CN106423183A - Preparation method of high-metal-content hydrogenation catalyst - Google Patents

Preparation method of high-metal-content hydrogenation catalyst Download PDF

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Publication number
CN106423183A
CN106423183A CN201610842532.9A CN201610842532A CN106423183A CN 106423183 A CN106423183 A CN 106423183A CN 201610842532 A CN201610842532 A CN 201610842532A CN 106423183 A CN106423183 A CN 106423183A
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preparation
carrier
hydrogenation catalyst
catalyst
roasting
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CN106423183B (en
Inventor
柴永明
郭阳
刘晨光
刘宾
殷长龙
郭海玲
赵会吉
柳云骐
左萌
谢坤
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China University of Petroleum East China
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China University of Petroleum East China
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • 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
    • 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
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/308—Gravity, density, e.g. API

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

Abstract

The invention relates to a preparation method of a high-metal-content hydrogenation catalyst, comprising the steps of depositing an aluminum source modifier to a carrier; mixing a metal, phosphoric acid, an organic complexing agent and deionized water; impregnating the mixture to the carrier on which the aluminum source modifier is deposited; drying and calcining the carrier on which the mixture is impregnated; wherein the metal is made from a main component, Mo in VIB, and an aid component, Ni in VIII, the aluminum source modifier is one, or a composition of any, of aluminum isopropoxide, aluminum chloride and aluminum nitrate, the carrier on which the aluminum source modifier is deposited is 1.3-2.3 ml/g in pore volume and 400-700 m<2>/g in specific surface area, and pores 14-18 nm in diameter accounts for greater than 50%. The preparation method of the high-metal-content hydrogenation catalyst provided herein has significantly improved activity and good pore structure and large specific surface area since metal carrying capacity is increased; the preparation process of the catalyst is simplified, and the preparation cost of high-metal-content hydrogenation catalyst is reduced.

Description

The preparation method of high metal content hydrogenation catalyst
Technical field
The present invention relates to technical field of petrochemical industry, and in particular to a kind of preparation side of high metal content hydrogenation catalyst Method.
Background technology
In recent years, with the raising of pay attention to day by day of the people to environmental quality and environmental consciousness, worldwide right Derv fuel sulfur content is particularly in vehicle fuel and Cetane number production is put forward higher requirement, state V and state VI diesel oil matter Figureofmerit require in derv fuel sulfur content need ultralow sulfuration (<10 μ g/g), the hexadecane of state V and state VI standard derv fuel Value is greater than 51 and 53 respectively, and diesel-fuel cetane number to be improved needs deep hydrogenation Arene removal.At present, hydrogenation process is real The most effective approach of this target existing, and high-performance hydrogenation catalyst is key therein.
For the study hotspot that researches and develops always in recent years prepared by hydrotreating catalyst, existing hydrogenation catalyst Agent is mainly prepared using infusion process, i.e., using active dipping solution direct impregnation in the duct of catalyst carrier.But it is limited by Carrier γ-Al2O3Pore volume and packing density of particle are limited, and are had preferably using hydrogenation catalyst prepared by metallic solution infusion process Pore passage structure and larger specific surface area, but the load capacity of active metal be；The catalyst being prepared If increasing load capacity again, active metal meeting blocking catalyst duct, so that the specific surface area of catalyst declines, catalyst activity Reduce.
However, catalyst is in the case of with certain pore passage structure, improve content of metal be one kind effectively improve plus The method of the activity of hydrogen catalyst.Therefore, need one kind at present badly and can improve content of metal, and the preparation stream of simplification catalyst Journey, so as to reduce the method for preparing catalyst of the preparation cost of the hydrogenation catalyst of high metal content.
Content of the invention
For defect of the prior art, the present invention is intended to provide a kind of preparation side of high metal content hydrogenation catalyst Method, significantly improve catalyst activity by increasing content of metal, and simplifies the preparation flow of catalyst, reduces high metal The preparation cost of the hydrogenation catalyst of content.
For this purpose, the present invention provides a kind of preparation method of high metal content hydrogenation catalyst, comprise the following steps：By silicon source Modifying agent is deposited on carrier；Metal, phosphoric acid, organic complexing agent and deionized water are mixed；Mixed product is impregnated into Deposition has on the carrier of silicon source modifying agent；Roasting after the carrier drying of mixed product will be impregnated with；Wherein, metal includes master Component and adjuvant component；Major constituent is the Mo of VI B race, and adjuvant component is the Ni of VIII race；Silicon source modifying agent is aluminum isopropylate., chlorination The compositionss of one or more in aluminum and aluminum nitrate；The pore volume that deposition has the carrier of silicon source modifying agent is 1.3～2.3ml/g, Specific surface area is that 400～700/g, 14～18nm hole aperture proportion is more than 50%.
Silicon source modifying agent is deposited on carrier, the special nature after being combined with carrier using silicon source modifying agent, prepares Pore volume is 1.3～2.3ml/g, and specific surface area is load of 400～700/g, the 14～18nm hole aperture proportion more than 50% Body；Metal, phosphoric acid, organic complexing agent and deionized water are mixed, is obtained the present invention and prepare high metal content hydrogenation catalyst institute The impregnation liquid for needing；Impregnation liquid is impregnated into deposition to be had on the carrier of silicon source modifying agent, and the presence of phosphoric acid and organic complexing agent is permissible Dispersion effect of the metal on carrier surface is improved, so as to weaken the interaction of metal major constituent Mo and carrier, weakens auxiliary agent The sulfuration of Ni, improves the state of cure (vulcanization) of metal major constituent Mo, makes structure and the form generation change of active phase, forms more II The modes such as type active center improve its hydrogenation activity；Roasting after the carrier drying of mixed product will be impregnated with；Finally obtaining While to high metal load capacity catalyst, the pore structure for having had catalyst and big specific surface area.Traditional by leaching When stain method prepares hydrogenation catalyst, the active metal load capacity of catalyst is only 25-35wt% or so；Improve content of metal work For a kind of method of the activity for effectively improving hydrogenation catalyst, improved using traditional infusion process active metal load capacity when, mistake Many active metal can blocking catalyst duct, cause the specific surface area of catalyst to decline, diffusibility variation, so that urging The activity decrease of agent；Though unsupported catalyst can improve content of metal, its catalysis for preparing to a certain extent Agent pore-size distribution disperse, pore volume are less, specific surface area is low, and activity is not satisfactory.However, the height for being provided using the present invention The preparation method of tenor hydrogenation catalyst, it is 1.3～2.3ml/ to be prepared with pore volume by the addition of silicon source modifying agent G, specific surface area is carrier of 400～700/g, the 14～18nm hole aperture proportion more than 50%, and then prepares and have The catalyst of high metal load capacity, so as to greatly improve the activity of hydrogenation catalyst.Meanwhile, the preparation method that the present invention is provided Flow process is simple, greatly reduces the preparation cost of high metal content hydrogenation catalyst.
That is, the preparation method of the high metal content hydrogenation catalyst of present invention offer, by increasing metal load While amount significantly improves catalyst activity, catalyst is made to have preferable pore structure and larger specific surface area；And letter Change the preparation flow of catalyst, reduce the preparation cost of the hydrogenation catalyst of high metal content.
In the further embodiment of the present invention, the atomic ratio of Ni/ (Ni+Mo) is the mass ratio of 0.23-0.30, P/Mo It is 0.5-2.0 for the mol ratio of 0.04-0.09, Ni/ organic complexing agent.
In the further embodiment of the present invention, carrier is silica supports, silica supports and silicon source modification The Si/Al atomic ratio of agent is 5～25.
In the further embodiment of the present invention, organic complexing agent is citric acid, in malic acid and ethylenediaminetetraacetic acid One or more of compositionss.
In the further embodiment of the present invention, the Mo of major constituent is in molybdenum trioxide, ammonium heptamolybdate and ammonium tetramolybdate One or more of compositionss；The Ni of adjuvant component be nickel oxide, nickel hydroxide, nickel nitrate, nickel acetate, basic nickel carbonate and The compositionss of one or more in nickelous carbonate.
In the further embodiment of the present invention, after being impregnated with the carrier drying of mixed product, roasting is concrete For：After the carrier for being impregnated with mixed product is dry 4～12h at 80-200 DEG C, 2～6h of roasting at 300-550 DEG C.
In the further embodiment of the present invention, the temperature for drying is 100～150 DEG C, and the time for drying is 6～8h； The temperature of roasting is 400～500 DEG C, and the time of roasting is 3～5h；Heating rate in roasting process is 2 DEG C/min.
In the further embodiment of the present invention, the mode of dipping is equi-volume impregnating, and dipping number of times is 1-2 time.
In the further embodiment of the present invention, the pore volume of the product after roasting is 0.2～0.6ml/g, 5～10nm hole Aperture ratio is more than 60%, and specific surface area is 160～350m2/g.
In the further embodiment of the present invention, it is standard that the load capacity of catalyst presses the quality of reactive metal oxides To calculate, the metal quality load capacity of the product after roasting is more than 50%.
Description of the drawings
Fig. 1 is the flow chart of the preparation method of the high metal content hydrogenation catalyst in the embodiment of the present invention.
Specific embodiment
Below in conjunction with accompanying drawing, the embodiment of technical solution of the present invention is described in detail.Following examples are only used for More clearly technical scheme being described, example is therefore only used as, and the protection model of the present invention can not be limited with this Enclose.
Fig. 1 is the flow chart of the preparation method of the high metal content hydrogenation catalyst in the embodiment of the present invention, as Fig. 1 institute Show that the preparation method of the high metal content hydrogenation catalyst that the present invention is provided is comprised the following steps：
S101：Silicon source modifying agent is deposited on carrier.Wherein, silicon source modifying agent is aluminum isopropylate., aluminum chloride and nitric acid The compositionss of one or more in aluminum；Carrier is silica supports, and silica supports are former with the Si/Al of silicon source modifying agent Son is than being 5～25.
S102：Metal, phosphoric acid, organic complexing agent and deionized water are mixed.Wherein, metal includes major constituent and auxiliary agent group Point；Major constituent is the Mo of VI B race, and adjuvant component is the Ni of VIII race；The atomic ratio of Ni/ (Ni+Mo) is 0.23-0.30, P/Mo Mass ratio is 0.5-2.0 for the mol ratio of 0.04-0.09, Ni/ organic complexing agent；The Mo of major constituent is molybdenum trioxide, seven molybdic acids The compositionss of one or more in ammonium and ammonium tetramolybdate；The Ni of adjuvant component is nickel oxide, nickel hydroxide, nickel nitrate, acetic acid The compositionss of one or more in nickel, basic nickel carbonate and nickelous carbonate；Organic complexing agent is citric acid, malic acid and ethylenediamine The compositionss of one or more in tetraacethyl.
Silicon source modifying agent is deposited on carrier, the special nature after being combined with carrier using silicon source modifying agent, prepares Pore volume is 1.3～2.3ml/g, and specific surface area is load of 400～700/g, the 14～18nm hole aperture proportion more than 50% Body.By Mo and Ni, phosphoric acid, organic complexing agent and deionized water according to Ni/ (Ni+Mo) atomic ratio for 0.23-0.30, P/Mo Mass ratio mixes for the ratio of 0.5-2.0 for the mol ratio of 0.04-0.09, Ni/ organic complexing agent, so as to obtain present invention preparation Impregnation liquid needed for high metal content hydrogenation catalyst.
S103：Mixed product is impregnated into deposition to be had on the carrier of silicon source modifying agent.Wherein, deposition has silicon source modification The pore volume of the carrier of agent is 1.3～2.3ml/g, and specific surface area is that 400～700/g, 14～18nm hole aperture proportion is big In 50%；The mode of dipping is equi-volume impregnating, and dipping number of times is 1-2 time.
Impregnation liquid is impregnated into deposition to be had on the carrier of silicon source modifying agent, and the presence of phosphoric acid and organic complexing agent can be improved Dispersion effect of the metal on carrier surface, so as to weaken the interaction of metal major constituent Mo and carrier, weakens auxiliary agent Ni's Sulfuration, improves the state of cure (vulcanization) of metal major constituent Mo, makes structure and the form generation change of active phase, forms more II types and live The modes such as property center improve its hydrogenation activity.Si/Al atomic ratio is 5～25, and deposition can be made to have the carrier hole of silicon source modifying agent Hold and specific surface area is more preferable, can more prepare the hydrogenation catalyst of the high metal content needed for the present invention.Soaked using equal-volume Stain method impregnates 1-2 time, effective ingredient in impregnation liquid can be made more fully to be impregnated in carrier, so as to prepare various aspects of performance More preferable catalyst.
S104：Roasting after the carrier drying of mixed product will be impregnated with.Wherein, mixed product will be impregnated with After carrier drying, roasting is specially：After the carrier for being impregnated with mixed product is dry 4～12h at 80-200 DEG C, 2～6h of roasting at 300-550 DEG C；The temperature for drying is preferably 100～150 DEG C, and the time for drying is preferably 6～8h；Roasting Temperature is preferably 400～500 DEG C, and the time of roasting is preferably 3～5h；Heating rate in roasting process is 2 DEG C/min；Roasting The pore volume of product afterwards is that 0.2～0.6ml/g, 5～10nm hole aperture ratio is more than 60%, and specific surface area is 160～350m2/ g；The load capacity of catalyst is calculated for standard by the quality of reactive metal oxides, the metal quality load of the product after roasting Amount is more than 50%.
Roasting after the carrier drying of mixed product will be impregnated with；Finally the same of high metal load capacity catalyst is being obtained When, the pore structure for having had catalyst and big specific surface area.The carrier of mixed product will be impregnated with 80-200 DEG C After lower 4～12h of drying, 2～6h of roasting at 300-550 DEG C；So as to obtain pore volume for 0.2～0.6ml/g, 5～10nm hole hole Footpath ratio is more than 60%, and specific surface area is 160～350m2/g；And the metal quality load capacity of the product after roasting is more than 50%, That is the metal quality load capacity of catalyst is more than 50%.Traditional when preparing hydrogenation catalyst by infusion process, the work of catalyst Property content of metal be only 25-35wt% or so；Content of metal is improved as a kind of activity for effectively improving hydrogenation catalyst Method, improved using traditional infusion process active metal load capacity when, excessive active metal can blocking catalyst duct, The specific surface area for causing catalyst declines, diffusibility is deteriorated, so that the activity decrease of catalyst；Though unsupported catalyst Can improve content of metal to a certain extent, but its catalyst pore-size distribution disperse for preparing, pore volume be less, specific surface area Low, activity is not satisfactory.However, the preparation method of the high metal content hydrogenation catalyst for being provided using the present invention, is led to Cross silicon source modifying agent addition prepare with pore volume be 1.3～2.3ml/g, specific surface area be 400～700/g, 14～ Carrier of the 18nm hole aperture proportion more than 50%, and then the catalyst with high metal load capacity is prepared, so as to significantly Improve the activity of hydrogenation catalyst.Meanwhile, the flow process of the preparation method that the present invention is provided is simple, greatly reduces high metal content The preparation cost of hydrogenation catalyst.
Illustrate with reference to specific embodiment：
Embodiment one
Weigh the big pore volume SiO of 50g2It is placed in beaker, 500ml normal hexane is added, then weighs 11.3g aluminum isopropylate., Si/ Al=15, under agitation with being added in beaker after a small amount of n-hexane dissolution；1500ml normal hexane is added, under room temperature, continues stirring 24 hours.Filter, washed using a large amount of normal hexane, 120 DEG C are dry 6h, then obtained to 550 DEG C of roasting 4h with 2 DEG C/min ramp To the modified silica supports of silicon source, S-1 is designated as.
Weigh the big pore volume SiO of 50g2It is placed in beaker, 500ml dehydrated alcohol is added, 7.4g anhydrous Aluminum chloride is then weighed, Si/Al=5, under agitation with being added in beaker after a small amount of anhydrous alcohol solution；Add and continue under 1500ml dehydrated alcohol, room temperature Continuous stirring 24 hours.Filter, using a large amount of absolute ethanol washings, 120 DEG C dry 6h, then with 2 DEG C/min ramp to 550 DEG C Roasting 4h obtains the modified silica supports of silicon source, is designated as S-2.
Weigh the big pore volume SiO of 50g2It is placed in beaker, 500ml dehydrated alcohol is added, then weighs nine water aluminum nitrate of 20.8g Si/Al=25, under agitation with being added in beaker after a small amount of anhydrous alcohol solution, adds 1500ml dehydrated alcohol, under room temperature Continue stirring 24 hours.Filter, using a large amount of absolute ethanol washings, 120 DEG C dry 6h, then with 2 DEG C/min ramp to 550 DEG C roasting 4h obtains the modified silica supports of silicon source, is designated as S-3.
In addition, the carrier S -1, carrier S -2 and carrier S -3 that are obtained according to embodiment one, prepare the catalyst of the present invention, Specifically there is implementation below：
Embodiment two
The water absorption rate of measurement carrier S -1 is 1.8ml/g, weighs 100g silicon source modified silica supports S-1,91.7g Molybdenum trioxide, 28.3g basic nickel carbonate, 24.4g strong phosphoric acid and 29.8g citric acid.By molybdenum trioxide, basic nickel carbonate, dense Phosphoric acid and 200mL deionized water are added in the glass beaker with white label of 500ml, are placed on magnetic force heating stirrer, plus Thermal agitation, boils 1-3h, as evaporation of water can supplement portions of de-ionized water in heating process, to clear, stop heating, Lower the temperature, when cooling to 60 DEG C, citric acid is added, continue stirring, to solution clear after the whole dissolvings of citric acid, to be impregnated After liquid temp is down to room temperature, 180mL is accurately settled to.Catalyst is prepared using equi-volume impregnating, after the completion of dipping, is put into steaming Send out ware, with sealed membrane sealed maintenance 2～3 hours, 200 DEG C of dryings 12 hours, 550 DEG C of roasting 2h (heating rate is 2 DEG C/min), Prepared catalyst B1.
Wherein, volume V of constant volume meets V=θ m；Wherein, θ is the water absorption rate of carrier, and unit is the matter of mL/g, m for carrier Amount, unit is g.Active metal load capacity is (MoO3+ NiO, is counted with the mass fraction of oxide) as 52wt%, Ni/ (Ni+Mo) Mass ratio=0.07 of=0.25, P/Mo, mol ratio=1.5 of Ni/ citric acid.
The catalyst with same active metal load capacity is prepared with S-2, S-3 respectively with same preparation process as carrier, Obtain catalyst B2, B3.
In addition, in order to highlight further the present invention offer super-active hydrogenation catalyst preparation method advantage, adopt The catalyst in comparative example is prepared with method of the prior art, carry out following contrast experiment：
Comparative example one
The support type FDS-1 catalyst of China Petroleum Univ. (East-China) CNPC catalysis key lab exploitation, as a comparison Catalyst D1.Wherein active metal load capacity is in terms of oxide, and it is 3.8%- that MoO3 content is 21%-23%, NiO content 4.2%, P2O5 content is 3.0-5.0%.
Comparative example two
NiMoW unsupported catalyst is prepared according to prior art：Weigh 66g nickel nitrate, 20g ammonium molybdate, 36g metatungstic acid Ammonium is added in 600ml deionized water, is placed on magnetic stirring apparatuss, adds 9g tetraethylammonium bromide in the case of stirring, plus It is 9 that ammonia (concentration is 25%) adjusts solution pH value, mixed liquor is placed in synthesis reaction vessel, hydro-thermal under 60 DEG C of airtight conditions Synthesis 9 hours, then cooling, filtration, washing, obtain filter cake, then dry 4 hours filter cake at 160 DEG C.Obtain contrast to urge Agent D2.
Comparative example three
NiMoW unsupported catalyst is prepared according to another prior art：Weigh 24g Nickel dichloride., the dissolving of 28g ammonium metatungstate In 300ml deionized water, acid solution A is configured to；Weigh 18g sodium metaaluminate to be dissolved in 300ml deionized water, proportionaling alkali-forming Property solution B.Solution A is added in retort, 45 DEG C of constant temperature, in the case of stirring, 90ml solution B is added, control serosity PH value is 9.5, then passes to CO2 gas, and concentration is 40v%, 45 DEG C of gelling temperature, and in retort, slurry pH value is 7.5, to repeat Aforesaid operations 2 times, during cemented into bundles, control reacting slurry pH value is 7.5, aging 2 hours.Then filter, filter cake adds 360ml Deionized water and 7.4g molybdenum trioxide, beating stirs, and filters, and filter cake is dry 4 hours at 100 DEG C, and then extrusion, washes Wash, wet bar in 120 DEG C of dryings 4 hours, roasting 4 hours at 500 DEG C, obtain comparative catalyst D3.
In addition, the preparation method for being provided using the present invention, prepares catalyst from the carrier for being not added with silicon source modifying agent, tool Body there is also implementation below：
It is 1.5 for the mass ratio of 0.25, P/Mo for the mol ratio of 0.07, Ni/ citric acid by the atomic ratio of Ni/ (Ni+Mo) Prepare impregnation liquid.The preparation method for being provided using the present invention, from the general carrier without silicon source modifying agent, prepares catalysis Agent.
Calculate by 100g catalyst is prepared：NiO+MoO3Load capacity 35wt%, wherein carrier water absorption rate are designed by 100% With preparation impregnation liquid.Wherein, the inventory for preparing impregnation liquid is specially：Carrier 65g, needs impregnation liquid volume 65mL, MoO329.8g, basic nickel carbonate 9.21g (are calculated for 44wt% by ni content), strong phosphoric acid：7.93g is (by purity 98%, concentration The H of 85wt%3PO4Calculate), citric acid：9.67g.According to aforementioned proportion, the impregnation liquid of 1000.0ml, each raw material components tool is configured Body is shown in Table 1.
The each raw material components list of table 1
Prepare 1000mL constant volume impregnation liquid：By the molybdenum trioxide of requirement, basic nickel carbonate, strong phosphoric acid and 1400- 1600mL deionized water is added in the glass beaker with white label of 2L, is placed on magnetic force heating stirrer, heated and stirred, is boiled Boiling 1-3h；Wherein, as evaporation of water can supplement portions of de-ionized water in the middle of heating, so that clear, stops heating, drop Temperature, adds citric acid when cooling to 60 DEG C, continues stirring, to solution clear, liquid to be impregnated after the whole dissolvings of citric acid After temperature is down to room temperature, it is standby to be accurately settled to 1000mL, is labeled as impregnation liquid A.
The preparation of catalyst：Measure big pore volume carrier S iO2Water absorption rate be 2.0ml/g；According to 2 impregnation liquid of table with go from The different additions of sub- water, prepare catalyst using equi-volume impregnating, after the completion of dipping, are put into evaporating dish, close with sealed membrane Envelope maintenance 2～3 hours, 100 DEG C of dryings 6 hours, 450 DEG C of roasting 4h；Wherein, the heating rate in roasting process is 2 DEG C/min, The NiMoP/SiO of prepared different loads amount2Catalyst, obtains catalyst A1, A2, A3, A4 and A5.
The different additions of 2 impregnation liquid of table and deionized water
In addition, the catalyst property obtained by various embodiments of the present invention carries out system evaluation：
First, to carrier S iO2, A1-A5, S1-S3, B1-B3 and D1-D3 carry out low temperature liquid nitrogen adsorption analyses, with each catalysis The properties such as the average pore size of agent, pore volume, specific surface area.
Experiment is determined using 2010 full-automatic specific surface area of U.S. Micromeritics ASAP and lacunarity analysis instrument and is urged The pore structure of agent.When determining catalyst pore structure, adsorption temp is set to -196 DEG C, relative pressure p/p0It is set to 0～0.995. Suction/the desorption isotherm of material is made with pressure changing in test substance surface excess by nitrogen, and then passes through BET side Method calculate sample BET specific surface area, BJH method calculate sample pore volume, BJH aperture be by low temperature N2In adsorption desorption curve Desorption prop up calculated.As a result as shown in table 3.
3 carrier of table and catalyst physical properties table
It can be seen from Table 3 that, with the modified SiO of silicon source2Have relatively for high metal load capacity catalyst prepared by carrier Big pore volume, specific surface area, aperture integrated distribution is in 5～10nm.Different loads amount NiMoP/SiO for preparing in embodiment one2 Catalyst A1-A5, with the increase of active metal load capacity, the specific surface area of catalyst, pore volume and average pore size accordingly reduce. Contrast A5, B1, B2 and B3 discovery, introduces silicon source and in the carrier using different silicon source modifying agent, the aperture of catalyst, hole Hold and specific surface area change is not obvious.Contrast A5, B1-B3 and D1 discovery, the specific surface area of high metal load capacity catalyst is than normal Rule loaded catalyst specific surface area is big, illustrates in the case that load capacity significantly increases, and catalyst prepared by the method is still There is good pore structure property.Contrast A5, B1-B3 and D2-D3 discovery, the pore volume of high metal load capacity catalyst and specific surface area All much larger than unsupported catalyst, with preferable pore structure and large specific surface area.
2nd, hydrogenation activity evaluation is carried out to A1-A5, B1-B3 and D1-D3
Activity rating of catalyst is carried out in 100ml high-pressure hydrogenation micro-reactor, and catalyst is first through pre- sulfur before evaluation Change, activity stabilized process.The appreciation condition of catalyst is stagnation pressure 6MPa, hydrogen-oil ratio 300:1,340 DEG C of reaction temperature, air speed 2.0h-1.Raw material oil nature used by active evaluation test is as shown in table 4.
The catalyst activity result of embodiment and comparative example is as shown in table 5.By analysis be hydrogenated with after oil product sulfur content and Density comparing hydrodesulfurization activity and the catalyst hydrogenation saturated activity of catalyst, by contrasting A1-A5 discovery, catalyst Reactivity increases with the increase of load capacity.The catalyst A5 and B1-B3 of contrast same metal content has found, compares more straight Connect with big pore volume SiO2The catalyst of carrier is made, the modified SiO of silicon source2When doing carrier, the activity increase of catalyst.Contrast B1, B2 Find with B3, when the silicon source modifying agent for adding is aluminum isopropylate., catalyst has best catalysis activity.Contrast B1 and D1 sends out Existing, high metal load capacity NiMoP/Al-SiO2Catalyst is higher than the reactivity of conventional supported catalyst.The present invention is adopted The high metal content hydrogenation catalyst that the method for offer is prepared has had good pore passage structure and high active site density concurrently Advantage.Contrast B1 and D1, D2 have found, high metal load capacity NiMoP/Al-SiO2Catalyst is urged than the non-loading type in the test Agent has higher hydrogenation and desulphurizing activated；The high metal content hydrogenation catalyst that i.e. prepared by the present invention both ensure that high work Property bit density, overcomes unsupported catalyst pore-size distribution disperse, pore volume is less, specific surface area is relatively low shortcoming again.
The property of diesel raw material tested by table 4
5 Activity evaluation of table
Certainly, except the situation that embodiment one and embodiment two are enumerated, other metal major constituents, adjuvant component, carrier, have Machine chelating agent, the atomic ratio of Ni/ (Ni+Mo), the mass ratio of P/Mo, the mol ratio of Ni/ organic complexing agent, baking temperature and when Between, sintering temperature and time and dipping number of times also possible.Simply in the case that embodiment one and embodiment two are enumerated, Catalyst is while with high content of metal, and catalysis activity is higher, and pore structure and specific surface area are more preferable.
The preparation method of the high metal content hydrogenation catalyst that the present invention is provided, makes catalyst by increasing content of metal While activity is significantly improved, catalyst is made to have preferable pore structure and larger specific surface area；And simplify catalyst Preparation flow, reduces the preparation cost of the hydrogenation catalyst of high metal content.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means specific features, structure, material or the spy for describing with reference to the embodiment or example Point is contained at least one embodiment or the example of the present invention.In this manual, to the schematic representation of above-mentioned term not Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be in office Combined in one or more embodiments or example in an appropriate manner.Additionally, in the case of not conflicting, the skill of this area The feature of the different embodiments described in this specification or example and different embodiments or example can be tied by art personnel Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned Embodiment is changed, changes, replacing and modification.

Claims (10)

1. a kind of preparation method of high metal content hydrogenation catalyst, it is characterised in that comprise the following steps：
Silicon source modifying agent is deposited on carrier；
Metal, phosphoric acid, organic complexing agent and deionized water are mixed；
Mixed product is impregnated into deposition to be had on the carrier of silicon source modifying agent；
Roasting after the carrier drying of mixed product will be impregnated with；
Wherein,
The metal includes major constituent and adjuvant component；
The major constituent is the Mo of VI B race, and the adjuvant component is the Ni of VIII race；
Source of aluminium modifying agent is the compositionss of one or more in aluminum isopropylate., aluminum chloride and aluminum nitrate；
The pore volume for depositing the carrier for having silicon source modifying agent is 1.3～2.3ml/g, and specific surface area is 400～700/g, 14 ～18nm hole aperture proportion is more than 50%.
2. the preparation method of high metal content hydrogenation catalyst according to claim 1, it is characterised in that
The atomic ratio of Ni/ (Ni+Mo) for 0.23-0.30, P/Mo mass ratio for 0.04-0.09, Ni/ organic complexing agent mole Than for 0.5-2.0.
3. the preparation method of high metal content hydrogenation catalyst according to claim 1, it is characterised in that
The carrier is silica supports, the Si/Al atomic ratio of the silica supports and source of aluminium modifying agent is 5～ 25.
4. the preparation method of high metal content hydrogenation catalyst according to claim 1, it is characterised in that
The organic complexing agent is the compositionss of one or more in citric acid, malic acid and ethylenediaminetetraacetic acid.
5. the preparation method of high metal content hydrogenation catalyst according to claim 1, it is characterised in that
The Mo of the major constituent is the compositionss of one or more in molybdenum trioxide, ammonium heptamolybdate and ammonium tetramolybdate；
The Ni of the adjuvant component is in nickel oxide, nickel hydroxide, nickel nitrate, nickel acetate, basic nickel carbonate and nickelous carbonate Plant or multiple compositionss.
6. the preparation method of high metal content hydrogenation catalyst according to claim 1, it is characterised in that
Described will be impregnated with the carrier drying of mixed product after roasting be specially：
To be impregnated with after the carrier of mixed product dries 4～12h at 80-200 DEG C, at 300-550 DEG C roasting 2～ 6h.
7. the preparation method of high metal content hydrogenation catalyst according to claim 6, it is characterised in that
The temperature of the drying is 100～150 DEG C, and the time for drying is 6～8h；
The temperature of the roasting is 400～500 DEG C, and the time of roasting is 3～5h；Heating rate in roasting process be 2 DEG C/ min.
8. the preparation method of high metal content hydrogenation catalyst according to claim 1, it is characterised in that
The mode of the dipping is equi-volume impregnating, and dipping number of times is 1-2 time.
9. the preparation method of the high metal content hydrogenation catalyst according to any one of claim 1-8, it is characterised in that
The pore volume of the product after the roasting is that 0.2～0.6ml/g, 5～10nm hole aperture ratio is more than 60%, and specific surface area is 160～350m2/g.
10. the preparation method of the high metal content hydrogenation catalyst according to any one of claim 1-8, it is characterised in that
The load capacity of catalyst is calculated for standard by the quality of reactive metal oxides, the metallic of the product after the roasting Amount load capacity is more than 50%.
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CN107349934A (en) * 2017-07-13 2017-11-17 湖北润驰环保科技有限公司 A kind of preparation method for exempting to be calcined presulfurization hydrogenation catalyst
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CN115555021A (en) * 2022-10-04 2023-01-03 中国石油大学(华东) Preparation method of catalyst for co-production of low-carbon olefin by liquid hydrocarbon prepared by carbon dioxide hydrogenation
CN115555021B (en) * 2022-10-04 2024-02-02 中国石油大学(华东) Preparation method of catalyst for co-production of liquid hydrocarbon and low-carbon olefin by hydrogenation of carbon dioxide

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