CN113000073A - Regeneration method of hydrogenation catalyst - Google Patents
Regeneration method of hydrogenation catalyst Download PDFInfo
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- CN113000073A CN113000073A CN201911316360.1A CN201911316360A CN113000073A CN 113000073 A CN113000073 A CN 113000073A CN 201911316360 A CN201911316360 A CN 201911316360A CN 113000073 A CN113000073 A CN 113000073A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/30—Regeneration or reactivation of catalysts comprising compounds of sulfur, selenium or tellurium
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
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- 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
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a regeneration method of a hydrogenation catalyst. The method comprises the following steps: (1) immersing the inactivated hydrogenation catalyst A in a solvent, carrying out ultrasonic treatment to obtain a catalyst B and a mixed material mixed with black powder, recovering the catalyst B, and filtering the mixed material mixed with the black powder to obtain powder C; (2) grinding the catalyst B into powder, and screening to obtain catalyst powder D; (3) forming, drying and roasting the catalyst powder D to obtain a regenerated carrier; (4) and (2) dissolving the powder C obtained in the step (1) in diesel oil, soaking the powder C on a regeneration carrier, and drying to obtain the regeneration hydrogenation catalyst. The method of the invention does not need to supplement active metal components additionally, basically eliminates the interaction between the carrier and the molybdenum metal in the preparation process of the catalyst, and can realize the uniform dispersion of the molybdenum sulfide, so that the regenerated hydrogenation catalyst has better physicochemical property and activity. And the consumption of vulcanizing agent can be reduced and the vulcanizing time can be shortened in the start-up stage of the industrial device.
Description
Technical Field
The present invention relates to a method for regenerating a catalyst, and more particularly, to a method for regenerating a hydrogenation catalyst.
Background
The residual oil hydrogenation technology has the characteristics of strong raw material adaptability, simple production operation flow and the like, can provide high-quality raw materials for the downstream catalytic cracking process, and becomes one of the most important heavy oil processing technologies in modern oil refining and petrochemical industries. In particular, the amount of residue hydrotreatment in china has been increasing in recent years, and the demand for residue hydrogenation catalysts has also been increasing considerably. In addition, the residual oil has high metal, colloid and asphaltene contents, so that the operation period of a residual oil hydrogenation device is generally 1-2 years, and the catalyst cannot be regenerated and used. Therefore, a large amount of residual oil hydrogenation catalyst is treated as solid waste after extracting a small amount of metal every year.
A layer of carbon deposit is attached to the surface of a commonly used catalyst, and the carbon deposit covers the metal active sites on the surface of the catalyst and is an important reason for the inactivation of the catalyst. In the common catalyst regeneration process, high-temperature carbon burning and sulfur burning treatment are carried out after residual oil on the catalyst is removed. The high-temperature treatment process can lead the active metal to generate aggregation and influence the activity of the catalyst, so that the activity of the regenerated catalyst is far lower than that of a fresh agent. At the same time, the pore structure of the catalyst cannot be restored to the extent of the fresh agent due to the clogging action of the substances such as the deposit metals, and the diffusion resistance of the feedstock oil on the catalyst is increased. In addition, the strength of the regenerant subjected to high-temperature treatment is greatly reduced, and the regenerant is easy to break in the transportation and reaction processes, so that the pressure drop of the bed is influenced.
Furthermore, the customary active components of hydrogenation catalysts are generally nickel-and/or cobalt-containing, molybdenum-and/or tungsten-containing. To improve activity and stability, such catalysts are typically presulfided prior to use to convert the hydrogenation metal component to sulfide. Therefore, during the regeneration of the catalyst, the oxygen of the sulfide is accompanied with the scorchAnd (4) carrying out a reaction. Under the condition of high-temperature oxygen enrichment, part of SO2Will be converted into SO3. These sulfur-containing substances react with water in the regeneration atmosphere to generate sulfurous acid and sulfuric acid, and the performance of the regenerated catalyst is easily deteriorated. In addition, the regenerated catalyst needs to be vulcanized again to convert the oxidation state metal into metal sulfide, so that the catalyst has hydrogenation activity. The pure high-temperature oxidation regeneration not only wastes the original sulfur element on the catalyst, but also needs to supplement a part of new sulfur element.
CN1125474C discloses a hydrogenation catalyst regeneration method, which is to preheat a hydrogenation catalyst with lost activity, heat the catalyst for 1-7 hours in a low-temperature section of 300-350 ℃, heat the catalyst for 1-7 hours in a medium-temperature section of 400-500 ℃ and heat the catalyst for 1-10 hours in a high-temperature section of 550-600 ℃, and naturally cool the catalyst to obtain the regenerated catalyst.
CN1921942A discloses a method for recovering the activity of a spent hydrotreating catalyst, which comprises the steps of carrying out carbon burning treatment on the spent hydrotreating catalyst with carbon deposition to obtain an intermediate catalyst with the carbon content reduced to 0.5-2.5 percent of the total amount, carrying out contact and aging treatment on the intermediate catalyst and a chelating agent solution containing nitrogen, wherein the aging treatment time is more than 10 hours, and finally carrying out drying treatment to obtain a regenerated catalyst, wherein more than 50 percent of the introduced chelating agent amount is remained in the dried catalyst.
CN1782030A discloses a method for regenerating a hydrogenation catalyst, which comprises the following steps: 1) mixing the granular alkaline substance with the inactivated hydrogenation catalyst, wherein the weight mixing ratio of the granular alkaline substance to the inactivated hydrogenation catalyst is 5: 95-50: 50; 2) contacting a mixture of a particulate basic material and a deactivated hydrogenation catalyst with an oxygen-containing gas under oxidative regeneration reaction conditions; 3) separating and regenerating the hydrogenation catalyst.
In conclusion, the prior art adopts the conventional sulfur and carbon burning method, and the physicochemical property and the structure of the regenerated hydrogenation catalyst can not meet the requirements of industrial production. Therefore, it is necessary to develop an effective regeneration method for hydrogenation catalysts.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a regeneration method of a hydrogenation catalyst. The method does not need to supplement active metal components additionally, can reduce the dosage of a vulcanizing agent and shorten the vulcanizing time, and the obtained regenerated hydrogenation catalyst has better physicochemical property and activity.
The invention provides a regeneration method of a hydrogenation catalyst, which comprises the following steps:
(1) soaking the inactivated hydrogenation catalyst A in a solvent, performing ultrasonic treatment to obtain a catalyst B and a mixed material mixed with black powder, recovering the catalyst B, and filtering the mixed material mixed with the black powder to obtain powder C;
(2) grinding the catalyst B into powder, and screening to obtain catalyst powder D;
(3) forming, drying and roasting the catalyst powder D to obtain a regenerated carrier;
(4) and (2) dissolving the powder C obtained in the step (1) in diesel oil, then soaking the powder C on a regenerated carrier, and drying to obtain the regenerated hydrogenation catalyst.
Wherein the deactivated hydrogenation catalyst A is a sulfurized deactivated hydrogenation catalyst. And the sulfurized deactivated hydrogenation catalyst is generally placed in a solvent for storage before regeneration reaction so as to avoid contacting water and air, wherein the solvent can be one or more of alcohols, ethers, diesel oil, aviation kerosene and the like.
Preferably, before step (1), the deactivated hydrogenation catalyst a is subjected to a deoiling treatment, which can be performed by a conventional method in the art, such as: and (3) putting the deactivated hydrogenation catalyst A into a toluene solvent, and performing heating extraction treatment for more than 24 hours.
In the step (1), the deactivated hydrogenation catalyst A at least contains active metal molybdenum, and the content of the active metal molybdenum in terms of oxide is 10% -30% by weight of the deactivated hydrogenation catalyst A from a fresh catalyst.
In the step (1), the content of the deposited metal on the deactivated hydrogenation catalyst a (the deposited metal comprises metallic iron and vanadium), and the content of the deposited metal calculated by metal simple substance is less than 2% by weight of the fresh catalyst from which the deactivated hydrogenation catalyst a is derived.
In the step (1), the solvent is one or more of ethanol, isopropanol, polyvinylpyrrolidone, dimethyl sulfoxide and dimethylformamide, or an aqueous solution of one or more of the above substances.
In the step (1), the ultrasonic treatment time is 0.5-3 hours; the ultrasonic treatment frequency is 35-40 KHz.
The ultrasonic treatment preferably adopts intermittent ultrasonic treatment, specifically, first ultrasonic treatment is carried out, then first standing is carried out, then second ultrasonic treatment is carried out, and then second standing is carried out, the process is repeated until the total time of the ultrasonic treatment reaches 0.5-3 hours, wherein the standing time of each time is preferably 5-15 min.
In the step (2), the particle size of the powder D is preferably smaller than 200 mesh, and may be, for example, 200 mesh, 300 mesh, 400 mesh, or the like.
In the step (3), extrusion aids can be added in the forming process. The extrusion aid can be one or more of sesbania powder, starch and polyethanol. The molding can be made into a conventional shape according to the requirement, for example, the molding is made into a clover-shaped strip with the length of 2-8 mm by extruding the strip.
In the step (3), the drying conditions are as follows: drying for 1-6 hours at 80-135 ℃, wherein the roasting conditions are as follows: roasting for 2-8 hours at 400-850 ℃.
In the step (4), the volume of the used diesel oil is the water absorption volume of the regeneration carrier.
In the step (4), a dispersant is preferably added into the diesel oil, wherein the dispersant is one or more of ethanol, isopropanol, polyvinylpyrrolidone, dimethyl sulfoxide and dimethylformamide.
In the step (4), the drying conditions are as follows: drying for 2-12 hours at 50-150 ℃ under vacuum.
The method provided by the invention is particularly suitable for regenerating deactivated residual oil hydrogenation catalysts and is also suitable for regenerating deactivated other hydrogenation catalysts widely used in the petroleum refining process, wherein the catalysts comprise: hydrorefining catalysts, hydrotreating catalysts, and the like.
Compared with the prior art, the invention has the following advantages:
(1) the invention can realize that most of active metal molybdenum is selectively taken out of the deactivated hydrogenation catalyst by adopting specific treatment, and can convert the metal deposited on the deactivated catalyst into the active metal without influencing other active metals loaded on the catalyst, so that the loading capacity of the active metal on the regenerated hydrogenation catalyst is equivalent to that of the original hydrogenation catalyst without additionally introducing new active metal components.
(2) The invention can make the active metal molybdenum uniformly disperse on the carrier in the form of molybdenum sulfide, and basically eliminates the interaction between the carrier and most of the active metal molybdenum, prevents the phenomena of metal structure change, interface charge transfer and the like, and improves the quality of the metal active site; and because the sulfur element is reserved in the form of molybdenum sulfide, the usage amount of a vulcanizing agent can be reduced in a pre-vulcanizing stage, the time of the vulcanizing stage is shortened, and the influence on the performance of the catalyst caused by the generation of sulfate radicals during scorching in the conventional catalyst regeneration method is avoided.
(3) The method of the invention skillfully utilizes the carbon deposition on the inactivated hydrogenation catalyst, retains the carbon deposition in the ground catalyst powder and forms the carbon deposition, and plays a role in pore-forming in the subsequent decarburization roasting process. The regenerated hydrogenation catalyst obtained by the method has a pore structure equivalent to that of the original catalyst, and other pore-expanding agents are not required to be introduced in the preparation process.
(4) The regenerated hydrogenation catalyst obtained by the method can recover the crushing strength of the original catalyst, and meets the requirement of the residual oil hydrogenation process on the strength property of the catalyst.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples.
Example 1
(1) Sampling the deactivated hydrogenation catalyst of sulfurized residual oil from the reactor, and sealing with alcohol. The catalyst was immersed in a toluene solution using a fat extractor, heated to a toluene boiling state and refluxed and condensed for 24 hours, and the extraction was completed and vacuum-dried to obtain a deactivated catalyst (the total content of the deposited metals iron and vanadium, in terms of metal simple substances, was 1.33% based on the weight of the fresh catalyst from which the deactivated hydrogenation catalyst was derived).
(2) Weighing 100g of the deactivated catalyst obtained in the step (1) and soaking the deactivated catalyst in 400mL of ethanol water solution, wherein the volume ratio of ethanol to water is 1: 1. And (3) placing the beaker filled with the ethanol water solution and the deactivated catalyst into an ultrasonic generator, keeping the ultrasonic wave for 15 minutes at the frequency of 40KHz, standing for 10 minutes, then carrying out ultrasonic treatment for 15 minutes, standing again, and repeating the process until the ultrasonic treatment time reaches 1 hour. At this time, the mixture was black, and the mixture was filtered through a 40-mesh sieve to recover the catalyst B. And then filtering the sieved mixed material to obtain molybdenum sulfide powder C. Powder C was stored under nitrogen.
(3) Drying the catalyst B obtained in the step (2), grinding the dried catalyst B into powder by using an air flow mill, sieving the powder by using a 200-mesh sieve, and collecting powder D under the sieve.
(4) And adding a proper amount of sesbania powder, deionized water and dilute nitric acid into the sieved powder D, kneading and extruding the mixture into strips, and preparing the strips with the shape of clover and the length of 2-8 mm. Then drying at 120 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the regenerated carrier.
(5) Dissolving molybdenum sulfide powder C in diesel oil, wherein the volume of the diesel oil is 334mL, adding a proper amount of ethanol dispersant to fully disperse the molybdenum sulfide in the diesel oil, and then soaking the diesel oil in a regenerated carrier. Then dried at a temperature of 80 ℃ for 4 hours under a vacuum environment to obtain a regenerated catalyst.
Example 2
(1) Sampling the deactivated hydrogenation catalyst of sulfurized residual oil from the reactor, and sealing with alcohol. Using a fat extractor to immerse the deactivated catalyst in a toluene solution, heating the toluene solution to a boiling state, refluxing and condensing the toluene solution, maintaining the toluene solution for 24 hours, finishing extraction, and performing vacuum drying to obtain the deactivated catalyst (the total content of the deposited metals of iron and vanadium, calculated as metal elementary substances, is 1.33 percent based on the weight of the fresh catalyst from which the deactivated hydrogenation catalyst is derived).
(2) 100g of the deactivated catalyst obtained in step (1) was weighed and immersed in 400mL of an aqueous polyvinylpyrrolidone solution having a concentration of 0.2 g/mL. The beaker containing the ketone and the catalyst was placed in an ultrasonic generator at a frequency of 35 KHz. Sonication continued for 15 minutes. Standing for 10 min, performing ultrasonic treatment for 15min, and standing. This procedure was repeated until the sonication time reached 45 minutes. At this time, the mixture was black, and the mixture was filtered through a 40-mesh sieve to recover the catalyst B. And then filtering the sieved mixed material to obtain molybdenum sulfide powder C. Powder C was stored under nitrogen.
(3) Drying the catalyst B obtained in the step (2), grinding the dried catalyst B into powder by using a jet mill, and sieving the powder by using a 200-mesh sieve. And collecting the sieved powder D.
(4) And adding a proper amount of sesbania powder, deionized water and dilute nitric acid into the sieved powder D, kneading and extruding the mixture into strips, and preparing the strips with the shape of clover and the length of 2-8 mm. Then drying at 110 ℃ for 4h, and roasting at 650 ℃ for 2.5h to obtain the regenerated carrier.
(5) Dissolving the molybdenum sulfide powder C into diesel oil, wherein the volume of the diesel oil is 334 mL. And adding a proper amount of isopropanol dispersant to fully disperse the molybdenum sulfide in the diesel oil, and dipping the molybdenum sulfide on the regenerated carrier. Then dried at 90 ℃ for 3 hours under vacuum to obtain a regenerated catalyst.
Example 3
(1) Sampling the deactivated hydrogenation catalyst of sulfurized residual oil from the reactor, and sealing with alcohol. Using a fat extractor to immerse the deactivated catalyst in a toluene solution, heating the toluene solution to a boiling state, refluxing and condensing the toluene solution, maintaining the toluene solution for 24 hours, finishing extraction, and performing vacuum drying to obtain the deactivated catalyst (the total content of the deposited metals of iron and vanadium, calculated as metal elementary substances, is 1.33 percent based on the weight of the fresh catalyst from which the deactivated hydrogenation catalyst is derived).
(2) Weighing 100g of the deactivated catalyst obtained in the step (1), soaking the deactivated catalyst in 400mL of isopropanol-ethanol solution, and placing the solution in an ultrasonic generator at the frequency of 40 KHz. The sonication was continued for 15 minutes, allowed to stand for 10 minutes, sonicated for another 15 minutes, allowed to stand again, and this procedure was repeated until the sonication time reached 1.5 hours. At this time, the mixture was black, and the mixture was filtered through a 40-mesh sieve to recover the catalyst B. And then filtering the sieved mixed material to obtain molybdenum sulfide powder C. Powder C was stored under nitrogen.
(3) Drying the catalyst B obtained in the step (2), grinding the dried catalyst B into powder by using a jet mill, and sieving the powder by using a 200-mesh sieve. And collecting the sieved powder D.
(4) And adding a proper amount of sesbania powder, deionized water and dilute nitric acid into the sieved powder D, kneading and extruding the mixture into strips, and preparing the strips with the shape of clover and the length of 2-8 mm. Then drying at 110 ℃ for 4h, and roasting at 650 ℃ for 2.5h to obtain the regenerated carrier.
(5) Dissolving the molybdenum sulfide powder C into diesel oil, wherein the volume of the diesel oil is 334 mL. And adding proper amount of dimethyl formamide dispersant to disperse molybdenum sulfide fully in diesel oil and soaking the diesel oil in the regenerated carrier. Then dried at 90 ℃ for 3 hours under vacuum to obtain a regenerated catalyst.
Example 4
The deactivated hydrogenation catalysts used in the examples and comparative examples of the present invention are fresh hydrogenation catalysts prepared by the following methods:
290g of pseudoboehmite (pore volume 0.95mL/g, specific surface area 308 m) is weighed2And/g, the dry basis is 69 wt%), adding a proper amount of sesbania powder, deionized water and dilute nitric acid, kneading and extruding the mixture into strips, and preparing the strips with the shape of clover and the length of 2-8 mm. Then drying at 120 ℃ for 4h, and roasting at 650 ℃ for 3h to obtain the catalyst carrier B-1.
Weighing 21.1g of molybdenum oxide and 9.7g of basic nickel carbonate, adding 50mL of water, uniformly mixing, adding 7.3 g of 85wt% phosphoric acid, heating for dissolving, and fixing the volume to obtain an impregnation solution, and then directly impregnating the impregnation solution on 100g of carrier B-1 by adopting a spray-dipping method. Then drying for 4h at 120 ℃, and roasting for 3h at 470 ℃ to obtain the fresh hydrogenation catalyst.
Comparative example 1
(1) Sampling the deactivated residual oil hydrogenation catalyst from the reaction device, taking out, and sealing with ethanol liquid. Using a fat extractor to immerse the deactivated catalyst in a toluene solution, heating the toluene solution to a boiling state, refluxing and condensing the toluene solution, maintaining the toluene solution for 24 hours, finishing extraction, and performing vacuum drying to obtain the deactivated catalyst (the total content of the deposited metals of iron and vanadium, calculated as metal elementary substances, is 1.33 percent based on the weight of the fresh catalyst from which the deactivated hydrogenation catalyst is derived).
(2) And (3) carrying out programmed temperature rise, oxidation, decarbonization and desulfurization on the deactivated catalyst to obtain the regenerated catalyst. The temperature programming process is as follows; heating the high-temperature furnace to 250 ℃ at the speed of 3 ℃/min, and roasting for 3 hours; then, the temperature is raised to 390 ℃ at the same temperature raising speed, and the mixture is roasted for 3 hours; then, the temperature was raised to 500 ℃ at the same rate of temperature rise, and the resultant was calcined for 2 hours.
Note: in order to analyze the physical and chemical properties such as pore structure of the regenerated catalyst, the obtained catalyst must be changed from a sulfided state to an oxidized state. Therefore, the regenerated catalyst obtained in the embodiment 1-3 is placed in the air, calcined at 200 ℃ for 4 hours, and then the temperature is programmed to 450 ℃ for 4 hours, and the obtained oxidation state catalyst is subjected to relevant characterization.
Test example 1
Under the same conditions, the catalysts obtained in examples 1 to 4 and comparative example 1 were subjected to pore structure analysis using a nitrogen desorption apparatus model ASAP2420 from michael corporation, usa. The analytical data are shown in table 1, and the results show that the pore structure of the catalyst regenerated by the method of the present invention can be restored to the level of the fresh catalyst.
TABLE 1 comparison of pore structure properties of catalysts
| Pore volume/cm3·g-1 | Specific surface area/m2·g-1 | |
| Example 1 | 0.44 | 183 |
| Example 2 | 0.47 | 155 |
| Example 3 | 0.46 | 161 |
| Example 4 (fresh catalyst) | 0.48 | 174 |
| Comparative example 1 | 0.33 | 115 |
It can be seen that the conventional carbon-fired, sulfur-fired regeneration of the catalyst (comparative example 1) lost a large amount of pore volume and specific surface area, and the catalyst failed to recover the original pore structure characteristics. The regeneration method of the invention can restore the pore structure property of the catalyst to the level of the fresh agent.
Test example 2
The catalysts described in examples 1 to 4 and comparative example 1 were analyzed for the content of the main active metal oxide under the same conditions. The analytical data are shown in the table below and the results show that the total amount of active metal on the catalyst regenerated by the process of the invention is comparable to, or even higher than, that of the fresh catalyst. It is demonstrated that the process of the present invention can convert metals deposited on deactivated catalysts to active metals. The method of the invention fully utilizes the advantages of the regenerated catalyst, so that the regeneration process does not need to supplement active components additionally.
Table 2 active metal content comparison of catalysts
| Molybdenum oxide, wt% | Nickel oxide, wt.% | Total weight percent | |
| Example 1 | 15.7 | 5.5 | 21.2 |
| Example 2 | 15.2 | 5.3 | 20.5 |
| Example 3 | 14.5 | 5.8 | 20.3 |
| Example 4 (fresh catalyst) | 16.1 | 3.9 | 20.0 |
| Comparative example 1 | 14.3 | 5.5 | 19.8 |
Test example 3
The analysis was performed under the same conditions using UV fluorescence, equivalent to the American society for testing and materials Standard ASTM D5453-1993. The sulfur content was analyzed for examples 1 to 4 and comparative example 1. The results obtained are shown in table 3 below:
TABLE 3 comparison of elemental sulfur content of catalysts
| Sulfur content, wt% | |
| Example 1 | 7.8 |
| Example 2 | 7.1 |
| Example 3 | 7.3 |
| Example 4 (fresh catalyst) | 0 |
| Comparative example 1 | 0.5 |
As can be seen from the results in the table, the sulfur content of the regenerated catalyst of the present invention is much higher than that of the catalyst regenerated by the fresh hydrogenation catalyst and the conventional method. It is stated that most of the active metal on the regenerated catalyst is already in a sulfided state, and therefore, about half of the sulfiding agent dosage will be reduced in the catalyst sulfiding step before the plant is started; meanwhile, the vulcanizing time can be reduced, and the enterprise cost is reduced.
Test example 4
The catalysts obtained in examples 1 to 4 and comparative example 1 were analyzed for their single-particle compressive strength under the same conditions. The results obtained are shown in table 4 and show that: the strength loss of the catalyst prepared by the conventional regeneration method is serious; the particle strength of the catalyst of the process of the invention can be restored to the level of fresh catalyst.
TABLE 4 catalyst Strength comparison
| Strength (N/cm) | |
| Example 1 | 147 |
| Example 2 | 135 |
| Example 3 | 150 |
| Example 4 (fresh catalyst) | 141 |
| Comparative example 1 | 89 |
Test example 5
And (3) carrying out residual oil hydrogenation reaction on the catalysts prepared in the examples 1-4 and the comparative example on a small fixed bed hydrogenation reactor under the same industrial conditions and the same catalyst volume. The raw oil adopts vacuum residue, the properties and the process conditions of which are shown in Table 5, and the desulfurization activity of which is shown in Table 6.
TABLE 5 Properties of the feed oils and reaction Process conditions
| Properties of crude oil | |
| Sulfur, wt.% | 3.1 |
| Nitrogen,. mu.g/g | 3324 |
| Carbon residue in wt% | 9.7 |
| Process conditions | |
| Reaction pressure, MPa | 15.0 |
| Liquid hourly volume space velocity, h-1 | 0.6 |
| Reaction temperature of | 360 |
| Volume ratio of hydrogen to oil | 500:1 |
TABLE 6 desulfurization Activity comparison of catalysts
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| Desulfurization rate of 48 hours run% | 89 | 88 | 86 | 92 | 79 |
It can be seen from table 6 that after 48 hours of operation, the desulfurization activity of the catalyst of the present invention reached about 90, which is substantially equivalent to the activity of the fresh catalyst of example 4.
The regenerated catalyst can effectively recover the properties of the catalyst such as pore structure, strength and the like, and the activity of the catalyst can also be recovered to the level of a fresh catalyst. In addition, the regenerated catalyst has great advantages in the vulcanization step, about half of the vulcanization time and the vulcanizing agent consumption can be reduced, and the cost is saved for refining enterprises.
The regenerated catalyst described in comparative example 1 is a conventional regeneration method, and the desulfurization activity of the regenerated catalyst of the method of the invention is far higher than that of the catalyst. This is because a part of the metals removed from the feed oil is deposited on the deactivated hydrogenation catalyst. These metals cover the active sites of the catalyst, greatly reducing the activity of the catalyst. In addition, metal is easy to deposit at the entrance of the catalyst pore channel, which seriously hinders the diffusion of residual oil molecules, so that the residual oil molecules can not enter the inside of the catalyst pore channel. The number of active centers on the inner surface of the catalyst pore channel is far higher than that on the outer surface of the catalyst, so that the higher the diffusion resistance is, the fewer the effective active centers on the catalyst are, and the lower the desulfurization activity of the catalyst on residual oil is, and the problems can be well solved only by the regeneration method of the invention.
Claims (11)
1. A method for regenerating a hydrogenation catalyst, comprising the steps of:
(1) soaking the inactivated hydrogenation catalyst A in a solvent, performing ultrasonic treatment to obtain a catalyst B and a mixed material mixed with black powder, recovering the catalyst B, and filtering the mixed material mixed with the black powder to obtain powder C;
(2) grinding the catalyst B into powder, and screening to obtain catalyst powder D;
(3) forming, drying and roasting the catalyst powder D to obtain a regenerated carrier;
(4) and (2) dissolving the powder C obtained in the step (1) in diesel oil, then soaking the powder C on a regenerated carrier, and drying to obtain the regenerated hydrogenation catalyst.
2. The method of claim 1, wherein: in the step (1), the deactivated hydrogenation catalyst A at least contains active metal molybdenum, and the content of the active metal molybdenum in terms of oxide is 10% -30% by weight of the deactivated hydrogenation catalyst A from a fresh catalyst.
3. The method of claim 1, wherein: in the step (1), the solvent is one or more of ethanol, isopropanol, polyvinylpyrrolidone, dimethyl sulfoxide and dimethylformamide, or an aqueous solution of one or more of the above substances.
4. The method of claim 1, wherein: in the step (1), the ultrasonic treatment time is 0.5-3 hours; the ultrasonic treatment frequency is 35-40 KHz.
5. The method of claim 4, wherein: the ultrasonic treatment adopts intermittent ultrasonic treatment, and specifically comprises the steps of firstly carrying out first ultrasonic treatment, then carrying out first standing, then carrying out second ultrasonic treatment, and then carrying out second standing.
6. The method of claim 1, wherein: in the step (2), the granularity of the powder D is smaller than 200 meshes.
7. The method of claim 1, wherein: in the step (3), the drying conditions are as follows: drying for 1-6 hours at 80-135 ℃, wherein the roasting conditions are as follows: roasting for 2-8 hours at 400-850 ℃.
8. The method of claim 1, wherein: in the step (4), the volume of the used diesel oil is the water absorption volume of the regeneration carrier.
9. The method of claim 1, wherein: in the step (4), a dispersant is added into the diesel oil, wherein the dispersant is one or more of ethanol, isopropanol, polyvinylpyrrolidone, dimethyl sulfoxide and dimethylformamide.
10. The method of claim 1, wherein: in the step (4), the drying conditions are as follows: drying for 2-12 hours at 50-150 ℃ under vacuum.
11. The method of claim 1, wherein: the deactivated hydrogenation catalyst is deactivated residual oil hydrogenation catalyst.
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|---|---|---|---|---|
| WO2000018508A1 (en) * | 1998-09-29 | 2000-04-06 | Idemitsu Kosan Co., Ltd. | Method of regenerating hydrogenation catalyst |
| JP2000144151A (en) * | 1998-11-06 | 2000-05-26 | Idemitsu Kosan Co Ltd | Regeneration of hydrogenation treatment catalyst |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN104549490A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for recycling and reusing waste hydrocracking catalyst through ultrasonication |
| CN106669866A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Regeneration method of inactivated hydrogenation catalyst |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000018508A1 (en) * | 1998-09-29 | 2000-04-06 | Idemitsu Kosan Co., Ltd. | Method of regenerating hydrogenation catalyst |
| JP2000144151A (en) * | 1998-11-06 | 2000-05-26 | Idemitsu Kosan Co Ltd | Regeneration of hydrogenation treatment catalyst |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN104549490A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for recycling and reusing waste hydrocracking catalyst through ultrasonication |
| CN106669866A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Regeneration method of inactivated hydrogenation catalyst |
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