CN114130418A - Method for regenerating hydrogenation catalyst - Google Patents

Method for regenerating hydrogenation catalyst Download PDF

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CN114130418A
CN114130418A CN202010917663.5A CN202010917663A CN114130418A CN 114130418 A CN114130418 A CN 114130418A CN 202010917663 A CN202010917663 A CN 202010917663A CN 114130418 A CN114130418 A CN 114130418A
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catalyst
powder
deactivated
regenerated
hydrogenation catalyst
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CN114130418B (en
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关月明
王永林
袁胜华
张�成
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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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
    • B01J27/28—Regeneration or reactivation
    • B01J27/30—Regeneration or reactivation of catalysts comprising compounds of sulfur, selenium or tellurium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
    • 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
    • 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
    • B01J38/56—Hydrocarbons
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/72—Regeneration or reactivation of catalysts, in general including segregation of diverse particles
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a regeneration method of a hydrogenation catalyst. The method comprises the following steps: (1) mixing the deactivated hydrogenation catalysts A1 and A2, soaking the mixture in a solvent, and performing ultrasonic treatment to obtain a catalyst B and a mixed material mixed with black powder; (2) recovering the catalyst B, and filtering the mixed material mixed with the black powder to obtain powder C; (3) grinding the catalyst B into powder, and screening to obtain catalyst powder D; forming, drying and roasting the catalyst powder D to obtain a regenerated carrier; (4) dissolving the powder C in liquid paraffin and stirring; then dipping the catalyst on a regenerated carrier, cooling, carbonizing, and performing hydrothermal treatment to obtain the regenerated hydrogenation catalyst. The method does not need to supplement active metal components additionally, the regenerated catalyst has good desulfurization performance, the dosage of a vulcanizing agent can be reduced, the vulcanizing time can be shortened, and the obtained regenerated hydrogenation catalyst has reasonable pore structure, strength and metal distribution.

Description

Method for regenerating hydrogenation catalyst
Technical Field
The present invention relates to a catalyst regeneration method, and more particularly, to a method for preparing a hydrodesulfurization catalyst by regenerating a spent 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.
In addition, the commonly used active components of hydrogenation catalysts are generally nickel and/or cobalt, molybdenum and/or tungsten, and in order to increase the activity and stability, such catalysts are usually presulfided before use, and the hydrogenation is carried outThe metal component is converted to sulfide. Therefore, the oxidation reaction of the sulfide is accompanied with the scorch in the catalyst regeneration process. 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 shortcomings of the prior art, the present invention aims to provide a method for preparing a hydrodesulfurization catalyst by regenerating a spent catalyst. The method does not need to supplement active metal components additionally, the obtained regenerated catalyst has good desulfurization performance, the dosage of a vulcanizing agent can be reduced, the vulcanizing time can be shortened, and the obtained regenerated hydrogenation catalyst has reasonable pore structure, strength and metal distribution.
The invention provides a regeneration method of a hydrogenation catalyst, which comprises the following steps:
(1) mixing the deactivated hydrogenation catalysts A1 and A2, soaking the mixture in a solvent, and performing ultrasonic treatment to obtain a catalyst B and a mixed material mixed with black powder;
(2) recovering the catalyst B, and filtering the mixed material mixed with the black powder to obtain powder C;
(3) grinding the catalyst B into powder, and screening to obtain catalyst powder D; forming, drying and roasting the catalyst powder D to obtain a regenerated carrier;
(4) dissolving the powder C in liquid paraffin and stirring; then dipping the catalyst on a regenerated carrier, cooling, carbonizing, and performing hydrothermal treatment to obtain the regenerated hydrogenation catalyst.
Wherein the deactivated hydrogenation catalysts A1 and A2 are both sulfurized deactivated hydrogenation catalysts. 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 alcohols, ethers, diesel oil, aviation kerosene and the like.
Preferably, before step (1), the deactivated hydrogenation catalysts a1 and a2 are subjected to a deoiling treatment, which can be performed by conventional methods in the art, such as: the deactivated hydrogenation catalyst is placed in a toluene solvent and is subjected to heating extraction treatment for more than 24 hours.
In the step (1), the deactivated hydrogenation catalyst A1 at least contains active metal molybdenum, and the content of the active metal molybdenum in terms of oxide is 10% -25% by weight of the deactivated hydrogenation catalyst A1 derived from a fresh catalyst.
In the step (1), the deactivated hydrogenation catalyst A2 is a bulk phase hydrofining catalyst, the catalyst at least contains active metals molybdenum and tungsten, and the content of all the active metals in terms of oxides is 40-80% by weight of the deactivated hydrogenation catalyst A2 which is a fresh catalyst; wherein the content of the active metal molybdenum is 10-30% by weight of oxide, and the content of the active metal tungsten is 20-60% by weight of oxide.
In the step (1), the mass ratio of the deactivated hydrogenation catalyst A1 to the deactivated hydrogenation catalyst A2 is as follows: 9.5: 0.5-7.5: 2.5.
In the step (1), the content of the deposited metal (the deposited metal comprises metallic iron and vanadium) on the deactivated hydrogenation catalyst a1 is less than 2.5% by weight of the fresh catalyst from which the deactivated hydrogenation catalyst a1 is derived.
In the step (1), the content of the deposited metal (the deposited metal comprises metallic iron and vanadium) on the deactivated hydrogenation catalyst a2 is less than 0.3% by weight of the fresh catalyst from which the deactivated hydrogenation catalyst a2 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 working frequency of the ultrasonic is 35-40 KHz.
The ultrasonic treatment preferably adopts intermittent ultrasonic treatment, 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, wherein the process is repeated until the total time of the ultrasonic treatment reaches 0.5-3 hours, and the standing time of each time is preferably 5-15 min.
In the step (3), the particle size of the powder D is preferably smaller than 200 mesh, and may be, for example, 300 mesh or 400 mesh.
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, and the dosage of the extrusion aid is 0.5-6.0 wt% of the mass of the alumina in the material. 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 liquid paraffin used is the water absorption volume of the regeneration carrier.
In the step (4), the cooling condition is cooling at a temperature of less than 5 ℃.
In the step (4), the carbonization needs to be carried out in an inert atmosphere, the required temperature is 300-450 ℃, the time is 3-8 h, and the required pressure is 1.0-2.5 MPa. The inert atmosphere is nitrogen and/or a live or inert gas, preferably argon.
In the step (5), the temperature of the hydrothermal treatment is 700-800 ℃, the water vapor is saturated water vapor, the flow rate of the water vapor is 0.1-0.5L/s, and the time is 0.5-2 hours.
The hydrogenation catalyst regeneration method provided by the invention is widely applicable to regeneration of various hydrogenation catalysts used in the petroleum refining process after deactivation, and produces a new catalyst suitable for the hydrodesulfurization process.
Compared with the prior art, the invention has the following advantages:
(1) the method can regenerate and treat two hydrogenation catalysts simultaneously, and has wide application range.
(2) The invention adopts the matching of two deactivated hydrogenation catalysts A1 and A2 to produce a new catalyst suitable for the hydrodesulfurization process, and compared with the fresh hydrogenation catalyst of the deactivated hydrogenation catalyst A1, the regenerated catalyst has higher hydrodesulfurization activity.
(3) 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.
(4) In the method, the paraffin is rapidly cooled and solidified, so that the molybdenum sulfide uniformly dispersed in the paraffin phase does not have enough time to deposit, the uniformly dispersed state is maintained, and the molybdenum sulfide is highly uniformly dispersed on the surface of the catalyst carrier. And the paraffin is decomposed and carbonized through further high-temperature treatment, and a small amount of carbon deposit is formed on the surface of the catalyst, so that the function of pre-depositing the carbon is achieved. Meanwhile, the amount of carbon deposition is controlled through hydrothermal treatment, so that two active centers of hydrogenation and cracking reach activity balance, the performance of the catalyst is improved, and the formation of hot spots is avoided to a certain extent.
(5) The method of the invention can take out most of the sulfur element in the deactivated hydrogenation catalyst and retain the sulfur element in the form of molybdenum sulfide, thereby reducing the usage amount of the vulcanizing agent in the pre-vulcanization stage and shortening the time of the vulcanization stage, and simultaneously avoiding the generation of sulfate radicals when the conventional catalyst regeneration method is burnt so as to influence the performance of the catalyst.
(6) 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 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.
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 sulfurized residual oil hydrogenating catalyst 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 after extraction, vacuum-dried to obtain a deactivated catalyst a1 (the content of active metal molybdenum in terms of oxide was 16% by weight of the fresh catalyst from which the deactivated hydrogenation catalyst a1 was derived, and the total content of deposited metals iron and vanadium in terms of elemental metal was 1.33% by weight of the fresh catalyst from which the deactivated hydrogenation catalyst was derived).
(2) Sampling the deactivated sulfurized phase hydrorefining catalyst 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 after extraction, vacuum-dried to obtain a deactivated hydrogenation catalyst a2 (containing 24% by weight of molybdenum as an active metal, 33% by weight of tungsten as an active metal, and 70% by weight of all active metals, based on the weight of a fresh catalyst from which the deactivated hydrogenation catalyst a2 was derived, and containing iron and vanadium as deposited metals in a total content of less than 0.3% by weight of elemental metals, based on the weight of the fresh catalyst from which the deactivated hydrogenation catalyst was derived).
(3) Weighing 90g of the deactivated catalyst A1 obtained in the step (1) and 10g of the deactivated catalyst A2 obtained in the step (2), fully mixing, and soaking in 400mL of ethanol water solution, wherein the volume ratio of ethanol to water is 1: 1. 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, and standing again. This procedure was repeated until the sonication time reached 1 hour. At this time, the mixture was black, and the mixture was filtered through a 40-mesh sieve to recover the catalyst B. The sieved mixture was then filtered to give powder C. Powder C was stored under nitrogen.
(4) And (4) drying the catalyst B obtained in the step (3), 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.
(5) 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 650 ℃ for 3h to obtain the regenerated carrier.
(6) Molybdenum sulfide powder C was dissolved in liquid paraffin in a volume of 334 mL. Fully stirring to fully disperse molybdenum sulfide in paraffin, soaking the molybdenum sulfide on a regeneration carrier, fully soaking, quickly cooling at 2 ℃ to quickly solidify liquid paraffin to obtain a catalyst precursor, and then filling the catalyst precursor into a reactor. Nitrogen was introduced into the reactor at a pressure of 1.5MPa and at a flow rate of 10L/h. And (3) pre-depositing carbon on the catalyst precursor at the constant temperature of 350 ℃ for 5 hours to obtain a catalyst E.
(7) And (3) carrying out hydrothermal treatment on the catalyst E at the temperature of 700 ℃, keeping the saturated steam flow at 0.25L/s, and keeping the temperature for 0.5 hour to obtain the regenerated catalyst.
Example 2
(1) Sampling the deactivated sulfurized residual oil hydrogenating catalyst 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 after extraction, vacuum-dried to obtain a deactivated catalyst a1 (the content of active metal molybdenum in terms of oxide was 16% by weight of the fresh catalyst from which the deactivated hydrogenation catalyst a1 was derived, and the total content of deposited metals iron and vanadium in terms of elemental metal was 1.33% by weight of the fresh catalyst from which the deactivated hydrogenation catalyst was derived).
(2) Sampling the deactivated sulfurized phase hydrorefining catalyst 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 after extraction, vacuum-dried to obtain a deactivated hydrogenation catalyst a2 (the content of molybdenum as an active metal, calculated as an oxide, was 24%, the content of tungsten as an active metal, calculated as an oxide, was 33%, the content of all active metals, calculated as an oxide, was 70%, based on the weight of the fresh catalyst from which the deactivated hydrogenation catalyst a2 was derived, and the total content of the deposited metals, iron and vanadium, calculated as elemental metals, was less than 0.3%, based on the weight of the fresh catalyst from which the deactivated hydrogenation catalyst was derived).
(3) 80g of the deactivated catalyst A1 obtained in step (1) and 20g of the deactivated catalyst A2 obtained in step (2) were weighed, mixed well and immersed in 400mL of an aqueous polyvinylpyrrolidone solution at a polyvinylpyrrolidone 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 filtering the sieved mixed material to obtain powder C, and storing the powder C in a nitrogen environment.
(4) And (4) drying the catalyst B obtained in the step (3), 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.
(5) 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 3h to obtain the regenerated carrier.
(6) Molybdenum sulfide powder C was dissolved in liquid paraffin in a volume of 334 mL. The molybdenum sulphide was dispersed well in paraffin and then impregnated on the regenerated support. And after full impregnation, rapidly cooling at 3 ℃ to rapidly solidify the liquid paraffin to obtain the catalyst precursor. The catalyst precursor is then charged to the reactor. Nitrogen was introduced into the reactor at a pressure of 1.5MPa and at a flow rate of 10L/h. And (3) pre-depositing carbon on the catalyst precursor at the constant temperature of 400 ℃ for 5 hours to obtain a catalyst E.
(7) And (3) carrying out hydrothermal treatment on the catalyst E, wherein the temperature of the hydrothermal treatment is 750 ℃, the flow of saturated steam is 0.25L/s, and keeping the temperature for 1 hour to obtain the regenerated catalyst.
Example 3
(1) Sampling the deactivated sulfurized residual oil hydrogenating catalyst 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 after extraction, vacuum-dried to obtain a deactivated catalyst a1 (the content of active metal molybdenum in terms of oxide was 16% by weight of the fresh catalyst from which the deactivated hydrogenation catalyst a1 was derived, and the total content of deposited metals iron and vanadium in terms of elemental metal was 1.33% by weight of the fresh catalyst from which the deactivated hydrogenation catalyst was derived).
(2) Sampling the deactivated sulfurized phase hydrorefining catalyst 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 after extraction, vacuum-dried to obtain a deactivated hydrogenation catalyst a2 (containing 24% by weight of molybdenum as an active metal, 33% by weight of tungsten as an active metal, and 70% by weight of all active metals, based on the weight of a fresh catalyst from which the deactivated hydrogenation catalyst a2 was derived, and containing iron and vanadium as deposited metals in a total content of less than 0.3% by weight of elemental metals, based on the weight of the fresh catalyst from which the deactivated hydrogenation catalyst was derived).
(3) Weighing 80g of the deactivated catalyst A1 obtained in the step (1) and 20g of the deactivated catalyst A2 obtained in the step (2), fully mixing, soaking in 400mL of isopropanol-ethanol solution, and placing the solution in an ultrasonic generator at the frequency of 40 KHz. Sonication continued for 20 minutes. Standing for 10 min, performing ultrasonic treatment for 20 min, and standing. This procedure was repeated until the sonication time reached 2 h. 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.
(4) And (4) drying the catalyst B obtained in the step (3), 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.
(5) 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 3h to obtain the regenerated carrier.
(6) Molybdenum sulfide powder C was dissolved in liquid paraffin in a volume of 334 mL. The molybdenum sulphide was dispersed well in paraffin and then impregnated on the regenerated support. And after full impregnation, rapidly cooling at 3 ℃ to rapidly solidify the liquid paraffin to obtain the catalyst precursor. The catalyst precursor is then charged to the reactor. Nitrogen was introduced into the reactor at a pressure of 1.5MPa and at a flow rate of 10L/h. And (3) pre-depositing carbon on the catalyst precursor at the constant temperature of 400 ℃ for 5 hours to obtain a catalyst E.
(7) And (3) carrying out hydrothermal treatment on the catalyst E, wherein the temperature of the hydrothermal treatment is 750 ℃, the flow of saturated steam is 0.4L/s, and keeping the temperature for 1.5 hours to obtain the regenerated catalyst.
Example 4
The deactivated hydrogenation catalyst A1 in the sulfurized state as residue used in the examples and comparative examples of the present invention is a fresh hydrogenation catalyst prepared by the following method:
1450g of pseudoboehmite (pore volume 0.9mL/g, specific surface area 295 m) was weighed2And/g), adding a proper amount of sesbania powder, deionized water and dilute nitric acid, kneading and extruding strips to prepare the clover-shaped strips with the length of 2-8 mm. Then drying at 120 ℃ for 4h, and roasting at 630 ℃ for 3h to obtain the catalyst carrier B-1.
Weighing 112g of molybdenum oxide and 48g of basic nickel carbonate, adding 250mL of water, uniformly mixing, adding 56g of 85wt% phosphoric acid, heating for dissolving, fixing the volume to obtain an impregnation solution, and directly impregnating the impregnation solution on 500g of carrier B-1 by adopting a spray-immersion method. Then drying for 4h at 120 ℃, and roasting for 3h at 470 ℃ to obtain a fresh hydrogenation catalyst A1-1.
Example 5
The deactivated hydrogenation catalyst a2 used in the examples and comparative examples related to the present invention was a fresh hydrogenation catalyst prepared by the following method:
mixing tungsten source, nickel source and aluminum source according to m (WO)3)∶m( NiO)∶m( Al2O3) Preparing a metal mixed solution according to a molar ratio of = 1.35: 0.51: 1.23, forming gel by the metal mixed solution and ammonia water in a cocurrent flow mode, preparing an active metal reactant containing W-Ni-Al, filtering, and then adding m (MoO) in the W-Ni-Al reactant3)∶m( Al2O3) MoO is uniformly added according to the mol ratio of 1: 1.233The obtained precursor is dried and molded, and then washed and roasted to prepare the fresh hydrogenation catalystReagent A2-1.
Comparative example 1
(1) The same procedure as in step (1) of example 1 gave a deactivated catalyst A1 which was dried and used.
(2) And (3) carrying out temperature programmed oxidation decarburization and desulfurization on the deactivated catalyst A1 to obtain a 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 catalyst was calcined for 2 hours to obtain a regenerated catalyst.
Comparative example 2
(1) The same procedure as in step (1) of example 1 gave a deactivated catalyst A1 which was dried and used.
(2) And (3) carrying out temperature programmed oxidation decarburization and desulfurization on the deactivated catalyst A1 to obtain a 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 catalyst was calcined for 2 hours to obtain regenerated catalyst F1.
(3) Weighing 21g of molybdenum oxide, adding 500mL of water, uniformly mixing, adding 29g of 85wt% phosphoric acid, and heating for dissolving; stopping heating, and adding 14.6g of nickel nitrate; and finally, 43g of ammonium metatungstate is added, and the volume is constant, so that the impregnation liquid is obtained. The impregnation solution was directly impregnated on 1kg of the carrier F1 by spray-dipping. Then drying for 4h at 120 ℃, and roasting for 3h at 460 ℃ to obtain the catalyst F1-1.
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 examples 1 to 2 were subjected to pore structure analysis using a nitrogen desorption apparatus model ASAP 2420, mike, usa. Analytical data are shown in table 1:
TABLE 1 comparison of pore structure properties of catalysts
Pore volume/cm3·g-1 Specific surface area/m2·g-1
Example 1 0.49 177
Example 2 0.48 185
Example 3 0.49 180
Example 4 (fresh catalyst A1-1) 0.47 166
Comparative example 1 0.33 115
Comparative example 2 0.27 130
The pore structure analysis results in table 1 show that the conventional methods for regenerating catalysts by burning carbon and sulfur lose a large amount of pore volume and specific surface area, and the regenerated catalysts cannot recover the pore structure characteristics of the original fresh agent. The simple method of loading active metal on the conventional regenerated catalyst has pore structure incapable of meeting the requirement of residual oil hydrogenating process. 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 5 and comparative examples 1 to 2 were analyzed for the content of the main active metal oxide on the catalyst under the same conditions. The analytical data are shown in table 2 and the results show that the total amount of active metal on the catalyst regenerated by the process of the invention is higher than that of the fresh catalyst. The method of the invention can convert the metal deposited on the deactivated catalyst into the active metal, and the method of the invention fully utilizes the advantages of the regenerated catalyst, thereby not only solving the problem of residual oil hydrogenation catalyst regeneration, but also preparing a new catalyst more suitable for hydrodesulfurization, and simultaneously saving the vulcanization step.
Table 2 active metal content comparison of catalysts
Molybdenum oxide, wt% Nickel oxide, wt.% Tungsten oxide, wt.% Total weight percent
Example 1 16.2 6.0 3.3 25.5
Example 2 15.7 6.5 3.3 25.5
Example 3 15.8 6.3 3.3 25.4
Example 4 (fresh catalyst A1-1) 17.1 4.0 21.1
Example 5 (fresh catalyst A2-1) 24.5 12.5 33.0 70.0
Comparative example 1 14.3 5.5 19.8
Comparative example 2 15.3 6.5 3.3 25.1
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 catalysts obtained in examples 1 to 5 and comparative examples 1 to 2 were analyzed for the content of sulfur element. The results obtained are shown in table 3 below:
TABLE 3 comparison of elemental sulfur content of catalysts
Sulfur content, wt%
Example 1 7.2
Example 2 6.1
Example 3 6.3
Example 4 (fresh catalyst A1-1) 0
Example 5 (fresh catalyst A2-1) 0
Comparative example 1 0.5
Comparative example 2 0.2
As can be seen from the results in Table 3, the regenerated catalyst of the present invention has a much higher sulfur content than the fresh hydrogenation catalyst described in example 4, while also exceeding the catalyst regenerated by the conventional method. It is stated that most of the active metal on the regenerated catalyst is already in the sulfided state, and therefore, the amount of sulfiding agent used will be reduced during the catalyst sulfiding step prior to start-up of the plant; 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 examples 1 to 2 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 a degree substantially comparable to that of fresh catalyst.
TABLE 4 catalyst Strength comparison
Strength (N/cm)
Example 1 131
Example 2 137
Example 3 130
Example 4 (fresh catalyst A1-1) 140
Comparative example 1 89
Comparative example 2 101
Test example 5
Residual oil hydrogenation reaction is carried out on the fresh catalyst A1-1 of examples 1-3 and 4 and the catalyst prepared in 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.% 2.8
Nitrogen,. mu.g/g 2840
Carbon residue in wt% 11.7
Process conditions
Reaction pressure, MPa 14.7
Volumetric space velocity h-1 0.4
Reaction temperature of 365
Volume ratio of hydrogen to oil 500:1
TABLE 6 desulfurization Activity comparison of catalysts
Numbering Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2
Desulfurization rate of 48 hours run% 91 93 93 89 81 85
As can be seen from the results in Table 6, after 48 hours of operation, the desulfurization activity of the catalyst of the present invention was higher compared to the regenerated catalyst of the comparative example as well as the fresh catalyst. The hydrogenation catalyst regenerated and prepared by the method has better desulfurization performance.
The method can effectively recover the properties of the regenerated catalyst such as pore structure, strength and the like. In addition, the regenerated catalyst has great advantages in the vulcanization step, can reduce the vulcanization time and the vulcanizing agent dosage, and saves the cost for refining enterprises.
The regenerated catalysts described in comparative examples 1 and 2 are conventional regeneration methods, and the desulfurization activity of the regenerated catalyst of the method of the invention is much higher than that of the regenerated catalyst obtained in the comparative examples. 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 pore channel of the catalyst is far higher than that of 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 by the regeneration method of the invention.

Claims (11)

1. A method for regenerating a hydrogenation catalyst, comprising the steps of:
(1) mixing the deactivated hydrogenation catalysts A1 and A2, soaking the mixture in a solvent, and performing ultrasonic treatment to obtain a catalyst B and a mixed material mixed with black powder;
(2) recovering the catalyst B, and filtering the mixed material mixed with the black powder to obtain powder C;
(3) grinding the catalyst B into powder, and screening to obtain catalyst powder D; forming, drying and roasting the catalyst powder D to obtain a regenerated carrier;
(4) dissolving the powder C in liquid paraffin and stirring; then dipping the catalyst on a regenerated carrier, cooling, carbonizing, and performing hydrothermal treatment to obtain the regenerated hydrogenation catalyst.
2. The regeneration method according to claim 1, wherein: in the step (1), the deactivated hydrogenation catalyst A1 at least contains active metal molybdenum, and the content of the active metal molybdenum in terms of oxide is 10% -25% by weight of the deactivated hydrogenation catalyst A1 derived from a fresh catalyst.
3. Regeneration method according to claim 1 or 2, characterized in that: in the step (1), the deactivated hydrogenation catalyst A2 is a bulk phase hydrofining catalyst, the catalyst at least contains active metals molybdenum and tungsten, and the content of all the active metals in terms of oxides is 40-80% by weight of the deactivated hydrogenation catalyst A2 which is a fresh catalyst; wherein the content of the active metal molybdenum is 10-30% by weight of oxide, and the content of the active metal tungsten is 20-60% by weight of oxide.
4. The regeneration method according to claim 1, wherein: in the step (1), the mass ratio of the deactivated hydrogenation catalyst A1 to the deactivated hydrogenation catalyst A2 is as follows: 9.5: 0.5-7.5: 2.5.
5. The regeneration method according to 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.
6. The regeneration method according to claim 1, wherein: in the step (1), the ultrasonic treatment time is 0.5-3 hours; the working frequency of the ultrasonic is 35-40 KHz.
7. The regeneration method according to claim 6, wherein: the ultrasonic treatment adopts intermittent ultrasonic treatment, 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, wherein the process is repeated until the total time of the ultrasonic treatment reaches 0.5-3 hours, and the preferred standing time of each time is 5-15 min.
8. The regeneration method according to 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 ℃.
9. The regeneration method according to claim 1, wherein: in the step (4), the volume of the liquid paraffin used is the water absorption volume of the regeneration carrier.
10. The regeneration method according to claim 1, wherein: in the step (4), the carbonization needs to be carried out in an inert atmosphere, the required temperature is 300-450 ℃, the time is 3-8 h, and the required pressure is 1.0-2.5 MPa.
11. The regeneration method according to claim 1, wherein: in the step (5), the temperature of the hydrothermal treatment is 700-800 ℃, the water vapor is saturated water vapor, the flow rate of the water vapor is 0.1-0.5L/s, and the time is 0.5-2 hours.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0472853A1 (en) * 1990-08-30 1992-03-04 Hüls Aktiengesellschaft Desactivated hydrogenation catalyst reactivation process
RU94036395A (en) * 1994-09-29 1996-07-20 Э.М. Сульман Method for regeneration of palladium hydrogenation 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
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0472853A1 (en) * 1990-08-30 1992-03-04 Hüls Aktiengesellschaft Desactivated hydrogenation catalyst reactivation process
RU94036395A (en) * 1994-09-29 1996-07-20 Э.М. Сульман Method for regeneration of palladium hydrogenation 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
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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