CN106582781B - High-sulfur-resistance hydrocracking catalyst and preparation method thereof - Google Patents
High-sulfur-resistance hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-sulfur-resistance hydrocracking catalyst and a preparation method thereof. Mainly solves the problem of poor sulfur resistance of the traditional hydrocracking catalyst. The catalyst is adopted, and comprises the following components in percentage by weight: the technical scheme is that 40-50% of at least one selected from FAU, BEA, MOR, MFI type zeolite or amorphous silica-alumina, 10-25% of pseudo-boehmite, 10-18% of molybdenum sulfide and 4-15% of at least one selected from nickel phosphide, cobalt phosphide, molybdenum phosphide or tungsten phosphide are used as active components, and the problems are well solved. The catalyst prepared by the method is suitable for the distillate oil hydrocracking process with the sulfur content not higher than 120 mu g/g, and has high cracking activity.
Description
Technical Field
The invention relates to a high-sulfur-resistance hydrocracking catalyst and a preparation method thereof.
Background
The hydrocracking technology has the characteristics of strong raw material adaptability, large product scheme flexibility, high target product selectivity, good product quality, high added value and the like, can directly convert various heavy and poor raw materials into clean fuel oil and high-quality chemical raw materials, becomes one of the most important heavy oil deep processing technologies in modern oil refining and petrochemical industries, and is increasingly widely applied at home and abroad. The hydrocracking catalyst is generally a bifunctional catalyst, the sulfur and nitrogen resistance is not high, particularly, the noble metal catalyst has strict requirements on the sulfur content in the raw material, if the noble metal catalyst is operated for a period of time beyond a specified value, the activity of the cracking catalyst is obviously reduced, so that the sulfur content in the raw material is generally required to be less than 50 mu g/g for the hydrocracking catalyst containing the molecular sieve, so as to prevent active center poisoning. However, due to the restriction of the development of the refining section catalyst before the cracking section, the refining section product still contains a certain amount of sulfide impurities, and the removal is difficult, which brings difficulty to the stable operation of the subsequent cracking catalyst. Therefore, the sulfur resistance of hydrocracking catalysts has long been the focus of developing such catalysts.
CN1415704A discloses a noble metal hydrocracking catalyst and a preparation method thereof, the catalyst takes modified Y zeolite alumina as a carrier and takes VIII group noble metal in the periodic table of elements as a hydrogenation active component, the unit cell parameter of the modified Y zeolite is 2.420-2.450 nm, and SiO is2/Al2O3The value is 10-100, the crystallinity is more than 95%, and the specific surface area is 700-900 m2Per g, pore volume of 0.35-0.55 ml/g, infrared acidity of 0.2-2.0 mmol/g, Na2The content of O is less than 0.20 percent by weight. The modified Y-type zeolite is treated through secondary hydrothermal treatment and acid treatment, so that the catalyst has the features of high heat stability, high middle oil selectivity, high sulfur resistance, high nitrogen resistance, etc. the catalyst may be used in the hydrocracking, hydrotreating and hydrogenating modification of fraction oil, especially in the deep hydrocracking reaction of heavy fraction oil.
CN 1458238A discloses a noble metal hydrocracking catalyst and a preparation method thereof. The catalyst contains a carrier component, a modified Y zeolite and one or two noble metal components. The catalyst is characterized in that a noble metal hydrogenation component is supported on a carrier component, and the modified super-hydrophobic Y zeolite does not contain the hydrogenation component. And the modified Y zeolite has the characteristics of high specific surface area, large pore volume, proper acid distribution, high silicon-aluminum ratio and the like after advanced treatment. The catalyst has high metal dispersity, strong carbon deposition resistance and certain sulfur resistance, can be used for the processes of hydrocracking, hydrotreating, hydro-upgrading and the like of distillate oil, and has high selectivity of middle distillate oil.
CN 104646043A discloses a method for preparing a hydrocracking catalyst by a sol-gel method; taking ethyl orthosilicate as a silicon oxide source, taking cesium heteropoly acid salt as an acidic component, nickel as a hydrogenation component and citric acid as a complexing agent, wherein the catalyst comprises the acidic component 10-50 wt%, the hydrogenation component 5-10 wt% and the balance of a carrier; the preparation method has the characteristics of simple preparation method, good repeatability, large specific surface area, good metal component dispersibility, higher catalytic performance and strong sulfur and nitrogen resistance, and cesium phosphotungstate is used as an acid component, so that the cesium phosphotungstate has higher thermal stability and is not easy to lose in the reaction process.
CN101670300A discloses an anti-sulfur and anti-nitrogen hydrocracking catalyst and a preparation method thereof, relating to a porous solid catalyst and a preparation method thereof. Provides a sulfur-nitrogen resistant hydrocracking catalyst with the advantages of difficult loss of catalyst components and high sulfur-nitrogen resistant performance and a preparation method thereof. The catalyst comprises an acidic component, a hydrogenation component and a carrier, wherein the acidic component is cesium phosphotungstate, the hydrogenation component is nickel, and the carrier is alumina; the catalyst comprises 30-50% of acid component, 3-8% of hydrogenation component and the balance of carrier according to mass percentage. Roasting the carrier for later use; respectively adding water-soluble nickel salt and water-soluble cesium salt solution into the carrier, and soaking; separating the impregnated liquid-solid mixture, drying the solid, and roasting; and (3) dipping the roasted solid by the heteropoly acid aqueous solution, standing and drying to obtain the sulfur-resistant and nitrogen-resistant hydrocracking catalyst.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a novel catalyst for hydrocracking in order to overcome the problem of poor sulfur resistance of the traditional hydrocracking catalyst. The catalyst has the advantages of strong sulfur resistance and high cracking activity.
The second technical problem to be solved by the present invention is to provide a method for preparing a hydrocracking catalyst with high sulfur resistance corresponding to the first technical problem.
The invention aims to solve the technical problem and provides an operation method of the high-sulfur-resistance hydrocracking catalyst corresponding to the solution of one of the technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a high sulfur resistant hydrocracking catalyst comprises the following components in percentage by weight:
(a) 40-50% of at least one selected from FAU, BEA, MOR, MFI type zeolite or amorphous silica-alumina;
(b) 10-25% of pseudo-boehmite;
(c) 10-18% of molybdenum sulfide is used as an active component;
(d) 4-15% of at least one selected from nickel phosphide, cobalt phosphide, molybdenum phosphide or tungsten phosphide is used as an active component;
in the above technical solution, the FAU zeolite in the part (a) is selected from at least one of USY, HY, NTY or SSY molecular sieves; the BEA zeolite is selected from hydrogen type or ammonium type Beta molecular sieve; the MOR zeolite is selected from the hydrogen or ammonium forms of mordenite; the MFI zeolite is selected from the hydrogen type or ammonium type ZSM-5 molecular sieve.
In the above embodiment, the part (a) is preferably a USY or Beta type zeolite.
In the technical scheme, the part (d) is preferably 4-8% of cobalt phosphide and molybdenum phosphide.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of a high-sulfur-resistance hydrocracking catalyst comprises the following steps:
① mixing at least one of FAU, BEA, MOR, MFI type zeolite or amorphous silica-alumina with pseudo-boehmite, molding, extruding, drying, and calcining at 450-650 deg.C for 0.5-24 h to obtain catalyst carrier;
② soaking a sulfide of molybdenum and a phosphide precursor solution of at least one of nickel, cobalt, molybdenum or tungsten at 10-60 deg.C on a catalyst carrier, aging for 0.5-24 h, and drying for later use;
③, heat-treating for 1-12 h at 280-450 ℃ in hydrogen or nitrogen atmosphere to obtain the catalyst finished product.
In the technical scheme, the precursor solution of the metal sulfide can be impregnated on the carrier before or after the precursor solution of the metal phosphide in the impregnation process.
The precursor of the metal sulfide molybdenum sulfide used in the technical scheme is ammonium thiomolybdate, and preferably an ammonium tetrathiomolybdate solution.
The precursor of the metal phosphide nickel phosphide used in the technical scheme is a solution containing nickel ions and hypophosphite ions, and preferably a nickel hypophosphite solution.
The precursor of the metal phosphide cobalt phosphide used in the technical scheme is a solution containing cobalt ions and hypophosphite ions, and preferably a cobalt hypophosphite solution.
The precursor of the metal phosphide molybdenum phosphide used in the technical scheme is a solution containing molybdate ions and hypophosphite ions, and preferably a mixed solution of ammonium paramolybdate and ammonium hypophosphite.
The precursor of the metal phosphide tungsten phosphide used in the technical scheme is a solution containing tungstate ions and hypophosphite ions, and preferably a mixed solution of ammonium metatungstate and ammonium hypophosphite.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: a high sulfur-resistant hydrocracking method comprises the steps of mixing sulfur-containing distillate oil with hydrogen, passing through a catalyst bed layer from top to bottom, and reacting at the temperature of 350-450 ℃, the reaction pressure of 4-10 MPa and the volume space velocity of 0.5-5 hr-1And the hydrogen-oil volume ratio is 800-1200, and the catalyst is contacted with any one of the catalysts to carry out hydrocracking reaction.
In the technical scheme, the sulfur content in the distillate oil is not higher than 120 mu g/g.
The invention uses a supercritical fixed bed reactor to carry out the performance test of hydrocracking reaction, and the inside diameter phi of the reactor is 12 mm, the length is 800 mm, and the reactor is made of stainless steel. The electric heating is adopted, and the temperature is automatically controlled. The bottom of the reactor is filled with glass beads of phi 2-3 mm as a support, the reactor is filled with 5g of catalyst, and the upper part of the reactor is filled with glass beads of phi 2-3 mm for preheating and vaporizing raw materials. The sulfur-containing distillate oil is mixed with hydrogen and passes through a catalyst bed layer from top to bottom for hydrocracking reaction.
The catalyst provided by the invention can be used for a distillate oil hydrocracking process with the sulfur content not higher than 120 mu g/g, and has high cracking activity. According to the invention, the combination of the metal sulfide and the metal phosphide is used as an active component, so that the activity of two reaction paths of hydrogenation and hydrogenolysis for desulfurization is obviously improved, and the desulfurization is further carried out under the synergistic effect of the metal sulfide and the metal phosphide, and then the desulfurization is contacted with the acid center of the molecular sieve to carry out cracking reaction, so that the toxic action on the acid center of the catalyst is reduced, the smooth proceeding of the cracking reaction is ensured, and the cracking activity is improved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
On a dry basis 60g of USY zeolite (ex Shandong Zibo) having a Si/Al ratio of 10 and 25g of pseudoboehmite (ex Shandong Zibo) were added to a mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a volume ratio of 1:1 were added to the mixture3The solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Soaking the carrier particles in an ammonium tetrathiomolybdate solution at 40 ℃, wherein the content of molybdenum sulfide in the soaking solution is 10 percent of the dry basis weight of the carrier, aging for 8 hours, drying, soaking the carrier particles in a nickel hypophosphite solution at 40 ℃, wherein the content of nickel phosphide in the soaking solution is 6 percent of the dry basis weight of the carrier, aging for 8 hours, drying, and performing heat treatment in hydrogen at 360 ℃ for 4 hours (which can be completed in a reactor) to obtain the finished catalyst 1.
The catalyst 1 was used for the evaluation of the hydrocracking performance of the refined light cycle oil, and the composition of the feedstock is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
[ example 2 ]
On a dry basis, 60g of zeolite Beta (from Shandong Zibo) having a Si/Al ratio of 15 and 25g of pseudoboehmite (from Shandong Zibo) were added to a mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a volume ratio of 1:1 were added to the mixture3The solution was mixed with 40g of deionized water and milled uniformly to make a blend suitable for extrusionAnd (4) dough. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Soaking the carrier particles in an ammonium tetrathiomolybdate solution at 40 ℃, wherein the content of molybdenum sulfide in the soaking solution is 10 percent of the dry basis weight of the carrier, aging for 8 hours, drying, soaking the carrier particles in a nickel hypophosphite solution at 40 ℃, wherein the content of nickel phosphide in the soaking solution is 6 percent of the dry basis weight of the carrier, aging for 8 hours, drying, and performing heat treatment in hydrogen at 360 ℃ for 4 hours (which can be completed in a reactor) to obtain the finished catalyst 2.
The catalyst 2 was used for the evaluation of the hydrocracking performance of the refined light cycle oil, and the composition of the feedstock is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
[ example 3 ]
On a dry basis, 60g of ZSM-5 zeolite (ex catapul, Shandong) having a silica-to-alumina ratio of 100 and 30g of pseudoboehmite (ex catapul, Shandong) were added to a mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a volume ratio of 1:1 were added to the mixture3The solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Soaking the carrier particles in an ammonium tetrathiomolybdate solution at 40 ℃, wherein the content of molybdenum sulfide in the soaking solution is 10 percent of the dry basis weight of the carrier, aging for 8 hours, drying, soaking the carrier particles in a nickel hypophosphite solution at 40 ℃, wherein the content of nickel phosphide in the soaking solution is 6 percent of the dry basis weight of the carrier, aging for 8 hours, drying, and performing heat treatment in hydrogen at 360 ℃ for 4 hours (which can be completed in a reactor) to obtain the finished catalyst 3.
Catalyst 3 is usedThe hydrocracking performance of the refined light cycle oil was evaluated, and the composition of the feedstock is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
[ example 4 ]
On a dry basis, 30g of USY zeolite (from catalpo, Shandong), 30g of amorphous aluminosilicate (from catalpo, Shandong) and 30g of pseudoboehmite (from catalpo, Shandong) were added to a mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a 1:1 by volume ratio were added to the mixture3The solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Soaking the carrier particles in an ammonium tetrathiomolybdate solution at 40 ℃, wherein the content of molybdenum sulfide in the soaking solution is 10 percent of the dry basis weight of the carrier, aging for 8 hours, drying, soaking the carrier particles in a nickel hypophosphite solution at 40 ℃, wherein the content of nickel phosphide in the soaking solution is 6 percent of the dry basis weight of the carrier, aging for 8 hours, drying, and performing heat treatment in hydrogen at 360 ℃ for 4 hours (which can be completed in a reactor) to obtain the finished catalyst 4.
Catalyst 4 was used for the evaluation of hydrocracking performance of the refined light cycle oil, and the composition of the feedstock is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
[ example 5 ]
On a dry basis 30g of USY zeolite (ex catalpo, Shandong), 30g of Beta zeolite (ex catalpo) with a Si/Al ratio of 10, 30g of zeolite Beta with a Si/Al ratio of 15 and 30g of pseudoboehmite (ex catalpo) were added to a mixer until homogeneous, and then 3g of sesbania powder, 5g of sesbania powder in a volume ratio of 1:1HNO3the solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Soaking the carrier particles in an ammonium tetrathiomolybdate solution at 40 ℃, wherein the content of molybdenum sulfide in the soaking solution is 10 percent of the dry basis weight of the carrier, aging for 8 hours, drying, soaking the carrier particles in a nickel hypophosphite solution at 40 ℃, wherein the content of nickel phosphide in the soaking solution is 6 percent of the dry basis weight of the carrier, aging for 8 hours, drying, and performing heat treatment in hydrogen at 360 ℃ for 4 hours (which can be completed in a reactor) to obtain the finished catalyst 5.
The catalyst 5 was used for the evaluation of the hydrocracking performance of the refined light cycle oil, and the composition of the feedstock is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
[ example 6 ]
On a dry basis 30g of USY zeolite (ex catalpo) having a silica to alumina ratio of 10, 30g of Beta zeolite (ex catalpo) having a silica to alumina ratio of 15 and 30g of pseudoboehmite (ex catalpo) were added to a mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a volume ratio of 1:1 were added to the mixture3The solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Soaking the carrier particles in an ammonium tetrathiomolybdate solution at 40 ℃, wherein the content of molybdenum sulfide in the soaking solution is 12 percent of the dry basis weight of the carrier, aging for 8 hours, drying, soaking the carrier particles in a nickel hypophosphite solution at 40 ℃, wherein the content of nickel phosphide in the soaking solution is 4 percent of the dry basis weight of the carrier, aging for 8 hours, drying, and performing heat treatment at 360 ℃ in hydrogen for 4 hours (which can be completed in a reactor) to obtain the finished catalyst 6.
The catalyst 6 was used for the evaluation of the hydrocracking performance of the refined light cycle oil, and the composition of the feedstock is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
[ example 7 ]
On a dry basis 30g of USY zeolite (ex catalpo) having a silica to alumina ratio of 10, 30g of Beta zeolite (ex catalpo) having a silica to alumina ratio of 15 and 30g of pseudoboehmite (ex catalpo) were added to a mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a volume ratio of 1:1 were added to the mixture3The solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Soaking the carrier particles in an ammonium tetrathiomolybdate solution at 40 ℃, wherein the content of molybdenum sulfide in the soaking solution is 12 percent of the dry basis weight of the carrier, aging for 8 hours, drying, soaking the carrier particles in a cobalt hypophosphite solution at 40 ℃, wherein the content of cobalt phosphide in the soaking solution is 4 percent of the dry basis weight of the carrier, aging for 8 hours, drying, and performing heat treatment at 360 ℃ for 4 hours (which can be completed in a reactor) in hydrogen to obtain the finished catalyst 7.
The catalyst 7 was used for evaluation of hydrocracking performance of the refined light cycle oil, and the composition of the raw material is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
[ example 8 ]
30g of USY zeolite (from Zibo, Shandong) with Si/Al ratio of 10 and 30g of Beta zeolite (from Zibo, Shandong) with Si/Al ratio of 15 on a dry basisBo) and 30g of pseudoboehmite (from Shandong Zibo) were added to the mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a volume ratio of 1:1 were added to the mixture3The solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Soaking the carrier particles in an ammonium tetrathiomolybdate solution at 40 ℃, wherein the content of molybdenum sulfide in the soaking solution is 10 percent of the dry basis weight of the carrier, aging for 8 hours, drying, soaking the carrier particles in a cobalt hypophosphite solution at 40 ℃, wherein the content of cobalt phosphide in the soaking solution is 6 percent of the dry basis weight of the carrier, aging for 8 hours, drying, and performing heat treatment at 360 ℃ for 4 hours (which can be completed in a reactor) in hydrogen to obtain the finished catalyst 8.
The catalyst 8 was used for the evaluation of the hydrocracking performance of the refined light cycle oil, and the composition of the feedstock is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
[ example 9 ]
On a dry basis 30g of USY zeolite (ex catalpo) having a silica to alumina ratio of 10, 30g of Beta zeolite (ex catalpo) having a silica to alumina ratio of 15 and 30g of pseudoboehmite (ex catalpo) were added to a mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a volume ratio of 1:1 were added to the mixture3The solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Soaking the carrier particles in an ammonium tetrathiomolybdate solution at 40 ℃, wherein the content of molybdenum sulfide in the soaking solution is 10 percent of the dry basis weight of the carrier on a reduced basis, aging for 8 hours, drying, soaking the carrier particles in a mixed solution of cobalt hypophosphite, ammonium hypophosphite and ammonium paramolybdate at 40 ℃, wherein the content of cobalt phosphide and molybdenum phosphide in the soaking solution is 3 percent of the dry basis weight of the carrier on a reduced basis, aging for 8 hours, drying, and performing heat treatment in hydrogen at 360 ℃ for 4 hours (which can be completed in a reactor) to obtain the finished catalyst 9.
The catalyst 9 was used for evaluation of hydrocracking performance of the refined light cycle oil, and the composition of the raw material is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 360 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
[ example 10 ]
On a dry basis 30g of USY zeolite (ex catalpo) having a silica to alumina ratio of 10, 30g of Beta zeolite (ex catalpo) having a silica to alumina ratio of 15 and 30g of pseudoboehmite (ex catalpo) were added to a mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a volume ratio of 1:1 were added to the mixture3The solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Soaking carrier particles in an ammonium tetrathiomolybdate solution at 40 ℃, wherein the content of molybdenum sulfide in the soaking solution is 10% of the dry basis weight of the carrier on a reduced basis, aging for 8 hours, drying, soaking the carrier particles in a mixed solution of cobalt hypophosphite, ammonium hypophosphite and ammonium metatungstate at 40 ℃, wherein the content of cobalt phosphide and tungsten phosphide in the soaking solution is 3% of the dry basis weight of the carrier on a reduced basis, aging for 8 hours, drying, and performing heat treatment in hydrogen at 360 ℃ for 4 hours (which can be completed in a reactor) to obtain the finished catalyst 10.
The catalyst 10 was used for evaluation of hydrocracking performance of refined light cycle oil, and the composition of the raw material is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1Contacting with catalyst under the condition of hydrogen-oil volume ratio of 1000, and recovering productThe fractions were collected and examined, and the conversion results are shown in Table 2.
[ COMPARATIVE EXAMPLE 1 ]
On a dry basis 30g of USY zeolite (ex catalpo) having a silica to alumina ratio of 10, 30g of Beta zeolite (ex catalpo) having a silica to alumina ratio of 15 and 30g of pseudoboehmite (ex catalpo) were added to a mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a volume ratio of 1:1 were added to the mixture3The solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
And (3) soaking the carrier particles in an ammonium paramolybdate solution containing 10% of molybdenum oxide at 40 ℃, aging for 8h, drying, then carrying out conventional pre-vulcanization, and carrying out reduction activation treatment to obtain the finished catalyst A.
The catalyst a was used for the evaluation of hydrocracking performance of the refined light cycle oil, and the composition of the feedstock is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
[ COMPARATIVE EXAMPLE 2 ]
On a dry basis 30g of USY zeolite (ex catalpo) having a silica to alumina ratio of 10, 30g of Beta zeolite (ex catalpo) having a silica to alumina ratio of 15 and 30g of pseudoboehmite (ex catalpo) were added to a mixer until homogeneous, and then 3g of sesbania powder and 5g of HNO in a volume ratio of 1:1 were added to the mixture3The solution was milled uniformly with 40g of deionized water to make a dough suitable for extrusion. Extruding the mixture through a die to form a slender cylinder (the diameter is 1.7mm), drying the cylinder at 120 ℃, roasting the cylinder at 550 ℃ for 4 hours, and cutting the cylinder into carrier particles with consistent sizes (1.7 multiplied by 4.0mm) for later use.
Mixing ammonium paramolybdate containing 10% of molybdenum oxide and nickel nitrate containing 6% of nickel oxide, impregnating carrier particles at 40 ℃, aging for 8 hours, drying, then carrying out conventional pre-vulcanization, and carrying out reduction activation treatment to obtain the finished catalyst B.
The catalyst B was used for the evaluation of the hydrocracking performance of the refined light cycle oil, and the composition of the feedstock is shown in table 1. Mixing liquid raw material with hydrogen, passing through catalyst bed layer from top to bottom at reaction temperature of 366 deg.C, reaction pressure of 6MPa, and volume space velocity of 1.0hr-1And the catalyst was contacted with the hydrogen-oil volume ratio of 1000, and the product was recovered and subjected to compositional examination, and the conversion results are shown in table 2.
TABLE 1
TABLE 2
[ examples 11 to 16 ]
The catalyst in example 1 is used for hydrocracking performance evaluation of refined light cycle oil. The liquid raw material was mixed with hydrogen and passed through the catalyst bed from top to bottom, the hydrocracking reaction was carried out with adjustment of the evaluation process conditions temperature, pressure, volume space velocity, hydrogen-oil volume ratio, and sulfur content in the raw material to recover the product and detect the components, and the conversion results are shown in table 3.
TABLE 3
Claims (8)
1. A high sulfur resistant hydrocracking catalyst comprises the following components in percentage by weight:
(a) 40-50% of at least one selected from FAU, BEA, MOR, MFI type zeolite or amorphous silica-alumina;
(b) 10-25% of pseudo-boehmite;
(c) 10-18% of molybdenum sulfide is used as an active component;
(d) 4-8% of cobalt phosphide and molybdenum phosphide.
2. A method for preparing the high sulfur resistance hydrocracking catalyst of claim 1, comprising the steps of:
① mixing at least one of FAU, BEA, MOR, MFI type zeolite or amorphous silica-alumina with pseudo-boehmite, molding, extruding, drying, and calcining at 450-650 deg.C for 0.5-24 h to obtain catalyst carrier;
② dipping a sulfide precursor of metal molybdenum and a phosphide precursor solution of metal cobalt and molybdenum on a catalyst carrier at the temperature of 10-60 ℃ for aging for 0.5-24 h, and drying for later use;
③, heat-treating for 1-12 h at 280-450 ℃ in hydrogen or nitrogen atmosphere to obtain the catalyst finished product.
3. The method for preparing a hydrocracking catalyst with high sulfur resistance according to claim 2, wherein the impregnation of the precursor solution of molybdenum sulfide may be preceded or followed by the impregnation of the precursor solution of metal phosphide on the support.
4. The method for preparing a hydrocracking catalyst with high sulfur resistance as recited in claim 2, wherein said sulfide precursor of metallic molybdenum is ammonium thiomolybdate.
5. The method for preparing a hydrocracking catalyst with high sulfur resistance according to claim 2, wherein the precursor of the metal phosphide cobalt phosphide is a solution containing cobalt ions and hypophosphite ions.
6. The method for preparing a hydrocracking catalyst with high sulfur resistance according to claim 2, wherein the precursor of the metal phosphide molybdenum phosphide is a solution containing molybdate ions and hypophosphite ions.
7. A process for preparing the sulfur-resistant hydrocracked distillate oil containing sulfur and hydrogenPassing through a catalyst bed layer from top to bottom at a reaction temperature of 350-450 ℃, a reaction pressure of 4-10 MPa and a volume space velocity of 0.5-5 hr-1And contacting with the catalyst of claim 1 or the catalyst prepared by the preparation method of any one of claims 2 to 6 under the condition of hydrogen-oil volume ratio of 800-1200 to perform hydrocracking reaction.
8. The sulfur-resistant hydrocracking process according to claim 7, wherein the sulfur content in the distillate is not higher than 120. mu.g/g.
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