CN108654700A - Three peak pore size distribution Hydrodemetalation catalysts of one kind and preparation method thereof - Google Patents

Three peak pore size distribution Hydrodemetalation catalysts of one kind and preparation method thereof Download PDF

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CN108654700A
CN108654700A CN201810518525.2A CN201810518525A CN108654700A CN 108654700 A CN108654700 A CN 108654700A CN 201810518525 A CN201810518525 A CN 201810518525A CN 108654700 A CN108654700 A CN 108654700A
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pore volume
catalyst
peak
preparation
pore size
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CN108654700B (en
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徐景东
车晓瑞
王娇红
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 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
    • B01J35/643—Pore diameter less than 2 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
    • B01J35/64—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
    • B01J35/695—Pore distribution polymodal
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C10G2300/205—Metal content

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of Hydrodemetalation catalysts and preparation method thereof.It is 50 200 m that the catalyst, which has three peak pore size distribution structures, 0.5 1.3 mL/g of Kong Rongwei, specific surface area,2/ g, pore volume of the bore dia less than 50 nm account for 30 50 % of total pore volume, and bore dia is that the pore volume of 50 100 nm accounts for 10 30 % of total pore volume, and bore dia accounts for 30 50 % of total pore volume more than the pore volume of 100 nm.Compared with prior art, the present invention uses the preparation method of the Hydrodemetalation catalyst of three completely new peak pore size distributions, hydro-thermal process is carried out to the alumina support of bimodal pore distribution, transitional pore is produced between macropore mesoporous, the mesoporous hole missing between macropore can be made up.The Hydrodemetalation catalyst of three peak pore size distributions prepared by the method for the present invention is more suitable for the heavy oil hydrogenation demetals such as residual oil, depitching matter catalyst.

Description

Three peak pore size distribution Hydrodemetalation catalysts of one kind and preparation method thereof
Technical field
The present invention relates to a kind of three peak pore size distribution Hydrodemetalation catalysts and preparation method thereof.
Background technology
In recent years, with the heaviness of crude resources, growth and environmental regulation to fuel oil consumption demand it is increasingly tight Lattice use hydrogen addition technology for good light-weight fuel oil and chemical products, to contribute to the heavy oil conversion including residual oil Improve the level of crude oil processing, reduce environmental pollution, improve yield of light oil and improve product quality etc..
Residual oil is enriched with most sulphur, nitrogen, condensed-nuclei aromatics, metal in crude oil（Mainly Fe, Ni and V etc.）.With desulfurization and Denitrogenation is different, after the hydrogenated removing of the metals such as Fe, Ni and V, will gradually be deposited in catalyst duct, and be covered in catalytic active site On, and blocking catalyst duct leads to the final complete deactivation of catalyst, it is therefore necessary to hydrogenation and removing is first carried out, in order to avoid poison downstream Hydrodesulfurization, hydrodenitrogeneration and catalytic cracking catalyst etc..Metal in the mink cell focuses such as residual oil is primarily present in colloid and drip In the macromolecular compounds such as green matter.This part of compounds is complicated, molecular dimension is big, and diffusion is difficult, and metal is often attached in aperture It closely deposits and makes catalyst premature inactivation, reduce the utilization rate of catalyst.Therefore in order to reach maximization residuum hydrogenating and metal-eliminating Performance, it is desirable that the reactivity that catalyst has not only had, while also needing to have rational pore distribution can effectively change Mass transfer diffusion, reaction and the metal deposit of kind macromolecule reactant.Solution is to prepare that there are the oxygen that different pore size is distributed Change alumina supporter, both there is macropore（Aperture is in 50 nm or more）Exist again mesoporous（Aperture is in 50 nm or less）, macropore can be containing gold The diffusions of the macromoleculars such as the asphalitine of category provides channel, promote impure macromolecular quickly spread to the internal gutter of catalyst and Deposition improves the utilization rate of catalyst, and mesoporous energy provide specific surface as big as possible for reaction, promote the removing of impurity and sink Product.Research report [J. Ancheyta et al./Catalysis Today 109 (2005) 3-15], contains a large amount of macropores Double-peak catalyst compared with unimodal catalyst, metal is more uniform in catalyst radial distribution.Activity and catalysis is being determined Under the porous optimal solution rule of agent, the multimodal hole diametrical deposition distribution of continuously distributed catalyst metals is more equal It is even.Therefore, three continuously distributed peaks of duct and other polymodal catalyst carriers, will make metal in catalyst duct evenly Deposition improves catalyst activity and holds impurity ability, contributes to the operation cycle for extending catalyst.
In the prior art, add for mink cell focuses such as residual oil the Hydrodemetalation catalyst of the bimodal pore distribution of hydrogen preparation and The report of application is more, and the report of three peaks and other multimodal Hydrodemetalation catalysts and preparation method thereof is few.Existing preparation The Hydrodemetalation catalyst with bimodal pore distribution in, bimodal to generally comprise mesoporous and macropore, mesopore diameter is in 2- 50 nm, diameter macropores are in 100 nm or more.The macropore of bimodal pore distribution catalyst and it is mesoporous between lack transitional pore, for example lack The hole of few 50-100 nm.The compound of some macromolecular sizes in residual oil, can be diffused using macropore, but cannot be fine Diffuse into it is mesoporous carry out reaction and deposited metal, cause metal be distributed in the duct of catalyst not enough uniformly.Therefore, it opens It sends out three peaks and heavy-oil hydrogenation processing especially hydrodemetallization, the property of depitching matter can be improved in other multimodal pore size distribution catalyst Energy.
US5266300 discloses a kind of heavy-oil hydrogenation catalyst with three peak pore size distributions and its preparation and application.It is described The preparation method of carrier includes mixing the boehmite containing bimodal pore distribution and its aluminium oxide, molding, drying and roast. The carrier have three peak pore size distributions, thirdly peak hole be respectively distributed to bore dia be 3-100 nm, bore dia be 100-1000 nm and Bore dia is 1000-10000 nm.The three peaks pore catalyst has higher plus hydrogen depitching matter and Tuo Jin than commercial catalysts Belong to activity.But there are two types of bore dias for the three peaks pore catalyst in 100 nm or more, mesoporous still to lack transitional pore, nothing between macropore Method realizes mesoporous and macropore pore distribution continuity.
US7790130 discloses a kind of preparation method of three peaks pore size distribution aluminium oxide.This method includes by hydrated alumina It mixes, be molded with carbonate and roast.Obtained alumina support has three peak pore size distributions, is mainly less than the small of 15 nm Hole, 15-50 nm be mesoporous and the macropore of 50 nm or more.The alumina pore appearance of three peak pore size distributions made from this method is relatively low, simultaneously Also a large amount of alkali metallic sodium, is not suitable as heavy oil hydrogenating treatment catalyst.
Invention content
Purpose of the present invention is to de- in residual hydrogenation for existing bimodal and three peak pore size distributions Hydrodemetalation catalysts Disadvantage present in asphalitine, demetalization provides a kind of Hydrodemetalation catalyst of three new peak pore size distributions, and provides one kind The method of new Hydrodemetalation catalyst of the preparation with three peak pore size distributions.It is bimodal and three peak pore size distributions with existing patent The preparation method of catalyst is compared, and the present invention uses the preparation method of the Hydrodemetalation catalyst of three completely new peak pore size distributions, Hydro-thermal process is carried out to the alumina support of bimodal pore distribution, transitional pore is produced between macropore mesoporous, Jie can be made up Hole missing between hole and macropore.The Hydrodemetalation catalyst of three peak pore size distributions prepared by the method for the present invention is more suitable for residual oil Equal heavy oil hydrogenation demetals, depitching matter catalyst.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of Hydrodemetalation catalyst provided by the invention.The catalyst contain a kind of pore size distribution of three peak alumina support and The active metal component of load on this carrier.It is measured using mercury injection method, which has typical three peaks pore size distribution structure, Its Kong Rongwei 0.5-1.3 mL/g, specific surface area are 50-200 m2/ g, pore volume of the bore dia less than 50 nm account for total pore volume 30-50 %, bore dia are that the pore volume of 50-100 nm accounts for the 10-30 % of total pore volume, and bore dia is accounted for more than the pore volume of 100 nm The 30-50 % of total pore volume.Active metal component contained by catalyst is the metal component and at least one of at least one group vib VIII group metal component, by oxide calculate and on the basis of catalyst, the metal component oxide of the group vib contains Amount is 0.1-15 wt%, and the content of the metal component oxide of the VIII group is 0.1-5 wt%.Catalyst also contains auxiliary agent Phosphorus, is calculated by oxide and on the basis of catalyst, the content of the oxide of auxiliary agent phosphorus is 0-5 wt%.
The present invention also provides a kind of preparation methods of three peaks pore size distribution Hydrodemetalation catalyst, and this method includes bimodal The preparation of alumina support, bimodal alumina support hydrothermal treatment prepare three peak alumina supports and in three peak alumina supports Upper load hydrogenation active metal component.
（1）The preparation of the bimodal alumina support：By alumina precursor and extrusion aid, glue containing boehmite Solvent kneading is molded and roasts.The alumina precursor can be selected from gibbsite, boehmite, boehmite and nothing Shape the mixture of one or more of aluminium hydroxide, can be commercial goods or any one method system in the prior art Standby product.Preferably boehmite.The extrusion aid can be in sesbania powder, methylcellulose, starch, polyvinyl alcohol One or several kinds, addition are aluminium oxide（The amount of aluminium oxide is converted by alumina precursor）1-5 wt%.The peptizing agent Can be the aqueous solution of inorganic acid or organic acid, a concentration of 0.05-5 wt % of acid solution；Inorganic acid aqueous solution is hydrochloric acid, sulphur Acid solution or salpeter solution；Aqueous solutions of organic acids is formic acid solution, acetic acid solution or citric acid solution.The forming method can be with Using tabletting, spin or extrusion etc..The shape of carrier can according to it is different requirement be made sheet, ball-type, cylindrical type, trifolium-shaped or Bunge bedstraw herb type etc..Calcination temperature is 500-1000 DEG C, and roasting time is 1-8 h.Obtained alumina support has bimodal hole Distributed architecture.It is measured using mercury injection method, Kong Rongwei the 0.6-1.4 mL/g, specific surface area 50-300 of bimodal alumina support m2/ g, pore volume of the bore dia less than 50 nm account for the 50-70 % of total pore volume, and bore dia is that the pore volume of 50-100 nm accounts for total hole The 0-5 % of appearance, pore volume of the bore dia more than 100 nm account for the 30-50 % of total pore volume.
（2）The bimodal alumina support hydrothermal treatment prepares three peak alumina supports：By prepared bimodal hole Distribution alumina support carries out hydro-thermal process in confined conditions, and drying simultaneously roasts to obtain three peak alumina supports.The hydro-thermal Processing be by bimodal alumina support and moisture every and put into the closed containers such as reaction kettle, in confined conditions, be heated to one Constant temperature degree, then hydro-thermal process is for a period of time under the hydrothermal temperature.The temperature of the hydro-thermal process is 150-300 DEG C, the time For 1-24 h.The dosage of water is the 5-200 % of bimodal carrying alumina weight in the hydro-thermal process.Drying temperature is 80-200 DEG C, drying time is 1-24 h.Calcination temperature is 400-800 DEG C, and roasting time is 1-8 h.Alumina support obtained has Three peak pore size distribution structures, are measured using mercury injection method, the Kong Rongwei 0.6-1.4 mL/g of three peak alumina supports, and specific surface area is 50-200 m2/ g, pore volume of the bore dia less than 50 nm account for the 30-50 % of total pore volume, and bore dia is the hole body of 50-100 nm Product accounts for the 10-30 % of total pore volume, and pore volume of the bore dia more than 100 nm accounts for the 30-50 % of total pore volume.
（3）The supported active metals component on three peak alumina supports：Carrying method is infusion process, including prepares and contain The solution of the compound of active metal component and with the solution impregnating carrier, is then dried, roasts or does not roast To catalyst.Hydrogenation active metal component contained by catalyst is selected from the metal component and at least one of at least one group vib The metal component of VIII group, by oxide calculating and on the basis of catalyst, the content of the metal component oxide of the group vib Content for 0.1-15 wt%, the metal component oxide of the VIII group is 0.1-5 wt%.Catalyst also contains auxiliary agent phosphorus, It is calculated by oxide and on the basis of catalyst, the content of the oxide of auxiliary agent phosphorus is 0-5 wt%.The dipping temperature is 10-60 DEG C, dip time is 1-24 h.The drying temperature is 80-200 DEG C, and drying time is 1-24 h.The roasting It is 300-600 DEG C to burn temperature, and roasting time is 1-10 h.
Beneficial effects of the present invention：The present invention provides Hydrodemetalation catalyst and the preparation side of a kind of three peak pore size distribution Method.Using hydro-thermal process, mesoporous from bimodal pore distribution alumina support produces transitional pore between macropore, realizes plus hydrogen is de- The serialization of metallic catalyst pore size distribution, to improve the activity of Hydrodemetalation catalyst.
The present invention can control hydrothermal condition, such as the addition and feed postition of water, the aperture of modulation transitional pore and ratio. The transitional pore can make up macropore and it is mesoporous between hole missing, realize that the hole of different pore size is continuously distributed.The method of the present invention letter It is single, it is easily operated.
Hydrodemetalation catalyst provided by the invention has three peak pore size distributions, can be used as the mink cell focuses such as residual oil and adds the de- gold of hydrogen Belong to, add the catalyst such as hydrogen depitching matter.
Catalyst provided by the invention can be used alone, and can also be used with other catalyst combinations.The present invention provides Catalyst and other hydrogenation catalysts be applied in combination, to heavy oil especially poor residuum carry out hydrotreating, be subsequent technique （Such as catalytic cracking）Qualified feedstock oil is provided.
Description of the drawings
Fig. 1 is the mercury injection method graph of pore diameter distribution of bimodal pore distribution carrier A1；
Fig. 2 is the mercury injection method graph of pore diameter distribution of three peak pore size distribution carrier Bs 2.
Specific implementation mode
The present invention is further illustrated the present invention with the following example, but protection scope of the present invention is not limited to following reality Apply example.
Embodiment 1-3 illustrates the alumina support and preparation method thereof with three peak pore-size distributions provided by the invention.
Embodiment 1
The 144 g commercially available boehmite P2 of commercially available boehmite P1 and 71 g are weighed respectively, and 4.5 g sesbania powders are added, It is uniformly mixed.250 g dilute nitric acid solutions are added（Containing 3.0 g nitric acid）, then kneading is extruded into diameter at plastic on banded extruder For the bar of the bunge bedstraw herb type of 1.3 mm.Wet bar is dried into 4 h at 120 DEG C, 900 DEG C of 2 h of constant temperature, obtain in roaster Alumina support A1.
80 g alumina support A1 are weighed, are placed in water heating kettle.8 g deionized waters are weighed in glass.Glass is put Enter in water heating kettle.By water heating kettle it is closed after be put into baking oven, rise to 220 DEG C, incubation water heating handles 6 h.Sample after hydro-thermal process At 120 DEG C, dry 4 h, 500 DEG C of 2 h of constant temperature in roaster obtain the alumina support B1 of hydro-thermal process to product.Its pore volume It is shown in Table 1 with pore-size distribution.
Embodiment 2
80 g alumina support A1 are weighed, are placed in water heating kettle.20 g deionized waters are weighed in glass.Glass is put into water In hot kettle.By water heating kettle it is closed after be put into baking oven, rise to 220 DEG C, incubation water heating handles 6h.Sample after hydro-thermal process exists 120 DEG C of 4 h of drying, 500 DEG C of 2 h of constant temperature in roaster obtain the alumina support B2 of hydro-thermal process.Its pore volume and hole Diameter distribution is shown in Table 1.
Embodiment 3
80 g alumina support A1 are weighed, are placed in water heating kettle.40 g deionized waters are weighed in glass.Glass is put into water In hot kettle.By water heating kettle it is closed after be put into baking oven, rise to 220 DEG C, incubation water heating handles 6 h.Sample after hydro-thermal process exists 120 DEG C of 4 h of drying, 500 DEG C of 2 h of constant temperature in roaster obtain the alumina support B3 of hydro-thermal process.Its pore volume and hole Diameter distribution is shown in Table 1.
Comparative example 1
By the alumina support A1 being prepared in embodiment 1 without hydro-thermal process.Its pore volume and pore-size distribution are shown in Table 1.
Table 1
Table 1 and Fig. 1-2's the result shows that, compared with comparative example 1, alumina support prepared by the method for the present invention has apparent Three peak pore size distribution structures.After hydro-thermal process, the ratio of the mesoporous transitional pore between macropore and aperture significantly increase, and pore size distribution is real Existing serialization.
Embodiment 4-6 illustrates catalyst provided by the invention and preparation method thereof
Embodiment 4
80 g carrier Bs 1 are taken, 100 mL are added and contain 12.7 g/L NiO, 62.2 g/L MoO3, 8.9 g/L P2O5Ni-Mo-P Solution impregnates 2 h, and 2 h are dried in 120 DEG C, and 400 DEG C of roastings 0.5 h, 500 DEG C of 2 h of roasting obtain catalyst C1.Catalyst C1 In nickel oxide and the content of molybdenum oxide be listed in table 2.
Embodiment 5
80 g carrier Bs 2 are taken, 95 mL are added and contain 13.4 g/L NiO, 65.5 g/L MoO3, 9.3 g/L P2O5Ni-Mo-P it is molten Liquid impregnates 2 h, and 2 h are dried in 120 DEG C, and 400 DEG C of roastings 0.5 h, 500 DEG C of 2 h of roasting obtain catalyst C2.In catalyst C2 Nickel oxide and the content of molybdenum oxide be listed in table 2.
Embodiment 6
80 g carrier Bs 3 are taken, 97 mL are added and contain 13.1 g/L NiO, 64.1 g/L MoO3, 9.2 g/L P2O5Ni-Mo-P it is molten Liquid impregnates 2 h, and 2 h are dried in 120 DEG C, and 400 DEG C of roastings 0.5 h, 500 DEG C of 2 h of roasting obtain catalyst C3.In catalyst C3 Nickel oxide and the content of molybdenum oxide be listed in table 2.
Comparative example 2
80 g carrier A1 are taken, 100 mL are added and contain 12.7 g/L NiO, 62.2 g/L MoO3, 8.9 g/L P2O5Ni-Mo-P Solution impregnates 2 h, and 2 h are dried in 120 DEG C, and 400 DEG C of roastings 0.5 h, 500 DEG C of 2 h of roasting obtain catalyst D1.Catalyst D1 In nickel oxide and the content of molybdenum oxide be listed in table 2.
Table 2
Embodiment 7 provides the specific implementation mode of the process for hydrogenating residual oil of the present invention, and illustrates the residual hydrogenation of catalyst Demetalization performance.
Embodiment 7
With nickel content be 15 ppm, content of vanadium is 50 ppm, sulfur content is 4.23 wt%, carbon residue is 10.1wt %, nitrogen content is The residual oil of 2607 ppm is raw material, evaluates catalyst on 100 milliliters of small fixed reactors, the results are shown in Table 3.
Catalyst packing volume is 100 mL.Evaluate the process conditions all same that each example catalyst uses.Reaction condition is： 380 DEG C of reaction temperature, 15 MPa of hydrogen partial pressure, liquid hourly space velocity (LHSV) are 1.0 h-1, hydrogen to oil volume ratio 760, reaction 200 hours after take Sample.Using inductive coupling plasma emission spectrograph（ICP-AES）Measure the content of nickel and vanadium in oil before and after hydrotreating（Tool Body method is referring to RIPP124-90）.Oily studies on asphaltene quality is divided before and after analyzing hydrotreating using asphalt compound mensuration method Number（Specific method is referring to NB/SH/T 0509-2010）.Metal and asphaltene removal are calculated according to the following formula：
Evaluation result is listed in table 3.
Comparative example 3
According to the depitching matter rate and demetallization per of the method evaluation catalyst D1 of embodiment 7.It the results are shown in Table 3.
Table 3
The result that table 3 provides is the result after evaluation response carries out 200 hours.Compare as can be seen that provided by the invention plus hydrogen The hydrodemetallization of catalyst for demetalation is active and the activity of hydrogen depitching matter is added to be higher than reference catalyst.
The foregoing is merely the preferable case study on implementation of the present invention, all equivalent changes done according to scope of the present invention patent With modification, it should all belong to the covering scope of the present invention.

Claims (10)

1. a kind of three peak pore size distribution Hydrodemetalation catalysts, it is characterised in that：The catalyst has three peak pore size distribution structures, Kong Rongwei 0.5-1.3 mL/g, specific surface area are 50-200 m2/ g, pore volume of the bore dia less than 50 nm account for the 30- of total pore volume 50 %, bore dia are that the pore volume of 50-100 nm accounts for the 10-30 % of total pore volume, and bore dia accounts for always more than the pore volume of 100 nm The 30-50 % of Kong Rong.
2. a kind of three peaks pore size distribution Hydrodemetalation catalyst according to claim 1, it is characterised in that：The catalyst contains There are the active metal component of the alumina support and load of a kind of pore size distribution of three peak on this carrier, the activity gold contained by catalyst Category group is divided into the metal component of the metal component and at least one VIII group of at least one group vib, is calculated simultaneously with oxide On the basis of catalyst, the content of the metal component oxide of the group vib is 0.1-15 wt%, the metal group of the VIII group The content of sub-oxide is 0.1-5 wt%.
3. a kind of three peaks pore size distribution Hydrodemetalation catalyst according to claim 2, it is characterised in that：The catalyst is also Containing auxiliary agent phosphorus, is calculated by oxide and on the basis of catalyst, the content of the oxide of auxiliary agent phosphorus is 0-5 wt%.
4. a kind of preparation method of pore size distribution Hydrodemetalation catalyst in three peaks as described in any one of claims 1-3, feature It is：Include the following steps：
（1）The preparation of bimodal alumina support：By alumina precursor and extrusion aid, peptizing agent kneading containing boehmite, Molding, drying simultaneously roast；
（2）Bimodal alumina support hydrothermal treatment prepares three peak alumina supports：Prepared bimodal alumina support is existed Hydro-thermal process is carried out under confined conditions, and drying simultaneously roasts to obtain three peak alumina supports；The hydro-thermal process is by bimodal oxidation Alumina supporter and moisture every and put into reaction kettle closed container, in confined conditions, certain temperature is heated to, then in the temperature Lower hydro-thermal process is for a period of time；
（3）The supported active metals component on three peak alumina supports：Carrying method is infusion process, including prepares and contain active gold Belong to the solution of the compound of component and with the solution impregnating carrier, is then dried, roasts or do not roast to obtain catalyst.
5. preparation method according to claim 4, it is characterised in that：Step（1）In the extrusion aid be sesbania powder, first One or several kinds in base cellulose, starch, polyvinyl alcohol, addition are the 1-5 wt% of aluminium oxide；The peptizing agent is nothing Machine aqueous acid or aqueous solutions of organic acids, a concentration of 0.05-5 wt % of acid solution.
6. preparation method according to claim 4, it is characterised in that：Step（1）In forming method using tabletting, spin Or extrusion；The shape of carrier is ball-type, cylindrical type, trifolium-shaped or bunge bedstraw herb type；The calcination temperature is 500-1000 DEG C, roasting time is 1-8 h.
7. preparation method according to claim 4, it is characterised in that：Step（1）Described in alumina support have it is double Peak pore size distribution structure, is measured using mercury injection method, Kong Rongwei the 0.6-1.4 mL/g, specific surface area 50- of bimodal alumina support 300 m2/ g, pore volume of the bore dia less than 50 nm account for the 50-70 % of total pore volume, and bore dia is that the pore volume of 50-100 nm accounts for The 0-5 % of total pore volume, pore volume of the bore dia more than 100 nm account for the 30-50 % of total pore volume.
8. preparation method according to claim 4, it is characterised in that：Step（2）Described in the temperature of hydro-thermal process be 150-300 DEG C, the time is 1-24 h；The dosage of water is the 5-200 % of bimodal carrying alumina weight in the hydro-thermal process； Drying temperature is 80-200 DEG C, and drying time is 1-24 h；Calcination temperature is 400-800 DEG C, and roasting time is 1-8 h.
9. preparation method according to claim 4, it is characterised in that：Step（2）In alumina support obtained have three Peak pore size distribution structure, is measured using mercury injection method, Kong Rongwei the 0.6-1.4 mL/g, specific surface area 50- of three peak alumina supports 200 m2/ g, pore volume of the bore dia less than 50 nm account for the 30-50 % of total pore volume, and bore dia is that the pore volume of 50-100 nm accounts for The 10-30 % of total pore volume, pore volume of the bore dia more than 100 nm account for the 30-50 % of total pore volume.
10. preparation method according to claim 4, it is characterised in that：Step（3）Described in dipping temperature be 10-60 DEG C, dip time is 1-24 h；The drying temperature is 80-200 DEG C, and drying time is 1-24 h；The calcination temperature It it is 300-600 DEG C, roasting time is 1-10 h.
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CN114100599A (en) * 2021-12-20 2022-03-01 中化长和科技有限责任公司 Preparation method of oil refining hydrogenation protection catalyst
CN114308090A (en) * 2022-01-14 2022-04-12 中化泉州石化有限公司 Hierarchical pore hydrotreating catalyst and preparation method thereof
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CN114425353A (en) * 2020-10-29 2022-05-03 中国石油化工股份有限公司 Residual oil hydrodemetallization catalyst and preparation thereof
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