CN109926094B - Hydrocracking catalyst and preparation method thereof - Google Patents
Hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrocracking catalyst and a preparation method thereof, wherein the hydrocracking catalyst comprises an acidic component, a hydrogenation metal component, an auxiliary agent and a carrier, and the acidic component is heteropoly acid ammonium salt. The preparation method of the hydrocracking catalyst comprises the steps of preparing a catalyst precursor, modifying the precursor to prepare a carrier, and loading an acidic component and a hydrogenation metal component. The catalyst obtained by the method of the invention has higher reaction activity and liquid hydrocarbon selectivity when being used for hydrocracking reaction of long-chain alkane.
Description
Technical Field
The invention belongs to the field of petrochemical industry, relates to a catalytic material and a preparation method thereof, and particularly relates to a hydrocracking catalyst and a preparation method thereof.
Background
In the oil refining industry, hydrocracking is an important process for producing high-quality light oil from heavy oil, and is a conversion process of raw oil in the presence of a catalyst under the conditions of high temperature, high pressure and hydrogen presence for carrying out chemical reactions such as hydrogenation, desulfurization, denitrification, molecular skeleton rearrangement, cracking and the like. The hydrocracking process can produce high quality light oil product and has high liquid phase product yield and catalyst as the technological core. The hydrocracking catalyst is a bifunctional catalyst which has both an acidic function and a hydrogenation function. The acid function of the hydrocracking catalysts referred to in US5,536,687, US5,447,623 and EP0028938a1 is provided primarily by molecular sieves, and the hydrogenation component is Mo-Ni or W-Ni. The catalyst related to CN1389545A contains 20-40% of Y zeolite, 5-20% of phosphotungstic heteropoly acid or silicotungstic heteropoly acid, 5-10% of nickel oxide and 40-60% of alumina. The hydrocracking catalyst containing the molecular sieve has the advantages of strong acidity and large specific surface, but has the defect that the pore diameter of the molecular sieve is small, so that the diffusion resistance of reactants and products is increased, and the probability of secondary cracking reaction is increased.
CN1927461A discloses a hydrocracking catalyst containing heteropoly acid, which can be phosphotungstic acid or silicotungstic acid, the content of the heteropoly acid is 40-60%, the preferred content of hydrogenation components (calculated by simple substances) is 5-10%, and the rest is a carrier. During preparation, the inorganic heat-resistant material particle carrier is selected as a catalyst carrier according to the proportion, a metal salt aqueous solution of the hydrogenation component is prepared, and the carrier is impregnated; drying and roasting the solid after liquid-solid separation; preparing heteropoly acid aqueous solution, dipping the prepared solid, standing, drying and roasting. The hydrocracking catalyst containing heteropoly acid has the advantages of strong acidity and large pore diameter, but has the defects of high water solubility of phosphotungstic acid, easy loss in the using process and increased possibility of secondary cracking reaction due to strong acidity of the catalyst.
Cn201110350796.x discloses a hydrocracking catalyst and a preparation method thereof. The catalyst comprises an acidic component, a hydrogenation component and a carrier, wherein the acidic component is heteropolyacid alkali metal salt, the hydrogenation component is nickel, and the carrier is silicon oxide; the catalyst comprises 10-20% of acid component, 3-8% of hydrogenation component and the balance of carrier according to mass percentage. The method is characterized in that a catalyst carrier is prepared by adopting a sol-gel method, a hydrogenation metal component and an alkali metal salt are introduced in the preparation process of the carrier, the carrier is immersed in a heteropoly acid solution, and the catalyst is obtained after drying. The catalyst of the invention has the advantages that the heteropolyacid salt is uniformly dispersed in the carrier, and the catalyst shows high liquid hydrocarbon selectivity due to weak acidity and low content, but the activity is relatively low.
CN201110350795.5 discloses a hydrocracking catalyst and a preparation method thereof. In the catalyst, the acidic component is silicotungstate, the hydrogenation metal component is nickel, and the carrier is silicon oxide. According to the method, the silicotungstate is introduced in the preparation process of the carrier, the silicotungstate is uniformly dispersed in the carrier, and the catalyst has good catalytic performance. However, the silicotungstate loaded in the pore channels of the catalyst can cause a part of products to have secondary cracking reaction, thereby reducing the selectivity of the catalyst and influencing the yield of target products.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a hydrocracking catalyst and a preparation method thereof. The catalyst prepared by the method of the invention shows higher reaction activity and liquid hydrocarbon selectivity when being used for hydrocracking reaction of long-chain alkane.
The first aspect of the present invention provides a preparation method of a hydrocracking catalyst, which comprises the following steps:
(1) preparing an aqueous solution containing a hydrogenation metal component and an auxiliary agent P from a compound containing the hydrogenation metal component, a phosphorus-containing compound and water;
(2) mixing pseudo-boehmite with water to form suspension;
(3) mixing the aqueous solution, the template agent and the heteropoly acid obtained in the step (1) with the suspension obtained in the step (2);
(4) stirring the mixed solution obtained in the step (3) at the temperature of 60-90 ℃ until the solution is evaporated to dryness, and drying and roasting to obtain a catalyst precursor A;
(5) modifying the catalyst precursor A obtained in the step (4) by adopting an auxiliary agent A to obtain a catalyst precursor B;
(6) adding the catalyst precursor B obtained in the step (5) into an auxiliary agent B, uniformly mixing, carrying out solid-liquid separation, and standing the obtained solid phase at-50-0 ℃, preferably-30-0 ℃;
(7) mixing the organic acid aqueous solution with the material obtained in the step (6), and carrying out solid-liquid separation after uniformly mixing;
(8) mixing an alkaline solution containing ammonium with the solid-phase material obtained in the step (7), and performing solid-liquid separation after uniform mixing;
(9) and (3) mixing the heteropoly acid aqueous solution with the solid-phase material obtained in the step (8), uniformly mixing, carrying out solid-liquid separation, drying and roasting the separated solid phase to obtain the catalyst.
In the preparation method, the compound containing the hydrogenation metal component in the step (1) is a compound containing a VIB group metal and/or a VIII group metal, the VIB group metal-containing compound can be one or more of a molybdenum-containing compound and a tungsten-containing compound, and the VIII group metal-containing compound is one or more of a cobalt-containing compound, a nickel-containing compound and an iron-containing compound. The molybdenum-containing compound may be molybdenum oxide and/or ammonium heptamolybdate; the cobalt-containing compound is basic cobalt carbonate and/or cobalt nitrate.
In the production method of the present invention, the compound containing a hydrogenation metal component in the step (1) is preferably a molybdenum-containing compound and a cobalt-containing compound. The molybdenum-containing compound may be molybdenum oxide and/or ammonium heptamolybdate; the cobalt-containing compound is basic cobalt carbonate and/or cobalt nitrate.
In the preparation method of the invention, the phosphorus-containing compound in the step (1) can be one or more of phosphoric acid, ammonium dihydrogen phosphate and ammonium monohydrogen phosphate.
In the preparation method, the concentration of the hydrogenation metal component in the aqueous solution containing the hydrogenation metal component and the assistant P in the step (1) is 0.03-0.3 g/mL (calculated by the hydrogenation metal oxide), and the concentration of the assistant P is 0.002-0.03 g/mL. The formulation can be carried out by methods known in the art.
In the preparation method, the mass ratio of the water to the pseudo-boehmite in the step (2) is 3-10. The pseudo-boehmite can be prepared by a conventional method, such as an aluminum chloride method, an aluminum sulfate method, a carbonization method and the like.
In the preparation method, the template agent in the step (3) is one or more of dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride and hexamethylene tetramine, and the molar ratio of the template agent to the alumina is 0.2-0.5.
In the preparation method, the heteropolyacid in the step (3) and the step (9) is one or more of phosphotungstic acid, silicotungstic acid and phosphomolybdic acid. The mole ratio of the heteropoly acid introduced in the step (3) and the step (9) is 4: 1-1: 4.
In the preparation method, the drying temperature in the step (4) is 90-120 ℃, and the drying time is 5.0-10.0 h; the roasting temperature is 400-550 ℃, and the roasting time is 2.0-6.0 h.
In the preparation method of the present invention, the catalyst precursor a in step (4) may be prepared into a shaped catalyst precursor, or may be a catalyst precursor without shaping, and those skilled in the art will determine the catalyst precursor according to the selected process. The shaped catalyst precursor may be shaped by conventional shaping techniques, such as extrusion, tabletting, and the like, and may be in the form of a bar, sphere, tablet, and the like. In the forming process, a binder and a forming aid can be added according to needs, and the binder is generally small-pore alumina. Forming aids such as peptizers, extrusion aids, and the like.
In the preparation method of the invention, the modification treatment process in the step (5) is as follows:
(5.1) mixing the auxiliary agent A with an organic solvent, and uniformly mixing to obtain a solution I;
and (5.2) mixing the alumina carrier with the solution I, reacting after uniformly mixing, and drying to obtain a catalyst precursor B.
In the step (5.1), the assistant A is one or more of octadecyltrimethoxysilane, hexadecyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrichlorosilane, hexadecyltrichlorosilane and dodecyltrichlorosilane.
In the step (5.1), the organic solvent is one or more of benzene, toluene and cyclohexane, wherein the mass ratio of the auxiliary A to the organic solvent is 1: 1-1: 50.
In the step (5.2), the reaction temperature is 40-60 ℃, and the reaction time is 1.0-5.0 h; the drying temperature is 70-90 ℃, and the drying time is 3.0-12.0 h.
In the preparation method, the auxiliary B in the step (6) is diesel oil, the condensation point of the diesel oil is-40-20 ℃, preferably-40-0 ℃, and further preferably-30-0 ℃, the diesel oil can be one or more of straight-run diesel oil, hydrogenated diesel oil, coked diesel oil and catalytic diesel oil, preferably hydrogenated diesel oil is adopted, specifically commercially available commercial diesel oil such as one or more of 5# diesel oil, 0# diesel oil, -10# diesel oil, -20# diesel oil and-35 # diesel oil can be adopted, and the volume ratio of the auxiliary B to alumina is 1-4: 1, preferably 1-2: 1.
In the preparation method, the organic acid in the step (7) is one or more of citric acid, tartaric acid and malic acid; the mass ratio of the organic acid to the alumina is 0.1-1.5.
In the preparation method, the ammonium-containing alkaline solution in the step (8) is one or more of ammonia water, ammonium carbonate solution and ammonium bicarbonate solution, and the dosage of the ammonium-containing alkaline solution is excessive.
In the preparation method, the drying in the step (9) is carried out in vacuum, the relative vacuum degree is-0.1 MPa, the drying temperature is 90-120 ℃, the drying time is 3.0-12.0 h, the roasting temperature is 300-550 ℃, and the roasting time is 2.0-6.0 h.
The second aspect of the invention provides a hydrocracking catalyst prepared by the method, which comprises an acidic component, a hydrogenation metal component, an auxiliary agent and a carrier, wherein the acidic component is heteropolyacid ammonium salt, the hydrogenation metal component is one or more of VIB group metals and/or VIII group metals, P is the auxiliary agent, the carrier is an alumina and silica composite carrier, and the weight of the catalyst is taken as a reference, the content of the acidic component is 30-40%, the content of the hydrogenation metal component is 6-25%, the content of the auxiliary agent is 1.0-4.6%, and the content of the carrier is 30.4-63.0%.
In the hydrocracking catalyst, the composite carrier contains silica coated with alumina, and the weight of the silica accounts for 3-15% of the weight of the alumina.
The hydrocracking catalyst of the inventionIn the hydrocracking catalyst, the specific surface area of the hydrocracking catalyst is 130-220 m2(iv)/g, pore volume of 0.3 to 0.5mL/g, and average pore diameter of 6.0 to 11.0 nm.
In the hydrocracking catalyst, the content of heteropolyacid ammonium salt distributed in the radius range from the center of the catalyst to 3/4 is 11.4-45.0 wt%, preferably 18.8-37.5 wt% of the total content; the content of the catalyst distributed on the radius of 3/4 to the outer surface of the catalyst is 55.0wt% to 88.6wt%, preferably 62.5wt% to 81.2wt% of the total content.
In the hydrocracking catalyst, the acid content of the catalyst is uniformly distributed in the range from the center of the catalyst to the radius of 3/4, the acid content is obviously increased in the range from the radius of 3/4 to the outer surface of the catalyst, and the ratio of the acid content in the range from the radius of 3/4 to the outer surface of the catalyst to the total acid content is 8.0-75.0 wt%, preferably 23.0-60.0 wt% higher than the ratio of the acid content in the range from the center of the catalyst to the radius of 3/4 to the total acid content.
In the hydrocracking catalyst of the invention, the molecular formula of the heteropolyacid salt is Hm(NH4)nYX12O40Wherein X represents W or Mo, Y represents Si or P; when Y represents Si, m + n =4, and n is 0.1-1.0; when Y represents P, m + n =3, and n is 0.1-1.0.
Compared with the prior art, the hydrocracking catalyst and the preparation method thereof have the following advantages:
1. the hydrocracking catalyst has the advantages of high content of the acid components on the outer surface and high utilization rate, and improves the acidity on the outer surface of the catalyst while ensuring the acidity in the catalyst, so that the hydrocracking catalyst has high activity and high selectivity.
2. In the preparation method of the hydrocracking catalyst, the additive A is introduced, so that the interaction between the additive B and the carrier can be promoted, the purpose of modifying the alumina carrier is realized, the possibility of secondary cracking reaction in the catalyst pore channel can be reduced under the combined action of the additive A and the additive B, and excessive low-carbon hydrocarbon is avoided. And the subsequent supported heteropoly acid ammonium salt can be distributed on the surface of the carrier, so that a larger part of heteropoly acid ammonium salt is dispersed on the surface of the carrier, a smaller part of heteropoly acid ammonium salt is dispersed in pore channels of the carrier, the acid content of the prepared catalyst is uniformly distributed in the range from the center to the radius of 3/4, the acid content is obviously increased in the range from the radius of 3/4 to the outer surface of the catalyst, and the ratio of the acid content in the range from the radius of 3/4 to the outer surface of the catalyst to the total acid amount is 23.0-60.0 wt% higher than that in the range from the center of the catalyst to the radius of 3/4 to the total acid amount.
3. In the preparation method of the hydrocracking catalyst, the ammonium-containing template agent is added, so that the specific surface and the pore volume of the alumina can be improved, the catalyst can also act with heteropoly acid to generate heteropoly acid salt, and the strong acidity of the heteropoly acid is prevented from damaging the pore structure of the alumina.
4. In the preparation method of the hydrocracking catalyst, the auxiliary agent A modifies the carrier, so that the outer surface of the alumina carrier is coated with silicon dioxide, the interaction between the generated heteropoly acid ammonium salt and the alumina can be reduced, and the acid content of the catalyst is improved.
5. The catalyst prepared by the method of the invention shows high reaction activity and higher liquid hydrocarbon selectivity when being used for hydrocracking reaction of long-chain alkane.
Detailed Description
The invention is further illustrated by the following examples, wherein the reaction hydrocarbon feedstock used in the examples is an n-decane solution containing 525 μ g/g thiophene and 170 μ g/g pyridine. In the present invention, wt% is a mass fraction.
The specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen physical adsorption method, and are particularly measured by adopting a low-temperature nitrogen adsorption instrument of American Mike company ASAP2420 model; the specific process comprises the following steps: and (3) carrying out vacuum treatment on a small amount of sample at 300 ℃ for 3-4 h, and finally placing the product under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen absorption-desorption test. Wherein the surface area is obtained according to a BET equation, and the pore size distribution is obtained according to a BJH model. SEM (scanning Electron microscope) specifically employed is a SEM (scanning electron microscope) of JSM-7500F type manufactured by JEOL corporation of Japan, equipped with EDAX-EDS, acceleration voltage: 20Kv, working distance: 8mm, resolution: 1 nm.
The hydrocracking activity is represented by the conversion of n-decane, and the selectivity is represented by "the number of moles of alkane containing 5 carbon atoms and 5 or more carbon atoms in the product divided by the total number of moles of the product", and is denoted as C5 +And (4) selectivity. This is because, in a general hydrocracking process, it is desirable that the amount of the primary cracking product is large and the amount of the secondary cracking product is small, and when n-decane is used as the reaction hydrocarbon raw material, since alkanes having 5 carbon atoms and 5 or more carbon atoms in the product are all the primary cracking products, C5 +Selectivity characterizes the relative amount of primary cleavage product in the product.
Example 1
(1) Preparation of Mo-Co-P aqueous solution:
2.3g of phosphoric acid H3PO4(the concentration is 85 wt%) is dissolved in 80mL of water, then 6.2g of molybdenum trioxide and 2.3g of basic cobalt carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the volume is 100mL after filtration, so that the Mo-Co-P aqueous solution is obtained. Wherein MoO3Is 0.06g/mL, Co2O3The concentration of (B) was 0.012g/mL, and the concentration of P was 0.006 g/mL.
(2) Preparation of the catalyst:
adding 53.4g of pseudo-boehmite (0.85 dry basis) into 300g of water, and pulping to form a suspension; adding 100mL of Mo-Co-P aqueous solution, 34.9g of octadecyl trimethyl ammonium bromide and 31.4g of phosphotungstic acid into the suspension in sequence, stirring at 70 ℃ until the solution is evaporated to dryness, drying at 110 ℃ for 8.0h, and then roasting at 400 ℃ for 3.0h to obtain a catalyst precursor A; then adding the mixture into 150mL of cyclohexane solution containing 36.3g of dodecyl trimethoxy silane, reacting for 3.0h at 50 ℃, and drying for 8h at 70 ℃ to obtain a catalyst precursor B; adding into 120mL5# diesel oil, soaking for 30min, filtering, placing the obtained material in a low-temperature reaction bath at 0 ℃, then adding 120mL aqueous solution containing 22.7g citric acid, soaking for 30min, pouring out the solution, then adding 120mL ammonium carbonate solution with the mass fraction of 30%, soaking for 5min, pouring out the solution, then adding 100mL aqueous solution containing 7.9g phosphotungstic acid, soaking for 5min, filtering, adding the obtained solid intoDrying at 110 deg.C for 8.0h under-0.1 MPa of relative vacuum degree, and calcining at 400 deg.C for 3.0h to obtain catalyst, wherein MoO3Content of 6wt%, Co2O31.2wt% of P, 0.6wt% (NH)4)0.7H2.3PW12O40The content is 38wt%, and the weight of the silicon dioxide accounts for 15% of the weight of the alumina. The physicochemical properties of the catalyst are shown in Table 1.
(3) Catalyst characterization:
elemental analysis of the catalyst by SEM revealed that the distribution of ammonium phosphotungstate on the catalyst is shown in Table 2.
(4) Evaluation of catalyst:
after 0.5g of catalyst is loaded in the middle isothermal section of the reaction tube, hydrogen is introduced, the pressure of the reaction system is gradually increased to 2.0MPa, and after no gas leakage is detected, the reaction system is introduced with a catalyst containing 2wt% of CS2Heating the reaction system to 320 ℃ for sulfurization for 3h, cutting in n-decane liquid containing 525 mug/g thiophene and 170 mug/g pyridine after the reaction is finished, heating the reaction system to 400 ℃, and keeping the hydrogen volume space velocity at 1500h-1The mass space velocity is 3.0h-1And starting to collect a sample after reacting for 1 hour, and detecting the hydrocracking activity and selectivity of the catalyst under the reaction condition, wherein the results are shown in Table 3.
Example 2
(1) Preparation of Mo-Co-P aqueous solution:
4.6g of phosphoric acid H3PO4(the concentration is 85 wt%) is dissolved in 80mL of water, then 12.4g of molybdenum trioxide and 5.8g of basic cobalt carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the volume is 100mL after filtration, so that the Mo-Co-P aqueous solution is obtained. Wherein MoO3Is 0.12g/mL, Co2O3The concentration of (B) was 0.03g/mL, and the concentration of P was 0.012 g/mL.
(2) Preparation of the catalyst:
adding 52.1g of pseudo-boehmite (dry basis 0.85) into 300g of water, and pulping to form a suspension; adding 100mL of Mo-Co-P aqueous solution, 47.5g of hexadecyl trimethyl ammonium bromide and 17.6g of phosphotungstic acid into the suspension in sequence, stirring at 70 ℃ until the solution is evaporated to dryness, and dissolving the solution in 1Drying at 10 ℃ for 8.0h, and then roasting at 470 ℃ for 3.0h to prepare a catalyst precursor A; then adding the mixture into 150mL of cyclohexane solution containing 21.1g of hexadecyl trimethoxy silane, reacting for 3.0h at 50 ℃, and drying for 8h at 70 ℃ to obtain a catalyst precursor B; then adding the mixture into 120mL of 0# diesel oil, soaking for 30min, filtering, placing the obtained material in a low-temperature reaction bath at the temperature of minus 10 ℃, then adding 120mL of aqueous solution containing 44.3g of citric acid, soaking for 30min, pouring out the solution, then adding 120mL of ammonium carbonate solution with the mass fraction of 30%, soaking for 5min, pouring out the solution, then adding 100mL of aqueous solution containing 17.6g of phosphotungstic acid, soaking for 5min, filtering, drying the obtained solid at the temperature of 110 ℃ for 8.0h under the relative vacuum degree of minus 0.1MPa, then roasting at the temperature of 470 ℃ for 3.0h to obtain the catalyst, wherein MoO is3Content of 12wt%, Co2O33.0wt% of P, 1.2wt% (NH)4)0.5H2.5PW12O40The content is 34wt%, and the weight of the silicon dioxide accounts for 8% of the weight of the alumina. The physicochemical properties of the catalyst are shown in Table 1.
(3) Catalyst characterization:
elemental analysis of the catalyst by SEM revealed that the distribution of ammonium phosphotungstate on the catalyst is shown in Table 2.
(4) Evaluation of catalyst:
the catalyst was evaluated for hydrocracking activity and selectivity under the reaction conditions as in example 1, and the results are shown in Table 3.
Example 3
(1) Preparation of Mo-Co-P aqueous solution:
6.9g of phosphoric acid H3PO4(the concentration is 85 wt%) is dissolved in 80mL of water, then 6.2g of molybdenum trioxide and 8.6g of basic cobalt carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the volume is 100mL after filtration, so that the Mo-Co-P aqueous solution is obtained. Wherein MoO3Is 0.18g/mL, Co2O3The concentration of (B) was 0.045g/mL, and the concentration of P was 0.018 g/mL.
(2) Preparation of the catalyst:
47.2g of pseudo-boehmite (0.85 on a dry basis) was added to 300g of water and slurried to form a suspensionTurbid liquid; adding 100mL of Mo-Co-P aqueous solution, 60.6g of dodecyl trimethyl ammonium bromide and 6.7g of phosphotungstic acid into the suspension in sequence, stirring at 70 ℃ until the solution is evaporated to dryness, drying at 110 ℃ for 8.0h, and then roasting at 500 ℃ for 3.0h to prepare a catalyst precursor A; then adding the mixture into 150mL of cyclohexane solution containing 7.0g of octadecyltrimethoxysilane, reacting for 3.0h at 50 ℃, and drying for 8h at 70 ℃ to obtain a catalyst precursor B; then adding the mixture into 120mL-10# diesel oil, soaking for 30min, filtering, placing the obtained material in a low-temperature reaction bath at the temperature of minus 20 ℃, then adding 120mL of aqueous solution containing 60.2g of citric acid, soaking for 30min, pouring out the solution, then adding 120mL of ammonium carbonate solution with the mass fraction of 30%, soaking for 5min, pouring out the solution, then adding 100mL of aqueous solution containing 26.5g of phosphotungstic acid, soaking for 5min, filtering, drying the obtained solid at the temperature of 110 ℃ for 8.0h under the relative vacuum degree of minus 0.1MPa, and then roasting at the temperature of 500 ℃ for 3.0h to obtain the catalyst, wherein MoO is318wt% of Co2O34.5wt% of P, 1.8wt% (NH)4)0.1H2.9PW12O40The content is 32wt%, and the weight of the silicon dioxide accounts for 3% of the weight of the alumina. The physicochemical properties of the catalyst are shown in Table 1.
(3) Catalyst characterization:
elemental analysis of the catalyst by SEM revealed that the distribution of ammonium phosphotungstate on the catalyst is shown in Table 2.
(4) Evaluation of catalyst:
the catalyst was evaluated for hydrocracking activity and selectivity under the reaction conditions as in example 1, and the results are shown in Table 3.
Example 4
(1) Preparation of the catalyst:
in example 3, a catalyst in which MoO was contained in a solution obtained by changing phosphotungstic acid to silicotungstic acid and ammonium carbonate solution having a mass fraction of 30% to ammonia water having a mass fraction of 20% was prepared in the same manner as in example 3318wt% of Co2O34.5wt% of P, 1.8wt% (NH)4)0.1H3.9SiW12O40The content is 32wt%,the weight of silica accounted for 3% of the alumina carrier weight. The physicochemical properties of the catalyst are shown in Table 1.
(2) Catalyst characterization:
elemental analysis of the catalyst by SEM revealed that the distribution of ammonium phosphotungstate on the catalyst is shown in Table 2.
(3) Evaluation of catalyst:
the catalyst was evaluated for hydrocracking activity and selectivity under the reaction conditions as in example 1, and the results are shown in Table 3.
Example 5
In example 3, the hydrocracking activity and selectivity of the catalyst under the reaction conditions were evaluated in the same manner as in example 3 except that the n-decane solution was changed to n-hexadecane solution, and the results are shown in Table 3.
Comparative example 1
(1) Preparation of the catalyst:
in example 3, 48.6g of pseudo-boehmite (0.85 on a dry basis) was added to 300g of water and slurried to form a suspension; adding 100mL of Mo-Co-P aqueous solution, 62.4g of dodecyl trimethyl ammonium bromide and 6.7g of phosphotungstic acid into the suspension in sequence, stirring at 70 ℃ until the solution is evaporated to dryness, drying at 110 ℃ for 8.0h, and then roasting at 500 ℃ for 3.0h to prepare a catalyst precursor A; then adding the mixture into 120mL of aqueous solution containing 62.0g of citric acid, soaking for 30min, pouring out the solution, then adding 120mL of ammonium carbonate solution with the mass fraction of 30%, soaking for 5min, pouring out the solution, then adding 100mL of aqueous solution containing 26.5g of phosphotungstic acid, soaking for 5min, filtering, drying the obtained solid for 8.0h at the temperature of 110 ℃ under the relative vacuum degree of-0.1 MPa, and then roasting for 3.0h at the temperature of 500 ℃ to prepare the catalyst, wherein MoO is the catalyst318wt% of Co2O34.5wt% of P, 1.8wt% (NH)4)0.1H2.9PW12O40The content was 32 wt%. The physicochemical properties of the catalyst are shown in Table 1.
(2) Catalyst characterization:
elemental analysis of the catalyst by SEM revealed that the distribution of ammonium phosphotungstate on the catalyst is shown in Table 2.
(3) Evaluation of catalyst:
the catalyst was evaluated for hydrocracking activity and selectivity under the reaction conditions as in example 1, and the results are shown in Table 3.
Comparative example 2
Substantially the same as in example 3, except that the catalyst precursor A was not modified with the aid of the auxiliary A.
(1) Preparation of the catalyst:
in example 3, 48.6g of pseudo-boehmite (0.85 on a dry basis) was added to 300g of water and slurried to form a suspension; adding 100mL of Mo-Co-P aqueous solution, 62.4g of dodecyl trimethyl ammonium bromide and 6.7g of phosphotungstic acid into the suspension in sequence, stirring at 70 ℃ until the solution is evaporated to dryness, drying at 110 ℃ for 8.0h, and then roasting at 500 ℃ for 3.0h to prepare a catalyst precursor A; adding a catalyst precursor A into 120mL-10# diesel oil, soaking for 30min, filtering, placing the obtained material in a low-temperature reaction bath at the temperature of minus 20 ℃, then adding 120mL of aqueous solution containing 60.2g of citric acid, soaking for 30min, pouring out the solution, then adding 120mL of ammonium carbonate solution with the mass fraction of 30%, soaking for 5min, pouring out the solution, then adding 100mL of aqueous solution containing 26.5g of phosphotungstic acid, soaking for 5min, filtering, drying the obtained solid at the temperature of 110 ℃ for 8.0h under the relative vacuum degree of minus 0.1MPa, and then roasting at the temperature of 500 ℃ for 3.0h to obtain the catalyst, wherein MoO is used as the catalyst318wt% of Co2O34.5wt% of P, 2.0wt% (NH)4)0.1H2.9PW12O40The content was 32 wt%. The physicochemical properties of the catalyst are shown in Table 1.
(2) Catalyst characterization:
elemental analysis of the catalyst by SEM revealed that the distribution of ammonium phosphotungstate on the catalyst is shown in Table 2.
(3) Evaluation of catalyst:
the catalyst was evaluated for hydrocracking activity and selectivity under the reaction conditions as in example 1, and the results are shown in Table 3.
The modification of the assistant A on the catalyst can weaken the acidity of the carrier on one hand, weaken the interaction between the carrier and the ammonium phosphotungstate on the other hand, and reduce the loss of the acidity of the ammonium heteropoly acid salt, so the modification of the assistant A plays a role in weakening the acidity in the pore channel of the catalyst and improving the acidity of the outer surface of the catalyst. Compared with the catalyst of the example 3, the catalyst of the comparative example 2 is not modified by the aid of the auxiliary A, the acidity in the pore channels of the catalyst is not weakened, and the acidity of the outer surface of the catalyst is weakened due to the interaction of the heteropoly acid ammonium salt and the carrier. Thus, both the conversion and the selectivity of the catalyst are reduced.
Comparative example 3
Substantially the same as in example 3, except that the catalyst precursor B was not modified with the aid of the assistant B.
(1) Preparation of the catalyst:
adding the catalyst precursor B into 120mL of aqueous solution containing 60.2g of citric acid, soaking for 30min, pouring out the solution, then adding 120mL of ammonium carbonate solution with the mass fraction of 30%, soaking for 5min, pouring out the solution, then adding 100mL of aqueous solution containing 26.5g of phosphotungstic acid, soaking for 5min, filtering, drying the obtained solid at the relative vacuum degree of-0.1 MPa at the temperature of 110 ℃ for 8.0h, and then roasting at the temperature of 500 ℃ for 3.0h to obtain the catalyst, wherein MoO is the catalyst318wt% of Co2O34.5wt% of P, 1.8wt% (NH)4)0.1H2.9PW12O40The content is 32wt%, and the weight of the silicon dioxide accounts for 3% of the weight of the alumina. The physicochemical properties of the catalyst are shown in Table 1.
(2) Catalyst characterization:
elemental analysis of the catalyst by SEM revealed that the distribution of ammonium phosphotungstate on the catalyst is shown in Table 2.
(3) Evaluation of catalyst:
the catalyst was evaluated for hydrocracking activity and selectivity under the reaction conditions as in example 1, and the results are shown in Table 3.
TABLE 1 physicochemical Properties of the catalyst
TABLE 2 percentage by weight of heteropolyacid ammonium salt content in different positions of the catalyst based on the total content
TABLE 3 hydrocracking activity and Selectivity of the catalysts
Claims (36)
1. A preparation method of a hydrocracking catalyst comprises the following steps:
(1) preparing an aqueous solution containing a hydrogenation metal component and an auxiliary agent P from a compound containing the hydrogenation metal component, a phosphorus-containing compound and water;
(2) mixing pseudo-boehmite with water to form suspension;
(3) mixing the aqueous solution, the template agent and the heteropoly acid obtained in the step (1) with the suspension obtained in the step (2);
(4) stirring the mixed solution obtained in the step (3) at the temperature of 60-90 ℃ until the solution is evaporated to dryness, and drying and roasting to obtain a catalyst precursor A;
(5) modifying the catalyst precursor A obtained in the step (4) by adopting an auxiliary agent A to obtain a catalyst precursor B, wherein the auxiliary agent A is one or more of octadecyl trimethoxy silane, hexadecyl trimethoxy silane, dodecyl trimethoxy silane, octadecyl trichlorosilane, hexadecyl trichlorosilane and dodecyl trichlorosilane;
(6) adding the catalyst precursor B obtained in the step (5) into an auxiliary agent B, uniformly mixing, carrying out solid-liquid separation, and standing the obtained solid phase at-50-0 ℃, wherein the auxiliary agent B is diesel oil;
(7) mixing the organic acid aqueous solution with the material obtained in the step (6), and carrying out solid-liquid separation after uniformly mixing;
(8) mixing an alkaline solution containing ammonium with the solid-phase material obtained in the step (7), and performing solid-liquid separation after uniform mixing;
(9) and (3) mixing the heteropoly acid aqueous solution with the solid-phase material obtained in the step (8), uniformly mixing, carrying out solid-liquid separation, drying and roasting the separated solid phase to obtain the catalyst.
2. The method of claim 1, wherein: and (6) adding the catalyst precursor B obtained in the step (5) into an auxiliary agent B, uniformly mixing, carrying out solid-liquid separation, and standing the obtained solid phase at-30-0 ℃.
3. The method of claim 1, wherein: the compound containing the hydrogenation metal component in the step (1) is a compound containing VIB group metal and/or VIII group metal.
4. The method of claim 3, wherein: the group VIB metal-containing compound is one or more of a molybdenum-containing compound and a tungsten-containing compound, and the group VIII metal-containing compound is one or more of a cobalt-containing compound, a nickel-containing compound and an iron-containing compound.
5. The method of claim 1, wherein: the compound containing the hydrogenation metal component in the step (1) is a molybdenum-containing compound and a cobalt-containing compound.
6. The production method according to claim 4 or 5, characterized in that: the molybdenum-containing compound is molybdenum oxide and/or ammonium heptamolybdate; the cobalt-containing compound is basic cobalt carbonate and/or cobalt nitrate.
7. The method of claim 1, wherein: in the step (1), the phosphorus-containing compound is one or more of phosphoric acid, ammonium dihydrogen phosphate and ammonium monohydrogen phosphate.
8. The method of claim 1, wherein: the concentration of the hydrogenation metal component in the aqueous solution containing the hydrogenation metal component and the auxiliary P in the step (1) is 0.03-0.3 g/mL, and the concentration of the auxiliary P is 0.002-0.03 g/mL.
9. The method of claim 1, wherein: the mass ratio of the water to the pseudo-boehmite in the step (2) is 3-10.
10. The method of claim 1, wherein: the template agent in the step (3) is one or more of dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride and hexamethylene tetramine.
11. The method of claim 1, wherein: the heteropolyacid in the step (3) and the step (9) is one or more of phosphotungstic acid, silicotungstic acid and phosphomolybdic acid.
12. The method of claim 1, wherein: in the step (4), the drying temperature is 90-120 ℃, and the drying time is 5.0-10.0 h; the roasting temperature is 400-550 ℃, and the roasting time is 2.0-6.0 h.
13. The method of claim 1, wherein: the modification treatment process in the step (5) is as follows:
(5.1) mixing the auxiliary agent A with an organic solvent, and uniformly mixing to obtain a solution I;
and (5.2) mixing the catalyst precursor A with the solution I, reacting after uniformly mixing, and drying to obtain a catalyst precursor B.
14. The method of claim 13, wherein: the assistant A in the step (5.1) is one or more of octadecyl trimethoxy silane, hexadecyl trimethoxy silane, dodecyl trimethoxy silane, octadecyl trichlorosilane, hexadecyl trichlorosilane and dodecyl trichlorosilane.
15. The method of claim 13, wherein: the organic solvent in the step (5.1) is one or more of benzene, toluene and cyclohexane.
16. The method of claim 13, wherein: the mass ratio of the auxiliary agent A to the organic solvent is 1: 1-1: 50.
17. The method of claim 13, wherein: in the step (5.2), the reaction temperature is 40-60 ℃, and the reaction time is 1.0-5.0 h; the drying temperature is 70-90 ℃, and the drying time is 3.0-12.0 h.
18. The method of claim 1, wherein: the condensation point of the diesel oil in the step (6) is-40-20 ℃.
19. The method of claim 1, wherein: in the step (6), the condensation point of the diesel oil is-40-0 ℃.
20. The method of claim 1, wherein: the condensation point of the diesel oil in the step (6) is-30-0 ℃.
21. The method of claim 1, wherein: in the step (6), the diesel oil is one or more of straight-run diesel oil, hydrogenated diesel oil, coked diesel oil and catalytic diesel oil.
22. The method of claim 1, wherein: in the step (6), the diesel oil is hydrogenated diesel oil.
23. The method of claim 1, wherein: in the step (6), the diesel oil is commercial diesel oil selected from one or more of 5# diesel oil, 0# diesel oil, -10# diesel oil, -20# diesel oil and-35 # diesel oil.
24. The method of claim 1, wherein: in the step (6), the volume ratio of the auxiliary agent B to the catalyst precursor B is 1-4: 1.
25. The method of claim 1, wherein: in the step (6), the volume ratio of the auxiliary agent B to the catalyst precursor B is 1-2: 1.
26. The method of claim 1, wherein: in the step (7), the organic acid is one or more of citric acid, tartaric acid and malic acid.
27. The method of claim 1, wherein: the alkaline solution containing ammonium in the step (8) is one or more of ammonia water, ammonium carbonate solution and ammonium bicarbonate solution.
28. The method of claim 1, wherein: and (4) drying in the step (9) under vacuum, wherein the relative vacuum degree is-0.1 MPa, the drying temperature is 90-120 ℃, the drying time is 3.0-12.0 h, the roasting temperature is 300-550 ℃, and the roasting time is 2.0-6.0 h.
29. The hydrocracking catalyst prepared by the method of any one of claims 1 to 28, which comprises an acidic component, a hydrogenation metal component, an auxiliary agent and a carrier, wherein the acidic component is heteropolyacid ammonium salt, the hydrogenation metal component is one or more of group VIB metals and/or group VIII metals, P is the auxiliary agent, the carrier is an alumina and silica composite carrier, and based on the weight of the catalyst, the content of the acidic component is 30 to 40 percent, the content of the hydrogenation metal component is 6 to 25 percent, the content of the auxiliary agent is 1.0 to 4.6 percent, and the content of the carrier is 30.4 to 63.0 percent.
30. Hydrocracking catalyst according to claim 29, characterized in that: the composite carrier is characterized in that the silica wraps the alumina, and the weight of the silica accounts for 3-15% of the weight of the alumina.
31. Hydrocracking catalyst according to claim 29, characterized in that: the specific surface area of the hydrocracking catalyst is 130-220 m2(iv)/g, pore volume of 0.3 to 0.5mL/g, and average pore diameter of 6.0 to 11.0 nm.
32. Hydrocracking catalyst according to claim 29, characterized in that: the content of the heteropoly acid ammonium salt distributed from the center of the catalyst to the radius of 3/4 is 11.4wt% -45.0 wt%, and the content distributed from the radius of 3/4 to the outer surface of the catalyst is 55.0wt% -88.6 wt%.
33. Hydrocracking catalyst according to claim 29, characterized in that: the content of the heteropoly acid ammonium salt distributed in the radius range from the center of the catalyst to 3/4 is 18.8wt% -37.5 wt% of the total content; the content distributed from 3/4 radius to the outer surface of the catalyst is 62.5wt% to 81.2wt% of the total content.
34. Hydrocracking catalyst according to claim 29, characterized in that: the catalyst acid content is uniformly distributed in the radius range from the center of the catalyst to 3/4, the acid content is obviously increased in the radius range from 3/4 to the outer surface of the catalyst, and the ratio of the acid content in the radius range from 3/4 to the outer surface of the catalyst to the total acid content is 8.0-75.0 wt% higher than the ratio of the acid content in the radius range from the center of the catalyst to 3/4 to the total acid content.
35. Hydrocracking catalyst according to claim 29, characterized in that: the catalyst acid content is uniformly distributed in the range from the center of the catalyst to the radius of 3/4, the acid content is obviously increased in the range from the radius of 3/4 to the outer surface of the catalyst, and the ratio of the acid content in the range from the radius of 3/4 to the outer surface of the catalyst to the total acid content is 23.0-60.0 wt% higher than the ratio of the acid content in the range from the center of the catalyst to the radius of 3/4 to the total acid content.
36. Hydrocracking catalyst according to claim 29, characterized in that: the molecular formula of the heteropolyacid salt is Hm(NH4)nYX12O40Wherein X represents W or Mo, Y represents Si or P; when Y represents Si, m + n =4, and n is 0.1-1.0; when Y represents P, m + n =3, and n is 0.1-1.0.
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| CN104588104A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method for catalyst used for preparation of dimethyl ether through dehydration of methanol |
| CN104588106A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for producing dimethyl ether through methanol dehydration, and preparation method thereof |
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