A method for utilizing spent hydroprocessing solid catalyst

Abstract

The application discloses a utilization method of waste bulk phase hydrogenation catalyst, and comprises the following contents: (1) a waste tungsten-molybdenum-nickel bulk phase hydrogenation catalyst is pretreated to obtain catalyst powder; (2) the catalyst powder, a ternary mixed alkali solution and a first organic additive are mixed and dissolved to obtain a tungsten-molybdenum-containing solution and a nickel-aluminum-containing solid phase; (3) the nickel-aluminum-containing solid phase, an inorganic acid and a second organic additive are mixed and dissolved to obtain a nickel-aluminum-containing solution; and (4) the tungsten-molybdenum-containing solution and the nickel-aluminum-containing solution are co-currently gelled, and the obtained gelling product is continuously subjected to multiple times of pH value decreasing aging, and the aged product is prepared into a catalyst. The method can efficiently recover active metals in the waste bulk phase hydrogenation catalyst, the prepared catalyst has less metal impurities, good active metal utilization rate and crushing strength, the catalyst has large pore volume and specific surface area, has excellent hydrogenation performance and activity stability, and turns waste into treasure, thereby greatly reducing the production cost of the catalyst.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of solid waste recycling, and particularly relates to a utilization method of waste hydrogenation bulk catalyst. BACKGROUND

[0002] With the development of chemical industry, especially the development of oil refining, chemical industry and other chemical industries using a large amount of catalyst, a large amount of waste catalyst will be produced. At the same time, with the increasingly strict environmental regulations, the treatment of these waste catalysts has become an important issue. Especially the bulk catalyst, the active metal content is high, if directly discarded, it will bring great loss in economy and environmental protection. The bulk catalyst is often used for processing heavy oil due to its high activity, and the impurity content in the waste catalyst is high, which further increases the difficulty of recycling the bulk catalyst, and an environmentally friendly method for recycling the waste catalyst is needed.

[0003] CN108067245A discloses a recycling method of a hydrogenation treatment catalyst. The molybdenum-nickel waste catalyst is extracted, calcined and crushed into catalyst powder, which is mixed with alkali to obtain an aluminate solution and a nickel oxide solid. The aluminate solution is used to prepare a pseudo-boehmite carrier by carbonization method, and the nickel oxide is prepared into basic nickel carbonate. The obtained molybdate basic nickel carbonate is prepared into a molybdenum-nickel-phosphorus solution, which is then impregnated on the carrier. This method is particularly suitable for recycling and preparing new catalysts from molybdenum and nickel waste catalysts, and has the characteristics of simple process and low treatment cost.

[0004] CN112619658A discloses a recycling method of waste hydrogenation catalyst. The waste hydrogenation catalyst is extracted to remove oil, calcined and crushed, mixed with alkali, calcined, impregnated with hot water and filtered to obtain a filtrate and a residue. Then, a polymer monomer is added to the filtrate to obtain solution I and solution II for co-current gelation reaction. The aged material is subjected to solid-liquid separation, extruded into strips, dried and calcined to obtain a hydrogenation catalyst.

[0005] CN108620083A discloses a recycling method of waste hydrogenation catalyst. The catalyst waste is crushed, sieved and then slurried to obtain a slurry with a solid content of 15wt%-55wt%. Nitric acid, phosphoric acid and an organic acid solution are added under stirring, and the temperature is raised to 65-100℃ and then cooled to room temperature. An organic amine is then added and mixed uniformly to obtain a sol slurry of the waste material. The sol slurry of the waste material, a mixture of modified large-pore alumina powder and small-pore alumina powder, and a extrusion aid are mixed uniformly, and then subjected to mixing, molding, drying and calcination to obtain an alumina carrier. The active component is loaded on the carrier to obtain a hydrogenation catalyst.

[0006] The metal content of the catalyst involved in the above method is small, and when the active metal of the active metal content of more than 60% of the bulk hydrogenation catalyst is treated, the active metal recovery rate is poor, at the same time, the impurities of the recovered active metal solution are more, and when the active metal is used again, the adhesion of the gelled material is poor, which affects the molding effect of the recovered catalyst, the crushing strength of the finished catalyst is poor, the catalyst impurities are more, and the activity and activity stability (life) of the catalyst are reduced. SUMMARY

[0007] In view of the deficiencies of the prior art, the application provides a utilization method of waste bulk hydrogenation catalyst. The method can efficiently recover active metals in waste bulk hydrogenation catalyst, and the prepared catalyst has less metal impurities, good active metal utilization rate and crushing strength, and large pore volume and specific surface area, and has excellent hydrogenation performance and activity stability, realizes waste-to-resource, and greatly reduces the production cost of the catalyst.

[0008] The utilization method of waste bulk hydrogenation catalyst of the application comprises the following contents:

[0009] (1) The waste tungsten-molybdenum-nickel bulk hydrogenation catalyst is extracted, deoiled, desulfurized, decarbonized and crushed to obtain catalyst powder;

[0010] (2) The catalyst powder, a ternary mixed alkali solution and a first organic additive are mixed and dissolved to react, and after the reaction, a tungsten-molybdenum-containing solution and a nickel-aluminum-containing solid phase are obtained through solid-liquid separation;

[0011] (3) The nickel-aluminum-containing solid phase, an inorganic acid and a second organic additive are mixed and dissolved to react, and after the reaction, a nickel-aluminum-containing solution is obtained;

[0012] (4) The tungsten-molybdenum-containing solution and the nickel-aluminum-containing solution are subjected to parallel flow gelation reaction to obtain a gelation product, and the gelation product is continuously subjected to multiple pH value decreasing aging, and the aged product is dried, molded, washed, and then dried and calcined to obtain a catalyst product.

[0013] In the method of the application, the waste tungsten-molybdenum-nickel bulk hydrogenation catalyst in step (1) comprises 70% to 90% of catalyst solid, 10% to 30% of petroleum distillate, 20% to 50% of tungsten oxide, 10% to 35% of nickel oxide, 10% to 50% of molybdenum oxide, 0.7% to 1.8% of iron oxide, 0.6% to 1.3% of vanadium oxide, 0.6% to 1.5% of arsenic oxide and 0.6% to 1.1% of sodium oxide by weight.

[0014] The organic solvent used in the extraction is toluene, petroleum ether, ethanol, etc., and the extraction temperature is 80-110℃. The process of removing sulfur and carbon is as follows: after removing sulfur at a temperature of 300-350℃ for 2-7 hours, the temperature is raised to 500-600℃ for 2-6 hours to remove carbon; the particle size of the crushed catalyst powder is 200-400 mesh, preferably 250-390 mesh.

[0015] In the method, the ternary mixed alkali solution in step (2) is a mixed alkali solution containing sodium carbonate, sodium phosphate and ammonia, wherein the molar ratio of the total moles of sodium carbonate, sodium phosphate and ammonia to the moles of the catalyst powder in terms of oxides is 2.0:1-6.0:1, preferably 2.2:1-5.5:1; the molar ratio of the sum of the moles of sodium carbonate and sodium phosphate to the moles of ammonia is 0.8:1-8:3, and the molar ratio of sodium carbonate to sodium phosphate is 4:6-3:1.

[0016] In the method, the first organic additive in step (2) is one or more of polyaspartic acid sodium, polyepoxysuccinic acid sodium, acrylic acid-hydroxypropyl acrylate copolymer, aminotrimethylene phosphonic acid pentasodium, polypropionic acid sodium, ethylenediamine tetramethylene phosphonic acid pentasodium, hydroxyethylidene diphosphonic acid tetrasodium, diethylene triamine pentamethylene phosphonic acid sodium, and 2-hydroxyphosphonic acid acyl acetic acid, preferably one or more of polyaspartic acid sodium, polyepoxysuccinic acid sodium, aminotrimethylene phosphonic acid pentasodium, polypropionic acid sodium, ethylenediamine tetramethylene phosphonic acid pentasodium, hydroxyethylidene diphosphonic acid tetrasodium, and diethylene triamine pentamethylene phosphonic acid sodium.

[0017] In the method, the molar ratio of the first organic additive in step (2) to Mo in the catalyst powder is 0.8:1-3.8:1, preferably 1:1-3.5:1.

[0018] In the method, the mixing and dissolving time in step (2) is 2-10 hours, which is generally carried out under stirring. The solid-liquid separation can be carried out by centrifugation, filtration, etc.

[0019] In the method, the inorganic acid in step (3) is nitric acid, sulfuric acid or hydrochloric acid, preferably sulfuric acid or nitric acid, and the molar ratio of the inorganic acid to nickel in the extracted catalyst is 0.8:1-2.9:1, preferably 0.9:1-2.7:1.

[0020] In the method, the second organic additive in step (3) is one or more of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, and dodecyl trimethyl ammonium chloride.

[0021] In the method, the second organic additive is added in the step (3) in a molar ratio of 0.6:1 to 2.5:1 to the Ni in the catalyst powder, and preferably in a molar ratio of 0.8:1 to 2.2:1.

[0022] In the method, the mixing and dissolving time in the step (3) is 1 to 8 hours, and is generally performed at room temperature.

[0023] In the method, the gelling reaction in the step (4) is performed at a temperature of 30 to 95 DEG C, and preferably at a temperature of 40 to 95 DEG C, and the pH value is controlled at 6.5 to 9.5 at the end of the reaction, and the reaction time is 0.5 to 3.5 hours.

[0024] In the method, the aging temperature in the step (4) is 60 to 98 DEG C, and preferably 65 to 92 DEG C.

[0025] In the method, the aging times of the step (4) in which the pH value is gradually decreased are 2 to 8 times.

[0026] In the method, the aging process of the step (4) in which the pH value is gradually decreased comprises the following steps: the reaction slurry is dropped into a portion of the sodium metaaluminate solution to control the pH value at 11.5 to 13.5, and is aged for 0.05 to 0.5 hours; then the pH value is adjusted to 8.5 to 10.5, and is aged for 0.05 to 0.5 hours; finally, the pH value is adjusted to 4.0 to 6.5, and is aged for 0.05 to 0.5 hours.

[0027] In the method, the sodium metaaluminate solution in the step (4) is divided into 2 to 8 portions according to the aging times, and is preferably equally divided according to the volume. The Al added by the sodium metaaluminate solution accounts for 5% to 48% of the total Al of the obtained catalyst in terms of Al2O3, and preferably accounts for 6% to 45% of the total Al of the obtained catalyst in terms of Al2O3.

[0028] In the aging process, the acid and the base used for adjusting the pH value except for the sodium metaaluminate solution used in the first step can be inorganic salts, inorganic acids and inorganic bases containing no aluminum element. The inorganic acid can be hydrochloric acid and acetic acid, and the inorganic base can be one or more of sodium carbonate, sodium bicarbonate, ammonia water and sodium hydroxide. The concentration and the amount of the acid and the base solution can be adjusted according to the actual preparation needs.

[0029] In the method of the present application, the drying, shaping and washing in step (4) can be carried out by using conventional methods in the art. The drying conditions are as follows: drying at 40-150°C for 1-48 hours, preferably at 50-120°C for 4-36 hours. During the shaping process, conventional shaping aids such as one or more of a peptizing agent, an extrusion aid and the like can be added as needed. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, and the extrusion aid refers to a substance that is beneficial to extrusion shaping, such as one or more of amaranth powder, carbon black, graphite powder, citric acid and the like, and the amount of the extrusion aid is 1wt%-10wt% of the total material dry basis. The product can be prepared into a sheet shape, a spherical shape, a cylindrical strip and a special-shaped strip (clover, four-leaf clover) and the like as needed. The washing is generally carried out by using deionized water or a solution containing decomposable salts (such as ammonium acetate, ammonium chloride, ammonium nitrate and the like) until neutral.

[0030] In the method of the present application, the calcination conditions in step (4) are as follows: calcination at 350-650°C for 1-24 hours, preferably at 400-600°C for 2-12 hours.

[0031] The catalyst obtained by the method of the present application can be applied to the ultra-deep hydrodesulfurization, denitrification and hydrodearomatization reactions of heavy diesel oil fractions.

[0032] Compared with the prior art, the present application has the following advantages:

[0033] 1. By using the ternary base solution and the organic aid in combination, the method of the present application can maximize the recycling of the active metals and alumina in the waste bulk catalyst, and at the same time remove the metal impurities dissolved in the active metal solution.

[0034] In the method of the present application, the Al-containing solution is added in several times, the amorphous oxide in the oxide particles is dissolved by pH swing, the size of the oxide particles is modified by adding the Al-containing solution again, the growth of the oxide particles is controlled by pH swing for n times, the oxide particles are more uniform, more active metals are exposed on the surface, and the active metals are uniformly dispersed, at the same time, the aluminum introduced by the Al-containing solution increases the surface hydroxyl group, further enhances the adhesion of the oxide, and is beneficial to the shaping of the bulk catalyst.

[0035] 3. The catalyst obtained by the method of the present application has less metal impurities and good crushing strength, realizes the recycling of the catalyst, greatly reduces the production cost of the catalyst, and improves the recycling efficiency of the bulk waste catalyst. DETAILED DESCRIPTION

[0036] The technical solutions and technical effects of the present application are further illustrated below in combination with examples, but are not limited to the following examples. In the present application, the specific surface area and pore volume are determined by low-temperature liquid nitrogen adsorption method, and the mechanical strength is determined by lateral pressure method. The active metal content on the surface of the catalyst is determined by X-ray photoelectron spectroscopy (XPS), and the active metal content in the bulk of the catalyst is determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The impurity content of the waste catalyst is determined by X-ray fluorescence spectrometer. In the present application, wt% is mass fraction, and v% is volume fraction.

[0037] The waste bulk catalyst used in the present application is discarded after the operation of a hydrocracking device in a certain refinery of Sinopec. The industrial bulk catalyst after operation is extracted to remove oil at 90 DEG C, dried at 120 DEG C for 3 hours, calcined at 500 DEG C for 2 hours, and sieved and crushed to 300 mesh. The mass content of active metal and impurities in the waste bulk catalyst after sulfur removal and carbon removal in the present application is as follows: MoO3 is 18.4%, NiO is 20.5%, WO3 is 34.6%, Al2O3 is 23.6, Fe2O3 is 0.987%, V2O5 is 0.746%, As2O3 is 0.487%, and Na2O is 0.680%. Example 1

[0038] The crushed catalyst powder is mixed with a mixed alkali solution of sodium carbonate, sodium phosphate and ammonia water. The molar ratio of sodium carbonate, sodium phosphate and ammonia in the mixed alkali solution to the active metals (as oxides) in the crushed catalyst is 3.5, the molar ratio of the sum of sodium carbonate and sodium phosphate to ammonia is 1.2, and the molar ratio of sodium carbonate to sodium phosphate is 1.5. Sodium polyaspartate is added, and the molar ratio of sodium polyaspartate to Mo in the catalyst powder is 2.5. The mixture is stirred and reacted for 6 hours, then filtered to obtain a solution containing tungsten and molybdenum and a filter residue containing nickel and aluminum. The residue is mixed with nitric acid, and the molar ratio of nitric acid to nickel in the catalyst powder is 2.0:1. Octadecyl trimethyl ammonium bromide is added, and the molar ratio of octadecyl trimethyl ammonium bromide to Ni in the catalyst powder is 1.3. The mixture is stirred and reacted for 5 hours, then filtered to obtain a solution containing nickel and aluminum. The sodium metaaluminate solution is divided into 5 equal parts, and the Al in the sodium metaaluminate solution accounts for 30% of the total Al (as Al2O3) in the obtained hydrogenation catalyst. Deionized water is added to a reactor, and the solution containing W and Mo and the solution containing Ni and Al are added to the reactor to perform a gelation reaction. The reaction pH is controlled at 8.3, and the reaction temperature is 60°C. After the reaction is performed for 1.0 hour, a precipitate slurry containing nickel, molybdenum, tungsten and aluminum is formed. The obtained slurry is aged. The aging temperature is 76°C. During the aging, the pH is controlled at 13.1 by adding the first part of the sodium metaaluminate solution. After the aging is performed for 0.2 hour, the pH is controlled at 9.5. After the aging is performed for 0.15 hour, the pH is controlled at 5.2. The aging is performed for 0.2 hour. The above process is repeated 5 times, and the aging is ended. The aged slurry is filtered, and the filter cake is dried at 100°C for 8 hours, then rolled and extruded into a strip. The strip is washed with deionized water at room temperature until neutral. The dried material is calcined at 530°C for 5 hours to obtain catalyst A. The composition and main properties of the catalyst are shown in Table 1. Example 2

[0039] The crushed catalyst powder is mixed with a mixed alkali solution of sodium carbonate, sodium phosphate and ammonia water. The molar ratio of sodium carbonate, sodium phosphate and ammonia in the mixed alkali solution to the active metals (as oxides) in the crushed catalyst is 4.0, the molar ratio of the sum of sodium carbonate and sodium phosphate to ammonia is 1.6, and the molar ratio of sodium carbonate to sodium phosphate is 1.6. Sodium polyepoxysuccinate is added, and the molar ratio of sodium polyepoxysuccinate to Mo in the catalyst powder is 1.8. The mixture is stirred and reacted for 6 hours, then filtered to obtain a solution containing tungsten and molybdenum and a filter residue containing nickel and aluminum. The residue is mixed with nitric acid, and the molar ratio of nitric acid to nickel in the catalyst powder is 1.8:1. Octadecyltrimethylammonium bromide is added, and the molar ratio of octadecyltrimethylammonium bromide to Ni in the catalyst powder is 1.7. The mixture is stirred and reacted for 4 hours, then filtered to obtain a solution containing nickel and aluminum. The Al in the sodium metaaluminate solution accounts for 35% of the total Al (as Al2O3) in the obtained hydrofining catalyst, and the solution is divided into 6 equal parts by volume. Deionized water is added to a reactor, and the solution containing W and Mo and the solution containing Ni and Al are added to the reactor to perform a gelation reaction. The reaction pH is controlled at 8.0, and the reaction temperature is 65°C. After the reaction is performed for 1.2 hours, a precipitate slurry containing nickel, molybdenum, tungsten and aluminum is formed. The obtained slurry is aged. The aging temperature is 82°C. During the aging, the first part of the sodium metaaluminate solution is added first, and the pH is controlled at 12.7. After the aging is performed for 0.15 hours, the pH is controlled at 9.2. After the aging is performed for another 0.15 hours, the pH is controlled at 4.9. After the aging is performed for another 0.15 hours, the above process is repeated 6 times, and the aging is ended. The aged slurry is filtered, and the filter cake is dried at 110°C for 7 hours, then crushed and extruded into strips. The extruded strips are washed with deionized water at room temperature until neutral. The dried material is dried at 100°C for 7 hours, then calcined at 520°C for 5 hours to obtain catalyst B. The composition and main properties of the catalyst are shown in Table 1. Example 3

[0040] The crushed catalyst powder is mixed with a mixed alkali solution of sodium carbonate, sodium phosphate and ammonia water. The molar ratio of sodium carbonate, sodium phosphate and ammonia in the mixed alkali solution to the active metals (as oxides) in the crushed catalyst is 3.8, the molar ratio of the sum of sodium carbonate and sodium phosphate to ammonia is 1.8, and the molar ratio of sodium carbonate to sodium phosphate is 1.9. Polyacrylic acid sodium is added, and the molar ratio of polyacrylic acid sodium to Mo in the catalyst powder is 2.0. The mixture is stirred and reacted for 5.5 hours, then filtered to obtain a solution containing tungsten and molybdenum and a filter residue containing nickel and aluminum. The residue is mixed with nitric acid, and the molar ratio of nitric acid to nickel in the catalyst powder is 1.6:1. Octadecyl trimethyl ammonium chloride is added, and the molar ratio of octadecyl trimethyl ammonium chloride to Ni in the catalyst powder is 1.4. The mixture is stirred and reacted for 4.5 hours, then filtered to obtain a solution containing nickel and aluminum. The solution is divided into 7 equal parts by volume, and each part is mixed with sodium metaaluminate solution, in which the Al accounts for 25% of the total Al (as Al2O3) in the obtained hydrofining catalyst. The solutions containing W and Mo and the solutions containing Ni and Al are added to a reaction tank to perform a coagulation reaction. The reaction is carried out at a pH of 7.8 and a temperature of 55°C for 1.3 hours to form a slurry containing a precipitate of nickel, molybdenum, tungsten and aluminum. The slurry is aged at a temperature of 81°C. During the aging, the pH is controlled at 12.5 for 0.15 hours by adding one part of the sodium metaaluminate solution, then controlled at 9.8 for 0.2 hours, then controlled at 5.5 for 0.2 hours. The above process is repeated 7 times to complete the aging. The aged slurry is filtered, and the filter cake is dried at 120°C for 8 hours, then rolled and extruded into strips. The strips are washed with deionized water at room temperature until neutral. The strips are dried at 90°C for 8 hours, then calcined at 500°C for 5 hours to obtain catalyst C. The composition and main properties of the catalyst are shown in Table 1. Example 4

[0041] The crushed catalyst powder is mixed with a mixed alkali solution of sodium carbonate, sodium phosphate and ammonia, the molar ratio of sodium carbonate, sodium phosphate and ammonia to the active metals (as oxides) in the crushed catalyst is 4.2, the molar ratio of the sum of sodium carbonate and sodium phosphate to ammonia is 1.4, and the molar ratio of sodium carbonate to sodium phosphate is 1.9. Pentasodium ethylenediaminetetramethylenephosphonate is added, the molar ratio of pentasodium ethylenediaminetetramethylenephosphonate to Mo in the catalyst powder is 2.4, and the mixture is stirred and reacted for 6 hours. The mixture is then filtered to obtain a solution containing tungsten and molybdenum and a residue containing nickel and aluminum. The residue is mixed with nitric acid, the molar ratio of nitric acid to nickel in the catalyst powder is 2.2:1. Dodecyltrimethylammonium chloride is added, the molar ratio of dodecyltrimethylammonium chloride to Ni in the catalyst powder is 1.4, and the mixture is stirred and reacted for 6.5 hours. The mixture is then filtered to obtain a solution containing nickel and aluminum. The solution is divided into five equal parts by volume, and each part is mixed with deionized water. The solution containing W and Mo and the solution containing Ni and Al are added to a reaction tank to perform a coagulation reaction, the pH value of the reaction is controlled at 8.1, and the reaction temperature is 68°C. After the reaction is performed for 1.1 hours, a slurry containing a precipitate of nickel, molybdenum, tungsten and aluminum is obtained. The slurry is aged, the aging temperature is 76°C, and the pH value of the slurry is controlled at 12.9 by adding the first part of the sodium metaaluminate solution during the first 0.2 hours of the aging. The pH value of the slurry is then controlled at 9.3 by adding the second part of the sodium metaaluminate solution during the next 0.15 hours of the aging. The pH value of the slurry is then controlled at 5.3 by adding the third part of the sodium metaaluminate solution during the next 0.2 hours of the aging. The above process is repeated five times, and the aging is completed. The aged slurry is filtered, the filter cake is dried at 90°C for 8 hours, and the dried filter cake is crushed and extruded into a strip. The strip is washed with deionized water at room temperature until the strip is neutral. The strip is dried at 80°C for 8 hours, and the dried strip is calcined at 540°C for 4 hours to obtain catalyst D. The composition and main properties of catalyst D are shown in Table 1.

[0042] Comparative Example 1

[0043] Catalyst E is prepared according to Example 1, but all of the sodium metaaluminate solution is added at one time during the aging process of the slurry containing the precipitate of nickel, molybdenum, tungsten and aluminum, and a fixed pH value (one-time aging) is used during the aging. The preparation process is as follows:

[0044] The crushed catalyst powder is mixed with a mixed alkali solution of sodium carbonate, sodium phosphate and ammonia water, the molar ratio of sodium carbonate, sodium phosphate and ammonia in the mixed alkali solution to the active metals (calculated as oxides) in the crushed catalyst is 3.5, the molar ratio of the sum of sodium carbonate and sodium phosphate to ammonia is 1.2, and the molar ratio of sodium carbonate to sodium phosphate is 1.5. Sodium polyaspartate is added, the molar ratio of sodium polyaspartate to Mo in the extracted catalyst is 2.5, and the reaction and dissolution are carried out under stirring for 6 hours. Then, filtration is carried out to obtain a tungsten-molybdenum-containing solution and a filter residue containing nickel and aluminum. The obtained residue is mixed with nitric acid, and octadecyltrimethylammonium bromide is added, the molar ratio of nitric acid to nickel in the catalyst powder is 2.0:1. The molar ratio of octadecyltrimethylammonium bromide to Ni in the extracted catalyst is 1.3, and the reaction and dissolution are carried out under stirring for 5 hours. Then, filtration is carried out to obtain a nickel-aluminum-containing solution. The Al in the sodium metaaluminate solution accounts for 30% of the total Al (calculated as Al2O3) in the obtained hydrofining catalyst. Deionized water is added into a reaction tank, and the tungsten-molybdenum-containing solution and the nickel-aluminum-containing solution are added into the reaction tank to carry out a gelation reaction, the pH value is controlled at 8.3, the reaction temperature is 60°C, and the reaction is carried out for 1.0 hour to generate a precipitate slurry containing nickel, molybdenum, tungsten and aluminum. The obtained slurry is aged, the aging temperature is 76°C, the total sodium metaaluminate solution is added during the aging, the pH value is controlled at 8.0, and the aging is carried out for 2 hours. Then, the aging is ended. The aged slurry is filtered, the filter cake is dried at 100°C for 8 hours, is rolled and is extruded into a strip. The strip is washed with deionized water at room temperature until neutral. The dried material is dried at 100°C for 8 hours, and is calcined at 530°C for 5 hours to obtain the catalyst E. The catalyst composition and main properties are shown in Table 1.

[0045] Comparative Example 2

[0046] The same as in Example 1, no organic reagent P1 is added during the preparation of the catalyst to prepare a reference agent F (containing many impurities and cannot be shaped).

[0047] Comparative Example 3

[0048] The same as in Example 1, no organic reagent P2 is added during the preparation of the catalyst to prepare a reference agent G (containing many impurities and cannot be shaped).

[0049] Comparative Example 4

[0050] The same as in Example 1, a mixed solution reaction of sodium carbonate and ammonia is used during the preparation of the catalyst, the total molar number of sodium carbonate and ammonia to the molar number of the catalyst powder calculated as oxides is 3.0:1. A reference agent H is prepared (containing many impurities and cannot be shaped).

[0051] Comparative Example 5

[0052] Similar to Example 1, the catalyst preparation process uses a mixture of sodium carbonate, sodium phosphate, and ammonia for dissolution reaction. The total molar ratio of sodium carbonate, sodium phosphate, and ammonia to the catalyst powder (based on oxides) is 1.1:1; the sum of the molar ratios of sodium carbonate and sodium phosphate to ammonia is 0.5, and the molar ratio of sodium carbonate to sodium phosphate is 0.4. Reference agent I (with many impurities and poor mechanical strength) is prepared. Example 5

[0053] This embodiment is an experiment to evaluate the catalyst activity of the present invention and compare it with a comparative example catalyst. Catalysts A, B, C, and D of the present invention and comparative example catalyst E were used in comparative evaluation experiments on a 200 mL small-scale hydrogenation unit. To further evaluate the catalyst's ability to saturate with aromatics, catalytic diesel with a high aromatic content was selected as the test feedstock. The main properties of the feedstock are shown in Table 3. The catalyst activity evaluation process conditions were: hydrogen partial pressure 6.4 MPa, reaction temperature 360 ​​°C, and liquid hourly space velocity 1.7 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1, and the evaluation results are shown in Tables 4-6. As can be seen from Tables 1-2, compared with the comparative example catalyst, the catalyst prepared by the method of this invention has less impurity content, larger pore volume and surface area, more surface-phase active metals, and higher active metal utilization. Table 3 shows that the catalyst activity evaluation used feedstock oil with high aromatic content, which will increase the difficulty of hydrosaturation, ultra-deep hydrodesulfurization, and denitrification of the feedstock oil. The evaluation results in Tables 4-5 show that the catalyst prepared by the method of this invention not only has excellent hydrodesulfurization and hydronitrogenation activity, but also excellent hydrosaturation performance, effectively reducing the aromatic content of heavy distillate oil. The catalyst prepared by the method of this invention, when used to process heavy distillate oil, especially for processing low-quality diesel fractions with high aromatic content and high processing difficulty, exhibits excellent hydrosaturation, hydrodesulfurization, and hydronitrogenation performance, effectively reducing polycyclic aromatic hydrocarbon content and improving the cetane number of diesel. Table 6 shows the activity evaluation results of the catalyst after 2000 hours of operation under unchanged evaluation conditions. It can be seen that the fresh catalyst prepared by the method of the present invention using waste bulk catalyst has good activity stability due to its low impurity content.

[0054] Table 1. Composition and properties of catalysts prepared in the Examples and Comparative Examples

[0055] Catalyst No. A B C D E F G H I NiO, wt% 18.2 18.8 17.9 17.6 18.3 10.2 13.4 14.7 15.2 WO3, wt% 30.4 29.6 30.1 30.7 30.1 19.4 20.8 18.9 22.4 MoO3, wt% 15.2 15.0 15.8 15.5 15.3 9.2 10.3 8.6 12.2 Al203, wt% balance balance balance balance balance balance balance balance balance Fe203, wt% 0.106 0.108 0.104 0.095 0.110 0.667 0.522 0.693 0.473 [V2O5, wt%] 0.084 0.088 0.079 0.093 0.092 0..476 0..414 0..505 0..383 As203, wt% 0.066 0.061 0.069 0.073 0.079 0.298 0.242 0.303 0.207 Na2O, wt% 0.052 0.043 0.048 0.040 0..051 0.401 0.352 0.423 0.241 Specific surface area, m 2 / g]] 292 283 297 304 197 - - - - balance 0.431 0.418 0.438 0.454 0.247 - - - - Pore volume, mL / g 19.3 19.6 19.9 19.5 19.0 Mechanical strength, N / mm Not formable Not formable 5.5 Not formable Pore distribution 5.13 6.56 4.87 4,54 33.67 - - - - < 4 nm 6.75 7.93 5.37 5.01 25.51 - - - - 4 nm - 6 nm 59.23 59.12 60.02 60.23 25.43 - - - - 6 nm - 10 nm 19.56 18.01 19.86 19.90 8.09 - - - - 10 nm - 15 nm 9,33 8.38 9.88 10.32 7.30 - - - -

[0056] Table 2. Weight ratio of active metal oxides in the catalyst surface and bulk phases

[0057] > 15 nm A B C D E Table phase I W+Ni Bulk phase I W+Ni ]]> 5.74 5.83 5.62 4.95 1.34 Table phase I Mo Ni Bulk phase I Mo Ni ]]> ​​ 4.87 4.91 4.73 4.99. 1.08

[0058] Table 3 Main Properties of Crude Oil

[0059] Catalyst No. Item Density (20°C), g / cm 3 ]] 0.9234 Analysis result 162-379 Distillation range, °C 14400 S, pg / g 812 N, pg / g 69.5 Aromatics, wt% 42.7 Polycyclic aromatics, wt% ＜24

[0060] Table 4 Catalyst activity evaluation results (250 hours)

[0061] Cetane number A B C D E Density of the produced oil (20°C), g / cm 3 ]] 0.8689 0.8685 0.8693 0.8683 0.8762 Catalyst No. 165-367 165-366 168-368 165-366 177-374 Distillation range, °C 8.9 8.2 9.5 8.0 132.7 S, pg / g 5.4 5.0 5.8 4.8 55.2 N, pg / g 36.0 35.8 36.5 35.4 44.7 Aromatics, wt% 4.9 4.6 5.4 4.4 13.2 Polycyclic aromatics, wt% 39.3 39.1 38.8 39.6 29.4

[0062] Table 5 Contents of different nitrogen compounds in hydrofinished oil (250 hours)

[0063] Cetane number A B C D E Catalyst No. 5.4 5.0 5.8 4.8 55.2 Nitrogen content in hydrofinished oil, pg / g 2.9 2.7 3.1 2.7 27,1 1-MCB, pg / g 1.6 1.5 1.6 1.4 18.0 1,8-BMCB, pg / g 0.9 0.8 1.1 0.7 10.1

[0064] Table 6 Catalyst activity evaluation results (2000 hours)

[0065] 1,4,8-TMCB, pg / g A B Density of the produced oil (20°C), g / cm 3 ]]> 0.8691 0.8687 Catalyst No. 166-368 166-367 Distillation range, °C 9.3 8.7 S, pg / g 5.6 5.2 N, pg / g 36.3 36.1 Aromatics, wt% 5.1 4.9 Polycyclic aromatics, wt% Cetane number Catalyst No. Distillation range, °C S, pg / g N, pg / g Aromatics, wt% Polycyclic aromatics, wt% Cetane number Catalyst No. Distillation range, °C S, pg / g N, pg / g Aromatics, wt% Polycyclic aromatics, wt% Cetane number Catalyst No. Distillation range, °C S, pg / g N, pg / g Aromatics, wt% Polycyclic aromatics, wt% Cetane number Catalyst No. Distillation range, °C S, pg / g N, pg / g Aromatics, wt% Polycyclic aromatics, wt% Cetane number Catalyst No. Distillation range, °C S, pg / g N, pg / g Aromatics, wt% Polycyclic aromatics, wt% Cetane number Catalyst No. Distillation range, °C S, pg / g N, pg / g Aromatics, wt% Polycyclic aromatics, wt% Cetane number Catalyst No. Distillation range, °C S, pg / g N, pg / g Aromatics, wt% Polycyclic aromatics, wt% Cetane number Catalyst No. Distillation range, °C S 39.1 39.0

Claims

1. A method for utilizing waste tungsten-molybdenum-nickel body phase hydrogenation catalyst, comprising the following steps: (1) extracting oil, sulfur, carbon and crushing the waste tungsten-molybdenum-nickel body phase hydrogenation catalyst to obtain catalyst powder; (2) mixing and dissolving the catalyst powder, a ternary mixed alkali solution, a first organic additive to obtain a tungsten-molybdenum-containing solution and a nickel-aluminum-containing solid phase after solid-liquid separation; (3) mixing and dissolving the nickel-aluminum-containing solid phase, an inorganic acid, a second organic additive to obtain a nickel-aluminum-containing solution; (4) carrying out a parallel flow gelation reaction of the tungsten-molybdenum-containing solution and the nickel-aluminum-containing solution to obtain a gelation product, continuously carrying out multiple pH value decreasing aging processes on the gelation product, drying, shaping, washing, and then drying and calcining the aged product to obtain a catalyst product; the ternary mixed alkali solution in step (2) is a mixed alkali solution containing sodium carbonate, sodium phosphate and ammonia water, wherein the molar ratio of the total moles of sodium carbonate, sodium phosphate and ammonia to the catalyst powder in terms of oxides is 2.0:1-6.0:1, the molar ratio of the sum of the moles of sodium carbonate and sodium phosphate to the moles of ammonia is 0.8:1-8:3, and the molar ratio of sodium carbonate to sodium phosphate is 4:6-3:1; the first organic additive in step (2) is one or more of polyaspartic acid sodium, polyepoxysuccinic acid sodium, acrylic acid-hydroxypropyl acrylate copolymer, aminotri(methylphosphonic acid) pentasodium, polypropionic acid sodium, ethylenediamine tetra(methylenephosphonic acid) pentasodium, hydroxyethylidene diphosphonic acid tetrasodium, diethylenetriamine penta(methylenephosphonic acid) sodium, and 2-hydroxyphosphonic acid acyl acetic acid; the second organic additive in step (3) is one or more of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, and dodecyl trimethyl ammonium chloride; the pH value decreasing aging process in step (4) comprises the following steps: dropping the reaction slurry into a portion of sodium metaaluminate solution to control the pH value at 11.5-13.5, and aging for 0.05-0.5 hours; then adjusting the pH value to 8.5-10.5, and aging for 0.05-0.5 hours; finally adjusting the pH value to 4.0-6.5, and aging for 0.05-0.5 hours; the sodium metaaluminate solution in step (4) is divided into 2-8 portions according to the number of aging processes.

2. The method of claim 1, wherein: The waste tungsten-molybdenum-nickel body phase hydrogenation catalyst in step (1) comprises 70%-90% of catalyst solid and 10%-30% of petroleum distillate in terms of weight content.

3. The method of claim 1, wherein: The organic solvent used in the extraction is one or more of toluene, petroleum ether and ethanol, and the extraction temperature is 80-110°C; the sulfur removal and carbon removal processes are as follows: removing sulfur at a constant temperature of 300-350°C for 2-7 hours, and then removing carbon at a constant temperature of 500-600°C for 2-6 hours; the particle size of the crushed catalyst powder is 200-400 mesh.

4. The method of claim 1, wherein: The molar ratio of the first organic additive in step (2) to Mo in the catalyst powder is 0.8:1-3.8:

1.

5. The method of claim 1, wherein: The mixing and dissolving time in step (2) is 2-10 hours.

6. The method of claim 1, wherein: The inorganic acid in step (3) is nitric acid, sulfuric acid or hydrochloric acid, and the molar ratio of the inorganic acid to the nickel in the catalyst after extraction is 0.8:1 to 2.9:

1.

7. The method of claim 1, wherein: The second organic additive in step (3) is added in an amount such that the molar ratio of the second organic additive to the Ni in the catalyst powder is 0.6:1 to 2.5:

1.

8. The method of claim 1, wherein: The mixing and dissolving time in step (3) is 1 to 8 hours.

9. The method of claim 1, wherein: The conditions for the gelation reaction in step (4) are as follows: the reaction temperature is 30 to 95°C, the pH value at the end of the reaction is controlled to be 6.5 to 9.5, and the reaction time is 0.5 to 3.5 hours.

10. The method of claim 1, wherein: The aging temperature in step (4) is 60 to 98°C.

11. The method of claim 1, wherein: The number of times of pH value reduction aging in step (4) is 2 to 8 times.

12. The method of claim 1, wherein: The Al added in step (4) by means of a sodium metaaluminate solution accounts for 5% to 48% of the total Al in the obtained catalyst in terms of Al2O3.