A hydrodenitrogenation catalyst, its preparation method and use

Abstract

The application discloses a kind of hydrodenitrogenation catalyst and its preparation method and application.The catalyst includes carrier and hydrogenation active metal component, wherein, the carrier is loaded with organic nitrogen-containing compound;The organic nitrogen-containing compound is selected from at least one of carbazole nitrogen-containing compound and acridine nitrogen-containing compound containing substituent group and / or functional group.The preparation method of the hydrodenitrogenation catalyst includes: using the solution containing organic nitrogen-containing compound to impregnate carrier, after drying, catalyst intermediate is obtained;Using impregnation solution containing hydrogenation active metal to impregnate the catalyst intermediate, after drying, the catalyst is obtained.The catalyst of the application is used in heavy distillate hydrodenitrogenation process, and can significantly improve the activity and stability of deep hydrodenitrogenation.

Description

Technical Field

[0001] This invention belongs to the field of hydrogenation technology, and specifically relates to a hydrogenation denitrification catalyst, its preparation method, and its application in the hydrogenation treatment of wax oil. Background Technology

[0002] Nitrogen compounds in distillate oils have a significant negative impact on their performance and subsequent processing. For example, in hydrocracking processes, the nitrogen content in the oil should be controlled to below 10 ppm, or even lower, during the pretreatment stage. This places high demands on the ultra-deep denitrification performance of catalysts. Improving the deep hydrodenitrification performance of catalysts is also one of the key research focuses in this field.

[0003] CN1030394C discloses a hydrodenitrification catalyst and its preparation method. The catalyst uses γ-Al₂O₃ as a support, with Group VIII and Group VIB metals, particularly Mo-Ni, as active components, and adds a Ti-B composite additive. The catalyst is prepared using a kneading method, where aluminum hydroxide dry gel (which can be converted to γ-Al₂O₃ by calcination), titanium trichloride solution, boric acid solution, molybdenum trioxide, basic nickel carbonate, and a colloidal solvent are kneaded into a plastic body, extruded, dried, and calcined to obtain the catalyst. This catalyst improves hydrodenitrification performance by increasing pore volume and adding a Ti-B composite additive; however, its hydrodenitrification performance for difficult-to-remove nitrogen-containing compounds in oils is poor.

[0004] CN106582734A discloses a light cycle oil hydrodenitrification catalyst and its preparation method. The catalyst uses alumina, silica, or amorphous silica-alumina as a support, and molybdenum sulfide, tungsten sulfide, and at least one selected from nickel phosphide or cobalt phosphide as active components. This catalyst improves hydrodenitrification performance by modifying the active components, but its ability to hydrodesorb difficult-to-remove nitrogen-containing compounds remains insufficient.

[0005] CN111821987B discloses a hydrodenitrification catalyst and its preparation method. The catalyst is prepared by impregnating a physical pore-expanding agent with an aluminum salt solution and a partial metal component solution, followed by drying and calcination to obtain a modified physical pore-expanding agent. The modified physical pore-expanding agent and boehmite are mixed, shaped, dried, and calcined to obtain an intermediate. This intermediate is then immersed in an ammonium bicarbonate solution for sealed heat treatment, followed by drying and calcination to obtain a modified alumina-based support. The remaining active metal components are then impregnated, dried, and calcined to obtain the hydrodenitrification catalyst. The catalyst prepared by this method can improve the hydrodenitrification and residual carbon removal capabilities, but it still cannot achieve ultra-deep denitrification for heavy distillate oils.

[0006] In the prior art, in order to improve the hydrodenitrification performance of hydrodenitrification catalysts, improvements have been made in terms of large pores, pore permeability, and types of active metals for hydrodenitrification. However, for nitrogen-containing compounds that are difficult to remove, their removal performance is still insufficient and cannot achieve deep hydrodenitrification. Summary of the Invention

[0007] To achieve deep hydrodenitrogenation of heavy distillate oils, this invention provides a hydrodenitrogenation catalyst, its preparation method, and its application. The catalyst of this invention, when used in the hydrodenitrogenation process of heavy distillate oils, can significantly improve the deep hydrodenitrogenation activity and stability of the catalyst.

[0008] In their research on the hydrodenitrogenation mechanism of heavy distillate oils, the inventors discovered that when nitrogen oxide removal is less than 30 ppm, the residual nitrogen oxides in the resulting oil are mainly carbazole or benzo[a]carbazole containing two or more substituents, and acridine or benzo[a]acrylidine containing two or more substituents. These nitrogen oxides have significant steric hindrance, making them difficult to effectively adsorb near conventional active sites, thus hindering their removal. Further research revealed that introducing an appropriate amount of these difficult-to-remove organic nitrogen oxides before loading the active metal component onto the hydrodenitrogenation catalyst support enables efficient adsorption and conversion of these organic nitrogen oxides during the hydrodenitrogenation process of heavy distillate oils.

[0009] The first aspect of the present invention provides a hydrodenitrification catalyst, comprising a support and a hydroactive metal component, wherein an organic nitrogen-containing compound is supported on the support; the organic nitrogen-containing compound is selected from at least one of carbazole nitrogen-containing compounds and acridine nitrogen-containing compounds containing substituents and / or functional groups.

[0010] Furthermore, the hydrogenation active metal component is selected from Group VIB metals and Group VIII metals, wherein the Group VIB metals are preferably one or more of molybdenum and tungsten, and the Group VIII metals are preferably one or more of cobalt and nickel, with nickel being the most preferred.

[0011] Further, the carbazole-based nitrogen-containing compound may contain at least two substituents, at least two functional groups, or at least one substituent and at least one functional group. The carbazole-based nitrogen-containing compound includes, but is not limited to, at least one of the following: 2-hydroxy-3-carboxybenzocarbazole, 1,4,5,8-tetramethyl-carbazole, benzocarbazole-2,3-acid, methyl 1-methoxy-9H-carbazole-3-carboxylate, 1,2:7,8-dibenzocarbazole, 3,6-(diphenylamino)carbazole, 10-methyl-11H-benzocarbazole-3,4-dione, 3,6-dicarboxy-9-ethylcarbazole, 3,6-dihexylcarbazole, and 6-formyl-5,11-dihydroindolocarbazole.

[0012] Further, the acridine nitrogen-containing compound may contain at least two substituents, at least two functional groups, or at least one substituent and at least one functional group. The acridine nitrogen-containing compound includes, but is not limited to, at least one of the following: 9-hydroxymethyl-10-carbamoyl dihydroacridine, 6,7-dimethyl-acridine, 4,9-acridinediol, dibenzoacridine, 3-methoxy-4-(piperidinylmethyl)-9(10H)-acridine ketone, 14-methyldiphenylacridine, 7-methyldibenzoacridine, retinoic acid, 7,8,11-trimethylbenzoacridine, 9-amino-2-acridine carboxylic acid, 1-hydroxy-N-methylacridine ketone, acridine orange, and 2-methoxy-9-phenylacridine.

[0013] Further, preferably, the organic nitrogen-containing compound contains both carbazole nitrogen-containing compounds and acridine nitrogen-containing compounds.

[0014] Furthermore, the support can be a conventional hydrodenitrification catalyst support. The support is an inorganic refractory oxide support, selected from at least one of alumina, silicon oxide, amorphous silicon-aluminum, titanium-aluminum composite oxide, and titanium-silicon composite oxide, preferably an alumina-based support, with γ-alumina being the most preferred. The support may also contain conventional additives, such as one or more of silicon, phosphorus, and boron. The conventional additives in the support account for less than 10% by mass, based on elemental composition.

[0015] Furthermore, the carrier has the following properties: specific surface area of ​​150-360 m². 2 / g, preferably 180-340m 2 / g, pore volume 0.5-1.2m 3 / g, preferably 0.6-1.0m 3 / g.

[0016] Furthermore, based on the mass of the catalyst, the mass content of the support is 50%-85%, preferably 55%-80%.

[0017] Furthermore, the organic nitrogen-containing compound accounts for 0.8%-15.0% of the carrier mass, preferably 1.5%-8.0%.

[0018] Furthermore, the organic nitrogen-containing compound contains both carbazole-based nitrogen-containing compounds and acridine-based nitrogen-containing compounds. Based on the carrier mass, the mass content of the carbazole-based nitrogen-containing compound is 0.5%-8.0%, preferably 1.0%-4.0%, and the mass content of the acridine-based nitrogen-containing compound is 0.5%-6.0%, preferably 0.8%-3.5%. More preferably, the mass ratio of carbazole-based nitrogen compounds to acridine-based nitrogen-containing compounds is 3:1-1:3, preferably 2:1-1:2.

[0019] Furthermore, based on the mass of the catalyst, the mass content of Group VIB metals, calculated as elements, is 5.0%-25.0%, preferably 8.0%-20.0%, and the mass content of Group VIII metals, calculated as elements, is 0.5%-4.0%, preferably 1.0%-3.0%.

[0020] Furthermore, the hydrogenation active metal component is introduced onto the catalyst after the organic nitrogen-containing compound is supported on the support. Preferably, the hydrogenation active metal component is introduced onto the catalyst by impregnation.

[0021] Further, preferably, the catalyst contains an auxiliary component, which is preferably selected from gallium. Based on the mass of the catalyst, the gallium content, calculated as an element, is 0.2%-4.0%.

[0022] A second aspect of the present invention provides a method for preparing the above-mentioned hydrodenitrification catalyst, comprising:

[0023] (1) The support is impregnated with a solution containing organic nitrogen compounds and then dried to obtain a catalyst intermediate;

[0024] (2) The catalyst intermediate is impregnated with an impregnation solution containing a hydrogenation active metal and then dried to obtain the catalyst.

[0025] Furthermore, the impregnation in step (1) can be carried out using conventional impregnation methods, preferably equal-volume impregnation methods.

[0026] Further, in step (1), the solute in the solution containing the organic nitrogen compound is a carbazole-based nitrogen compound and / or an acridine-based nitrogen compound. Preferably, the concentration of the carbazole-based nitrogen compound is 5.0-80.0 g / L, more preferably 10.0-60.0 g / L, and the concentration of the acridine-based nitrogen compound is 4.0-60.0 g / L, more preferably 8.0-50.0 g / L. The solvent used in the solution containing the organic nitrogen compound is one or more of xylene, toluene, ethylbenzene, cyclohexane, tetrahydronaphthalene, and decahydronaphthalene.

[0027] Further, in step (1), the drying temperature is 80-150℃, preferably 100-140℃, and the drying time is 2.0-10.0 hours, preferably 4.0-8.0 hours.

[0028] Furthermore, the impregnation in step (2) can be carried out using conventional impregnation methods, preferably equal-volume impregnation methods.

[0029] Furthermore, in step (2), the impregnation solution containing the hydrogenated active metal can be selected from at least one of commonly used soluble salts or metal oxides that can be dissolved by acid or alkali. For example, the tungsten source is selected from at least one of ammonium tungstate, ammonium metatungstate, and ammonium paratungstate; the molybdenum source is selected from one or more of ammonium tetramolybdate, ammonium heptamolybdate, and molybdenum trioxide; and the nickel source is selected from one or more of nickel nitrate, nickel acetate, nickel citrate, and basic nickel carbonate.

[0030] Further, in step (2), the impregnation solution containing the hydrogenated active metal has a concentration of Group VIB metals (based on elemental composition) of 0.3-4.0 mol / L, preferably 0.5-4.0 mol / L, and a concentration of Group VIIII metals (based on elemental composition) of 0.2-2.0 mol / L, preferably 0.3-1.5 mol / L. Preferably, the impregnation solution containing the hydrogenated active metal also contains an auxiliary component (preferably gallium), with a concentration of the auxiliary component (based on elemental composition) of 0.1-1.0 mol / L, preferably 0.2-0.8 mol / L. The gallium source is selected from one or more of gallium nitrate, gallium oxide, gallium acetylacetonate, gallium hydroxide, and gallium carbonate.

[0031] Furthermore, in step (2), the drying temperature is 80-150℃, preferably 100-140℃, and the drying time is 2.0-10.0 hours, preferably 4.0-8.0 hours.

[0032] The third aspect of the present invention provides the application of the above-mentioned hydrodenitrogenation catalyst in the hydrodenitrogenation of heavy distillate oil.

[0033] Furthermore, the catalyst of the present invention needs to be sulfided before use. The sulfidation method can be a conventional sulfidation method, such as dry sulfidation or wet sulfidation, with wet sulfidation being preferred.

[0034] Furthermore, in the aforementioned application, the catalyst is used as a hydrodenitrification catalyst.

[0035] Furthermore, the heavy distillate feedstock can be a feedstock for wax oil fractions, such as straight-run wax oil, coking wax oil, fluidized bed generated wax oil, catalytic cracking heavy cycle oil, or one or more of these.

[0036] Further, the reaction conditions for the hydrodenitrification are as follows: reaction temperature 280-450℃, preferably 300-420℃; reaction pressure 4.0-20.0 MPa, preferably 6.0-18.0 MPa; hydrogen-to-oil volume ratio 400-1500, preferably 600-1300; and liquid hourly space velocity (LISH) 0.3-3.0 h⁻¹. -1 Preferably 0.5-2.5h -1 .

[0037] Compared with the prior art, the present invention has the following advantages:

[0038] The catalyst of this invention employs a support containing an organic nitrogen-containing compound and a hydrogenation active metal component. The organic nitrogen-containing compound is selected from at least one of carbazole-based and acridine-based nitrogen-containing compounds containing substituents and / or functional groups. This invention utilizes the pre-adsorption occupancy effect of the organic nitrogen-containing compound and the effect of a plastic active phase to create a catalytic space that can effectively adsorb and transform difficult-to-remove organic nitrogen compounds during the formation of the sulfide-state active phase by the active metal. This achieves efficient adsorption and removal of difficult-to-remove organic nitrogen compounds during the hydrodenitrogenation of heavy distillate oils. Preferably, introducing gallium as a hydrodenitrogenation promoter can further improve the hydrodenitrogenation activity of the catalyst.

[0039] The catalyst of this invention is particularly suitable for the hydrotreating of wax oil feedstocks, and has high hydrodenitrification activity, especially capable of ultra-deep hydrodenitrification. Detailed Implementation

[0040] The present invention will be further described below with reference to embodiments, but it should be understood that the scope of protection of the present invention is not limited to the embodiments. In the present invention, unless otherwise expressly stated, percentages and contents are all expressed by mass.

[0041] The alumina support S-0 used in the following embodiments and comparative examples of this invention was prepared by the following method:

[0042] Weigh 2000.0g of alumina dry adhesive powder, add 10.0g of acetic acid, 20.0g of citric acid, 20.0g of butylene terephthalol, 30.0g of polyethylene glycol (average molecular weight 8000), 20.0g of guar gum powder, and 10.0g of cellulose. Mix well, then add 1800.0g of an aqueous solution containing 1.5% nitric acid. Compress for 30.0min, then extrude using a 1.8mm diameter four-leaf perforated plate. Dry at 120℃ for 6.0h, then calcine at 650℃ for 6.0h. The calcined carrier is designated S-0. The properties of the S-0 carrier are as follows: specific surface area is 293m². 2 / g, pore volume is 0.88cm 3 / g.

[0043] Example 1

[0044] Weigh 4.0 g of 1,2:7,8-dibenzocarbazole and 3.0 g of 6,7-dimethyl-acridine, dissolve them in 100 ml of toluene, and the resulting solution is denoted as NQ-1.

[0045] Weigh 100g of S-0, impregnate S-0 with NQ-1, and dry at 120℃ for 5.0 hours. The resulting catalyst intermediate is denoted as T-1.

[0046] Weigh out 30.0g of ammonium metatungstate, 15.0g of nickel nitrate hexahydrate, and 5.2g of gallium nitrate, dissolve them in 100ml of water, and the resulting solution is denoted as MQ-1.

[0047] The catalyst obtained by impregnating T-1 with MQ-1 and drying it at 120°C for 5.0 hours is designated as Cat-1.

[0048] Example 2

[0049] Weigh 4.0 g of 1,4,5,8-tetramethyl-carbazole and 3.0 g of 4,9-acrididine diol, dissolve them in 100 ml of tetrahydronaphthalene, and the resulting solution is denoted as NQ-2.

[0050] Weigh 100g of S-0, impregnate S-0 with NQ-2, and dry at 120℃ for 5.0 hours. The resulting catalyst intermediate is denoted as T-2.

[0051] Weigh out 30.0 g of ammonium heptamolybdate tetrahydrate, 15.0 g of nickel nitrate hexahydrate, and 5.2 g of gallium nitrate, dissolve them in 100 ml of water, and the resulting solution is denoted as MQ-2.

[0052] The catalyst obtained by impregnating T-2 with MQ-2 and drying it at 120°C for 5.0 hours is designated as Cat-2.

[0053] Example 3

[0054] Weigh 4.0g of 3,6-(diphenylamino)carbazole and 3.0g of 7-methyldibenzo-acrylidine, dissolve them in 100ml of decahydronaphthalene, and the resulting solution is denoted as NQ-3.

[0055] Weigh 100g of S-0, impregnate S-0 with NQ-3, and dry at 120℃ for 5.0 hours. The resulting catalyst intermediate is denoted as T-3.

[0056] Weigh 40.0g ammonium metatungstate, 20.0g nickel acetate tetrahydrate, and 4.0g gallium hydroxide, and dissolve them in 100ml of 5.0wt% dilute nitric acid to obtain a solution labeled MQ-3.

[0057] The catalyst obtained by impregnating T-3 with MQ-3 and drying it at 120°C for 5.0 hours is designated as Cat-3.

[0058] Example 4

[0059] Weigh 3.0 g of 3,6-dicarboxy-9-ethylcarbazole and 3.0 g of 7,8,11-trimethylbenzoacridine, dissolve them in 100 ml of p-xylene, and the resulting solution is denoted as NQ-4.

[0060] Weigh 100g of S-0, impregnate S-0 with NQ-4, and dry at 120℃ for 5.0 hours. The resulting catalyst intermediate is denoted as T-4.

[0061] Weigh 40.0g ammonium heptamolybdate tetrahydrate, 20.0g nickel acetate tetrahydrate, and 4.0g gallium hydroxide, and dissolve them in 100ml of 5.0wt% dilute nitric acid to obtain a solution labeled MQ-4.

[0062] The catalyst obtained by impregnating T-4 with MQ-4 and drying it at 120°C for 5.0 hours is designated as Cat-4.

[0063] Example 5

[0064] Weigh 7.0 g of 1,2:7,8-dibenzocarbazole and dissolve it in 100 ml of toluene. The resulting solution is denoted as NQ-5.

[0065] Weigh 100g of S-0, impregnate S-0 with NQ-5, and dry at 120℃ for 5.0 hours. The resulting catalyst intermediate is denoted as T-5.

[0066] The preparation method of MQ-1 is the same as in Example 1.

[0067] The catalyst obtained by impregnating T-5 with MQ-1 and drying it at 120°C for 5.0 hours is designated as Cat-5.

[0068] Example 6

[0069] Weigh 7.0 g of 6,7-dimethyl-acridine and dissolve it in 100 ml of toluene. The resulting solution is denoted as NQ-6.

[0070] Weigh 100g of S-0, impregnate S-0 with NQ-6, and dry at 120℃ for 5.0 hours. The resulting catalyst intermediate is denoted as T-6.

[0071] The preparation method of MQ-1 is the same as in Example 1.

[0072] The catalyst obtained by impregnating T-6 with MQ-1 and drying it at 120°C for 5.0 hours is designated as Cat-6.

[0073] Example 7

[0074] Weigh 8.0 g of 6,7-dimethyl-acridine and 6.0 g of 1,2:7,8-dibenzocarbazole, dissolve them in 100 ml of toluene, and the resulting solution is denoted as NQ-7.

[0075] Weigh 100g of S-0, impregnate S-0 with NQ-7, and dry at 120℃ for 5.0 hours. The resulting catalyst intermediate is denoted as T-7.

[0076] The preparation method of MQ-1 is the same as in Example 1.

[0077] The catalyst obtained by impregnating T-7 with MQ-1 and drying it at 120°C for 5.0 hours is designated as Cat-7.

[0078] Example 8

[0079] T-5 was prepared according to Example 5.

[0080] Weigh out 30.0g of ammonium metatungstate and 15.0g of nickel nitrate hexahydrate, dissolve them in 100ml of water, and the resulting solution is denoted as MQ-8.

[0081] The catalyst obtained by impregnating T-5 with MQ-8 and drying it at 120°C for 5.0 hours is designated as Cat-8.

[0082] Comparative Example 1

[0083] The preparation method of solution MQ-1 is the same as in Example 1.

[0084] The catalyst obtained by impregnating 100.0g of S-0 with MQ-1 and drying at 120℃ for 5.0 hours is designated as DCT-1.

[0085] Comparative Example 2

[0086] The preparation method of solution MQ-2 is the same as in Example 2.

[0087] The catalyst obtained by impregnating 100.0g of S-0 with MQ-2 and drying at 120℃ for 5.0 hours is designated as DCT-2.

[0088] Comparative Example 3

[0089] Weigh 4.0g acridine and 3.0g carbazole, dissolve them in 100ml toluene, and the resulting solution is denoted as DQ-3.

[0090] Weigh 100g of S-0, impregnate S-0 with DQ-3, and dry at 120℃ for 5.0 hours. The resulting catalyst intermediate is denoted as DT-3.

[0091] The preparation method of MQ-1 is the same as in Example 1.

[0092] The catalyst obtained by impregnating DT-3 with MQ-1 and drying it at 120°C for 5.0 hours is designated as DCT-3.

[0093] Comparative Example 4

[0094] The preparation method of MQ-1 is the same as in Example 1.

[0095] The catalyst obtained by impregnating S-0 with MQ-1 and drying at 120°C for 5.0 hours is designated as DT-4.

[0096] Weigh 4.0 g of 6,7-dimethyl-acridine and 3.0 g of 2-hydroxy-3-carboxybenzocarbazole, dissolve them in 100 ml of toluene, and the resulting solution is denoted as DQ-4.

[0097] The catalyst obtained by impregnating DT-4 with DQ-4 and drying it at 120°C for 5.0 hours is designated as DCT-4.

[0098] Table 1. Composition of the catalysts obtained in each example.

[0099] Cat-1 14.5 - 1.9 0.8 Cat-2 - 10.7 1.8 0.8 Cat-3 17.8 - 2.8 1.3 Cat-4 - 13.0 2.7 1.2 Cat-5 14.4 - 1.8 0.8 Cat-6 14.5 - 1.9 0.8 Cat-7 14.1 - 1.7 0.7 Cat-8 14.6 - 1.9 - DCT-1 15.2 - 2.0 0.9 DCT-2 - 11.1 2.0 0.8 DCT-3 14.8 - 1.9 0.8 DCT-4 14.9 - 2.0 0.9

[0100] Examples 9-16

[0101] Catalysts Cat-1, Cat-2, Cat-3, Cat-4, Cat-5, Cat-6, Cat-7, and Cat-8 were subjected to conventional wet sulfidation. The sulfidation solution was a cyclohexane solution of dimethyl disulfide with a mass concentration of 5.0%. The sulfidation conditions were as follows: sulfidation solution flow rate of 2.0 ml / h·g catalyst, sulfidation temperature of 340℃, sulfidation time of 12 hours, reaction pressure of 6.0 MPa, and hydrogen flow rate of 20.0 N ml / min·g catalyst. The samples obtained after sulfidation were designated as Cat-1S, Cat-2S, Cat-3S, Cat-4S, Cat-5S, Cat-6S, Cat-7S, and Cat-8S, respectively.

[0102] Comparative Examples 5-8

[0103] Catalysts DCT-1, DCT-2, DCT-3, and DCT-4 were subjected to conventional wet sulfidation. The sulfidation solution was a cyclohexane solution of dimethyl disulfide with a mass concentration of 5.0%. The sulfidation conditions were as follows: sulfidation solution flow rate of 2.0 ml / h·g catalyst, sulfidation temperature of 340℃, sulfidation time of 12 hours, reaction pressure of 6.0 MPa, and hydrogen flow rate of 20.0 N ml / min·g catalyst. The samples obtained after sulfidation were designated as DCT-1S, DCT-2S, DCT-3S, and DCT-4S, respectively.

[0104] Examples 17-24

[0105] Straight-run wax oils were used as raw materials to conduct hydrogenation evaluation experiments on Cat-1S, Cat-2S, Cat-3S, Cat-4S, Cat-5S, Cat-6S, Cat-7S, and Cat-8S. The properties of the straight-run wax oils are shown in Table 2.

[0106] Table 2 Properties of Straight-Run Wax Oils

[0107] <![CDATA[Density / g·cm -3 > 0.926 H / C atomic ratio 1.76 Sulfur content, μg / g 19370 Monocyclic aromatic hydrocarbons, wt% 20.9 Nitrogen content, μg / g 1443 Bicyclic and higher aromatic hydrocarbons, wt% 25.3

[0108] The hydrogenation operating conditions were: reaction temperature 370℃, total reaction pressure 15.0 MPa, hydrogen-to-oil volume ratio 1000:1, and liquid hourly space velocity (LHSV) 1.0 h⁻¹. -1 After 1000 hours of reaction evaluation, the nitrogen content of the hydrogenated oil fraction at a temperature not lower than 180℃ was analyzed, and the results are shown in Table 3.

[0109] Comparative Examples 9-12

[0110] Straight-run wax oil was used as raw material to conduct hydrogenation evaluation experiments on DCT-1S, DCT-2S, DCT-3S, and DCT-4S. The properties of the straight-run wax oil are shown in Table 2. The hydrogenation operating conditions were: reaction temperature 370℃, total reaction pressure 15.0 MPa, hydrogen-to-oil volume ratio 1000:1, and liquid hourly space velocity 1.0 h⁻¹. -1 After 800 hours of reaction evaluation, the nitrogen content of the hydrogenated oil fraction at a temperature not lower than 180℃ was analyzed, and the results are shown in Table 3.

[0111] Table 3 Nitrogen content in hydrotreated oils

[0112]

[0113]

[0114] As can be seen from the evaluation results in Table 3, the catalyst of the present invention has good hydrodenitrification performance when processing wax oil raw materials.

Claims

1. A hydrodenitrification catalyst, comprising a support and a hydroactive metal component, wherein, The support is loaded with an organic nitrogen-containing compound; the organic nitrogen-containing compound is selected from at least one of carbazole nitrogen-containing compounds and acridine nitrogen-containing compounds containing substituents and / or functional groups; The nitrogen-containing carbazole compound is selected from at least one of 2-hydroxy-3-carboxybenzocarbazole, 1,4,5,8-tetramethyl-carbazole, benzocarbazole-2,3-acid, methyl 1-methoxy-9H-carbazole-3-carboxylate, 1,2:7,8-dibenzocarbazole, 3,6-(diphenylamino)carbazole, 10-methyl-11H-benzocarbazole-3,4-dione, 3,6-dicarboxy-9-ethylcarbazole, 3,6-dihexylcarbazole, and 6-formyl-5,11-dihydroindolocarbazole. The acridine nitrogen-containing compounds are selected from at least one of the following: 9-hydroxymethyl-10-carbamoyl dihydroacridine, 6,7-dimethyl-acridine, 4,9-acridinediol, dibenzoacridine, 3-methoxy-4-(piperidinylmethyl)-9(10H)-acridine ketone, 14-methyldiphenylacridine, 7-methyldibenzoacridine, retinoic acid choline, 7,8,11-trimethylbenzoacridine, 9-amino-2-acridine carboxylic acid, 1-hydroxy-N-methylacridine ketone, acridine orange, and 2-methoxy-9-phenylacridine. The organic nitrogen-containing compound accounts for 0.8%-15.0% of the carrier mass; The preparation method of the hydrogenation denitrification catalyst includes: (1) The support is impregnated with a solution containing organic nitrogen compounds and then dried to obtain a catalyst intermediate; (2) The catalyst intermediate is impregnated with an impregnation solution containing a hydrogenation active metal and then dried to obtain the catalyst.

2. The catalyst according to claim 1, characterized in that, The active metal component for hydrogenation is selected from Group VIB and Group VIII metals.

3. The catalyst according to claim 2, characterized in that, Group VIB metals are one or more of molybdenum and tungsten, and Group VIII metals are one or more of cobalt and nickel.

4. The catalyst according to claim 3, characterized in that, Nickel is a metal in Group VIII.

5. The catalyst according to claim 1, characterized in that, The organic nitrogen-containing compound contains both carbazole-type nitrogen-containing compounds and acridine-type nitrogen-containing compounds.

6. The catalyst according to claim 1, characterized in that, In the organic nitrogen-containing compounds, the mass ratio of carbazole nitrogen-containing compounds to acridine nitrogen-containing compounds is 3:1 to 1:

3.

7. The catalyst according to claim 6, characterized in that, In the organic nitrogen-containing compounds, the mass ratio of carbazole nitrogen-containing compounds to acridine nitrogen-containing compounds is 2:1 to 1:

2.

8. The catalyst according to claim 1, characterized in that, The carrier is an inorganic refractory oxide carrier, selected from at least one of alumina, silicon oxide, amorphous silicon-aluminum, titanium-aluminum composite oxide, and titanium-silicon composite oxide.

9. The catalyst according to claim 1, characterized in that, The carrier is an alumina-based carrier.

10. The catalyst according to claim 8 or 9, characterized in that, The carrier also contains one or more conventional additives, such as silicon, phosphorus, and boron.

11. The catalyst according to claim 8, characterized in that, The carrier has the following properties: specific surface area of ​​150-360 m² 2 / g, pore volume 0.5-1.2 m 3 / g.

12. The catalyst according to claim 11, characterized in that, The carrier has the following properties: specific surface area of ​​180-340 m² 2 / g, pore volume 0.6-1.0 m 3 / g.

13. The catalyst according to claim 1, characterized in that, Based on the quality of the catalyst, the mass content of the support is 50%-85%.

14. The catalyst according to claim 13, characterized in that, Based on the quality of the catalyst, the mass content of the support is 55%-80%.

15. The catalyst according to claim 1, characterized in that, The organic nitrogen-containing compound accounts for 1.5%-8.0% of the carrier mass.

16. The catalyst according to claim 1 or 15, characterized in that, Based on the carrier mass, the mass content of carbazole nitrogen compounds is 0.5%-8.0%, and the mass content of acridine nitrogen compounds is 0.5%-6.0%.

17. The catalyst according to claim 16, characterized in that, Based on the carrier mass, the mass content of carbazole nitrogen compounds is 1.0%-4.0%, and the mass content of acridine nitrogen compounds is 0.8%-3.5%.

18. The catalyst according to claim 2, characterized in that, Based on catalyst mass, the mass content of Group VIB metals is 5.0%-25.0% and the mass content of Group VIII metals is 0.5%-4.0%.

19. The catalyst according to claim 18, characterized in that, Based on catalyst mass, the mass content of Group VIB metals is 8.0%-20.0% and the mass content of Group VIII metals is 1.0%-3.0%.

20. The catalyst according to claim 1, characterized in that, The catalyst contains an auxiliary component, which is gallium, and the mass content of gallium, based on the mass of the catalyst, is 0.2%-4.0% by element.

21. A method for preparing the hydrodenitrification catalyst according to any one of claims 1-19, comprising: (1) The support is impregnated with a solution containing organic nitrogen compounds and then dried to obtain a catalyst intermediate; (2) The catalyst intermediate is impregnated with an impregnation solution containing a hydrogenation active metal and then dried to obtain the catalyst.

22. The preparation method according to claim 21, characterized in that, In step (1), the solute in the solution containing organic nitrogen compounds is a carbazole nitrogen compound and / or an acridine nitrogen compound, and the solvent is one or more of xylene, toluene, ethylbenzene, cyclohexane, tetrahydronaphthalene, and decahydronaphthalene. And / or, in step (1), the drying temperature is 80-150°C and the drying time is 2.0-10.0 hours.

23. The preparation method according to claim 22, characterized in that, In step (1), the drying temperature is 100-140°C and the drying time is 4.0-8.0 hours.

24. The preparation method according to claim 21, characterized in that, In step (2), the impregnation solution containing hydrogenated active metal contains a tungsten source and / or a molybdenum source, as well as a nickel source. The tungsten source is selected from at least one of ammonium tungstate, ammonium metatungstate, and ammonium paratungstate. The molybdenum source is selected from one or more of ammonium tetramolybdate, ammonium heptamolybdate, and molybdenum trioxide. The nickel source is selected from one or more of nickel nitrate, nickel acetate, nickel citrate, and basic nickel carbonate. And / or, in step (2), the drying temperature is 80-150°C and the drying time is 2.0-10.0 hours.

25. The preparation method according to claim 24, characterized in that, In step (2), the impregnation solution containing the hydrogenated active metal also contains the auxiliary component gallium, and the gallium source is selected from one or more of gallium nitrate, gallium oxide, gallium acetylacetonate, gallium hydroxide, and gallium carbonate; And / or, in step (2), the drying temperature is 100-140°C and the drying time is 4.0-8.0 hours.

26. The application of the hydrodenitrification catalyst according to any one of claims 1-20 in the hydrodenitrification of heavy distillate oil.

27. The application according to claim 26, characterized in that, The heavy distillate feedstock is selected from one or more of the following: straight-run wax oil, coking wax oil, fluidized bed generated wax oil, and catalytic cracking heavy cycle oil.

28. The application according to claim 26, characterized in that, The reaction conditions for hydrodenitrification are as follows: reaction temperature 280-450℃, reaction pressure 4.0-20.0 MPa, hydrogen-to-oil volume ratio 400-1500, and liquid hourly space velocity 0.3-3.0 h⁻¹. -1 .

29. The application according to claim 28, characterized in that, The reaction conditions for hydrodenitrification are as follows: reaction temperature 300-420℃, reaction pressure 6.0-18.0 MPa, hydrogen-to-oil volume ratio 600-1300, and liquid hourly space velocity 0.5-2.5 h⁻¹. -1 .

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