CN107159279A - A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of one-stage selective hydrogenation of gasoline splitting catalyst, catalyst includes the alumina support with macroporous structure and the metal active component palladium being carried on carrier, and gross weight of the content based on the catalyst of palladium is 0.2 0.35wt%.Catalyst holds glue ability more preferably, and anti-arsenic, sulfur resistive, suppression coking ability are strong.

Description

A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof

Technical field

The present invention relates to a kind of for selective hydrogenation catalyst of petroleum hydrocarbon product and preparation method thereof, it is particularly suitable for use in A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof.

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.

The carrier of aluminum oxide with macroporous structure is relatively more.CN03126434.4 discloses a kind of macropore alumina supporter, Containing aluminum oxide, also containing a kind of halogen, on the basis of carrier total amount, the carrier contains 95-99 weight % aluminum oxide, with member Element meter, 0.1-5 weight % halogen, its acid amount is less than 0.2 mM/gram.The preparation method of macropore alumina supporter includes will A kind of precursor of aluminum oxide is molded and is calcined, before shaping and roasting, and the precursor of aluminum oxide is mixed with a kind of expanding agent Close, the expanding agent includes a kind of organic expanding agent and a kind of halide, sintering temperature is 600-850 DEG C, roasting time 1-10 Hour, the consumption of each component contains final alumina support, on the basis of carrier total amount, 95-99 weight % aluminum oxide, In terms of element, 0.1-5 weight % halogen.Organic expanding agent is in starch, synthetic cellulose, polymeric alcohol, surfactant One or more.Synthetic cellulose is in carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxylated cellulose It is one or more of.One or more of the polymeric alcohol in polyethylene glycol, poly- propyl alcohol, polyvinyl alcohol, surfactant is selected from fat Fat alcohol APEO, fatty alkanol amide, molecular weight are 200-10000 acrylic copolymer, in maleic acid copolymer It is one or more of.CN201110410339.5 provides a kind of high temperature-resistant active aluminum oxide material and preparation method thereof, described oxygen Change aluminum to be made by following steps：After macropore boehmite, high viscous boehmite are mixed with additive with water, turning Speed adds the dilute nitric acid reaction that concentration is 30% to be stirred under 100-1000r/min, to the peptization that pH is 2.0-5.5 During state, 3-6h is aged under the stirring of 80 DEG C of -100 DEG C of temperature, add at room temperature pore creating material stir, it is slurrying, spraying, dry It is dry, 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. It can be kept for a long time than surface in 110m at a temperature of 1000-1100 DEG C²/ more than g；The work of the alumina material preparation method Skill process is simple, with low cost.Wherein described sky agent of making is selected from polyvinyl alcohol, polyethylene glycol, polyacrylamide or methyl fibre One kind in dimension element, its consumption is the 0-40% of oxide gross weight in alumina material.《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, so The ethanol solution of aluminum nitrate and citric acid is added drop-wise under suction filtration on glue crystalline substance afterwards, allows it fully to penetrate into the gap of microballoon, Through drying and being calcined, polystyrene moulding is removed, macroporous aluminium oxide is obtained.《Acta PhySico-Chimica Sinica》(2006,22 (7):831- 835) method that granular formwork method prepares three-dimensional ordered macroporous alumina is described, this method is as follows：Emulsion polymerization is used first Method obtains polystyrene microsphere, and aluminum nitrate plus weak aqua ammonia are made into alumina sol, and both are then stirred into mixed by a certain percentage Close, it is ultrasonically treated, 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, oxidation Alumina gel and coagulant are well mixed with certain proportion, and the mixture is scattered in oil phase, form w/o type drop, Ran Houzai Above-mentioned mixed phase system is heated, makes the alumina sol gelling balling-up in aqueous phase, the gel for isolating shaping from oil phase afterwards is micro- Ball, then obtain described spherical integral macroporous alumina after aged, dry and roasting in aqueous ammonia medium.The aluminum oxide Macropore diameter is homogeneous controllable in the range of less than 1 μm, and the size of spheric granules is controllable, and mechanical strength is higher, is molded Journey is simple and easy to do, is easy to be prepared on a large scale.Polymer microballoon diameter 50-1000nm, the type of polymer microballoon is polystyrene The esters microballoons such as microballoon, polyaerylic 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 is used Lipid microballoon and coagulant etc..Preparation technology is complicated, and reagent raw material used is relatively more.Due to polymer microballoon cause Alumina support internal gutter 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.CN101200297A discloses whole The preparation method of build macroporous aluminium oxide：Reverse concentrated emulsions method is used to prepare monoblock type using styrene and divinylbenzene as monomer big Hole organic formwork；The Al2O3 hydrosols are prepared using aluminium isopropoxide or boehmite as predecessor；The Al2O3 hydrosols are 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 NH3 and CO2, the generation and effusion of these gases can manufacture some macropores in decomposable process.While oxygen The pattern for changing aluminium is transformed by the pattern topology of aluminium carbonate ammonium.Slower heating rate is conducive to gas in roasting process Material 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)：With chitosan and inorganic aluminate AlCl₃·6H₂O is raw material, is passed through Sol-gel process, uses CO respectively₂Supercritical drying means and freeze-drying means are prepared for new chitosan/oxidized aluminium 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.

CN201010622227.1 is related to a kind of catalyst for selective hydrogenation of cracked gasoline, and it includes and is used as carrier Magnesia-titania-alumina composite oxide, and the Metal Palladium active component being carried on the composite oxide carrier And Group IIA and/or IIIB races metal promoter metal, wherein metal palladium content is 0.25-0.35 weight %, and promoter metal content is 0.2-3 weight %, and content based on oxidation aluminium magnesia in carrier is 0.1-3 weight % and the content of titanium oxide is 5-20 Weight %.The catalyst can be used for selective hydrogenation of cracked gasoline, and its low temperature active is high, and selectivity is high, anti-As, S, O, N impurity energy Power is strong, and charging capacity is greatly and activity stabilized under long-term operation.Moreover, it relates to the preparation of the catalyst and selection Application in hydrocracking gasoline.Finally, composite oxides used are prepared using co-precipitation method the invention further relates to one kind The method of carrier.CN201310379189.5 discloses a kind of pyrolysis gasoline selective hydrogenation catalyst, including carrier and is carried on Metal active constituent on carrier, described active component containing high molecular polymer aqueous phase without the micro- of cosurfactant It is prepared in emulsion law system；Described carrier be selected from aluminum oxide, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve, At least one of kaolin, cordierite；Described active component is main active component and helps active component, wherein main activearm It is divided into palladium, content is the 0.01wt%-1.0wt% of carrier gross weight, and described high molecular polymer is water miscible polyphosphazene polymer Compound.The activity of the catalyst in the reaction is higher, and selectivity more preferably, holds glue ability more preferably, its preparation technology is easy, catalyst Particle shape can be controlled well.CN201110089806.9 is related to a kind of for drippolene or its cut selective hydrogenation Palladium-silver/alumina-silica titanium catalyst, the catalyst includes the aluminium oxide-titanium oxide compound as carrier, and negative Active component Pd and Ag on the carrier are loaded in, it is 0.15-0.5 weights that wherein Pd content, which is based on the total catalyst weight, % is measured, it is 0.8-4.5 weight % that Ag content, which is based on the total catalyst weight,.Compared with similar catalyst, present invention catalysis Agent can be used for drippolene or the hydrogenation of its cut, and its low temperature hydrogenation selectivity is high, and anti-As impurity ability is strong, and charging capacity is big, and It is activity stabilized.Moreover, it relates to the preparation method of Above-mentioned catalytic agent.Catalyst of the present invention can also be used for other petroleum hydrocarbons The selective hydrogenation of the alkynes and/or diolefin of class.CN200610029962.5 is related to a kind of full-cut fraction pyrolysis gasoline that is used for and selected The method of selecting property hydrogenation, mainly solves presence in the prior art and is difficult to the full-cut fraction pyrolysis gasoline high to colloid and free water content Carry out the technical problem of selective hydrogenation.The present invention by using the hydrocarbon compound cut with C5 hydrocarbon-do for 204 DEG C cracking Gasoline and hydrogen are raw material, are 30-80 DEG C in reaction temperature, and reaction pressure is 2.0-3.0MPa, and green oil air speed is 2.5-5.0 Hour^{- 1}, hydrogen/oil volume ratio is 60-120：Under conditions of 1, raw material is contacted with catalyst, is reacted, and makes the diene in raw material Hydrocarbon and alkylene aromatic component change into monoolefine and alkylaromatic hydrocarbon, and wherein catalyst includes alumina support, activearm parting Belong to palladium or its oxide, at least one IA in the periodic table of elements or IIA element or its oxide, at least one selected from member IVA or VA element or its oxide in plain periodic table, carrier specific surface area are 2/ gram of 40-160 rice, and total pore volume is 0.3-1.2 Ml/g, and carrier has the technical scheme of compound pore size distribution, preferably solves the problem, and vapour is cracked available for full cut In the industrial production of oily selective hydrogenation.The preparation method of catalyst of the present invention is identical with common lamella catalyst dipping technique： First carrier is presoaked with a kind of liquid that can be dissolved each other with maceration extract, then with the salt solution impregnation containing palladium, the carrier after dipping is through washing Wash, dry, in atmosphere 300-600 DEG C of roasting produce oxidative catalyst finished product.Finished catalyst need to only lead in the reactor Hydrogen reducing is that can be used.The catalyst that the present invention is used has a composite pore structural, it is larger can several apertures, and rich in abundant It is mesoporous.The catalyst of the present invention is when for full-cut fraction pyrolysis gasoline selective hydrogenation with good low temperature active, selection Property and stability, and with good anti-interference, resistance to high colloid and high content free water performance.40 DEG C of inlet temperature, Reaction pressure 2.7Mpa, hydrogen/oil volume compare 80：1, green oil air speed is under the conditions of 3.8 hours -1, be 150 milligrams to gum level/ Full cut that 100 grams of oil, free water contents are 1000ppm (the hydrocarbon compound cut of C5 hydrocarbon-do for 204 DEG C) drippolene enters Row selective hydrogenation reaction, it is 0.0 gram of iodine/100 gram oil that it, which exports diene average value, and diolefin hydrogenation rate is 100%, is achieved preferably Technique effect.The preparation method of the invention carrier includes mixing aluminum oxide and modifying agent, peptizing agent, water in the desired amount, squeezing After bar shaping, first dried at 50-120 DEG C 1-24 hours, be then calcined 1-10 hours at 800-1150 DEG C, obtain aluminum oxide Carrier.The invention is not expressly recited in modifying agent, peptizing agent, embodiment 1 and has used polyvinyl alcohol, thus knows that the invention has The carrier for having compound pore size distribution is obtained with polyvinyl alcohol.Mainly solve to exist in the prior art and be difficult to colloid and dissociate The high full-cut fraction pyrolysis gasoline of water content carries out the technical problem of selective hydrogenation.It is similar also have CN200610029963.X with And CN200610029961.0.CN02111016.6 is related to a kind of catalyst for one-stage selective hydrogenation of gasoline splitting.It is main When solving to use one-component Metal Palladium in conventional art, the problem of diolefin hydrogenation is selectively relatively low.The present invention is by using in δ Phase alumina supported on carriers palladium, wherein carrier pore volume are 0.6-0.9 mls/g, and specific surface area is 2/ gram of 140-170 rice, is urged Agent shell thickness preferably solves the problem for 0.03-0.09 millimeters of technical scheme, available for one section of choosing of drippolene In the industrial production of selecting property hydrogenation.The invention diolefin hydrogenation selectively relatively low shortcoming new is used for drippolene there is provided a kind of The catalyst of one-stage selective hydrogenation.The catalyst has hydrogenation activity moderate, and diolefin hydrogenation selectivity is high, resists with stronger Poisoning capability, the characteristics of operational stability is good.Invention uses the cylinder carrier containing at least one hole, therefore carrier due to carrier Geometrical surface is larger, reaction bed pressure drop is reduced, is conducive to reaction to remove heat, while bed temperature can be made more uniform, has Beneficial to the selectivity for improving purpose product, high-speed operating is adapted to；Be conducive to the scattered of palladium simultaneously, reduce the content of palladium.Carrier Pore volume it is larger, the burnt ability of appearance of catalyst can be improved.By the control of Metal Palladium shell thickness in 0.03-0.09 millimeters, a side Face is conducive to suppressing the side reaction of deep hydrogenation, is on the other hand also beneficial to the dispersed of Metal Palladium, improves the utilization rate of palladium, Help to reach the purpose for improving selectivity.Catalyst produced by the present invention, tests prove that, diolefin hydrogenation is selectively reachable More than 38%, while having preferable stability, achieve preferable technique effect.CN200810102240.7 one kind cracking vapour Oil distillate section selective hydrogenation method, is provided using palladium series hydrocatalyst, after catalyst reduction and used, it is characterised in that plus Hydrogen process conditions are：Liquid volume air speed≤5h-1,28-120 DEG C of reactor inlet temperature, reaction pressure >=2.4MPa, hydrogen oil Volume ratio 50-500；Palladium series hydrocatalyst used, θ, α mixing crystal formation carrying alumina with θ types aluminum oxide or based on θ types Body, using Metal Palladium as active component, in terms of catalyst weight 100%, contains active component Pd 0.2-0.5wt%, auxiliary agent 2- 8wt% lanthanums and/or cerium, 2-8wt% alkali earth metals；Offer is remained to after catalyst coking and deactivation by regeneration to use.Herein Under application process and process conditions, catalyst has good Hydrogenation, especially when in hydrogenating materials carry minor amount of water, colloid When, still with good hydrogenation activity and stability.CN200310124229.8 one kind is used for drippolene C5-C9 cuts, Especially C8-C9 double distilleds component selections are hydrogenated into the catalyst of alkene, including aluminum oxide as carrier, are covered in the carrier table Alkaline-earth metal or its oxide on face and the metal Pd and Mo or Pd and W being carried on as active component on the carrier, Wherein the content of alkaline-earth metal is based on the total catalyst weight and is based on the total catalyst weight for 1-3 ω %, Pd content It is 1 for 0.24-0.35 ω %, Pd and Mo or Pd and W weight ratio：0.5-2.5.Catalyst crushing strength of the present invention is more than 18N/ mm.The catalyst can be used for drippolene C5-C9 cuts, particularly C8-C9 heavy fractioning hydrogenations, and its low temperature active is high, anti-As, S, O, N impurity ability are strong, and charging capacity is big and activity stabilized.The invention alumina catalyst carrier introduces alkaline-earth metal and changed Property, it can also be used to the alkynes of other petroleum hydrocarbons or the selection hydrogenation of diolefin.A kind of unsaturated hydrocarbons of CN200810114744.0 Selective hydrogenation catalyst and preparation method thereof.The catalyst is included using aluminum oxide as carrier on the basis of the gross weight of catalyst Following components：Using palladium as active component, palladium content is 0.1-1.0%, and rare earth metal content is 0.3-8.0%, and alkaline-earth metal contains Measure as 0.1-5.0%, fluorine can be also contained in addition, Oil repellent is 0-3.0%.Catalyst carrier is θ or mixes crystal formation Al₂O₃, with θ Based on crystal formation.Palladium catalyst distribution is preferably in the secondary outer layer of catalyst；The catalyst has certain anti-impurity and anti-coking Energy；The catalyst is applied to full-cut fraction pyrolysis gasoline one-stage selective hydrogenation process, is also applied in other distillates unsaturated Hydrocarbon-selective hydrogenation process.

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 one-stage selective hydrogenation of gasoline splitting catalyst, and the catalyst is anti- Activity in answering is higher, and more preferably, appearance glue ability is more preferable for selectivity, and anti-arsenic, sulfur resistive, the coking ability that suppresses are strong, its preparation technology letter Just, the carrier of catalyst is the alumina support with macroporous structure, and catalyst is particularly suitable for use in drippolene C₆-C₈Cut is selected Selecting property is hydrogenated with.

The present invention provides a kind of one-stage selective hydrogenation of gasoline splitting catalyst, and the catalyst is included with macroporous structure Alumina support and the metal active component palladium being carried on carrier, gross weight of the content based on the catalyst of palladium is 0.2- 0.35wt%, preferably 0.25-0.3wt%, alumina support, as expanding agent, are synthesized with macroporous structure using chitosan Alumina support.There is macroporous aluminium oxide pore size can adjust, the characteristics of macropore ratio can be controlled effectively.

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%, hole Footpath is distributed 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%.

Active component palladium can be impregnated using methods such as dipping, sprayings, sprayed to carrier by the preparation method of catalyst On, then catalyst is dried, is calcined and obtains described catalyst.Catalyst can be for example prepared according to the following steps：Match somebody with somebody Alumina support of the palladium-containing solution dipping with macroporous structure processed, is dried 3-9 hours, 400-650 DEG C of roasting 4- through 110-160 DEG C 9 hours, finally give catalyst prod.

In the preparation method of catalyst of the present invention, palladium compound used can be any disclosed in prior art Suitable for the palladium compound of palladium catalyst processed, the sour aluminium of such as palladium bichloride, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium, four nitre Base palladium acid sodium, acylate such as oxalic acid palladium etc. of palladium.There is no any specifically limited to preparing the solvent used in palladium compound solution, As long as it can dissolve used palladium compound.It is preferred that solvent be for example water, watery hydrochloric acid, dust technology, dilute sulfuric acid or Their mixed liquor.

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 rate of palladium, improves cracking vapour Oily selectivity hydrogenation activity.And concentration of component different structure inside and outside this carrier, alkynes and alkadienes is not easily accessed hole Polymerisation occurs inside road and blocks duct.Improvement to carrier surface should not use dipping method, and impregnated carrier surface can make greatly Amount moisture enters carrier, does 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.

Palladium bichloride is added into 150ml water, is added and is diluted to 1L with ionized water again after dissolving with hydrochloric acid and is made into palladium solution, according to Required shell thickness adjusts pH value；Carrier is presoaked with ionized water again, is filtered dry after moisture and uses palladium solution impregnating carrier, be filtered dry after moisture 130 DEG C of drying, 450 DEG C are calcined 5 hours, obtain catalyst 1.The palladium content of catalyst 1 is 0.27wt%.

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.

Palladium solution impregnation of alumina carrier 2 is configured, is dried at 120 DEG C 6 hours, 500 DEG C are calcined 5 hours, are catalyzed Agent 2.The palladium content of catalyst 2 is 0.31wt%.

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.

Palladium solution impregnation of alumina carrier 3 is configured, is dried at 120 DEG C 6 hours, 500 DEG C are calcined 5 hours, are catalyzed Agent 3.The palladium content of catalyst 3 is 0.29wt%.

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.

Palladium solution impregnation of alumina carrier 4 is configured, is dried at 125 DEG C 7 hours, 480 DEG C are calcined 6 hours, are catalyzed Agent 4.The palladium content of catalyst 4 is 0.30wt%.

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, in 120 DEG C of temperature, the body of hydrogen and catalyst Product compares 200：Reduced 7 hours under the conditions of 1, cool to 40 DEG C of laggard feedstock oils, drippolene C8 cut dienes content is 19.13g Iodine/100g oil, gum level be 208mg/100ml oil, bromine valency be 38.94g bromines/100g oil, sulfur content is 103ppm and arsenic contains Measure as 190ppb；Reaction process condition is：40 DEG C of inlet temperature, hydrogen to oil volume ratio 110：1, reaction pressure 2.8MPa, green oil Air speed 6.0h^-1；The average diene for operating the hydrogenated products of 180h catalyst 1 is 0.52 gram of iodine/100 gram oil, and bromine valency is 20.83 grams Bromine/100 gram oil, diolefin hydrogenation rate 97.1%；The average diene for operating the hydrogenated products of 180h catalyst 2 is 0.35 gram of iodine/100 gram Oil, bromine valency is 19.21 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.2%.The average diene of the hydrogenated products of catalyst 3 is 0.41 gram Iodine/100 gram oil, bromine valency is 19.52 grams of bromine/100 gram oil, diolefin hydrogenation rate 97.5%.The average diene of the hydrogenated products of catalyst 4 For 0.31 gram of iodine/100 gram oil, bromine valency is 19.04 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.5%.

It is under the conditions of 208mg/100ml oil, sulfur content are 103ppm and arsenic content is 190ppb in feedstock oil gum level, 0.52 gram of iodine/100 gram of average diene oil left and right of hydrogenated products, diolefin hydrogenation rate more than 97.1%, catalyst activity is higher, choosing Selecting property more preferably, holds glue ability more preferably, and anti-arsenic, sulfur resistive, suppression coking ability are strong.

After catalyst 1-4 operatings 450h, the average diene of the hydrogenated products of catalyst 1 is 0.89 gram of iodine/100 gram oil, diene Hydrogenation rate 96.7%；The average diene of the hydrogenated products of catalyst 2 is 0.42 gram of iodine/100 gram oil, diolefin hydrogenation rate 97.9%.Urge The average diene of the hydrogenated products of agent 3 is 0.61 gram of iodine/100 gram oil, diolefin hydrogenation rate 97.3%.The hydrogenated products of catalyst 4 Average diene is 0.33 gram of iodine/100 gram oil, diolefin hydrogenation rate 98.4%.Catalyst appearance glue ability is good, anti-arsenic, sulfur resistive, suppression knot Burnt ability is strong, catalyst performance stabilised.

Catalyst 3 and 4 is respectively charged into the adiabatic bed reaction devices of 100ml, in 120 DEG C of temperature, hydrogen and catalyst Volume ratio 200：Reduced 7 hours under the conditions of 1, cool to 40 DEG C of laggard feedstock oils, drippolene C6-C8 cuts, diene content is 17.24g iodine/100g oil, bromine valency be 28.03g bromines/100g oil, gum level be 34mg/100ml oil, sulfur content be 142ppm and Arsenic content is 143ppb；Reaction process condition is：45 DEG C of inlet temperature, hydrogen to oil volume ratio 250：1, reaction pressure 3.0MPa, newly Fresh oily air speed 3.0h^-1；The average diene for operating the hydrogenated products of 180h catalyst 3 is 0.40 gram of iodine/100 gram oil, and bromine valency is 16.31 Gram bromine/100 gram.The average diene for operating the hydrogenated products of 180h catalyst 4 is 0.32 gram of iodine/100 gram oil, and bromine valency is 16.12 grams Bromine/100 gram oil.It is that 34mg/100ml is oily, sulfur content is 142ppm and arsenic content is 143ppb conditions in feedstock oil gum level Under, 0.40 gram of iodine/100 gram of average diene oil left and right of hydrogenated products, catalyst appearance glue ability is good, anti-arsenic, sulfur resistive, suppression coking Ability is strong, and catalyst is adaptable to the feedstock oil of different sulfur contents, gum level, arsenic content.

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 (10)

1. a kind of one-stage selective hydrogenation of gasoline splitting catalyst, it is characterised in that：

Catalyst includes the alumina support with macroporous structure and the metal active component palladium being carried on carrier, the content of palladium Gross weight based on the catalyst is 0.2-0.35wt%, and alumina support uses chitosan as expanding agent, with macropore knot Containing adjuvant component phosphorus and magnesium in the alumina support of structure, the content of adjuvant component phosphorus and magnesium accounts for the percentage composition point of carrier quality Wei not P₂O₅0.1-2.5wt%, 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 one-stage selective hydrogenation of gasoline splitting catalyst according to claim 1, it is characterised in that：The catalysis The content of agent palladium is 0.25-0.3wt%.

3. a kind of one-stage selective hydrogenation of gasoline splitting catalyst according to claim 1, it is characterised in that：It is described to have Also contain adjuvant component cerium in the alumina support of macroporous structure, the percentage that the content of adjuvant component cerium oxide accounts for carrier quality contains Measure as 0.1-2.5wt%.

4. a kind of a kind of preparation method of one-stage selective hydrogenation of gasoline splitting catalyst described in claim 1, its feature exists In：Comprise the following steps：Alumina support of the palladium-containing solution dipping with macroporous structure is prepared, it is small through 110-160 DEG C of drying 3-9 When, 400-650 DEG C is calcined 4-9 hours, finally gives catalyst prod.

5. a kind of one-stage selective hydrogenation of gasoline splitting catalyst according to claim 1, it is characterised in that：The oxidation Alumina supporter also contains meso-hole structure simultaneously, and macropore range is in 5-50nm, mesoporous ratio 15-75%.

6. a kind of one-stage selective hydrogenation of gasoline splitting catalyst according to claim 1, it is characterised in that：It is described to have The preparation method of the alumina support of macroporous structure comprises the following steps：First, acid solution acidified chitosan is used, then will intend thin Diaspore and sesbania powder are added in kneader and are well mixed, and add the mixed solution of phosphoric acid and magnesium nitrate, will finally contain shell The acid solution of glycan, 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.

7. a kind of one-stage selective hydrogenation of gasoline splitting catalyst according to claim 6, it is characterised in that：The acid is molten The process of liquid acidified chitosan is as follows：Chitosan expanding agent is added in 30-95 DEG C of deionized water first, is added dropwise afterwards Acid, until chitosan dissolving is complete, obtains the acid solution containing expanding agent.

8. a kind of one-stage selective hydrogenation of gasoline splitting catalyst according to claim 3, it is characterised in that：It is described to have The preparation method of the alumina support of macroporous structure comprises the following steps：First, acid solution acidified chitosan is used, then will intend thin Diaspore and sesbania powder are added in kneader and are well mixed, and add the mixed solution of phosphoric acid, magnesium nitrate and cerous nitrate, finally The acid solution of chitosan-containing is added in boehmite and mediated uniformly, the addition of the acid solution containing expanding agent is the thin water of plan The 0.1-8wt% of aluminium stone, by extrusion-shaping-drying-roasting, obtains the alumina support with macroporous structure.

9. a kind of one-stage selective hydrogenation of gasoline splitting catalyst according to claim 6, it is characterised in that：Will to right The 6 obtained alumina supports with macroporous structure are sought, carrier surface is modified using phosphorus and magnesium：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 exist respectively in modified alumina support, alumina support of the control with macroporous structure In the range of 0.1-2.5wt% and 0.1-2.5wt%, and make carrier surface phosphorus pentoxide and magnesia content be inside five Aoxidize 1.1-1.6 times of two phosphorus and content of magnesia.

10. a kind of one-stage selective hydrogenation of gasoline splitting catalyst according to claim 8, it is characterised in that：To right It is required that the 8 obtained alumina supports with macroporous structure, are modified using phosphorus, magnesium and cerium to carrier surface：Configuration is phosphorous Alumina support of the aqueous solution spray with macroporous structure of acid, magnesium nitrate and cerous nitrate, used additives are obtained through drying, roasting Phosphorus, magnesium and cerium carry out phosphorus pentoxide, oxygen in the alumina support of surface modification, alumina support of the control with macroporous structure The content of change magnesium and cerium oxide makes carrier surface phosphorus pentoxide, magnesia and oxidation all in the range of 0.1-2.5wt% The content of cerium is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.