CN111375438A - Heavy oil hydrotreating catalyst carrier, catalyst and preparation method thereof - Google Patents

Heavy oil hydrotreating catalyst carrier, catalyst and preparation method thereof Download PDF

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Publication number
CN111375438A
CN111375438A CN201811648082.5A CN201811648082A CN111375438A CN 111375438 A CN111375438 A CN 111375438A CN 201811648082 A CN201811648082 A CN 201811648082A CN 111375438 A CN111375438 A CN 111375438A
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carrier
heavy oil
catalyst
preparing
catalyst support
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Inventor
金浩
杨光
朱慧红
刘璐
孙素华
杨涛
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof

Abstract

The invention discloses a heavy oil hydrotreating catalyst carrier, a catalyst and a preparation method thereof, wherein the carrier preparation method comprises the steps of mixing pseudo-boehmite powder and an ammonium phosphate salt aqueous solution, and forming to obtain a carrier precursor; treating the carrier precursor by using vapor-containing gas, further drying and roasting to obtain a catalyst carrier, and further loading a hydrogenation active metal component on the obtained catalyst carrier to obtain the catalyst. The method can improve the strength and the abrasion resistance of the carrier, thereby integrally improving the activity and the stability of the catalyst.

Description

Heavy oil hydrotreating catalyst carrier, catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of oil refining chemical industry, relates to a catalytic material and a preparation method thereof, and particularly relates to a hydrogenation catalyst carrier, a hydrogenation catalyst and a preparation method thereof.
Background
In recent years, the quality of crude oil is increasingly poor, and the demand of light oil products is increased year by year, so that the development of deep processing of heavy oil and the increase of the added value of products have important practical significance. The hydrogenation technology as a main processing means faces a great challenge, and the development of a better hydrogenation process and a hydrogenation catalyst with higher activity are urgently needed. The reaction performance of the heavy oil hydrogenation catalyst depends on the inherent catalytic characteristics of the active components and is closely related to the properties of the catalyst carrier. The specific surface area, pore structure, surface acidity, etc. of the carrier have important effects on the dispersion degree of the active component, the interaction between the active component and the carrier, the diffusion of reactant molecules and the anti-poisoning capability of the catalyst. At present, alumina is the most widely used carrier in the field of heavy oil hydrogenation, and has good mechanical properties and low price. Along with the continuous improvement of the requirement on the catalytic performance of the hydrogenation catalyst, the index requirement of the alumina carrier is also continuously improved, so that a great deal of alumina modification research work is carried out by the researchers.
At present, the alumina carrier with high pore volume and high pore diameter can be obtained by a pore-enlarging method, and the pore-enlarging method mainly comprises a physical pore-enlarging method and a chemical pore-enlarging method. Usually, a surfactant and an organic compound (such as PVA, carbon black and the like) pore-expanding agent are adopted to change the pore structure of alumina, and a series of macropores are manufactured on the basis of the original pore structure. Both CN1103009A and US4,448,896 disclose carriers prepared by mixing, molding and calcining alumina or an alumina precursor with carbon black. Adding a physical pore-expanding agent and a chemical pore-expanding agent into an alumina carrier in CN1206037A in the preparation process, kneading into a plastic body, extruding into strips, molding, drying and roasting to obtain the carrier. The preparation of the alumina carrier in CN104549332A is to mix and knead the carbon black powder which is dipped with part of active components, pseudo-boehmite dry glue powder, chemical pore-enlarging agent, extrusion aid and peptizing agent into a plastic carrier, extrude, dry and roast to obtain the alumina carrier. The said process can produce alumina with great pores and improved carrier pore structure, but with the increased carrier pore volume and great pore proportion, the catalyst strength is lowered.
The fixed bed hydrogenation technology has higher requirement on the strength of the catalyst, while the boiling bed hydrogenation technology not only requires high strength of the catalyst, but also requires high wear resistance, so that the alumina carrier is required to have high strength and wear resistance while improving the pore volume so as to meet the industrial requirement.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a heavy oil hydrotreating catalyst carrier, a heavy oil hydrotreating catalyst and a preparation method thereof. The preparation method can improve the macroporous proportion and acidity of the alumina carriers, enhance the interaction force among the alumina carriers, improve the strength and abrasion resistance of the carriers, and further ensure the activity and stability of the catalyst in the long-period operation process.
The first aspect of the present invention provides a preparation method of a heavy oil hydrotreating catalyst carrier, which comprises the following steps:
(1) mixing pseudo-boehmite powder, an auxiliary agent and an ammonium phosphate aqueous solution, and forming to obtain a carrier precursor;
(2) and treating the carrier precursor by using vapor-containing gas, and further drying and roasting to obtain the catalyst carrier.
In the preparation method of the heavy oil hydrotreating catalyst carrier, the pseudo-boehmite powder in the step (1) can be a commercially available product or can be pseudo-boehmite powder prepared according to the existing method.
In the preparation method of the heavy oil hydrotreating catalyst carrier, the auxiliary agent in the step (1) is one or more of sesbania powder, methyl cellulose and starch, preferably sesbania powder, and the addition amount of the auxiliary agent is 1-5% of the mass of the final carrier.
In the preparation method of the heavy oil hydrotreating catalyst carrier, the ammonium phosphate in the step (1) is one or more of ammonium dihydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate, and the concentration of the ammonium phosphate aqueous solution is 0.01-0.20 g/mL.
The heavy oil hydrotreating catalyst of the inventionIn the preparation method of the agent carrier, the ammonium phosphate salt in the step (1) is added in an amount (as P)2O5By mass) is 1 to 5wt% of the final carrier content.
In the preparation method of the heavy oil hydrotreating catalyst carrier, the forming technology in the step (1) is the prior art known by the technicians in the field, and the concrete forming operation is selected by the technicians in the field according to the actual needs, such as any one or more of extrusion molding, extrusion ball-throwing molding, rolling molding, tabletting molding and the like, and the shape can be spherical, cylindrical strip, clover shape, sheet shape and the like.
In the preparation method of the heavy oil hydrotreating catalyst carrier, the vapor-containing gas in the step (2) is vapor or a mixed gas of the vapor and a carrier gas, and the volume ratio of the vapor to the carrier gas in the mixed gas is 1: 5-2: 1, preferably 1: 4-1: 1; the carrier gas is air, nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
In the preparation method of the heavy oil hydrotreating catalyst carrier, the treatment process in the step (2) is to introduce vapor-containing gas to treat the precursor, the treatment temperature is 150-250 ℃, preferably 180-220 ℃, and the treatment time is 2-6 h.
In the preparation method of the heavy oil hydrotreating catalyst carrier, the volume space velocity of the vapor-containing gas and the carrier precursor in the step (2) is 500-2000 h-1。
In the preparation method of the heavy oil hydrotreating catalyst carrier, the drying temperature in the step (2) is 90-120 ℃, and the drying time is 3-12 h; the roasting temperature is 500-1000 ℃, and the roasting time is 1-5 h.
In the preparation method of the heavy oil hydrotreating catalyst carrier, other metals, such as one or more of Fe, Zr, Ti, B, La and Ce, can be introduced into the catalyst carrier obtained in the step (2).
The second aspect of the invention provides a heavy oil hydrotreating catalyst carrier obtained by the preparation method.
The third aspect of the invention provides a heavy oil hydrotreating catalyst, which comprises a hydrogenation active metal component and the carrier of the invention, wherein the hydrogenation active metal component is one or more of VIB group metals and/or VIII group metals.
In the heavy oil hydrotreating catalyst, the group VIB metal is Mo and/or W, and the group VIII metal is Ni and/or Co.
In the heavy oil hydrotreating catalyst, the hydrogenation metal component is more preferably Mo and Ni.
In the heavy oil hydrotreating catalyst, the catalyst comprises an auxiliary agent, and the auxiliary agent is P.
In the heavy oil hydrotreating catalyst, the content of the auxiliary agent is 1wt% -8 wt% based on the weight of the catalyst.
In the heavy oil hydrotreating catalyst, other metals, such as one or more of Fe, Zr, Ti, B, La, Ce, can be introduced on the catalyst carrier.
The heavy oil hydrotreating catalyst of the present invention can be prepared by conventional methods such as impregnation, kneading, etc., and preferably by impregnation. The carrier is prepared by a conventional impregnation method by adopting an impregnation method to load the active metal component, and can adopt a spray impregnation method, a saturated impregnation method or a supersaturated impregnation method. If the method for loading the hydrogenation active metal component on the carrier is an impregnation method, the method comprises the steps of preparing a solution containing a hydrogenation active metal compound, impregnating the carrier by using the solution, and then drying, roasting or not roasting, wherein the hydrogenation active metal component is one or more of VIB group metals and/or VIII group metals, and the concentration of the hydrogenation active metal containing compound in the solution and the dosage of the solution enable the content of the VIB group metal component in the final catalyst to be 1-30 wt% calculated by oxides and based on the catalyst; the content of the VIII group metal component is 1wt% -15 wt%. The drying conditions include: the temperature is 90-120 ℃, and the time is 1-10 h; the roasting conditions include: the temperature is 300-700 ℃, and the time is 1-10 h.
In the heavy oil hydrotreating catalyst, the properties of the heavy oil hydrotreating catalyst carrier are as follows: the specific surface area is 120-400 m2The pore volume is 0.60-1.10 mL/g.
Compared with the prior art, the heavy oil hydrotreating catalyst carrier, the catalyst and the preparation method thereof have the following advantages:
1. according to the heavy oil hydrotreating catalyst carrier and the preparation method of the catalyst, ammonium phosphate is introduced in the kneading process of pseudo-boehmite, and then the carrier precursor is further treated by adopting vapor-containing gas, wherein in the process, the ammonium phosphate is firstly decomposed to release ammonia gas, so that the pore expansion effect on the carrier can be realized, and the number of macropores of an alumina carrier is increased; the generated phosphoric acid interacts with the pseudo-boehmite, so that the interaction force between alumina carriers can be enhanced, and the strength and the abrasion resistance of the carriers are improved; and finally, in the roasting process, phosphoric acid interacts with alumina, so that the acidity of the carrier can be improved, the pore-expanding effect on the alumina carrier can be played again, and the number of macropores of the alumina carrier is increased.
2. The preparation method of the heavy oil hydrogenation catalyst has the advantages of novel route, simple method, easy implementation and operation and low energy consumption.
Detailed Description
The embodiments and effects of the present invention are further illustrated by the following specific examples. In the present invention, wt% is a mass fraction.
The spherical carrier abrasion in the invention is tested by a high-speed air jet method. This Method has been established by the American ASTM as a Standard for Attrition testing of small particle Catalysts, see ASTM D5757-00 (Standard Test Method for determination of the initiation and inhibition of Powdered Catalysts by Air Jets). The basic principle is that under the action of high-speed airflow, catalyst particles are in a fluidized state, fine powder is generated by the friction between particles and between the particles and the wall of the catalyst, and the amount of the fine powder generated by unit mass of the catalyst in unit time, namely, the abrasion index (abrasion) is used as an index for evaluating the abrasion resistance of the catalyst.
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.
Example 1
(1) Preparation of the support
1000g of pseudo-boehmite powder (commercially available, with a specific surface area of 350 m)2The pore volume is 1.15 mL/g) is prepared into spherical particles by rolling forming in a ball rolling machine, 14g of sesbania powder is added and 850mL of ammonium dihydrogen phosphate aqueous solution with the concentration of 0.027g/mL is sprayed in the process of ball rolling, the rotating speed of the ball rolling machine is 35 r/min, and after the ball rolling is finished, a carrier precursor is prepared; then carrying out water vapor treatment on the carrier precursor at the temperature of 190 ℃ for 4h, wherein the volume space velocity of the water vapor and the carrier precursor A is 800h-1. And drying the treated material at 110 ℃ for 8h, and then roasting at 700 ℃ for 3h to obtain the spherical carrier with the particle size of 0.2-0.8 mm. The physicochemical properties of the carrier are shown in Table 1, and the abrasion data are shown in Table 2.
(2) Catalyst preparation
4.3g of phosphoric acid H3PO4(the concentration is 85 wt%) is dissolved in 50mL of water, 11.6g of molybdenum trioxide and 4.7g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the volume is adjusted to 85mL after the mixture is filtered, so that the Mo-Ni-P aqueous solution is obtained.
Adding Mo-Ni-P aqueous solution into 100g of prepared carrier, mixing uniformly, standing for 3h, drying at 110 ℃ for 4h, and roasting at 450 ℃ for 3h to obtain the catalyst, wherein MoO is3The content was 10.0wt%, the NiO content was 2.2wt%, and the P content was 1.7 wt%.
(3) Catalyst evaluation
The activity of the catalyst was evaluated in an autoclave, the properties of the feedstock oils used are shown in Table 3, and the evaluation conditions were as follows: the reaction pressure was 15.0MPa, the reaction temperature was 420 ℃, the reaction time was 1 hour, the oil ratio was 13:1, and the evaluation results are shown in Table 4.
Example 2
(1) Preparation of the support
1000g of pseudo-boehmite powder (commercially available, with a specific surface area of 350 m)2Per gram, the pore volume is 1.15 mL/g) is prepared into spherical particles by rolling forming in a ball rolling machine, 14g of sesbania powder is added and 850mL of diammonium hydrogen phosphate aqueous solution with the concentration of 0.046g/mL is sprayed in the process of ball rolling, the rotating speed of the ball rolling machine is 35 revolutions per minute, and after ball rolling is finished, a carrier precursor is prepared; then carrying out water vapor treatment on the carrier precursor at the temperature of 200 ℃ for 4h, wherein the volume space velocity of the water vapor and the carrier precursor A is 800h-1. And drying the treated material at 110 ℃ for 8h, and then roasting at 700 ℃ for 3h to obtain the spherical carrier with the particle size of 0.2-0.8 mm. The physicochemical properties of the carrier are shown in Table 1, and the abrasion data are shown in Table 2.
(2) Catalyst preparation
7.0g of phosphoric acid H3PO4(the concentration is 85 wt%) is dissolved in 50mL of water, 18.9g of molybdenum trioxide and 8.1g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the volume is adjusted to 85mL after the mixture is filtered, so that the Mo-Ni-P aqueous solution is obtained.
Adding Mo-Ni-P aqueous solution into 100g of prepared carrier, mixing uniformly, standing for 3h, drying at 110 ℃ for 4h, and roasting at 450 ℃ for 3h to obtain the catalyst, wherein MoO is3The content was 15.0wt%, the NiO content was 3.5wt%, and the P content was 2.5 wt%.
(3) Catalyst evaluation
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 4.
Example 3
(1) Preparation of the support
1000g of pseudo-boehmite powder (commercially available, with a specific surface area of 350 m)2Per gram, the pore volume is 1.15 mL/g) is made into spherical particles by rolling forming in a ball rolling machine, during the balling process, 14g of sesbania powder is added and 850mL of ammonium phosphate aqueous solution with the concentration of 0.069g/mL is sprayed, the rotating speed of the ball rolling machine is 35 r/min, and after the balling is finished, a carrier precursor is prepared; then carrying out water vapor treatment on the carrier precursor at the temperature of 210 ℃ for 4h, wherein the volume space velocity of the water vapor and the carrier precursor A is 800h-1. Drying the treated material at 110 deg.CAnd roasting for 3 hours at 700 ℃ after 8 hours to obtain the spherical carrier with the particle size of 0.2-0.8 mm. The physicochemical properties of the carrier are shown in Table 1, and the abrasion data are shown in Table 2.
(2) Catalyst preparation
10.2g of phosphoric acid H3PO4(the concentration is 85 wt%) is dissolved in 50mL of water, 27.6g of molybdenum trioxide and 12.1g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the volume is adjusted to 85mL after the mixture is filtered, so that the Mo-Ni-P aqueous solution is obtained.
Adding Mo-Ni-P aqueous solution into 100g of prepared carrier, mixing uniformly, standing for 3h, drying at 110 ℃ for 4h, and roasting at 450 ℃ for 3h to obtain the catalyst, wherein MoO is3The content was 20.0wt%, the NiO content was 4.8wt%, and the P content was 3.2 wt%.
(3) Catalyst evaluation
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 4.
Example 4
(1) Preparation of the support
1000g of pseudo-boehmite powder (commercially available, with a specific surface area of 350 m)2Per gram, the pore volume is 1.15 mL/g) is made into spherical particles by rolling forming in a ball rolling machine, 14g of sesbania powder is added and 850mL of ammonium phosphate aqueous solution with the concentration of 0.086g/mL is sprayed in during the process of ball forming, the rotating speed of the ball rolling machine is 35 r/min, and after the ball forming is finished, a carrier precursor is prepared; then carrying out water vapor treatment on the carrier precursor at the temperature of 210 ℃ for 4h, wherein the volume space velocity of the water vapor and the carrier precursor A is 800h-1. And drying the treated material at 110 ℃ for 8h, and then roasting at 700 ℃ for 3h to obtain the spherical carrier with the particle size of 0.2-0.8 mm. The physicochemical properties of the carrier are shown in Table 1, and the abrasion data are shown in Table 2.
(2) Catalyst preparation
14.0g of phosphoric acid H3PO4(the concentration is 85 wt%) is dissolved in 50mL of water, then 38.0g of molybdenum trioxide and 16.7g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the volume is adjusted to 85mL after filtration, so that the Mo-Ni-P aqueous solution is obtained.
Adding Mo-Ni-P aqueous solution into 100g of prepared carrier, mixing uniformly, standing for 3hThen drying at 110 ℃ for 4h, and roasting at 450 ℃ for 3h to obtain the catalyst, wherein the MoO is3The content was 25.0wt%, the NiO content was 6.0wt%, and the P content was 3.9 wt%.
(3) Catalyst evaluation
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 4.
Example 5
In example 3, a catalyst was prepared as in example 1 except that 12.1g of basic nickel carbonate was changed to 11.9g of basic cobalt carbonate. MoO in catalyst3The content was 20.0wt%, the CoO content was 4.8wt%, and the P content was 3.2 wt%.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 4.
Comparative example 1
In example 1, 850mL of deionized water was used instead of 850mL of ammonium dihydrogen phosphate aqueous solution having a concentration of 0.027g/mL, and the physicochemical properties of the carrier and the abrasion data are shown in Table 1 and Table 2, respectively, in the same manner as in example 1.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 4.
Comparative example 2
Compared with the example 1, the water vapor treatment step is omitted, the carrier precursor is directly dried and roasted to obtain the final carrier, the rest is the same as the example 1, the physicochemical properties of the carrier are shown in the table 1, and the abrasion data are shown in the table 2.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 4.
TABLE 1 physicochemical Properties of the vectors
Figure RE-303871DEST_PATH_IMAGE001
TABLE 2 wear of the carriers
Figure RE-831411DEST_PATH_IMAGE002
TABLE 3 Properties of the feed oils
Figure RE-288937DEST_PATH_IMAGE004
TABLE 4 catalyst evaluation results
Figure RE-729408DEST_PATH_IMAGE005
The results of the evaluation of the activity of comparative example 1 are shown in Table 4, where the activity is 100.

Claims (14)

1. A preparation method of a heavy oil hydrotreating catalyst carrier comprises the following steps:
mixing pseudo-boehmite powder, an auxiliary agent and an ammonium phosphate aqueous solution, and forming to obtain a carrier precursor;
and treating the carrier precursor by using vapor-containing gas, and further drying and roasting to obtain the catalyst carrier.
2. The method for preparing a heavy oil hydroprocessing catalyst support according to claim 1, wherein: in the step (1), the auxiliary agent is one or more of sesbania powder, methyl cellulose and starch, and preferably sesbania powder.
3. The method for preparing a heavy oil hydroprocessing catalyst support according to claim 2, wherein: the addition amount of the auxiliary agent is 1-5% of the mass of the final carrier.
4. The method for preparing a heavy oil hydroprocessing catalyst support according to claim 1, wherein: the ammonium phosphate in the step (1) is one or more of ammonium dihydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.
5. The method for preparing a heavy oil hydroprocessing catalyst support according to claim 1, wherein: the concentration of the ammonium phosphate salt aqueous solution is 0.01-0.20 g/mL.
6. The method for preparing a heavy oil hydroprocessing catalyst support according to claim 1, wherein: the adding amount of the ammonium phosphate in the step (1) is 1 to 5 weight percent of the final carrier content.
7. The method for preparing a heavy oil hydroprocessing catalyst support according to claim 1, wherein: the vapor-containing gas in the step (2) is vapor or a mixed gas of the vapor and a carrier gas, and the volume ratio of the vapor to the carrier gas in the mixed gas is 1: 5-2: 1, preferably 1: 4-1: 1; the carrier gas is air, nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
8. The method for preparing a heavy oil hydroprocessing catalyst support according to claim 1, wherein: and (3) in the treatment process in the step (2), introducing steam-containing gas to treat the precursor, wherein the treatment temperature is 150-250 ℃, preferably 180-220 ℃, and the treatment time is 2-6 h.
9. The method for preparing a heavy oil hydroprocessing catalyst support according to claim 1, wherein: the volume space velocity of the vapor-containing gas and the carrier precursor in the step (2) is 500-2000 h-1。
10. The method for preparing a heavy oil hydroprocessing catalyst support according to claim 1, wherein: the drying temperature in the step (2) is 90-120 ℃, and the drying time is 3-12 h; the roasting temperature is 500-1000 ℃, and the roasting time is 1-5 h.
11. The method for preparing a heavy oil hydroprocessing catalyst support according to claim 1, wherein: introducing other metals, such as one or more of Fe, Zr, Ti, B, La and Ce on the catalyst carrier obtained in the step (2).
12. A heavy oil hydroprocessing catalyst support obtained by the process of any one of claims 1-11.
13. A heavy oil hydrotreating catalyst comprising a hydrogenation-active metal component and a carrier, characterized in that: the carrier is obtained by the preparation method of any one of claims 1 to 11.
14. The heavy oil hydroprocessing catalyst as recited in claim 12, wherein: the hydrogenation active metal component is one or more of VIB group metals and/or VIII group metals.
CN201811648082.5A 2018-12-29 2018-12-29 Heavy oil hydrotreating catalyst carrier, catalyst and preparation method thereof Pending CN111375438A (en)

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CN114471507A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Catalytic carrier material, preparation method thereof, catalytic material and application
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