CN107185567A - A kind of nickel system selective hydrocatalyst and preparation method thereof - Google Patents

A kind of nickel system selective hydrocatalyst and preparation method thereof Download PDF

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CN107185567A
CN107185567A CN201710408450.8A CN201710408450A CN107185567A CN 107185567 A CN107185567 A CN 107185567A CN 201710408450 A CN201710408450 A CN 201710408450A CN 107185567 A CN107185567 A CN 107185567A
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catalyst
alumina support
nickel
alumina
content
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CN107185567B (en
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晁会霞
张海燕
颜曦明
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Qinzhou University
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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
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
    • 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
    • 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
    • B01J35/651—50-500 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • 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
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds 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
    • 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
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Organic Chemistry (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The present invention relates to a kind of nickel system selective hydrocatalyst, catalyst includes the alumina support with macroporous structure and the metal active constituent nickel and tungsten that are carried on carrier, gross weight of the content of nickel oxide based on the catalyst is 12 22wt%, gross weight of the content of tungsten oxide based on the catalyst is 1.5 8wt%, alumina support is used as expanding agent using chitosan, containing adjuvant component phosphorus and magnesium in alumina support with macroporous structure, the content of adjuvant component phosphorus and magnesium accounts for the percentage composition respectively P of carrier quality2O50.1 2.5wt%, MgO 0.1 2.5wt%, the 180nm of pore-size distribution 60, macropore ratio 2 75%, the 2.0ml/g of pore volume 0.8, the 300m of specific surface area 2502/g.Catalyst holds glue ability more preferably, and anti-arsenic, sulfur resistive, suppression coking ability are strong.

Description

A kind of nickel system selective hydrocatalyst and preparation method thereof
Technical field
It is especially a kind of the present invention relates to a kind of for selective hydrogenation catalyst of petroleum hydrocarbon product and preparation method thereof Nickel system selective hydrocatalyst, for one-stage selective hydrogenation of gasoline splitting.
Background technology
Drippolene is the important by-product of steam cracking industrial production ethene, propylene, including C5-C10 fractions.Drippolene Composition is very complicated, mainly there is benzene,toluene,xylene, monoolefine, diolefin, linear paraffin, cycloalkane and nitrogen, sulphur, oxygen, chlorine With the organic compound of heavy metal etc., more than totally 200 component, wherein benzene,toluene,xylene (being referred to as BTX) about 50-90%, no Saturated hydrocarbons 25-30%.According in drippolene contain a large amount of aromatic hydrocarbons the characteristics of, its is widely used, both can as gasoline tune And component, high-octane gasoline is produced, can also be by separating production aromatic hydrocarbons etc..
Because drippolene composition is complicated, heat endurance is poor, generally, first alkadienes and benzene are removed through one-stage selective hydrogenation After ethene, Secondary hydrodesulfurization, it is mainly used in Aromatics Extractive Project.Industrial catalyst for selective hydrogenation of cracked gasoline is mainly at present Pd systems or Ni series catalysts, midbarrel (C6-C8 hydrocarbon compounds cut) hydrogenation or full the cut (hydrocarbon of C5 hydrocarbon-do for 204 DEG C Compound cut) hydrogenation technique.Due to the difference of each ethylene unit cracking stock and cracking condition, each device drippolene raw material Composition difference is larger, and particularly (polymerisation occurs for the unsaturation component such as alkadienes and styrene for the diene of drippolene, colloid The high molecular polymer of generation) and As, content of beary metal there is larger difference；Some device raw pyrolysis gasoline dienes, colloid Height, and the toxic content such as colloid and As, heavy metal is higher in some device raw pyrolysis gasoline raw materials, individual device raw pyrolysis gasoline The toxic content such as diene, colloid and As, heavy metal is high.
Alkadienes and alkynes in drippolene easily polymerize collagen at high temperature, are deposited on catalyst surface, Yi Zao Into catalyst inactivation, it is necessary to frequently activation and regeneration.Pyrolysis gasoline hydrogenation catalyst mainly has Pd/Al2O3And Ni/Al2O3 Two kinds of catalyst.Pd series catalysts have initial temperature low, and hydrogenation activity is big, and adaptation air speed is high, the advantages of service life is long, The catalyst mode for having commercial Application includes Pd-Cr/Al2O3, Pd/Al2O3。
Usual pyrolysis gasoline hydrogenation catalyst is using the metal salt of active component or the solution dipping of organo-metallic compound The carrier, then arrives carrier surface by active component is oxide carried by processes such as drying, roastings, using preceding needing logical hydrogen Pyrolysis gasoline hydrogenation reaction could be used for after gas reduction.Common carrying alumina body aperture is too small, when colloid, arsenic contain in raw material When amount, sulfur content are exceeded, the easy coking and blocking in hole on catalyst influences catalyst activity and stabilized hydrogenation.
Macroporous oxide due to larger pore passage structure, higher specific surface area, good heat endurance, using extensively In fields such as heterogeneous catalyst, catalyst carrier, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance materials.
Carrier with macroporous aluminium oxide is relatively more.CN03126434.4 discloses a kind of macropore alumina supporter, containing aerobic Change aluminium, also containing a kind of halogen, on the basis of carrier total amount, the carrier contains 95-99 weight % aluminum oxide, in terms of element, 0.1-5 weight % halogen, its acid amount is less than 0.2 mM/gram.The preparation method of macropore alumina supporter is included a kind of oxygen The precursor for changing aluminium is molded and is calcined, and before shaping and roasting, the precursor of aluminum oxide is mixed with a kind of expanding agent, described Expanding agent includes a kind of organic expanding agent and a kind of halide, and sintering temperature is 600-850 DEG C, roasting time 1-10 hours, respectively The consumption of component contains final alumina support, on the basis of carrier total amount, 95-99 weight % aluminum oxide, with element Meter, 0.1-5 weight % halogen.The one kind of organic expanding agent in starch, synthetic cellulose, polymeric alcohol, surfactant Or it is several.One kind in carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxylated cellulose of synthetic cellulose or It is several.One or more of the polymeric alcohol in polyethylene glycol, poly- propyl alcohol, polyvinyl alcohol, surfactant is selected from poly alkyl alcohol Oxygen vinethene, fatty alkanol amide, molecular weight are 200-10000 acrylic copolymer, one kind in maleic acid copolymer or It is several.CN201110410339.5 provides a kind of high temperature-resistant active aluminum oxide material and preparation method thereof, described oxidation aluminium Material is made by following steps：After macropore boehmite, high viscous boehmite are mixed with additive with water, it is in rotating speed Stirred under 100-1000r/min, add the dilute nitric acid reaction that concentration is 30%, to the peptization state that pH is 2.0-5.5 When, be aged 3-6h under the stirring of 80 DEG C of -100 DEG C of temperature, add at room temperature pore creating material stir, slurrying, spraying, drying, It is calcined at 900 DEG C and aluminum oxide is made.The alumina material has the advantages that to be easy to batch production and high-ratio surface.In 1000- It can be kept for a long time than surface in more than 110m2/g at a temperature of 1100 DEG C；The technique mistake of the alumina material preparation method Journey is simple, with low cost.Wherein described sky agent of making is selected from polyvinyl alcohol, polyethylene glycol, polyacrylamide or methylcellulose In one kind, its consumption be alumina material in oxide gross weight 0-40%.《Zhongshan University's journal》(2002,41 (2): Method 121-122) introduced is as follows：A diameter of 600nm polystyrene colloidal crystal microballoon is placed on a buchner funnel, then will The ethanol solution of aluminum nitrate and citric acid is added drop-wise under suction filtration on glue crystalline substance, allows it fully to penetrate into the gap of microballoon, through dry Dry and roasting, removes polystyrene moulding, obtains macroporous aluminium oxide.《Acta PhySico-Chimica Sinica》(2006,22 (7):831-835) it is situated between The method that the granular formwork method that continued prepares three-dimensional ordered macroporous alumina, this method is as follows：Obtained first using emulsion polymerization Polystyrene microsphere, alumina sol is made by aluminum nitrate plus weak aqua ammonia, then will both stirring mixing by a certain percentage, ultrasound Processing, then through drying and being calcined, obtain macroporous aluminium oxide.CN201010221302.3 (CN102311134A) is open a kind of spherical Integral macroporous alumina and preparation method thereof.This method comprises the following steps：By polymer microballoon emulsion, alumina sol and Coagulant is well mixed with certain proportion, and the mixture is scattered in oil phase, forms w/o type drop, then reheats above-mentioned Mixed phase system, makes the alumina sol gelling balling-up in aqueous phase, isolates the gel micro-ball of shaping from oil phase afterwards, then in ammonia Described spherical integral macroporous alumina is obtained after aged in aqueous medium, dry and roasting.The macropore diameter of the aluminum oxide Homogeneous controllable in the range of less than 1 μm, the size of spheric granules is controllable, and mechanical strength is higher, and forming process is easy easily OK, it is easy to be prepared on a large scale.Polymer microballoon diameter 50-1000nm, the type of polymer microballoon is polystyrene microsphere, polyphenyl The esters microballoons such as olefin(e) acid N-butyl microballoon, polyacrylate.Coagulant is hexamethylenetetramine, urea.Oil phase is organic hydrocarbon. The invention, which is mainly, prepares Integral macroporous alumina, and macropore diameter is homogeneous controllable.Preparation process has used lipid microballoon And coagulant etc..Preparation technology is complicated, and reagent raw material used is relatively more.Due to polymer microballoon cause carrying alumina Internal portion pore passage structure is blind bore, that is to say, that alumina support internal gutter does not have connectivity. CN201010221297.6 discloses a kind of preparation method of Integral macroporous alumina.This method comprises the following steps：Aluminium Source, polyethylene glycol and after low-carbon alcohol and water at least one is well mixed, will low-carbon epoxyalkane add it is described mixed In compound, Integral macroporous alumina is obtained through aging, immersion, dry and roasting.Preparation method of the invention is simple and easy to apply, ring Border pollution is small, and its aperture of gained Integral macroporous alumina is controllable at 0.05-10 μm.The monoblock type macropore oxidation that the present invention is provided Thing can be applied to the fields such as macromolecular heterogeneous catalysis, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance material. CN201410347665.X discloses a kind of big pore volume, the preparation method of high-strength alumina, by adding polyacrylamide, gathering The expanding agents such as vinyl alcohol, alkylcellulose, sesbania powder, starch, obtain containing eurypyloue alumina support, the consumption of its expanding agent The 10-30% of aluminum oxide is accounted for, but specific pore diameter range is not disclosed.Although hard mould agent method can obtain preferable macropore oxidation Alumina supporter, but the consumption of its template causes processing cost to greatly improve more preferably greater than 20%, the decomposition of a large amount of templates The demand for development of low-carbon environment-friendly is not met.CN201010509425.7 discloses the side of a kind of hydro-thermal and the common reaming of template Method, to prepare the alumina support containing macroporous structure, is acted on, the consumption of template can be reduced by the complementary reaming of hydro-thermal To 3-10%, but auxiliary hydro-thermal causes the rise of energy consumption.CN200310103035.X discloses a kind of macroporous aluminium oxide Preparation method, reaming is carried out using polyvinyl alcohol, poly- propyl alcohol, polyethylene glycol soft template, by adding 1% polyethylene glycol, The pore volume that aperture is more than 100nm accounts for the 26.2% of total pore volume.Soft template has the advantages that consumption is low, reaming effect is good, still Solubility property of the alcohols soft template of higher molecular weight in water is poor, causes it to be used to expanding super large porous aluminum oxide and limited System.CN200910204238.5 (CN102040235) discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The party Method comprises the following steps：Monodispersed polymer microballoon is assembled into glue crystal template, certain party legal system is then filled into template Standby alumina sol, most obtains macroporous aluminium oxide through dry and roasting afterwards.This method can be good at control Alumina gel and The recombination process of Alumina gel and polymer microballoon, the network structure of alumina gel is not destroyed as far as possible, makes prepared oxidation Aluminium not only has the macropore duct of three-dimensional order but also with higher specific surface area.The invention is burnt by the appropriateness to template Small fenestra formed by knot, makes the macropore in material be connected with the macropore of surrounding by 12 small fenestras.The oxidation of the invention Aluminium is suitable for use as the adsorption and separation material of mink cell focus catalyst carrier and organic macromolecule.Have in catalyst carrier material application Beneficial to the mass transfer ability of material in the catalyst is improved, be conducive to improving the activity and selectivity of catalyst. CN201410148773.4 discloses a kind of preparation method of aluminum oxide porous microballoon, comprises the following steps：1) by surface-active Agent is dissolved in deionized water, stirring, is used as aqueous phase；2) chelating agent, alumina precursor and n-octyl alcohol are mixed, stirred, as Oil phase；3) Span80 and pore-foaming agent, stirring are added in oil phase；4) by step 3) gained clarification oil phase be poured into aqueous phase Continue stirring and emulsifying；5) by step 4) gains vacuum filtration, dry after gained Washing of Filter Cake, obtain aluminum oxide porous microballoon.Should Microballoon has internal closing macroporous structure, and Microsphere Size is 1 μm -100 μm, and the invention is coagulated using pore-foaming agent with the colloidal sol in emulsion Glue process obtains the metal porous microballoon with internal closing macroporous structure.Porous microsphere is prepared using phase separation principle.It is internal It is 50nm-5 μm to close aperture.Inside closing aperture is 50nm-5 μm.Aperture is closing inside the aluminum oxide porous microballoon, That is alumina support internal gutter does not have connectivity.Pore-foaming agent is polyvinylpyrrolidone, polyacrylamide or poly- third Olefin(e) acid.The invention has used substantial amounts of surfactant, chelating agent, pore-foaming agent, and preparing raw material is more, and synthesis technique is complicated.
Above macroporous aluminium oxide mainly prepares macropore oxygen using cellulose, polymeric alcohol, polystyrene etc. as expanding agent Change aluminium.
Alumina support with macropore and mesoporous i.e. composite pore structural also compares many.CN 101200297A are disclosed The preparation method of integral macroporous alumina：Reverse concentrated emulsions method is used to prepare monoblock type using styrene and divinylbenzene as monomer Macropore organic formwork；Al is prepared using aluminium isopropoxide or boehmite as predecessor2O3The hydrosol；By Al2O3The hydrosol is filled into In monoblock type macropore organic formwork；Monolithic devices organic/inorganic composite after filling is de- in 600 DEG C of -900 DEG C of roastings through drying Removing template, obtains integral macroporous alumina.The advantage of this method is that preparation process is simple and easy to apply, obtained monoblock type macropore Aluminum oxide has the macropore duct that micron order is interconnected, and aperture is 1-50 μm.This method prepares Integral macroporous alumina letter It is single easy, but the volume fraction of aqueous phase accounts for 75%-90% in this method, and correspondingly the volume fraction of organic monomer is relatively low, This method is while organic monomer consumption is reduced, and the preparation efficiency of prepared template is relatively low, is unfavorable for subsequent step big It is prepared by the batch of porous aluminum oxide.A kind of preparation methods of the alumina support of composite pore structural of CN201110032234.0, including Calorize will be contained selected from least one of aluminium isopropoxide, aluminium secondary butylate, aluminum nitrate, aluminium chloride, Alumina gel and boehmite powder Compound and composite mould plate agent are mixed and are calcined, and the composite mould plate agent is mesoporous template and macroporous granules template, is given an account of Hole template is selected from polyethylene glycol propane diols-polyethylene glycol triblock polymer, polyethylene glycol, lauryl amine, hexadecane At least one of base trimethylammonium bromide, laurate, stearic acid and AEO, the macroporous granules template choosing It is more than 50nm polystyrene microsphere, poly (methyl methacrylate) micro-sphere, particles of bioglass, pitch particle or heavy oil from particle diameter Residue；The weight ratio of the mesoporous template, macroporous granules template and aluminum contained compound is 0.1-2:0.1-0.7:1, wherein The weight of the aluminum contained compound is in terms of aluminum oxide.The invention also discloses have mesoporous hole while preparation by the above method Road and the alumina support in macropore duct, its intermediary hole account for the 40%-90% of total pore volume, and macropore accounts for the 10%-60% of total pore volume. CN201210328824.2 discloses a kind of method for preparing solid phase of gradient distribution hole gama-alumina.This method is anti-by solid phase Precursor aluminium carbonate ammonium should be obtained, the gamma oxidation of a kind of high specific surface area, gradient distribution hole and larger pore volume is obtained after roasting Aluminium.What the present invention was protruded the most is technically characterized in that using raw material solid phase reactive synthesis technique, as obtained by being controlled synthesis condition The property of gama-alumina.Meanwhile, the inventive method is simple, it is easy to operate, it is not necessary to add expanding agent, cost-effective, is adapted to work Industryization is produced in batches.The preparation process of alumina support of the present invention comprises the following steps：(1) aluminum nitrate, ammonium hydrogen carbonate and table Face activating agent is fully ground uniformly, and ageing certain time obtains precursor aluminium carbonate ammonium in the closed container of specified temp；(2) Aftershaping is well mixed with peptizing agent after precursor aluminium carbonate ammonium obtained by (1) is dried, can typically be squeezed using banded extruder Bar is molded；(3) it is (2) are obtained that article shaped is dried, final alumina support is made in aerobic roasting.Luring described in step (1) Lead the polyethylene glycol that agent is liquid form, 0.1-10.0% of the addition equivalent to aluminum nitrate weight.Carbonic acid described in step (2) The drying process of aluminium ammonium is generally dried 1-20 hours at 50-180 DEG C.Roasting process described in step (3) is in 350-900 It is calcined 1-10 hours at DEG C.The invention prepares gama-alumina using the decomposition at a certain temperature of precursor aluminium carbonate ammonium.Aluminium carbonate Ammonium produces gas, such as NH in decomposable process3And CO2, the generation and effusion of these gases can manufacture some macropores.Simultaneous oxidation The pattern of aluminium is transformed by the pattern topology of aluminium carbonate ammonium.Slower heating rate is conducive to gas thing in roasting process Matter is slowly escaped, and carrier is not easily caused and is caved in.Method is simple, it is not necessary to add any physics expanding agent. CN201310097588.2 discloses a kind of gama-alumina particle and preparation method thereof：1) aluminum soluble salt is dissolved in by acid The pH value of acidifying is less than or equal in 3 aqueous solution, and the amount that the aluminum soluble salt is added causes obtained containing aluminium in aluminum water solution The molar concentration of ion is 0.01-5mol/L；2) to step 1) it is obtained contain in aluminum water solution add alkaline precipitating agent, the alkali Property precipitating reagent add amount cause reaction after solution ph between 5-12；3) by step 2) obtained mixed sediment solution exists At room temperature after stirring 0.1-3h, it is put into water-bath or water heating kettle, 6-24h is aged at a temperature of 50-150 DEG C；4) by step 3) after the solution after being aged stirs, dried using spray drying process, it is 150-400 that EAT is controlled during spray drying DEG C, leaving air temp is 60-110 DEG C, and the thermal efficiency of spray drying is more than 50%；5) by step 4) obtained dried oxidation Aluminium precursor powder is at room temperature with the first heating rate to 250 DEG C -350 DEG C, then with the second heating rate extremely 400 DEG C -800 DEG C, insulation 0.5-20h obtains final product gama-alumina particle；Wherein, first rate of heat addition is less than the Two rates of heat addition, and first rate of heat addition and second rate of heat addition are in the range of 0.1-10 DEG C/min.It is obtained Gama-alumina is experiments verify that test, its specific surface area is in 180m2/g-260m2In/g range, with high-specific surface area.It is made Gama-alumina particle observed under ESEM with hollow foam shape pattern, it is and compound with micropore-mesopore-macropore Aperture structure.So, when gama-alumina is as catalyst carrier, its hollow foam shape pattern can be effectively in dispersed catalyst Active component.And hollow foam shape pattern and composite bore diameter structure, be conducive to the mass transfer in catalytic process, so as to accelerate Rate of catalysis reaction.The composite bore diameter structure refers to both include the micropore that aperture is less than 2nm, again including aperture in 2nm-50nm Between it is mesoporous, in addition to aperture be more than 50nm macropore.Step 1) in also include to it is obtained contain add and make in aluminum water solution Hole agent, the molar concentration that the amount that the pore creating material is added to add pore creating material in rear solution is aluminum ions molar concentration 0.01-5 times.The pore creating material is cetyl trimethylammonium bromide (CTAB), neopelex (SDBS), polyethylene One or more in alcohol (PVA), polyethylene glycol (PEG) and calgon.CN101863499A (201010187094.X) provides a kind of preparation method of macroporous-mesoporous alumina.Comprise the following steps：A. first reaction is helped Agent and aluminium salt are dissolved in organic solvent solution, reaction promoter：Two kinds of material mol ratios of aluminium ion are 3-5：1, then by template Add above-mentioned solution and dissolve, aluminium ion is 1 with template mol ratio：0.015-0.025, the pH value control of final solution exists 3.5-6.0；B., a is walked to the solution prepared and carries out burin-in process, making it, progressively organic solvent and moisture are obtained greatly in removing system Hole-meso-porous alumina presoma；C. macroporous-mesoporous alumina powder is obtained through 400-800 DEG C of calcination process.Present invention process letter Single, duct rule, pore-size distribution is concentrated and controllable adjustment can be realized according to concrete application situation, thus many in petrochemical industry Mutually catalysis, adsorbing separation and as having important application value in terms of catalyst carrier, energy and material.Make full use of anti- The space frame effect and coordination of auxiliary agent and template, and intermediary's organic polymer, reaction promoter are answered to inorganic ions Complexing so that a step prepares the adjustable macroporous-mesoporous alumina material in aperture.Prepared foramen magnum-mesoporous oxidation The specific surface area of aluminum is up to 250-320m2/g, duct rule, pore-size distribution in mesoporous 5-40nm, macropore 50-150nm, and It can be realized and adjusted according to actual conditions.Reaction promoter is organic acid, and aluminium salt is inorganic aluminate.Template is triblock copolymer. Organic solvent is anhydrous alcohols, ethers or ketones solvent.Organic acid is citric acid or laurate.Triblock copolymer is P123 or F127.(Langmuir, 2004,20 such as Tie-Zhen Ren：1531-1534) use nonionic surfactant The aluminium secondary butylates of Brij 56 in acid condition use hydro-thermal method and Microwave-assisted synthesis macroporous-mesoporous alumina, synthesis it is porous 0.8-2 μm of alumina powder macropore diameter, mesoporous pore size 5-8nm, the aluminum oxide of 0.4-1.4 μm of hole wall.Its deficiency is aluminium-alcohol salt Expensive, the macroporous-mesoporous alumina pore volume of synthesis is small, duct is irregular, pore-size distribution is excessive and can not realize pore structure Effective regulation, thus, have significant limitation in using effect and scope.Jean-Philippe Dacquin etc. (J.Am.Chem.Soc., 2009,131：12896-12897) use sol-gel process using P123 be template in mixed solution It is middle to be introduced into the polystyrene droplet with single dispersed phase to realize the formation of macropore in macroporous-mesoporous alumina.Deficiency Place is that macropore diameter size (300nm or 400nm) is determined by the size of secondary introducing polystyrene drop completely, i.e. macropore diameter Size depends on polystyrene droplet size.Organic molecule in the part change to solution itself component and system can not be passed through Interact to realize the adjustment in aperture.(the Inorganic Chemistry, 2009,48 such as Huining Li：4421) equally adopt The polymethyl methacrylate with single dispersed phase is introduced in mixed solution by template of F127 with sol-gel process (PMMA) droplet realizes the formation of macropore in macroporous-mesoporous alumina, weak point be macropore diameter size also completely by Secondary introducing polymethyl methacrylate droplet size is determined, it is impossible to changed by the part to solution system itself component come real Show the adjustment in aperture to realize the formation of foramen magnum-mesoporous composite pore structural, thus can not also realize the controllable of foramen magnum-mesoporous aperture Regulation, in use, in particular for during the bulky molecular catalysis of complicated ingredient by significant limitation.
Above composite holes alumina support is typically used as mould using organic polymer such as polyvinyl alcohol, polymethylacrylic acid etc. Plate agent either expanding agent.So that the preparation of composite holes and macroporous aluminium oxide material exist template monomer have certain toxicity, Template consumption is larger, prepare the problems such as cost is higher, preparation process is cumbersome.Meanwhile, also there is the discharge in roasting process The problem of thing environmental pollution.Also there is the patent of the adding carbohydrate compound in polymer microballoon emulsion.
CN201310142454.8 discloses a kind of preparation method of alumina hollow ball, preparation chitosan-acetic acid-water-soluble Liquid；By polystyrene spheres:Chitosan-acetic acid-aqueous solution is 5:1-10：1 mass ratio, by polystyrene spheres：Alpha-alumina Body is 1:5-1:15 mass ratio takes each raw material；Polystyrene spheres and chitosan-acetic acid-aqueous solution are mixed, make polyphenyl Ethene ball surface uniformly coats one layer of chitosan-acetic acid-aqueous solution；The polyphenyl second of chitosan-acetic acid-aqueous solution is coated with again Alkene ball is put into ball mill device with alpha-alumina powder, with 5-30r/s rotating speed rotation cladding 2-24h, and core-shell structure copolymer ball is made；Will After the calcining of core-shell structure copolymer ball warp, that is, the alumina hollow ball that a diameter of 0.2-2mm, wall thickness are 20-100 μm is made. CN201110170283.0 discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The three-dimensional ordered macroporous oxidation Aluminium, diameter macropores are 50-1000nm, and grain diameter is 1-50mm, and mechanical strength is 80-280g/mm.This method includes following step Suddenly：Will into monodisperse polymer micro-sphere emulsion adding carbohydrate compound and the concentrated sulfuric acid, obtain the brilliant mould of polymer-modified microballoon glue Plate, is subsequently filled alumina sol, then through aging and roasting, obtains three-dimensional ordered macroporous alumina.The polymer microballoon A diameter of 50-1000nm, can using polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polyacrylic acid N-butyl microballoon and One or more in the different monooctyl ester microballoon of polyacrylic acid, preferably polystyrene microsphere.Described single dispersing refers to polymer microballoon The standard deviation of diameter is not more than 10%.The carbohydrate organic matter is the one or more in Soluble Monosaccharide and polysaccharide, preferably For the one or more in sucrose, glucose, chitosan.This method can increase substantially the adhesion amount of aluminum oxide precursor, increase The strong mechanical strength of material, it is trickle powder that when removing template is removed in high-temperature roasting, large pore material is not easily broken, can still be protected Hold higher integrity degree.Chitosan is in ceramic coating sorbing material field using more.《Mesoporous chitosan-aluminium hydroxide is combined Material Study on adsorption properties》(author：Peng Shaohua] University Of Suzhou,《Suzhou Institute of Science and Technology journal：Natural science edition》2013 30 Rolled up for 4 phases)：Using chitosan and AlCl3 as raw material, chitosan and the composites of α-Al (OH) 3 are prepared for.With X-ray powder diffraction, Transmission electron microscope, infrared, thermogravimetric and specific surface instrument have carried out sign results to it and shown：α-Al (OH) 3 and chitosan complexes are in Existing typical mesoporous characteristic, BET specific surface area is 55.4m2·g-1, BJH average pore sizes are 3.3nm；Specifically preparation method is：Claim Take 2.0g Aluminium chloride hexahydrates to be dissolved in the hydrochloric acid that 5.0mL pH value is 1, add 2.0g chitosans, then add 10.0mL distilled water Stirring, and the pH value of solution is adjusted to 1 with watery hydrochloric acid.Still aging 30min (solution becomes pasty state), with the NaOH that pH value is 14 The pH value of solution regulation solution has white flock precipitate generation, suction filtration washes away the NaOH of residual with distilled water, is put into baking to 8 Case, product is obtained after being incubated 5h at 120 DEG C.As above step, it is respectively 1 that chitosan and aluminium chloride mass ratio are prepared respectively:2、1:3、 2:1、3:1 product.
《The preparation of chitosan/oxidized aluminium composite aerogel and sign》(Chang Xinhong；The chemicalization engineering of Luoyang Normal College Institute,《Luoyang Normal College's journal》, 11 phases of volume 31 in 2012)：Using chitosan and inorganic aluminate AlCl3.6H2O as raw material, pass through Sol-gel process, is prepared for new chitosan/oxidized aluminium with CO2 supercritical dryings means and freeze-drying means respectively Composite aerogel.As a result show, the property such as specific surface area and pore volume of the content influence composite aerogel of chitosan, with shell The increase of glycan content, the specific surface area of mixing aeroge is gradually reduced.Ratio table of the different drying means to composite aerogel The properties such as area also have obvious influence.Composite aerogel contains micropore and mesoporous.CN201110022814.1 one kind has super The ordered mesoporous metal oxide material of large aperture, it is characterised in that utilize the amphipathic block with ultrahigh molecular weight hydrophobic section Copolymer is as structure directing agent, according to the principle of part assisted self assembling, before mesoporous material is made during solvent volatilizees Drive and acted between body and structure directing agent, and microphase-separated is differently formed according to hydrophilic and hydrophobic, ultimately form to be situated between in order and see knot Structure；Remove again after structure directing agent, form the ordered mesoporous metal oxide material with ultra-large aperture；Wherein, block copolymerization The molecular weight of the hydrophobic block of thing is more than 10000g/mol；The ordered mesoporous metal oxide material mesoporous pore size is in 10-50nm Between, mesoporous wall thickness of material is between 4-20nm.The hydrophilic block of the block copolymer is polyoxyethylene blocks；Institute The hydrophobic block for stating block copolymer is polystyrene or derivatives thereof, polyacrylate or derivatives thereof, polymethylacrylic acid One kind of ester or derivatives thereof, PLA pole or derivative, or two or more polymer described above copolymer.The invention system Standby is meso-porous alumina, and similar also has CN101153051A, CN1631796A, CN101134567A, CN101823706A, CN101863499A.CN201310258011.5 is related to a kind of tooth spherical alumina support, tooth ball-aluminium oxide hydrotreating and urged Agent and preparation method thereof, including following components：Peptizing agent, 0.5-4 parts by weight；Lubricant, 0.2-2 parts by weight；Dispersant, 0.2-3 parts by weight；Expanding agent, 0.3-4 parts by weight；Aluminium hydroxide, 100 parts by weight.Expanding agent is polyvinyl alcohol, polyacrylic acid One kind or mixture in sodium, starch derivatives or carbon black.The invention, which with the addition of anion surfactant, reduces various help Specific surface area increases 246m while agent composition addition2/ g, expanding agent Sodium Polyacrylate.Tooth spherical alumina described in the invention Alumina supporter, due to the wherein various auxiliary agents such as group such as peptizing agent, expanding agent, dispersant, anion surfactant is greatly lowered Point content, not only saved cost, it is also big with specific surface area, the advantages of high mechanical strength.The invention has used peptizing agent, Lubricant, dispersant, the reagent such as expanding agent, obtained alumina support is unimodal pore size distribution.CN201110116418.5 is carried A kind of mesoporous sphere aluminum oxide is supplied and the method for preparing the mesoporous sphere aluminum oxide is oriented to using template.Using oil column into Type method, is adding the template with guide function, Alumina gel is in shaping and aging into Alumina gel during preparing Alumina gel During, because the presence of the template with guide function makes to produce substantial amounts of meso-hole structure in alumina balls.Template For organic monomer or linear polymer, organic monomer is one kind in acrylic acid, ammonium acrylate, acrylamide, allyl alcohol.Jie Hole spherical alumina aluminum ratio surface is 150-300m2/ g, particle diameter 0.1-5mm, pore volume is 0.7-1.5ml/g, and bore dia is 2-40nm hole is more than 97%, and heap density is 0.30-0.80g/cm3, crushing strength is 70-250N/.The invention utilizes template Mesoporous sphere alumina pore diameter prepared by agent compares concentration, and this kind of mesoporous sphere aluminum oxide can be used for petrochemical industry and become more meticulous Work as catalyst or catalyst carrier.
Macroporous aluminium oxide and compound porous aluminum oxide have different journeys to activity, selectivity and the stability aspect of catalyst The improvement result of degree.Solubility of the polyvinyl alcohol template in water is influenceed by the degree of polymerization, causes it to be used for super big hole oxygen Also it is subject to certain restrictions in the preparation for changing aluminium.
CN200610029962.5 is related to a kind of method for full-cut fraction pyrolysis gasoline selective hydrogenation, mainly solves existing Have in technology to exist and be difficult to the technical problem that the full-cut fraction pyrolysis gasoline high to colloid and free water content carries out selective hydrogenation. The present invention is by using using the drippolene and hydrogen of the hydrocarbon compound cut of C5 hydrocarbon-do for 204 DEG C as raw material, in reaction temperature Spend for 30-80 DEG C, reaction pressure is 2.0-3.0MPa, green oil air speed is 2.5-5.0 hours- 1, hydrogen/oil volume ratio is 60- 120：Under conditions of 1, raw material is contacted with catalyst, is reacted, and makes the diolefin in raw material and the conversion of alkylene aromatic component Into monoolefine and alkylaromatic hydrocarbon, wherein catalyst includes alumina support, activity component metal palladium or its oxide, at least one Selected from IA in the periodic table of elements or IIA element or its oxide, at least one IVA in the periodic table of elements or VA element Or its oxide, carrier specific surface area is 40-160 meters2/ gram, total pore volume is 0.3-1.2 mls/g, and carrier has composite holes The technical scheme of distribution, preferably solves the problem, in the industrial production available for full-cut fraction pyrolysis gasoline selective hydrogenation. The preparation method of catalyst of the present invention is identical with common lamella catalyst dipping technique：First with a kind of liquid that can be dissolved each other with maceration extract Body presoaks carrier, then with the salt solution impregnation containing palladium, the carrier after dipping is scrubbed, drys, in atmosphere 300-600 DEG C roast Burning produces oxidative catalyst finished product.It is that can be used that finished catalyst, which only need to lead to hydrogen reducing in the reactor,.The present invention is used Catalyst there is composite pore structural, it is larger can several apertures, and rich in abundant mesoporous.The present invention catalyst for With good low temperature active, selectivity and stability during full-cut fraction pyrolysis gasoline selective hydrogenation, and resist with good Interference, resistance to high colloid and high content free water performance.In 40 DEG C of inlet temperature, reaction pressure 2.7Mpa, hydrogen/oil volume ratio 80：1, green oil air speed is that 150 milligrams/100 grams oil, free water contents are under the conditions of 3.8 hours -1, to gum level 1000ppm full cut (the hydrocarbon compound cut of C5 hydrocarbon-do for 204 DEG C) drippolene carries out selective hydrogenation reaction, and it goes out Mouth diene average value is 0.0 gram of iodine/100 gram oil, and diolefin hydrogenation rate is 100%, achieves preferable technique effect.The invention is carried The preparation method of body includes in the desired amount mixing aluminum oxide and modifying agent, peptizing agent, water, after extruded moulding, first in 50-120 Dried at DEG C 1-24 hours, be then calcined 1-10 hours at 800-1150 DEG C, obtain alumina support.The invention is not clear and definite Record in modifying agent, peptizing agent, embodiment 1 and used polyvinyl alcohol, thus know that the invention has the carrier of compound pore size distribution Obtained with polyvinyl alcohol.Mainly solve to exist in the prior art and be difficult to the full cut high to colloid and free water content and split Solve the technical problem that gasoline carries out selective hydrogenation.It is similar also have CN200610029963.X and CN200610029961.0.A kind of unsaturated hydrocarbon selective hydrogenation catalysts of CN200810114744.0 and preparation method thereof.This is urged Agent includes following components using aluminum oxide as carrier on the basis of the gross weight of catalyst：Using palladium as active component, palladium content is 0.1-1.0%, rare earth metal content is 0.3-8.0%, and alkaline earth metal content is 0.1-5.0%, and fluorine can be also contained in addition, and fluorine contains Measure as 0-3.0%.Catalyst carrier is θ or mixes crystal formation Al2O3, based on θ crystal formations.Palladium catalyst distribution is preferably in catalysis The secondary outer layer of agent；The catalyst has certain anti-impurity and anticoking capability；The catalyst is applied to full-cut fraction pyrolysis gasoline one Section selective hydrogenation process, is also applied for unsaturated hydrocarbons selective hydrogenation process in other distillates.
CN200610118522.7 is related to a kind of Raney nickel with composite pore structural for selective hydrogenation, mainly The low temperature active that solves to exist in the prior art catalyst is low, antijamming capability is weak, hold that glue ability is low, stability is poor, resistance to free The technical problem of water poor performance.The present invention is by using by weight percentage including following components：(a) 5.0-40.0% gold Belong to nickel or its oxide；(b) 0.01-20.0% be selected from least one of molybdenum or tungsten element or its oxide；(c)0.01- 10.0% selected from least one of rare earth element or its oxide；(d) the 0.01-2.0% IA in the periodic table of elements Or at least one of IIA element or its oxide；(e) 0-15.0% selected from least one of silicon, phosphorus, boron or fluorine element Or its oxide；(f) 0-10.0% at least one of IVB elements in the periodic table of elements or its oxide；(g) surplus Alumina catalyst support, wherein the total pore volume of carrier be 0.5-1.2 mls/g, the pore volume that 30 nanometers of bore dia ＜ accounts for total pore volume 5-65%, the pore volume that 30-60 nanometers of bore dia accounts for the 20-80% of total pore volume, and the pore volume that 60 nanometers of bore dia ＞ accounts for total pore volume 20-50% technical scheme preferably solves the problem, in the industrial production available for drippolene selective hydrogenation. CN200710043944.7 is related to a kind of large hole nickel-based catalyst, mainly solves present in prior art that nickel content is low, activity , technical problem that average pore size small lower than surface.The present invention is by using a kind of nickel-base catalyst, and its preparation method includes successively Following steps：(a) under conditions of 45-80 DEG C of temperature, nickel salt aqueous solution or nickel ammine is added into Alumina gel, nickel is obtained Alumina gel；(b) pH value of regulation nickel Alumina gel is 3.0-11.0；(c) at 45-120 DEG C of temperature, nickel Alumina gel is through static aging Or heat resolve nickel ammine, obtain nickel alumina gel, gained gel is scrubbed, dry, reducing agent reduction or roasting after with also Former agent reduction obtains required nickel-base catalyst；Wherein, with catalyst weight, the content of metallic nickel or its oxide is 5- 75%；Ni/Al2O3 specific surface areas of catalyst are 0.3-1.5 mls/g in 2/ gram of 150-350 rice, pore volume, and average pore size is 4.0-25.0 nanometers, wherein can technical scheme of several pore-size distributions -3 nanometers and/or -12 nanometers of position preferably solve The problem, can be widely used for light oil distillate, heavy oil fraction, consaturated oil, drippolene especially crack carbon nine and its more than In the industrial production of hydrocarbon hydrotreating.
CN200610118523.1 is the present invention relates to a kind of method for full-cut fraction pyrolysis gasoline selective hydrogenation, mainly Solve to ask in the presence of the technology for being difficult to the full-cut fraction pyrolysis gasoline progress selective hydrogenation high to colloid and water content in the prior art Topic.The present invention is by using using the drippolene and hydrogen of the hydrocarbon compound cut of C5 hydrocarbon-do for 204 DEG C as raw material, anti- It is 40-60 DEG C to answer temperature, and reaction pressure is 2.0-3.0MPa, and green oil air speed is 3.75-5.0 hours- 1, hydrogen/oil volume ratio is 80-120：Under conditions of 1, raw material is contacted with catalyst, is reacted, and turns diolefin and alkylene aromatic component in raw material Monoolefine and alkylaromatic hydrocarbon are melted into, wherein catalyst includes alumina catalyst support, activity component metal nickel or its oxide, at least one Kind selected from least one of molybdenum or tungsten element or its oxide, at least one element in rare earth or its oxide, extremely It is few a kind of IA in the periodic table of elements or the element in IIA or its oxide, at least one in silicon, phosphorus, boron or fluorine Element or its oxide, the ratio surface of at least one element or its oxide in the periodic table of elements in IVB, wherein carrier Product is 100-180 meters2/ gram, total pore volume is 0.5-1.2 mls/g, and carrier has the technical scheme of compound pore size distribution, preferably Ground solves the problem, in the industrial production available for full-cut fraction pyrolysis gasoline selective hydrogenation.
The invention discloses a kind of method of selective hydrogenation of cracked gasoline by CN201310461242.6, it is characterised in that 35-120 DEG C of reaction temperature, reaction pressure 2.0-5.0MPa, green oil liquid air speed 1-16/ hours, hydrogen to oil volume ratio 25-300's Under the conditions of, drippolene C6-C8 and/or C5-C9 hydrocarbon compound midbarrel and/or the hydrocarbonylation of C5-204 DEG C of drippolene are closed The liquid phase stream and hydrogen of the full cut of thing are raw material and a kind of high-molecular organic material supported catalyst being fitted into fixed bed reactors Agent contact reacts.The CN200810102242.6 present invention provides a kind of full-cut fraction pyrolysis gasoline diolefin selection hydrogenation side Method, includes reduction, passivation and the application of process conditions of catalyst.Used catalyst is nickel series hydrogenating catalyst, catalyst warp Passivated rear provide uses again after reduction or reduction, and hydrogenation process conditions are：Liquid volume air speed≤4h-1, reactor inlet 40-130 DEG C of temperature, reaction pressure >=2MPa, hydrogen-oil ratio 100-500 (v/v)；Nickel catalyst is used using aluminum oxide as carrier Infusion process is prepared from, and is counted using catalyst weight as 100%, contains nickel oxide 14-20%, lanthana and/or cerium oxide 1-8% With VI B oxides additive 1-8%, silica 2-8%, alkaline earth oxide 1-8%, catalyst specific surface 60-150m2/ G, pore volume 0.4-0.6ml/g.Present invention also offers reduction of the catalyst on hydrogenation plant, passivating method.Herein using side Under method and process conditions, Raney nickel has good Hydrogenation, especially with stronger anti-impurity and anticol mass-energy power, and There is good stabilized hydrogenation performance.The CN201210349977.5 present invention is a kind of drippolene nickel system selective hydrocatalyst And preparation method thereof.Belong to the catalyst comprising metal or metal oxide or hydroxide.It is characterized in that with mesoporous-big Hole or double composite mesoporous ducts, carrier is made with aluminum oxide, using nickel as main active constituent, and molybdenum is to help active component, metal oxide For auxiliary agent, the weight percent of the drippolene nickel system selective hydrocatalyst constitutes as follows：Nickel oxide 15-19, molybdenum oxide 6.5-20.0, auxiliary agent, 2.2-4.5, aluminum oxide surplus；The auxiliary agent be one kind in potassium oxide, magnesia, lanthana or its The two or more combinations of meaning.Big, higher than surface there is provided a kind of pore volume, with good reactivity, hydrogenation reaction selectivity is high, Stability is good, excellent appearance arsenic, anticol ability, drippolene nickel system's selective hydrocatalyst and its system with compound duct Preparation Method.When the catalyst of the present invention is used for full-cut fraction pyrolysis gasoline selective hydrogenation, diolefin hydrogenation rate average out to 99%. CN200610118523.1 is mainly solved existing the present invention relates to a kind of method for full-cut fraction pyrolysis gasoline selective hydrogenation Exist in technology and be difficult to the technical problem that the full-cut fraction pyrolysis gasoline high to colloid and water content carries out selective hydrogenation.The present invention By using using the drippolene and hydrogen of the hydrocarbon compound cut of C5 hydrocarbon-do for 204 DEG C as raw material, it is in reaction temperature 40-60 DEG C, reaction pressure is 2.0-3.0MPa, and green oil air speed is 3.75-5.0 hours- 1, hydrogen/oil volume ratio is 80-120：1 Under conditions of, raw material is contacted with catalyst, is reacted, and the diolefin in raw material and alkylene aromatic component is changed into monoene Hydrocarbon and alkylaromatic hydrocarbon, wherein catalyst include alumina catalyst support, activity component metal nickel or its oxide, at least one and are selected from molybdenum Or at least one of tungsten element or its oxide, at least one element in rare earth or its oxide, at least one choosing Element or its oxide from the periodic table of elements in IA or IIA, at least one element in silicon, phosphorus, boron or fluorine or its Oxide, at least one element or its oxide in the periodic table of elements in IVB, the wherein specific surface area of carrier are 100- 180 meters 2/ gram, total pore volume is 0.5-1.2 mls/g, and carrier has the technical scheme of compound pore size distribution, preferably solves In the problem, the industrial production available for full-cut fraction pyrolysis gasoline selective hydrogenation.Carrier specific surface area is 120-160 rice 2/ Gram, total pore volume is 0.8-1.1 mls/g, and the pore volume that 30 nanometers of bore dia ＜ accounts for the 20-50% of total pore volume, and bore dia 30-60 receives The pore volume of rice accounts for the 20-45% of total pore volume, and the pore volume that 60 nanometers of bore dia ＞ accounts for the 25-45% of total pore volume.The preparation side of carrier Method includes in the desired amount mixing aluminum oxide and modifying agent, peptizing agent, water, after extruded moulding, 1- is first dried at 50-120 DEG C 24 hours, then it is calcined 1-10 hours at 700-1150 DEG C, obtains carrier.Modifying agent, peptization is not expressly recited in the invention Polyvinyl alcohol has been used in agent, embodiment, has thus known that there is the carrier of compound pore size distribution obtained with polyvinyl alcohol for the invention Arrive.The catalyst used for full cut (the hydrocarbon compound cut of C5 hydrocarbon-do for 204 DEG C) drippolene selectively plus With good low temperature active, selectivity and stability during hydrogen, and contain with good anti-interference, resistance to high colloid and Nai Gao Measure aqueous energy.
Prior art is mainly change support chemistry composition and type, and addition coagent to lift catalyst performance Energy.Because the impurity such as As, S, O, N and gum level are higher in drippolene, catalyst is set easily to inactivate, it is therefore desirable to crack vapour Oily catalyst has appearance glue ability good, the strong characteristic of anti-arsenic, sulfur resistive, suppression coking ability.
The content of the invention
The problem to be solved in the present invention is to provide a kind of nickel system selective hydrocatalyst, for one section of selection of drippolene Property hydrogenation.Active higher, selective more preferably to hold glue ability more preferably, anti-arsenic, sulfur resistive, the suppression coking of the catalyst in the reaction Ability is strong, and its preparation technology is easy, and the carrier of catalyst is the alumina support with macroporous structure, and catalyst is particularly suitable for use in Drippolene selective hydrogenation.
The present invention provides a kind of nickel system selective hydrocatalyst, and the catalyst includes the carrying alumina with macroporous structure Body and the metal active constituent nickel and tungsten being carried on carrier, gross weight of the content based on the catalyst of nickel oxide is 12- 22wt%, gross weight of the content based on the catalyst of tungsten oxide is 1.5-8wt%, and alumina support is used as expansion using chitosan Hole agent, synthesizes the alumina support with macroporous structure.There is macroporous aluminium oxide pore size can adjust, and macropore ratio can be with The characteristics of effectively controlling.
Preferably, the one-stage selective hydrogenation of gasoline splitting catalyst composition is：The content of nickel oxide is based on the catalysis The gross weight of agent is 15-20wt%, and gross weight of the content based on the catalyst of tungsten oxide is 2.5-6wt%.
Contain adjuvant component phosphorus and magnesium in a kind of alumina support with macroporous structure of the present invention, carrier, help The content of agent component phosphorus and magnesium accounts for the percentage composition respectively P of carrier quality2O50.1-2.5wt%, MgO 0.1-2.5wt%, Pore-size distribution 60-180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, pore volume 0.8-2.0ml/g, preferably 0.8-1.3ml/g or preferred 1.6-2.0ml/g, specific surface area 250-300m2/g.Carrier uses chitosan as expanding agent.
Preferably, adjuvant component cerium, adjuvant component cerium oxide are also contained in the alumina support with macroporous structure Content account for carrier quality percentage composition be 0.1-2.5wt%.
The preparation method of catalyst by active component nickel and tungsten dipping, can spray to load using methods such as dipping, sprayings On body, then catalyst is dried, is calcined and obtains described catalyst.Catalyst can be for example prepared according to the following steps： Alumina support of the solution dipping with macroporous structure of soluble nickeliferous and tungsten is prepared, is dried 3-9 hours through 110-160 DEG C, 400-650 DEG C is calcined 4-9 hours, finally gives catalyst prod.
In the preparation method of catalyst of the present invention, nickel used and the compound of tungsten can be disclosed of prior arts What a kind of compound suitable for catalyst processed, such as nickel nitrate, nickel sulfate, nickel acetate, the preferred ammonium tungstate of compound of tungsten.
The present invention has the alumina support of macroporous structure, and aperture can be by changing addition and the reaming of expanding agent The molecular size range of agent is adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-160nm, The scopes such as 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, 35-50%, the scope such as 55-75%.
The present invention also provides a kind of preparation method of the alumina support with macroporous structure, first, is acidified with acid solution Boehmite and sesbania powder, are then added in kneader and are well mixed by chitosan, add phosphoric acid, magnesium nitrate and mix molten The acid solution of chitosan-containing, is finally added in boehmite and mediates uniform, the addition of the acid solution containing expanding agent by liquid For the 0.1-8wt% of boehmite, preferably 0.2-5.0wt%, by extrusion-shaping-drying-roasting, obtain with macropore The alumina support of structure.
The preparation method of alumina support with macroporous structure may be incorporated into cerium, such as by cerous nitrate and magnesium nitrate one Play mixing to add in carrier, obtain the alumina support of phosphorous, magnesium, cerium.
The process of the acid solution acidified chitosan is as follows：First by chitosan expanding agent be added to 30-95 DEG C go from In sub- water, acid is added dropwise afterwards, until chitosan dissolving is complete, the acid solution containing expanding agent is obtained.The acid can be inorganic acid Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The addition of acid is advisable with that can be completely dissolved chitosan.Also may be used To select water soluble chitosan, such as carboxyl chitosan, chitosan salt, sulfated chitosan etc..Chitosan acid solution is best With ultrasonic oscillation or magnetic agitation.More than ultrasonic oscillation 10min, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent Ripple shakes or magnetic agitation, and expanding agent good dispersion, alumina support is more prone to macropore, and pore-size distribution more collects In, pore-size distribution is in 70-180nm.The addition of the sesbania powder is the 0.1-7wt% of boehmite.
Mediate or extrusion technique is that the acid solution containing expanding agent configured is added in sesbania powder and boehmite Well mixed, extrusion, shaping afterwards is dried 3-9 hours, 650-800 DEG C is calcined 4-8 hours, finally gives by 100-160 DEG C Alumina support with macroporous structure.
Alumina support of the present invention uses chitosan for expanding agent, and the alumina support of preparation contains macroporous structure, simultaneously Also contain meso-hole structure, macropore range is in 2-50nm, mesoporous ratio 15-75%, preferably 15-50%, be a kind of containing Jie-macropore Alumina support.And the not homogeneous aperture structure in aperture.
The alumina support with macroporous structure obtained using preparation method of the present invention, can also utilize phosphorus and magnesium Carrier surface is modified, the concentration of phosphorus and magnesium is unsuitable too high, and preferably configuration concentration is less than phosphorus when preparing complex carrier Acid and magnesium nitrate aqueous solution spray carrier surface, and carrier surface modification is preferably carried out as follows：Configure phosphoric acid and nitre Alumina support of the aqueous solution spray with macroporous structure of sour magnesium, obtains used additives phosphorus through drying, roasting and magnesium carries out surface Phosphorus pentoxide and content of magnesia are in 0.1- in modified alumina support, alumina support of the control with macroporous structure In the range of 2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is set to be internal phosphorus pentoxide and magnesia 1.1-1.6 times of content.
The above-mentioned alumina support containing adjuvant component phosphorus, magnesium and cerium, can also be entered using phosphorus, magnesium and cerium to carrier surface Row is modified, the aqueous solution spray carrier surface of configuration phosphoric acid, magnesium nitrate and cerous nitrate, and carrier is preferably carried out as follows Surface is modified：Alumina support of the aqueous solution spray with macroporous structure of phosphoric acid, magnesium nitrate and cerous nitrate is configured, through dry Dry, roasting obtains the alumina support that used additives phosphorus, magnesium and cerium carry out surface modification, carrying alumina of the control with macroporous structure The content of phosphorus pentoxide, magnesia and cerium oxide is all in the range of 0.1-2.5wt% in body, and makes the oxidation of carrier surface five The content of two phosphorus, magnesia and cerium oxide is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
Compared with prior art, the present invention has advantages below：
1st, catalyst carrier of the present invention is using chitosan as expanding agent, and expanding agent chitosan is cheap, and environmental protection It is nontoxic, it is adapted to industrialized production.The obtained alumina support with macroporous structure, pore size can adjust, and macropore ratio can Effectively to control.And carrier is also containing mesoporous, is a kind of Jie-macropore alumina supporter.Catalyst carrier has macroporous structure, Hold glue ability good, suppress coking ability by force, anti-arsenic, sulfur resistive effect are good.
2nd, the present invention can also in alumina support and carrier surface introduce cerium, make carrier surface cerium content higher than load Internal portion, should be prepared into one-stage selective hydrogenation of gasoline splitting catalyst with the alumina support of macroporous structure, and can suppress Olefinic polymerization, improves diolefin hydrogenation selectivity.
3rd, the alumina support with macroporous structure that the present invention is obtained, using phosphorus and magnesium or phosphorus, magnesium and cerium to big The alumina carrier surface of pore structure is modified, and makes carrier surface phosphorus pentoxide, magnesia, the content of cerium oxide be interior Portion's phosphorus pentoxide, magnesia, 1.1-1.6 times of cerium-oxide contents.Carrier surface is modified by the way of spray, energy The partial pore of enough effective peptization carrier surfaces, so advantageously reduces the micropore ratio of carrier surface, improve carrier surface be situated between- Macropore ratio, promotes carrier surface to produce more active sites load centres, effectively improves the utilization of active component nickel and tungsten Rate, improves drippolene selective hydrogenation activity.And concentration of component different structure inside and outside this carrier, make alkynes and alkadienes It is not easily accessed inside duct and occurs polymerisation blocking duct.Improvement to carrier surface should not use dipping method, and dipping is carried Body surface face can make large quantity of moisture enter carrier, not reach the purpose for improving carrier surface Jie-macropore ratio.
Brief description of the drawings
Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.
Embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as the limit to the present invention System.
Primary raw material used in catalyst is prepared to originate：Source chemicals used in the present invention are commercially available prod.
Embodiment 1
8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water first, acetic acid is added dropwise afterwards, until Chitosan dissolving is complete, obtains the acid solution containing expanding agent.Phosphatase 11 .46g, magnesium nitrate 7.35g are weighed respectively, by phosphoric acid and nitre Sour magnesium, which is dissolved completely in 70g distilled water, is made into phosphorous, magnesium the aqueous solution.Weigh 350g boehmite powder and 20.0g fields Cyanines powder is added in kneader, and is well mixed, and adds the mixed solution of phosphoric acid and magnesium nitrate, finally by the acid of chitosan-containing Solution, which is added in boehmite, to be mediated uniformly, is clover shape by kneading-extruded moulding.It is small that 8 are dried at 120 DEG C When, 700 DEG C are calcined 4 hours, obtain phosphorous and magnesium alumina support 1.Phosphorus pentoxide 0.5wt%, magnesia in carrier 1 0.8wt%.Alumina support specific surface area with macroporous structure is shown in Table 1 with pore-size distribution.
Ammonium tungstate, nickel nitrate are added into 120ml water, then adjusting pH value is impregnated ammonium tungstate, nickel nitrate whole dissolving Liquid；Maceration extract impregnated carrier is used again, 130 DEG C of drying after moisture are filtered dry, and 500 DEG C are calcined 5 hours, obtain catalyst 1.Catalyst 1 Constitute and be：The content 18wt% of the content 4.3wt% nickel oxide of tungsten oxide, alumina support content 77.7wt%
Embodiment 2
8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water, acetic acid is added dropwise afterwards, until shell gathers Sugar dissolving is complete, obtains the acid solution containing expanding agent.Phosphatase 11 .09g, magnesium nitrate 9.12g are weighed respectively, by phosphoric acid and magnesium nitrate It is dissolved completely in 70g distilled water and is made into phosphorous, magnesium the aqueous solution.Weigh 350g boehmite powder and 20.0g sesbania powders It is added in kneader, and is well mixed, add the mixed solution of phosphoric acid and magnesium nitrate, finally by the acid solution of chitosan-containing It is added in boehmite and mediates uniformly, is clover shape by kneading-extruded moulding.8 hours, 700 are dried at 120 DEG C DEG C roasting 4 hours, obtains phosphorous and magnesium alumina support 1.Recycle phosphorus and magnesium to be modified carrier surface, configure phosphorous Alumina support 1 of the aqueous solution spray with macroporous structure of acid and magnesium nitrate, is dried 8 hours, 700 DEG C of roastings 4 are small through 120 DEG C When obtain the content of the alumina support 2 that used additives phosphorus and magnesium carry out surface modification, carrier surface phosphorus pentoxide and magnesia It is 1.2 times of internal phosphorus pentoxide and content of magnesia.Alumina support specific surface area and aperture point with macroporous structure Cloth is shown in Table 1.
Nickeliferous and tungsten the solution impregnation of alumina carrier 2 of configuration, is dried 6 hours, 550 DEG C are calcined 5 hours at 120 DEG C, Obtain catalyst 2.Catalyst 2 is constituted：The content 15.5wt% of the content 6.5wt% nickel oxide of tungsten oxide, alumina support Content 78wt%
Embodiment 3
The preparation method of carrier is carried out according to embodiment 1.Difference is in carrier that adjuvant component also contains cerium, by water Soluble chitosan expanding agent is replaced by water-insoluble chitosan expanding agent, 30 points of magnetic stirrer of chitosan formic acid liquid Clock, obtains the alumina support 3 with macroporous structure.The content of adjuvant component phosphorus, magnesium and cerium accounts for the hundred of carrier quality in carrier Point content is respectively 1.8wt%, 2.0wt%, 0.6wt%.Its specific surface area is shown in Table 1 with pore-size distribution.
Nickeliferous and tungsten the solution impregnation of alumina carrier 3 of configuration, is dried 6 hours, 500 DEG C are calcined 6 hours at 120 DEG C, Obtain catalyst 3.Catalyst 3 is constituted：The content 14wt% of the content 5.5wt% nickel oxide of tungsten oxide, alumina support contains Measure 80.5wt%
Embodiment 4
The preparation method of carrier is carried out according to embodiment 3.Difference is water soluble chitosan expanding agent being replaced by Water-insoluble chitosan expanding agent, chitosan acetic acid solution ultrasonic oscillation 15 minutes.Obtain the aluminum oxide with macroporous structure Carrier.The percentage composition that the content of adjuvant component phosphorus, magnesium and cerium accounts for carrier quality in carrier be respectively 1.6wt%, 1.6wt%, 0.6wt%.Recycle phosphorus, magnesium and cerium to be modified carrier surface, obtain carrier 4, the surface phosphorus pentoxide of carrier 4, oxidation The content of cerium and magnesia is 1.5 times of internal phosphorus pentoxide, cerium oxide and content of magnesia.Oxidation with macroporous structure The specific surface area of alumina supporter 4 is shown in Table 1 with pore-size distribution.
Nickeliferous and tungsten the solution impregnation of alumina carrier 4 of configuration, is dried 7 hours, 480 DEG C are calcined 7 hours at 125 DEG C, Obtain catalyst 4.Catalyst 4 is constituted：The content 20wt% of the content 3.0wt% nickel oxide of tungsten oxide, alumina support contains Measure 77wt%
The alumina support specific surface area and pore-size distribution of the macropore of table 1
Catalyst 1-4 is respectively charged into the adiabatic bed reaction devices of 100ml, 7 are reduced under 450 DEG C of hydrogen atmospheres of temperature small When, cool to after 50 DEG C with hexamethylene 3 hours laggard feedstock oil of passivation, drippolene C5-C9Cut, diene content is 37.53g Iodine/100g oil, iodine value are that 86.6g iodine/100g oil, gum level are that 45mg/100ml oil, sulfur content are 123ppm and arsenic content For 106ppb；Reaction process condition is：50 DEG C of inlet temperature, hydrogen to oil volume ratio 110：1, reaction pressure 2.8MPa, green oil are empty Fast 3.5h-1；Operate after 150h, the diene of the hydrogenated products of catalyst 1 is 1.10 grams of iodine/100 gram oil, and iodine value is 38.2g iodine/100g Oil；The diene of the hydrogenated products of catalyst 2 is 0.95 gram of iodine/100 gram oil, and iodine value is 37.3g iodine/100g oil；The hydrogenation production of catalyst 3 The diene of product is 0.88 gram of iodine/100 gram oil, and iodine value is 37.8g iodine/100g oil；The diene of the hydrogenated products of catalyst 4 is 0.91 gram Iodine/100 gram oil, iodine value is 36.6g iodine/100g oil.Feedstock oil gum level be 45mg/100ml oil, sulfur content be 123ppm With arsenic content under the conditions of 106ppb, the diene of hydrogenated products is not higher than 1.10 grams of iodine/100 gram oil left and right, and iodine value is not higher than 38.2g iodine/100g is oily, and catalyst activity is higher, and selectivity more preferably, holds glue ability more preferably, anti-arsenic, sulfur resistive, suppression coking ability By force.
After catalyst 1-4 operatings 420h, the diene of the hydrogenated products of catalyst 1 is 1.15 grams of iodine/100 gram oil, and iodine value is 38.5g iodine/100g oil；The diene of the hydrogenated products of catalyst 2 is 0.98 gram of iodine/100 gram oil, and iodine value is 37.5g iodine/100g oil； The diene of the hydrogenated products of catalyst 3 is 0.89 gram of iodine/100 gram oil, and iodine value is 38.2g iodine/100g oil；The hydrogenated products of catalyst 4 Diene be 0.93 gram of iodine/100 gram oil, iodine value is 36.8g iodine/100g oil.Catalyst appearance glue ability is good, anti-arsenic, sulfur resistive, suppression Coking ability is strong, catalyst performance stabilised.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art Protection scope of the present invention should all be belonged to.

Claims (9)

1. a kind of nickel system selective hydrocatalyst, it is characterised in that：
Catalyst includes the alumina support with macroporous structure and the metal active constituent nickel and tungsten that are carried on carrier, oxidation Gross weight of the content of nickel based on the catalyst is 12-22wt%, and gross weight of the content based on the catalyst of tungsten oxide is 1.5-8wt%, alumina support, as expanding agent, contains auxiliary agent group using chitosan in the alumina support with macroporous structure The content of point phosphorus and magnesium, adjuvant component phosphorus and magnesium accounts for the percentage composition respectively P of carrier quality2O50.1-2.5wt%, MgO 0.1-2.5wt%, pore-size distribution 60-180nm, macropore ratio 2-75%, pore volume 0.8-2.0ml/g, specific surface area 250- 300m2/g。
2. a kind of nickel system selective hydrocatalyst according to claim 1, it is characterised in that：The catalyst composition For：Gross weight of the content of nickel oxide based on the catalyst is 15-20wt%, gross weight of the content based on the catalyst of tungsten oxide Measure as 2.5-6wt%.
3. the preparation method of catalyst described in a kind of claim 1, it is characterised in that：Comprise the following steps：Solubility is prepared to contain Alumina support of the solution dipping with macroporous structure of nickel and tungsten, is dried 3-9 hours, 400-650 DEG C of roasting through 110-160 DEG C 4-9 hours, finally give catalyst prod.
4. a kind of nickel system selective hydrocatalyst according to claim 1, it is characterised in that：It is described that there is macroporous structure Alumina support in also contain adjuvant component cerium, the percentage composition that the content of adjuvant component cerium oxide accounts for carrier quality is 0.1- 2.5wt%.
5. a kind of nickel system selective hydrocatalyst according to claim 1, it is characterised in that：The alumina support is same When also contain meso-hole structure, macropore range is in 5-50nm, mesoporous ratio 15-75%.
6. a kind of nickel system selective hydrocatalyst according to claim 1, it is characterised in that：It is described that there is macroporous structure The preparation method of alumina support comprise the following steps：First, use acid solution acidified chitosan, then by boehmite and Sesbania powder is added in kneader and is well mixed, and the mixed solution of phosphoric acid and magnesium nitrate is added, finally by the acid of chitosan-containing Solution, which is added in boehmite, to be mediated uniformly, and the addition of the acid solution containing expanding agent is the 0.1- of boehmite 8wt%, by extrusion-shaping-drying-roasting, obtains the alumina support with macroporous structure.
7. a kind of nickel system selective hydrocatalyst according to claim 6, it is characterised in that：The acid solution is acidified shell The process of glycan is as follows：Chitosan expanding agent is added in 30-95 DEG C of deionized water first, acid is added dropwise afterwards, until shell Glycan dissolving is complete, obtains the acid solution containing expanding agent.
8. a kind of nickel system selective hydrocatalyst according to claim 4, it is characterised in that：It is described that there is macroporous structure The preparation method of alumina support comprise the following steps：First, use acid solution acidified chitosan, then by boehmite and Sesbania powder is added in kneader and is well mixed, and adds the mixed solution of phosphoric acid, magnesium nitrate and cerous nitrate, will finally contain shell and gather The acid solution of sugar, which is added in boehmite, to be mediated uniformly, and the addition of the acid solution containing expanding agent is boehmite 0.1-8wt%, by extrusion-shaping-drying-roasting, obtains the alumina support with macroporous structure.
9. a kind of nickel system selective hydrocatalyst according to claim 8, it is characterised in that：Claim 8 is obtained The alumina support with macroporous structure, carrier surface is modified using phosphorus, magnesium and cerium：Configure phosphoric acid, magnesium nitrate With alumina support of the aqueous solution spray with macroporous structure of cerous nitrate, obtain used additives phosphorus, magnesium and cerium through drying, roasting and enter Phosphorus pentoxide, magnesia and oxidation in the alumina support that row surface is modified, alumina support of the control with macroporous structure The content of cerium makes the content of carrier surface phosphorus pentoxide, magnesia and cerium oxide be all in the range of 0.1-2.5wt% 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
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CN114126756A (en) * 2019-07-31 2022-03-01 Ifp 新能源公司 Catalyst comprising an active nickel phase and a nickel-copper alloy in the form of small particles distributed in a shell
CN114126756B (en) * 2019-07-31 2023-12-19 Ifp 新能源公司 Catalyst comprising an active nickel phase in the form of small particles distributed in a shell and a nickel-copper alloy
CN114206497B (en) * 2019-07-31 2023-10-31 Ifp 新能源公司 Catalyst comprising active nickel phase distributed in shell
CN114206497A (en) * 2019-07-31 2022-03-18 Ifp 新能源公司 Catalyst comprising an active nickel phase distributed in a shell
CN114206491A (en) * 2019-07-31 2022-03-18 Ifp 新能源公司 Catalyst comprising an active nickel phase in the form of small particles distributed in a shell
CN113559889A (en) * 2020-04-28 2021-10-29 中国石油化工股份有限公司 Modified phosphorus-containing pseudo-boehmite, preparation method thereof, modified phosphorus-containing alumina and hydrogenation catalyst
CN113559889B (en) * 2020-04-28 2023-09-05 中国石油化工股份有限公司 Modified phosphorus-containing pseudo-boehmite, preparation method thereof, modified phosphorus-containing alumina and hydrogenation catalyst
CN114433051B (en) * 2020-10-19 2023-05-05 中国石油化工股份有限公司 Magnesia-containing alumina carrier, and preparation method and application thereof
CN114433051A (en) * 2020-10-19 2022-05-06 中国石油化工股份有限公司 Magnesium-containing alumina carrier and preparation method and application thereof
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CN114433094A (en) * 2020-10-20 2022-05-06 中国石油化工股份有限公司 High-activity nickel catalyst and preparation method and application thereof
CN114433094B (en) * 2020-10-20 2024-01-09 中国石油化工股份有限公司 Nickel catalyst and preparation method and application thereof
CN114433095B (en) * 2020-10-20 2024-05-03 中国石油化工股份有限公司 Nickel catalyst and preparation method and application thereof
CN113477254A (en) * 2021-06-10 2021-10-08 中国船舶重工集团公司第七一九研究所 Three-dimensional ordered macroporous structure Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Catalyst and preparation method thereof
CN114192184A (en) * 2021-12-31 2022-03-18 新疆理工学院 Cracking catalyst and preparation method and application thereof
CN114192184B (en) * 2021-12-31 2023-08-11 新疆理工学院 Cracking catalyst and preparation method and application thereof
CN115069263A (en) * 2022-07-25 2022-09-20 东营科尔特新材料有限公司 Nickel-based catalyst, preparation method thereof and application thereof in butadiene selective hydrogenation
CN115069263B (en) * 2022-07-25 2023-07-25 东营科尔特新材料有限公司 Nickel-based catalyst, preparation method thereof and application thereof in butadiene selective hydrogenation
CN115608329A (en) * 2022-09-22 2023-01-17 四川大学 Novel preparation method of through hierarchical porous polysaccharide microspheres
CN115608329B (en) * 2022-09-22 2024-01-26 四川大学 New preparation method of polysaccharide microsphere penetrating through multistage holes

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