CN110237856B - Preparation method of poor quality/heavy diesel oil hydrocracking catalyst - Google Patents
Preparation method of poor quality/heavy diesel oil hydrocracking catalyst Download PDFInfo
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
The invention discloses a white carbon black modified hydrocracking catalyst and a preparation method thereof. The hydrocracking catalyst adopts a Y molecular sieve acidic cracking component, adds VIB group and VIII group metal salts as a hydrogenation component, adopts white carbon black as a binder matrix, and adopts a method of combining kneading and dipping to prepare a catalyst finished product. Experimental results show that the white carbon black can well weaken the interaction between the metal component and the carrier. The catalyst is used for producing naphtha by hydrocracking of poor heavy diesel oil, has higher hydrogenation selectivity, and has the characteristics of high heavy naphtha aromatic potential, low tail oil BMCI value and high C5+ liquid yield.
Description
Technical Field
The invention relates to a preparation method of a hydrocracking catalyst, and particularly relates to a method for weakening interaction force between a catalyst carrier and metal by adding white carbon black and improving hydrogenation activity and hydrogenation selectivity of the catalyst. In particular to a hydrogenation tail oil catalyst with high yield of high aromatic latent naphtha and low BMCI value in hydrocracking of inferior and heavy diesel oil and a preparation method thereof.
Background
In recent years, with the rapid development of ethylene, PX, catalytic reforming and other devices in China, the whole China naphtha market shows a situation of short supply and demand. In 2015, despite the drastic increase in import of Chinese naphtha to 665 ten thousand tons (80% of the same year), the supply gap of Chinese naphtha was maintained at 419 ten thousand tons/year. Therefore, the problem of shortage of chemical raw materials becomes one of the main restriction factors for the development of the downstream chemical industry in China, and the development of the related research work on how to produce more chemical raw materials from the oil refining secondary processing device has important practical significance for promoting the conversion of oil refining to chemical industry. In 2020, the diesel-gasoline ratio consumed in China is predicted to be reduced to about 1.06:1, the reduction of the diesel-gasoline ratio consumed in China brings great challenges to the structural adjustment of the Chinese oil refining device, and the processing and conversion of surplus diesel oil are compelled to be at first! Diesel oil is converted into naphtha and high-quality hydrogenation tail oil through hydrocracking of inferior diesel oil and heavy diesel oil, so that the diesel oil ratio is reduced, the naphtha gap in the domestic market is made up, the added value of products is improved, and the quality and efficiency of enterprises are improved.
The hydrocracking catalyst is a bifunctional catalyst and has hydrogenation performance and cracking performance. Non-noble VIB group and VIII group metals are generally selected as hydrogenation components, molecular sieves and/or amorphous silicon-aluminum are selected as cracking components, and the molecular sieves are key components for cracking in the catalysts. The main active component of the hydrocracking catalyst is a Y-type molecular sieve, and the silicon-aluminum ratio of the Y-type molecular sieve directly influences the hydrothermal stability and acid resistance of the molecular sieve. The silicon-aluminum ratio is increased, the acid center density is reduced, the acid strength is increased, the ratio of cracking to hydrogen transfer activity reaction can be improved, the coke generation is reduced, and the product distribution is improved. In addition, the molecular sieve with higher silicon-aluminum ratio can bear more severe reaction conditions of hydrocracking, and the service life of the catalyst is prolonged. The higher the silica-alumina ratio, the better the heat resistance, steam resistance and acid resistance of the molecular sieve, and the application field of the molecular sieve can be further expanded.
Patent CN200610134152.6 discloses a preparation method of a hydrocracking catalyst, which adopts a material containing a molecular sieve and amorphous silica-alumina, and adopts a dipping or coprecipitation method to load a hydrogenation metal active component to prepare the final catalyst. The carrier material is prepared by directly adding the molecular sieve in the gelling process of the amorphous silicon-aluminum, so that the agglomeration phenomenon of the amorphous silicon-aluminum is easily caused, the carrier material also easily enters opposite pore passages or blocks the pore openings of the molecular sieve, the distribution of the amorphous silicon-aluminum on the molecular sieve is influenced, the through property of the molecular sieve and the pore passages of the amorphous silicon-aluminum is poor, the specific surface area and the pore volume of the catalyst are reduced, the distribution of active metals is not easy to control, the hydrogenation function and the cracking function of the catalyst are not matched, and the performance of the catalyst is influenced.
Patents US4762813 and US4860803 propose to mix alumina with molecular sieve to form, then to calcine at high temperature, then to impregnate the hydrogenation metal, with the purpose of increasing the yield of middle distillate and solving the problem of unstable product quality. The Y molecular sieve is firstly subjected to ultra-stabilization treatment, the crystal package constant is 2.440-2.465 nm, and the crystal package constant is further reduced to 2.420-2.435 nm through deep steam treatment after forming, so that the molecular sieve is super-hydrophobized, secondary pores of a carrier are increased, the acid density is reduced, and the strength is improved, thereby achieving the purpose of improving the high selectivity of middle distillate oil. Compared with the molecular sieve which is formed after hydrothermal treatment and then soaked in metal, the molecular sieve is formed before alumina and then subjected to hydrothermal treatment, so that molecular sieve particles can be in more uniform contact with water vapor, and the quality of each batch of materials is easier to guarantee. The method has the defect that the energy consumption of hydrothermal treatment is higher after the aluminum oxide and the molecular sieve are mixed and formed.
Patent CN200710158361.9 discloses a heavy oil hydrotreating catalyst and a preparation method thereof, wherein the catalyst is prepared by a kneading method, the active metal solution of the catalyst contains a nonionic surfactant, and the catalyst prepared by the method has the characteristics of large pore volume, proper specific surface area and uniform dispersion of active metal.
The hydrocracking catalysts disclosed in patents CN200810117102.6, CN200710012770.8, CN00109747.4, etc. are all prepared by mechanically mixing single raw materials such as molecular sieve, alumina, etc. The catalyst prepared by the method influences the performance of each component because of uneven mixing of various raw materials.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a hydrocracking catalyst for inferior and heavy diesel oil and a preparation method thereof. The catalyst prepared by the method is used for producing naphtha by hydrocracking of poor diesel oil, has high hydrogenation selectivity, and has the characteristics of high heavy naphtha aromatic potential, low tail oil BMCI value and high C5+ liquid yield.
Therefore, the invention provides a preparation method of a poor/heavy diesel hydrocracking catalyst, which is used for producing high aromatic hydrocarbon naphtha and low BMCI value tail oil, and comprises the following steps:
s1, adding a binder taking white carbon black as a matrix into the modified Y molecular sieve and the macroporous alumina, extruding into strips, and drying and roasting to obtain a catalyst carrier;
s2, preparing a salt solution containing VIB group metals and VIII group metals as an impregnation solution, impregnating the catalyst carrier in the impregnation solution in an equal volume, and drying and roasting to obtain the hydrocracking catalyst.
The preparation method of the poor quality/heavy diesel oil hydrocracking catalyst provided by the invention is characterized in that the hydrocracking catalyst has a specific surface area of preferably 200-500 m2The pore volume is preferably 0.2 to 0.6 ml/g.
The preparation method of the poor quality/heavy diesel oil hydrocracking catalyst comprises the following steps of preferably 30.0-80.0% of modified Y molecular sieve, 10.0-60.0% of macroporous alumina and 10.0-60.0% of white carbon black, wherein the total mass of catalyst carrier dry basis is taken as percentage.
The preparation method of the poor-quality/heavy diesel hydrocracking catalyst comprises the following steps of (1) preferably selecting tungsten as the VIB group metal, wherein the VIB group metal accounts for 15.0-30.0% of the total mass of the catalyst by tungsten oxide; the VIII group metal is preferably nickel, and accounts for 3.0-15.0% of the total mass of the catalyst in terms of nickel oxide.
The preparation method of the poor quality/heavy diesel oil hydrocracking catalyst comprises the following steps of (1) preferably, the tungsten accounts for 22.0-26.0% of the total mass of the catalyst by tungsten oxide; the nickel preferably accounts for 4.0-8.0% of the total mass of the catalyst in terms of nickel oxide.
The preparation method of the poor quality/heavy diesel oil hydrocracking catalyst provided by the invention has the advantages that the crystal package constant of the modified Y molecular sieve is preferably 2.430-2.460 nm, the silicon-aluminum ratio is preferably 5-20, and the content of sodium oxide is preferably less than or equal to 0.2 wt%.
The preparation method of the poor quality/heavy diesel oil hydrocracking catalyst provided by the invention is characterized in that the specific surface area of the macroporous alumina is preferably 200-400 m2The pore volume is preferably 0.5 to 1.0 ml/g.
The preparation method of the poor quality/heavy diesel oil hydrocracking catalyst provided by the invention is characterized in that the specific surface area of the white carbon black is preferably 100-500 m2/g, the particle size is preferably 5 to 30 nm.
The preparation method of the poor quality/heavy diesel hydrocracking catalyst, provided by the invention, is preferably as follows: dissolving inorganic acid in deionized water, mixing with white carbon black, and stirring to obtain paste; the nitric acid in the adhesive accounts for 5-45% of the mass of the white carbon black, and the dry basis ratio of the adhesive is 5-40 wt%.
The preparation method of the poor quality/heavy diesel oil hydrocracking catalyst comprises the step of selecting at least one of nitric acid, phosphoric acid, hydrochloric acid and sulfuric acid as the inorganic acid.
The preparation method of the poor quality/heavy diesel oil hydrocracking catalyst, provided by the invention, is characterized in that the VIB group metal salt is preferably selected from one or more of tungstic acid, ammonium metatungstate and ethyl ammonium metatungstate; the salt of the VIII group metal is preferably selected from one or more of nitrate, acetate and carbonate.
The preparation method of the hydrocracking catalyst comprises the following steps: carrying out kneading and strip extruding molding on a binder taking the modified Y molecular sieve, the macroporous alumina and the white carbon black as matrixes, drying at 80-150 ℃ for 2-8 hours, then placing the dried carrier in a muffle furnace, and roasting at 400-600 ℃ for 2-8 hours; adding VIB group and VIII group metal salt solutions into a carrier strip in an isovolumetric impregnation mode, drying at 80-150 ℃ for 2-8 hours, then placing the dried catalyst in a muffle furnace, and roasting at 400-600 ℃ for 2-8 hours to obtain a catalyst finished product.
The hydrocracking catalyst comprises a modified Y molecular sieve, macroporous alumina and white carbon black, wherein Ni-W is used as a hydrogenation metal component, and the catalyst carrier component comprises 30-80%, preferably 40-60% of the modified Y molecular sieve in terms of the dry-base mass percentage of the catalyst; 10-60%, preferably 10-50% of macroporous alumina; 10.0 to 40.0 percent of white carbon black, preferably 10 to 30 percent; WO3The content is 15-30%, preferably 22-26%, and the content of NiO is 3-15%, preferably 4-8%.
The crystal pack constant of the modified Y molecular sieve used in the invention is 2.430-2.460 nm, the silicon-aluminum ratio is 5-20, the preferred crystal pack constant is 2.440-2.455 nm, and the silicon-aluminum ratio is 8-15.
In step S1, the modified Y molecular sieve is prepared by modifying a common commercially available NaY molecular sieve by hydrothermal and acid combination, and the physical parameters of the common commercially available NaY molecular sieve are preferably a silica-alumina ratio of 4.2:1, and Na2The O content is 12.5 wt%, the crystal package constant is 2.468nm, and the relative crystallinity is 96%.
The preparation method of the modified Y molecular sieve comprises the following steps: and (3) sequentially carrying out ammonium exchange, first hydrothermal treatment, acid modification and second hydrothermal treatment on a common commercially available NaY molecular sieve to obtain the modified Y molecular sieve. The preparation method comprises the following steps:
(1) ammonium exchange, wherein the NaY raw powder is subjected to ammonium exchange for 3 times in the method, the ammonium exchange temperature is 80-110 ℃, preferably 85-95 ℃, the used ammonium salt is one or more of ammonium chloride, ammonium nitrate and ammonium sulfate, preferably ammonium chloride, the concentration of the used ammonium salt is 0.1-2.0 mol/L, preferably 0.5-1.0 mol/L, the solid-to-solid mass ratio of ammonium exchange liquid is 5: 1-30: 1, preferably 10: 1-20: 1, and the ammonium exchange time is 0.5-3 hours, preferably 1-2 hours.
(2) And (3) carrying out hydrothermal treatment on the Y molecular sieve for 3 times, wherein the temperature of the hydrothermal treatment is 500-750 ℃, preferably 550-650 ℃, the time of the hydrothermal treatment is 0.5-4 hours, preferably 1.0-2.0 hours, the pressure of the hydrothermal treatment is 0.05-0.5 MPa, preferably 0.1-0.3 MPa, the hydrothermal treatment process is preferably carried out under the condition of water injection, and the water injection amount is 50-600 ml/h, preferably 100-400 ml/h.
The macroporous alumina used in the invention has a specific surface area of 200-400 m2The pore volume is 0.5-1.0 ml/g, the specific surface area is preferably 250-380 m2The pore volume is 0.6-0.9 ml/g.
The specific surface area of the white carbon black used in the invention is 100-500 m2The particle diameter is 5-30 nm, and the preferable specific surface area is 150-300 m2(ii)/g, the particle diameter is 8-20 nm.
The acid used in the binder of the invention is inorganic acid, and can be one or more of nitric acid, phosphoric acid, hydrochloric acid and sulfuric acid, preferably nitric acid. The mass fraction of nitric acid in the binder is 5-45%, preferably 10-30%, and the dry basis ratio of the binder is 5-40%, preferably 15-25%.
The VIB group metal salt used in the invention can be one or more of tungstic acid, ammonium metatungstate and ethyl ammonium metatungstate, and preferably ammonium metatungstate; the VIII group metal salt may be one or several of nickel nitrate, nickel acetate and basic nickel carbonate, and is preferably nickel nitrate.
The drying temperature of the carrier and the catalyst is 80-150 ℃, and preferably 110-130 ℃; the drying time is 2 to 8 hours, preferably 4 to 6 hours. Roasting the carrier for 4-8 hours at 400-600 ℃, preferably for 3-7 hours at 450-550 ℃; the roasting condition of the catalyst is roasting for 2-8 hours at 400-600 ℃, preferably roasting for 3-7 hours at 450-550 ℃.
The invention has the following beneficial effects:
in step S1 of the preparation method of the present invention, a binder using white carbon black as a matrix is added to the modified Y molecular sieve and the macroporous alumina, and the catalyst carrier is prepared by extrusion molding, drying and roasting.
The method is characterized in that a binder taking white carbon black as a matrix is added, so that the interaction between the hydrogenation metal component and the carrier can be weakened well, and more II-type hydrogenation active centers with 2-5 microcrystalline layers and 6-12 nm of length are formed.
The catalyst prepared by the preparation method is used for producing naphtha by hydrocracking of poor diesel oil, has higher hydrogenation selectivity, and has the characteristics of high aromatic potential of the heavy naphtha, low BMCI value of tail oil and high yield of C5+ liquid.
Drawings
FIG. 1 shows NH of C-1 catalyst and C-4 catalyst3-TPD spectrum.
Detailed Description
The technical effects of the present invention are further illustrated and demonstrated by the following examples, which should not be construed as limiting the invention.
The preparation process of the hydrocracking catalyst comprises the following steps:
(1) mixing commercial NaY molecular sieve (Si/Al ratio 4.2:1, Na)2The O content is 12.5 wt%, the crystal packing constant is 2.468nm, and the relative crystallinity is 96%) is subjected to ammonium exchange, first hydrothermal treatment, acid modification and second hydrothermal treatment sequentially to obtain the modified Y molecular sieve;
(2) adding white carbon black into deionized water solution containing nitric acid, kneading to paste, preparing into binder, sealing and storing for later use.
(3) Mixing, kneading and extruding a binder taking a modified Y molecular sieve, macroporous alumina and white carbon black as matrixes to form strips, drying at 80-150 ℃ for 2-8 hours, then placing the dried carrier in a muffle furnace, and roasting at 400-600 ℃ for 2-8 hours to prepare a catalyst carrier;
(4) adding VIB group and VIII group metal salt solutions into a carrier strip in an isovolumetric impregnation mode, drying at 80-150 ℃ for 2-8 hours, then placing the dried catalyst in a muffle furnace, and roasting at 400-600 ℃ for 2-8 hours to obtain a catalyst finished product.
Wherein the specific surface area of the hydrocracking catalyst is preferably 200-500 m2The pore volume is preferably 0.2-0.6 ml/g;
wherein, the content of each component is preferably 30.0-80.0% of modified Y molecular sieve, 10.0-60.0% of macroporous alumina and 10.0-60.0% of white carbon black by taking the total dry-based mass of the catalyst carrier as the percentage;
the VIB group metal is preferably tungsten, and accounts for 15.0-30.0% of the total mass of the catalyst in terms of tungsten oxide; the VIII group metal is preferably nickel, and accounts for 3.0-15.0% of the total mass of the catalyst in terms of nickel oxide;
wherein, the tungsten accounts for 22.0-26.0% of the total mass of the catalyst preferably in terms of tungsten oxide; the nickel preferably accounts for 4.0-8.0% of the total mass of the catalyst in terms of nickel oxide;
the crystal packing constant of the modified Y molecular sieve is preferably 2.430-2.460 nm, the silicon-aluminum ratio is preferably 5-20, and the content of sodium oxide is preferably less than or equal to 0.2 wt%;
wherein the specific surface area of the macroporous alumina is preferably 200-400 m2The pore volume is preferably 0.5-1.0 ml/g;
wherein the specific surface area of the white carbon black is preferably 100-500 m2/g, the particle size is preferably 5 to 30 nm.
The preparation method of the adhesive is preferably as follows: dissolving inorganic acid in deionized water, mixing with white carbon black, and stirring to obtain paste; the nitric acid in the binder accounts for 5-45% of the mass of the white carbon black, and the dry basis ratio of the binder is 5-40 wt%;
wherein the inorganic acid is at least one selected from nitric acid, phosphoric acid, hydrochloric acid and sulfuric acid.
Wherein, the salt of the VIB group metal is preferably selected from one or more of tungstic acid, ammonium metatungstate and ethyl ammonium metatungstate; the salt of the VIII group metal is preferably selected from one or more of nitrate, acetate and carbonate.
The preparation method of the modified Y molecular sieve comprises the following steps: and (3) sequentially carrying out ammonium exchange, first hydrothermal treatment, acid modification and second hydrothermal treatment on a common commercially available NaY molecular sieve to obtain the modified Y molecular sieve. The preparation method comprises the following steps:
(1) ammonium exchange, wherein the NaY raw powder is subjected to ammonium exchange for 3 times in the method, the ammonium exchange temperature is 80-110 ℃, preferably 85-95 ℃, the used ammonium salt is one or more of ammonium chloride, ammonium nitrate and ammonium sulfate, preferably ammonium chloride, the concentration of the used ammonium salt is 0.1-2.0 mol/L, preferably 0.5-1.0 mol/L, the solid-to-solid mass ratio of ammonium exchange liquid is 5: 1-30: 1, preferably 10: 1-20: 1, and the ammonium exchange time is 0.5-3 hours, preferably 1-2 hours.
(2) And (3) carrying out hydrothermal treatment on the Y molecular sieve for 3 times, wherein the temperature of the hydrothermal treatment is 500-750 ℃, preferably 550-650 ℃, the time of the hydrothermal treatment is 0.5-4 hours, preferably 1.0-2.0 hours, the pressure of the hydrothermal treatment is 0.05-0.5 MPa, preferably 0.1-0.3 MPa, the hydrothermal treatment process is preferably carried out under the condition of water injection, and the water injection amount is 50-600 ml/h, preferably 100-400 ml/h.
Example 1
Preparation of modified Y molecular sieve
(1) Mixing commercial NaY molecular sieve (Si/Al ratio 4.2:1, Na)212.5 wt% of O, 2.468nm of crystal package constant and 96% of relative crystallinity) and 0.5mol/L of ammonium chloride solution are mixed, the liquid-solid weight ratio is 10:1, the temperature is raised to 85 ℃, ion exchange is carried out for 1.0 hour under stirring, mother liquor is filtered, water washing is repeated for 3 times, and suction filtration is carried out. Repeating the above process for 3 times, filtering, and washing to obtain NH4And (4) Y molecular sieve.
(2) Adding NH in the step (1)4The Y molecular sieve is treated under hydrothermal conditions. The hydrothermal treatment temperature is 550 ℃, the hydrothermal treatment time is 1.0 hour, the hydrothermal treatment pressure is 0.1MPa, and the water injection amount is 100 ml/h. After the first hydrothermal treatment is completed, repeating the step (1) to perform ammonium exchange, and then performingThe hydrothermal treatment is repeated twice under the hydrothermal conditions to obtain the hydrothermal modified Y molecular sieve which is marked as Y-1, and the properties of the hydrothermal modified Y molecular sieve are shown in Table 1.
Example 2
Preparation of modified Y molecular sieve
(1) Mixing commercial NaY molecular sieve (Si/Al ratio 4.2:1, Na)212.5 wt% of O, 2.468nm of crystal package constant and 96% of relative crystallinity) and 1.0mol/L of ammonium chloride solution are mixed, the liquid-solid weight ratio is 20:1, the temperature is raised to 95 ℃, ion exchange is carried out for 2.0 hours under stirring, mother liquor is filtered, water washing is repeated for 3 times, and suction filtration is carried out. Repeating the above process for 3 times, filtering, and washing to obtain NH4And (4) Y molecular sieve.
(2) Adding NH in the step (1)4The Y molecular sieve is treated under hydrothermal conditions. The hydrothermal treatment temperature is 650 ℃, the hydrothermal treatment time is 2.0 hours, the hydrothermal treatment pressure is 0.3MPa, and the water injection quantity is 400 ml/h. And (3) after the first hydrothermal treatment is finished, repeating the step (1) to perform ammonium exchange, and repeating the hydrothermal treatment twice according to the hydrothermal conditions to obtain the hydrothermal modified Y molecular sieve, wherein the property is marked as Y-2 and is shown in Table 1.
Example 3
Preparation of modified Y molecular sieve
(1) Mixing commercial NaY molecular sieve (Si/Al ratio 4.2:1, Na)212.5 wt% of O, 2.468nm of crystal package constant and 96% of relative crystallinity) and 0.8mol/L of ammonium chloride solution are mixed, the liquid-solid weight ratio is 15:1, the temperature is raised to 90 ℃, ion exchange is carried out for 1.5 hours under stirring, mother liquor is filtered, water washing is repeated for 3 times, and suction filtration is carried out. Repeating the above process for 3 times, filtering, and washing to obtain NH4And (4) Y molecular sieve.
(2) Adding NH in the step (1)4The Y molecular sieve is treated under hydrothermal conditions. The hydrothermal treatment temperature is 600 ℃, the hydrothermal treatment time is 1.5 hours, the hydrothermal treatment pressure is 0.2MPa, and the water injection amount is 200 ml/h. And (3) after the first hydrothermal treatment is finished, repeating the step (1) to perform ammonium exchange, and repeating the hydrothermal treatment twice according to the hydrothermal conditions to obtain the hydrothermal modified Y molecular sieve, wherein the property is marked as Y-3 and is shown in Table 1.
TABLE 1 modified molecular Sieve Properties
| Molecular sieve numbering | Y-1 | Y-2 | Y-3 |
| Constant of crystal pack, nm | 2.460 | 2.449 | 2.455 |
| Framework silicon to aluminum ratio | 6.7 | 11.5 | 8.5 |
| Relative degree of crystallinity,% | 79 | 78 | 85 |
| Specific surface area, m2/g | 621.5 | 588.9 | 576.7 |
| Pore volume, ml/g | 0.334 | 0.456 | 0.422 |
| Pore size, nm | 3.4 | 3.6 | 3.8 |
As can be seen from Table 1, as the pressure and temperature of the hydrothermal treatment are increased, the dealumination degree of the Y molecular sieve is increased, the silicon-aluminum ratio is increased from 6.6 of Y-1 to 12.5 of Y-2, and the crystal packing constant is also shrunk from 2.460 of Y-1 to 2.449 of Y-2. The Y molecular sieve has developed secondary pore passages after hydrothermal treatment, and the most probable pore diameter is between 3.4 and 3.8 nm.
Example 4
Preparation of hydrocracking catalyst
31.0g of nitric acid solution (65 wt%) is diluted with 1302.33g of refined water and slowly added into a kneader filled with 200g of white carbon black, and the mixture is fully kneaded into paste, so that the binder B-1 with 10 wt% of nitric acid content and 15 wt% of dry basis is prepared.
41.45 g of molecular sieve Y-1 (dry basis 98 wt%), 66.67 g of binder B-1 and 69.44g of macroporous alumina are kneaded, extruded into strips, dried at 110 ℃ for 4 hours and calcined at 450 ℃ for 4 hours to obtain the catalyst carrier S-1.
15.57g of nickel nitrate and 30.2g of ammonium metatungstate are dissolved in deionized water, and after complete dissolution, the nickel nitrate and the ammonium metatungstate are immersed in 70g of the carrier S-1 in equal volume, dried at 110 ℃ for 4 hours, and calcined at 450 ℃ for 4 hours to obtain the catalyst C-1, wherein the properties of the catalyst C-1 are shown in Table 2.
Example 5
Preparation of hydrocracking catalyst
92.3g of nitric acid solution (65 wt%) is diluted by 707.7g of refined water and slowly added into a kneader filled with 200g of white carbon black, and the mixture is fully kneaded into paste, so that the binder B-2 with 30 wt% of nitric acid content and 25 wt% of dry basis is prepared.
62.18 g of molecular sieve Y-2 (dry basis 98 wt%), 120 g of binder B-2 and 13.89g of macroporous alumina are kneaded, extruded into strips, dried at 130 ℃ for 6 hours and roasted at 550 ℃ for 7 hours to obtain the catalyst carrier S-2.
31.14g of nickel nitrate and 25.6g of ammonium metatungstate are dissolved in deionized water, and after complete dissolution, the nickel nitrate and the ammonium metatungstate are immersed in 70g of the carrier S-2 in equal volume, dried at 130 ℃ for 6 hours, and calcined at 550 ℃ for 7 hours to obtain the catalyst C-2, wherein the properties of the catalyst C-2 are shown in Table 2.
Example 6
Preparation of hydrocracking catalyst
61.5g of nitric acid solution (65 wt%) is diluted with 938.5g of refined water and slowly added into a kneader filled with 200g of white carbon black, and the mixture is fully kneaded into paste, so that the binder B-3 with 20 wt% of nitric acid content and 20 wt% of dry basis is prepared.
58.81 g of molecular sieve Y-3 (dry basis 98 wt%), 100 g of binder B-3 and 27.78g of macroporous alumina are kneaded, extruded into strips, dried at 115 ℃ for 5 hours and calcined at 500 ℃ for 5 hours to obtain the catalyst carrier S-3.
19.46g of nickel nitrate and 29.1g of ammonium metatungstate are dissolved in deionized water, and after complete dissolution, the nickel nitrate and the ammonium metatungstate are immersed in 70g of the carrier S-3 in equal volume, dried at 115 ℃ for 5 hours, and calcined at 500 ℃ for 5 hours to obtain the catalyst C-3, wherein the properties of the catalyst C-3 are shown in Table 2.
Comparative example 1
Preparation of hydrocracking catalyst
31.0g of nitric acid solution (65 wt%) was diluted with 1302.33g of purified water and slowly added to a kneader containing 200g of fine-pore alumina, and the mixture was kneaded into a paste-like state to prepare a binder D-1 having a nitric acid content of 10 wt% and a dry basis of 15 wt%.
41.45 g of molecular sieve Y-1 (dry basis 98 wt%), 66.67 g of binder D-1 and 69.44g of macroporous alumina are kneaded, extruded into strips, dried at 110 ℃ for 4 hours and calcined at 450 ℃ for 4 hours to obtain the catalyst carrier S-4.
15.57g of nickel nitrate and 30.2g of ammonium metatungstate are dissolved in deionized water, and after complete dissolution, the nickel nitrate and the ammonium metatungstate are immersed in 70g of the carrier S-4 in equal volume, dried at 110 ℃ for 4 hours, and calcined at 450 ℃ for 4 hours to obtain the catalyst C-4, wherein the properties of the catalyst C-4 are shown in Table 2.
TABLE 2 catalyst Properties
| Catalyst numbering | C-1 | C-2 | C-3 | C-4 |
| Specific surface area, m2/g | 333.7 | 331.8 | 363.8 | 321.2 |
| Pore volume, ml/g | 0.355 | 0.367 | 0.356 | 0.366 |
| Pore size, nm | 3.87 | 3.46 | 3.55 | 3.68 |
| NiO，wt％ | 4.1 | 7.9 | 4.9 | 4.0 |
| WO3，wt％ | 26.2 | 22.5 | 25.0 | 26.5 |
| Mechanical Strength, N/cm | 232 | 235 | 244 | 242 |
As can be seen from Table 2, the specific surface areas of the catalysts C1-C4 are 331.8-363.8 m2The catalyst has a mechanical strength of 232-244N/cm. From these results, it was found that the addition of silica to the binder did not significantly affect the physical properties such as the specific surface area and pore volume of the catalyst. Meanwhile, the catalyst has better mechanical strength.
Example 7
Evaluation of hydrocracking catalyst
The C1-C4 catalyst was evaluated on a 200ml hydrogenation evaluation apparatus using a straight-run diesel oil and catalytic diesel oil blend.
The raw oil is hydrofined in the 1 reverse refining stage and then enters the cracking stage, and the properties of the raw oil are shown in Table 3. The process conditions of the cracking section are as follows: the reaction pressure is 8.0MPa, the volume ratio of hydrogen to oil is 700:1, and the volume is 1.5h-1The evaluation results are shown in Table 4.
TABLE 3 Properties of the feed oils
TABLE 4 hydrogenation evaluation results
The results in Table 4 show that in the catalysts of C-1, C-2, C-3 and C-4, the cracking activity of the catalyst C-1 is moderate, the yield of C5+ liquid is as high as 97.8 percent, and the aromatic potential of heavy naphtha is as high as 54; the C-2 catalyst has higher cracking activity, the yield of heavy naphtha reaches 55 percent, the BMCI value of hydrogenated tail oil is lower, and the catalyst can be used as a high-quality ethylene cracking material; the hydrocracking activity of the C-3 catalyst is between C-1 and C-2. Comparing C-1 with the reference agent C-4, the hydrocracking activity and selectivity of the catalyst can be effectively improved by using the white carbon black as the binder. Comparing the four catalysts, the hydrocracking catalyst modified by white carbon black has higher hydrogenation activity and selectivity, and the development of the mesoporous Y molecular sieve can meet the requirement of appropriate hydrogenation of naphtha fraction to maximally retain monocyclic aromatic hydrocarbon and naphthenic hydrocarbon and improve naphtha aromatic hydrocarbon potential. The diesel fraction is selectively and deeply hydrogenated, aromatic hydrocarbons are subjected to large-scale hydrogenation saturation, the property of hydrogenated tail oil is improved, and the diesel fraction can be used as a high-quality ethylene cracking material and a high-quality diesel fraction.
In addition, as can be seen from fig. 1, the white carbon black is used as a binder, so that the acid amount of the catalyst can be effectively increased, and the hydrocracking performance of the catalyst can be improved.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (11)
1. A preparation method of a poor quality/heavy diesel oil hydrocracking catalyst, which is used for producing high aromatic latent naphtha and tail oil with low BMCI value, is characterized in that the preparation method of the hydrocracking catalyst comprises the following steps:
s1, adding a binder taking white carbon black as a matrix into the modified Y molecular sieve and the macroporous alumina, extruding into strips, and drying and roasting to obtain a catalyst carrier;
s2, preparing a salt solution containing VIB group metals and VIII group metals as an impregnation solution, impregnating the catalyst carrier in the impregnation solution in an equal volume, and drying and roasting to obtain a hydrocracking catalyst;
the crystal package constant of the modified Y molecular sieve is 2.440-2.460 nm, the silicon-aluminum ratio is 8-15, and the content of sodium oxide is less than or equal to 0.2 wt%;
the preparation method of the adhesive comprises the following steps: dissolving inorganic acid in deionized water, mixing with white carbon black, and stirring to obtain paste; the nitric acid in the adhesive accounts for 5-45% of the mass of the white carbon black, and the dry basis ratio of the adhesive is 5-40 wt%.
2. The method for preparing the poor quality/heavy diesel hydrocracking catalyst as claimed in claim 1, wherein the preparation of the modified Y molecular sieve comprises the following steps: and (3) sequentially carrying out ammonium exchange, first hydrothermal treatment, acid modification and second hydrothermal treatment on a common commercially available NaY molecular sieve to obtain the modified Y molecular sieve.
3. The method for preparing the poor quality/heavy diesel oil hydrocracking catalyst of claim 1, wherein the hydrocracking catalyst has a specific surface area of 200-500 m2The pore volume is 0.2 to 0.6 mL/g.
4. The preparation method of the poor quality/heavy diesel hydrocracking catalyst as claimed in claim 1, wherein the catalyst carrier comprises, by dry basis total mass, 30.0-80.0% of the modified Y molecular sieve, 10.0-60.0% of the macroporous alumina and 10.0-40.0% of the white carbon black.
5. The preparation method of the poor quality/heavy diesel hydrocracking catalyst as claimed in claim 1, wherein the catalyst carrier comprises, by dry basis total mass, 40.0-60.0% of the modified Y molecular sieve, 10.0-50.0% of the macroporous alumina and 10.0-30.0% of the white carbon black.
6. The preparation method of the poor quality/heavy diesel hydrocracking catalyst according to claim 1, wherein the VIB group metal is tungsten, and accounts for 15.0-30.0% of the total mass of the catalyst in terms of tungsten oxide; the VIII group metal is nickel, and accounts for 3.0-15.0% of the total mass of the catalyst in terms of nickel oxide.
7. The method for preparing the poor quality/heavy diesel hydrocracking catalyst of claim 6, wherein the tungsten, calculated as tungsten oxide, accounts for 22.0-26.0% of the total mass of the catalyst; the nickel accounts for 4.0-8.0% of the total mass of the catalyst in terms of nickel oxide.
8. The preparation method of the poor quality/heavy diesel oil hydrocracking catalyst as claimed in claim 1, wherein the macroporous alumina has a specific surface area of 200-400 m2The pore volume is 0.5 to 1.0 mL/g.
9. The preparation method of the poor quality/heavy diesel oil hydrocracking catalyst as claimed in claim 1, wherein the white carbon black specific surface area is 100-500 m2(iv) g, particle size of 5 to 30 nm.
10. The method of claim 1, wherein the inorganic acid is at least one selected from nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid.
11. The method for preparing the poor quality/heavy diesel hydrocracking catalyst as claimed in claim 1, wherein the group VIB metal salt is one or more selected from tungstic acid, ammonium metatungstate and ethyl ammonium metatungstate; the salt of the VIII group metal is selected from one or more of nitrate, acetate and carbonate.
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