CN107177370B - A method of being used for FCC gasoline removal of mercaptans - Google Patents

Abstract

The present invention relates to a kind of methods for FCC gasoline removal of mercaptans, using fixed bed reactors, used catalyst includes the alumina support and the metal active constituent nickel being carried on carrier and molybdenum for having macroporous structure, by weight percentage, alumina support with macroporous structure is 66 91wt%, and alumina support is used as expanding agent using chitosan, and adjuvant component phosphorus and magnesium are contained in carrier, nickel oxide content is 5 19wt%, and oxidation molybdenum content is 2 15wt%；Reaction process condition is：110 220 DEG C of reaction temperature, 1.1 3.5MPa of reaction pressure, 1.2 4.0h of volume space velocity^‑1, hydrogen to oil volume ratio 7 25:1.For inventive desulfurization alcohol method to different sulfur contents, the oil product of mercaptan sulfur content and olefin(e) centent is adaptable.

Description

A method of being used for FCC gasoline removal of mercaptans

Technical field

The present invention relates to one kind being used for FCC gasoline removal of mercaptans method.

Background technology

Increasingly strict with environmental regulation, countries in the world, which propose the quality of refinery products, to be increasingly stringenter It is required that being especially increasingly stringenter to the limitation of refinery products sulfur content.Vulcanize owner contained in oils To be mercaptan (RSH), thioether (RSR) etc., wherein influence of the mercaptan to product quality is maximum, not only has foul smell, very strong Corrosivity can also influence the stability of product.

CN1229838A discloses a kind of method for transformation of hydrocarbon ils, and this method is to be catalyzed feedstock oil and a kind of hydrofinishing Agent removal of mercaptans under the process conditions of hydro-sweetening, the Hydrobon catalyst contain the oxygen of load on the alumina support Change tungsten (molybdenum), nickel oxide and cobalt oxide, the wherein content of tungsten oxide (molybdenum) is 4-10wt%, and the content of nickel oxide is 1-5wt%, The content of cobalt oxide is 0.01-0.1wt%, and the total atom number and the ratio between the total atom number of nickel, cobalt, tungsten (molybdenum) of nickel and cobalt are 0.3- 0.9.CN102451694A discloses a kind of hydrodesulfurization alcohol catalyst and its preparation method and application.The catalyst is with aluminium oxide Or silicon-containing alumina is carrier, and using phosphorus as adjuvant component, using copper and zinc as active component, on the basis of catalyst quality, auxiliary agent The content of phosphorus is 0.5-3.0wt%, and the content of zinc oxide is 3-15wt%, and the content of copper oxide is 5-30wt%.Because of the catalysis Agent has very strong hydrogenation activity, and when for handling full fraction FCC gasoline, mercaptans content is reduced to 3 μ g/g by 38 μ g/g, together When olefin(e) centent 20v% is also reduced to by 25v%, RON losses are up to 1.3 units.CN00136870.2 provides a kind of use In the selectively mercaptan-eliminating catalyst and preparation method thereof for removing mercaptan sulfur in aviation fuel.Catalyst is counted in parts by weight Following component:1. molybdenum oxide 7-20；2. cobalt oxide 0.1-5；3. nickel oxide 0-5；4. silica 0-10；5. phosphorus or boron or fluorine 0- 4；6. aluminium oxide 0-40；7. titanium dioxide 60-100.The preparation method of catalyst is that catalyst carrier maceration extract is impregnated 1-2 Hour, it is then dry at 100-130 DEG C；It is finally roasted at 400-550 DEG C 2-6 hours and obtains catalyst.This catalyst pair Mercaptan sulfur in jet fuel has good removal effect and preferable low temperature active.CN201210393263.4 is related to a kind of new The preparation method and application of type demercaptaning for gasoline adsorbent.The preparation method of the demercaptaning for gasoline adsorbent includes the following steps： Solvent, metal ion presoma, mesoporous material are uniformly mixed, are aged, organic ligand is added, carries out hydrothermal crystallizing processing；So Afterwards, the product of hydrothermal crystallizing processing filtered, washed, dried, it is compound to obtain zeolite imidazole class framework material/mesoporous material Object；Compression molding, crushing and screening are carried out to the zeolite imidazole class framework material/mesoporous material compound, obtain gasoline desulfurization Alcohol adsorbent.In zeolite imidazole class framework material/mesoporous material compound provided by the invention, zeolite imidazole class framework material Specific surface area is high, while being in high dispersion state on mesoporous material, spreads limitation caused by efficiently solving reunion.It is described molten Agent is the combination of one or more of deionized water, methanol, ethyl alcohol and n,N-Dimethylformamide；The metal ion is Zn²⁺、Cu²⁺And Co²⁺One or more of combination；The metal ion presoma is the nitrate and/or second of metal ion The combination of one or more of hydrochlorate；The organic ligand is in imidazoles, 2-methylimidazole, 2- nitroimidazoles and benzimidazole One or more；The mesoporous material is modified ordered mesoporous molecular sieve.CN200910082945.1 is related to one kind and urges Change cracking gasoline selective hydrocatalyst and preparation method thereof.Catalyst of the present invention is by Al₂O₃-TiO₂Composite oxide carrier It is formed with reactive metal oxides, based on the weight percent to catalyst, the NiO contents in reactive metal oxides are 10-20w%, MoO3 content are 5-12w%；Wherein carrier Al₂O₃-TiO₂Oxide TiO₂：Al₂O₃Weight ratio be 0.01-1： 1.Catalyst of the present invention is in low temperature (100-200 DEG C), low pressure (1-3.0MPa), low hydrogen/gasoline ratio (hydrogen to oil volume ratio 5：1-100：1) Under conditions of, catalytically cracked gasoline is handled, very high de- diolefin and removal of mercaptans activity, selectivity and stability are shown. CN200910187903.4 discloses a kind of hydrodesulfurization alcohol catalyst and its preparation method and application.The catalyst is with HZSM-5 Molecular sieve is main carrier component, using copper and zinc as active component.In terms of oxide weight, the content of copper oxide is active component The content of 5%-27%, zinc oxide are 3%-15%, are prepared using saturation total immersion technology.The catalyst of the present invention is suitable for light Matter oil product carries out selective hydrodesulfurization alcohol reaction, has the characteristics that removal of mercaptans activity is high, hydrogenation of olefins activity is low, and after reaction Liquid yield is high, loss of octane number is seldom.It is de- that CN201610187374.8 provides the light hydrocarbons regulated and controled based on aluminium oxide crystal face Mercaptan catalyst and its preparation method, the catalyst are using the gama-alumina after hydro-thermal process of the present invention regulation and control as carrier, with nickel And molybdenum is active metal.Light hydrocarbons mercaptan-eliminating catalyst of the present invention is high activity and high-selectivity catalyst, be can be used Macromolecular sulfide is generated with alkadienes effect in being catalyzed mercaptan in light hydrocarbons, and the selectivity that can be also catalyzed diolefin adds Hydrogen is saturated, and compared with existing catalyst, catalyst desulfurizing alcohol activity provided by the present invention is high, diolefin hydrogenation selectivity is high, And active component is not lost in, not easy in inactivation, thus the catalyst runs period is long, has preferable prospects for commercial application.The invention Gama-alumina after hydro-thermal process regulation and control, as described above, the gama-alumina is characterized in that it with highly exposed (111) (110) crystal face so that active metal nickel (Ni) and molybdenum (Mo) in catalyst of the present invention can be in the gama-alumina crystal faces Upper realization crystal face selection preferably loads, and W metal is preferentially supported on newly (111) crystal face of exposure, and metal Mo is preferentially supported on Newly on (110) crystal face of exposure.Meanwhile two kinds of active metals also by respectively with modified gama-alumina (111) and (110) effect of crystal face forms two different active crystal faces, to obtain high activity and highly selective light hydrocarbons Mercaptan-eliminating catalyst.The catalyst can be in efficient removal liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and coker gasoline etc. In the case of mercaptan and/or alkadienes in light fraction, retain the alkene in raw material, the octane number RON of gasoline only reduces by 0.3 Point or so, to realize the high value added utilization of light hydrocarbons.

The composition and comparision contents of above-mentioned catalyst are more, and preparation process is complicated, and produce catalyst prod matter in enormous quantities Amount is difficult control.

Macroporous oxide due to larger pore passage structure, higher specific surface area, good thermal stability, 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 aluminium oxide with macroporous structure is relatively more.CN03126434.4 discloses a kind of macropore alumina supporter, Containing aluminium oxide, also contain a kind of halogen, on the basis of carrier total amount, which contains the aluminium oxide of 95-99 weight %, with member Element meter, the halogen of 0.1-5 weight %, acid amount are less than 0.2 mM/gram.The preparation method of macropore alumina supporter includes will A kind of precursor of aluminium oxide is molded and roasts, and before molding and roasting, the precursor of aluminium oxide and a kind of expanding agent are mixed It closes, the expanding agent includes a kind of organic expanding agent and a kind of halide, and calcination temperature is 600-850 DEG C, roasting time 1-10 Hour, the dosage of each component makes final alumina support contain, on the basis of carrier total amount, the aluminium oxide of 95-99 weight %, Based on the element, the halogen of 0.1-5 weight %.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.Polymeric alcohol is selected from one or more of polyethylene glycol, poly- propyl alcohol, polyvinyl alcohol, and surfactant is selected from fat Fat alcohol polyoxyethylene ether, fatty alkanol amide, molecular weight are in the acrylic copolymer of 200-10000, maleic acid copolymer It is one or more of.A kind of high temperature-resistant active aluminum oxide material of CN201110410339.5 offers and preparation method thereof, the oxygen Change aluminum material to be made by following steps：After macropore boehmite, high viscous boehmite are mixed with additive with water, turning Speed is to be stirred evenly under 100-1000r/min, adds a concentration of 30% dilute nitric acid reaction, until pH is the peptization of 2.0-5.5 When state, 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, slurrying, spraying, do It is 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. Specific surface can be kept in 110m for a long time at a temperature of 1000-1100 DEG C²/ g or more；The work of the alumina material preparation method Skill process is simple, of low cost.The wherein described sky agent of making is selected from polyvinyl alcohol, polyethylene glycol, polyacrylamide or methyl fibre One kind in dimension element, dosage are 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 of a diameter of 600nm 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 its fully penetrated into the gap of microballoon, Through dry and roasting, 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 alumina sol is made in aluminum nitrate plus weak aqua ammonia, then stirs the two by a certain percentage mixed It closes, is ultrasonically treated, then through dry and roasting, obtain macroporous aluminium oxide.CN201010221302.3 (CN102311134A) is open A kind of spherical integral macroporous alumina and preparation method thereof.This approach includes the following steps：By polymer microballoon lotion, oxidation Aluminum sol and coagulant are uniformly mixed with certain proportion, which is scattered in oil phase, form w/o type drop, then again Above-mentioned mixed phase system is heated, makes the alumina sol gelling balling-up in water phase, it is micro- to isolate molding gel from oil phase later Ball, then in aqueous ammonia medium the spherical integral macroporous alumina is obtained after aged, dry and roasting.The aluminium oxide Macropore diameter is uniform 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, convenient for being prepared on a large scale.The type of polymer microballoon diameter 50-1000nm, polymer microballoon are polystyrene The esters microballoons such as microballoon, polyaerylic acid N-butyl microballoon, polyacrylate.Coagulant is hexamethylenetetramine, urea.Oil phase is Organic hydrocarbon.The invention mainly prepares Integral macroporous alumina, and macropore diameter is uniform controllable.Preparation process uses Lipid microballoon and coagulant etc..Preparation process is complicated, and reagent raw material used is relatively more.Due to polymer microballoon make 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 approach includes the following steps：Aluminium Source, polyethylene glycol and after low-carbon alcohol and water at least one is uniformly mixed, will low-carbon epoxyalkane be added it is described mixed It closes in object, Integral macroporous alumina is obtained through aging, immersion, drying and roasting.Preparation method is simple, ring by the present invention 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 obtain containing eurypyloue alumina support, the dosage of expanding agent The 10-30% of aluminium 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 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 a kind of side 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 auxiliary hydro-thermal causes 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 more 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 Method includes 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 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 The aluminium not only macropore duct with three-dimensional order but also with higher specific surface area.The invention passes through the appropriateness burning to template The small fenestra tied and formed, makes the macropore in material pass through 12 small fenestras with the macropore of surrounding and is connected.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, includes 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 Oil phase；3) Span80 and pore-foaming agent, stirring are added in oil phase；4) clear oil phase obtained by step 3) is 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 It is 1 μm -100 μm that microballoon, which has internal closing macroporous structure, Microsphere Size, and the invention is solidifying using pore-foaming agent and the colloidal sol in lotion 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 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 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 more.CN101200297A discloses whole The preparation method of build macroporous aluminium oxide：Use reversed concentrated emulsions method big as monomer preparation monoblock type using styrene and divinylbenzene Hole organic formwork；Using aluminium isopropoxide or boehmite Al is prepared as predecessor₂O₃The hydrosol；By Al₂O₃The hydrosol is filled into whole In body formula macropore organic formwork；Monolithic devices organic/inorganic composite after filling is through drying, in 600 DEG C of -900 DEG C of roasting removings Template obtains integral macroporous alumina.The advantages of this method is that preparation process is simple and practicable, monoblock type macropore oxygen obtained Change the macropore duct that there is aluminium micron order to interconnect, aperture is 1-50 μm.It is simple that this method prepares Integral macroporous alumina It is 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, this For method while reducing organic monomer consumption, the preparation efficiency of prepared template is relatively low, is unfavorable for subsequent step macropore It is prepared by the batch of aluminium oxide.A kind of preparation methods of the alumina support of composite pore structural of CN201110032234.0, including will Closing containing calorize selected from least one of aluminium isopropoxide, aluminium secondary butylate, aluminum nitrate, aluminium chloride, Aluminum sol and boehmite powder Object and composite mould plate agent are mixed and are roasted, the composite mould plate agent be mesoporous template and macroporous granules template, it is described mesoporous Template is selected from polyethylene glycol propylene glycol-polyethylene glycol triblock polymer, polyethylene glycol, lauryl amine, cetyl At least one of trimethylammonium bromide, lauric acid, stearic acid and fatty alcohol polyoxyethylene ether, the macroporous granules template are selected from Grain size is residual more than the polystyrene microsphere of 50nm, poly (methyl methacrylate) micro-sphere, particles of bioglass, pitch particle or heavy oil Slag；The weight ratio of the mesoporous template, macroporous granules template and aluminum contained compound is 0.1-2:0.1-0.7:1, wherein institute The weight of aluminum contained compound is stated in terms of aluminium oxide.The invention also discloses have mesopore orbit while preparation by the above method With the alumina support in macropore duct, intermediary hole accounts 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, expanding agent need not be added, it is cost-effective, it is suitble to work Industryization is produced in batches.The preparation process of alumina support of the present invention includes the following steps：(1) aluminum nitrate, ammonium hydrogen carbonate and table Face activating agent is fully ground uniformly, in the closed container of specific temperature be aged certain time obtain precursor aluminium carbonate ammonium；(2) It will be uniformly mixed aftershaping with peptizing agent after precursor aluminium carbonate ammonium drying obtained by (1), banded extruder generally may be used and squeeze Item is molded；(3) (2) are obtained that final alumina support is made in molding drying, aerobic roasting.Luring described in step (1) The polyethylene glycol that agent is liquid form is led, addition 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 effusion of these gases can manufacture some macropores.Simultaneous oxidation The pattern of aluminium is transformed by the pattern topology of aluminium carbonate ammonium.Slower heating rate is conducive to gas object in roasting process Matter slowly escapes, and does not easily cause carrier and caves in.Method is simple, need not 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 acidification is less than or equal in 3 aqueous solution, and 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 After stirring 0.1-3h at room temperature, 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) it after the solution after being aged stirs evenly, is dried using spray drying process, 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 with first rate of heat addition at room temperature, 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 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, 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 there is hollow foam shape pattern, and it is compound with micropore-mesopore-macropore 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 refer to not only included micropore that aperture is less than 2nm, but also including aperture in 2nm-50nm Between it is mesoporous, further include aperture be more than 50nm macropore.Further include being made to obtained containing being added in aluminum water solution in step 1) Hole agent, the amount that the pore creating material is added so that it is aluminum ions molar concentration that the molar concentration of pore creating material in rear solution, which is added, 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.Include 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 Above-mentioned solution is added and dissolves, aluminium ion is 1 with template molar ratio：The pH value control of 0.015-0.025, final solution exist 3.5-6.0；B. solution prepared by a steps is subjected to burin-in 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- Answer auxiliary agent and template space frame effect and coordination and intermediary's organic polymer, reaction promoter to inorganic ions Complexing, prepare the adjustable macroporous-mesoporous alumina material in aperture to a step.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 It can be realized and be 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 lauric acid.Triblock copolymer is P123 or F127.Tie-Zhen Ren etc. (Langmuir, 2004,20：1531-1534) use nonionic surfactant 56 aluminium secondary butylates of Brij 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 aluminium oxide of 0.4-1.4 μm of hole wall.Its deficiency is aluminium-alcohol salt Expensive, the macroporous-mesoporous alumina hole appearance of synthesis is small, 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. (J.Am.Chem.Soc., 2009,131：It using P123 is template in mixed solution 12896-12897) to use 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.It can not be by organic molecule in the part change of solution itself component and system It interacts to realize the adjustment in aperture.Huining Li et al. (Inorganic Chemistry, 2009,48：4421) it equally adopts The polymethyl methacrylate with single dispersed phase is introduced in mixed solution by template of F127 with sol-gel method (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 come real by the part to solution system itself component Existing aperture adjusts to realize the formation of foramen magnum-mesoporous composite pore structural, thus also cannot achieve the controllable of foramen magnum-mesoporous aperture 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. to be used 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, manufacturing 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 of the adding carbohydrate compound 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 is 5:1-10：1 mass ratio presses 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, polyphenyl is made Ethylene ball surface uniformly coats one layer of chitosan-acetic acid-aqueous solution；It is coated with the polyphenyl second of chitosan-acetic acid-aqueous solution again Alkene ball coats 2-24h in alpha-alumina powder input ball-milling device, with the rotating speed rotation of 5-30r/s, and core-shell structure copolymer ball is made；It will After the calcining of core-shell structure copolymer ball warp, a diameter of 0.2-2mm is obtained, the alumina hollow ball that wall thickness is 20-100 μm. 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 Suddenly：Will into monodisperse polymer micro-sphere lotion adding carbohydrate compound and the concentrated sulfuric acid, 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 A diameter of 50-1000nm, can be used polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polyacrylic acid N-butyl microballoon and It is one or more in the different monooctyl ester microballoon of polyacrylic acid, preferred polystyrene microsphere.The monodisperse refers to polymer microballoon The standard deviation of diameter is not more than 10%.The carbohydrate organic matter is one or more in Soluble Monosaccharide and polysaccharide, preferably It is one or more in sucrose, glucose, chitosan.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 sorbing 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)₃It is in chitosan complexes Now typical mesoporous characteristic, BET specific surface area 55.4m²·g^-1, BJH average pore sizes are 3.3nm；Specifically preparation method is：Claim It takes 2.0g Aluminium chloride hexahydrates to be dissolved in the hydrochloric acid that 5.0mL pH value is 1,2.0g chitosans is added, then add 10.0mL distilled water Stirring is used in combination dilute hydrochloric acid to adjust the pH value of solution to 1.Still aging 30min (solution becomes paste), the NaOH for being 14 with pH value Solution adjusts the pH value of solution to 8, there is white flock precipitate generation, filters, washes away remaining NaOH with distilled water, be put into baking Case obtains product after keeping the temperature 5h at 120 DEG C.Step as above, it is respectively 1 to prepare chitosan and aluminium chloride mass ratio respectively:2、1:3、 2:1、3:1 product.

《The preparation of chitosan/oxidized aluminium composite aerogel and characterization》(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 novel chitosan/oxidized aluminium 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 volatilizees 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 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 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, 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 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；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 in sodium, starch derivatives or carbon black or mixture.The invention, which is added to anion surfactant, reduces various help Specific surface area increases 246m2/g, expanding agent Sodium Polyacrylate while agent ingredient additive amount.Tooth spherical shape oxidation described in the invention Alumina supporter, since the groups such as wherein various auxiliary agents such as peptizing agent, expanding agent, dispersant, anion 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, dispersant, the reagents such as expanding agent, obtained alumina support are unimodal pore size distributions.CN201110116418.5 is carried 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 kind in 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 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, 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.

The prior art mainly changes support chemistry composition and type, and addition coagent to promote catalyst performance Energy.Influence due to mercaptan to oil product product quality is maximum, and not only there is foul smell, very strong corrosivity can also influence The stability of product.Therefore mercaptan-eliminating catalyst is needed to have catalyst desulfurizing alcohol activity high, diolefin hydrogenation selectivity is high, pungent Alkane value loses low characteristic, and solution demercaptaning for gasoline environmental pollution is serious, the not high problem of activity.

Invention content

The problem to be solved in the present invention is to provide a kind of method for FCC gasoline removal of mercaptans, and the catalyst used includes Alumina support with macroporous structure and the active component nickel and molybdenum that are carried on carrier, the catalyst is with removal of mercaptans activity Height, diolefin hydrogenation selectivity is high, the low feature of loss of octane number.Using aluminium oxide as carrier, alumina support uses catalyst Chitosan synthesizes the alumina support with macroporous structure as expanding agent.Macroporous aluminium oxide is adjustable with pore size, The characteristics of macropore ratio can be controlled effectively.

The present invention provides a kind of method for FCC gasoline removal of mercaptans, and using fixed bed reactors, catalyst includes having The alumina support of macroporous structure and the metal active constituent nickel and molybdenum being carried on carrier have big by weight percentage The alumina support of pore structure is 66-91wt%, and alumina support is used as expanding agent using chitosan, and auxiliary agent group is contained in carrier It is respectively P that the content of point phosphorus and magnesium, 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, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, hole holds 0.8- 2.0ml/g, preferably 0.8-1.3ml/g or preferred 1.6-2.0ml/g, specific surface area 250-300m²/g；Nickel oxide content is 5- 19wt%, oxidation molybdenum content are 2-15wt%；Reaction process condition is：110-220 DEG C of reaction temperature, reaction pressure 1.1- 3.5MPa, volume space velocity 1.2-4.0h^-1, hydrogen to oil volume ratio 7-25:1.

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%.

Preferably, by weight percentage, the alumina support with macroporous structure is 71-88wt% to the catalyst, Nickel oxide content is 6-17wt%.Oxidation molybdenum content is 5-12wt%.

Preferably, reaction process condition is：120-180 DEG C of reaction temperature, reaction pressure 1.1-3.0MPa, volume space velocity 1.2-3.0h^-1, hydrogen to oil volume ratio 7-20:1；

The mercaptan-eliminating catalyst preparation method includes the following steps：Nickeliferous and containing molybdenum soluble-salt is made into dipping Liquid impregnates the alumina support with macroporous structure, and it is small to roast 5-9 at 4-8 hours, 650-800 DEG C dry at 120-160 DEG C When, obtain mercaptan-eliminating catalyst.

The present invention has the alumina support of macroporous structure, the addition and reaming that aperture can be by change 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 the alumina support with macroporous structure to be acidified first 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 uniform, the addition of the acid solution containing expanding agent by liquid It is obtained with macropore by extrusion-molding-drying-roasting 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 dissolving is complete, 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 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.Ultrasonic oscillation 10min or more, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent Wave 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.

Extrusion technique is that the acid solution containing expanding agent configured is added in sesbania powder and boehmite and is mixed Even, extrusion, molding later is dried 3-9 hours by 100-160 DEG C, and 650-800 DEG C roasts 4-8 hours, finally obtains with big The alumina support of pore 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 less than phosphorus when preparing complex carrier Acid and magnesium nitrate aqueous solution spray carrier surface, preferably carry out carrier surface modification 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 Modified alumina support controls in the alumina support with macroporous structure phosphorus pentoxide 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 utilize 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：Alumina support of the aqueous solution spray with macroporous structure for configuring phosphoric acid, magnesium nitrate and cerous nitrate, through dry Dry, roasting obtains the alumina support that used additives phosphorus, magnesium and cerium carry out surface modification, 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 carrier surface five is made to aoxidize 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 the following advantages：

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 contain it is mesoporous, be a kind of Jie-macropore alumina supporter.Catalyst carrier has macroporous structure, Catalyst is not easy coking and deactivation, and stability is good.

2, the present invention can also in alumina support and carrier surface introduce cerium, make carrier surface cerium content higher than carry Internal portion should be prepared into mercaptan-eliminating catalyst with the alumina support of macroporous structure, and can inhibit olefinic polymerization, improve diene 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 1.1-1.6 times of portion's phosphorus pentoxide, magnesia, 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, improves removal of mercaptans activity.And in this carrier Outer concentration of component is different, so that alkadienes is not easily accessed inside duct and polymerisation blocking duct occurs.Carrier surface is changed Into dipping method, impregnated carrier surface should not be used large quantity of moisture to be made to enter carrier, it is not achieved and improves carrier surface Jie-big boring ratio The purpose of example.

4, the catalyst that inventive desulfurization alcohol method uses is suitable for removing liquefied petroleum gas, FCC gasoline, catalytic pyrolysis vapour Oil and/or the mercaptan in coker gasoline and/or alkadienes；Or for being catalyzed diolefin selective hydrogenation.That is catalyst Hydrogen, the light hydrocarbons such as removing liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/or coker gasoline are not added with to the alkene in raw material Mercaptan in class and/or alkadienes, catalyst choice are good.Octane number RON loss 0.3-0.4 points of gasoline or so.Catalyst Removal of mercaptans activity is high, and diolefin hydrogenation selectivity is high, and loss of octane number is low.Inventive desulfurization alcohol method is to different sulfur contents, sulphur The oil product of alcohol sulfur content and olefin(e) centent is adaptable.

Description of the drawings

Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.

Specific implementation mode

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.

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 agents are added in 50 DEG C of deionized water first, acetic acid is added dropwise later, 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 aqueous solution.Weigh 350g boehmite powder and the fields 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.At 120 DEG C, dry 8 is small 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 with macroporous structure is shown in Table 1 with pore-size distribution.

Nickel nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide is added and adjusts oxide impregnation aluminium load after pH value makes salt all dissolve Body 1,6 hours dry at 130 DEG C, 680 DEG C roast 8 hours, obtain catalyst 1.Catalyst 1 mainly forms：With macropore knot The alumina support of structure is 79wt%, and nickel oxide content 12wt%, oxidation molybdenum content is 9wt%.

Embodiment 2

8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water, acetic acid is added dropwise later, until shell is poly- 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 aqueous solution.Weigh 350g boehmite powder and 20.0g sesbania powders 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, obtains phosphorous and magnesium alumina support 1.Phosphorus and magnesium is recycled to be modified carrier surface, configuration is phosphorous Alumina support 1 of the aqueous solution of the acid and magnesium nitrate spray with macroporous structure, 8 hours dry through 120 DEG C, 700 DEG C of roastings 4 are small When obtain the alumina support 2 that used additives phosphorus and magnesium carries out surface modification, 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 with macroporous structure and aperture point Cloth is shown in Table 1.

Nickel nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide is added and adjusts oxide impregnation aluminium load after pH value makes salt all dissolve Body 2,6 hours dry at 130 DEG C, 720 DEG C roast 5 hours, obtain catalyst 2.Catalyst 2 mainly forms：With macropore knot The alumina support of structure is 79.5wt%, and nickel oxide content 10.5wt%, oxidation molybdenum content is 10wt%.

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 is shown in Table 1 with pore-size distribution.

Nickel nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide is added and adjusts oxide impregnation aluminium load after pH value makes salt all dissolve Body 3,6 hours dry at 130 DEG C, 750 DEG C roast 5 hours, obtain catalyst 3.Catalyst 3 mainly forms：With macropore knot The alumina support of structure is 81.5wt%, and nickel oxide content 6wt%, oxidation molybdenum content is 12.5wt%.

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 ultrasonic oscillation 15 minutes.Obtain the aluminium 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%.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 is shown in Table 1 with pore-size distribution.

Nickel nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide is added and adjusts oxide impregnation aluminium load after pH value makes salt all dissolve Body 4,6 hours dry at 130 DEG C, 750 DEG C roast 5 hours, obtain catalyst 4.Catalyst 4 mainly forms：With macropore knot The alumina support of structure is 77.5wt%, and nickel oxide content 16wt%, oxidation molybdenum content is 6.5wt%.

Embodiment 5

The preparation method of carrier is carried out according to embodiment 1, and catalyst 5 mainly forms：Carrying alumina with macroporous structure Body is 76wt%, and nickel oxide content 18wt%, oxidation molybdenum content is 6wt%.

Embodiment 6

The preparation method of carrier is carried out according to embodiment 2, except that carrier surface phosphorus pentoxide and magnesia Content is 1.4 times of internal phosphorus pentoxide and content of magnesia.Catalyst 6 mainly forms：Aluminium oxide with macroporous structure Carrier is 80.5wt%, and nickel oxide content 5.5wt%, oxidation molybdenum content is 14wt%.

Embodiment 7

The preparation method of carrier according to embodiment 3 carry out, except that in carrier adjuvant component phosphorus, magnesium and cerium content The percentage composition for accounting for carrier quality is respectively 0.9wt%, 0.7wt%, 0.7wt%.Catalyst 7 mainly forms：With macropore knot The alumina support of structure is 80wt%, and nickel oxide content 10.5wt%, oxidation molybdenum content is 9.5wt%.

Embodiment 8

The preparation method of carrier is carried out according to embodiment 4, except that surface phosphorus pentoxide, cerium oxide and magnesia Content be 1.3 times of internal phosphorus pentoxide, cerium oxide and content of magnesia.Catalyst 8 mainly forms：With macroporous structure Alumina support be 78wt%, nickel oxide content 13.5wt%, oxidation molybdenum content be 8.5wt%.

The alumina support specific surface area and pore-size distribution of 1 macropore of table

Catalyst 1-4 is loaded into fixed bed reactors respectively, carries out evaluation catalyst reaction performance.With sulfurized oil pair Catalyst carries out presulfurization, and sulfide stress 3.2MPa, hydrogen to oil volume ratio 300, sulfurized oil volume space velocity is 3.5h^-1, vulcanization Program is respectively in 240 DEG C, 280 DEG C of vulcanizing treatment 6h.After waiting for vulcanizing treatment, it is switched at full fraction FCC gasoline displacement 6h is managed, reaction process condition is then adjusted to, carries out sweetening reaction.FCC feedstock content of sulfur in gasoline 556 μ g/g, 35 μ of mercaptan sulfur G/g, olefin(e) centent 47.35v%, RON 88.36.Reaction process condition is：115 DEG C of temperature of reactor, volume space velocity 3.3h^-1, Hydrogen to oil volume ratio 11:1, reaction pressure 2.1MPa.Sampling analysis after reaction about 55h.Catalyst 1-4 reaction results are as follows：Catalysis 1 sulfur content of agent, 544 μ g/g, mercaptan sulfur 5 μ g/g, olefin(e) centent 46.59v%, RON 87.93, yield of gasoline 97.8wt%；Catalysis 2 sulfur content of agent, 547 μ g/g, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.83v%, RON 87.95, yield of gasoline 98.2wt%；Catalysis 3 sulfur content of agent, 545 μ g/g, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.85v%, RON 88.01, yield of gasoline 98.0wt%；Catalysis 4 sulfur content of agent, 548 μ g/g, mercaptan sulfur 2 μ g/g, olefin(e) centent 46.82v%, RON 88.03, yield of gasoline 98.5wt%；Catalysis Agent product mercaptan sulfur is less than 4 μ g/g, and olefin(e) centent is basically unchanged, and for reaction loss of octane number in 0.3-0.4, catalyst activity is high, Selectivity is good, and loss of octane number is low.Stability test, reaction operation 400h, 1 sulfur content of catalyst, 542 μ g/ are carried out to catalyst G, mercaptan sulfur 4 μ g/g, olefin(e) centent 46.56v%, RON 87.91, yield of gasoline 97.9wt%；2 sulfur content of catalyst, 546 μ g/ G, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.82v%, RON 87.94, yield of gasoline 98.0wt%；3 sulfur content of catalyst, 545 μ g/ G, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.84v%, RON 87.98, yield of gasoline 98.1wt%；4 sulfur content of catalyst, 547 μ g/ G, mercaptan sulfur 2 μ g/g, olefin(e) centent 46.83v%, RON 88.04, yield of gasoline 98.4wt%；It is produced after catalyst operation 400h Product mercaptan sulfur is less than 4 μ g/g, and olefin(e) centent is basically unchanged, and catalyst is not easy coking and deactivation, and stability is good.

Catalyst 5-8 is loaded into fixed bed reactors respectively, carries out evaluation catalyst reaction performance.With sulfurized oil pair Catalyst carries out presulfurization, and sulfide stress 3.2MPa, hydrogen to oil volume ratio 300, sulfurized oil volume space velocity is 3.5h^-1, vulcanization Program is respectively in 240 DEG C, 280 DEG C of vulcanizing treatment 6h.After waiting for vulcanizing treatment, it is switched at full fraction FCC gasoline displacement 6h is managed, reaction process condition is then adjusted to, carries out sweetening reaction.FCC feedstock content of sulfur in gasoline 733 μ g/g, 28 μ of mercaptan sulfur G/g, olefin(e) centent 44.68v%, RON 89.24.Reaction process condition is：145 DEG C of temperature of reactor, volume space velocity 2.2h^-1, Hydrogen to oil volume ratio 14:1, reaction pressure 2.7MPa.5 sulfur content of catalyst, 721 μ g/g, 4 μ g/g of mercaptan sulfur, olefin(e) centent 43.70v%, RON 88.62, yield of gasoline 97.6wt%；6 sulfur content of catalyst, 724 μ g/g, 2 μ g/g of mercaptan sulfur, olefin(e) centent 43.95v%, RON 88.95, yield of gasoline 98.3wt%；7 sulfur content of catalyst, 722 μ g/g, 3 μ g/g of mercaptan sulfur, olefin(e) centent 44.15v%, RON 88.84, yield of gasoline 98.0wt%；8 sulfur content of catalyst, 725 μ g/g, 2 μ g/g of mercaptan sulfur, olefin(e) centent 44.19v%, RON 89.01, yield of gasoline 98.6wt%.Catalyst activity is high, and selectivity is good, and loss of octane number is low, catalyst To different sulfur contents, the oil product of mercaptan sulfur content and olefin(e) centent is adaptable.

Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art It should all belong to the scope of protection of the present invention.

Claims (5)

1. a kind of method for FCC gasoline removal of mercaptans, it is characterised in that：

Using fixed bed reactors, used catalyst includes the alumina support with macroporous structure and the gold being carried on carrier Belong to active component nickel and molybdenum, by weight percentage, the alumina support with macroporous structure is 66-91wt%, carrying alumina Body is used as expanding agent using chitosan, and adjuvant component phosphorus and magnesium are contained in carrier, also contains adjuvant component cerium, adjuvant component phosphorus with The percentage composition that the content of magnesium accounts for carrier quality is respectively phosphorus pentoxide 0.1-2.5wt%, magnesia 0.1-2.5wt%, is helped The percentage composition that the content of agent component cerium accounts for carrier quality is cerium oxide 0.1-2.5wt%, nickel oxide content 5-19wt%, oxygen Change molybdenum content is 2-15wt%；Catalyst pore-size distribution 60-180nm, macropore ratio 2-75%, hole hold 0.8-2.0ml/g, compare table Area 250-300m²/g；

Reaction process condition is：110-220 DEG C of reaction temperature, reaction pressure 1.1-3.5MPa, volume space velocity 1.2-4.0h^-1, hydrogen Oil volume ratio 7-25:1；

The method for preparing catalyst includes the following steps：Nickeliferous and containing molybdenum soluble-salt is made into maceration extract, dipping has The alumina support of macroporous structure is roasted 5-9 hours at 4-8 hours, 650-800 DEG C dry at 120-160 DEG C, is catalyzed Agent；

The preparation method of the alumina support with macroporous structure includes the following steps：First, 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 Addition 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, carrier surface is modified using phosphorus, magnesium and cerium：It configures 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 the alumina support of surface modification, 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. a kind of method for FCC gasoline removal of mercaptans according to claim 1, it is characterised in that：The reaction process Condition is：120-180 DEG C of reaction temperature, reaction pressure 1.1-3.0MPa, volume space velocity 1.2-3.0h^-1, hydrogen to oil volume ratio 7-20: 1。

3. a kind of method for FCC gasoline removal of mercaptans according to claim 1, it is characterised in that：The catalyst with Weight percent meter, the alumina support with macroporous structure are 71-88wt%, nickel oxide content 6-17wt%, molybdenum oxide Content is 5-12wt%.

4. a kind of method for FCC gasoline removal of mercaptans according to claim 1, it is characterised in that：The carrying alumina Body also contains meso-hole structure simultaneously, and macropore range is in 2-50nm, mesoporous ratio 15-75%.

5. a kind of method for FCC gasoline removal of mercaptans according to claim 1, it is characterised in that：The acid solution acid The process for changing chitosan is as follows：Chitosan expanding agent is added in 30-95 DEG C of deionized water first, acid is added dropwise later, directly It is complete to chitosan dissolving, obtain the acid solution containing expanding agent.