CN116060056A - Residual oil hydrodemetallization catalyst and preparation method and application thereof - Google Patents

Residual oil hydrodemetallization catalyst and preparation method and application thereof Download PDF

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CN116060056A
CN116060056A CN202111268536.8A CN202111268536A CN116060056A CN 116060056 A CN116060056 A CN 116060056A CN 202111268536 A CN202111268536 A CN 202111268536A CN 116060056 A CN116060056 A CN 116060056A
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catalyst
aluminum salt
salt solution
solution
residuum
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刘文洁
隋宝宽
穆福军
袁胜华
耿新国
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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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J35/613—10-100 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
    • B01J35/61—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
    • B01J35/635—0.5-1.0 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
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a residual oil hydrodemetallization catalyst, a preparation method and application thereof. The method comprises the following steps: (1) Preparing a first acidic aluminum salt solution and an alkaline aluminum salt solution respectively, and then carrying out a neutralization reaction on the first acidic aluminum salt solution and the alkaline aluminum salt solution; (2) Performing first-stage aging on the slurry obtained in the step (1); after the first stage aging, adding a water-soluble polymer A, and performing the second stage aging; (3) Filtering, washing and drying the material after the second aging stage in the step (2) to obtain pseudo-boehmite; (4) Dipping the microemulsion containing the active metal on the active carbon; (5) And (3) kneading the impregnated activated carbon obtained in the step (4) with the pseudo-boehmite obtained in the step (3), forming, drying and roasting to obtain the catalyst. The catalyst prepared by the invention has proper specific surface area, large pore volume and proper acidity, and has high desulfurization and demetallization rate and large metal capacity when being used for residual oil hydrodemetallization reaction.

Description

Residual oil hydrodemetallization catalyst and preparation method and application thereof
Technical Field
The invention relates to a residual oil hydrodemetallization catalyst and a preparation method thereof, which are particularly suitable for heavy and inferior oil, especially residual oil hydrodemetallization reactions.
Background
With the increasing degree of heaviness of crude oils and the increasing demand for clean products, the lightening of heavy oils, including residuum, is increasingly urgent. Among them, the residuum hydrogenation technology is receiving a great deal of attention as one of the important means for lightening heavy oil. The fixed bed process has low investment and operation cost and safe operation, and is the residual oil hydrogenation technology with the most industrial application and the most mature technology at present.
The fixed bed residual oil hydrogenation technology is mature and is increasingly widely applied, but the fixed bed reactor has lower conversion rate, large system pressure drop and severe requirements on raw material carbon residue and metal, and the catalyst is easy to have the phenomena of metal enrichment and catalyst pore carbon deposition blocking reaction, so that the operation period is shortened, and the technology is greatly limited. The operation period of the fixed bed residuum hydrogenation process is short (about 12 months), the device must be stopped to replace new catalyst after the catalyst is deactivated, and the operation period is generally not matched with the operation period (2-3 years) of the upstream and downstream devices, so that the operation period of the fixed bed residuum hydrogenation device has great influence on the overall operation and economic benefit of a refinery. Carbon deposition and metal deposition are main factors causing deactivation of a residual oil hydrogenation catalyst, and the metal capacity of the catalyst can be improved by modulating the physicochemical properties of the catalyst, so that the running period of the device is prolonged.
CN201410604041.1 discloses a method for preparing hydrodemetallization catalyst. The method comprises the steps of preparing at least two polyalcohol and/or monosaccharide water solutions with different concentrations, and spraying and dipping the polyalcohol and/or monosaccharide water solutions on an alumina carrier according to the sequence from high concentration to low concentration; and drying the impregnated alumina carrier, impregnating the alumina carrier by using an impregnating solution containing active components and urea, performing hydrothermal treatment on a wetting agent in a sealed container, drying the obtained material, and performing anaerobic high-temperature treatment to obtain the hydrodemetallization catalyst. The method adopts the polyalcohol and the urea to prepare the catalyst, and the anaerobic carbonization treatment is adopted in the preparation process, so that the prepared catalyst is beneficial to improving the activity of the catalyst, but the introduction of the urea is also not beneficial to the environmental protection of production.
CN201510061806.6 discloses a catalyst containing TiO 2 A preparation method of a large Kong Zhayou hydrodemetallization catalyst. The method comprises the following steps: mixing pseudo-boehmite, sesbania powder, pore-expanding agent, adhesive and nano titanium hydroxide mixed water solution, forming and roasting to form carrier, impregnating metal active component and roasting to obtain the invented TiO-containing material 2 Large Kong Zhayou hydrodemetallization catalyst. However, the method requires the roasting temperature of the carrier to be higher than 700 ℃ and consumes large energy.
CN201510058687.9 discloses a residuum hydrodemetallization catalyst and a preparation method thereof, the method comprises: mixing one or more selected from aluminum oxide trihydrate, boehmite, pseudo-boehmite and amorphous aluminum hydroxide with peptizing agent, extrusion aid and organic solution uniformly, molding, drying and roasting to obtain carrier; the resulting support is impregnated with a solution containing nickel and molybdenum and dried and calcined to produce the final catalyst. However, the roasting temperature of the carrier is higher than 760 ℃ and the energy consumption is higher in the method.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a residual oil hydrodemetallization catalyst, a preparation method and application thereof, and the catalyst prepared by the method has proper specific surface area, large pore volume and proper acidity, does not need to bake a carrier under a high temperature condition, and has high desulfurization and demetallization rate and large metal capacity when being used for residual oil hydrodemetallization reaction.
The invention provides a preparation method of a residual oil hydrodemetallization catalyst, which comprises the following steps:
(1) Preparing a first acidic aluminum salt solution and an alkaline aluminum salt solution respectively, and then carrying out a neutralization reaction on the first acidic aluminum salt solution and the alkaline aluminum salt solution;
(2) Performing first-stage aging on the slurry obtained in the step (1); after the first stage aging, adding a water-soluble polymer A, and performing the second stage aging;
(3) Filtering, washing and drying the material after the second aging stage in the step (2) to obtain pseudo-boehmite;
(4) Dipping the microemulsion containing the active metal on the active carbon;
(5) And (3) kneading the impregnated activated carbon obtained in the step (4) with the pseudo-boehmite obtained in the step (3), forming, drying and roasting to obtain the catalyst.
Further, in the step (1), the first acidic aluminum salt solution is prepared with Al 2 O 3 The concentration is 5g/100 mL-18 g/100mL.
Further, in the step (1), the first acidic aluminum salt solution may be prepared by dissolving an acidic aluminum salt in a solvent, where the acidic aluminum salt is one or more selected from aluminum sulfate and aluminum nitrate.
Further, the first acidic aluminum salt solution in step (1) may be formulated as follows: adding catalyst powder containing active metal components and an alumina carrier into an acidic solution (at least one of nitric acid, sulfuric acid, hydrochloric acid or citric acid), controlling the pH value of a system to be 1.0-3.5, filtering, and taking supernatant to obtain an aluminum-containing solution; and mixing the aluminum-containing solution with the second acidic aluminum salt solution to prepare a first acidic aluminum salt solution. The second acidic aluminum salt solution can be prepared by dissolving acidic aluminum salt in a solvent, wherein the acidic aluminum salt is one or more of aluminum sulfate and aluminum nitrate solution. The aluminum-containing solution prepared from the catalyst fines provides less than 20% of the total amount of aluminum in the first acidic aluminum salt solution. Wherein the catalyst fines containing the active metal component and alumina may be derived from waste materials generated during the preparation of the hydrogenation catalyst, wherein the active metal component is at least one of group VIII and at least one of group VIB metals, preferably containing nickel and molybdenum. In the catalyst powder containing the active metal component and the alumina, the carrier component is the alumina, the carrier component accounts for 80-95% of the mass of the catalyst powder, and the active metal component accounts for 5-20% of the mass of the catalyst powder. The active metal component-containing catalyst fines may provide at least a portion of the active metal source.
Further, the alkaline aluminum salt solution in the step (1) is one or more of sodium metaaluminate solution and potassium metaaluminate solution; the alkaline aluminum salt solution is prepared by using Al 2 O 3 The concentration of the meter is 15g/100mL～45g/100mL。
Further, the temperature of the neutralization reaction in the step (1) is 85-110 ℃, the time is 30-120 min, and the pH value of the slurry is controlled to be 7.0-9.0 in the neutralization reaction process. The pH value of the slurry is controlled by controlling the addition amount of the first acidic aluminum salt solution and the alkaline aluminum salt solution or additionally adding an acid-base regulator in the neutralization reaction process.
Further, in the step (1), the first acidic aluminum salt solution and the alkaline aluminum salt solution are added into the reaction kettle in a parallel flow mode, and the adding time is 30-120 min.
Further, the temperature of the first stage aging in the step (2) is 130-250 ℃, the time is 60-200 min, and the pH value is 9.0-11.0.
Further, in the step (2), the water-soluble polymer A is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose.
Further, the water-soluble polymer A in the step (2) is added in the following amount: the concentration of the water-soluble high polymer A in the system after the addition is 1-10 g/100mL. The viscosity (20 ℃) of the system after the addition of the water-soluble polymer A is 100 to 500 mPas.
Further, after the first stage aging in step (2) is completed, the slurry is preferably concentrated so that the volume after concentration is 40% -70% of the original volume.
Further, the temperature of the second stage aging in the step (2) is 150-300 ℃ and the time is 45-200 minutes. And the temperature of the second stage aging is higher than that of the first stage aging, preferably 20 to 50 ℃.
Further, the filtration, washing and drying in the step (3) are conventional technical means in the art. The dry basis content of the pseudo-boehmite obtained after drying is 40-60 wt%.
Further, the preparation of the microemulsion containing the active metal in the step (4) is prepared from an active metal solution, a high polymer B and an emulsifier.
Further, the active metal component in the active metal solution in the step (4) is at least one of group VIII and at least one of group VIB metals, wherein the group VIII metal is preferably Ni and the group VIB metal is preferably Mo. Wherein, the content of the VIB group metal in the active metal solution is 5.0-25.0 g/100mL, and the content of the VIII group metal is 1.0-6.0 g/100mL.
Further, the solution of the active metal component in the step (4) may further contain an auxiliary agent such as phosphorus, and the content of phosphorus is 0.5-3.0 g/100mL.
Further, adding a water-soluble polymer B into the active metal solution in the step (4), wherein the water-soluble polymer B is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, methylcellulose and the like. The addition amount of the water-soluble high polymer B is as follows: the concentration of the water-soluble high polymer B in the microemulsion containing the active metal component is 5-30 g/100mL.
Further, the emulsifier in the step (4) is a nonionic emulsifier, preferably one or more of polyoxyethylene ether, polyoxypropylene ether, ethylene oxide and propylene oxide block copolymer, polyoxyethylene ester, polyol fatty acid ester, polyvinyl alcohol and polysorbate. The concentration of the emulsifier in the microemulsion containing the active metal component is 1-20 g/100mL.
Further, the activated carbon in the step (4) is powdered activated carbon. The mesh number of the activated carbon is preferably 200-300 meshes; the water absorption rate of the activated carbon is 60-120%.
Further, in the step (5), the mass ratio of the activated carbon to the pseudo-boehmite obtained in the step (3) is 1:5-1:20.
Further, the drying conditions in step (5) are: drying at 80-180 deg.c for 3-10 hr. The roasting conditions are as follows: roasting at 450-600 deg.c for 2-6 hr. The calcination is performed under an oxygen-containing atmosphere. The molar ratio of the oxygen inlet amount to the total carbon content in the system is 0.70-0.98.
The invention also provides a residual oil hydrodemetallization catalyst obtained by the preparation method.
Further, the residual oil hydrodemetallization catalyst comprises a metal active component of VIII group and VIB group metals, wherein the VIII group metals are preferably Ni, and the VIB group metals are preferably Mo. The weight content of the VIII metal in the catalyst is 1.0-6.0% calculated by oxide, and the weight content of the VIB metal in the catalyst is 5.0-22.5% calculated by oxide.
Further, the residuum hydrodemetallization catalyst has the following properties: specific surface area of 160-240 m 2 Per g, pore volume is 0.80-1.0 mL/g, and pore diameter is 15-28 nm.
Further, the residuum hydrodemetallization catalyst also has the following properties: the total acid amount is 10.5-15.0 mL/g, the acid amount at 150-250 ℃ is 6.75-9.0 mL/g, the acid amount at 250-400 ℃ is 3.0-5.3 mL/g, and the acid amount at 400-500 ℃ is 1.0-1.7 mL/g.
The third aspect of the invention provides the application of the hydrodemetallization catalyst in a residual oil hydrogenation process.
Further, the residuum and hydrogen-containing gas are contacted and reacted under hydrogenation reaction conditions in the presence of the residuum hydrogenation catalyst or hydrodemetallization catalyst obtained according to the above preparation method.
In the residuum hydrogenation process, the residuum material is at least one of atmospheric residuum, vacuum residuum and high-temperature coal tar.
In the residuum hydrogenation process, the residuum hydrogenation operating conditions are as follows: the reaction pressure is 8.0-20.0 MPa, the reaction temperature is 280-410 ℃, and the liquid hourly space velocity is 0.1-3.0 h -1 The volume ratio of the hydrogen oil is 100-1000.
The method of the invention has the following advantages:
(1) The acidic aluminum salt solution in the method contains catalyst powder dissolved with the hydrogenation active metal component, and the catalyst powder generated in the catalyst production process is recycled.
(2) The slurry obtained after the neutralization reaction adopts two-stage aging, the water-soluble high polymer A is added before the second-stage aging, the second-stage aging adopts a higher aging temperature, in addition, the water-soluble high polymer B is preferably added into the solution containing the active metal component, and the whole process is matched; and the active metal-containing microemulsion is adopted for impregnating the carrier, so that the interaction between the carrier and the active metal is weakened due to the existence of the emulsifying agent in the impregnation process, and the uniform distribution of the active metal is facilitated. Under the integral coordination, the finally obtained catalyst has proper specific surface area, pore volume and acidity.
(3) The residual oil hydrodemetallization catalyst obtained by the preparation method has proper specific surface area, pore volume and acid property, and has high demetallization rate, good desulfurization performance, good stability and large metal capacity when being used for residual oil hydrodemetallization reaction.
Detailed Description
The technical scheme and effect of the present invention are further described below by examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
In the present invention, the surface acidity of the catalysts of the examples and comparative examples was measured using a us microphone Micromeritics TriStar 2920 chemisorber, and the acid amount and total acid amount at 150-250 ℃,250-400 ℃ and 400-500 ℃ were measured, respectively; the specific surface area, pore volume and pore diameter of the catalysts of the examples and comparative examples were measured using a physical adsorption analyzer of us microphone apparatus Micromeritics TriStar 2420; the metal element contents in the solutions and catalysts of the examples and comparative examples were analyzed by an inorganic method.
Example 1
20g of a catalyst powder containing a hydrogenation-active metal component, in which the weight content of molybdenum oxide was 9.1%, the weight content of nickel oxide was 2.1% and the weight content of aluminum oxide was 88.8%, was added to 200mL of a nitric acid solution, the pH was adjusted to 2.5, and 0.2L of an aluminum-containing acidic solution (as Al) was obtained by filtration 2 O 3 The concentration was 14.8g/100 mL). After mixing the aluminum-containing acidic solution with 1.3L of an aqueous solution of aluminum sulfate (as Al 2 O 3 The measured concentration is 9g/100mL, the initial temperature is 80 ℃, and 1L of sodium metaaluminate aqueous solution (Al is used) is introduced into a reaction kettle provided with 5L of water purification with a stirrer and a heating sleeve from the upper part 2 O 3 The measured concentration was 34g/100mL, and the initial temperature was 1Introducing the mixture into a reaction kettle from the bottom of the kettle at the temperature of 00 ℃ and controlling the neutralization reaction temperature to be 100 ℃; continuously adding an aluminum sulfate solution and a sodium metaaluminate solution, controlling the pH value to be 8.5, and stabilizing for 60 minutes; after the parallel flow is finished, aging is carried out in the first stage, wherein the aging temperature is 150 ℃, the aging time is 120 minutes, and the aging pH value is 9.5; concentrating until the volume of the slurry reaches 5L after the aging in the first stage, adding 120g of polyethylene glycol with the viscosity (20 ℃) of 280 mPa.s, heating to 170 ℃, aging in the second stage for 180 minutes, washing and drying to obtain pseudo-boehmite with the dry basis of 45%;
preparing an active metal solution, wherein the content of molybdenum oxide in the solution is 11.7.0g/100mL, the content of nickel oxide is 2.9g/100mL, the content of phosphorus is 1.2g/100mL, and polyacrylamide is added, and the concentration of the polyacrylamide in the solution is 10g/100mL; adding polysorbate 80 into the active metal solution, wherein the adding amount is 5g/100mL, and preparing active metal-containing microemulsion;
weighing 25g of powdered activated carbon (the liquid absorption rate is 100%) and saturated impregnating the microemulsion containing the active metal; kneading 175g of pseudo-boehmite and active carbon, extruding, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 3 hours, and introducing 1.5mol of oxygen in the roasting process to obtain the catalyst A.
Example 2
The procedure of example 1 was repeated except that the neutralization reaction temperature was 95℃and the first-stage aging temperature was 140℃and the first-stage aging time was 180 minutes. The preparation of example 2 gives catalyst B.
Example 3
The procedure of example 1 was followed except that the mass of polyethylene glycol added after the first stage of aging was changed to 90g and the viscosity (20 ℃ C.) was controlled to 258 mPas. The preparation of example 3 gives catalyst C.
Example 4
The same as in example 1, except that the first stage aging temperature was 150℃and the aging time was 90 minutes, the temperature was raised to 180℃and the second stage aging was conducted for 90 minutes. The preparation of example 4 gives catalyst D.
Example 5
The difference is 1 as in example 1.5L of an aqueous solution of aluminum sulfate was mixed (with Al 2 O 3 The process of preparing the acidic aluminum salt solution in example 1 is replaced by introducing the solution with the concentration of 9g/100mL and the initial temperature of 80 ℃ into a reaction kettle provided with a 5L water purification belt stirrer and a heating jacket from the upper part;
in addition, the active metal solution prepared in example 1 was found to have a molybdenum oxide content of 13.1g/100mL, a nickel oxide content of 3.0g/100mL, a phosphorus content of 1.3g/100mL, a molybdenum oxide content of 11.7.0g/100mL, a nickel oxide content of 2.9g/100mL, and a phosphorus content of 1.2g/100mL. The preparation of example 5 gives catalyst E.
Comparative example 1
1.5L of aluminum sulfate solution (as Al 2 O 3 The measured concentration is 9g/100mL, the initial temperature is 80 ℃, and 1L of sodium metaaluminate aqueous solution (Al is used) is introduced into a reaction kettle provided with 5L of water purification with a stirrer and a heating sleeve from the upper part 2 O 3 The concentration is 34g/100mL, the initial temperature is 100 ℃, the mixture is introduced into a reaction kettle from the bottom of the kettle, and the neutralization reaction temperature is controlled at 100 ℃; continuously adding an aluminum sulfate solution and a sodium metaaluminate solution, controlling the pH value to be 8.5, and stabilizing for 60 minutes; after the parallel flow is finished, aging is carried out for 20 minutes, the aging temperature is 100 ℃, the aging pH value is 9.5, and the pseudo-boehmite with the dry basis of 68% is obtained after washing and drying; kneading pseudo-boehmite and an auxiliary agent, forming, drying and roasting at 900 ℃ to obtain a carrier; preparing a molybdenum nickel phosphorus solution (the content of molybdenum oxide in the solution is 13.1g/100mL, the content of nickel oxide is 3.0g/100mL, and the content of phosphorus is 1.3g/100 mL), carrying out saturated impregnation on a carrier, drying at 150 ℃, and roasting at 500 ℃ for 3h to obtain the catalyst F.
Comparative example 2
The same as in example 1, except that the second stage aging was directly carried out without adding the water-soluble polymer A after the first stage aging was completed and concentrated; meanwhile, active carbon is not adopted, and the pseudo-boehmite is directly mixed and kneaded with the microemulsion containing the active metal to obtain the catalyst G.
Comparative example 3
Catalyst H was obtained as in example 1, except that the active metal solution impregnated with activated carbon was free of emulsifiers and high polymers B.
Example 6
The catalysts prepared in examples 1-5 and comparative examples 1-3, respectively, were evaluated on a 200mL apparatus and the properties of the residuum feedstock employed are set forth in Table 1. The fixed bed process was used, the process conditions for the evaluation are shown in Table 2, and the catalyst properties and the evaluation results are shown in Table 3.
TABLE 1 Properties of raw oil
Properties of the feedstock
S，wt％ 3.19
Ni+V，μg/g 99.3
Ni，μg/g 24.1
V，μg/g 75.2
Table 2 evaluation of the process conditions
Reaction conditions Parameters (parameters)
Temperature, DEG C 395
The pressure, the MPa, 16.0
hydrogen to oil volume ratio 700:1
Liquid hourly space velocity, h -1 0.5
Table 3 evaluation results of catalysts obtained in examples and comparative examples
Figure BDA0003327818550000071
As can be seen from Table 3, the hydrodemetallization catalyst prepared by the invention has high hydrodemetallization rate, high desulfurization rate and high diesel oil yield when being used for hydrotreating residual oil, and is superior to the comparative example.

Claims (19)

1. The preparation method of the residuum hydrodemetallization catalyst comprises the following steps:
(1) Preparing a first acidic aluminum salt solution and an alkaline aluminum salt solution respectively, and then carrying out a neutralization reaction on the first acidic aluminum salt solution and the alkaline aluminum salt solution;
(2) Performing first-stage aging on the slurry obtained in the step (1); after the first stage aging, adding a water-soluble polymer A, and performing the second stage aging;
(3) Filtering, washing and drying the material after the second aging stage in the step (2) to obtain pseudo-boehmite;
(4) Dipping the microemulsion containing the active metal on the active carbon;
(5) And (3) kneading the impregnated activated carbon obtained in the step (4) with the pseudo-boehmite obtained in the step (3), forming, drying and roasting to obtain the catalyst.
2. The method of claim 1, wherein in step (1), the first acidic aluminum salt solution is prepared as Al 2 O 3 The calculated concentration is 5g/100 mL-18 g/100mL; the first acidic aluminum salt solution is prepared by dissolving acidic aluminum salt in a solvent, wherein the acidic aluminum salt is one or more of aluminum sulfate and aluminum nitrate.
3. The preparation method according to claim 1, wherein the alkaline aluminum salt solution in the step (1) is one or more of sodium metaaluminate solution and potassium metaaluminate solution; the alkaline aluminum salt solution is prepared by using Al 2 O 3 The concentration is 15g/100 mL-45 g/100mL.
4. The method according to claim 1, wherein the neutralization reaction in step (1) is carried out at a temperature of 85 to 110 ℃ for 30 to 120 minutes, and the pH of the slurry is controlled to 7.0 to 9.0 during the neutralization reaction.
5. The method according to claim 1, wherein the first stage aging in step (2) is carried out at a temperature of 130 to 250 ℃ for 60 to 200 minutes at a ph of 9.0 to 11.0.
6. The preparation method according to claim 1, wherein the water-soluble polymer a in the step (2) is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose.
7. The method according to claim 1, wherein the water-soluble polymer a is added in the step (2) in an amount of: the concentration of the water-soluble high polymer A in the system after the addition is 1-10 g/100mL; the viscosity (20 ℃) of the system after the addition of the water-soluble polymer A is 100 to 500 mPas.
8. The method according to claim 1, wherein the second stage aging in step (2) is carried out at a temperature of 150 to 300 ℃ for 45 to 200 minutes; and the temperature of the second stage aging is higher than that of the first stage aging, preferably 20 to 50 ℃.
9. The method of claim 1, wherein the reactive metal-containing microemulsion of step (4) is formulated from a reactive metal solution, a polymer B, and an emulsifier.
10. The method according to claim 9, wherein the active metal component in the active metal solution in step (4) is at least one of group VIII and at least one of group VIB metals, wherein group VIII is preferably Ni and group VIB is preferably Mo; wherein, the content of the VIB group metal in the active metal solution is 5.0-25.0 g/100mL, and the content of the VIII group metal is 1.0-6.0 g/100mL.
11. The preparation method according to claim 9, wherein in the step (4), the water-soluble high polymer B is added into the active metal solution, and the water-soluble high polymer B is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, methylcellulose and the like; the addition amount of the water-soluble high polymer B is as follows: the concentration of the water-soluble high polymer B in the microemulsion containing the active metal component is 5-30 g/100mL.
12. The method according to claim 9, wherein the emulsifier in step (4) is a nonionic emulsifier, preferably one or more of polyoxyethylene ether, polyoxypropylene ether, ethylene oxide and propylene oxide block copolymer, polyoxyethylene ester, polyol fatty acid ester, polyvinyl alcohol, polysorbate; the concentration of the emulsifier in the microemulsion containing the active metal component is 1-20 g/100mL.
13. The method of claim 1, wherein the activated carbon in step (4) is powdered activated carbon; the mesh number of the activated carbon is preferably 200 to 300 mesh.
14. The preparation method according to claim 1, wherein in the step (5), the mass ratio of the activated carbon to the pseudo-boehmite obtained in the step (3) is 1:5-1:20.
15. A residuum hydrodemetallization catalyst as obtained by the process of any one of claims 1-14.
16. The residuum hydrodemetallization catalyst of claim 15, wherein the residuum hydrodemetallization catalyst has metal active components of group VIII and group VIB metals, wherein the group VIII metal is preferably Ni and the group VIB metal is preferably Mo; the weight content of the VIII metal in the catalyst is 1.0-6.0% calculated by oxide, and the weight content of the VIB metal in the catalyst is 5.0-22.5% calculated by oxide.
17. The residuum hydrodemetallization catalyst of claim 15, wherein the residuum hydrodemetallization catalyst has the following properties: specific surface area of 160-240 m 2 Per g, the pore volume is 0.80-1.0 mL/g, and the pore diameter is 15-28 nm; optionally, the total acid amount is 10.5-15.0 mL/g, the acid amount at 150-250 ℃ is 6.75-9.0 mL/g, the acid amount at 250-400 ℃ is 3.0-5.3 mL/g, and the acid amount at 400-500 ℃ is 1.0-1.7 mL/g.
18. Use of the residuum hydrodemetallization catalyst of any of claims 15-17 in residuum hydrogenation processes.
19. The use according to claim 18, wherein the residuum hydroprocessing conditions are: the reaction pressure is 8.0-20.0 MPa, the reaction temperature is 280-410 ℃, and the liquid hourly space velocity is 0.1-3.0 h -1 The volume ratio of hydrogen to oil is 100-1000。
CN202111268536.8A 2021-10-29 2021-10-29 Residual oil hydrodemetallization catalyst and preparation method and application thereof Pending CN116060056A (en)

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