CN116262231A - Preparation method of distillate aromatic saturation catalyst - Google Patents
Preparation method of distillate aromatic saturation catalyst Download PDFInfo
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- CN116262231A CN116262231A CN202111536353.XA CN202111536353A CN116262231A CN 116262231 A CN116262231 A CN 116262231A CN 202111536353 A CN202111536353 A CN 202111536353A CN 116262231 A CN116262231 A CN 116262231A
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- acid
- catalyst
- active metal
- aromatic hydrocarbon
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method of a distillate aromatic saturation catalyst, which comprises the following steps: (1) Uniformly mixing pseudo-boehmite powder and sesbania powder, adding a peptizing agent and deionized water, kneading, extruding strips, drying and roasting to obtain a carrier; (2) Preparing active metal impregnating solution, and adding active metal guiding auxiliary agents such as nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid and diethylenetriamine pentaacetic acid in the preparation process; (3) And (3) dipping the carrier in the step (1) in the active metal dipping liquid in the step (2), drying and roasting in an oxygen-containing atmosphere to obtain the distillate aromatic saturated catalyst. The catalyst obtained by the preparation method can form an active stack with a specific morphology, prolongs the residence time and the reaction time of aromatic hydrocarbon molecules in raw oil, promotes the conversion of the aromatic hydrocarbon molecules to cycloparaffin molecules, and achieves the aim of aromatic hydrocarbon saturation.
Description
Technical Field
The invention relates to a preparation method of a distillate aromatic hydrocarbon saturation catalyst, in particular to a high-activity supported non-noble metal aromatic hydrocarbon saturation catalyst and a preparation method thereof.
Background
Along with the acceleration of the inferior and heavy trends of crude oil, the aromatic hydrocarbon content of raw oil is continuously increased in the hydrofining process of aviation kerosene and diesel oil. The aromatic hydrocarbons in petroleum fractions mainly include the following four classes:
(1) Monocyclic aromatic hydrocarbons including benzene and alkylbenzenes, benzocycloalkanes, and the like;
(2) Bicyclic aromatic hydrocarbons including naphthalene and alkyl naphthalene, biphenyl and naphthacene, and the like;
(3) Tricyclic aromatic hydrocarbons including anthracene, phenanthrene, fluorene, alkyl derivatives thereof, and the like;
(4) Polycyclic aromatic hydrocarbons such as pyrene, fluoranthene, and the like.
Aromatic nuclei in aromatic hydrocarbons are very stable and difficult to directly break open loops. The condensed rings and polycyclic rings of the macromolecules can be opened and further subjected to cracking reaction only after the aromatic rings are hydrogenated and saturated. Research shows that the aromatic hydrocarbon hydrogenation reaction has the following rules:
(1) the equilibrium constant of the aromatic hydrogenation reaction decreases with the increase of the reaction temperature;
(2) in the range of 600K-700K, the equilibrium constant lgKp of the complete hydrogenation saturation reaction of the aromatic hydrocarbon is reduced along with the increase of the number of rings in the molecule;
(3) in the interval of 600K-700K, the equilibrium constant of the first ring hydrogenation saturation reaction in the polycyclic aromatic hydrocarbon is the largest, and the equilibrium constants of the second ring saturation reaction and the third ring saturation reaction are sequentially reduced;
(4) when the temperature exceeds 600K, the equilibrium constant of the aromatic hydrogenation saturation reaction is smaller, so that the equilibrium conversion rate can be improved under higher pressure;
(5) the first aromatic ring in the polycyclic aromatic hydrocarbon is easily hydrogenated and saturated, the relative reaction rate constant is 1.38, which is 10 times that of benzene hydrogenation, and the last remaining aromatic ring is difficult to be hydrogenated and saturated, and the reaction rate is close to that of benzene.
In industry, the aromatic saturation process of distillate oil is mainly divided into two types: the catalyst adopted in the one-stage process and the two-stage process is two kinds of supported metal sulfide and supported noble metal catalyst. When the sulfur and nitrogen content in the raw oil is high, gamma-Al is usually used 2 O 3 NiMo, niW, coMo catalyst in the supported sulfided state. When the sulfur and nitrogen content in the feed oil is sufficiently low, the use of a high activity supported noble metal catalyst works well.
The one-stage process has the advantages that the process is not influenced by poison in raw materials to be treated; the method has the defects of low hydrogenation activity, slow reaction speed under common hydrotreating conditions, and generally demanding reaction conditions (360-425 ℃) for reaching higher aromatic hydrocarbon removal depth, and limitation of thermodynamic equilibrium on aromatic hydrocarbon hydrogenation depth at high temperature.
The two-stage process is to carry out desulfurization and dearomatization in sections, wherein the first stage adopts a traditional sulfide catalyst, the S content is reduced through severe hydrotreating, and the second stage adopts a noble metal catalyst to carry out arene saturation. The method has the advantages that aromatic hydrocarbon can be deeply removed, and the reaction condition is mild (150-350 ℃); the disadvantage is that the second stage catalyst is very sensitive to sulphides in the feed and requires that the S content in the product after one stage of purification is reduced to the ppm level.
The aromatic hydrocarbon content has a direct relation with the smoke point of jet fuel, and the volume content of the aromatic hydrocarbon is required to be not more than 20.0% in the specification of No. 3 jet fuel, and the smoke point is not less than 25.0mm. For straight run kerosene fraction, it mainly contains monocyclic and bicyclic aromatic hydrocarbons, and it is basically free of tricyclic and above aromatic hydrocarbons. Wherein the monocyclic aromatic hydrocarbon mainly comprises alkylbenzene, indane, tetrahydronaphthalene and indene, and the bicyclic aromatic hydrocarbon mainly comprises naphthalene and naphthalene. The difficulty of the hydrogenation saturation of the monocyclic aromatic hydrocarbon and the dicyclic aromatic hydrocarbon is higher than that of the polycyclic aromatic hydrocarbon, so that the development of the catalyst with higher aromatic hydrocarbon saturation activity is of great significance for producing No. 3 jet fuel by taking low smoke point kerosene as a raw material.
At present, the more studied aromatic hydrocarbon saturation catalysts mainly comprise the following three types:
(1) The non-noble metal sulfur state catalyst has the advantages of insensitivity to poisoning of sulfur species in raw materials, strong adaptability, and the most widely applied industrial at present, but generally has the problem of low hydrogenation activity;
(2) The noble metal catalyst has higher hydrogenation activity, can realize deep saturation of aromatic hydrocarbon under milder conditions, but is extremely easy to cause poisoning and deactivation of the catalyst and has higher production cost when the raw material contains higher sulfide;
(3) Other catalysts mainly comprise amorphous alloy catalysts, transition metal carbon or nitride catalysts and the like, but the catalysts have the defects of harsh preparation conditions, poor stability and higher production cost, and limit the large-scale application of the catalysts.
Chinese patent CN101099934a discloses a metal nitride catalyst for aromatic hydrocarbon saturation hydrogenation, loading nickel-molybdenum bimetallic nitride on alumina, stirring and impregnating for 2-4 hours at room temperature, filtering, fully airing, vacuum drying for 5-8 hours at 60-100 ℃, tabletting, shaping, sieving, directly heating and roasting, the process is: in Ar gas flow, the temperature is raised to 650-680 ℃ from room temperature at the speed of 10 ℃/min, the Ar gas space velocity is kept for 2h, and the Ar gas space velocity is 500-1500 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Handover H 2 The gas flow is maintained for 2H, then at H 2 Cooling to room temperature, H 2 The airspeed is 500 to 1500 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the Finally in the content 1%O 2 N of (2) 2 The catalyst is passivated for 4 hours, is used for the saturated hydrogenation reaction of monocyclic and bicyclic aromatic hydrocarbon, and has higher catalytic activity. The disadvantages of this technique or the shortcomings with respect to the present invention: the catalyst prepared by the method has the advantages of complicated roasting process, high production cost and uneconomical.
Chinese patent CN105521797B discloses a supported bimetallic catalyst and a method for preparing the same, comprising impregnating a support with a compound containing a first active metal component and a compound containing a second active metal component, reducing and activating the support, impregnating the reduced and activated product with a solution containing the second active metal component in a reducing or inert atmosphere, and preparing the catalyst having significantly higher aromatic saturation activity. The disadvantages of this technique or the shortcomings with respect to the present invention: the catalyst prepared by the method needs noble metal, and has higher economic cost.
The Chinese patent CN106582707B discloses a supported alloy type aromatic hydrocarbon saturation catalyst and a preparation method thereof, which mainly solve the problem of low hydrogenation saturation of polycyclic aromatic hydrocarbon in the prior art, and the catalyst takes at least one of alumina, silica, titania or amorphous silica-alumina as a carrier, and takes an alloy formed by noble metal and non-noble metal as an active component, so that the catalyst has the characteristic of high hydrogenation saturation activity. The disadvantages of this technique or the shortcomings with respect to the present invention: the catalyst prepared by the method needs noble metal, and has higher economic cost.
U.S. patent No. 5308814 discloses a variety of support materials for noble metal dearomatization catalyst compositions in which a support is prepared from Y and a refractory inorganic oxide (e.g., silica, alumina, or silica and alumina), supported with platinum and palladium, wherein the specific gravity of the Y zeolite in the support is from 10 to 90%. The disadvantages of this technique or the shortcomings with respect to the present invention: noble metal and molecular sieve are adopted, and the production cost is high.
Therefore, it is necessary to provide a high activity catalyst for the saturation of distillate aromatics.
Disclosure of Invention
The invention aims to solve the technical problem of developing a preparation method of a high-activity aromatic hydrocarbon saturation catalyst, which is used for aromatic hydrocarbon saturation of distillate oil, and is particularly suitable for producing No. 3 jet fuel with aromatic hydrocarbon content not more than 20.0v% and smoke point not less than 25.0mm by taking straight-run kerosene as a raw material.
In order to solve the problems, the invention provides a preparation method of a distillate aromatic hydrocarbon saturation catalyst, which is characterized in that an active metal guiding auxiliary agent is added in the preparation process of an active metal impregnating solution to guide active metal to generate an active stack which is favorable for aromatic hydrocarbon molecule adsorption on the surface of a carrier, so that the residence time and the reaction time of aromatic hydrocarbon molecules in raw oil on the catalyst are selectively prolonged, and the aromatic hydrocarbon saturation activity of the catalyst is greatly improved.
The preparation method of the distillate aromatic saturation catalyst comprises the following steps:
(1) Uniformly mixing pseudo-boehmite powder and sesbania powder, adding a peptizing agent and deionized water, kneading, extruding strips, drying and roasting to obtain a carrier;
(2) Preparing active metal impregnating solution, and adding active metal guiding auxiliary agents such as nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid and diethylenetriamine pentaacetic acid in the preparation process;
(3) And (3) dipping the carrier in the step (1) in the active metal dipping liquid in the step (2), drying and roasting in an oxygen-containing atmosphere to obtain the distillate aromatic saturated catalyst.
In the step (1), the proportions of the pseudo-boehmite powder, the sesbania powder, the peptizing agent and the deionized water are (100-300): (5-20): (4-18): (80-260).
The invention relates to a preparation method of a distillate aromatic saturation catalyst, wherein the peptizing agent is citric acid and nitric acid.
The active metal is at least one of Co, mo, ni and W.
In the step (2), the mass ratio of the nitrilotriacetic acid, the cyclohexanediamine tetraacetic acid, the citric acid, the diethylenetriamine pentaacetic acid and the active metal Mo, ni, W, co is (10-35): (13-42): (28-65): (8-47): (150-1200): (50-500): (200-1800): (50-500).
The preparation method of the distillate aromatic saturation catalyst comprises the following steps of (14-33) mass ratio of nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid, diethylenetriamine pentaacetic acid to active metal: (16-37): (31 to 59): (11-43): (200-1000): (80-300): (400-1500): (80-300).
In the step (3), the drying temperature is 50-150 ℃, the time is 2-40 h, the roasting temperature is 300-600 ℃, and the time is 2-20 h.
The preparation method of the distillate aromatic saturated catalyst provided by the invention has the advantages that the drying temperature is 50-120 ℃, the time is 2-20 h, the roasting temperature is 300-500 ℃, and the time is 2-10 h.
In the step (1), the drying temperature is 50-150 ℃ and the time is 2-40 h; the roasting temperature is 300-800 ℃ and the roasting time is 2-20 h.
The invention relates to a preparation method of a distillate aromatic saturation catalyst, wherein the carrier is gamma-Al 2 O 3 Supports or gamma-Al modified by Ti, mg, B, P auxiliary 2 O 3 A carrier; the Ti, mg, B, P auxiliary agent is added in the production process of pseudo-boehmite or in the extrusion process.
The invention can be further described as follows:
the preparation method of the supported non-noble metal hydrogenation catalyst with higher aromatic saturation activity comprises the following steps:
(1) Mixing pseudo-boehmite powder and a certain proportion of sesbania powder uniformly, adding peptizing agent, deionized water and the like, kneading, extruding strips, drying and roasting to obtain gamma-Al 2 O 3 Carrier or gamma-Al modified by Ti, mg, B, P auxiliary agent 2 O 3 A carrier.
(2) Preparing active metal impregnating solution by adopting one or more compounds in Co, mo, ni, W, and simultaneously adding substances such as nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid, diethylenetriamine pentaacetic acid and the like and active metal species according to a certain proportion to generate a precursor when preparing the impregnating solution. The preferable mass ratio of the four species of nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid and diethylenetriamine pentaacetic acid is (10-35): (13-42): (28-65): (8-47). The precursor is generated by substances such as nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid, diethylenetriamine pentaacetic acid and the like and active metal species, so that when the active metal is loaded on the surface of a carrier, an active stack which is favorable for the adsorption of aromatic hydrocarbon molecules is formed, the residence time and the reaction time of the aromatic hydrocarbon molecules in the raw oil on the catalyst are selectively prolonged, and the aromatic hydrocarbon saturation activity of the catalyst is greatly improved. More preferred mass ratios of the four species of nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid, diethylenetriamine pentaacetic acid are (14 to 33): (16-37): (31 to 59): (11-43).
(3) And (3) impregnating the carrier obtained in the step (1) by adopting the impregnating solution in the step (2), drying and roasting in an oxygen-containing atmosphere to obtain a catalyst finished product. The drying process is carried out at 50-150 ℃ for 2-40 h. The roasting process is carried out for 2 to 20 hours at the temperature of 300 to 600 ℃. More preferred conditions are: drying at 50-120 deg.c for 2-20 hr and roasting at 300-500 deg.c for 2-10 hr.
The invention discloses a preparation method of a distillate aromatic saturation catalyst, wherein one or more of Co, mo, ni, W are contained in an active metal component of the catalyst. In the preparation process of the catalyst, substances such as nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid, diethylenetriamine pentaacetic acid and the like are added into the impregnating solution according to a certain proportion, so that active metals are guided to generate active stacks which are favorable for adsorption of aromatic hydrocarbon molecules on the surface of a carrier, the residence time and the reaction time of the aromatic hydrocarbon molecules in the raw oil on the catalyst are selectively prolonged, and the aromatic hydrocarbon saturation activity of the catalyst is greatly improved.
The substances such as nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid, diethylenetriamine pentaacetic acid and the like with a certain proportion can form a complex with the active metal ions such as Co, mo, ni, W and the like in a solution. The formation of the complex has a great influence on the structure of the active metal species, so that the number of stacked layers and the edge length of the complex are changed, an active phase with a high stacking state and a small sheet length can be generated at a certain concentration, and a more suitable physical and chemical environment is provided for the arene saturation reaction. On the other hand, the formation of the complex has the functions of viscosity and anchoring to the active metal, and prevents the active metal from surface aggregation and migration during the drying and roasting processes to form oversized particle metal, thereby improving the utilization efficiency of the active metal.
The catalyst prepared by the invention is characterized in that: by adding the active metal guiding auxiliary agent into the impregnating solution, the active metal is guided to be loaded on the surface of the carrier in a stacking mode to form an active stack with a specific morphology, the residence time and the reaction time of aromatic hydrocarbon molecules in the raw oil are prolonged, and the conversion of the aromatic hydrocarbon molecules into naphthene hydrocarbon molecules is promoted, so that the aim of aromatic hydrocarbon saturation is fulfilled.
Drawings
FIG. 1 is a drawing showing a transmission electron micrograph of the catalyst of example 1.
FIG. 2 is a drawing showing a transmission electron micrograph of the catalyst of example 2.
FIG. 3 is a drawing showing a transmission electron micrograph of the catalyst of example 3.
FIG. 4 is a drawing showing a transmission electron micrograph of the catalyst of comparative example 1.
FIG. 5 is a drawing showing a transmission electron micrograph of the catalyst of comparative example 2.
FIG. 6 is a drawing showing a transmission electron micrograph of the catalyst of comparative example 3.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
Example 1:
(1)γ-Al 2 O 3 preparation of the Carrier
Weighing 1000g of pseudo-boehmite powder, 55g of sesbania powder, 25g of citric acid and 650mL of 3-5% dilute nitric acid, uniformly mixing, extruding and molding by a strip extruder, drying at 110 ℃ for 10 hours, roasting at 520 ℃ under air atmosphere to obtain gamma-Al 2 O 3 A carrier.
(2) Preparing Mo-Ni impregnating solution containing active metal guiding auxiliary agent
500g of deionized water was weighed, 8.5g of concentrated phosphoric acid was added thereto, and the temperature was raised to 75℃with stirring, and 185g of molybdenum trioxide and 68g of basic nickel carbonate were added thereto. After the solution is completely dissolved and is in a transparent state, 3.3g of nitrilotriacetic acid, 4.7g of cyclohexanediamine tetraacetic acid, 10.4g of citric acid and 5.2g of diethylenetriamine pentaacetic acid are added, the temperature is raised to 90 ℃ and the temperature is kept for 4 hours. And after the constant temperature is finished, naturally cooling to room temperature, and fixing the volume to 700mL by using deionized water for standby.
(3)Mo-Ni/γ-Al 2 O 3 Preparation of the catalyst
Weighing 500g of the carrier prepared in the step (1), weighing 350mL of the impregnating solution prepared in the step (2), carrying out isovolumetric impregnation for 60 minutes, drying at 110 ℃ for 4 hours, and roasting at 480 ℃ for 8 hours to obtain a catalyst finished product.
Example 2:
(1) Ti-containing gamma-Al 2 O 3 Preparation of the Carrier
Weighing 950g of pseudo-boehmite powder, 50g of meta-titanic acid, 55g of sesbania powder, 25g of citric acid and 660mL of 3-5% dilute nitric acid, uniformly mixing, extruding and molding by a strip extruder, drying at 120 ℃ for 10 hours, roasting at 520 ℃ in air atmosphere to obtain Ti-containing gamma-Al 2 O 3 A carrier.
(2) Preparing W-Ni impregnating solution containing active metal guiding auxiliary agent
500g of deionized water was weighed out, and 247g of ammonium metatungstate and 178g of nickel nitrate were added thereto while stirring. After the solution is completely dissolved and is in a transparent state, the temperature is raised to 95 ℃, 7.8g of nitrilotriacetic acid, 5.9g of cyclohexanediamine tetraacetic acid, 7.3g of citric acid and 2.6g of diethylenetriamine pentaacetic acid are added, and the temperature is kept for 7.5 hours. And after the constant temperature is finished, naturally cooling to room temperature, and fixing the volume to 700mL for later use.
(3)W-Ni/γ-Al 2 O 3 Preparation of the catalyst
Weighing 500g of the carrier prepared in the step (1), weighing 360mL of the impregnating solution prepared in the step (2), carrying out isovolumetric impregnation for 55 minutes, drying at 105 ℃ for 4 hours, and roasting at 500 ℃ for 6 hours to obtain a catalyst finished product.
Example 3:
(1) Boron-containing gamma-Al 2 O 3 Preparation of the Carrier
Weighing 10Mixing 00g boron modified pseudo-boehmite powder, 50g sesbania powder, 13g citric acid and 3-5% dilute nitric acid 640mL uniformly, extruding and molding by a strip extruder, drying at 120 ℃ for 10h, roasting at 520 ℃ under air atmosphere to obtain gamma-Al containing B 2 O 3 A carrier.
(2) Preparing W-Mo-Ni impregnating solution containing active metal guiding auxiliary agent
500g of deionized water is weighed, 22g of phosphoric acid is added into the deionized water while stirring, the temperature is raised to 80 ℃, 65g of molybdenum trioxide and 78g of nickel nitrate are added, after the solution is completely dissolved, the temperature is reduced to 40 ℃ after the solution is in a transparent state, 167g of ammonium metatungstate is added and completely dissolved. Heating to 95 ℃, adding 3.3g of nitrilotriacetic acid, 4.0g of cyclohexanediamine tetraacetic acid, 11.6g of citric acid and 4.7g of diethylenetriamine pentaacetic acid, and keeping the temperature for 9 hours. And after the constant temperature is finished, naturally cooling to room temperature, and fixing the volume to 700mL for later use.
(3)W-Mo-Ni/γ-Al 2 O 3 Preparation of the catalyst
Weighing 500g of the carrier prepared in the step (1), weighing 355mL of the impregnating solution prepared in the step (2), impregnating for 75 minutes in an equal volume, drying for 4 hours at 115 ℃, and roasting for 5 hours at 500 ℃ to obtain a catalyst finished product.
Example 4:
(1) Mg-containing gamma-Al 2 O 3 Preparation of the Carrier
Weighing 1000g of Mg modified pseudo-boehmite powder, 50g of sesbania powder, 13g of citric acid and 640mL of 3-5% dilute nitric acid, uniformly mixing, extruding and molding by a strip extruder, drying at 120 ℃ for 10 hours, roasting at 520 ℃ in air atmosphere to obtain the gamma-Al containing Mg 2 O 3 A carrier.
(2) Preparing Mo-Co impregnating solution containing active metal guiding auxiliary agent
500g of deionized water is weighed, 24g of phosphoric acid is added into the deionized water while stirring, the temperature is raised to 80 ℃, 215g of molybdenum trioxide and 78g of cobalt nitrate are added, the temperature is raised to 95 ℃, 3.3g of nitrilotriacetic acid, 4.0g of cyclohexanediamine tetraacetic acid, 11.6g of citric acid and 4.7g of diethylenetriamine pentaacetic acid are added until the solution is completely dissolved, and the constant temperature is continued for 9 hours. After the solution was in a transparent state, the temperature was reduced to 40 ℃. And after the constant temperature is finished, naturally cooling to room temperature, and fixing the volume to 700mL for later use.
(3)Mo-Co/γ-Al 2 O 3 Preparation of the catalyst
Weighing 500g of the carrier prepared in the step (1), weighing 355mL of the impregnating solution prepared in the step (2), impregnating for 75 minutes in an equal volume, drying for 4 hours at 115 ℃, and roasting for 5 hours at 500 ℃ to obtain a catalyst finished product.
Example 5:
(1) P-containing gamma-Al 2 O 3 Preparation of the Carrier
Weighing 1000g P modified pseudo-boehmite powder, 52g of sesbania powder, 14g of citric acid and 630mL of 3-5% dilute nitric acid, uniformly mixing, extruding and molding by a strip extruder, drying at 120 ℃ for 10 hours, roasting at 520 ℃ in air atmosphere to obtain gamma-Al containing P 2 O 3 A carrier.
(2) Preparing Mo-Co impregnating solution containing active metal guiding auxiliary agent
500g of deionized water is weighed, 24g of phosphoric acid is added into the deionized water while stirring, the temperature is raised to 80 ℃, 215g of molybdenum trioxide and 78g of cobalt nitrate are added, the temperature is raised to 95 ℃, 3.5g of nitrilotriacetic acid, 1.3g of cyclohexanediamine tetraacetic acid, 2.8g of citric acid and 2.4g of diethylenetriamine pentaacetic acid are added until the solution is completely dissolved, and the constant temperature is continued for 9 hours. After the solution was in a transparent state, the temperature was reduced to 40 ℃. And after the constant temperature is finished, naturally cooling to room temperature, and fixing the volume to 700mL for later use.
(3)Mo-Co/γ-Al 2 O 3 Preparation of the catalyst
Weighing 500g of the carrier prepared in the step (1), weighing 355mL of the impregnating solution prepared in the step (2), impregnating for 75 minutes in an equal volume, drying for 4 hours at 115 ℃, and roasting for 5 hours at 500 ℃ to obtain a catalyst finished product.
Comparative example 1:
(1)γ-Al 2 O 3 preparation of the Carrier
Weighing 1000g of pseudo-boehmite powder, 55g of sesbania powder, 25g of citric acid and 650mL of 3-5% dilute nitric acid, uniformly mixing, extruding and molding by a strip extruder, drying at 110 ℃ for 10 hours, roasting at 520 ℃ under air atmosphere to obtain gamma-Al 2 O 3 A carrier.
(2) Preparing an impregnating solution containing active metal Mo-Ni
500g of deionized water was weighed, 8.5g of concentrated phosphoric acid was added thereto, and the temperature was raised to 75℃with stirring, and 185g of molybdenum trioxide and 68g of basic nickel carbonate were added thereto. After the solution is completely dissolved and is in a transparent state, naturally cooling to room temperature, and fixing the volume to 700mL for standby.
(3)Mo-Ni/γ-Al 2 O 3 Preparation of the catalyst
Weighing 500g of the carrier prepared in the step (1), weighing 350mL of the impregnating solution prepared in the step (2), carrying out isovolumetric impregnation for 60 minutes, drying at 110 ℃ for 4 hours, and roasting at 480 ℃ for 8 hours to obtain a catalyst finished product.
Comparative example 2:
(1) Ti-containing gamma-Al 2 O 3 Preparation of the Carrier
Weighing 950g of pseudo-boehmite powder, 50g of meta-titanic acid, 55g of sesbania powder, 25g of citric acid and 660mL of 3-5% dilute nitric acid, uniformly mixing, extruding and molding by a strip extruder, drying at 120 ℃ for 10h, roasting at 520 ℃ in air atmosphere to obtain Ti-containing gamma-Al 2 O 3 A carrier.
(2) Preparing impregnation liquid containing active metal W-Ni
500g of deionized water was weighed out, and 247g of ammonium metatungstate and 178g of nickel nitrate were added thereto while stirring. After the solution is completely dissolved and is in a transparent state, the volume is fixed to 700mL for standby.
(3)W-Ni/γ-Al 2 O 3 Preparation of the catalyst
Weighing 500g of the carrier prepared in the step (1), weighing 360mL of the impregnating solution prepared in the step (2), carrying out isovolumetric impregnation for 55 minutes, drying at 105 ℃ for 4 hours, and roasting at 500 ℃ for 6 hours to obtain a catalyst finished product.
Comparative example 3:
(1) Boron-containing gamma-Al 2 O 3 Preparation of the Carrier
Weighing 1000g of boron modified pseudo-boehmite powder, 50g of sesbania powder, 13g of citric acid and 640mL of 3-5% dilute nitric acid, uniformly mixing, extruding and molding by a strip extruder, drying at 120 ℃ for 10 hours, roasting at 520 ℃ in air atmosphere to obtain gamma-Al containing B 2 O 3 A carrier.
(2) Preparing active metal-containing W-Mo-Ni impregnating solution
500g of deionized water is weighed, 22g of phosphoric acid is added into the deionized water while stirring, the temperature is raised to 80 ℃, 65g of molybdenum trioxide and 78g of nickel nitrate are added, after the solution is completely dissolved, the temperature is reduced to 40 ℃ after the solution is in a transparent state, 167g of ammonium metatungstate is added and completely dissolved, the solution is naturally cooled to room temperature, and the volume is fixed to 700mL for standby.
(3)W-Mo-Ni/γ-Al 2 O 3 Preparation of the catalyst
Weighing 500g of the carrier prepared in the step (1), weighing 355mL of the impregnating solution prepared in the step (2), impregnating for 75 minutes in an equal volume, drying for 4 hours at 115 ℃, and roasting for 5 hours at 500 ℃ to obtain a catalyst finished product.
Examples 1 and comparative examples 1, 2 and 2, and examples 3 and 3, respectively, each of which was added with a metal active guiding aid in a certain proportion, and each of which was not added with a metal active guiding aid.
The transmission electron micrographs of the catalysts prepared in examples 1 to 3 and comparative examples 1 to 3 above are shown in FIGS. 1 to 6. As can be seen from the figure, the catalyst surface prepared according to the method of the present invention has a remarkable stacked structure, whereas the catalyst surface active metal prepared by the conventional method is in a uniformly dispersed state, and the structure is not found.
The catalysts prepared in the examples and comparative examples were evaluated for hydrogenation activity on a 200mL scale, and the raw oil was evaluated as a poor kerosene of a petrochemical company. The properties of the raw oil and the evaluation results of examples are shown in Table 1, and the evaluation results of comparative examples are shown in Table 2. As can be seen from tables 1 and 2, the hydrogenation activity of the catalysts of the examples was significantly improved, the aromatic hydrocarbon saturation ratio and smoke point were increased more, and the desulfurization and denitrification rates were also higher, as compared with the three comparative examples.
Table 1 results of evaluation of catalyst Activity
Table 2 comparative catalyst Activity evaluation results
Note that: (1) vulcanization conditions: the catalyst is firstly presulfided for 20 hours under the pressure of 7.0MPa by kerosene containing 2 omega% of carbon disulfide under the hydrogen atmosphere of 330 ℃, and then raw materials are fed;
(2) Reaction conditions: the reaction temperature is 330 ℃, the pressure is 6.0MPa, and the space velocity (volume) is 1.5h -1 Hydrogen oil (volume) ratio 400.
Claims (10)
1. The preparation method of the distillate aromatic saturation catalyst is characterized by comprising the following steps of:
(1) Mixing pseudo-boehmite powder and sesbania powder uniformly, adding peptizing agent and deionized water, kneading, extruding, drying and roasting to obtain gamma-Al 2 O 3 A carrier;
(2) Preparing active metal impregnating solution, and adding active metal guiding auxiliary agents such as nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid and diethylenetriamine pentaacetic acid in the preparation process;
(3) And (3) dipping the carrier in the step (1) in the active metal dipping liquid in the step (2), drying and roasting in an oxygen-containing atmosphere to obtain the distillate aromatic saturated catalyst.
2. The method for preparing a distillate aromatic saturation catalyst according to claim 1, wherein in the step (1), the proportions of pseudo-boehmite powder, sesbania powder, peptizing agent and deionized water are (100 to 300): (5-20): (4-18): (80-260).
3. The method for preparing a distillate aromatic saturation catalyst according to claim 1, wherein the peptizing agent is citric acid or nitric acid.
4. The method for producing a distillate aromatic hydrocarbon saturation catalyst according to claim 1, wherein the active metal is at least one of Co, mo, ni, and W.
5. The method for producing a distillate aromatic hydrocarbon saturation catalyst according to claim 4, wherein in the step (2), the mass ratio of the nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid, diethylenetriamine pentaacetic acid and the active metal Mo, ni, W, co is (10 to 35): (13-42): (28-65): (8-47): (150-1200): (50-500): (200-1800): (50-500).
6. The method for preparing a distillate aromatic hydrocarbon saturation catalyst according to claim 5, wherein the mass ratio of nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, citric acid, diethylenetriamine pentaacetic acid and active metal Mo, ni, W, co is (14 to 33): (16-37): (31 to 59): (11-43): (200-1000): (80-300): (400-1500): (80-300).
7. The method for preparing a distillate aromatic saturated catalyst according to claim 1, wherein in the step (3), the drying temperature is 50-150 ℃ for 2-40 hours, the baking temperature is 300-600 ℃ for 2-20 hours.
8. The process for preparing a catalyst for saturation of aromatic hydrocarbon with distillate oil according to claim 7, wherein the drying temperature is 50 to 120 ℃ for 2 to 20 hours, the baking temperature is 300 to 500 ℃ for 2 to 10 hours.
9. The method for preparing a distillate aromatic saturation catalyst according to claim 1, wherein in the step (1), the drying temperature is 50-150 ℃ and the time is 2-40 h; the roasting temperature is 300-800 ℃ and the roasting time is 2-20 h.
10. The distillate aromatic saturation of claim 1And a process for preparing a catalyst, characterized in that the carrier is gamma-Al 2 O 3 Supports or gamma-Al modified by Ti, mg, B, P auxiliary 2 O 3 A carrier; the Ti, mg, B, P auxiliary agent is added in the production process of pseudo-boehmite or in the extrusion process.
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