more preferably one or more C5 to C13 alkanes, more preferably one or more C5 to C11 alkanes, more preferably one or more C5 to C9 alkanes, more preferably one or more C5 and / or C9 alkanes, and more preferably one or more C9 alkanes.

[0106] 10. The method according to any one of embodiments 1 to 9, wherein the unsaturated hydrocarbon feedstock comprises one or more compounds selected from C5 resin, C9 resin, C5 / C9 copolymer resin, dicyclopentadiene resin, and mixtures of two or more thereof, preferably selected from C5 resin, C9 resin, C5 / C9 copolymer resin, and mixtures of two or more thereof, more preferably selected from C5 resin, C9 resin, and mixtures of two or more thereof, wherein more preferably the unsaturated hydrocarbon feedstock comprises C9 resin, and more preferably the hydrocarbon feedstock is composed of C5 and / or C9 resin, preferably composed of C9 resin.

[0107] 11. The method according to any one of embodiments 1 to 10, wherein the unsaturated hydrocarbon feedstock contains 800 wppm or less sulfur by element, preferably 500 wppm or less, more preferably 300 wppm or less, more preferably 250 wppm or less, more preferably 200 wppm or less, more preferably 180 wppm or less, more preferably 150 wppm or less, more preferably 130 wppm or less, 100 wppm or less, more preferably 80 wppm or less, more preferably 60 wppm or less, more preferably 40 wppm or less, more preferably 20 wppm or less, more preferably 10 wppm or less, more preferably 5 wppm or less.

[0108] 12. The method according to any one of embodiments 1 to 11, wherein the solvent system comprises one or more hydrocarbons, preferably one or more alkanes, more preferably one or more C5-C18 alkanes, more preferably one or more C5-C16 alkanes, more preferably one or more C5-C14 alkanes, more preferably one or more C6-C13 alkanes, more preferably one or more C7-C12 alkanes, more preferably one or more C8-C11 alkanes, and more preferably one or more C9-C10 alkanes.

[0109] 13. The method according to any one of embodiments 1 to 12, wherein the weight ratio of the hydrogenation catalyst to one or more organic compounds in the particles of the particulate material in (1) is 5:95 to 75:25, preferably 10:90 to 60:40, more preferably 15:85 to 50:50, more preferably 20:80 to 45:55, more preferably 23:77 to 40:60, more preferably 25:75 to 34:66, and more preferably from 27:73 to 32:68.

[0110] 14. The method according to any one of embodiments 1 to 13, wherein the hydrogenation catalyst in (1) comprises nickel, wherein preferably, the amount of nickel in the hydrogenation catalyst is in the range of 5 to 95 wt%, calculated in elements and based on 100 wt% of the hydrogenation catalyst, preferably 10 to 90 wt%, more preferably 20 to 80 wt%, more preferably 30 to 70 wt%, more preferably 35 to 65 wt%, more preferably 40 to 60 wt%, more preferably 45 to 55 wt%.

[0111] 15. The method according to embodiment 14, wherein the amount of nickel present in elemental form is 10-99 wt%, based on 100 wt% of nickel contained in the hydrogenation catalyst calculated in elements, preferably in the range of 30 to 98 wt%, more preferably 50 to 95 wt%, more preferably 60 to 90 wt%, more preferably 70 to 85 wt%, more preferably 75 to 82 wt%, and more preferably 78 to 80 wt%.

[0112] 16. The method according to any one of embodiments 1 to 15, wherein the hydrogenation catalyst in (1) comprises one or more transition metals selected from rhodium, iridium, ruthenium, platinum, palladium and combinations thereof, wherein preferably, the hydrogenation catalyst in (1) comprises platinum and / or palladium, preferably platinum.

[0113] 17. The method according to embodiment 16, wherein the amount of one or more transition metals in the hydrogenation catalyst is calculated in elements and is in the range of 0.01 to 10 wt% based on 100 wt% of the hydrogenation catalyst, preferably 0.05 to 7 wt%, more preferably 0.1 to 5 wt%, more preferably 0.5 to 3 wt%, more preferably 0.7 to 2 wt%, more preferably 0.8 to 1.5 wt%, and more preferably 0.9 to 1 wt%.

[0114] 18. According to the method of embodiment 16 or 17, the amount of one or more transition metals present in elemental form is 50 wt% or more, based on 100 wt% of one or more transition metals calculated as elements, preferably 80 wt% or more, more preferably 90 wt% or more, more preferably 95 wt% or more, more preferably 98 wt% or more, more preferably 99 wt% or more, and more preferably 99.9 wt% or more.

[0115] 19. The method according to any one of embodiments 1 to 18, wherein the hydrogenation catalyst in (1) comprises one or more oxides selected from refractory metal oxides and mixtures thereof, preferably selected from silicon dioxide, alumina, magnesium oxide and mixtures of two or more thereof, wherein more preferably the hydrogenation catalyst comprises silicon dioxide and / or alumina, preferably silicon dioxide or silicon dioxide and alumina, more preferably silicon dioxide.

[0116] 20. The method according to embodiment 19, wherein the amount of one or more oxides in the hydrogenation catalyst is based on oxides and is in the range of 5 to 95 wt% based on 100 wt% of the hydrogenation catalyst, preferably from 8 to 90 wt%, more preferably from 10 to 80 wt%, more preferably from 13 to 70 wt%, more preferably from 15 to 65 wt%, more preferably from 18 to 60 wt%, more preferably from 20 to 55 wt%.

[0117] 21. The method according to any one of embodiments 1 to 20, wherein the hydrogenation catalyst in (1) further comprises one or more metal oxides selected from oxides of silver, lanthanum, antimony, nickel, bismuth, cadmium, lead, tin, vanadium, calcium, strontium, barium, cobalt, copper, tungsten, zinc, molybdenum, manganese and iron, including mixed oxides of two or more of them, wherein preferably, the hydrogenation catalyst in (1) further comprises zinc and / or iron, preferably zinc oxide.

[0118] 22. The method according to any one of embodiments 1 to 21, wherein the pore volume of the hydrogenation catalyst in (1) is 0.1 to 1.5 ml / g, wherein the pore volume refers to the hydrogenation catalyst without any compound, preferably 0.2 to 1.2 ml / g, more preferably 0.3 to 1 ml / g, more preferably 0.4 to 0.8 ml / g, more preferably 0.5 to 0.7 ml / g, more preferably 0.55 to 0.6 ml / g, wherein the pore volume is preferably determined according to ISO 15901-3:2007.

[0119] 23. The method according to any one of embodiments 1 to 22, wherein the average pore size of the hydrogenation catalyst in (1) is 10 to 500, wherein the average pore size means that the hydrogenation catalyst does not contain any compounds, preferably 30 to 400, more preferably 50 to 300, more preferably 60 to 250, more preferably 70 to 200, more preferably 80 to 150, more preferably 90 to 120, more preferably 95 to 105, wherein the average pore size is preferably determined according to ISO 15901-1:2016.

[0120] 24. The method according to any one of embodiments 1 to 23, wherein the BET surface area of ​​the hydrogenation catalyst in (1) is between 100 and 600 m². 2 Within the range of / g, where the BET surface area refers to the hydrogenation catalyst whose pores do not contain any compounds, more preferably 120 to 500 m². 2 / g, more preferably 140 to 450m 2 / g, more preferably 160 to 400m 2 / g, more preferably 180 to 350 mg 2 / g, more preferably 200 to 300 m2 / g, more preferably 220 to 280 m2 / g, more preferably 240 to 260 m2 / g, wherein the BET surface area is preferably determined according to ISO 9277:2010.

[0121] 25. The method according to any one of embodiments 1 to 24, wherein the average particle size D50 of the hydrogenation catalyst by volume is in the range of 1 to 50 μm, preferably 3 to 25 μm, more preferably 4 to 15 μm, more preferably 5 to 10 μm, more preferably 6 to 8 μm, more preferably 6.5 to 7 μm, wherein the average particle size D50 by volume is preferably determined according to ISO 13320:2009.

[0122] 26. The method according to any one of embodiments 1 to 25, wherein the weight ratio of particulate material to unsaturated hydrocarbon feedstock in the mixture in (3) is in the range of 1:99 to 40:60, preferably 3:97 to 35:65, more preferably 5:95 to 30:70, more preferably 7:93 to 25:75, more preferably 9:91 to 23:77, more preferably 11:89 to 21:79, more preferably 13:87 to 19:81, more preferably 15:85 to 17:83.

[0123] 27. The method according to any one of embodiments 1 to 26, wherein the weight ratio of unsaturated hydrocarbon feedstock to solvent system in the mixture in (3) is 5:95 to 95:5, preferably 10:90 to 90:10, more preferably 20:80 to 80:20, more preferably 25:75 to 75:25, more preferably 30:70 to 70:30, more preferably 35:65 to 65:35, more preferably 40:60 to 60:40, more preferably 45:55 to 55:45.

[0124] 28. The method according to any one of embodiments 1 to 27, wherein (4) is carried out at a pressure of 10 to 250 bar, preferably 20 to 200 bar, more preferably 30 to 180 bar, more preferably 40 to 150 bar, more preferably 50 to 120 bar, more preferably 60 to 100 bar, more preferably 70 to 90 bar, more preferably 75 to 85 bar.

[0125] 29. The method according to embodiment 28, wherein the gas phase of the mixture prepared in (3) and heated in (4) contains 50 volume-% or more, preferably 80 volume-% or more, more preferably 90 volume-% or more, more preferably 95 volume-% or more, more preferably 98 volume-% or more, more preferably 99 volume-% or more, and more preferably 99.9 volume-% or more.

[0126] 30. The method according to any one of embodiments 1 to 29, wherein (4) is carried out in the range of 0.1 hours to 20 hours, preferably 0.25 hours to 10 hours, more preferably 0.5 hours to 5 hours, more preferably 1 hour to 3 hours, and more preferably 1.5 hours to 2.5 hours.

[0127] 31. The method according to any one of embodiments 1 to 30, wherein in order to provide the hydrogenation catalyst precursor in (1), the method comprises: (i) providing an aqueous solution containing one or more salts of one or more transition metals; (ii) providing an aqueous solution containing one or more bases; (iii) providing an aqueous dispersion containing one or more refractory metal oxides in water; (iv) adding the aqueous solution provided in (i) and the aqueous solution provided in (ii) to the aqueous dispersion provided in (iii) to precipitate the hydrogenation catalyst precursor; (v) separating the hydrogenation catalyst precursor obtained in (iv); and (vi) optionally washing and / or drying and / or calcining the hydrogenation catalyst precursor separated in (v).

[0128] 32. The method according to any one of embodiments 1 to 31, wherein, in order to provide the hydrogenation catalyst in (1), the method of embodiment 30 further includes: (vii) reducing the hydrogenation catalyst precursor obtained in (v) or (vi) in a hydrogen atmosphere to obtain the hydrogenation catalyst.

[0129] 33. The method according to any one of embodiments 1 to 32, wherein, in order to provide the hydrogenation catalyst in (1), the method of embodiment 31 further includes: (viii) passivating the hydrogenation catalyst obtained in (vii) in an atmosphere containing air, preferably in an atmosphere composed of air.

[0130] 34. The method according to any one of embodiments 31 to 33, wherein in (i), the one or more transition metals are selected from nickel, rhodium, iridium, ruthenium, platinum, palladium and combinations of two or more thereof, preferably from the group consisting of nickel, platinum, palladium and combinations of two or more thereof, more preferably, the one or more transition metals include nickel and / or platinum, preferably nickel, and more preferably, the one or more transition metals are nickel and / or platinum, preferably nickel.

[0131] 35. The method according to any one of embodiments 31 to 34, wherein the one or more bases described in (ii) comprise one or more compounds selected from inorganic bases and organic bases, preferably selected from the group consisting of inorganic bases, wherein the one or more bases are preferably selected from hydroxides, carbonates, aluminates and mixtures of two or more thereof, more preferably selected from alkali metal hydroxides, alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof, more preferably selected from alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof, wherein the one or more bases are more preferably comprise one or more alkali metal carbonates, wherein the alkali metal is preferably selected from lithium, sodium, potassium, rubidium, cesium and mixtures of two or more thereof, more preferably selected from lithium, sodium, potassium and mixtures of two or more thereof, wherein the alkali metal is more preferably sodium and / or potassium, preferably sodium.

[0132] 36. The method according to any one of embodiments 31 to 35, wherein in (iii), the one or more refractory metal oxides are selected from silicon dioxide, aluminum oxide, magnesium oxide and mixtures of two or more thereof, wherein preferably the one or more refractory metal oxides include silicon dioxide and / or aluminum oxide, preferably silicon dioxide or silicon dioxide and aluminum oxide, more preferably silicon dioxide, wherein more preferably, the one or more refractory metal oxides are composed of silicon dioxide and / or aluminum oxide, preferably silicon dioxide or silicon dioxide and aluminum oxide, and more preferably silicon dioxide.

[0133] 37. The method of any one of embodiments 31 to 36, wherein in (iii), the pore volume of the one or more refractory metal oxides is 0.3 to 5 ml / g, more preferably 0.5 to 4 ml / g, more preferably 0.8 to 3.5 ml / g, more preferably 1 to 3 ml / g, more preferably 1.3 to 2.5 ml / g, more preferably 1.5 to 2 ml / g, more preferably 1.6 to 1.8 ml / g, more preferably 1.7 to 1.75 ml / g, wherein the pore volume is preferably determined according to ISO 15901-3:2007.

[0134] 38. The method according to any one of embodiments 31 to 37, wherein in (iv) the aqueous solution provided in (i) and the aqueous solution provided in (ii) are added to the aqueous dispersion provided in (iii) subsequently or simultaneously, preferably simultaneously.

[0135] 39. The method according to any one of embodiments 31 to 38, wherein (iv) is carried out at a temperature range of 25 to 95°C, preferably 30 to 90°C, more preferably 35 to 85°C, more preferably 40 to 80°C, more preferably 45 to 75°C, more preferably 50 to 70°C, and more preferably 55 to 65°C.

[0136] 40. The method according to any one of embodiments 31 to 39, wherein in (iv), the pH is maintained in the range of 5 to 10 during the precipitation of the mixed oxides, preferably 5.5 to 9.5, more preferably 6 to 9, even more preferably 6.5 to 8.5, and even more preferably 7 to 8.

[0137] 41. The method according to any one of embodiments 32 to 40, wherein the reduction of (vii) is carried out in a temperature range of 200 to 500°C, more preferably 300 to 470°C, more preferably 350 to 450°C, more preferably 400 to 440°C, and more preferably 420 to 430°C.

[0138] 42. The method according to any one of embodiments 32 to 41, wherein the reduction of (vii) is carried out in the range of 0.25 to 5 hours, preferably 0.5 to 4 hours, more preferably 1 to 3.5 hours, more preferably from 1.25 to 3 hours, more preferably 1.5 to 2.5 hours, and more preferably 1.75 to 2.25 hours.

[0139] 43. The method according to any one of embodiments 33 to 42, wherein the passivation in (viii) is performed in a temperature range of 75 to 150°C, preferably 80 to 130°C, more preferably 85 to 120°C, more preferably 90 to 110°C, and even more preferably 95 to 105°C.

[0140] 44. The method according to any one of embodiments 33 to 43, wherein the passivation in (viii) is performed in the range of 0.25 to 4 hours, preferably 0.5 to 3 hours, more preferably 0.75 to 2.5 hours, more preferably 1 to 2 hours, and more preferably 1.25 to 1.75 hours.

[0141] 45. The method according to any one of embodiments 1 to 30, wherein, in order to provide the hydrogenation catalyst precursor in (1), the method comprises: (i) providing an aqueous solution containing one or more salts of one or more transition metals; (ii) providing an aqueous solution containing one or more silica precursor salts; (iii) providing an aqueous solution containing one or more alumina precursor salts; (iv) adding the aqueous solution provided in (i) and the aqueous solution provided in (ii) to the aqueous solution provided in (iii) to precipitate the hydrogenation catalyst precursor; (v) separating the hydrogenation catalyst precursor obtained in (iv); and (vi) optionally washing and / or drying and / or calcining the hydrogenation catalyst precursor separated in (v).

[0142] 46. ​​The method according to any one of embodiments 1 to 30, wherein, in order to provide the hydrogenation catalyst in (1), the method according to embodiment 45 further includes: (vii) reducing the hydrogenation catalyst precursor obtained in (v) or (vi) in a hydrogen atmosphere to obtain the hydrogenation catalyst.

[0143] 47. The method according to any one of embodiments 1 to 30, wherein, in order to provide the hydrogenation catalyst in (1), the method according to embodiment 46 further includes: (viii) passivating the hydrogenation catalyst obtained in (vii) in an atmosphere containing air, preferably in an atmosphere composed of air.

[0144] 48. The method according to any one of embodiments 45 to 47, wherein in (i), the one or more transition metals are selected from nickel, rhodium, iridium, ruthenium, platinum, palladium and combinations of two or more thereof, preferably from the group consisting of nickel, platinum, palladium and combinations of two or more thereof, more preferably, the one or more transition metals include nickel and / or platinum, preferably nickel, and more preferably, the one or more transition metals are nickel and / or platinum, preferably nickel.

[0145] 49. The method according to any one of embodiments 45 to 48, wherein in (iv) the aqueous solutions provided in (i) and (ii) are added to the aqueous solution provided in (iii) subsequently or simultaneously, preferably simultaneously.

[0146] 50. The method according to any one of embodiments 45 to 49, wherein (iv) is carried out at a temperature range of 35 to 100°C, preferably 50 to 99°C, more preferably 70 to 98°C, more preferably 80 to 97°C, more preferably 85 to 96°C, and more preferably 90 to 95°C.

[0147] 51. The method according to any one of embodiments 45 to 50, wherein in (iv), the pH is maintained in the range of 6 to 10 during the precipitation of the mixed oxides, preferably 6.5 to 9.5, more preferably 7 to 9, and even more preferably 7.5 to 8.5.

[0148] 52. The method according to any one of embodiments 45 to 51, wherein the calcination in (vi) is carried out at a temperature range of 200 to 700°C, preferably 250 to 600°C, more preferably 300 to 500°C, more preferably 325 to 450°C, and even more preferably 350 to 400°C.

[0149] 53. The method according to any one of embodiments 45 to 52, wherein the reduction of (vii) is carried out in the range of 200 to 500°C, preferably 300 to 470°C, more preferably 350 to 450°C, more preferably 400 to 440°C, and more preferably 420 to 430°C.

[0150] 54. The method according to any one of embodiments 46 to 53, wherein the reduction of (vii) is carried out in the range of 0.25 to 5 hours, preferably 0.5 to 4 hours, more preferably 1 to 3.5 hours, more preferably 1.25 to 3 hours, more preferably 1.5 to 2.5 hours, and more preferably 1.75 to 2.25 hours.

[0151] 55. The method according to any one of embodiments 47 to 54, wherein the passivation in (viii) is performed at a temperature of 75 to 150°C, preferably 80 to 130°C, more preferably 85 to 120°C, more preferably 90 to 110°C, and even more preferably 95 to 105°C.

[0152] 56. The method according to any one of embodiments 47 to 55, wherein the passivation in (viii) is performed in the range of 0.25 to 4 hours, preferably 0.5 to 3 hours, more preferably 0.75 to 2.5 hours, more preferably 1 to 2 hours, and more preferably 1.25 to 1.75 hours.

[0153] 57. The method according to any one of embodiments 1 to 56, wherein the particulate material is in the form of a tablet, a sheet, or a droplet.

[0154] 58. The method according to any one of embodiments 1 to 57, wherein the average particle size of the particulate material is in the range of 1 to 25 mm, preferably 2 to 15 mm, more preferably 3 to 10 mm, more preferably 4 to 8 mm, and more preferably 5 to 6 mm. Attached Figure Description

[0155] Figure 1 The IR spectra of the mixture of Reference Example 4 are shown before and after hydrogenation treatment.

[0156] Figure 2 The HPLC analysis of the mixture components of Reference Example 4 before and after hydrogenation treatment is shown.

[0157] Experimental Section

[0158] Reference Example 1: Preparation of Nickel-Containing Hydrogenation Catalyst

[0159] A nickel catalyst was prepared according to Example 2 of WO 2015 / 008247 A2, with slight modifications. Solutions containing nickel and aluminum salts, silicates, and sodium carbonate were mixed in a well-stirred precipitation vessel at 90°C. The resulting slurry had a pH of approximately 7.5, and precipitation was complete after 1 hour. After washing the precipitate, the catalyst precursor was filtered and dried in an oven at 110°C. The dried solid material was then activated with hydrogen at 425°C for two hours, followed by passivation in air at 100°C.

[0160] Reference Example 2: Preparation of catalyst droplets containing a nickel-containing hydrogenation catalyst

[0161] Catalyst droplets were prepared according to Example 1 of WO 2004 / 035204 A1, except that hydrogenated palm oil was used instead of hardened soybean fat. The final catalyst droplets contained approximately 20 wt% nickel, and the droplets exhibited an average particle size of 6 mm.

[0162] Reference Example 3: Preparation of catalyst droplets containing nickel supported on silica as a hydrogenation catalyst

[0163] Nickel supported on silica was prepared as a hydrogenation catalyst according to Example 3 of US 9,045,410 B2. For Reference Example 2, the catalyst was then coated with hydrogenated palm oil according to the procedure described in Example 1 of WO 2004 / 035204 A1 to provide catalyst droplets containing about 11% by weight of nickel, wherein the average droplet size was 5 to 6 mm.

[0164] Reference Example 4: Deoxygenation of Catalyst Droplets

[0165] The nickel catalyst from Reference Example 1 was mixed with hardened palm oil and a C9-C11 hydrocarbon solvent, and the resulting mixture was subjected to hydrogenation conditions (260-280°C and 80 bar H2). The IR spectra of the mixture before and after hydrogenation are shown in [the figures]. Figure 1 It can be seen that the ester fraction of the hardened palm oil in the unhydrogenated mixture is at 1749 cm⁻¹. -1 The C=O vibration at that point is completely absent in the IR spectrum after hydrogenation. Furthermore, as... Figure 2 As shown, HPLC analysis of the mixture before and after hydrogenation reveals that the C16 and C18 alkyl chains of the hardened palm oil are completely converted to C15 and C17 alkanes. For this purpose, dodecane, tetradecane, and hexadecane were injected into the HPLC as reference compounds. Figure 1 and Figure 2 The results indicate that hydrogenation leads to deoxygenation of hardened palm oil, thereby converting the oil into hydrocarbons via decarbonylation and / or decarboxylation of the fatty acid moiety. Surprisingly, it was found that hydrogenation catalysts used for hydrogenating hydrocarbon feedstocks can be effectively protected by coating them with one or more organic compounds containing one or more carboxylic acids and / or one or more ester moieties, wherein said compounds undergo in-situ deoxygenation under the conditions of hydrocarbon feedstock hydrogenation, resulting in their conversion into water, CO and / or CO2 and hydrocarbons. More surprisingly, it was found that the protective coating does not contaminate the hydrocarbon feedstock but instead provides hydrocarbons that can be easily separated from the hydrogenated hydrocarbon products by distillation or similar methods.

[0166] Example 1: Hydrogenation of hydrocarbon feedstock

[0167] Resin hydrogenation tests were conducted in a batch reactor HP-9 using high-sulfur C9 resin feed 4 (125 ppm). The standard test conditions were:

[0168] Stirring: 1100 rpm;

[0169] Pressure: 80 bar;

[0170] Temperature: 270℃;

[0171] Feed: 75g resin / 75g Exxsol D40 (ExxonMobil);

[0172] Runtime: 2 hours;

[0173] Catalyst loading: Reference Example 1: 0.75 g; Reference Example 2: 2.5 g; Reference Example 3: 4.5 g; wherein the amount of droplets was selected to make the nickel loading in each sample the same.

[0174] Hydrogenation activity was calculated using linear regression between 0-30% and / or 30-70% activity. UV activity was calculated based on the decrease in UV peak height (measured at 274 nm) relative to the non-hydrogenated resin. The hydrogenation cracking activity of the samples was expressed as a shift of the molecular weight distribution curve to lower molecular weights after 2 hours of hydrogenation. Cracking was represented using two methods:

[0175] According to dMp=(Mp) 进料 –Mp 产品 ) / Mp 进料 x100% is calculated from the offset of the peak value;

[0176] According to dHv = (weight < 5000) 进料 -Weight <5000 产品 ) / weight<5000 进料 x100%, calculated from the reduction in molecular weight fraction above 5000 g / mol relative to the feed.

[0177]

[0178] Therefore, as can be deduced from the results obtained using the catalyst from Reference Example 2, its performance is comparable to that of the catalyst from Reference Example 1, indicating that protecting the catalyst with a hydrogenated palm oil coating does not lead to a significant reduction in catalyst activity. On the other hand, Reference Example 3, which contains nickel supported on silica as a hydrogenation catalyst, exhibits superior hydrogenation activity compared to the uncoated catalyst of Reference Example 1.

[0179] References to existing technologies cited:

[0180] WO 2015 / 008247 A2

[0181] WO 2017 / 208164 A1

[0182] WO 2004 / 035204 A1

[0183] US 9,045,410 B2

[0184] US 2008 / 161588 A1

[0185] US 2005 / 027136 A1

[0186] US 2014 / 336287 A1

Claims

1. A method for hydrogenating an unsaturated hydrocarbon feedstock, comprising: (1) Preparing particulate material, wherein the particles of the particulate material comprise a hydrogenation catalyst or its precursor, and one or more organic compounds, wherein the one or more organic compounds have a melting point in the range of 30 to 100°C and comprise one or more carboxylic acids and / or one or more esters and / or one or more ether moieties; (2) Providing an unsaturated hydrocarbon feedstock; (3) Preparing a mixture comprising the particulate material obtained in (1), the unsaturated hydrocarbon feedstock provided in (2), hydrogen, and an optional solvent system; (4) Heating the mixture prepared in (3) to a temperature in the range of 210-360°C for hydrogenating the unsaturated hydrocarbon feedstock. The unsaturated hydrocarbon raw material contains one or more compounds selected from C5 resin, C9 resin, C5 / C9 copolymer resin, and dicyclopentadiene resin.

2. The method according to claim 1, wherein, The method for preparing the particulate material described in (1) comprises: (1.a) providing a hydrogenation catalyst; (1.b) providing one or more organic compounds comprising one or more carboxylic acids and / or one or more esters and / or one or more ether moieties; (1.c) optionally heating the one or more organic compounds provided in (1.b) to a temperature above the melting point of the one or more organic compounds; (1.d) dispersing the hydrogenation catalyst provided in (1.a) in the one or more organic compounds provided in (1.b) and optionally heating in (1.c); (1.e) shaping the dispersion obtained in (1.d); and (1.f.) cooling the shaped dispersion obtained in (1.e) to a temperature below the melting point of the one or more organic compounds.

3. The method according to claim 2, wherein, In (1.e), the dispersion obtained in (1.d) is shaped into particles.

4. The method according to claim 1, wherein, In (1), the one or more organic compounds include one or more compounds selected from those containing triglycerides and fatty acids.

5. The method according to claim 2, wherein, In (1), the one or more organic compounds include one or more compounds selected from those containing triglycerides and fatty acids.

6. The method according to claim 3, wherein, In (1), the one or more organic compounds include one or more compounds selected from those containing triglycerides and fatty acids.

7. The method according to any one of claims 1 to 6, wherein, The unsaturated hydrocarbon feedstock also contains one or more alkanes.

8. The method according to any one of claims 1 to 6, wherein, The solvent system contains one or more hydrocarbons.

9. The method according to claim 7, wherein, The solvent system contains one or more hydrocarbons.

10. The method according to any one of claims 1 to 6 and 9, wherein, The weight ratio of the hydrogenation catalyst to the one or more organic compounds in the particles of the particulate material in (1) is from 5:95 to 75:

25.

11. The method according to claim 8, wherein, The weight ratio of the hydrogenation catalyst to the one or more organic compounds in the particles of the particulate material in (1) is from 5:95 to 75:

25.

12. The method according to any one of claims 1 to 6, 9 and 11, wherein, The hydrogenation catalyst in (1) comprises one or more transition metals selected from nickel, rhodium, iridium, ruthenium, platinum and palladium.

13. The method according to claim 10, wherein, The hydrogenation catalyst in (1) comprises one or more transition metals selected from nickel, rhodium, iridium, ruthenium, platinum and palladium.

14. The method according to claim 12, wherein, The amount of one or more transition metals in the hydrogenation catalyst is calculated in elements and ranges from 5 to 95% by weight based on 100% by weight of the hydrogenation catalyst.

15. The method according to claim 13, wherein, The amount of one or more transition metals in the hydrogenation catalyst is calculated in elements and ranges from 5 to 95% by weight based on 100% by weight of the hydrogenation catalyst.

16. The method according to claim 12, wherein, The amount of the one or more transition metals present in elemental form is 50% by weight or more, based on 100% by weight of the one or more transition metals calculated as the element.

17. The method according to any one of claims 13 to 15, wherein, The amount of the one or more transition metals present in elemental form is 50% by weight or more, based on 100% by weight of the one or more transition metals calculated as the element.

18. The method according to any one of claims 1 to 6, 9, 11 and 13 to 16, wherein, (1) The pore volume of the hydrogenation catalyst is 0.1 to 1.5 ml / g, wherein the pore volume refers to the pore volume of the hydrogenation catalyst in which no compound is contained.

19. The method according to claim 17, wherein, (1) The pore volume of the hydrogenation catalyst is 0.1 to 1.5 ml / g, wherein the pore volume refers to the pore volume of the hydrogenation catalyst in which no compound is contained.

20. The method according to any one of claims 1 to 6, 9, 11, 13 to 16 and 19, wherein, In the mixture described in (3), the weight ratio of the particulate material to the unsaturated hydrocarbon feedstock is 1:99 to 40:

60.

21. The method according to claim 18, wherein, In the mixture described in (3), the weight ratio of the particulate material to the unsaturated hydrocarbon feedstock is 1:99 to 40:

60.

22. The method according to any one of claims 1 to 6, 9, 11, 13 to 16, 19 and 21, wherein, In the mixture described in (3), the weight ratio of the unsaturated hydrocarbon feedstock to the solvent system is 5:95 to 95:

5.

23. The method according to claim 20, wherein, In the mixture described in (3), the weight ratio of the unsaturated hydrocarbon feedstock to the solvent system is 5:95 to 95:

5.

24. The method according to any one of claims 1 to 6, 9, 11, 13 to 16, 19, 21 and 23, wherein, The method of providing the hydrogenation catalyst of (1) comprises: (i) providing an aqueous solution containing one or more salts of one or more transition metals; (ii) providing an aqueous solution containing one or more bases; (iii) providing an aqueous dispersion containing one or more refractory metal oxides in water; (iv) adding the aqueous solution provided in (i) and the aqueous solution provided in (ii) to the aqueous dispersion provided in (iii) to precipitate oxides of one or more transition metals; (v) separating the oxide particles obtained in (iv); (vi) optionally washing and / or drying and / or calcining the oxide particles separated in (v); and (vii) reducing the oxide particles obtained in (v) or (vi) in a hydrogen atmosphere.

25. The method according to claim 22, wherein, The method of providing the hydrogenation catalyst of (1) comprises: (i) providing an aqueous solution containing one or more salts of one or more transition metals; (ii) providing an aqueous solution containing one or more bases; (iii) providing an aqueous dispersion containing one or more refractory metal oxides in water; (iv) adding the aqueous solution provided in (i) and the aqueous solution provided in (ii) to the aqueous dispersion provided in (iii) to precipitate oxides of one or more transition metals; (v) separating the oxide particles obtained in (iv); (vi) optionally washing and / or drying and / or calcining the oxide particles separated in (v); and (vii) reducing the oxide particles obtained in (v) or (vi) in a hydrogen atmosphere.

26. The method according to any one of claims 1 to 6, 9, 11, 13 to 16, 19, 21, 23 and 25, wherein, The method of providing the hydrogenation catalyst of (1) comprises: (i) providing an aqueous solution containing one or more salts of one or more transition metals; (ii) providing an aqueous solution containing one or more silica precursor salts; (iii) providing an aqueous solution containing one or more alumina precursor salts; (iv) adding the aqueous solution provided in (i) and the aqueous solution provided in (ii) to the aqueous solution provided in (iii) to precipitate a mixed oxide; (v) separating the mixed oxide obtained in (iv); (vi) optionally washing and / or drying and / or calcining the mixed oxide separated in (v); and (vii) reducing the mixed oxide obtained in (v) or (vi) in a hydrogen atmosphere.

27. The method according to claim 24, wherein, The method of providing the hydrogenation catalyst of (1) comprises: (i) providing an aqueous solution containing one or more salts of one or more transition metals; (ii) providing an aqueous solution containing one or more silica precursor salts; (iii) providing an aqueous solution containing one or more alumina precursor salts; (iv) adding the aqueous solution provided in (i) and the aqueous solution provided in (ii) to the aqueous solution provided in (iii) to precipitate a mixed oxide; (v) separating the mixed oxide obtained in (iv); (vi) optionally washing and / or drying and / or calcining the mixed oxide separated in (v); and (vii) reducing the mixed oxide obtained in (v) or (vi) in a hydrogen atmosphere.

Images