CN112844369B - Heavy oil slurry bed hydrogenation carbon-carried monoatomic molybdenum catalyst and preparation and application method thereof - Google Patents
Heavy oil slurry bed hydrogenation carbon-carried monoatomic molybdenum catalyst and preparation and application method thereof Download PDFInfo
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- 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
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Abstract
The invention belongs to the technical field of heavy oil slurry bed hydrocracking catalysis, and particularly relates to a heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst and a preparation and application method thereof. The preparation method has the advantages of simple and reliable flow, environmental protection, no loss of metal active components, easily obtained raw materials, high product purity and low production cost; the prepared catalyst has high dispersity of molybdenum monoatomic atoms, obviously improves catalytic activity and stability compared with the existing heavy oil hydrogenation catalyst, has high atom economy, can effectively reduce the cost of the catalyst, and has obvious advantages in industrial application. A carbon-supported monatomic molybdenum catalyst for hydrogenation of a heavy oil slurry bed comprises: a heteroatom-doped porous carbon-based carrier and an active metal component dispersed on the surface of the porous carbon-based carrier; the heteroatom is any one or more of sulfur and nitrogen; the active metal component is one or more of single atoms or atom clusters of molybdenum.
Description
Technical Field
The invention belongs to the technical field of heavy oil slurry bed hydrocracking catalysis, and particularly relates to a heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst and a preparation and application method thereof.
Background
At present, with the progress of exploitation, the reserves of light crude oil are decreasing, and petroleum refining enterprises are beginning to look at heavy oil which is harder to exploit and harder to use. However, heavy oil recovery not only needs to solve the problem of heavy oil lightening, but also needs to meet various environmental protection index requirements of heavy oil treatment in the processing process. The slurry bed hydrocracking technology is different from the traditional fixed bed and moving bed, not only has the capability of processing the inferior heavy oil with high carbon residue, high metal and high sulfur, but also can effectively inhibit coking, has the advantages of high conversion rate, high light oil yield and the like, and is a necessary trend for the development of the heavy oil hydrogenation technology.
The hydrocracking technology of the heavy oil slurry bed at the present stage mainly comprises the following processes: EST process of ENI corporation of Italy, HDHPLUS-SHP process developed by Intevep of Venezuela in cooperation with Axens of France, VRSH process of Chevron corporation, VCC process developed by KBR and BP corporation, Uniflex process of UOP corporation, and (HCAT/HC3) process of Headwater corporation, etc. After further research, the bottleneck limiting the large-scale application of the heavy oil slurry bed hydrocracking process is found to be the catalyst. The low-cost catalyst with double high turnover frequency and atomic efficiency can improve the utilization rate of molecular hydrogen and the conversion rate of light heavy oil, effectively inhibit coke formation and avoid the problems of equipment abrasion, blockage and the like caused by scaling and coke formation. In fact, the slurry bed hydrogenation catalyst is introduced into a heavy oil system at one time to assist in the lightening of the asphaltene/colloid, thereby completing the heavy oil conversion process and the service experience, and then the subsequent separation process exits or enters tail oil. Therefore, the conversion frequency and the atomic efficiency of the catalyst directly determine the processing cost of the slurry bed hydrogenation process, the high turnover frequency ensures that each catalytic active center works with high efficiency, and the high atomic efficiency means that each atom forming the catalyst can fully play a catalytic role like a single-atom catalyst. For those skilled in the art, it is an urgent technical problem to be solved in the art to provide a catalyst with low cost, high turnover frequency, high atom utilization rate and long life cycle, and the catalyst has important theoretical and practical significance.
Disclosure of Invention
The invention provides a heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst and a preparation and application method thereof, and the preparation method has the advantages of simple and reliable process, environmental protection, no loss of metal active components, easy obtainment of raw materials, high product purity and low production cost; the prepared catalyst has high dispersity of molybdenum monoatomic atoms, remarkably improves catalytic activity and stability compared with the existing heavy oil hydrogenation catalyst, has high atom economy, can effectively reduce the cost of the catalyst, and has obvious advantages in industrial application.
In order to solve the technical problems, the invention adopts the following technical scheme:
a carbon-supported monatomic molybdenum catalyst for hydrogenation of a heavy oil slurry bed comprises: a heteroatom-doped porous carbon-based carrier and an active metal component dispersed on the surface of the porous carbon-based carrier;
the heteroatom is any one or more of sulfur and nitrogen;
the active metal component is any one or more of single atoms or atom clusters of molybdenum.
Preferably, the mass fraction of molybdenum in the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst is 1-10%, and the mass fraction of S atoms playing a synergistic effect with the molybdenum is 1-8%.
Preferably, the single atom or atom cluster of molybdenum is prepared from a molybdenum source compound; the molybdenum source compound is any one or combination of ammonium molybdate tetrahydrate, molybdenum acetylacetonate and molybdenum hexacarbonyl.
Preferably, the carbon carrier in the heavy oil slurry bed hydrogenation carbon-supported single-atom molybdenum catalyst is any one or more of glucose, polydextrose, starch and chitosan.
Preferably, the nitrogen source of nitrogen in the heteroatom is any one or more of hydroxylamine chloride, melamine and dicyanodiamine.
Preferably, the sulfur source of sulfur in the heteroatom is any one or more of sulfur powder, trithiocyanuric acid, thioacetamide and dibenzyl disulfide.
In another aspect, a method for preparing a heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst, the method being used to produce the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst of any of claims 1 to 6, comprising the steps of:
(1) mixing a molybdenum source compound, a nitrogen source and deionized water to obtain a mixed solution A;
(2) adding absolute ethyl alcohol into the mixed solution A obtained in the step (1), and continuously adding glucose to obtain a mixed solution B;
(3) mixing a sulfur source and deionized water, and adding the mixture into the mixed solution B obtained in the step (2) to obtain a reaction solution; after the reaction liquid reacts, drying at the temperature of 60-80 ℃ to obtain a precursor of the molybdenum-based monatomic catalyst;
(4) and (4) roasting the precursor of the molybdenum-based monatomic catalyst obtained in the step (3) in an inert atmosphere to obtain the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst.
Preferably, the weight ratio of the molybdenum source compound, the nitrogen source, the glucose and the sulfur source added in the preparation method of the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst is 1-10: 120-250: 25-50: 25-250.
Preferably, in the step (4), the roasting temperature is 500-900 ℃, the roasting time is 4-6 h, and the inert atmosphere is nitrogen or argon.
On the other hand, the application method of the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst comprises the following steps:
(a) adding the hydrogenated carbon-supported monatomic molybdenum catalyst prepared in advance into FCC diesel oil for uniform dispersion;
(b) adding the FCC diesel oil dispersed with the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst into the inferior heavy oil to be treated, and uniformly dispersing;
the dosage of the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst is expressed by the mass ratio of the molybdenum atomic mass fraction to the inferior heavy oil being 50-2000 mug/g;
(c) and operating the slurry bed hydrogenation reaction according to the following operating conditions: the initial reaction pressure is 6-10Mpa, the reaction temperature is 410-440 ℃, and the reaction time is 1 h.
The invention provides a heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst and a preparation and application method thereof, wherein the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst comprises a heteroatom-doped porous carbon-based carrier and an active metal component dispersed on the surface of the porous carbon-based carrier; the heteroatom is any one or more of sulfur and nitrogen; the active metal component is one or more of single atoms or atom clusters of molybdenum. The heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst with the characteristics, the preparation method and the application method thereof at least have the following characteristics:
1. the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst prepared by the invention has good heavy oil slurry bed hydrogenation activity, and can well treat high-sulfur, high-carbon residue and high-metal vacuum residue oil.
2. Compared with the existing heavy oil hydrogenation catalyst, the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst prepared by the method has the advantages of obviously improved catalytic activity and stability, high atom economy, capability of effectively reducing the catalyst cost and obvious advantages in industrial application.
3. The carbon-supported monatomic molybdenum catalyst prepared by the invention has a stable structure under the condition of heavy oil slurry bed hydrogenation operation, does not agglomerate, has strong interaction between monatomic molybdenum and a carbon carrier, has wide application in the aspect of high-efficiency catalytic conversion of heavy oil, and can effectively solve the key technical problems of high cost, incapability of recycling and the like of catalyst raw materials in the industrial application of the current heavy oil slurry bed hydrogenation catalyst.
4. The preparation method of the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst provided by the invention has the advantages of simple and reliable flow, environmental protection, no loss of metal active components, cheap and easily available raw materials, and can well solve the bottleneck problem of the application of the current heavy oil slurry bed hydrogenation catalyst: i.e. high cost, non-recyclable and disposable use. Has great research value and wide application market.
Drawings
FIG. 1 is a scanning transmission electron microscope photograph of the spherical aberration correction of the hydrogenated carbon-supported monatomic molybdenum catalyst in a heavy oil slurry bed provided by the invention.
Detailed Description
The invention provides a heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst and a preparation and application method thereof, the preparation method has simple and reliable flow, environmental protection, no loss of metal active components, easily obtained raw materials, high product purity and low production cost; the prepared catalyst has high dispersity of molybdenum monoatomic atoms, obviously improves catalytic activity and stability compared with the existing heavy oil hydrogenation catalyst, has high atom economy, can effectively reduce the cost of the catalyst, and has obvious advantages in industrial application.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships illustrated in the drawings, and are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, are not to be construed as limiting the present invention. Further, in the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The invention provides a hydrogenated carbon-supported single-atom molybdenum catalyst for a heavy oil slurry bed, which is shown in figure 1, and figure 1 shows a scanning transmission electron microscope photograph for correcting spherical aberration of the hydrogenated carbon-supported single-atom molybdenum catalyst for the heavy oil slurry bed. Specifically, the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst comprises: a heteroatom-doped porous carbon-based carrier and an active metal component dispersed on the surface of the porous carbon-based carrier; the heteroatom is any one or more of sulfur and nitrogen; the active metal component is one or more of single atoms or atom clusters of molybdenum. Wherein the mass fraction of molybdenum in the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst is 1-10%, and the mass fraction of S atoms playing a synergistic effect with the molybdenum is 1-8%.
Further, as a more preferred embodiment of the present invention, a single atom or atom cluster of molybdenum is prepared from a molybdenum source compound; the molybdenum source compound is any one or combination of ammonium molybdate tetrahydrate, molybdenum acetylacetonate and molybdenum hexacarbonyl. In the heavy oil slurry bed hydrogenation carbon-carried single-atom molybdenum catalyst, the carbon carrier is preferably any one or more of glucose, polydextrose, starch and chitosan. The nitrogen source of nitrogen in the heteroatom is any one or more of hydroxylamine chloride, melamine and dicyanodiamine. The sulfur source of sulfur in the heteroatom is any one or more of sulfur powder, trithiocyanuric acid, thioacetamide and dibenzyl disulfide.
In another aspect, the present invention provides a method for preparing a heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst, wherein the method is used for preparing the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst. Specifically, the preparation method of the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst comprises the following steps:
(1) mixing a molybdenum source compound, a nitrogen source and deionized water to obtain a mixed solution A;
(2) adding absolute ethyl alcohol into the mixed solution A obtained in the step (1), and continuously adding glucose to obtain a mixed solution B;
(3) mixing a sulfur source and deionized water, and adding the mixture into the mixed solution B obtained in the step (2) to obtain a reaction solution; after the reaction liquid reacts, drying at the temperature of 60-80 ℃ to obtain a precursor of the molybdenum-based monatomic catalyst;
(4) and (4) roasting the precursor of the molybdenum-based monatomic catalyst obtained in the step (3) in an inert atmosphere to obtain the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst.
Specifically, as a more preferred embodiment, the weight ratio of the molybdenum source compound, the nitrogen source, the glucose and the sulfur source added in the preparation method of the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst is 1-10: 120-250: 25-50: 25-250. In the step (4), the roasting temperature is 500-900 ℃, the roasting time is 4-6 h, and the used inert atmosphere is nitrogen or argon.
In another aspect, the invention further provides an application method of a heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst, which specifically comprises the following steps:
(a) adding the prepared heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst into FCC diesel oil for uniform dispersion;
(b) adding the FCC diesel oil dispersed with the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst into the inferior heavy oil to be treated, and uniformly dispersing;
the dosage of the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst is expressed by the mass ratio of the molybdenum atomic mass fraction to the inferior heavy oil being 50-2000 mug/g;
(c) and operating the slurry bed hydrogenation reaction according to the following operating conditions: the initial reaction pressure is 7Mpa, the reaction temperature is 425 ℃, and the reaction time is 1 h.
In order to verify the authenticity and reliability of the quality of the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst provided by the invention, the following properties of heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst examples, reference examples and refined vacuum residue under different component ratios are supplemented.
Example one
Weighing 19.3mg of ammonium molybdate tetrahydrate, adding 40mL of deionized water, then adding 690mg of hydroxylamine chloride, carrying out ultrasonic treatment for five minutes until the ammonium molybdate tetrahydrate is completely dissolved, then measuring and adding 40mL of absolute ethyl alcohol and 144mg of glucose, and carrying out ultrasonic treatment for ten minutes until the ammonium molybdate tetrahydrate solution is completely dissolved to obtain the ammonium molybdate tetrahydrate solution. Weighing 0.5g of trithiocyanuric acid, dissolving in 40mL of deionized water, and performing ultrasonic treatment for ten minutes until the trithiocyanuric acid is completely dissolved to obtain the trithiocyanuric acid solution. Dropwise adding the cyanuric sulfate solution into the ammonium molybdate tetrahydrate solution under the condition of stirring, and stirring for 12 hours. The mixed solution was put into a 70 ℃ dry box for 24h to solid. And taking out the precursor, roasting for 4 hours at 650 ℃ to obtain the carbon-supported monatomic molybdenum catalyst, dispersing the catalyst into 100g of Qingdao refining vacuum residue oil according to the active metal input amount of 500 mu g/g, and performing hydrogenation performance evaluation on the heavy oil slurry bed, wherein the name of the catalyst is MS-1.
Example two
Weighing 19.3mg of ammonium molybdate tetrahydrate, adding 40mL of deionized water, then adding 690mg of hydroxylamine chloride, carrying out ultrasonic treatment for five minutes until the ammonium molybdate tetrahydrate is completely dissolved, then measuring and adding 40mL of absolute ethyl alcohol and 144mg of glucose, and carrying out ultrasonic treatment for ten minutes until the ammonium molybdate tetrahydrate solution is completely dissolved to obtain the ammonium molybdate tetrahydrate solution. Weighing 0.5g of trithiocyanuric acid, dissolving in 40mL of deionized water, and performing ultrasonic treatment for ten minutes until the trithiocyanuric acid is completely dissolved to obtain a trithiocyanuric acid solution. Dropwise adding the thiocyanic acid solution into the ammonium molybdate tetrahydrate solution under the condition of stirring, and stirring for 12 hours. The mixed solution was put into a 70 ℃ dry box for 24h to solid. And taking out the precursor, roasting for 4 hours at 650 ℃ to obtain the carbon-supported monatomic molybdenum catalyst, dispersing the catalyst into 100g of Qingdao refining vacuum residue oil according to the active metal input amount of 300 mu g/g, and performing hydrogenation performance evaluation on the heavy oil slurry bed, wherein the name of the heavy oil slurry bed is MS-2.
EXAMPLE III
Weighing 19.3mg of ammonium molybdate tetrahydrate, adding 40mL of deionized water, then adding 690mg of hydroxylamine chloride, carrying out ultrasonic treatment for five minutes until the ammonium molybdate tetrahydrate is completely dissolved, then measuring and adding 40mL of absolute ethyl alcohol and 144mg of glucose, and carrying out ultrasonic treatment for ten minutes until the ammonium molybdate tetrahydrate is completely dissolved to obtain an ammonium molybdate tetrahydrate solution. Weighing 0.5g of trithiocyanuric acid, dissolving in 40mL of deionized water, and performing ultrasonic treatment for ten minutes until the trithiocyanuric acid is completely dissolved to obtain a trithiocyanuric acid solution. Dropwise adding the thiocyanic acid solution into the ammonium molybdate tetrahydrate solution under the condition of stirring, and stirring for 12 hours. The mixed solution was put into a 70 ℃ dry box for 24h to solid. And taking out the precursor, roasting for 4 hours at 650 ℃ to obtain the carbon-supported monatomic molybdenum catalyst, dispersing the catalyst into 100g of Qingdao refining vacuum residue oil according to the active metal input amount of 200 mug/g, and performing hydrogenation performance evaluation on the heavy oil slurry bed, wherein the name is MS-3.
Example four
Weighing 13.6mg of ammonium molybdate tetrahydrate, adding 40mL of deionized water, then adding 690mg of hydroxylamine chloride, carrying out ultrasonic treatment for five minutes until the ammonium molybdate tetrahydrate is completely dissolved, then measuring and adding 40mL of absolute ethyl alcohol and 144mg of glucose, and carrying out ultrasonic treatment for ten minutes until the ammonium molybdate tetrahydrate solution is completely dissolved to obtain the ammonium molybdate tetrahydrate solution. Weighing 0.5g of trithiocyanuric acid, dissolving in 40mL of deionized water, and performing ultrasonic treatment for ten minutes until the trithiocyanuric acid is completely dissolved to obtain a trithiocyanuric acid solution. Dropwise adding the thiocyanic acid solution into the ammonium molybdate tetrahydrate solution under the condition of stirring, and stirring for 12 hours. The mixed solution was put into a 70 ℃ dry box for 24h to solid. And taking out the precursor, roasting for 4 hours at 650 ℃ to obtain the carbon-supported monatomic molybdenum catalyst, dispersing the catalyst into 100g of Qingdao refining vacuum residue oil according to the active metal input amount of 200 mug/g, and performing hydrogenation performance evaluation on the heavy oil slurry bed, wherein the name of the heavy oil slurry bed hydrogenation performance evaluation is MS-4.
EXAMPLE five
Weighing 7.7mg of ammonium molybdate tetrahydrate, adding 40mL of deionized water, then adding 690mg of hydroxylamine chloride, carrying out ultrasonic treatment for five minutes until the ammonium molybdate tetrahydrate is completely dissolved, then measuring and adding 40mL of absolute ethyl alcohol and 144mg of glucose, and carrying out ultrasonic treatment for ten minutes until the ammonium molybdate tetrahydrate solution is completely dissolved to obtain the ammonium molybdate tetrahydrate solution. Weighing 0.25g of trithiocyanuric acid, dissolving in 40mL of deionized water, and performing ultrasonic treatment for ten minutes until the trithiocyanuric acid solution is completely dissolved to obtain the trithiocyanuric acid solution. Dropwise adding the cyanuric sulfate solution into the ammonium molybdate tetrahydrate solution under the condition of stirring, and stirring for 12 hours. The mixed solution was put into a 70 ℃ dry box for 24h to solid. And taking out the precursor, roasting for 4 hours at 650 ℃ to obtain the carbon-supported monatomic molybdenum catalyst, dispersing the catalyst into 100g of Qingdao refining vacuum residue oil according to the active metal input amount of 200 mug/g, and performing hydrogenation performance evaluation on the heavy oil slurry bed, wherein the name is MS-5.
Reference example 1
0.041g of ammonium molybdate tetrahydrate is weighed as a molybdenum catalyst to be dispersed in 100g of Qingdao refined vacuum residue, namely 200 mu g/g of molybdenum catalyst is subjected to heavy oil slurry bed hydrogenation performance evaluation and is named as M-1.
Reference example 2
0.03g of molybdenum trioxide as a molybdenum catalyst was weighed and dispersed in 100g of Qingdao refinery vacuum residue, that is, 200. mu.g/g, to evaluate the hydrogenation performance of the heavy oil slurry bed, and the catalyst was named M-2.
Reference example three
The hydrogenation performance evaluation is directly carried out on 100g of Qingdao refined vacuum residue without adding a catalyst, and the name is B-1.
The specific comparison of the properties of the products can be referred to as follows: the Qingdao refined vacuum residue oil is used as a raw material (properties are shown in table 1), the reaction temperature is 425 ℃, the initial hydrogen pressure is 7MPa, the dosage of the catalyst is 50-2000 mu g/g calculated by molybdenum metal, the reaction time is 1 hour, and the experimental comparison effect of the comparative example and the reference example is shown in table 2.
Wherein, Table 1 shows the properties of Qingdao refined vacuum residue
Table 2 shows the results of comparing the experiments of the examples and the reference examples of hydrocracking vacuum residue
As can be seen from the above table, under the specified operating conditions (initial reaction pressure of 7MPa, reaction temperature of 425 ℃ and reaction time of 1 hour), the coke formation in the three-wall of the reference example without catalyst reaches 9.46%, and the coke formation in the first and second reference examples using ammonium molybdate tetrahydrate and molybdenum trioxide as catalysts is also quite serious. In the first example, the total coke amount was reduced to 1.01% at a catalyst loading of 500. mu.g/g. In example two, the total coke formation was also reduced to 1.02% at a catalyst loading of 300. mu.g/g, which presumably resulted in very good hydrogenation activity at low metal loadings. In example three, when the catalyst addition was reduced to 200. mu.g/g, the total coke formation increased to 1.49% compared to example two. In the fourth and fifth examples, the molybdenum content of the catalyst is reduced compared with the first, second and third examples, and the catalytic effect is not obviously weakened when the catalyst is still added in an amount of 200 μ g/g, but the catalytic activity is better when the metal content in the catalyst is lower, which shows that the better the dispersion of the metal monoatomic group on the carrier is, the better the catalytic effect is. Of course, errors within 0.5% are normal and are not explained further. Thus, the carbon-supported molybdenum-based monatomic catalyst prepared by the method has good heavy oil slurry bed hydrogenation activity, can greatly reduce coke and gas yield, and well realizes the lightening of heavy oil.
The invention provides a heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst and a preparation and application method thereof, wherein the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst comprises a heteroatom-doped porous carbon-based carrier and an active metal component dispersed on the surface of the porous carbon-based carrier; the heteroatom is any one or more of sulfur and nitrogen; the active metal component is one or more of single atoms or atom clusters of molybdenum. The heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst with the characteristics, the preparation method and the application method thereof at least have the following characteristics:
1. the heavy oil slurry bed hydrogenation carbon-carried monoatomic molybdenum catalyst prepared by the invention has good heavy oil slurry bed hydrogenation activity, and can well treat high-sulfur, high-carbon residue and high-metal vacuum residue.
2. Compared with the existing heavy oil hydrogenation catalyst, the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst prepared by the method has the advantages of obviously improved catalytic activity and stability, high atom economy, capability of effectively reducing the catalyst cost and obvious advantages in industrial application.
3. The carbon-supported monatomic molybdenum catalyst prepared by the invention has a stable structure under the condition of heavy oil slurry bed hydrogenation operation, does not agglomerate, has strong interaction between monatomic molybdenum and a carbon carrier, has wide application in the aspect of high-efficiency catalytic conversion of heavy oil, and can effectively solve the key technical problems of high cost, incapability of recycling and the like of catalyst raw materials in the industrial application of the current heavy oil slurry bed hydrogenation catalyst.
4. The preparation method of the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst provided by the invention has the advantages of simple and reliable process, environmental protection, no loss of metal active components, low cost and easy obtainment of raw materials, and can well solve the bottleneck problem of the application of the current heavy oil slurry bed hydrogenation catalyst: i.e. high cost, non-recyclable and disposable use. Has great research value and wide application market.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. The carbon-supported monatomic molybdenum catalyst for hydrogenation of heavy oil slurry bed is characterized by comprising: a heteroatom-doped porous carbon-based carrier and an active metal component dispersed on the surface of the porous carbon-based carrier;
the heteroatoms are sulfur and nitrogen;
the active metal component is a single atom or cluster of atoms of molybdenum;
the single atom or atom cluster of molybdenum is prepared from a molybdenum source compound; the molybdenum source compound is any one or more of ammonium molybdate tetrahydrate, molybdenum acetylacetonate and molybdenum hexacarbonyl;
the carbon carrier in the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst is glucose;
the nitrogen source of nitrogen in the heteroatom is any one or more of hydroxylamine chloride, melamine and dicyanodiamine;
the sulfur source of sulfur in the heteroatom is any one or more of sulfur powder, trithiocyanuric acid, thioacetamide and dibenzyl disulfide;
the weight fraction of molybdenum in the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst is 1-10%, and the weight fraction of sulfur atoms playing a synergistic effect with the molybdenum is 1-8%;
the preparation method of the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst comprises the following steps:
(1) mixing a molybdenum source compound, a nitrogen source and deionized water to obtain a mixed solution A;
(2) adding absolute ethyl alcohol into the mixed solution A obtained in the step (1), and continuously adding glucose to obtain a mixed solution B;
(3) mixing a sulfur source and deionized water, and adding the mixture into the mixed solution B obtained in the step (2) to obtain a reaction solution; after the reaction liquid reacts, drying at the temperature of 60-80 ℃ to obtain a precursor of the molybdenum-based monatomic catalyst;
(4) and (4) roasting the precursor of the molybdenum-based monatomic catalyst obtained in the step (3) in an inert atmosphere to obtain the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst.
2. A process for preparing a heavy oil slurry bed hydrogenated carbon supported monatomic molybdenum catalyst as set forth in claim 1, comprising the steps of:
(1) mixing a molybdenum source compound, a nitrogen source and deionized water to obtain a mixed solution A;
(2) adding absolute ethyl alcohol into the mixed solution A obtained in the step (1), and continuously adding glucose to obtain a mixed solution B;
(3) mixing a sulfur source and deionized water, and adding the mixture into the mixed solution B obtained in the step (2) to obtain a reaction solution; after the reaction liquid reacts, drying at the temperature of 60-80 ℃ to obtain a precursor of the molybdenum-based monatomic catalyst;
(4) and (4) roasting the precursor of the molybdenum-based monatomic catalyst obtained in the step (3) in an inert atmosphere to obtain the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst.
3. The method for preparing a heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst as claimed in claim 2, wherein the ratio of the mass fractions of the molybdenum source compound, the nitrogen source, the glucose, and the sulfur source added in the method for preparing a heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst is 1 to 10: 120-250: 25-50: 25-250.
4. The method for preparing the heavy oil slurry bed hydrogenation carbon-supported monatomic molybdenum catalyst according to claim 2, wherein in the step (4), the roasting temperature is 500 to 900 ℃, the roasting time is 4 to 6 hours, and the inert atmosphere used is nitrogen or argon.
5. The application method of the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst is characterized by comprising the following steps:
(a) adding the prepared heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst into FCC diesel oil for uniform dispersion;
(b) adding the FCC diesel oil dispersed with the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst into the inferior heavy oil to be treated, and uniformly dispersing;
the dosage of the heavy oil slurry bed hydrogenation carbon-carried monatomic molybdenum catalyst is expressed by the mass ratio of the molybdenum atomic mass fraction to the inferior heavy oil being 50-2000 mug/g;
(c) and operating the slurry bed hydrogenation reaction according to the following operating conditions: the initial reaction pressure is 6-10Mpa, the reaction temperature is 410-440 ℃, and the reaction time is 1 h.
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