CN107185567B - 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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CN107185567B
CN107185567B CN201710408450.8A CN201710408450A CN107185567B CN 107185567 B CN107185567 B CN 107185567B CN 201710408450 A CN201710408450 A CN 201710408450A CN 107185567 B CN107185567 B CN 107185567B
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alumina support
catalyst
magnesium
alumina
cerium
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CN107185567A (en
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晁会霞
张海燕
颜曦明
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Qinzhou University
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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
    • B01J35/615—
    • B01J35/635—
    • B01J35/638—
    • B01J35/651—
    • 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

Abstract

The present invention relates to a kind of nickel system selective hydrocatalysts, catalyst includes the alumina support and the metal active constituent nickel being carried on carrier and tungsten with macroporous structure, total weight of the content of nickel oxide based on the catalyst is 12-22wt%, total weight of the content of tungsten oxide based on the catalyst is 1.5-8wt%, alumina support is using chitosan as expanding agent, contain adjuvant component phosphorus and magnesium in alumina support with macroporous structure, it is respectively P that the content of adjuvant component phosphorus and magnesium, which accounts for the percentage composition of carrier quality,2O50.1-2.5wt%, MgO 0.1-2.5wt%, pore-size distribution 60-180nm, macropore ratio 2-75%, Kong Rong 0.8-2.0ml/g, specific surface area 250-300m2/g.Catalyst appearance glue ability is more preferable, and anti-arsenic, inhibits coking ability strong at sulfur resistive.

Description

A kind of nickel system selective hydrocatalyst and preparation method thereof
Technical field
The selective hydrogenation catalyst and preparation method thereof that the present invention relates to a kind of for petroleum hydrocarbon product, it is especially a kind of Nickel system selective hydrocatalyst is used for one-stage selective hydrogenation of gasoline splitting.
Background technique
Drippolene is the important by-product of steam cracking industrial production ethylene, propylene, including C5-C10 fraction.Drippolene It forms 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., a component more than totally 200, wherein benzene,toluene,xylene (being referred to as BTX) about 50-90%, no Saturated hydrocarbons 25-30%.It is the characteristics of according to a large amount of aromatic hydrocarbons are contained in drippolene, widely used, it both can be used as the tune of gasoline And component, high-octane gasoline is produced, separation production aromatic hydrocarbons etc. can also be passed through.
Since drippolene complicated composition, thermal stability are poor, in general, first removing alkadienes and benzene through one-stage selective hydrogenation Ethylene after Secondary hydrodesulfurization, is mainly used for Aromatics Extractive Project.Industrial catalyst for selective hydrogenation of cracked gasoline is mainly at present (C5 hydrocarbon-does the hydrocarbon for 204 DEG C for Pd system or Ni series catalysts, midbarrel (C6-C8 hydrocarbon compound fraction) plus hydrogen or full fraction Compound fraction) 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 especially (polymerization reaction 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 are larger differences；Some device raw pyrolysis gasoline dienes, colloid Height, and the toxic contents such as colloid and As, heavy metal are higher in some device raw pyrolysis gasoline raw materials, individual device raw pyrolysis gasoline The toxic contents such as diene, colloid and As, heavy metal are high.
Alkadienes and alkynes in drippolene are easy polymerization collagen at high temperature, are deposited on catalyst surface, Yi Zao At catalyst inactivation, it is necessary to frequently activation and regeneration.Pyrolysis gasoline hydrogenation catalyst mainly has Pd/Al2O3And Ni/Al2O3 Two kinds of catalyst.The advantages that Pd series catalysts have initial temperature low, and hydrogenation activity is big, and adaptation air speed is high, long service life, The catalyst mode for having industrial 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, it is then by processes such as dry, roastings that active component is oxide carried to carrier surface, logical hydrogen is needed before use 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 is due to using extensively with biggish cellular structure, higher specific surface area, good thermal stability 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 contains a kind of halogen, on the basis of carrier total amount, which contains the aluminium oxide of 95-99 weight %, based on the element, The halogen of 0.1-5 weight %, acid amount is less than 0.2 mM/gram.The preparation method of macropore alumina supporter includes by a kind of oxygen The precursor for changing aluminium is formed and is roasted, and before molding and roasting, the precursor of aluminium 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 maturing temperature is 600-850 DEG C, and calcining time 1-10 hours, respectively The dosage of component contains final alumina support, on the basis of carrier total amount, the aluminium oxide of 95-99 weight %, with element Meter, the halogen of 0.1-5 weight %.Organic expanding agent is selected from one of starch, synthetic cellulose, polymeric alcohol, surfactant Or it is several.Synthetic cellulose be selected from one of carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxylated cellulose or It is several.Polymeric alcohol is selected from one or more of polyethylene glycol, poly- propyl alcohol, polyvinyl alcohol, and surfactant is selected from poly alkyl alcohol Ethylene oxide ether, fatty alkanol amide, molecular weight be one of the acrylic copolymer of 200-10000, maleic acid copolymer or It is several.CN201110410339.5 provides a kind of high temperature-resistant active aluminum oxide material and preparation method thereof, the oxidation aluminium Material is made by following steps: after macropore boehmite, high viscous boehmite are mixed with additive with water, being in revolving speed It is stirred evenly under 100-1000r/min, adds the dilute nitric acid reaction that concentration is 30%, until pH is the peptization state of 2.0-5.5 When, it is aged 3-6h in the case where 80 DEG C of -100 DEG C of temperature stir, pore creating material is added at room temperature and stirs evenly, is slurrying, spraying, dry, It is roasted at 900 DEG C and aluminium oxide is made.The alumina material has many advantages, such as convenient for batch production and high-ratio surface.In 1000- Specific surface can be kept in 110m2/g or more for a long time at a temperature of 1100 DEG C；The technique mistake of the alumina material preparation method Journey is simple, low in cost.Wherein the sky agent of making is selected from polyvinyl alcohol, polyethylene glycol, polyacrylamide or methylcellulose One of, dosage is the 0-40% of oxide total weight in alumina material." Zhongshan University's journal " (2002,41 (2): Method 121-122) introduced is as follows: the polystyrene colloidal crystal microballoon that diameter is 600nm being placed on a buchner funnel, then will The ethanol solution of aluminum nitrate and citric acid is added drop-wise on glue crystalline substance under suction filtration, is allowed in its fully penetrated gap into microballoon, through dry Dry and roasting, removes polystyrene moulding, obtains macroporous aluminium oxide." Acta PhySico-Chimica Sinica " (2006,22 (7): 831-835) are situated between The method that the granular formwork method that continued prepares three-dimensional ordered macroporous alumina, this method are as follows: being obtained first using emulsion polymerization Aluminum nitrate plus weak aqua ammonia are made alumina sol, are then stirred the two by a certain percentage by polystyrene microsphere, ultrasound Processing, then through dry and roasting, obtain macroporous aluminium oxide.CN201010221302.3 (CN102311134A) discloses a kind of spherical shape Integral macroporous alumina and preparation method thereof.Method includes the following steps: by polymer microballoon lotion, alumina sol and Coagulant is mixed in a certain proportion uniformly, which is scattered in oily phase, is formed w/o type drop, is then reheated above-mentioned Mixed phase system makes the alumina sol gelling balling-up in water phase, isolates molding gel micro-ball from oily phase later, then in ammonia The spherical integral macroporous alumina is obtained after aged in aqueous medium, dry and roasting.The macropore diameter of the aluminium oxide Uniform 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 Row, convenient for being prepared on a large scale.Polymer microballoon diameter 50-1000nm, the type of polymer microballoon are polystyrene microsphere, polyphenyl The esters microballoons such as olefin(e) acid N-butyl microballoon, polyacrylate.Coagulant is hexamethylenetetramine, urea.Oily is mutually organic hydrocarbon. The invention mainly prepares Integral macroporous alumina, and macropore diameter is uniform controllable.Preparation process has used lipid microballoon And coagulant etc..Preparation process is complicated, and reagent raw material used is relatively more.Due to polymer microballoon make carrying alumina Internal portion cellular 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.Method includes the following steps: aluminium Source, polyethylene glycol and after being uniformly mixed selected from low-carbon alcohol and water at least one, will low-carbon epoxyalkane be added it is described mixed It closes in object, obtains Integral macroporous alumina through aging, immersion, drying and roasting.Of the invention preparation method is simple, ring Border pollution is small, its aperture of gained Integral macroporous alumina is controllable at 0.05-10 μm.Monoblock type macropore oxidation provided by the invention Object 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 disclose a kind of macropore hold, the preparation method of high-strength alumina, by the way that polyacrylamide, poly- is added The expanding agents such as vinyl alcohol, alkylcellulose, sesbania powder, starch are obtained containing eurypyloue alumina support, the dosage of expanding agent The 10-30% of aluminium oxide is accounted for, but not publicly specific pore diameter range.The although available preferable macropore oxidation of hard mould agent method Alumina supporter, but the dosage 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 is acted on, the dosage of template can be reduced with preparing the alumina support containing macroporous structure by the complementary reaming of hydro-thermal To 3-10%, but hydro-thermal is assisted to cause the raising of energy consumption.CN200310103035.X discloses a kind of macroporous aluminium oxide Preparation method carries out reaming using polyvinyl alcohol, poly- propyl alcohol, polyethylene glycol soft template, by the way that 1% polyethylene glycol is added, Kong Rong of the aperture greater than 100nm accounts for the 26.2% of total pore volume.Soft template has the advantages that dosage is low, reaming effect is good, still The solubility property of the alcohols soft template of higher molecular weight in water is poor, causes it to be used to expand super large porous aluminum oxide and is limited System.CN200910204238.5 (CN102040235) discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The party Then method fills certain party legal system the following steps are included: monodispersed polymer microballoon is assembled into glue crystal template into template Standby alumina sol most obtains macroporous aluminium oxide through dry and roasting afterwards.This method can be good at control Aluminum sol and The recombination process of Aluminum sol and polymer microballoon does not destroy the network structure of alumina gel as far as possible, makes prepared oxidation Aluminium not only has the macropore duct of three-dimensional order but also specific surface area with higher.The invention is burnt by the appropriateness to template The small fenestra tied and formed, 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 Conducive to the mass transfer ability of material in the catalyst is improved, be conducive to the activity and selectivity for improving catalyst. CN201410148773.4 discloses a kind of preparation method of aluminum oxide porous microballoon, comprising the following steps: 1) by surface-active Agent is dissolved in deionized water, stirring, as water phase；2) chelating agent, alumina precursor and n-octyl alcohol are mixed, is stirred, as Oily phase；3) Span80 and pore-foaming agent, stirring are added in oily phase；4) clear oil obtained by step 3) is mutually poured into water phase Continue stirring and emulsifying；5) step 4) gains are filtered by vacuum, it is dry after gained Washing of Filter Cake, obtain aluminum oxide porous microballoon.It should Microballoon has internal closing macroporous structure, and Microsphere Size is 1 μm -100 μm, and the invention is solidifying using the colloidal sol in pore-foaming agent and lotion Glue process obtains the metal porous microballoon with internal closing macroporous structure.Porous microsphere is prepared using phase separation principle.It is internal Closing aperture is 50nm-5 μm.Inside closing aperture is 50nm-5 μm.Aperture is closed 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 a large amount of surfactant, chelating agent, pore-foaming agent, and it is more to prepare raw material, and synthesis technology is complicated.
The above macroporous aluminium oxide mainly uses cellulose, polymeric alcohol, polystyrene etc. to prepare macropore oxygen as expanding agent Change aluminium.
Alumina support with macropore and mesoporous i.e. composite pore structural also compares more.CN 101200297A is disclosed The preparation method of integral macroporous alumina: reversed 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；Filled monolithic devices organic/inorganic composite is de- in 600 DEG C of -900 DEG C of roastings through drying Removing template obtains integral macroporous alumina.The advantages of this method is that preparation process is simple and easy, monoblock type macropore obtained The macropore duct that there is aluminium oxide micron order to interconnect, aperture are 1-50 μm.This method prepares Integral macroporous alumina letter It is single easy, but the volume fraction of water phase accounts for 75%-90% in this method, and correspondingly the volume fraction of organic monomer is relatively low, For this method while reducing organic monomer consumption, the preparation efficiency of prepared template is relatively low, and it is big to be unfavorable for subsequent step It is prepared by the batch of porous aluminum oxide.A kind of preparation method 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, Aluminum sol and boehmite powder It closes object and composite mould plate agent is mixed and roasted, the composite mould plate agent is mesoporous template and macroporous granules template, is given an account of Hole template is selected from polyethylene glycol propylene glycol-polyethylene glycol triblock polymer, polyethylene glycol, lauryl amine, hexadecane At least one of base trimethylammonium bromide, lauric acid, stearic acid and fatty alcohol polyoxyethylene ether, the macroporous granules template choosing It is greater than polystyrene microsphere, poly (methyl methacrylate) micro-sphere, particles of bioglass, pitch particle or the heavy oil of 50nm from partial size 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 aluminium oxide.The invention also discloses have mesoporous hole while preparation by the above method The alumina support in road and macropore duct, 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 that a kind of high specific surface area, gradient distribution hole and large hole are held is obtained after roasting Aluminium.The present invention is the most outstanding to be technically characterized in that using raw material solid phase reactive synthesis technique, as obtained by synthesis condition control The property of gama-alumina.Meanwhile the method for the present invention is simple, and it is easily operated, addition expanding agent is not needed, save the cost is suitble to work Industryization batch production.The preparation process of alumina support of the present invention the following steps are included: (1) aluminum nitrate, ammonium hydrogen carbonate and table Face activating agent is fully ground uniformly, and certain time is aged in the closed container of specific temperature and obtains precursor aluminium carbonate ammonium；(2) It will form after mixing after the drying of precursor aluminium carbonate ammonium obtained by (1) with peptizing agent, can generally be squeezed using banded extruder Item molding；(3) (2) are obtained that final alumina support is made in molding drying, aerobic roasting.Step lures described in (1) The polyethylene glycol that agent is liquid form is led, additional amount is equivalent to the 0.1-10.0% of aluminum nitrate weight.Carbonic acid described in step (2) The drying process of aluminium ammonium is 1-20 hours dry generally at 50-180 DEG C.Roasting process described in step (3) is in 350-900 It is roasted 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 generates gas, such as NH in decomposable process3And CO2, the generation and evolution 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 object in roasting process Matter slowly escapes, and does not easily cause carrier to collapse.Method is simple, does not need to add any physics expanding agent. CN201310097588.2 discloses a kind of gama-alumina particle and preparation method thereof: 1) aluminum soluble salt being dissolved in by acid In aqueous solution of the pH value of acidification less than or equal to 3, the amount that the aluminum soluble salt is added makes obtained containing aluminium in aluminum water solution The molar concentration of ion is 0.01-5mol/L；2) obtained containing alkaline precipitating agent, the alkali is added in aluminum water solution to step 1) Property precipitating reagent be added amount make reaction after solution ph between 5-12；3) the mixed sediment solution that step 2) obtains is existed At room temperature stir 0.1-3h after, be put into water-bath or water heating kettle, 50-150 DEG C at a temperature of be aged 6-24h；4) by step 3) solution after being aged is after mixing evenly, dry using spray drying process, and control inlet air temperature is 150-400 when spray drying DEG C, leaving air temp is 60-110 DEG C, and the thermal efficiency of spray drying is 50% or more；5) oxidation after the drying for obtaining step 4) Aluminium precursor powder is heated to 250 DEG C -350 DEG C at room temperature with first rate of heat addition, is then heated to second rate of heat addition 400 DEG C -800 DEG C, heat preservation 0.5-20h obtains final product gama-alumina particle；Wherein, first rate of heat addition is less than 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, and specific surface area is in 180m2/g-260m2In/g range, there is high-specific surface area.It is made Gama-alumina particle observed under scanning electron microscope have hollow foam shape pattern, and have micropore-mesopore-macropore it is compound Aperture structure.In this way, when gama-alumina is as catalyst carrier, 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, to accelerate Rate of catalysis reaction.The composite bore diameter structure refers to not only include micropore of the aperture less than 2nm, but also including aperture in 2nm-50nm Between it is mesoporous, further include aperture be greater than 50nm macropore.It further include making to obtained containing being added in aluminum water solution in step 1) Hole agent, the amount that the pore creating material is added that the molar concentration of pore creating material in rear solution is added to be aluminum ions molar concentration 0.01-5 times.The pore creating material is cetyl trimethylammonium bromide (CTAB), neopelex (SDBS), polyethylene One or more of alcohol (PVA), polyethylene glycol (PEG) and calgon.CN101863499A (201010187094.X) provides a kind of preparation method of macroporous-mesoporous alumina.The following steps are included: a. first helps reaction 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 Above-mentioned solution is added and dissolves, aluminium ion and template molar ratio are 1:0.015-0.025, and the pH value control of final solution exists 3.5-6.0；B. the solution by a step preparation carries out aging process, so that it is gradually removed organic solvent and moisture in system and obtains greatly 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 can realize controllable adjustment according to concrete application situation, thus more in petrochemical industry Mutually catalysis, adsorbing separation and have important application value as catalyst carrier, energy and material etc..It makes full use of anti- The space frame effect and coordination and intermediary's organic polymer, reaction promoter for answering auxiliary agent and template are 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 material is up to 250-320m2/g, duct rule, pore-size distribution in mesoporous 5-40nm, macropore 50-150nm, and Adjusting can be realized according to the actual situation.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 lauric acid.Triblock copolymer is P123 or F127.Tie-Zhen Ren etc. (Langmuir, 2004,20:1531-1534) uses nonionic surfactant 56 aluminium secondary butylate of Brij uses hydro-thermal method and Microwave-assisted synthesis macroporous-mesoporous alumina in acid condition, synthesis it is porous 0.8-2 μm of alumina powder macropore diameter, mesoporous pore size 5-8nm, 0.4-1.4 μm of hole wall of aluminium oxide.Its deficiency is aluminium-alcohol salt Expensive, the macroporous-mesoporous alumina Kong Rong little of synthesis, duct is irregular, pore-size distribution is excessive and cannot achieve pore structure Effective adjusting thus have significant limitation in using effect and range.Jean-Philippe Dacquin etc. It using P123 is template in mixed solution that (J.Am.Chem.Soc., 2009,131:12896-12897), which uses sol-gel method, 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 secondary size for introducing polystyrene drop completely, i.e. macropore diameter Size depends on polystyrene droplet size.Organic molecule in the change of the part to solution itself component and system can not be passed through It interacts to realize the adjustment in aperture.Huining Li et al. (Inorganic Chemistry, 2009,48:4421) is equally adopted The polymethyl methacrylate with single dispersed phase is introduced in mixed solution with sol-gel method by template of F127 (PMMA) droplet realizes the formation of macropore in macroporous-mesoporous alumina, shortcoming be macropore diameter size also completely by Secondary introducing polymethyl methacrylate droplet size determines, can not be changed by the part to solution system itself component come real The adjustment in existing aperture also cannot achieve the controllable of foramen magnum-mesoporous aperture to realize the formation of foramen magnum-mesoporous composite pore structural Adjust, in use, in particular for complicated ingredient bulky molecular catalysis during by significant limitation.
The above composite holes alumina support generally uses organic polymer such as polyvinyl alcohol, polymethylacrylic acid etc. as mould Plate agent either expanding agent.So that the preparation of composite holes and macroporous aluminium oxide material there are the monomer of template have certain toxicity, The problems such as template consumption is larger, preparation cost is higher, preparation process is cumbersome.Meanwhile there is also the discharges in roasting process The problem of object environmental pollution.Also there is the patent that saccharide compound is added in polymer microballoon lotion.
CN201310142454.8 discloses a kind of preparation method of alumina hollow ball, and it is water-soluble to prepare chitosan-acetic acid- Liquid；By polystyrene spheres: chitosan-acetic acid-aqueous solution be 5:1-10:1 mass ratio, press polystyrene spheres: alpha-alumina Body is that the mass ratio of 1:5-1:15 takes each raw material；Polystyrene spheres and chitosan-acetic acid-aqueous solution are mixed, polyphenyl is made Ethylene ball surface uniformly coats one layer of chitosan-acetic acid-aqueous solution；It is coated with chitosan-acetic acid-aqueous solution polyphenyl second again In alkene ball and alpha-alumina powder investment ball-milling device, with the revolving speed rotation cladding 2-24h of 5-30r/s, obtained core-shell structure copolymer ball；It will After the calcining of core-shell structure copolymer ball warp, the alumina hollow ball that diameter is 0.2-2mm, wall thickness is 20-100 μm is obtained. CN201110170283.0 discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The three-dimensional ordered macroporous oxidation Aluminium, diameter macropores 50-1000nm, grain diameter 1-50mm, mechanical strength 80-280g/mm.This method includes following step It is rapid: saccharide compound and the concentrated sulfuric acid will to be added into monodisperse polymer micro-sphere lotion, obtain polymer-modified microballoon glue crystalline substance mould Plate is subsequently filled alumina sol, then through aging and roasting, obtains three-dimensional ordered macroporous alumina.The polymer microballoon Diameter is 50-1000nm, can be used polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polyacrylic acid N-butyl microballoon and One of different monooctyl ester microballoon of polyacrylic acid is a variety of, preferably polystyrene microsphere.The monodisperse refers to polymer microballoon The standard deviation of diameter is not more than 10%.The carbohydrate organic matter be one of Soluble Monosaccharide and polysaccharide or a variety of, preferably For one of sucrose, glucose, chitosan or a variety of.This method can increase substantially the adhesion amount of aluminium oxide precursor, increase The strong mechanical strength of material, it is subtle 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 adsorbent material field using more." mesoporous chitosan-aluminium hydroxide is compound 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, it is prepared for 3 composite material of chitosan and α-Al (OH).With X-ray powder diffraction, Transmission electron microscope, infrared, thermogravimetric and specific surface instrument characterization has been carried out to it the result shows that: α-Al (OH) 3 and chitosan complexes are in Now typical mesoporous characteristic, BET specific surface area 55.4m2·g-1, BJH average pore size is 3.3nm；Specifically the preparation method comprises the following steps: claiming It takes 2.0g Aluminium chloride hexahydrate to be dissolved in the hydrochloric acid that 5.0mL pH value is 1,2.0g chitosan, then plus 10.0mL distilled water is added Stirring, and the pH value of solution is adjusted to 1 with dilute hydrochloric acid.Still aging 30min (solution becomes paste), the NaOH for being 14 with pH value Solution adjusts the pH value of solution to 8, has white flock precipitate generation, filters, wash away remaining NaOH with distilled water, be put into baking Case obtains product after 120 DEG C of heat preservation 5h.Step as above, prepare chitosan respectively and aluminium chloride mass ratio be respectively 1:2,1:3, The product of 2:1,3:1.
" preparation and characterization of chitosan/oxidized aluminium composite aerogel " (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 novel chitosan/oxidized aluminium with CO2 supercritical drying means and freeze-drying means respectively Composite aerogel.The result shows that the content of chitosan influences the properties such as specific surface area and the pore volume of composite aerogel, with shell The increase of glycan content, the specific surface area for mixing aeroge are gradually reduced.Ratio table of the different drying means to composite aerogel The properties such as area also have apparent 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 ligand assisted self assembling, before making mesoporous material during solvent volatilization It drives and is acted between body and structure directing agent, and microphase-separated is differently formed according to hydrophilic and hydrophobic, ultimately form orderly to be situated between and see knot Structure；After removing structure directing agent again, the ordered mesoporous metal oxide material with ultra-large aperture is formed；Wherein, block copolymerization The molecular weight of the hydrophobic block of object is greater 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 The copolymer of ester or derivatives thereof, one kind of polylactic acid pole or derivative or two or more polymer described above.The invention system Standby is meso-porous alumina, similar also CN101153051A, CN1631796A, CN101134567A, CN101823706A, CN101863499A.CN201310258011.5 is related to a kind of tooth spherical alumina support, tooth ball-aluminium oxide hydrotreating is urged Agent and preparation method thereof, including following components: peptizing agent, 0.5-4 parts by weight；Lubricant, 0.2-2 parts by weight；Dispersing agent, 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 of sodium, starch derivatives or carbon black or mixture.The invention, which is added to anionic surfactant, reduces various help Specific surface area increases 246m while agent ingredient additive amount2/ g, expanding agent Sodium Polyacrylate.The oxidation of tooth spherical shape described in the invention Alumina supporter, since the wherein groups such as various auxiliary agents such as peptizing agent, expanding agent, dispersing agent, anionic surfactant are greatly lowered The content divided, has not only saved cost, has also had many advantages, such as large specific surface area, high mechanical strength.The invention has used peptizing agent, Lubricant, dispersing agent, the reagents such as expanding agent, obtained alumina support are unimodal pore size distributions.CN201110116418.5 is mentioned It has supplied a kind of mesoporous sphere aluminium oxide and has been oriented to the method for preparing the mesoporous sphere aluminium oxide using template.Using oil column at The template with guide function is added in type method during preparing Aluminum sol into Aluminum sol, and Aluminum sol is in molding and aging In the process, since the presence of the template with guide function makes to produce a large amount of meso-hole structure in alumina balls.Template For organic monomer or linear polymer, organic monomer is one of acrylic acid, ammonium acrylate, acrylamide, allyl alcohol.Jie Hole ball-aluminium oxide specific surface is 150-300m2/ g, particle diameter 0.1-5mm, pore volume 0.7-1.5ml/g, bore dia are The hole of 2-40nm is greater than 97%, and heap density is 0.30-0.80g/cm3, crushing strength is 70-250N/.The invention utilizes template The mesoporous sphere alumina pore diameter of agent preparation compares concentration, this kind of mesoporous sphere aluminium oxide can be used for petrochemical industry and fining Work is 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.The solubility of polyvinyl alcohol template in water is influenced by the degree of polymerization, it is caused to be used for super big hole oxygen Change and is also subject to certain restrictions in the preparation of aluminium.
CN200610029962.5 is related to a kind of method for full-cut fraction pyrolysis gasoline selective hydrogenation, mainly solves existing Have and there is technical issues that be difficult to the full-cut fraction pyrolysis gasoline progress high to colloid and free water content in technology. The present invention as raw material, is reacting temperature by using the drippolene and hydrogen for doing the hydrocarbon compound fraction for 204 DEG C using C5 hydrocarbon- Degree is 30-80 DEG C, reaction pressure 2.0-3.0MPa, and green oil air speed is 2.5-5.0 hours- 1, hydrogen/oil volume ratio is 60- Under conditions of 120:1, raw material is contacted with catalyst, is reacted, and diolefin and the conversion of alkylene aromatic component in raw material are made At monoolefine and alkylaromatic hydrocarbon, wherein catalyst includes alumina support, activity component metal palladium or its oxide, at least one The element of element or its oxide, at least one IVA in the periodic table of elements or VA selected from IA in the periodic table of elements or IIA Or its oxide, carrier specific surface area are 40-160 meters2/ gram, total pore volume is 0.3-1.2 mls/g, and carrier has composite holes The technical solution of distribution, preferably solves the problems, such as this, can be used in the industrial production of full-cut fraction pyrolysis gasoline selective hydrogenation. The preparation method of catalyst of the present invention is identical as common lamella catalyst dipping technique: first with a kind of liquid that can be dissolved each other with maceration extract Body presoaks carrier, then uses salt solution impregnation containing palladium, the carrier after dipping is washed, it is dry, in air 300-600 DEG C roast It burns up to oxidative catalyst finished product.Finished catalyst need to only lead to hydrogen reducing in the reactor can be used.The present invention uses Catalyst there is composite pore structural, it is biggish can several apertures, and rich in abundant mesoporous.Catalyst of the invention is being used for There is good low temperature active, selectivity and stability when full-cut fraction pyrolysis gasoline selective hydrogenation, and have good anti- 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 is that 150 milligrams/100 grams oil, free water contents are to gum level under the conditions of green oil air speed 3.8 hours -1 Full fraction (the hydrocarbon compound fraction that C5 hydrocarbon-is done as the 204 DEG C) drippolene of 1000ppm carries out selective hydrogenation reaction, goes out Mouth diene average value is 0.0 gram of iodine/100 gram oil, and diolefin hydrogenation rate is 100%, achieves preferable technical effect.The invention carries The preparation method of body includes mixing aluminium oxide and modifying agent, peptizing agent, water, after extruded moulding in the desired amount, first in 50-120 It is 1-24 hours dry at DEG C, it is then roasted 1-10 hours at 800-1150 DEG C, obtains alumina support.The invention is not clear Modifying agent, peptizing agent are recorded, has used polyvinyl alcohol in embodiment 1, thus knows that the invention has the carrier of compound pore size distribution It is obtained with polyvinyl alcohol.It mainly solves to exist in the prior art to be difficult to the full fraction high to colloid and free water content and split Solve the technical issues of gasoline carries out selective hydrogenation.It is similar there are also CN200610029963.X and CN200610029961.0.A kind of unsaturated hydrocarbon selective hydrogenation catalyst of CN200810114744.0 and preparation method thereof.This is urged Agent is using aluminium oxide as carrier, and include following components on the basis of the total weight of catalyst: using palladium as active component, palladium content is In addition 0.1-1.0%, rare earth metal content 0.3-8.0%, alkaline earth metal content 0.1-5.0% can also contain fluorine, fluorine contains Amount is 0-3.0%.Catalyst carrier is θ or mixes crystal form Al2O3, based on θ crystal form.Palladium catalyst distribution is preferably being catalyzed The secondary outer layer of agent；The catalyst has certain anti-impurity and anticoking capability；The catalyst is suitable for 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 catalyst exists in the prior art in solution is low, anti-interference ability is weak, appearance glue ability is low, stability is poor, resistance to free Aqueous technical problem that can be poor.The present invention is by using by weight percentage including following components: (a) gold of 5.0-40.0% 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) IA in the periodic table of elements of 0.01-2.0% 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) at least one of IVB element in the periodic table of elements or its oxide of 0-10.0%；(g) surplus Alumina catalyst support, wherein the total pore volume of carrier be 0.5-1.2 mls/g, the Kong Rong that 30 nanometers of bore dia < accounts for total pore volume 5-65%, the Kong Rong that 30-60 nanometers of bore dia account for the 20-80% of total pore volume, and the Kong Rong that 60 nanometers of bore dia > accounts for total pore volume The technical solution of 20-50% preferably solves the problems, such as this, can be used in the industrial production of drippolene selective hydrogenation. CN200710043944.7 is related to a kind of large hole nickel-based catalyst, and it is low, active mainly to solve nickel content existing in the prior art The technical problem that specific surface is low, average pore size is small.The present invention successively includes by using a kind of nickel-base catalyst, preparation method Following steps: (a) under conditions of 45-80 DEG C of temperature, nickel salt aqueous solution or nickel ammine is added into Aluminum sol, obtains nickel Aluminum sol；(b) pH value for adjusting nickel Aluminum sol is 3.0-11.0；(c) at 45-120 DEG C of temperature, nickel Aluminum sol is through static aging Or heat resolve nickel ammine, nickel alumina gel is obtained, with also after gained gel is washed, dry, reducing agent restores or roasting Former agent restores to obtain required nickel-base catalyst；Wherein, with catalyst weight, the content of metallic nickel or its oxide is 5- 75%；At 2/ gram, Kong Rongwei 0.3-1.5 ml/g of 150-350 rice, average pore size is Ni/Al2O3 specific surface area of catalyst 4.0-25.0 nanometers, wherein can technical solution 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.
The present invention relates to a kind of methods for full-cut fraction pyrolysis gasoline selective hydrogenation by CN200610118523.1, mainly It solves to exist in the prior art and is difficult to the full-cut fraction pyrolysis gasoline high to colloid and water content and carries out the technology of selective hydrogenation to ask Topic.The present invention by using the drippolene and hydrogen for doing the hydrocarbon compound fraction for 204 DEG C using C5 hydrocarbon-as raw material, anti- Answering temperature is 40-60 DEG C, reaction pressure 2.0-3.0MPa, and green oil air speed is 3.75-5.0 hours- 1, hydrogen/oil volume ratio is Under conditions of 80-120:1, raw material is contacted with catalyst, is reacted, and diolefin and alkylene aromatic component in raw material are turned It is melted into monoolefine and alkylaromatic hydrocarbon, 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 a kind of few 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, at least one element or its oxide in the periodic table of elements in IVB, the wherein specific surface of carrier Product is 100-180 meters2/ gram, total pore volume is 0.5-1.2 mls/g, and carrier has the technical solution of compound pore size distribution, preferably Ground solves the problems, such as this, can be used in the industrial production of full-cut fraction pyrolysis gasoline selective hydrogenation.
The invention discloses a kind of methods of selective hydrogenation of cracked gasoline by CN201310461242.6, which is characterized 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 C5-204 DEG C of drippolene of hydrocarbonylation are closed The liquid phase stream and hydrogen of the full fraction of object are one of raw material and loading fixed bed reactors high-molecular organic material supported catalyst Agent contact reacts.The CN200810102242.6 present invention provides a kind of selection of full-cut fraction pyrolysis gasoline diolefin plus hydrogen side Method, the application of reduction, passivation and process conditions including catalyst.Used catalyst is nickel series hydrogenating catalyst, catalyst warp Passivated rear offer use again, hydrogenation process conditions are as follows: liquid volume air speed≤4h-1, reactor inlet after reduction or reduction 40-130 DEG C of temperature, reaction pressure >=2MPa, hydrogen-oil ratio 100-500 (v/v)；Nickel catalyst is used using aluminium oxide as carrier Infusion process is prepared, and is to contain nickel oxide 14-20%, lanthana and/or cerium oxide 1-8% in terms of 100% by catalyst weight With VI B oxides additive 1-8%, silica 2-8%, alkaline earth oxide 1-8%, catalyst specific surface 60-150m2/ G, Kong Rong 0.4-0.6ml/g.The reduction that the present invention also provides catalyst on hydrogenation plant, passivating method.Herein using side Under method and process conditions, Raney nickel has good Hydrogenation, especially has 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 having mesoporous-big Hole or double composite mesoporous ducts, make carrier with aluminium oxide, and with nickel for main active constituent, molybdenum is to help active component, metal oxide Weight percent composition for auxiliary agent, the drippolene nickel system selective hydrocatalyst is as follows: nickel oxide 15-19, molybdenum oxide 6.5-20.0, auxiliary agent, 2.2-4.5, aluminium oxide surplus；The auxiliary agent be one of potassium oxide, magnesia, lanthana or its It anticipates two or more combinations.It is high to provide a kind of Kong Rong great, specific surface, there is 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 catalyst of the 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 There is technical issues that being difficult to the full-cut fraction pyrolysis gasoline high to colloid and water content carries out in technology.The present invention By using the drippolene and hydrogen for doing the hydrocarbon compound fraction for 204 DEG C using C5 hydrocarbon-as raw material, it is in reaction temperature 40-60 DEG C, reaction pressure 2.0-3.0MPa, 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 diolefin and the alkylene aromatic component in raw material is made to be converted to monoene Hydrocarbon and alkylaromatic hydrocarbon, wherein catalyst includes alumina catalyst support, activity component metal nickel or its oxide, at least one 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 select 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, wherein the specific surface area of carrier is 100- 180 meters 2/ gram, total pore volume is 0.5-1.2 mls/g, and carrier has the technical solution of compound pore size distribution, preferably solves The problem can be used in the industrial production of 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 Kong Rong that 30 nanometers of bore dia < accounts for the 20-50% of total pore volume, and bore dia 30-60 receives The Kong Rong of rice accounts for the 20-45% of total pore volume, and the Kong Rong that 60 nanometers of bore dia > accounts for the 25-45% of total pore volume.The preparation side of carrier Method includes mixing aluminium oxide and modifying agent, peptizing agent, water, after extruded moulding in the desired amount, first the dry 1- at 50-120 DEG C It 24 hours, is then roasted 1-10 hours at 700-1150 DEG C, obtains carrier.Modifying agent, peptization is not expressly recited in the invention Agent has used polyvinyl alcohol in embodiment, and thus knowing that the invention has the carrier of compound pore size distribution is obtained with polyvinyl alcohol It arrives.The catalyst used is selectively adding for full fraction (the hydrocarbon compound fraction that C5 hydrocarbon-is done as 204 DEG C) drippolene There is good low temperature active, selectivity and stability when hydrogen, and there is good anti-interference, resistance to high colloid and Nai Gao to contain Measure aqueous energy.
The prior art changes support chemistry composition and type, and addition coagent mainly to promote catalyst performance Energy.Since the impurity such as As, S, O, N and gum level are higher in drippolene, catalyst is set to be easy inactivation, it is therefore desirable to crack vapour Oily catalyst has appearance glue ability good, anti-arsenic, sulfur resistive, the characteristic for inhibiting coking ability strong.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of nickel system selective hydrocatalysts, for one section of drippolene selection Property adds hydrogen.The activity of the catalyst in the reaction is higher, and selectivity is more preferable, and appearance glue ability is more preferable, and anti-arsenic, inhibits coking at sulfur resistive Ability is strong, and preparation process is easy, and the carrier of catalyst is the alumina support with macroporous structure, and catalyst is particularly suitable for Drippolene selective hydrogenation.
The present invention provides a kind of nickel system selective hydrocatalyst, which includes the carrying alumina with macroporous structure Body and the metal active constituent nickel and tungsten being carried on carrier, the content of nickel oxide are 12- based on the total weight of the catalyst 22wt%, the content of tungsten oxide are 1.5-8wt% based on the total weight of the catalyst, and alumina support is using chitosan as expansion Hole agent synthesizes the alumina support with macroporous structure.Macroporous aluminium oxide is adjustable with pore size, and macropore ratio can be with The characteristics of effectively controlling.
Preferably, the one-stage selective hydrogenation of gasoline splitting catalyst composition are as follows: the content of nickel oxide is based on the catalysis The total weight of agent is 15-20wt%, and the content of tungsten oxide is 2.5-6wt% based on the total weight of the catalyst.
A kind of alumina support with macroporous structure of the present invention contains adjuvant component phosphorus and magnesium in carrier, helps The percentage composition that the content of agent component phosphorus and magnesium accounts for carrier quality is respectively P2O50.1-2.5wt%, MgO 0.1-2.5wt%, Pore-size distribution 60-180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, Kong Rong 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 the methods of dipping, spraying On body, then catalyst is dried, roasts and obtains the catalyst.Such as catalyst can be prepared according to the following steps: Prepare the alumina support that soluble nickeliferous and tungsten solution dipping has macroporous structure, through 110-160 DEG C drying 3-9 hours, 400-650 DEG C roasting 4-9 hours, finally obtain catalyst prod.
In the preparation method of catalyst of the present invention, the compound of nickel used and tungsten can be prior art disclosed A kind of what compound suitable for catalyst processed, such as nickel nitrate, nickel sulfate, nickel acetate, the preferred ammonium tungstate of the compound of tungsten.
The present invention has the alumina support of macroporous structure, and aperture can pass through the additional amount and reaming of variation 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 ranges such as 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, the ranges such as 35-50%, 55-75%.
The present invention also provides a kind of preparation methods of alumina support with macroporous structure, firstly, being acidified with acid solution Chitosan, then by boehmite and sesbania powder be added in kneader be uniformly mixed, add phosphoric acid, magnesium nitrate mixing it is molten The acid solution of chitosan-containing is finally added in boehmite and mediates uniformly by liquid, the additional amount of the acid solution containing expanding agent It is obtained by extrusion-molding-drying-roasting with macropore for the 0.1-8wt% of boehmite, preferably 0.2-5.0wt% 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 It plays mixing to be added in carrier, obtains 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 later, until chitosan dissolution is completely, obtains the acid solution containing expanding agent.The acid can be inorganic acid Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The additional amount of acid is advisable with that can be completely dissolved chitosan.It can also 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.Ultrasonic oscillation 10min or more, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent Wave concussion or magnetic agitation, expanding agent good dispersion, alumina support is more prone to produce macropore, and pore-size distribution more collects In, pore-size distribution is in 70-180nm.The additional amount of the sesbania powder is the 0.1-7wt% of boehmite.
It mediates or extrusion technique is that the configured acid solution containing expanding agent is added in sesbania powder and boehmite Be uniformly mixed, later extrusion, molding, by 100-160 DEG C drying 3-9 hours, 650-800 DEG C roasting 4-8 hours, finally obtain 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 a kind of containing Jie-macropore in 2-50nm, mesoporous ratio 15-75%, preferably 15-50% Alumina support.And aperture is not uniform aperture structure.
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 excessively high, and preferably configuration concentration is lower than phosphorus when preparing complex carrier Acid and magnesium nitrate aqueous solution spray carrier surface, preferably carry out carrier surface modification as follows: configuration phosphoric acid and nitre The aqueous solution spray of sour magnesium has the alumina support of macroporous structure, obtains used additives phosphorus through drying, roasting and magnesium carries out surface Modified alumina support, control is with phosphorus pentoxide in the alumina support of macroporous structure and content of magnesia in 0.1- In the range of 2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is made 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 using phosphorus, magnesium and cerium to carrier surface into Row is modified, and the aqueous solution of configuration phosphoric acid, magnesium nitrate and cerous nitrate sprays carrier surface, preferably carries out carrier as follows Surface is modified: the aqueous solution spray of configuration phosphoric acid, magnesium nitrate and cerous nitrate has the alumina support of macroporous structure, through dry Dry, roasting obtains used additives phosphorus, magnesium and cerium and carries out the modified alumina support in surface, controls the carrying alumina 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 aoxidizes 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 invention has the following advantages that
1, for catalyst carrier of the present invention using chitosan as expanding agent, expanding agent chitosan is cheap, and environmental protection It is nontoxic, it is suitble to industrialized production.The obtained alumina support with macroporous structure, pore size is adjustable, and macropore ratio can Effectively to control.And carrier also contains mesoporous, is a kind of Jie-macropore alumina supporter.Catalyst carrier has macroporous structure, It is good to hold glue ability, inhibits coking ability strong, anti-arsenic, sulfur resistive effect are good.
2, the present invention can also in alumina support and carrier surface introduce cerium, make carrier surface cerium content be higher than carry Internal portion, there is the alumina support of macroporous structure to be prepared into one-stage selective hydrogenation of gasoline splitting catalyst, be able to suppress for this Olefinic polymerization improves diolefin hydrogenation selectivity.
3, the alumina support with macroporous structure that the present invention obtains is big to having using phosphorus and magnesium or phosphorus, magnesium and cerium The alumina carrier surface of pore structure is modified, and make carrier surface phosphorus pentoxide, magnesia, cerium oxide content 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, advantageously reduces the micropore ratio of carrier surface in this way, improves carrier surface Jie- 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 polymerization reaction blocking duct occurs.Dipping method should not be used to the improvement of carrier surface, dipping carries Body surface face can make large quantity of moisture enter carrier, be not achieved and improve carrier surface Jie-macropore ratio purpose.
Detailed description of the invention
Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.
Embodiment 1
8.0g water soluble chitosan expanding agent is added in 50 DEG C of deionized water first, acetic acid is added dropwise later, until Chitosan dissolution completely, 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 aqueous solution.Weigh 350g boehmite powder and the field 20.0g Cyanines powder is added in kneader, and is uniformly 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, is clover shape by kneading-extruded moulding.It is small in 120 DEG C of dryings 8 When, 700 DEG C roast 4 hours, obtain phosphorous and magnesium alumina support 1.Phosphorus pentoxide 0.5wt%, magnesia in carrier 1 0.8wt%.Alumina support specific surface area and pore-size distribution with macroporous structure are shown in Table 1.
120ml water is added in ammonium tungstate, nickel nitrate, then adjusting pH value impregnates ammonium tungstate, nickel nitrate whole dissolution Liquid；Maceration extract impregnated carrier is used again, is filtered dry 130 DEG C of drying after moisture, and 500 DEG C roast 5 hours, obtain catalyst 1.Catalyst 1 Composition are as follows: 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 agent is added in 50 DEG C of deionized water, acetic acid is added dropwise later, until shell is poly- Sugar dissolution completely, 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 aqueous solution.Weigh 350g boehmite powder and 20.0g sesbania powder It is added in kneader, and is uniformly 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, be clover shape by kneading-extruded moulding.It is 8 hours dry at 120 DEG C, 700 DEG C roasting 4 hours, obtain phosphorous and magnesium alumina support 1.It recycles phosphorus and magnesium to be modified carrier surface, configures phosphorous The aqueous solution of acid and magnesium nitrate spray has the alumina support 1 of macroporous structure, and 8 hours dry through 120 DEG C, 700 DEG C of roastings 4 are small When obtain used additives phosphorus and magnesium and carry out the modified alumina support 2 in surface, the content of 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 solution impregnation of alumina carrier 2 is configured, 6 hours dry at 120 DEG C, 550 DEG C roast 5 hours, Obtain catalyst 2.Catalyst 2 forms are as follows: 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.The difference is that adjuvant component also contains cerium in carrier, by water Soluble chitosan expanding agent is changed to water-insoluble chitosan expanding agent, and chitosan formic acid liquid magnetic stirrer 30 is divided 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 and pore-size distribution are shown in Table 1.
Nickeliferous and tungsten solution impregnation of alumina carrier 3 is configured, 6 hours dry at 120 DEG C, 500 DEG C roast 6 hours, Obtain catalyst 3.Catalyst 3 forms are as follows: the content 14wt% of the content 5.5wt% nickel oxide of tungsten oxide, alumina support contain Measure 80.5wt%
Embodiment 4
The preparation method of carrier is carried out according to embodiment 3.The difference is that water soluble chitosan expanding agent is changed to Water-insoluble chitosan expanding agent, chitosan acetic acid solution was with ultrasonic oscillation 15 minutes.Obtain the aluminium oxide with macroporous structure Carrier.In carrier the content of adjuvant component phosphorus, magnesium and cerium account for the percentage composition of carrier quality be respectively 1.6wt%, 1.6wt%, 0.6wt%.It recycles phosphorus, magnesium and cerium to be modified carrier surface, obtains carrier 4,4 surface phosphorus pentoxide of carrier, 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 4 specific surface area of alumina supporter and pore-size distribution are shown in Table 1.
Nickeliferous and tungsten solution impregnation of alumina carrier 4 is configured, 7 hours dry at 125 DEG C, 480 DEG C roast 7 hours, Obtain catalyst 4.Catalyst 4 forms are as follows: the content 20wt% of the content 3.0wt% nickel oxide of tungsten oxide, alumina support contain Measure 77wt%
The alumina support specific surface area and pore-size distribution of 1 macropore of table
Catalyst 1-4 is respectively charged into 100ml insulation bed reaction device, it is small that 7 are restored under 450 DEG C of hydrogen atmospheres of temperature When, 3 hours laggard feedstock oil, drippolene C are passivated with hexamethylene after cooling to 50 DEG C5-C9Fraction, diene content are 37.53g Iodine/100g oil, iodine value are 86.6g iodine/100g oil, gum level is 45mg/100ml oil, sulfur content is 123ppm and arsenic content For 106ppb；Reaction process condition are as follows: 50 DEG C of inlet temperature, hydrogen to oil volume ratio 110:1, reaction pressure 2.8MPa, green oil is empty Fast 3.5h-1；After operating 150h, the diene of 1 hydrogenated products of catalyst is 1.10 grams of iodine/100 gram oil, and iodine value is 38.2g iodine/100g Oil；The diene of 2 hydrogenated products of catalyst is 0.95 gram of iodine/100 gram oil, and iodine value is 37.3g iodine/100g oil；Catalyst 3 plus hydrogen produce 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 4 hydrogenated products of catalyst is 0.91 gram Iodine/100 gram oil, iodine value are 36.6g iodine/100g oil.It is 45mg/100ml oil, sulfur content 123ppm in feedstock oil gum level Under the conditions of being 106ppb with arsenic content, not higher than 1.10 grams iodine/100 gram of the diene oil left and right of hydrogenated products, iodine value is not higher than 38.2g iodine/100g oil, catalyst activity is higher, and selectivity is more preferable, and appearance glue ability is more preferable, and anti-arsenic, inhibits coking ability at sulfur resistive By force.
After catalyst 1-4 operates 420h, the diene of 1 hydrogenated products of catalyst is 1.15 grams of iodine/100 gram oil, and iodine value is 38.5g iodine/100g oil；The diene of 2 hydrogenated products of catalyst is 0.98 gram of iodine/100 gram oil, and iodine value is 37.5g iodine/100g oil； The diene of 3 hydrogenated products of catalyst is 0.89 gram of iodine/100 gram oil, and iodine value is 38.2g iodine/100g oil；4 hydrogenated products of catalyst 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, inhibition Coking ability is strong, catalyst performance stabilised.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art It all should belong to protection scope of the present invention.

Claims (3)

1. a kind of nickel system selective hydrocatalyst, it is characterised in that:
Catalyst includes the alumina support and the metal active constituent nickel being carried on carrier and tungsten with macroporous structure, oxidation Total weight of the content of nickel based on the catalyst is 15-20wt%, and the content of tungsten oxide is based on the total weight of the catalyst 2.5-6wt%, alumina support, as expanding agent, contain auxiliary agent group in the alumina support with macroporous structure using chitosan Divide phosphorus, magnesium and cerium, the percentage composition that the content of adjuvant component phosphorus, magnesium and cerium accounts for carrier quality is respectively P2O50.1-2.5wt%, MgO 0.1-2.5wt%, CeO20.1-2.5%；
The alumina support contains pore diameter range 60-180nm, and macropore ratio 2-75%, Kong Rong 0.8-2.0ml/g compares table Area 250-300m2/g；
The alumina support contains meso-hole structure, and macropore range is in 5-50nm, mesoporous ratio 15-75%；
The preparation method of the alumina support with macroporous structure includes the following steps: firstly, poly- with acid solution acidification shell Then boehmite and sesbania powder are added in kneader and are uniformly mixed, add phosphoric acid, magnesium nitrate and cerous nitrate by sugar The acid solution of chitosan-containing is finally added in boehmite and mediates uniformly by mixed solution, the acid solution containing expanding agent Additional amount is that the 0.1-8wt% of boehmite obtains the oxidation with macroporous structure by extrusion-molding-drying-roasting Alumina supporter；
To the obtained alumina support with macroporous structure, be modified using phosphorus, magnesium and cerium to carrier surface: configuration is phosphorous The aqueous solution spray of acid, magnesium nitrate and cerous nitrate has the alumina support of macroporous structure, obtains used additives through drying, roasting Phosphorus, magnesium and cerium carry out the modified alumina support in surface, control phosphorus pentoxide, oxygen in the alumina support with macroporous structure Change the content of magnesium and cerium oxide all in the range of 0.1-2.5wt%, and makes carrier surface phosphorus pentoxide, magnesia and oxidation The content of cerium is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
2. the preparation method of a kind of nickel system selective hydrocatalyst described in claim 1, it is characterised in that: including walking as follows It is rapid:
The alumina support that soluble nickeliferous and tungsten solution dipping has macroporous structure is prepared, it is small through 110-160 DEG C of drying 3-9 When, 400-650 DEG C roasting 4-9 hours, finally obtain catalyst prod；
The preparation method of the alumina support with macroporous structure includes the following steps: firstly, poly- with acid solution acidification shell Then boehmite and sesbania powder are added in kneader and are uniformly mixed, add phosphoric acid, magnesium nitrate and cerous nitrate by sugar The acid solution of chitosan-containing is finally added in boehmite and mediates uniformly by mixed solution, the acid solution containing expanding agent Additional amount is that the 0.1-8wt% of boehmite obtains the oxidation with macroporous structure by extrusion-molding-drying-roasting Alumina supporter；
To the obtained alumina support with macroporous structure, be modified using phosphorus, magnesium and cerium to carrier surface: configuration is phosphorous The aqueous solution spray of acid, magnesium nitrate and cerous nitrate has the alumina support of macroporous structure, obtains used additives through drying, roasting Phosphorus, magnesium and cerium carry out the modified alumina support in surface, control phosphorus pentoxide, oxygen in the alumina support with macroporous structure Change the content of magnesium and cerium oxide all in the range of 0.1-2.5wt%, and makes carrier surface phosphorus pentoxide, magnesia and oxidation The content of cerium is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
3. a kind of preparation method of nickel system selective hydrocatalyst according to claim 2, it is characterised in that: the use Acid solution acidified chitosan is: chitosan expanding agent being added in 30-95 DEG C of deionized water first, acid is added dropwise later, directly Completely to chitosan dissolution, the acid solution containing expanding agent is obtained.
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CN101433841A (en) * 2007-12-13 2009-05-20 中国石油天然气股份有限公司 Selectively hydrogenating catalyst and preparation method thereof
CN101863499A (en) * 2010-05-31 2010-10-20 中南大学 Preparation method of macroporous-mesoporous alumina
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