CN116037177A - Hydrofining catalyst and preparation method and application thereof - Google Patents

Hydrofining catalyst and preparation method and application thereof Download PDF

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Publication number
CN116037177A
CN116037177A CN202111265080.XA CN202111265080A CN116037177A CN 116037177 A CN116037177 A CN 116037177A CN 202111265080 A CN202111265080 A CN 202111265080A CN 116037177 A CN116037177 A CN 116037177A
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Prior art keywords
catalyst
pore
pore volume
alumina
group
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Chinese (zh)
Inventor
陈文斌
刘清河
张乐
习远兵
鞠雪艳
丁石
张润强
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN202111265080.XA priority Critical patent/CN116037177A/en
Publication of CN116037177A publication Critical patent/CN116037177A/en
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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
    • B01J35/615—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
    • 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
    • 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
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, 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

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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 relates to the technical field of hydrofining catalyst preparation, and discloses a hydrofining catalyst, a preparation method and application thereof. A hydrofining catalyst, wherein the catalyst comprises at least one VIII group metal element, at least one VIB group metal element and alumina, and the pore volume of the catalyst is 0.2-0.4cm 3 And/g, the average pore diameter is 6-18nm, wherein the pore diameter of the catalyst shows bimodal pore distribution in the range of 2-6nm and 8-20nm. The hydrofining catalyst has the advantages of good stability, high activity and simple preparation flow, and has excellent desulfurization and dearomatization effects when being applied to diesel oil.

Description

Hydrofining catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of hydrogenation catalyst preparation, in particular to a hydrofining catalyst and a preparation method and application thereof.
Background
In the last five years, along with the continuous enhancement of environmental protection consciousness of society, the quality standard of clean fuel in China is in an accelerating trend. The quality standard of diesel oil rapidly advances from four to five to six, the sulfur content and polycyclic aromatic hydrocarbon in diesel oil are required to be respectively reduced to 10mg/kg and 7%, and the polycyclic aromatic hydrocarbon has a trend of further reduction in future. This presents a serious challenge for the choice of refinery diesel hydrogenation catalyst and for the operating operation of the unit. Although the product quality is qualified by increasing the reaction temperature of the device, the catalyst deactivation rate is greatly increased, and meanwhile, the outlet temperature of the reactor is faster to approach to the thermodynamic equilibrium zone of aromatic hydrocarbon so as to suppress the saturated reaction of polycyclic aromatic hydrocarbon, thereby greatly shortening the service cycle of the catalyst. The existing diesel hydrogenation catalyst technology faces a bottleneck, and development of a diesel hydrogenation catalyst with high activity and high stability is needed.
The active metals in the diesel hydrodesulfurization catalyst are mainly composed of group VIB metals (Mo and/or W) and group VIII metals (Co and/or Ni). In the catalyst, the active metal is highly dispersed on the surface of the carrier to form a large number of active centers. Generally, hydrogenation catalysts contain a certain pore structure, and reactants react by contacting active centers through the pores of the catalyst during the reaction. Thus, not only should the diesel hydrogenation catalyst have a large number of active sites, but the active sites should have good accessibility.
The Chinese patent application with the application number of 202010395989.6 discloses a hydrofining catalyst and a preparation method and application thereof, wherein the catalyst comprises 50-80wt% of carrier and 20-50wt% of active metal component, the carrier adopts composite oxide to regulate and control the interaction force between active metal and carrier in the catalyst, thereby improving the concentration of active hydrogen species on the surface of the active metal and improving the hydrodesulfurization and hydrodenitrogenation reaction activities of the catalyst.
The Chinese patent application No. 201811455219.5 discloses a preparation method of a supported hydrogenation catalyst, which adopts one or more of ethylenediamine tetramethylene sodium phosphate, tetrabutylammonium fluoride and tartaric acid as active metal positioning and supporting guiding agents to position gamma-Al 2 O 3 The catalyst is prepared by contacting a carrier with a solution containing an active metal positioning and loading guiding agent, and has higher hydrodesulfurization activity, denitrification activity and aromatic saturation activity.
The Chinese patent application No. 201711023399.5 discloses a diesel hydrofining catalyst which comprises 1-30% of TS-1 molecular sieve and gamma-Al 2 O 3 20-50%, zirconia 0.01-10%, graphene 0.01-5%, heteropolyacid 10-40% calculated by metal oxide, and catalyst specific surface area 250-500m 2 Per g, pore volume 0.5-0.8mL/g. The catalyst has higher hydrodesulfurization activity.
The Chinese patent application with the application number of 201710984468.2 discloses a bulk hydrofining catalyst which comprises W, ni metal components and Mo, wherein the preparation steps of the catalyst comprise 1) carrying out a gel forming reaction on a mixed solution A containing Ni, W and Al, an organic auxiliary agent and a precipitant in parallel flow, and aging the obtained slurry; 2) And then the mixed solution B, moO containing W, al 3 Adding the slurry and the precipitant into the aged slurry in parallel, and then aging; 3) Drying, forming and the like; the catalyst has higher hydrodesulfurization and hydrodenitrogenation reaction activities, and particularly treats diesel oil raw materials with high nitrogen and high sulfur content.
Chinese patent application No. 201610542732.2 discloses a hydrogenation catalyst consisting of gamma-Al 2 O 3 Loading active components of Co, ni and W/Mo and simultaneously containing F as active componentThe auxiliary agent is at least one of tetrabutylammonium fluoride, trifluoroacetic acid, hexafluoroacetone and hexafluoroisopropanol, and has higher hydrodesulfurization activity and aromatic hydrocarbon saturation activity.
Chinese patent application No. 201610388357.0 discloses a hydrodesulfurization catalyst comprising NiO, moO 3 And WO 3 AlOOH and TiO 2 The composite carrier is a pasty catalyst with high reaction activity and good stability synthesized by a complete liquid phase method, and can meet the requirement of ultra-deep hydrodesulfurization of diesel oil.
From the above, the research and the invention of the diesel hydrodesulfurization catalyst improve the properties of the catalyst from a plurality of angles, and greatly improve the activity of the diesel hydrodesulfurization catalyst. The preparation flow in the invention is relatively complex, the implementation cost and convenience of the invention have certain defects, and the stability of the catalyst can not completely meet the requirements of national sixth diesel oil production.
Disclosure of Invention
The invention aims to solve the problems of poor stability and complex preparation flow of a hydrofining catalyst in the prior art, and provides a hydrofining catalyst, a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a hydrofinishing catalyst, wherein the catalyst comprises at least one group VIII metal element, at least one group VIB metal element, and alumina, the catalyst having a pore volume of 0.2 to 0.4cm 3 And/g, wherein the average pore diameter is 6-18nm, and the pore diameter of the catalyst is in bimodal pore distribution in the range of 2-6nm and 8-20nm.
Preferably, in the catalyst, the pore volume with a pore size distribution of from 2 to 6nm is from 8 to 15%, preferably from 9 to 12%, of the total pore volume of the catalyst.
In a second aspect, the present invention provides a method for producing the hydrofinishing catalyst according to the first aspect, comprising:
the alumina is impregnated with a group VIII metal precursor, a group VIB metal precursor, a phosphorus-containing compound, and optionally an organic alcohol compound and/or a carboxylic acid compound, and then dried.
In a third aspect, the present invention provides the use of a hydrofinishing catalyst according to the first aspect in a hydrodesulphurisation reaction.
The inventors found in the study that the hydrofining catalyst consists of a carrier and an active metal component (the active metal component in the present invention contains a group VIII metal element and a group VIB metal element), the active metal component being dispersed on the surface of the carrier. The support required in the catalyst has pore size structures of varying sizes and reactant molecules need to pass smoothly through the contact active sites during the reaction. One effective method for increasing the activity of hydrofined catalysts is to increase the amount of active metal components in the catalyst and thus the number of active sites in the catalyst. The active metal component is distributed on the surface of the carrier to cause the shrinkage of the pore diameter, and the stacking height of the active metal on the surface of the carrier is increased when the metal loading is increased. If the metal loading is too high, the active metal will cause the pore channels of the support to become very narrow and passage of reactant molecules will be hindered. If the metal loading is low, the pore space of the catalyst is not fully utilized, and the function of the pore space of the carrier cannot be exerted to the maximum. According to the invention, the carrier with a proper pore structure is selected, and the active metal components with proper stacking height are loaded on the surface of the carrier, so that the purposes of improving the active metal loading capacity and fully utilizing the active components are achieved.
The catalyst provided by the invention has the advantages of simple preparation method, and has better stability and desulfurization activity in the hydrodesulfurization reaction process.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a hydrofining catalyst, wherein the catalyst comprises at least one metal element of VIII family, at least one metal element of VIB family and alumina, and the pore volume of the catalyst is 0.2-0.4cm 3 And/g, the average pore diameter is 6-18nm, wherein the pore diameter of the catalyst shows bimodal pore distribution in the range of 2-6nm and 8-20nm.
In the invention, the pore diameter of the catalyst shows bimodal pore distribution in the range of 2-6nm and 8-20nm, which means that the pore diameter distribution of the catalyst shows two peaks in the pore diameter range of 2-6nm and 8-20nm. Typically, the support also has a certain number of pore size distributions at 2-6nm, but this portion of the pores of the support do not peak and do not form bimodal pores.
In the invention, preferably, in the catalyst, the pore volume with the pore diameter distributed at 2-6nm accounts for 8-15% of the total volume of the catalyst, and more preferably 9-12%, and by adopting the preferred embodiment, the effect of active metal components in smaller pores and larger pores can be fully exerted, the reaction efficiency of the catalyst on sulfur-containing compounds with different sizes is improved, and the purpose of fully utilizing active metals is achieved.
In a preferred case, the specific surface area of the catalyst is 130-170m 2 /g。
In a preferred case, the catalyst has an average pore diameter of 8 to 10nm.
In a preferred case, the catalyst has a pore volume of 0.25 to 0.4cm 3 /g。
Typically, the channels of the hydrofinishing catalyst are concentrated at 6-20 nm. The diesel fuel has reactant molecules of different sizes, and the larger reaction channel is wider for smaller reactant molecules. The pore diameter of 2-6nm can provide a good reaction space for smaller reactant molecules, so that the utilization efficiency of the internal pore canal of the catalyst is improved, and the aim of improving the activity is fulfilled. The part of pore channels are from the loaded active metal component, so that the synergistic effect of active centers of pore walls can be promoted, and further, the hydrodesulfurization and aromatic hydrocarbon saturation reaction can be better promoted.
Because of the proper loading of active metal components (VIII family metal element and VIB family metal element), the pore canal of the catalyst presents double-peak pore distribution, one part of pores are concentrated at the position of pore diameter concentrated distribution in the carrier, and the other part of pores are concentrated at 2-6nm. The pore at 2-6nm is generated due to the loading of the active metal component, and the bimodal pore diameter structure can meet the requirement of the diffusion of reaction molecules to the active center, and can also load enough active metal component, so that the performance of the hydrofining catalyst is greatly improved.
The hydrofining catalyst containing the specific bimodal pore structure provided by the invention is applied to desulfurization and dearomatization in diesel oil, and has good stability and excellent desulfurization and dearomatization performance.
In the invention, the determination of the specific surface area, pore volume, pore distribution and average pore diameter of the hydrofining catalyst refers to the determination of the catalyst after roasting for 3 hours at 400 ℃.
In the present invention, the specific surface area, pore distribution, average pore diameter and pore volume of the catalyst are measured by the low temperature nitrogen adsorption method (BET) (see "petrochemical analysis method (RIPP test method)", yang Cuiding et al, scientific Press, 1990). Wherein the pore volume of 2-100nm is calculated according to the BET result.
In the present invention, when not specifically described, the 2-6nm hole means a hole having a diameter of 2nm or more and less than 6nm, the 2-4nm hole means a hole having a diameter of 2nm or more and less than 4nm, the 4-6nm hole means a hole having a diameter of 4nm or more and less than 6nm, and the 8-20nm hole means a hole having a diameter of 8nm or more and less than 20nm.
In the present invention, the type of carrier is not particularly limited in the present invention, and a suitable carrier is selected as the carrier of the catalyst in order to satisfy the performance of the catalyst, and is commercially available. Preferably, the alumina has a water absorption of greater than 0.9mL/g, preferably 0.9-1.2mL/g.
Preferably, the specific surface area of the alumina is greater than 260m 2 Preferably 260-400m 2 /g。
Preferably, the alumina has an average pore diameter of more than 8nm, more preferably 8-14nm, and the pore distribution form is unimodal. The advantage of adopting this kind of preferred embodiment is that can guarantee that the pore space is abundant, can form the aperture of a certain amount of 2-6nm on the one hand, on the other hand can exert the effect of all active metal components again.
In a preferred case, the alumina has a pore volume with a pore size distribution of 2 to 6nm of not more than 10%, more preferably not more than 8%, still more preferably 5 to 8% of the total pore volume of the alumina.
In a particularly preferred case, the alumina has a pore volume with a pore size distribution of from 2 to 4nm of not more than 4%, more preferably not more than 2%, of the total volume of the alumina.
The adoption of the preferable carrier is more beneficial to improving the utilization of active metal, so that active metal components can better enter larger holes, and the pore channels are not blocked when the metal loading capacity is higher.
According to a preferred embodiment of the present invention, the catalyst further comprises P 2 O 5 。
In the invention, in order to enable the active metal components to be loaded on the pore channels of the carrier, the pore channels of the catalyst are more reasonably utilized. Preferably, the catalyst composition is as defined in (Xi ai )·(Yi bi )·(Zi ci ) Sup, where Xi is the group VIB metal oxide, ai is the mass of the group VIII metal oxide relative to 1 gram of support Xi, bi is the mass of the group VIII metal oxide relative to 1 gram of support Yi, zi is P 2 O 5 Ci is 1 g of carrier P 2 O 5 Sup refers to the mass of the support in the catalyst, calculated as 1 gram, which satisfies the following conditions: (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup Has a value of 0.4 to 0.9nm, preferably 0.5 to 0.8nm, ρ Xi 、ρ Yi 、ρ Zi Respectively a group VIB metal oxide, a group VIII metal oxide and P 2 O 5 Density, SA of sup Is the specific surface area of the carrier. The advantage of using this preferred embodiment is that a better bimodal form can be ensured inside the catalystThe pore canal structure makes partial pore canal concentrated at 2-6nm.
In the present invention ρMoO 3 、ρWO 3 、ρNiO、ρCoO、ρP 2 O 5 According to the proportion of 4.69g/cm 3 、7.16g/cm 3 、6.67g/cm 3 、6.45g/cm 3 And 2.39g/cm 3 And (5) calculating.
In the present invention, the group VIII metal element includes, but is not limited to, at least one of Fe, co, ni, ru, pt and Pd, preferably Co and/or Ni.
In a preferred case, the group VIB metal element includes, but is not limited to, at least one of Cr, mo, and W, preferably Mo and/or W.
In the present invention, P in the catalyst 2 O 5 And the amount of the group VIB metal oxide is not particularly limited as long as the performance of the catalyst is improved. Preferably, the molar ratio Zi/Xi in the catalyst is from 0.05 to 0.3, more preferably from 0.08 to 0.2. The advantage of adopting this kind of preferred embodiment is that adopting this kind of metal combination mode makes each metal component can better exert mutual synergism, and then makes the activity of catalyst reach the best.
In a preferred case, in order to further improve the performance of the catalyst, the atomic concentration of the group VIB metal element in the catalyst on the surface of the carrier is 5-13atom/nm 2 Preferably 5-11 atoms/nm 2 . The advantage of adopting this preferred embodiment is that the amount of active metal is relatively moderate, which can promote the generation of pore diameters of 2-6nm.
In the invention, the atomic concentration of the group VIB metal element on the surface of the carrier refers to the average atomic concentration of the group VIB metal element on the surface of the carrier, and the average atomic concentration is obtained by measuring the metal loading and calculating the specific surface area of the carrier, specifically, the average atomic concentration can be obtained by the following calculation: atomic concentration= (ai/M Xi )×N A /(1×SA sup ) Wherein N is A For the Avoder constant, ai is the mass relative to 1 gram of carrier Xi, M Xi Molecular weight of Xi, SA sup Is the specific surface area of the carrier.
In a preferred case, the atomic ratio of the group VIII metal element to the total of the group VIII metal element and the group VIB metal element in the catalyst is 0.05 to 0.35, preferably 0.1 to 0.3.
In the present invention, preferably, the catalyst further comprises one or more organic alcohol compounds and/or carboxylic acid compounds containing-OH, and the molar ratio of the organic alcohol compounds and/or carboxylic acid compounds to the group VIII metal element is 1 to 6, preferably 2 to 5. The preferred embodiment is adopted to ensure that the VIII group metal element has higher dispersing capability, weaken the interaction force between the carrier and the metal and promote the generation of more active phases.
The organic alcohol compound containing-OH may be at least one of monohydric alcohol, dihydric alcohol and polyhydric alcohol. In a preferred case, the organic alcohol compound containing-OH is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol and trimethylolethane, preferably at least one of glycerol, propanol and ethylene glycol.
In a preferred case, the carboxylic acid compound is selected from one or more of formic acid, acetic acid, propionic acid, citric acid, caprylic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, caproic acid, capric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid and tartaric acid, preferably at least one of formic acid, citric acid and acetic acid.
In a particularly preferred case, the catalyst further comprises one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol, trimethylolethane and/or formic acid, acetic acid, propionic acid, citric acid, octanoic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, caproic acid, capric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid, tartaric acid.
In the present invention, the size of the catalyst is selected from a wide range, and those skilled in the art can appropriately select the catalyst according to the specific application of the catalyst. Preferably, the equivalent diameter of the catalyst is from 0.5 to 1.8mm, more preferably from 0.8 to 1.6mm.
In the present invention, the shape of the catalyst is not particularly limited, and the catalyst shape conventional in the art is applicable to the present invention. Preferably, the shape of the catalyst is cylindrical, clover, butterfly, honeycomb or other irregular shape, more preferably butterfly.
The present invention is not particularly limited as long as the catalyst having the above composition and structure can be produced by the method of the present invention.
In a second aspect, the present invention provides a method for preparing the hydrofining catalyst according to the first aspect, which comprises:
the alumina is impregnated with a group VIII metal precursor, a group VIB metal precursor, a phosphorus-containing compound, and optionally an organic alcohol compound and/or a carboxylic acid compound, and then dried.
In the present invention, the "optionally-OH-containing organic alcohol compound and/or carboxylic acid-based compound" means that the-OH-containing organic alcohol compound and/or carboxylic acid-based compound may or may not be incorporated into the alumina, and is preferably incorporated.
In the present invention, the types of the group VIII metal, the group VIB metal, the-OH-containing organic alcohol compound, and the carboxylic acid compound are described in the first aspect, and will not be described here.
In the present invention, the kinds of the metal elements in the group VIB metal oxides and the group VIII metal oxides are provided from precursors containing the above metal elements. Preferably, the group VIB metal precursor is selected from at least one of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate, molybdenum oxide, ammonium metatungstate, ammonium ethyl metatungstate, and tungsten oxide.
In a preferred case, the group VIII metal precursor is selected from at least one of cobalt nitrate, basic cobalt carbonate, cobalt acetate, cobalt oxide, nickel nitrate, basic nickel carbonate, nickel acetate, and nickel oxide.
In a particularly preferred embodiment, the group VIB metal and group VIII metal precursors are selected from at least one of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate, molybdenum oxide, ammonium meta-tungstate, ammonium ethyl meta-tungstate, tungsten oxide, cobalt nitrate, basic cobalt carbonate, cobalt acetate, cobalt oxide, nickel nitrate, basic nickel carbonate, nickel acetate, and nickel oxide.
In the invention, P 2 O 5 Provided by a phosphorus-containing compound. Preferably, the phosphorus-containing compound is selected from at least one of phosphoric acid, hypophosphorous acid, ammonium phosphate and ammonium dihydrogen phosphate.
In the present invention, preferably, the group VIII metal precursor, the group VIB metal precursor, and the phosphorus-containing compound are used in amounts such that the catalyst obtained satisfies the above pair (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup Is required for the value of (2).
The method according to the present invention is not particularly limited, and any impregnation method conventional in the art is applicable to the present invention. The impregnation may be co-impregnation, stepwise impregnation, saturation impregnation, or supersaturation impregnation. Preferably, co-impregnation is used. Preferably, the impregnation method comprises: impregnating the alumina with an impregnating solution containing a group VIII metal precursor, a group VIB metal precursor, a phosphorus-containing compound, and optionally an organic alcohol compound containing-OH and/or a carboxylic acid-based compound.
In the present invention, the order of addition of the group VIII metal precursor, the group VIB metal precursor, the phosphorus-containing compound, and optionally the-OH-containing organic alcohol compound and/or the carboxylic acid compound is not particularly limited as long as it is advantageous for uniform mixing of the components. In a preferred case, the-OH containing organic alcohol compound and/or carboxylic acid compound, group VIII metal precursor, group VIB metal precursor are added to an aqueous solution of a phosphorus containing compound to provide the impregnation solution. The order of addition of the-OH-containing organic alcohol compound and/or carboxylic acid compound, phosphorus-containing compound and metal precursor may also be interchanged.
According to the method provided by the invention, the prepared catalyst has the structure and the composition of the first aspect according to the physical parameters of the carrier and the dosage of each material. The present invention is not particularly limited in this regard, and for the purpose of fully describing the technical aspects of the present invention, it is convenient to understand that the method provided by the present invention will now be described by way of example, and the present invention is not limited thereto. For example, hydrofinishing catalysts can be prepared by the following methods: (1) Determining the feeding amount of the group VIB metal precursor relative to each g of the carrier according to the atomic concentration of the group VIB metal element and the specific surface area of the carrier (alumina); (2) Determining the amount of group VIII metal precursor per g of support based on the atomic ratio of group VIII metal element to the total amount of group VIII metal element and group VIB metal element; (3) According to (ai/ρ Xi +bi/ρ Yi +ci/ρ Zi )/SA sup To calculate P 2 O 5 Further determining the amount of phosphorus-containing compound per g of carrier; (4) Calculating the dosage of the organic alcohol compound and/or carboxylic acid compound containing-OH according to the mole ratio of the organic alcohol compound and/or carboxylic acid compound containing-OH to the VIII group metal element; (5) According to the feeding amounts of the VIB group metal precursor, the VIII group metal precursor, the phosphorus-containing compound and the organic alcohol compound and/or the carboxylic acid compound containing-OH, impregnating alumina by using an impregnating solution according to a pore saturation impregnation method, and then drying. Specifically, firstly dissolving a phosphorus-containing compound in water, then adding an organic alcohol compound and/or carboxylic acid compound containing-OH, a VIB group metal precursor and a VIII group metal precursor, stirring under heating until the phosphorus-containing compound and the VIII group metal precursor are completely dissolved, and keeping the temperature constant to obtain an impregnating solution; (6) Measuring the water absorption of the carrier, and calculating the liquid absorption of the carrier according to the formula of the water absorption-0.1 of the carrier; (7) According to the liquid absorption rate of the carrier, the impregnating solution is fixed to a corresponding volume (the liquid absorption rate of the carrier is multiplied by the mass of the carrier), and the impregnating solution and the carrier with corresponding mass are uniformly mixed and kept stand, and then dried, so that the catalyst is prepared.
In the present invention, the range of selection of the drying conditions is wide. Preferably, the drying conditions include: the temperature is 80-200deg.C, and the time is 1-10h.
In a third aspect, the present invention provides the use of a hydrofinishing catalyst according to the first aspect in a hydrodesulphurisation reaction.
In the present invention, the hydrofining catalyst is used for hydrodesulfurization of distillate oil. Preferably, the sulfur content in the distillate to be treated is 5000-30000ppm, and the aromatic hydrocarbon content is 20-80 wt%.
In a preferred case, the catalyst is sulfided to convert the oxidation state catalyst to sulfided state catalyst prior to use. In the present invention, the vulcanization method is not particularly limited, and any vulcanization method conventional in the art is applicable to the present invention. Preferably, for example, one of dry vulcanization and wet vulcanization is possible. The kind of the vulcanizing agent is not particularly limited, and may be selected according to a conventional scheme in the art.
Preferably, the vulcanization conditions include: the vulcanization temperature is 280-420 ℃, the time is 10-48 hours, the pressure is 0.1-15MPa, and the volume airspeed is 0.5-20 hours -1 The volume ratio of the hydrogen oil is 100-2000:1, preferably at a heating rate of 5-60 ℃/hr.
In a preferred case, the hydrodesulfurization conditions include: the pressure is 5-15MPa, the temperature is 260-410 ℃, and the volume airspeed is 0.5-10 hours -1 The volume ratio of the hydrogen oil is 200-1000:1.
the present invention will be described in detail by examples. In the following examples, the hydrodesulfurization performance of the catalyst was measured on a 20mL high pressure microreactor and the oxidation state catalyst was converted directly to a sulfided catalyst using a temperature programmed sulfidation process. The vulcanization conditions are as follows: the vulcanization pressure is 6.4MPa, and the vulcanized oil contains CS 2 2 wt% kerosene, volume space velocity 2 hours -1 The hydrogen-oil volume ratio is 300v/v, the constant temperature is kept for 6 hours at 230 ℃/h, then the temperature is raised to 360 ℃ for 8 hours of vulcanization, and the temperature raising rate of each stage is 10 ℃/h. And after vulcanization, switching the reaction raw materials for carrying out hydrodesulfurization activity test, wherein the sulfur content of the reaction raw materials is 10890ppm, and the aromatic hydrocarbon content is 39.0wt% of high aromatic hydrocarbon distillate oil. The test conditions were: the pressure is 6.4MPa, and the volume space velocity is 1.5h -1 The hydrogen-oil volume ratio was 300v/v and the reaction temperature was 340 ℃. The product properties were analyzed after 2 days of reaction stabilization. To examine the stability of the catalyst, the mass fraction of sulfur in the reaction product was maintained at 10ppm, the reaction temperature was adjusted every day, the operation was continued for 5 days, and the change in the reaction temperature before and after 5 days was compared to measure the stability of the catalyst.
The composition of the catalyst is calculated according to the feeding amount. The specific surface area, pore distribution, pore diameter and pore volume of the catalyst and carrier of 2-100nm are measured by low temperature nitrogen adsorption (see petrochemical analysis method (RIPP test method), yang Cuiding et al, scientific Press, 1990). The sulfur mass fraction in the product was analyzed by a sulfur-nitrogen analyzer (model TN/TS3000, manufactured by Siemens, inc.), and the content of aromatic hydrocarbon was analyzed by near infrared spectroscopy.
The amounts of each material dosed in the following examples were determined in accordance with the specific exemplary illustrations given herein.
Example 1
Selecting a gamma-alumina carrier, wherein the water absorption rate is 0.98mL/g, and the specific surface area is 280m 2 And/g, wherein the average pore diameter is 10.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 4%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into phosphoric acid aqueous solution, heating and stirring at 85 ℃ for 2 hours until the basic nickel carbonate and the glycerol are completely dissolved, and keeping the temperature for 3 hours to obtain the impregnation liquid containing the active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst was 7atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.29, P 2 O 5 /MoO 3 The molar ratio was 0.13, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 2 at 0.5 nm.
Catalyst warp 40After roasting at 0 ℃ for 3 hours, the pore size distribution is analyzed by a low-temperature nitrogen adsorption method. The specific surface area of the catalyst was 165m 2 Per gram, pore volume of 0.38cm 3 And/g, wherein the average pore diameter is 9.2nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 9.2%. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 8ppm, and the aromatic hydrocarbon content is 23.5%. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 3.2 ℃ after 5 days of reaction.
Example 2
Selecting a gamma-alumina carrier, wherein the water absorption rate is 0.98mL/g, and the specific surface area is 280m 2 And/g, wherein the average pore diameter is 10.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 4%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into phosphoric acid aqueous solution, heating and stirring at 90 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and keeping the temperature for 3 hours to obtain an impregnation liquid containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst was 11atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.2, P 2 O 5 /MoO 3 Molar ratio of 0.1, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 5at 0.72 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 151m 2 Per gram, pore volume of 0.32cm 3 And/g, wherein the average pore diameter is 8.5nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 9%. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 4.2ppm, and the aromatic hydrocarbon content is 22.6%. Keeping the sulfur content of the product at 10ppm, and reacting for 5 daysThe temperature was raised by 2.8 ℃.
Example 3
Selecting a gamma-alumina carrier, wherein the water absorption rate is 0.98mL/g, and the specific surface area is 280m 2 And/g, wherein the average pore diameter is 10.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 4%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into phosphoric acid aqueous solution, heating and stirring at 90 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and keeping the temperature for 3 hours to obtain the impregnation liquid containing the active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 2 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst is 8atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.28, P 2 O 5 /MoO 3 Molar ratio of 0.2, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 3at 0.623 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 164m 2 Per gram, pore volume of 0.35cm 3 And/g, wherein the average pore diameter is 8.5nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the pore volume with the pore diameter of 2-6nm accounts for 8% of the total pore volume. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 9.8ppm, and the aromatic hydrocarbon content is 23.6%. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 3.3 ℃ after 5 days of reaction.
Example 4
Selecting a gamma-alumina carrier, wherein the water absorption rate is 0.98mL/g, and the specific surface area is 280m 2 And/g, wherein the average pore diameter is 10.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 4%, and the pore diameter distribution is mainly concentrated at 8-20nm.
Respectively adding ammonium metatungstate, basic nickel carbonate and citric acid into a phosphoric acid aqueous solution, heating and stirring for 2 hours at 90 ℃ until the ammonium metatungstate, the basic nickel carbonate and the citric acid are completely dissolved, and keeping the temperature for 3 hours to obtain an impregnating solution containing active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 2 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 3 hours at 130 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
w in the catalyst had an atomic concentration of 5atom/nm 2 Ni/(Ni+W) atomic ratio of 0.3, P 2 O 5 /WO 3 Molar ratio of 0.2, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of citric acid to Ni was 2 at 0.407 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 162m 2 Per gram, pore volume of 0.39cm 3 And/g, wherein the average pore diameter is 9.6nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 10.5%. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 5.6ppm, and the aromatic hydrocarbon content is 23.1%. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 3.2 ℃ after 5 days of reaction.
Example 5
Selecting a gamma-alumina carrier, wherein the water absorption rate is 1.04mL/g, and the specific surface area is 270m 2 And/g, wherein the average pore diameter is 11.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 1%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and citric acid into phosphoric acid aqueous solution, heating and stirring at 85 ℃ for 3 hours until the basic nickel carbonate and the citric acid are completely dissolved, and keeping the temperature for 2 hours to obtain the impregnation liquid containing the active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst is 9atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.25, P 2 O 5 /MoO 3 Molar ratio of 0.12, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of citric acid to Ni was 2 at 0.62 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 154m 2 Per gram, pore volume of 0.36cm 3 And/g, wherein the average pore diameter is 9.4nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 9.8%. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 7.8ppm, and the aromatic hydrocarbon content is 23.2%. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 2.9 ℃ after 5 days of reaction.
Example 6
Selecting a gamma-alumina carrier, wherein the water absorption rate is 1.04mL/g, and the specific surface area is 270m 2 And/g, wherein the average pore diameter is 11.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 1%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and citric acid into phosphoric acid aqueous solution, heating and stirring at 95 ℃ for 3 hours until the basic nickel carbonate and the citric acid are completely dissolved, and keeping the temperature for 2 hours to obtain the impregnation liquid containing the active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst is 10atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.28, P 2 O 5 /MoO 3 Molar ratio of 0.27, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of citric acid to Ni was 2 at 0.85 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. Specific surface area of catalyst is 135m 2 Per gram, pore volume of 0.27cm 3 And/g, wherein the average pore diameter is 8.0nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 12.5%. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 8.6ppm, and the aromatic hydrocarbon content is 23.2%. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 3.1 ℃ after 5 days of reaction.
Comparative example 1
The same support as in example 1 was selected to prepare a catalyst. MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into phosphoric acid aqueous solution, heating and stirring at 85 ℃ for 2 hours until the basic nickel carbonate and the glycerol are completely dissolved, and keeping the temperature for 3 hours to obtain the impregnation liquid containing the active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 2 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst was 4atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.22, P 2 O 5 /MoO 3 Molar ratio of 0.3, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup 0.34nm, and the molar ratio of glycerol to Ni was 2.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 205m 2 Per gram, pore volume of 0.48cm 3 And/g, wherein the average pore diameter is 9.5nm, the pore diameter distribution of the catalyst is unimodal pores, and the position of the unimodal pores is 8.9 nm. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 32ppm, and the aromatic hydrocarbon content is 27.2%. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 4.3 ℃ after 5 days of reaction.
Comparative example 2
The same support as in example 1 was selected to prepare a catalyst. MoO is carried out 3 Adding basic nickel carbonate and glycerol into phosphoric acid water solution, stirring at 85 ℃ for 2 hours until the basic nickel carbonate and the glycerol are completely dissolved, and keeping the temperature for 3 hours to obtain an impregnating solution containing active metal components. Mixing the impregnating solution with a carrierMixing uniformly, standing for 2h, and drying at 120 ℃ for 5h to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst is 15atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.2, P 2 O 5 /MoO 3 Molar ratio of 0.2, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 1.13nm and 2.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. Specific surface area of the catalyst was 118m 2 Per gram, pore volume of 0.19cm 3 And/g, wherein the average pore diameter is 6.4nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 14.0%. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 46ppm, and the aromatic hydrocarbon content is 28.2%. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 4.7 ℃ after 5 days of reaction.
Comparative example 3
The same support as in example 1 was selected to prepare a catalyst. MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into phosphoric acid aqueous solution, heating and stirring at 85 ℃ for 2 hours until the basic nickel carbonate and the glycerol are completely dissolved, and keeping the temperature for 3 hours to obtain the impregnation liquid containing the active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst was 5.5atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.15, P 2 O 5 /MoO 3 Molar ratio of 0.1, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 2 at 0.35 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 186m 2 Per gram, pore volume of 0.46cm 3 And/g, wherein the average pore diameter is 9.9nm, the pore structure shows unimodal pore distribution characteristics, and the position of unimodal pores is 8.6nm. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 38ppm, and the aromatic hydrocarbon content is 27.9%. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 4.2 ℃ after 5 days of reaction.
As can be seen from the data of examples and comparative examples, the invention has better effect, and the prepared hydrofining catalyst has higher activity and stability and has excellent desulfurization and dearomatization performance in distillate oil.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (10)

1. A hydrofining catalyst, wherein the catalyst comprises at least one VIII group metal element, at least one VIB group metal element and alumina, and the pore volume of the catalyst is 0.2-0.4cm 3 And/g, wherein the average pore diameter is 6-18nm, and the pore diameter of the catalyst shows bimodal pore distribution in the range of 2-6nm and 8-20nm.
2. Catalyst according to claim 1, wherein in the catalyst the pore volume with a pore size distribution of 2-6nm represents 8-15%, preferably 9-12% of the total pore volume of the catalyst;
preferably, the specific surface area of the catalyst is 130-170m 2 /g；
Preferably, the average pore diameter of the catalyst is 8-10nm;
preferably, the catalyst has a pore volume of 0.25 to 0.4cm 3 /g。
3. The catalyst of claim 1, wherein theThe water absorption rate of the alumina is more than 0.9mL/g, and the specific surface area is more than 260m 2 And/g, wherein the average pore diameter is more than 8nm, and the pore distribution form is unimodal pore distribution;
preferably, in the alumina, the pore volume with a pore size distribution of 2-6nm is no more than 10%, preferably no more than 8% of the total pore volume of the alumina;
preferably, in the alumina, the pore volume with a pore size distribution of 2-4nm represents no more than 4%, preferably no more than 2% of the total pore volume of the alumina.
4. A catalyst according to any one of claims 1 to 3, wherein the catalyst composition is as defined in (Xi ai )·(Yi bi )·(Zi ci ) Sup, where Xi is the group VIB metal oxide, ai is the mass of the group VIII metal oxide relative to 1 gram of support Xi, bi is the mass of the group VIII metal oxide relative to 1 gram of support Yi, zi is P 2 O 5 Ci is relative to 1 g of carrier P 2 O 5 Sup refers to the mass of the support in the catalyst, calculated as 1 gram, which satisfies the following conditions: (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup Has a value of 0.4 to 0.9nm, preferably 0.5 to 0.8nm, ρ Xi 、ρ Yi 、ρ Zi Respectively a group VIB metal oxide, a group VIII metal oxide and P 2 O 5 Density, SA of sup Is the specific surface area of the carrier;
preferably, the molar ratio Zi/Xi in the catalyst is between 0.05 and 0.3, preferably between 0.08 and 0.2.
5. The catalyst according to any one of claims 1 to 4, wherein the atomic concentration of the group VIB metal element on the surface of the support in the catalyst is 5-13atom/nm 2 Preferably 5-11 atoms/nm 2 ；
Preferably, the atomic ratio of the group VIII metal element to the total of the group VIII metal element and the group VIB metal element in the catalyst is 0.05 to 0.35, preferably 0.1 to 0.3.
6. The catalyst according to any one of claims 1 to 5, wherein the catalyst further comprises one or more organic alcohol compounds and/or carboxylic acid compounds containing-OH, the molar ratio of organic alcohol compounds and/or carboxylic acid compounds to group VIII metal element being 1 to 6, preferably 2 to 5.
7. Catalyst according to any of claims 1-6, wherein the equivalent diameter of the catalyst is 0.5-1.8mm, preferably 0.8-1.6mm;
preferably, the shape of the catalyst is cylindrical, clover, butterfly, honeycomb or other irregular shape.
8. The method for producing a hydrofinishing catalyst according to any one of claims 1 to 7, which comprises:
the alumina is impregnated with a group VIII metal precursor, a group VIB metal precursor, a phosphorus-containing compound, and optionally an organic alcohol compound and/or a carboxylic acid compound, and then dried.
9. The production method according to claim 8, wherein the impregnation method comprises: impregnating the alumina with an impregnating solution containing a group VIII metal precursor, a group VIB metal precursor, a phosphorus-containing compound, and optionally an organic alcohol compound containing-OH and/or a carboxylic acid-based compound;
preferably, the organic alcohol compound and/or carboxylic acid compound containing-OH, the group VIII metal precursor, the group VIB metal precursor are added to an aqueous solution of a phosphorus-containing compound to provide the impregnation solution;
preferably, the drying conditions include: the temperature is 80-200deg.C, and the time is 1-10h.
10. Use of the hydrofinishing catalyst of any one of claims 1-7 in a hydrodesulphurisation reaction.
CN202111265080.XA 2021-10-28 2021-10-28 Hydrofining catalyst and preparation method and application thereof Pending CN116037177A (en)

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