Hydrogenation catalyst active metal impregnation liquid and preparation method thereof

Abstract

The invention provides a hydrogenation catalyst active metal impregnation liquid and a preparation method thereof, and the preparation method comprises the following steps: step 1, mixing a metal precursor, organic acid and hydrogen peroxide to form a metal solution; 2, the metal solution is mixed with a composite complexing agent, and metal impregnation liquid is obtained; wherein the composite complexing agent is a polycarboxylic acid scale inhibitor and an organic phosphorus-containing compound. The hydrogenation catalyst prepared from the metal impregnation liquid is good in activity stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of heavy oil residue treatment, in particular to a hydrogenation catalyst active metal impregnation solution and a preparation method thereof. BACKGROUND

[0002] Hydrogenation is a key technical means for refineries to produce high-quality clean oil, increase production of chemical raw materials, and improve heavy oil conversion capacity, and is a key path to address current pressures and challenges.

[0003] Catalysts are the core of oil hydrogenation technology and play a decisive role in the smooth and efficient operation of hydrogenation devices. For heavy oil and residue hydrogenation processes, catalyst activity stability is an important performance indicator. Residue oil is the heaviest and poorest component of petroleum, containing a large amount of gum and asphaltene, with high molecular weight, density, viscosity, and polarity, and high sulfur and carbon residue content, and it is rich in almost all metal impurities in petroleum. Catalysts are easily deactivated due to coking and metal deposition during residue oil hydrogenation treatment, affecting long-term operation. Therefore, in addition to good hydrogenation and impurity removal activity, the operating stability of residue oil hydrogenation treatment catalysts is crucial.

[0004] The activity stability of hydrogenation treatment catalysts is determined by the structure of the active phase, and the active metal needs to be highly dispersed on the surface of the carrier. Generally, the shorter the size of the active metal platelets, the fewer the layers, the better the dispersion, and the better the activity stability of the catalyst.

[0005] The dispersion state of the active metal of the hydrogenation catalyst is closely related to the loading method. Preparing an impregnation solution to load the active metal is the most common way. Therefore, the dispersion state of the active metal of the catalyst is directly related to the properties of the impregnation solution, especially the state of the metal in the solution. The preparation method, composition, pH value, and complexing agent of the impregnation solution all have important effects on the properties of the solution.

[0006] Patent CN1230491C discloses a preparation method of a catalyst impregnation solution, characterized in that 12-24w% ammonia solution is used to dissolve the salt containing VIB group metal or VIII group metal or their mixture during the preparation of the impregnation solution, and the solution is treated with ultrasonic waves during and / or after the dissolution process.

[0007] Patent CN114425354B discloses a preparation method of heavy oil hydrogenation catalyst, which prepares a water solution containing citric acid, phosphoric acid, amine compound, surfactant and at least one active metal as impregnation solution. When preparing the solution, first use phosphoric acid and citric acid to dissolve the compound containing molybdenum and nickel under heating conditions, then add amine compound and surfactant to obtain active metal impregnation solution. The impregnation solution of the invention has good stability, does not use volatile ammonia, and is environmentally friendly. However, the invention uses phosphoric acid to prepare the metal solution, which increases the acid content of the catalyst, the metal components in the solution exist in the form of heteropoly acid or isopoly acid salt, the content of two-dimensional aggregate octahedral molybdenum in the active phase structure is high, the metal dispersion is poor, and when processing poor residual oil feedstock, the catalyst is easy to coke and the hydrogenation activity stability is poor.

[0008] Patent CN103007949B discloses a preparation method of hydrogenation catalyst, which includes the following steps: dissolving the salts of group ⅥB metal and group Ⅷ metal in 10-45w%, preferably 30w% hydrogen peroxide solution to obtain impregnation solution, while adding binary organic carboxylic acid or ternary organic carboxylic acid (including citric acid, tartaric acid and oxalic acid) containing 2-12 carbons as dispersant to impregnate the carrier, then drying and calcining to obtain hydrogenation catalyst with double metal components. This method improves the dispersion of active components on the carrier and has good hydrogenation performance. However, this method uses high concentration of hydrogen peroxide to dissolve metal salts, which has certain safety hazards in drying and calcining links; in addition, the solution stability is poor, and decomposition and precipitation of metal components are easy to occur during impregnation and drying, which is not conducive to the efficient use of active metals.

[0009] With the increasing strictness of domestic environmental regulations, the demand for clean production technology of hydroprocessing catalysts is more urgent, and the traditional catalysts use ammonia-containing metal solution system in the production process, which produces a large amount of ammonia-containing gas in the production links such as solution preparation, impregnation, drying and calcination, which not only harms the health of workers in the workshop but also pollutes the atmospheric environment. The catalyst prepared by using acidic metal solution system has the problems of poor dispersion of active metal components and unstable activity of catalyst in the hydrogenation reaction process. Therefore, it is an urgent technical problem in the field to improve the preparation method of catalyst, construct a new ammonia-free acidic active metal solution system, solve the pollution problem of ammonia in the production process of catalyst, reduce the emission of pollutants, and ensure the safe, environmentally friendly and efficient production of catalyst plant. SUMMARY

[0010] The main purpose of the present application is to provide a hydrogenation catalyst active metal impregnation solution and a preparation method thereof, to overcome the defects of using acid and alkali to pollute the environment and poor dispersion of active components in the hydrogenation catalyst for residual oil in the prior art.

[0011] In order to achieve the above object, the present application provides a preparation method of a hydrogenation catalyst active metal impregnation solution, comprising the following steps:

[0012] Step 1, mixing a metal precursor, an organic acid and hydrogen peroxide to form a metal solution;

[0013] Step 2, mixing the metal solution with a composite complexing agent to obtain a metal impregnation solution;

[0014] Among them, the composite complexing agent is a polycarboxylic acid type scale inhibitor and an organic phosphorus-containing compound.

[0015] The preparation method of the hydrogenation catalyst active metal impregnation solution, wherein the polycarboxylic acid type scale inhibitor is at least one selected from polyepoxysuccinic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, maleic acid-acrylic acid copolymer, polyaspartic acid, acrylic acid-hydroxypropyl acrylate copolymer, acrylic acid-2-acrylamide-2-methylpropane sulfonic acid copolymer; and the organic phosphorus-containing compound is at least one selected from aminotri(methylene) phosphonic acid, diethylene triaminopenta(methylene) phosphonic acid, hydroxyethylidene diphosphonic acid, and ethylenediamine tetra(methylene) phosphonic acid.

[0016] The preparation method of the hydrogenation catalyst active metal impregnation solution, wherein the metal precursor comprises at least one Group VIII metal compound and at least one Group ⅥB metal compound.

[0017] The preparation method of the hydrogenation catalyst active metal impregnation solution, wherein the organic acid is at least one selected from tartaric acid, oxalic acid, malic acid, citric acid, succinic acid, and maleic acid.

[0018] The preparation method of the hydrogenation catalyst active metal impregnation solution, wherein in the metal impregnation solution, the Group VIII metal compound is added in an amount of 0.5-5.0 g / 100 cm 3 , the Group ⅥB metal compound is added in an amount of 2.0-18.0 g / 100 cm 3 , the organic acid is added in an amount of 1.0-12.0 g / 100 cm 3 , and the hydrogen peroxide is added in an amount of 0.1-4.0 g / 100 cm 3 .

[0019] The preparation method of the hydrogenation catalyst active metal impregnation solution, wherein in the metal impregnation solution, the polycarboxylic acid type scale inhibitor is added in an amount of 0.5-15.0 g / 100 cm 3 , and the organic phosphorus-containing compound is added in an amount of 0.5-10.0 g / 100 cm 3 .

[0020] The application discloses a preparation method of a hydrogenation catalyst active metal impregnation solution, wherein the Group VIII metal compound is a nickel-containing compound and / or a cobalt-containing compound, and the Group VI B metal compound is a molybdenum-containing compound and / or a tungsten-containing compound.

[0021] The application discloses a preparation method of a hydrogenation catalyst active metal impregnation solution, wherein the Group VIII metal compound is a nickel-containing compound and / or a cobalt-containing compound, and the Group VI B metal compound is a molybdenum-containing compound and / or a tungsten-containing compound.

[0022] The application discloses a preparation method of a hydrogenation catalyst active metal impregnation solution, wherein the Group VIII metal compound is a nickel-containing compound and / or a cobalt-containing compound, and the Group VI B metal compound is a molybdenum-containing compound and / or a tungsten-containing compound.

[0023] Step 1a, the Group VI B metal compound, the organic acid and water are mixed to make the Group VI B metal compound completely dissolved;

[0024] Step 1b, the mixture obtained in step 1a is mixed with hydrogen peroxide;

[0025] Step 1c, the mixture obtained in step 1b is mixed with the Group VI B metal compound to form a metal solution.

[0026] The application discloses a preparation method of a hydrogenation catalyst active metal impregnation solution, wherein the Group VIII metal compound is a nickel-containing compound and / or a cobalt-containing compound, and the Group VI B metal compound is a molybdenum-containing compound and / or a tungsten-containing compound.

[0027] In order to achieve the above object, the application further provides a hydrogenation catalyst active metal impregnation solution which comprises a metal precursor, an organic acid, hydrogen peroxide and a composite complexing agent, wherein the composite complexing agent is a polycarboxylic acid scale inhibitor and an organic phosphorus-containing compound; the hydrogenation catalyst active metal impregnation solution has spectrum peak structures simultaneously appearing in the ranges of chemical shift 500cm -1 -600cm -1 1000cm -1 -1100cm -1 and no spectrum peak appearing in the range of chemical shift less than 320cm -1 .

[0028] The application has the following beneficial effects:

[0029] The organic acid radical ion has coordination sites that can form coordination bonds with metal ions, and the organic acid can form stable complexes by coordinating with active metal ions. In addition, the organic acid has weak acidity, which can reduce the corrosion loss of the carrier. Hydrogen peroxide can undergo redox reactions under acidic conditions, promoting the formation of relatively stable oxidation products of active metals, weakening the interaction between active components and the carrier, and being able to positively affect the activity and stability of the final residual oil hydroprocessing catalyst.

[0030] The composite complexing agent used in the present application has strong complexing ability and good solution stability. Through efficient complexation, the length of metal active phase crystal chips can be shortened, the number of chip layers can be reduced, and a higher proportion of 1-2 layer chip structure can be generated, achieving high dispersion of active metal loading and improving catalyst activity and stability. In addition, the use of organic phosphorus compounds in the composite complexing agent introduces an appropriate amount of phosphorus into the acidic active metal solution system, which can effectively weaken the strong interaction between active components and the carrier, optimize the structure of the active metal phase, and further improve the dispersion of the active metal in the residual oil hydroprocessing catalyst. At the same time, it avoids the problems of excessive phosphorus, excessive acidity, and metal component aggregation caused by using phosphoric acid to prepare the active metal solution, prevents the increase in the number and length of the catalyst active phase chips, and avoids the decline in catalyst stability during the hydrogenation reaction process. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 Laser Raman spectra of metal impregnation solutions for examples and comparative examples.

[0032] Figure 2 TEM transmission electron micrograph of catalyst 1.

[0033] Figure 3 TEM transmission electron micrograph of catalyst 2.

[0034] Figure 4 TEM transmission electron micrograph of catalyst 3. DETAILED DESCRIPTION

[0035] The technical solutions of the present application are described in detail below. The following embodiments are implemented based on the technical solutions of the present application, and a detailed implementation process is given. However, the protection scope of the present application is not limited to the following embodiments. The structures or experimental methods not specified in the following embodiments are usually performed under conventional conditions.

[0036] In the preparation method of the hydrogenation catalyst, the active metal needs to be prepared into a stable solution and then impregnated on the carrier. The traditional ammonia-containing alkaline system metal impregnation solution uses a large amount of ammonia water, causing environmental pollution problems. A large amount of ammonia gas is overflowed in the production and preparation process, which is not environmentally friendly. In order to solve the ammonia pollution problem, the prior art uses phosphoric acid to prepare the active metal impregnation solution, but the active metal dispersion of the catalyst prepared by the phosphoric acid is poor, and the high phosphorus content leads to excessive acidity of the catalyst, the catalyst is easy to coke and deactivate during the hydrogenation treatment process, the stability is insufficient, and it cannot adapt to the hydrogenation treatment requirements of poor heavy oil. In order to solve the problems of the prior art, the present application provides a preparation method of a green and environmentally friendly, stable, and highly dispersed hydrogenation catalyst active metal impregnation solution. By developing an environmentally friendly active metal impregnation solution system, the ammonia pollution problem in the production process of the hydrogenation catalyst is eliminated, and at the same time, the active metal components are well dispersed on the surface of the carrier, the hydrogenation catalyst activity and stability are improved, and the adaptability to poor raw materials is enhanced.

[0037] The preparation method of the hydrogenation catalyst active metal impregnation solution of the present application comprises the following steps:

[0038] Step 1, mixing the metal precursor, organic acid and hydrogen peroxide to form a metal solution;

[0039] Step 2, mixing the metal solution with a composite complexing agent to obtain a metal impregnation solution;

[0040] The composite complexing agent is a polycarboxylic acid scale inhibitor and an organic phosphorus-containing compound.

[0041] In the present application, the metal precursor is used to provide the active metal of the hydrogenation catalyst, and any metal suitable for the hydrogenation catalyst in the art can be used as the active metal in the present application. In an embodiment, the metal precursor comprises at least one Group VIII metal compound and at least one Group 6B metal compound. The Group VIII metal compound is preferably a nickel compound and / or a cobalt compound, and most preferably a nickel compound; the Group 6B metal compound is preferably a molybdenum compound and / or a tungsten compound, and most preferably a molybdenum compound. The metal precursor is an oxide of the metal, a metal-containing salt, etc., and the metal-containing salt is, for example, an alkaline carbonate of the metal, a sulfate of the metal, a nitrate of the metal, an acetate of the metal, a chloride of the metal, etc. Specifically, the nickel compound can be nickel carbonate, nickel sulfate, nickel nitrate, nickel acetate, nickel chloride, etc., and is preferably nickel nitrate and nickel acetate; the molybdenum compound can be molybdenum trioxide, ammonium heptamolybdate (molybdenum tetrahydrate), ammonium tetratungstate, ammonium orthotungstate, ammonium octatungstate, ammonium dodecatungstate, etc., and is preferably molybdenum trioxide and ammonium heptamolybdate.

[0042] In another embodiment, the amount of the Group VIII metal compound added in the metal impregnation solution is 0.5-5.0 g / 100 cm 3The Group VI B metal compound is added in an amount of 2.0-18.0 g / 100 cm 3 .

[0043] The organic acid can form a coordination bond with metal ions. The organic acid can form a stable complex by coordinating with active metal ions. The organic acid is not particularly limited in the present application, and can be at least one of tartaric acid, oxalic acid, malic acid, citric acid, succinic acid, and maleic acid, and is preferably oxalic acid. The organic acid is added in an amount of 1.0-12.0 g / 100 cm 3 .

[0044] The concentration of hydrogen peroxide is not particularly limited in the present application. In one embodiment, the hydrogen peroxide is added in an amount of 0.1-4.0 g / 100 cm 3 of H2O2 in the metal impregnation solution. The hydrogen peroxide can undergo a redox reaction under acidic conditions, promote the formation of a relatively stable oxidation product of the active metal, and weaken the interaction between the active component and the carrier, which can positively affect the activity and stability of the final residual oil hydroprocessing catalyst. Moreover, the amount of hydrogen peroxide added in the present application is low, and there is no safety problem.

[0045] In one embodiment, the step 1 of the present application comprises the following steps:

[0046] Step 1a, mixing the Group VI B metal compound, the organic acid, and water to completely dissolve the Group VI B metal compound;

[0047] Step 1b, mixing the mixture obtained in step 1a with the Group VIII metal compound to obtain a metal mixture solution;

[0048] Step 1c, mixing the metal mixture solution obtained in step 1b with hydrogen peroxide to form a metal solution.

[0049] In one embodiment, the Group VI B metal compound, the organic acid, and water can be heated and stirred during the mixing process in step 1a to completely dissolve the Group VI B metal compound. The heating temperature is, for example, 60-100°C, and is preferably 80-100°C. The mixing time is 5-45 minutes.

[0050] In one embodiment, the mixture obtained in step 1a can also be heated and stirred during the mixing process with the Group VIII metal compound to obtain a metal mixture solution.

[0051] In another embodiment, the step 1 of the present application comprises the following steps:

[0052] Step 1d, mixing the Group VI B metal compound, the organic acid, and water;

[0053] Step 1e, the mixture obtained in step 1d is mixed with hydrogen peroxide;

[0054] Step 1f, the mixture obtained in step 1e is mixed with a Group VIII metal compound to form a metal solution.

[0055] In one embodiment, the Group VI B metal compound, organic acid and water are mixed with heating and stirring to completely dissolve the Group VI B metal compound, the heating temperature is for example 60-100℃, preferably 80-100℃, and the mixing time is 5-45 minutes.

[0056] In one embodiment, the mixture obtained in step 1d is mixed with hydrogen peroxide at a temperature of 60-90℃, and the reaction is continued until the metal raw material is completely dissolved.

[0057] In one embodiment, the mixture obtained in step 1e is mixed with a Group VIII metal compound at a temperature of 25-60℃ to obtain a metal solution.

[0058] The present application uses a composite complexing agent, a polycarboxylic acid type scale inhibitor and an organic phosphorus-containing compound, which has strong complexing ability and good solution stability.

[0059] In one embodiment, the polycarboxylic acid type scale inhibitor is selected from at least one of polyepoxysuccinic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, maleic acid-acrylic acid copolymer, polyaspartic acid, acrylic acid-hydroxypropyl acrylate copolymer (T-225), and acrylic acid-2-acrylamide-2-methylpropane sulfonic acid copolymer. All the organic phosphorus-containing compounds are selected from at least one of aminotri(methylene) phosphonic acid, diethylene triaminopenta(methylene) phosphonic acid, hydroxyethylidene diphosphonic acid, and ethylenediamine tetra(methylene) phosphonic acid. In the metal impregnation solution, the amount of the polycarboxylic acid type scale inhibitor added is 0.5-15.0 g / 100 cm 3 The amount of the organic phosphorus-containing compound added is 0.5-10.0 g / 100 cm 3 .

[0060] The active metal impregnation solution of the hydrogenation catalyst obtained by the method of the present application has spectral peak structures simultaneously appearing in the chemical shift range of 500 cm -1 -600 cm -1 and the chemical shift range of 1000 cm -1 -1100 cm -1 , and no obvious spectral peak appears at a chemical shift of less than 320 cm -1 . The laser Raman spectrum analysis of the present application uses a 325 nm ultraviolet laser light source.

[0061] The active metal impregnation solution of the hydrogenation catalyst obtained by the preparation method of the present application can be used to impregnate a carrier to obtain a hydrogenation catalyst.

[0062] The carrier can comprise alumina and can also contain an auxiliary agent, a molecular sieve, etc. The shape of the carrier is not particularly limited in the present application and can be changed as needed, including but not limited to a bar shape, a spherical shape, a Raschig ring, a tooth ball, a honeycomb, a vane, etc., wherein the bar shape includes but is not limited to a cylinder, a trilobal, a quadrilobal, a butterfly shape, etc. The alumina carrier can be selected from commercially available carriers or can be prepared by the present application. The auxiliary agent includes but is not limited to one or more of silicon, phosphorus, boron, titanium, zirconium, chlorine, fluorine, etc. The molecular sieve includes but is not limited to one or more of X, Y, ZSM-5, β, phosphorus aluminum, titanium silicon, ZSM-41, SBA-15 molecular sieve, etc.

[0063] In an embodiment, the specific surface area of the carrier of the present application is 20-400 m 2 / g, preferably 80-320 m 2 / g; the pore volume of the carrier is 0.2-1.6 cm 3 / g, preferably 0.5-1.3 cm 3 / g.

[0064] The impregnation of the carrier by the impregnation solution can be carried out by an equal volume impregnation method or a supersaturation impregnation method, etc. The metal impregnation solution can be sprayed onto the surface of the carrier or the carrier can be immersed in the metal impregnation solution. The carrier can be vacuumed during the impregnation process or can be directly immersed. The carrier can be heated during the impregnation process or can be carried out at room temperature. The impregnation process can be assisted by ultrasonic or microwave technology, etc.

[0065] The impregnated sample is subjected to a curing treatment under airtight conditions at a temperature of 20-100℃, preferably 20-60℃, for 0.5-6 hours, preferably 1.0-4 hours. Then, drying is carried out at a temperature of 80-180℃, preferably 100-140℃, for 1-6 hours, preferably 2-4 hours. Then, calcination is carried out at a temperature of 400-700℃, preferably 420-600℃, for 0.5-6 hours, preferably 1-4 hours.

[0066] The catalyst of the present application can be used for the hydrogenation treatment of oil products, and is particularly suitable for the hydrogenation of heavy oil, such as residual oil. The hydrogenation catalyst of the present application does not use ammonia water, inorganic acid and other materials that pollute the environment, the metal components have good dispersion effect on the surface of the carrier, the catalyst preparation process is simple, the solution has good stability and strong operability; the catalyst has good stability and high hydrogenation activity, and is particularly suitable for the hydrogenation treatment process of poor residual oil raw materials.

[0067] The technical solutions of the present application are described in detail below through specific examples. It is necessary to point out here that the following examples are only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application according to the above content of the present application.

[0068] Example 1:

[0069] Take 2.0 g of molybdenum trioxide and 1.0 g of oxalic acid, respectively, and place them in a beaker. Add 60 g of deionized water and heat at 95℃ for 5 minutes with stirring. Cool to 60℃, and add 1.0 g of 20wt% hydrogen peroxide in portions, and stir until the material is completely dissolved. Take 2.08 g of nickel nitrate and add it, and stir to dissolve. Cool the solution to 25℃, and add 0.5 g of DR-001 polyacrylic acid produced by Dongrun Chemical Technology Co., Ltd. and 0.5 g of diethylene triaminopentamethylene phosphonic acid produced by Shandong Yayuan Environmental Protection Technology Co., Ltd., and stir to dissolve. Mark to 100 cm 3 , to obtain active metal impregnation solution A.

[0070] Example 2:

[0071] Take 7.68 g of molybdenum trioxide and 4.0 g of oxalic acid, respectively, and place them in a beaker. Add 60 g of deionized water and heat at 80℃ for 20 minutes with stirring. Control the solution temperature to 90℃, and add 6.0 g of 20wt% hydrogen peroxide in portions, and stir until the material is completely dissolved. Cool to 40℃, and take 5.54 g of nickel nitrate and add it, and stir to dissolve. Add 4.0 g of polyepoxysuccinic acid produced by Runyang Chemical Co., Ltd. and 3.0 g of aminotri(methylene) phosphonic acid produced by Zibo Yueyang Chemical Technology Co., Ltd. under stirring, and stir to dissolve. Mark the solution to 100 cm 3 , to obtain active metal impregnation solution B.

[0072] Example 3:

[0073] Take 11.53 g of ammonium tungstate and 6.0 g of citric acid, respectively, and place them in a beaker. Add 60 g of deionized water and heat at 100℃ for 15 minutes with stirring. Control the solution temperature to 70℃, and add 7.5 g of 20wt% hydrogen peroxide in portions, and stir until the material is completely dissolved. Cool to 60℃, and take 6.47 g of nickel acetate and add it, and stir to dissolve. Add 4.0 g of hydrolyzed polymaleic anhydride produced by Kason Chemical Co., Ltd. and 10.0 g of HEDP60 hydroxyethylidene diphosphonic acid produced by Runyang Chemical Co., Ltd. under stirring, and stir to dissolve. Mark the solution to 100 cm 3 , to obtain active metal impregnation solution C.

[0074] Example 4:

[0075] Take 11.81 g of molybdenum trioxide, 8.0 g of oxalic acid, and place them in a beaker. Add 65 g of deionized water, and gradually add 9.0 g of 20 wt% hydrogen peroxide. Stir at 90°C until the material is completely dissolved. Cool to 70°C, add 8.33 g of cobalt nitrate, and stir to dissolve. Cool to 40°C, and under stirring conditions, add 6.0 g of hydrolyzed polymaleic anhydride and 4.0 g of ethylenediaminetetramethylene phosphonic acid produced by Jiangsu Haolong Chemical Co., Ltd. Stir to dissolve, and calibrate the solution to 100 cm 3 to obtain active metal impregnation solution D.

[0076] Example 5:

[0077] Take 14.31 g of molybdenum trioxide and 11.0 g of maleic acid, and place them in a beaker. Add 65 g of deionized water, and stir at 85°C for 30 minutes. Control the solution temperature to 80°C, gradually add 12.0 g of 20 wt% hydrogen peroxide, and stir until the material is completely dissolved. Cool to 65°C, add 8.73 g of nickel nitrate, and stir to dissolve. Cool to 40°C, and under stirring conditions, add 15.0 g of polyacrylic acid and 6.0 g of ethylenediaminetetramethylene phosphonic acid. Stir to dissolve, and calibrate the solution to 100 cm 3 to obtain active metal impregnation solution E.

[0078] Example 6:

[0079] Take 18.0 g of molybdenum trioxide and 12.0 g of oxalic acid, and place them in a beaker. Add 60 g of deionized water, and stir at 90°C for 20 minutes. Control the solution temperature to 75°C, gradually add 15.0 g of 20 wt% hydrogen peroxide, and stir until the material is completely dissolved. Cool to 75°C, add 20.83 g of nickel nitrate, and stir to dissolve. Cool to 40°C, and under stirring conditions, add 8.0 g of polyepoxysuccinic acid and 5.0 g of hydroxyethylidene diphosphonic acid. Stir to dissolve, and calibrate the solution to 100 cm 3 to obtain active metal impregnation solution F.

[0080] Comparative Examples 1-3 are prior art methods and active metal impregnation solutions for hydrogenation catalysts prepared by prior art methods.

[0081] Comparative Example 1:

[0082] Comparative Example 1 refers to the preparation of the metal impregnation solution according to the method provided in CN114425354B, and the amount of metal added is the same as Example 2.

[0083] Take the molybdenum trioxide 7.68g, basic nickel carbonate 2.61g, placed in a beaker, stirring, take the phosphoric acid 3.76g, dilution after slow adding beaker, room temperature reaction for 15 minutes; heating to 95℃, heating 35 minutes; take citric acid 3.0g, continue to constant temperature heating 25 minutes, until the raw material is completely dissolved, closed heating to room temperature; stirring state 10.0g triethanolamine and 3g Tween-80, stirring after calibration to 100cm 3 , get metal impregnation liquid G.

[0084] Comparative example 2:

[0085] Comparative example 2 refers to the method disclosed in CN103007949B for the preparation of metal impregnation liquid, the same metal addition amount as example 2.

[0086] Take the concentration of 30wt% hydrogen peroxide, drop into 9.48g ammonium heptamolybdate, stirring dissolution; add nickel nitrate 5.54g, stirring dissolution, add 1.5g terephthalic acid, calibration to 100cm 3 , get metal impregnation liquid H.

[0087] Comparative example 3

[0088] Comparative example 3 refers to the method disclosed in CN1230491C for the preparation of metal impregnation liquid, the same metal addition amount as example 2.

[0089] Take ammonium heptamolybdate 9.48g, nickel nitrate 5.54g, use 20wt% concentration of ammonia to dissolve the metal salt, use ultrasonic treatment during and after the preparation process, get metal impregnation liquid I.

[0090] The above metal impregnation liquid physical and chemical properties are listed in table 1, the laser Raman spectrum of metal impregnation liquid of example 1 and comparative example is as Figure 1 .

[0091] The metal impregnation liquid B obtained in example 2 is used for the preparation of hydrogenation catalyst.

[0092] Take the four clover strip shaped alumina carrier 105.2g, the specific surface area of the carrier is 170m 2 / g, the pore volume is 0.84cm 3 / g; the above impregnation liquid B is impregnated on the alumina carrier by equal volume impregnation method in the form of spraying, the impregnated sample is treated for 4 hours under the condition of closed incubation at 40℃; dried at 120℃ for 4 hours; the dried sample is calcined at 500℃ for 2 hours, get residual oil hydroprocessing catalyst 1.

[0093] The metal impregnation liquid G obtained in comparative example 1 is used for the preparation of hydrogenation catalyst.

[0094] Take four clover strip-shaped alumina carrier 105.2g, carrier specific surface area 170m 2 / g, pore volume 0.84cm 3 / g; the above impregnation solution G is impregnated on the alumina carrier by using the equal volume impregnation method in the spray way, the impregnated sample is treated for 4 hours under the closed condition at 40℃; dried for 4 hours under the condition of 120℃; the dried sample is baked for 2 hours under the constant temperature of 500℃, to obtain the residual oil hydroprocessing catalyst 2.

[0095] The metal impregnation solution H obtained in the comparative example 2 is used for the preparation of the hydrogenation catalyst.

[0096] Take four clover strip-shaped alumina carrier 105.2g, carrier specific surface area 170m 2 / g, pore volume 0.84cm 3 / g; the above impregnation solution H is impregnated on the alumina carrier by using the equal volume impregnation method in the spray way, the impregnated sample is treated for 4 hours under the closed condition at 40℃; dried for 4 hours under the condition of 120℃; the dried sample is baked for 2 hours under the constant temperature of 500℃, to obtain the residual oil hydroprocessing catalyst 3.

[0097] The above catalyst is sulfided, and the transmission electron microscope (TEM) thereof is as shown in Figures 2-4 , and the analysis results are shown in Table 2.

[0098] The above obtained catalyst is subjected to the activity evaluation test, which is used for comparing the hydrogenation reaction performance of the catalyst prepared by using different metal impregnation solutions.

[0099] The aforementioned catalyst 1, catalyst 2 and catalyst 3 are subjected to the performance test under the same raw material oil and process conditions on the fixed bed residual oil hydrogenation evaluation device. The raw material oil properties and process conditions are shown in Table 3, and the evaluation results are shown in Table 4.

[0100] As shown in Table 1, the metal impregnation solution obtained by the method of the present application does not contain volatile ammonia, which is green and environmentally friendly; does not contain phosphoric acid component, which is weakly acidic and has good component dispersity; has good solution stability, and has large production operation flexibility; in the laser Raman spectrum, the spectrum peak structure exists in the chemical shift range of 500-600cm -1 and 1000-1100cm -1 , and no spectrum peak appears in the range less than 320cm -1 , which is obviously different from the impregnation solution of the comparative example, indicating that the existence state of the metal component in the solution is different from that of the comparative example.

[0101] As shown in Table 2, the hydrogenation catalyst platelets prepared by the impregnating solution of the present application have less layers, mainly single-layer and double-layer MoS2, short length, good dispersion of active phase, and obvious characteristics of high dispersion, low stacking and short platelets, which are more suitable for the hydrotreating of heavy and poor quality residual oil; while the catalyst prepared by the impregnating solution of the comparative example has high proportion of platelets with more than 3 layers, long length, and poor dispersion of active component.

[0102] As shown in Table 4, compared with the comparative catalyst, the catalyst prepared by the present application has better activity stability of desulfurization, de-carbon residue and metal removal, and stronger adaptability to poor quality feedstock, which is beneficial to prolong the operation cycle of the device and improve the economic benefit.

[0103] Table 1 properties of different metal impregnating solutions

[0104]

[0105] Table 2 TEM characterization results of catalysts

[0106]

[0107]

[0108] Table 3 feed oil and process conditions for evaluation test

[0109] Feed oil properties Middle East Resid Density (20°C) / g-cm -3 ]] 0.9884 Sulfur content, w% 4.478 Carbon residue value, w% 13.20 Metal (Ni + V), pg g -1 ]] 79.44 Process conditions Reaction temperature, °C 380 Hydrogen partial pressure, MPa 16.0 volume space velocity, h -1 ]]> 1.0 Hydrogen / oil ratio, V / V 700

[0110] Table 4 evaluation results of catalysts

[0111]

[0112]

[0113] Of course, the present application can have other various embodiments, and those skilled in the art can make various corresponding changes and modifications according to the present application without departing from the spirit and essence of the present application, but these corresponding changes and modifications should all belong to the protection scope of the claims of the present application.

Claims

1. A process for the preparation of a hydrogenation catalyst active metal impregnation solution, characterized in that, The method comprises the following steps: Step 1, mixing a metal precursor, an organic acid and hydrogen peroxide to form a metal solution; Step 2, mixing the metal solution with a composite complexing agent to obtain a metal impregnation solution; The composite complexing agent is a polycarboxylic acid type scale inhibitor and an organic phosphorus-containing compound.

2. The method for preparing the active metal impregnation solution for hydrogenation catalyst according to claim 1, characterized in that, The polycarboxylic acid type scale inhibitor is at least one selected from the group consisting of polyepoxysuccinic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, maleic acid-acrylic acid copolymer, polyaspartic acid, acrylic acid-hydroxypropyl acrylate copolymer, acrylic acid-2-acrylamide-2-methylpropane sulfonic acid copolymer; and the organic phosphorus-containing compound is at least one selected from the group consisting of aminotri(methylene) phosphonic acid, diethylene triaminopenta(methylene) phosphonic acid, hydroxyethylidene diphosphonic acid and ethylenediamine tetra(methylene) phosphonic acid.

3. The method for preparing the active metal impregnation solution for hydrogenation catalyst according to claim 1, characterized in that, The metal precursor comprises at least one Group VIII metal compound and at least one Group 6B metal compound.

4. The method for preparing the active metal impregnation solution for hydrogenation catalyst according to claim 1, characterized in that, The organic acid is at least one selected from the group consisting of tartaric acid, oxalic acid, malic acid, citric acid, succinic acid and maleic acid.

5. The method for preparing the active metal impregnation solution for hydrogenation catalyst according to claim 3, characterized in that, The Group VIII metal compound is added in an amount of 0.5-5.0 g / 100 cm 3 of metal oxide, the Group VIB metal compound is added in an amount of 2.0-18.0 g / 100 cm 3 of metal oxide; the organic acid is added in an amount of 1.0-12.0 g / 100 cm 3 ; and the hydrogen peroxide is added in an amount of 0.1-4.0 g / 100 cm 3 of H2O2.

6. The method for preparing the active metal impregnation solution for hydrogenation catalyst according to claim 2, characterized in that, The amount of the polycarboxylic acid type scale inhibitor added in the metal impregnation solution is 0.5-15.0 g / 100 cm 3 The amount of the organic phosphorus-containing compound added is 0.5-10.0 g / 100 cm 3 .

7. The method for preparing the active metal impregnation solution for hydrogenation catalyst according to claim 3, characterized in that, The Group VIII metal compound is a nickel-containing compound and / or a cobalt-containing compound, and the Group 6B metal compound is a molybdenum-containing compound and / or a tungsten-containing compound.

8. The method for preparing the active metal impregnation solution for hydrogenation catalyst according to claim 7, characterized in that, The Group VIII metal compound is a basic carbonate, sulfate, nitrate, acetate or chloride of nickel or cobalt; and the Group 6B metal compound is molybdenum trioxide, ammonium heptamolybdate, ammonium tetramolybdate, ammonium orthomolybdate, ammonium octamolybdate, ammonium dodecamolybdate, tungsten trioxide, ammonium tungstate, ammonium metatungstate and ammonium paratungstate.

9. The method for preparing the active metal impregnation solution for hydrogenation catalyst according to claim 3, characterized in that, Step 1 comprises the following steps: Step 1a, mixing the Group 6B metal compound, the organic acid and water to completely dissolve the Group 6B metal compound; Step 1b, mixing the mixture obtained in step 1a with hydrogen peroxide; Step 1c, mixing the mixture obtained in step 1b with the Group 6B metal compound to form a metal solution.

10. A hydrogenation catalyst active metal impregnation solution characterized in that, The metal precursor, organic acid, hydrogen peroxide and complexing agent, the complexing agent is polycarboxylic acid scale inhibitor and organic phosphorus-containing compound; the laser Raman spectrum of the active metal impregnation solution of the hydrogenation catalyst under the irradiation of 325nm ultraviolet laser light source has the spectrum peak structure appearing simultaneously in the chemical shift range of 500cm -1 to 600cm -1 and 1000cm -1 to 1100cm -1 , and no spectrum peak in the chemical shift range of less than 320cm -1 .

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