CN107177371B - A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline - Google Patents

A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline Download PDF

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CN107177371B
CN107177371B CN201710409067.4A CN201710409067A CN107177371B CN 107177371 B CN107177371 B CN 107177371B CN 201710409067 A CN201710409067 A CN 201710409067A CN 107177371 B CN107177371 B CN 107177371B
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catalyst
alumina support
acid
alumina
chitosan
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CN107177371A (en
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罗祥生
晁会霞
莫钊桓
劳海静
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Qinzhou University
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Qinzhou University
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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

Abstract

The invention discloses a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline, and using fixed bed reactors, for catalyst using aluminium oxide as carrier, active component is cobalt oxide and nickel oxide, and reaction process condition is：190 310 DEG C of reaction temperature, 1.3 2.6MPa of reaction pressure, 1.3 3.5h of volume space velocity‑1, hydrogen to oil volume ratio 180 400:1.Hydrodesulfurization mild condition, adaptable to different material, loss of octane number is low, and desulfurization degree is high.

Description

A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline
Technical field
The present invention relates to a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline, more specifically using one kind with macropore The aluminium oxide of structure is the FCC gasoline Hydrobon catalyst of carrier, is used for catalytic gasoline selective hydrodesulfurizationmodification.
Background technology
Since the general sulfur content of catalytically cracked gasoline is in 100-500v%, or even also high-sulfur, high olefin feedstock oil, sulphur contain Amount is in 500mg/kg or more, and olefin(e) centent is also above 40%.Selective hydrodesulfurization technology when carrying out deep hydrodesulfurizationof not Evitable that hydrocarbon fraction can be caused to be saturated and reduce octane number, this requires kept away as possible while Hydrobon catalyst desulfurization It is excessive to exempt from loss of octane number.
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)：With chitosan and AlCl3For raw material, it is prepared for chitosan and α-Al (OH)3Composite material.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 246m while agent ingredient additive amount2/ g, expanding agent Sodium Polyacrylate.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.
Aluminium oxide is catalytically cracked gasoline desulfurization common vector, and CN200710177578.4 is related to a kind of combined aluminum oxide-based Catalyst for selectively hydrodesulfurizing and preparation method thereof.The catalyst carrier is 280-300m by specific surface area2/ g, Kong Rongwei The macroporous aluminium oxide and specific surface area of 0.8-0.9mL/g is 250-280m2The small porous aluminum oxide of/g, Kong Rongwei 0.3-0.4mL/g It is combined, active component is cobalt and molybdenum, and auxiliary agent is magnesium and boron.The preparation method of the catalyst includes：By macroporous aluminium oxide and Small porous aluminum oxide mixing, is added sesbania powder and nitric acid, then after kneading, molding, drying and roasting, and alumina composite load is made Then body loads auxiliary agent magnesium and boron and active component cobalt and molybdenum, then through dry and roasting, catalyst is made successively.Catalyst Have many advantages, such as that gasoline selective hydrodesulfurizationmodification activity is good, product research method loss of octane number is low and liquid yield is high. CN201210359156.X is related to a kind of gasoline deep hydrodesulfurizationcatalytic catalytic material and the preparation method of catalyst.Above-mentioned preparation side Method is then to mix its cocurrent by preparing related presoma microemulsion and ammonia microemulsion and react, most afterwards through flocculation, Demulsification, washing of precipitate and roasting obtain the gasoline deep hydrodesulfurizationcatalytic catalytic material of high-specific surface area, by changing microemulsion system Composition and synthesis condition control product grain surface nature, the specific surface area and surface acidity of modulation composite material.This Invention also provides the method that the material synthesized using gained prepares gasoline hydrodesulfurizationcatalyst catalyst as carrier, with the multiple elements design material Material uses microemulsion method supported active metals component, and the metal loaded not only has smaller particle, while having higher Load capacity.The catalyst that the preparation method provided through the invention is prepared shows excellent in terms of gasoline hydrodesulfurizationmethod Catalytic performance.
Invention content
The present invention provides a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline, is produced for catalytic gasoline hydrogenation desulfurization Gasoline products.Hydrodesulfurization mild condition, adaptable to different material, loss of octane number is low, and desulfurization degree is high.
A kind of hydrodesulfurizationprocess process of gasoline of the present invention, includes the following steps：
Using fixed bed reactors, presulfurization is carried out to catalyst with sulfurized oil, presulfurization after treatment is switched to complete Fraction FCC gasoline replacement Treatment；
After waiting for pre-vulcanization process, it is adjusted to reaction process condition, carries out catalytically cracked gasoline reaction；
The catalyst is supported cobalt molybdenum catalyst, and the carrier of catalyst is the aluminium oxide for having macroporous structure Carrier, the composition of catalyst is with oxidation material gauge, including following component：Alumina support 78.0- with macroporous structure 94.0wt%, carrier use chitosan as expanding agent；Active component cobalt oxide 2.0-10.5wt%, molybdenum oxide 2.5- 15.0wt%；
The preparation method of the catalyst, includes the following steps：Soluble-salt containing cobalt and containing molybdenum is made into maceration extract, is soaked Stain has the alumina support of macroporous structure, roasts 5-9 hours, obtains at 4-8 hours, 650-800 DEG C dry at 120-160 DEG C To Hydrobon catalyst.
A kind of catalyst for catalytic gasoline hydrogenation desulfurization of the present invention, it is composed of the following components：Have The alumina support 78.0-94.0wt% of macroporous structure, active component cobalt oxide 2.0-10.5wt%, molybdenum oxide 2.5- 15.0wt%.
Preferably, a kind of catalyst for catalytic gasoline hydrogenation desulfurization, it is composed of the following components：Have The alumina support 80.0-90.0wt% of macroporous structure, active component cobalt oxide 2.0-7.5wt%, molybdenum oxide 2.5- 12.0wt%.
Fixed bed reactors of the present invention, it is preferably solid for fixed bed adiabatic reactor or fixed bed isothermal reactor Fixed bed adiabatic reactor.
The catalytically cracked gasoline reaction, process conditions are：190-310 DEG C of reaction temperature, reaction pressure 1.3- 2.6MPa, volume space velocity 1.3-3.5h-1, hydrogen to oil volume ratio 180-400:1；
210-280 DEG C of preferable reaction temperature, reaction pressure 1.5-2.6MPa, volume space velocity 1.5-3.2h-1, hydrogen to oil volume ratio 210-300:1。
Preferably, the catalyst, it is composed of the following components：Alumina support 78.0- with macroporous structure 85.0wt%, active component cobalt oxide 2.0-7.5wt%, molybdenum oxide 2.5-12.0wt%.
Drying of the present invention, roasting obtain catalyst, 4-6 hours dry preferably at 110-150 DEG C, 650-720 It is roasted 6-8 hours at DEG C and obtains Hydrobon catalyst.
Alumina support of the present invention with macroporous structure is synthesized using chitosan as expanding agent with big The alumina support of pore structure.
Alumina support of the present invention with macroporous structure contains adjuvant component phosphorus and magnesium, adjuvant component in carrier The percentage composition that the content of phosphorus and magnesium accounts for carrier quality is respectively P2O50.1-2.5wt%, MgO 0.1-2.5wt%, aperture point Cloth 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.Carrier uses chitosan as expanding agent.
The present invention has the alumina support of macroporous structure, the addition and reaming that aperture can be by variation expanding agent The molecular size range of agent is adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-160nm, The ranges such as 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, the ranges such as 35-50%, 55-75%.
The preparation method of alumina support of the present invention with macroporous structure, includes the following steps：First, molten with acid Then boehmite and sesbania powder are added in kneader and are uniformly mixed, add phosphoric acid and nitric acid by liquid acidified chitosan The acid solution of chitosan-containing is finally added in boehmite powder and mediates uniformly, containing expanding agent by the mixed solution of magnesium The addition of acid solution is 0.1-8wt%, the preferably 0.2-5.0wt% of boehmite, by extrusion-molding-drying-roasting It burns, obtains the alumina support with macroporous structure.
The acid solution acidified chitosan, is preferably prepared by the following preparation method：Chitosan expanding agent is added first Enter into 30-95 DEG C of deionized 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..Acid addition with Chitosan, which can be completely dissolved, to be advisable.Water soluble chitosan, such as carboxyl chitosan, chitosan salt, chitosan can also be selected Sulfuric ester etc..
The most handy ultrasonic oscillation of chitosan acid solution or magnetic agitation.Ultrasonic oscillation 10min or more, magnetic agitation 0.5-2h.Ultrasonic oscillation is carried out to expanding agent or magnetic agitation, expanding agent good dispersion, alumina support are more prone to Macropore, and pore-size distribution is more concentrated, and pore-size distribution is in 70-180nm.
The addition of the sesbania powder is the 0.1-7wt% of boehmite.
It mediates or extrusion technique is that the acid solution containing expanding agent configured is added in sesbania powder and boehmite It is uniformly mixed, later extrusion, molding, is dried 3-9 hours by 100-160 DEG C, 650-800 DEG C roasts 4-8 hours, finally obtains 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, Also contain meso-hole structure simultaneously, macropore range is a kind of big containing Jie-in 2-50nm, mesoporous ratio 15-75%, preferably 15-50% The alumina support in hole.And aperture is not uniform aperture structure.
The alumina support with macroporous structure obtained using above-mentioned preparation method can also utilize phosphorus and magnesium to carrier Surface is modified, and the concentration of phosphorus and magnesium is unsuitable excessively high, and preferably configuration concentration is less than phosphoric acid and nitre when preparing complex carrier Sour magnesium aqueous solution sprays carrier surface, preferably carries out carrier surface modification as follows：Configure phosphoric acid and magnesium nitrate Alumina support of the aqueous solution spray with macroporous structure obtains used additives phosphorus through drying, roasting and magnesium carries out surface modification Alumina support controls in the alumina support with macroporous structure phosphorus pentoxide and content of magnesia respectively in 0.1- In the range of 2.5wt% and 0.1-2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is made to be that inside five aoxidizes 1.05-1.6 times of two phosphorus and content of magnesia.
Compared with prior art, the present invention has the following advantages：
1, for carrier of the present invention using chitosan as expanding agent, expanding agent chitosan is cheap, and environmentally friendly nothing Poison is suitble to industrialized production.The obtained alumina support with macroporous structure, pore size are adjustable, and macropore ratio can be with Effectively control.And carrier also contain it is mesoporous, be a kind of Jie-macropore alumina supporter.
2, the present invention can also introduce phosphorus and magnesium in alumina support, the obtained carrying alumina with macroporous structure Body, the carrier are prepared into Hydrobon catalyst, such as the catalyst such as cobalt molybdenum or nickel molybdenum, can inhibit alkene saturated activity, urge Agent desulfurization degree is high, and alkene saturation factor (HYD) is low, has good hydrodesulfurization selectivity.
3, the alumina support with macroporous structure that the present invention obtains, using phosphorus and magnesium to the oxidation with macroporous structure Alumina supporter surface is modified, and the content of carrier surface phosphorus pentoxide and magnesia is made to be internal phosphorus pentoxide and oxidation 1.05-1.6 times of content of magnesium.Carrier surface is modified by the way of spray, is capable of the portion of effective peptization carrier surface Divide micropore, advantageously reduce the micropore ratio of carrier surface in this way, improve carrier surface Jie-macropore ratio, promotes carrier surface More active sites load centres are produced, catalyst desulfurizing activity is effectively improved.Dipping should not be used to the improvement of carrier surface Method, impregnated carrier surface can make large quantity of moisture enter carrier, and intensity is deteriorated, and is not achieved and improves carrier surface Jie-macropore ratio Purpose.
4, the hydrodesulfurizationprocess process of gasoline of the invention, hydrodesulfurization mild condition, to different material adaptability By force, catalyst carrier is the alumina support for having Jie-macroporous structure, and catalyst loss of octane number is low, and desulfurization degree is high.
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 powder, to be mediated uniformly, is clover shape by kneading-extruded moulding.Dry 8 at 120 DEG C Hour, 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.
Cobalt 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 1,5 hours dry at 130 DEG C, 650 DEG C roast 7 hours, obtain Hydrobon catalyst 1.Catalyst 1 mainly forms：Oxygen Change cobalt 3.5wt%, molybdenum oxide 9.5wt%, changes alumina supporter 87.0wt%.
Catalyst 1 is fitted into 10ml fixed bed reactors, evaluation catalyst reaction performance is carried out.With sulfurized oil to catalysis Agent carries out presulfurization, and sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, a concentration of 1.0wt%；Sulfide stress is 2.8MPa, hydrogen Oil volume ratio is 300, and sulfurized oil volume space velocity is 3.0h-1, vulcanization program is respectively in 220 DEG C, 280 DEG C of vulcanizing treatment 6h.Sulphur Change after treatment, is switched to full fraction FCC gasoline replacement Treatment 8h, after waiting for pre-vulcanization process, is adjusted to reaction process Condition is reacted into catalytically cracked gasoline.Reaction process condition is：250 DEG C, reaction pressure 1.7MPa of temperature of reactor, volume are empty Fast 1.8h-1, hydrogen to oil volume ratio 240.Sampling analysis after reaction about 55h, 1 product desulfurization degree 80.9% of Hydrobon catalyst, alkene Hydrocarbon drop amount 3.1%, loss of octane number are 0.3 unit, and alkene saturation factor (HYD) is 10%.
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 powder and mediates uniformly, be 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.It recycles phosphorus and magnesium to be modified carrier surface, matches Alumina support 1 of the aqueous solution spray with macroporous structure of phosphoric acid and magnesium nitrate is set, it is 8 hours, 700 DEG C dry through 120 DEG C Roasting obtains used additives phosphorus for 4 hours and magnesium carries out the alumina support 2 of surface modification, carrier surface phosphorus pentoxide and magnesia Content be 1.2 times of internal phosphorus pentoxide and content of magnesia.Alumina support specific surface area with macroporous structure with Pore-size distribution is shown in Table 1.
Cobalt 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 110 DEG C, 600 DEG C roast 5 hours, obtain Hydrobon catalyst 2.Catalyst 2 mainly forms：Oxygen Change cobalt 6.2wt%, molybdenum oxide 11.1wt%, alumina support 82.7wt%.
Catalyst 2 is fitted into 10ml fixed bed reactors, evaluation catalyst reaction performance is carried out.With sulfurized oil to catalysis Agent carries out presulfurization, and sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, a concentration of 1.0wt%；Sulfide stress is 2.8MPa, hydrogen Oil volume ratio is 300, and sulfurized oil volume space velocity is 3.0h-1, vulcanization program is respectively in 220 DEG C, 280 DEG C of vulcanizing treatment 6h.Sulphur Change after treatment, is switched to full fraction FCC gasoline replacement Treatment 8h, after waiting for pre-vulcanization process, is adjusted to reaction process Condition is reacted into catalytically cracked gasoline.Reaction process condition is：270 DEG C, reaction pressure 1.5MPa of temperature of reactor, volume are empty Fast 2.2h-1, hydrogen to oil volume ratio 260.Sampling analysis after reaction about 55h, 2 product desulfurization degree 82.5% of Hydrobon catalyst, alkene Hydrocarbon drop amount 3.2%, loss of octane number are 0.4 unit, and alkene saturation factor (HYD) is 9%.Hydrobon catalyst octane number damages Low, desulfurization degree height is lost, it is active good, there is good hydrodesulfurization selectivity.Reaction operation 500h, Hydrobon catalyst 2 produce Product desulfurization degree is 82.4%, alkene drop amount 3.0%, and loss of octane number is 0.3 unit, and alkene saturation factor (HYD) is 9%, is urged The complex carrier surface of agent produces more active sites load centres, effectively improves catalyst desulfurizing activity, and catalyst is anti- Performance is answered to stablize.
Embodiment 3
The preparation method of carrier is carried out according to embodiment 1.The difference is that water soluble chitosan expanding agent is changed to Water-insoluble chitosan expanding agent, chitosan formic acid liquid magnetic stirrer 30 minutes.Obtain the oxygen with macroporous structure Change alumina supporter 3.The percentage composition that the content of adjuvant component phosphorus and magnesium accounts for carrier quality in carrier is respectively P2O51.8wt%, MgO 2.0wt%.Its specific surface area is shown in Table 1 with pore-size distribution.
Cobalt 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 120 DEG C, 650 DEG C roast 5 hours, obtain Hydrobon catalyst 3.Catalyst 3 mainly forms：Oxygen Change cobalt 5.1wt%, molybdenum oxide 7.6wt%, alumina support 87.3wt%.
Embodiment 4
The preparation method of carrier is carried out according to embodiment 1.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 and magnesium accounts for carrier quality in carrier is respectively P2O50.8wt%, MgO 1.0wt%.It recycles phosphorus and magnesium to be modified carrier surface, obtains carrier 4,4 surface phosphorus pentoxide of carrier and magnesia Content be 1.5 times of internal phosphorus pentoxide and content of magnesia.4 specific surface area of alumina support with macroporous structure with Pore-size distribution is shown in Table 1.
Cobalt 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 120 DEG C, 580 DEG C roast 6 hours, obtain Hydrobon catalyst 4.Catalyst 4 mainly forms：Oxygen Change cobalt 2.2wt%, molybdenum oxide 10.3wt%, alumina support 87.5wt%.
Catalyst 3 and 4 is respectively charged into 10ml fixed bed reactors, evaluation catalyst reaction performance is carried out.With vulcanization Oil carries out presulfurization to catalyst, and sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, a concentration of 1.0wt%；Sulfide stress is 2.8MPa, hydrogen to oil volume ratio 300, sulfurized oil volume space velocity are 3.0h-1, vulcanization program is respectively in 220 DEG C, 280 DEG C of vulcanizations Handle 6h.After vulcanizing treatment, it is switched to full fraction FCC gasoline replacement Treatment 8h, after waiting for pre-vulcanization process, is adjusted to Reaction process condition is reacted into catalytically cracked gasoline.Reaction process condition is：230 DEG C of temperature of reactor, reaction pressure 1.4MPa, volume space velocity 2.0h-1, hydrogen to oil volume ratio 210.Sampling analysis after reaction about 55h, 3 product of Hydrobon catalyst are de- Sulphur rate 81.2%, alkene drop amount 2.4%, loss of octane number are 0.2 unit, and alkene saturation factor (HYD) is 10%.Hydrodesulfurization 4 product desulfurization degree 82.9% of catalyst, alkene drop amount 2.0%, loss of octane number are 0.3 unit, and alkene saturation factor (HYD) is 8%.Hydrobon catalyst loss of octane number is low, and desulfurization degree is high, and activity is good, has good hydrodesulfurization selectivity.Reaction 500h is run, 4 product desulfurization degree of Hydrobon catalyst is 82.7%, and alkene drop amount 2.3%, loss of octane number is 0.3 list Position, alkene saturation factor (HYD) are 9%, and the complex carrier surface of catalyst produces more active sites load centres, effectively carries High catalyst is desulphurizing activated, and catalyst reaction performance is stablized.
The alumina support specific surface area and pore-size distribution of 1 macropore of table
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 (7)

1. a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline, which is characterized in that include the following steps:
Using fixed bed reactors, presulfurization is carried out to catalyst with sulfurized oil, presulfurization after treatment is switched to full fraction FCC gasoline replacement Treatment；After waiting for pre-vulcanization process, it is adjusted to reaction process condition, carries out catalytically cracked gasoline reaction；
The catalytically cracked gasoline reaction, process conditions are：190-310 DEG C of reaction temperature, reaction pressure 1.3-2.6MPa, Volume space velocity 1.3-3.5h-1, hydrogen to oil volume ratio 180-400:1；
The catalyst is supported cobalt molybdenum catalyst, and the carrier of catalyst is the carrying alumina for having macroporous structure Body, the composition of catalyst is with oxidation material gauge, including following component：Alumina support 78.0- with macroporous structure 94.0wt%, carrier use chitosan as expanding agent；Active component cobalt oxide 2.0-10.5wt%, molybdenum oxide 2.5- 15.0wt%；
Contain adjuvant component phosphorus and magnesium in the alumina support with macroporous structure, the content of adjuvant component phosphorus and magnesium accounts for load The percentage composition of weight is respectively phosphorus pentoxide 0.1-2.5wt%, magnesia 0.1-2.5wt%, pore-size distribution 60- 180nm, macropore ratio 2-75%, hole hold 0.8-2.0ml/g, specific surface area 250-300m2/g；
The preparation method of the catalyst, includes the following steps：Soluble-salt containing cobalt and containing molybdenum is made into maceration extract, dipping tool The alumina support for having macroporous structure roasts 5-9 hours at 4-8 hours, 650-800 DEG C dry at 120-160 DEG C, is added Hydrogen desulphurization catalyst；
The preparation method of the alumina support, includes the following steps：It first, then will be quasi- thin with acid solution acidified chitosan Diaspore and sesbania powder are added in kneader and are uniformly 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 powder, to be mediated uniformly, and the addition of the acid solution containing expanding agent is to intend thin water aluminium The 0.1-8wt% of stone obtains the alumina support with macroporous structure by extrusion-molding-drying-roasting；
To the obtained alumina support with macroporous structure, carrier surface is modified using phosphorus and magnesium：Configure phosphoric acid With alumina support of the aqueous solution spray with macroporous structure of magnesium nitrate, obtains used additives phosphorus through drying, roasting and magnesium carries out The alumina support that surface is modified controls phosphorus pentoxide and content of magnesia difference in the alumina support with macroporous structure In the range of 0.1-2.5wt% and 0.1-2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is made to be internal 1.05-1.6 times of phosphorus pentoxide and content of magnesia.
2. a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline according to claim 1, it is characterised in that：The catalysis Cracking gasoline reacts, and process conditions are：210-280 DEG C of reaction temperature, reaction pressure 1.5-2.6MPa, volume space velocity 1.5- 3.2h-1, hydrogen to oil volume ratio 210-300:1.
3. a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline according to claim 1, it is characterised in that：The fixation Bed reactor is fixed bed adiabatic reactor or fixed bed isothermal reactor.
4. a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline according to claim 1, it is characterised in that：The catalysis Agent is composed of the following components：Alumina support 78.0-85.0wt% with macroporous structure, active component cobalt oxide 2.0- 7.5wt%, molybdenum oxide 2.5-12.0wt%.
5. a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline according to claim 1, it is characterised in that：The aluminium oxide The pore-size distribution of carrier holds 0.8-1.3ml/g in 65-150nm, macropore ratio 5-65%, hole；Alumina support also contains simultaneously Meso-hole structure, macropore range is in 5-50nm, mesoporous ratio 15-75%.
6. a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline according to claim 1, it is characterised in that：The acid solution The process of acidified chitosan is as follows：Chitosan expanding agent is added in 30-95 DEG C of deionized water first, acid is added dropwise later, Until chitosan dissolving is complete, the acid solution containing expanding agent is obtained.
7. a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline according to claim 6, it is characterised in that：The acid is vinegar One or more of acid, formic acid, malic acid or lactic acid, chitosan acid solution ultrasonic oscillation or magnetic agitation.
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