A reforming oil hydrodeolefination catalyst and its preparation method

Abstract

The present invention provides a reforming oil hydrodeolefination catalyst, with alumina as a carrier, on which a molecular sieve and an active component are loaded, the active component including Ni and an auxiliary metal, the auxiliary metal being selected from at least one of Mo, Co and W, and based on the total weight of the catalyst, the molecular sieve accounts for 1 12%, the Ni content is 5 20%, and the auxiliary metal is 1 10% in terms of a simple substance, and the molecular sieve is loaded on the outer surface of the catalyst. By first impregnating a carrier alumina with a solution containing an organic auxiliary agent and an auxiliary metal salt, drying and calcining under an inert atmosphere, then loading nickel, drying and calcining under an inert atmosphere, and then introducing a molecular sieve, and obtaining a catalyst after reduction treatment. The molecular sieve utilization rate in the catalyst is higher, which is conducive to giving full play to the ability of the molecular sieve to adsorb olefins and provide H protons, thereby improving the hydrogenation activity of the catalyst; compared with preparing the carrier by kneading a molecular sieve and alumina powder, the utilization rate of the molecular sieve is improved, the amount of the molecular sieve is reduced, thereby reducing the catalyst cost.

Description

Technical Field

[0001] The present invention relates to the technical field of oil hydrogenation, and in particular to a catalyst for selective hydrogenation and deolefination of reformed oil and a preparation method thereof. Background Art

[0002] Catalytic reforming is a key process for producing aromatics and high-octane gasoline fractions. With the development and application of high-performance reforming catalysts and advances in reforming technology, the operating requirements of the plant have increased. This has resulted in a significant increase in the olefin content of the reformate oil, while increasing aromatics production. Trace olefins can easily polymerize to form macromolecular compounds or form byproducts during downstream processing, complicating the subsequent processing of aromatics. Therefore, olefin impurities in the reformate oil must be thoroughly removed. Currently, methods for removing olefins from reformate oil primarily include clay refining and hydrorefining. Traditional clay refining processes have low olefin removal activity and poor stability, requiring frequent replacement. Furthermore, deactivated clay cannot be recycled and must be disposed of in landfills, resulting in high clay usage and environmental pollution. Hydrorefining processes involve selective saturated hydrogenation of olefins using a catalyst, primarily employing precious metal catalysts. These catalysts offer high activity, high throughput, and excellent selectivity, making them widely used for selective hydrorefining of reformate oil. However, they also suffer from disadvantages such as high cost, excessive initial catalyst activity, and significant aromatics losses. Therefore, it is necessary to develop non-precious metal catalysts with high activity and selectivity to reduce costs and meet the needs of industrial production.

[0003] CN1394937A discloses a method for saturated hydrogenation of olefins in reformed oil. The reformed oil is contacted with hydrogen at a temperature of 200-320°C, a pressure of not less than 0.7 MPa, and a liquid hourly space velocity of 1-8 h -1 The hydrogen-to-oil ratio by volume is no less than 30. The catalyst used contains tungsten oxide and / or molybdenum oxide, nickel oxide, and cobalt oxide supported on an alumina carrier. This catalyst must be sulfurized before use. However, the hydrogen atmosphere used in the hydrogenation of reforming olefins does not contain sulfur. Sulfurized catalysts are easily deactivated by sulfur loss, and the high reaction temperature results in significant aromatics loss.

[0004] CN108636399A discloses a non-precious metal catalyst for selective hydrodeolefination of reformate oil. The catalyst comprises an active component oxide, a promoter oxide, and a carrier. The active component oxide is at least one oxide of Cu, Fe, Co, Mo, and Ni, used in an amount of 1-15% of the total catalyst weight. The promoter oxide is one oxide of Na or K, used in an amount of 0.5-10% by weight of the total catalyst weight. The catalyst reaction conditions are: temperature 150-250°C, pressure 1.0-3.0 MPa, and volume space velocity 1.0-6.0 h / min. -1, the hydrogen to oil volume ratio is 3-300. The catalyst needs to be sulfided before use, and the volume space velocity during the reaction is low, and the unit processing capacity of the raw materials is small.

[0005] CN110841650A discloses a non-precious metal catalyst for the selective hydrodeolefination of reformate oil and its preparation method. The catalyst comprises a carrier, an active component comprising nickel, a first auxiliary component comprising at least one of Group IVA or Group VA elements, and a second auxiliary component comprising a Group IIA element. The catalyst is used for the selective hydrodeolefination of reformate oil, resulting in a product bromine index of less than 50 mgBr / 100 g and an aromatics loss of less than 0.05 wt%. Although the product bromine index is low, the feedstock treated has a bromine index of approximately 2400 mgBr / 100 g, indicating a low olefin content in the feedstock. Summary of the Invention

[0006] In response to the deficiencies of the prior art, the present invention provides a reforming oil hydrogenation deolefination catalyst and a preparation method thereof, which uses non-precious metals as active components, is suitable for olefin hydrogenation reactions, has high olefin hydrogenation activity and selectivity, and is particularly suitable for reforming oil hydrogenation deolefination reactions.

[0007] The technical purpose of the first aspect of the present invention is to provide a reforming oil hydrodeolefination catalyst, which uses alumina as a carrier, on which a molecular sieve and an active component are loaded, the active component including Ni and a promoter metal, the promoter metal being selected from at least one of Mo, Co and W. Based on the total weight of the catalyst, the molecular sieve accounts for 1-12%, preferably 1-10%, and more preferably 2-8%; the Ni content is 5-20%, preferably 8-15%, and the promoter metal, calculated as a single substance, accounts for 1-10%, preferably 3-8%; the molecular sieve is loaded on the outer surface of the catalyst.

[0008] Furthermore, the Ni and the promoter metal in the catalyst exist in elemental form.

[0009] Furthermore, the molecular sieve loaded on the outer surface of the catalyst is loaded on Ni metal, and / or loaded on an auxiliary metal, and / or loaded on a carrier alumina.

[0010] Furthermore, the molecular sieve is at least one selected from the group consisting of Y-type molecular sieve, ZSM-5 molecular sieve, β-type molecular sieve, and MCM-22 molecular sieve. The molecular sieve can be commercially available or synthesized by existing methods, and the present invention is not particularly limited thereto.

[0011] The technical purpose of the second aspect of the present invention is to provide a method for preparing the above-mentioned reformed oil hydrodeolefination catalyst, comprising the following steps:

[0012] (1) impregnating a support alumina with a solution containing an organic additive and an additive metal salt, drying and calcining under an inert atmosphere to obtain a catalyst precursor A;

[0013] (2) loading nickel onto catalyst precursor A, drying and calcining under an inert atmosphere to obtain catalyst precursor B;

[0014] (3) introducing molecular sieves into catalyst precursor B, drying, and calcining;

[0015] (4) Reduction treatment to obtain the reformed oil hydrodeolefination catalyst.

[0016] Furthermore, the organic auxiliary agent in step (1) is an alcohol or organic acid having 2 to 10 carbon atoms and containing hydroxyl and / or carboxyl groups. Specifically, it is at least one selected from ethylene glycol, glycerol, butanediol, pentanediol, acetic acid, citric acid, malonic acid, succinic acid, and glutaric acid. The amount of the organic auxiliary agent added is 2 to 10 wt%, preferably 3 to 8 wt%, of the carrier alumina.

[0017] Furthermore, the auxiliary metal salt in step (1) is selected from nitrates, acetates or sulfates of Mo, Co and W, and the preparation method thereof is well known to those skilled in the art. Step (1) adopts an equal volume impregnation method.

[0018] Furthermore, the inert atmosphere in step (1) refers to an atmosphere that does not participate in the reaction, including but not limited to at least one of nitrogen, helium, argon and neon.

[0019] Furthermore, the drying conditions in step (1) include: a temperature of 20-90°C for 4-16 hours. The calcination conditions include: a temperature of 200-400°C for 3-8 hours; preferably, a temperature of 250-350°C for 3-5 hours.

[0020] Furthermore, step (2) is to load nickel on the catalyst precursor A by impregnation, and impregnate the catalyst precursor A with an impregnation solution containing a nickel salt. The nickel salt is selected from at least one of nickel nitrate, nickel acetate and nickel sulfate, and its preparation method is well known to those skilled in the art, and is used in the form of equal volume impregnation or supersaturated impregnation.

[0021] Furthermore, the drying conditions in step (2) are: drying temperature 60-100° C., drying time 3-6 hours, and the roasting conditions are: roasting temperature 200-300° C., roasting time 3-6 hours.

[0022] Furthermore, the amounts of the catalyst precursor B and the molecular sieve are such that the content of the molecular sieve in the prepared catalyst is 1-12 wt %, preferably 1-10 wt %, and more preferably 2-8 wt %, based on the total weight of the catalyst. The range of the molecular sieve type selected in step (3) can be the same as the range of the molecular sieve type selected in the hydrogenation catalyst described in the first aspect above, and the present invention will not be repeated here.

[0023] Furthermore, the method of introducing the molecular sieve into the catalyst precursor in step (3) is not particularly limited, and the catalyst precursor and the molecular sieve may be directly mixed, or the catalyst precursor and the molecular sieve precursor may be mixed and then subjected to hydrothermal treatment.

[0024] Preferably, the method of introducing the molecular sieve into the catalyst precursor in step (3) is carried out in at least one of the following ways:

[0025] (a) subjecting the catalyst precursor and the molecular sieve precursor to hydrothermal treatment, and performing the drying and calcining as described in step (3);

[0026] (b) mixing the catalyst precursor with the ball-milled molecular sieve in the presence of a solvent, and then performing the drying and calcining as described in step (3).

[0027] According to the present invention, it is understood that the molecular sieve precursor can be a gel formed by hydrothermal treatment to produce the above-mentioned molecular sieve. Preferably, in method (a), the molecular sieve precursor comprises a gel formed by mixing a silicon source and / or an aluminum source, a precipitant, a template, and water. The preparation method is well known to those skilled in the art, and the molecular sieve can be formed by precipitation or sol-gel method.

[0028] Furthermore, the types of the silicon source and / or aluminum source, precipitant, and template are well known to those skilled in the art. The silicon source is preferably selected from at least one of sodium silicate, tetraethyl orthosilicate, silica sol, and chromatographic silica gel. The aluminum source is preferably selected from at least one of sodium metaaluminate, aluminum hydroxide, and pseudo-boehmite; and the precipitant is preferably selected from at least one of sodium hydroxide, aqueous ammonia, and potassium hydroxide. The template is preferably selected from at least one of hexadecyltrimethylammonium bromide, ethylenediamine, n-butylamine, tetrapropylammonium bromide, ethanol, tetraethylammonium hydroxide, tetraethylammonium bromide, triethylamine, di-n-propylamine, diisopropylamine, and methylcellulose.

[0029] Furthermore, when the molecular sieve is a silica-alumina molecular sieve, preferably, the molar composition of the gel is n(SiO2):n(Al2O3):n(Na2O):n(template):n(H2O)=(5-30):1:(1-10):(1-10):(100-300).

[0030] Furthermore, when the molecular sieve is an all-silicon molecular sieve, preferably, the molar composition of the gel is n(SiO2):n(Na2O):n(template):n(H2O)=100:(10-30):(10-30):(1500-3000).

[0031] The present invention has a wide range of conditions for the hydrothermal treatment, based on the ability to obtain the molecular sieve. Preferably, the hydrothermal treatment conditions include: temperature of 90-200°C, preferably 120-200°C; pressure of 0.1-2MPa, pH of 7.5-9, and time of 5-48 hours.

[0032] Furthermore, in method (b), the particle size of the molecular sieve after ball milling is 0.1-10 nm, more preferably 0.1-5 nm. This preferred embodiment is more conducive to the effectiveness of the molecular sieve. The present invention does not specifically limit the parameters and equipment of the ball milling.

[0033] Furthermore, the drying conditions in step (3) are: drying temperature 90-200° C., drying time 3-6 hours, and the roasting conditions are: roasting temperature 300-550° C., roasting time 3-6 hours.

[0034] Furthermore, the reduction treatment method described in step (4) is well known to those skilled in the art, and the specific conditions are: reduction with hydrogen-containing gas, reduction temperature of 200-550°C, reduction pressure of 0.1-4.0 MPa, and reduction time of 3-10 hours.

[0035] The technical purpose of the third aspect of the present invention is to provide a hydrotreatment process for reformed oil, wherein the oil product is contacted and reacted with the above-mentioned reformed oil hydrodeolefination catalyst or the reformed oil hydrodeolefination catalyst prepared by the above-mentioned method.

[0036] Furthermore, in the above-mentioned hydrotreatment process, the catalyst catalyzes the hydrodeolefination of the reforming oil, and the reaction temperature is 130-250°C, preferably 150-190°C; the pressure is 0.1-3.0 MPa; and the volume ratio of hydrogen to feedstock oil is 10-1000.

[0037] The catalyst of the present invention can effectively remove olefins from reformed oil with a bromine index higher than 3000 mgBr / 100 g oil, has a good selective deolefination effect, and has a small loss of aromatics.

[0038] Compared with the prior art, the catalyst of the present invention has the following advantages:

[0039] (1) In the catalyst of the present invention, the molecular sieve is loaded on the outer surface of the catalyst, the molecular sieve interacts with the active metal, and the molecular sieve is more exposed, thereby having a higher utilization rate, which is conducive to giving full play to the ability of the molecular sieve to adsorb olefins and provide H protons, thereby improving the hydrogenation activity of the catalyst; compared with the preparation of the carrier by mixing molecular sieve and alumina powder, the utilization rate of the molecular sieve is improved, the amount of molecular sieve used is reduced, and the cost of the catalyst is reduced.

[0040] (2) In the preparation method of the present invention, an inert carbon surface layer is formed on the surface of the carrier by adding an organic additive to the impregnation solution and drying and calcining under an inert atmosphere. This can reduce the affinity between the molecular sieve and the carrier when the molecular sieve is introduced, allowing more molecular sieves to directly react with the metal, thereby improving the hydrogenation activity of the catalyst.

[0041] (3) In the preparation method of the present invention, the catalyst is prepared by pretreating the carrier with organic additives and additive metals, then loading the active metal Ni, and finally loading the molecular sieve. The organic additives and additive metals can modify the high active sites on the surface of the carrier, weaken the interaction between Ni and the carrier, and improve the dispersion of Ni. In addition, the inert carbon surface layer formed by the organic additive on the surface of the carrier allows Ni to interact more with the additive metal and the molecular sieve and the metal together, which is more conducive to the synergistic effect of the additive metal and the utilization rate of the molecular sieve, thereby improving the activity and selectivity of the catalyst. The direct interaction between the molecular sieve and the metal can also modify the metal active center with higher activity, slow down carbon deposition, and improve the selectivity and stability of the catalyst.

[0042] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0043] The method of the present invention is further described in detail below through examples. The examples are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operating processes, but the scope of protection of the present invention is not limited to the following examples.

[0044] Example 1

[0045] (1) An aqueous solution containing ammonium heptamolybdate and glycerol (5% of the weight of the carrier) was impregnated into an alumina carrier in equal volumes, and then dried at 90°C for 4 hours in a N2 atmosphere and calcined at 350°C for 3 hours to obtain a catalyst precursor A.

[0046] (2) Impregnating the nickel nitrate solution into the catalyst precursor A prepared in step (1), then drying at 90° C. for 3 h in a N 2 atmosphere, and then calcining at 300° C. for 5 h to obtain the catalyst precursor B.

[0047] (3) Sodium hydroxide, silica sol, sodium aluminate and ethylenediamine are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(ethylenediamine):n(H2O)=10:1:5:2:160, and stirred to form a uniform sol, i.e., a precursor of Y molecular sieve, and then mixed with the catalyst precursor B prepared in step (2), and then hydrothermally treated at 160°C for 15h; then filtered, washed with deionized water until neutral, dried at 110°C for 3h, and calcined at 450°C for 3h.

[0048] (4) Hydrogen was used for reduction treatment at a reduction temperature of 400° C., a reduction pressure of 2.0 MPa, and a reduction time of 5 hours to obtain catalyst C-1.

[0049] The weight percentages of the components in catalyst C-1 are as follows: Ni is 15.2%, Mo is 5.0%, Y molecular sieve is 3.5%, and the rest is alumina carrier.

[0050] Example 2

[0051] (1) An aqueous solution containing cobalt nitrate and ethylene glycol (4% of the weight of the carrier) was impregnated into an alumina carrier in equal volumes, and then dried at 80°C for 5 hours in a N2 atmosphere and calcined at 300°C for 4 hours to obtain a catalyst precursor A.

[0052] (2) The catalyst precursor A prepared in step (1) was impregnated with a nickel nitrate solution, and then dried at 80° C. for 5 h in a N 2 atmosphere, and then calcined at 300° C. for 5 h to obtain a catalyst precursor B.

[0053] (3) Add silica sol, sodium aluminate, sodium hydroxide and n-butylamine to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(n-butylamine):n(H2O)=25:1:8:6:240, and stir until a uniform sol is formed, i.e., a precursor of ZSM-5 molecular sieve, and then mix it with the catalyst precursor B prepared in step (2), and then hydrothermally treat it at 150°C for 15h; then filter, wash with deionized water until neutral, dry at 110°C for 5h, and calcine at 450°C for 3h.

[0054] (4) Hydrogen was used for reduction treatment at a reduction temperature of 400° C., a reduction pressure of 3.0 MPa, and a reduction time of 5 hours to obtain catalyst C-2.

[0055] The weight percentages of the components in catalyst C-2 are: Ni is 12.1%, Co is 6.3%, ZSM-5 molecular sieve is 3.7%, and the rest is alumina support.

[0056] Example 3

[0057] (1) An aqueous solution containing ammonium metatungstate and citric acid (7% of the weight of the carrier) was impregnated into an alumina carrier in equal volumes, and then dried at 70°C for 5 hours in a N2 atmosphere and calcined at 350°C for 3 hours to obtain a catalyst precursor A.

[0058] (2) Impregnating the nickel nitrate solution into the catalyst precursor A prepared in step (1), drying the catalyst precursor A at 90° C. for 4 h in a N 2 atmosphere, and calcining the catalyst precursor B at 300° C. for 5 h.

[0059] (3) Sodium hydroxide, silica sol, pseudo-boehmite and tetraethylammonium bromide are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(tetraethylammonium bromide):n(H2O)=30:1:7:9:480, and stirred to form a uniform sol, i.e., a precursor of β molecular sieve, and then mixed with the catalyst precursor B prepared in step (2), and then hydrothermally treated at 150°C for 20h; then filtered, washed with deionized water until neutral, dried at 110°C for 5h, and calcined at 540°C for 3h.

[0060] (4) Hydrogen was used for reduction treatment at a reduction temperature of 450° C., a reduction pressure of 3.0 MPa, and a reduction time of 6 hours to obtain catalyst C-3.

[0061] The weight percentages of the components in catalyst C-3 are as follows: Ni is 17.2%, W is 3.2%, β molecular sieve is 4.0%, and the rest is alumina carrier.

[0062] Example 4

[0063] (1) An aqueous solution containing ammonium heptamolybdate and acetic acid (7% of the weight of the carrier) was impregnated into an alumina carrier in equal volumes, and then dried at 80°C for 5 hours in a N2 atmosphere and calcined at 350°C for 4 hours to obtain a catalyst precursor A.

[0064] (2) The catalyst precursor A prepared in step (1) was impregnated with a nickel nitrate solution, and then dried at 100° C. for 3 h in a N 2 atmosphere, and then calcined at 300° C. for 5 h to obtain a catalyst precursor B.

[0065] (3) Sodium hydroxide, silica sol, sodium aluminate and hexamethyleneimine are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(hexamethyleneimine):n(H2O)=25:1:4:8:350, and stirred to form a uniform sol, i.e., a precursor of MCM-22 molecular sieve, and then mixed with the catalyst precursor B prepared in step (2), and then hydrothermally treated at 150°C for 24h; then filtered, washed with deionized water until neutral, dried at 110°C for 3h, and calcined at 500°C for 3h.

[0066] (4) Hydrogen was used for reduction treatment at a reduction temperature of 400° C., a reduction pressure of 3.0 MPa, and a reduction time of 4 hours to obtain catalyst C-4.

[0067] The weight percentages of the components in catalyst C-4 are as follows: Ni is 12.5%, Mo is 8.1%, MCM-22 molecular sieve is 3.5%, and the rest is alumina carrier.

[0068] Example 5

[0069] (1) An aqueous solution containing cobalt nitrate and malonic acid (5% of the weight of the carrier) was impregnated into an alumina carrier in equal volumes, followed by drying at 70°C for 6 hours in a N2 atmosphere and calcining at 350°C for 3 hours to obtain a catalyst precursor A.

[0070] (2) Impregnating the nickel nitrate solution into the catalyst precursor A prepared in step (1), drying the catalyst precursor A at 100° C. for 4 h in a N 2 atmosphere, and calcining the catalyst precursor B at 250° C. for 6 h.

[0071] (3) Sodium silicate, aluminum sulfate and tetrapropylammonium bromide are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(tetrapropylammonium bromide):n(H2O)=25:1:8:4:280, and stirred to form a uniform sol, i.e., a precursor of the ZSM-5 molecular sieve, and then mixed with the catalyst precursor B prepared in step (2), and then hydrothermally treated at 170°C for 10 hours; then filtered, washed with deionized water until neutral, dried at 110°C for 5 hours, and calcined at 500°C for 3 hours.

[0072] (4) Hydrogen was used for reduction treatment at a reduction temperature of 450° C., a reduction pressure of 1.0 MPa, and a reduction time of 6 hours to obtain catalyst C-5.

[0073] The weight percentages of the components in catalyst C-5 are as follows: Ni is 15.5%, Co is 5.4%, ZSM-5 molecular sieve is 3.9%, and the rest is alumina support.

[0074] Example 6

[0075] (1) An aqueous solution containing ammonium metatungstate and glycerol (the content is 6% of the weight of the carrier) is impregnated into an alumina carrier in equal volumes, and then dried at 80°C for 8 hours in a N2 atmosphere and calcined at 300°C for 5 hours to obtain a catalyst precursor A.

[0076] (2) Impregnating the nickel nitrate solution into the catalyst precursor A prepared in step (1), drying the catalyst precursor A at 100° C. for 5 h in a N 2 atmosphere, and calcining the catalyst precursor B at 280° C. for 6 h.

[0077] (3) Sodium silicate, sodium metaaluminate and ethanol are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(ethanol):n(H2O)=12:1:8:3:180, and stirred to form a uniform sol, i.e., a precursor of Y molecular sieve, and then mixed with the catalyst precursor B prepared in step (2), and then hydrothermally treated at 140°C for 20h; then filtered, washed with deionized water until neutral, dried at 110°C for 3h, and calcined at 500°C for 3h.

[0078] (4) Hydrogen was used for reduction treatment at a reduction temperature of 450° C., a reduction pressure of 3.0 MPa, and a reduction time of 5 hours to obtain catalyst C-6.

[0079] The weight percentages of the components in catalyst C-6 are as follows: Ni is 10.9%, W is 7.8%, Y molecular sieve is 5.2%, and the rest is alumina support.

[0080] Comparative Example 1

[0081] (1) Y molecular sieve is mixed evenly with alumina powder, nitric acid, starch, and deionized water, wherein the mass ratio of Y molecular sieve: alumina powder: nitric acid: starch: deionized water is 4.4:95.6:3:3:70, and then kneaded and extruded into strips, and then dried at 90°C for 3 hours and calcined at 650°C for 3 hours to obtain a modified alumina carrier.

[0082] (2) An aqueous solution containing ammonium heptamolybdate and glycerol (5% of the weight of the carrier) in equal volumes was impregnated into the modified alumina carrier, followed by drying at 90°C for 4 hours in a N2 atmosphere and calcining at 350°C for 3 hours to obtain a catalyst precursor.

[0083] (3) Impregnating the nickel nitrate solution into the catalyst precursor prepared in step (2), drying at 90°C in a N2 atmosphere for 3 hours, and then calcining at 300°C for 5 hours.

[0084] (4) Hydrogen was used for reduction treatment at a reduction temperature of 400° C., a reduction pressure of 2.0 MPa, and a reduction time of 5 hours to obtain a comparative catalyst DC-1.

[0085] The weight percentages of the components in the comparative catalyst DC-1 are as follows: Ni is 15.2%, Mo is 5.1%, Y molecular sieve is 3.5%, and the rest is alumina support.

[0086] Comparative Example 2

[0087] (1) An aqueous solution containing ammonium heptamolybdate and glycerol (5% of the weight of the carrier) was impregnated into an alumina carrier in equal volumes, and then dried at 90°C for 4 hours in a N2 atmosphere and calcined at 350°C for 3 hours to obtain a catalyst precursor.

[0088] (2) Impregnating the nickel nitrate solution into the catalyst precursor prepared in step (1), then drying at 90° C. for 3 h, and then calcining at 300° C. for 5 h.

[0089] (3) Hydrogen was used for reduction treatment at a reduction temperature of 400° C., a reduction pressure of 2.0 MPa, and a reduction time of 5 hours to obtain catalyst DC-2.

[0090] The weight percentages of the components in the comparative catalyst DC-2 are as follows: Ni is 15.2%, Mo is 5.0%, and the rest is alumina support.

[0091] Comparative Example 3

[0092] (1) A solution containing ammonium heptamolybdate, glycerol (5% of the weight of the carrier) and nickel nitrate was impregnated into an alumina carrier, then dried at 90°C for 3 hours and calcined at 300°C for 5 hours to obtain a catalyst precursor.

[0093] (2) Sodium hydroxide, silica sol, sodium aluminate and ethylenediamine are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(ethylenediamine):n(H2O)=10:1:5:2:160, and stirred to form a uniform sol, i.e., a precursor of Y molecular sieve, which is then mixed with the catalyst precursor prepared in step (1), and then hydrothermally treated at 160°C for 15h; then filtered, washed with deionized water until neutral, dried at 110°C for 3h, and calcined at 450°C for 3h.

[0094] (3) Hydrogen was used for reduction treatment at a reduction temperature of 400° C., a reduction pressure of 2.0 MPa, and a reduction time of 5 hours to obtain catalyst DC-3.

[0095] The weight percentages of the components in the catalyst DC-3 are as follows: Ni is 15.1%, Mo is 5.0%, Y molecular sieve is 3.5%, and the rest is alumina carrier.

[0096] Example 7

[0097] This example illustrates the performance of the catalyst provided by the present invention in the olefin hydrogenation reaction of reformed oil.

[0098] The raw oil used for evaluation was reformed oil provided by a refinery of Sinopec, with a bromine index of 3450 mgBr / 100 g and a total aromatics content of 72%.

[0099] The olefin hydrogenation performance of catalysts C-1 to C-6 and comparative examples DC-1 to DC-3 was evaluated using a 200 mL fixed-bed hydrogenation apparatus.

[0100] The reaction conditions for evaluation were: operating pressure 2.0 MPa, reaction temperature 170°C, hydrogen / oil volume ratio 100:1, and volume space velocity 10.0 h -1 , the evaluation results are shown in Table 1.

[0101] Table 1.

[0102] Catalyst No. Olefin removal rate, % Aromatic hydrocarbon loss, % C-1 94 0.21 C-2 85 0.18 C-3 93 0.23 C-4 90 0.19 C-5 88 0.20 C-6 83 0.17 DC-1 75 2.2 DC-2 69 1.7 DC-3 71 1.8

[0103] As can be seen from Table 1, the reformed oil hydrodeolefination catalyst of the present invention has higher olefin saturation activity and selectivity.

Claims

1. A catalyst for hydrodeolefination of reformed oil, characterized in that: Alumina is used as a carrier, on which a molecular sieve and an active component are loaded. The active component includes Ni and a promoter metal, and the promoter metal is selected from at least one of Mo, Co and W. Based on the total weight of the catalyst, the molecular sieve accounts for 1-12%, the Ni content is 5-20%, and the promoter metal as a single substance accounts for 1-10%; the molecular sieve is loaded on the outer surface of the catalyst; The catalyst is prepared by the following steps: (1) impregnating a support alumina with a solution containing an organic auxiliary agent and an auxiliary metal salt, drying and calcining under an inert atmosphere to obtain a catalyst precursor A, wherein the organic auxiliary agent is an alcohol and / or an organic acid having 2 to 10 carbon atoms; (2) Catalyst precursor A is loaded with nickel, dried and calcined under an inert atmosphere to obtain catalyst precursor B; (3) Introducing molecular sieves into catalyst precursor B, drying, and calcining; (4) Reduction treatment to obtain the reformed oil hydrodeolefination catalyst.

2. The reformed oil hydrodeolefination catalyst according to claim 1, characterized in that Based on the total weight of the catalyst, the molecular sieve accounts for 1-10%.

3. The reformed oil hydrodeolefination catalyst according to claim 2, characterized in that Based on the total weight of the catalyst, the molecular sieve accounts for 2-8%.

4. The reformed oil hydrodeolefination catalyst according to claim 1, characterized in that The Ni content is 8-15% based on the total weight of the catalyst.

5. The reformed oil hydrodeolefination catalyst according to claim 1, characterized in that Based on the total weight of the catalyst, the promoter metal is 3-8% in terms of elemental weight.

6. The reformed oil hydrodeolefination catalyst according to claim 1, characterized in that The Ni and promoter metals in the catalyst exist in elemental form.

7. The reformed oil hydrodeolefination catalyst according to claim 1, characterized in that The molecular sieve is loaded on the outer surface of the catalyst, which means that the molecular sieve is loaded on Ni metal, and / or the molecular sieve is loaded on an auxiliary metal, and / or the molecular sieve is loaded on a carrier alumina.

8. The reformed oil hydrodeolefination catalyst according to claim 1, characterized in that The molecular sieve is at least one selected from Y-type molecular sieve, ZSM-5 molecular sieve, β-type molecular sieve and MCM-22 molecular sieve.

9. The method for preparing the reformate hydrodeolefination catalyst according to any one of claims 1 to 8, comprising the following steps: (1) impregnating a support alumina with a solution containing an organic auxiliary agent and an auxiliary metal salt, drying and calcining under an inert atmosphere to obtain a catalyst precursor A, wherein the organic auxiliary agent is an alcohol and / or an organic acid having 2 to 10 carbon atoms; (2) Catalyst precursor A is loaded with nickel, dried and calcined under an inert atmosphere to obtain catalyst precursor B; (3) Introducing molecular sieves into catalyst precursor B, drying, and calcining; (4) Reduction treatment to obtain the reformed oil hydrodeolefination catalyst.

10. The preparation method according to claim 9, characterized in that The organic auxiliary agent in step (1) is selected from at least one of ethylene glycol, propylene glycol, butylene glycol, pentanediol, acetic acid, citric acid, malonic acid, succinic acid and glutaric acid.

11. The preparation method according to claim 10, characterized in that: The amount of the organic additive added is 2-10 wt% of the carrier alumina.

12. The preparation method according to claim 11, characterized in that The amount of the organic additive added is 3-8 wt % of the carrier alumina.

13. The preparation method according to claim 9, characterized in that The drying conditions in step (1) include: a temperature of 20-90° C. and a time of 4-16 hours; the roasting conditions include: a temperature of 200-400° C. and a time of 3-8 hours.

14. The preparation method according to claim 9, characterized in that The drying conditions of step (2) are: drying temperature 60-100°C, drying time 3-6 hours; the roasting conditions are: roasting temperature 200-300°C, roasting time 3-6 hours.

15. The preparation method according to claim 9, characterized in that The catalyst precursor B and the molecular sieve are used in such an amount that the content of the molecular sieve in the prepared catalyst is 1-12 wt % based on the total weight of the catalyst.

16. The preparation method according to claim 9, characterized in that The method of introducing the molecular sieve into the catalyst precursor B in step (3) is carried out in at least one of the following ways: (a) subjecting the catalyst precursor B and the molecular sieve precursor to hydrothermal treatment, and performing the drying and calcining as described in step (3); (b) In the presence of a solvent, the catalyst precursor B is mixed with the ball-milled molecular sieve, and then the mixture is dried and calcined as described in step (3).

17. The preparation method according to claim 16, characterized in that In method (a), the molecular sieve precursor includes a silicon source or a silicon source and an aluminum source, which are mixed with a precipitant, a template and water to form a gel.

18. The preparation method according to claim 17, characterized in that: The silicon source is selected from at least one of sodium silicate, ethyl orthosilicate, silica sol and chromatographic silica gel; the aluminum source is selected from at least one of sodium aluminate, aluminum hydroxide and pseudo-boehmite; the precipitant is selected from at least one of sodium hydroxide, ammonia water and potassium hydroxide; and the template is selected from at least one of hexadecyltrimethylammonium bromide, ethylenediamine, n-butylamine, tetrapropylammonium bromide, ethanol, tetraethylammonium hydroxide, tetraethylammonium bromide, triethylamine, di-n-propylamine, diisopropylamine and methylcellulose.

19. The preparation method according to claim 16, characterized in that The conditions of the hydrothermal treatment include: temperature of 90-200° C., pressure of 0.1-2 MPa, pH of 7.5-9, and time of 5-48 hours.

20. The preparation method according to claim 16, characterized in that In method (b), the particle size of the molecular sieve after ball milling is 0.1-10 nm.

21. A process for hydrotreating reformed oil, comprising contacting the oil with the reformed oil hydrodeolefination catalyst according to claim 1 for reaction.

22. The hydroprocessing process according to claim 21, characterized in that The reaction temperature is 130-250° C., the pressure is 0.1-3.0 MPa, and the volume ratio of hydrogen to raw oil is 10-1000.