CN107081155B - A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization - Google Patents
A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization Download PDFInfo
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- CN107081155B CN107081155B CN201710408432.XA CN201710408432A CN107081155B CN 107081155 B CN107081155 B CN 107081155B CN 201710408432 A CN201710408432 A CN 201710408432A CN 107081155 B CN107081155 B CN 107081155B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
The catalyst and preparation method thereof that the invention discloses a kind of for catalytic gasoline hydrogenation desulfurization, the composition of catalyst is with oxidation material meter, including following component: the alumina support 78.0-94.0wt% with macroporous structure, carrier use chitosan as expanding agent；Active component cobalt oxide 2.0-10.5wt%, molybdenum oxide 2.5-15.0wt%.Hydrobon catalyst loss of octane number is low, and desulfurization degree is high.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization.
Background technique
Since the general sulfur content of catalytically cracked gasoline is in 100-500v%, or even there are also high-sulfur, high olefin feedstock oil, sulphur contains
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 to will cause hydrocarbon fraction saturation and reduce octane number, this requires keep away as far as possible while Hydrobon catalyst desulfurization
It is excessive to exempt from loss of octane number.
Macroporous oxide is due to using extensively with biggish cellular structure, higher specific surface area, good thermal stability
In fields such as heterogeneous catalyst, catalyst carrier, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance materials.
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 is less than 0.2 mM/gram.The preparation method of macropore alumina supporter includes will
A kind of precursor of aluminium oxide is formed and is roasted, 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 maturing temperature is 600-850 DEG C, calcining time 1-10
Hour, the dosage of each component contains final alumina support, 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 rouge
Fat alcohol polyoxyethylene ether, fatty alkanol amide, molecular weight are the acrylic copolymer of 200-10000, in maleic acid copolymer
It is one or more of.CN201110410339.5 provides a kind of high temperature-resistant active aluminum oxide material and preparation method thereof, the oxygen
Change aluminum material to be made by following steps: after macropore boehmite, high viscous boehmite are mixed with additive with water, turn
Speed is to stir evenly under 100-1000r/min, adds the dilute nitric acid reaction that concentration is 30%, 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, is slurrying, spraying, dry
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, low in cost.Wherein the sky agent of making is selected from polyvinyl alcohol, polyethylene glycol, polyacrylamide or methyl fibre
One of element is tieed up, dosage is the 0-40% of oxide total weight in alumina material." Zhongshan University's journal " (2002,41
(2): 121-122 the method) introduced is as follows: the polystyrene colloidal crystal microballoon that diameter is 600nm is placed on a buchner funnel, so
The ethanol solution of aluminum nitrate and citric acid is added drop-wise to afterwards on glue crystalline substance under suction filtration, is allowed in its fully penetrated gap into 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: first using emulsion polymerization
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, ultrasonic treatment, then through dry and roasting, obtains macroporous aluminium oxide.CN201010221302.3 (CN102311134A) is open
A kind of spherical integral macroporous alumina and preparation method thereof.Method includes the following steps: by polymer microballoon lotion, oxidation
Aluminum sol and coagulant are mixed in a certain proportion uniformly, which is scattered in oily 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 oily phase later
Ball, then the spherical integral macroporous alumina is obtained after aged, dry and roasting in aqueous ammonia medium.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, forms
Journey is simple and easy to do, convenient for being prepared on a large scale.Polymer microballoon diameter 50-1000nm, the type of polymer microballoon are polystyrene
The esters microballoons such as microballoon, polyaerylic acid N-butyl microballoon, polyacrylate.Coagulant is hexamethylenetetramine, urea.Oil is mutually
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.Method includes the following steps: aluminium
Source, polyethylene glycol and after being uniformly mixed selected from low-carbon alcohol and water at least one, will low-carbon epoxyalkane be added it is described mixed
It closes in object, obtains Integral macroporous alumina through aging, immersion, drying and roasting.Of the invention preparation method is simple, ring
Border pollution is small, its aperture of gained Integral macroporous alumina is controllable at 0.05-10 μm.Monoblock type macropore oxidation provided by the invention
Object can be applied to the fields such as macromolecular heterogeneous catalysis, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance material.
CN201410347665.X disclose a kind of macropore hold, the preparation method of high-strength alumina, by the way that polyacrylamide, poly- is added
The expanding agents such as vinyl alcohol, alkylcellulose, sesbania powder, starch are obtained containing eurypyloue alumina support, the dosage of expanding agent
The 10-30% of aluminium oxide is accounted for, but not publicly specific pore diameter range.The although available preferable macropore oxidation of hard mould agent method
Alumina supporter, but the dosage of its template causes processing cost to greatly improve more preferably greater than 20%, the decomposition of a large amount of templates
The demand for development of low-carbon environment-friendly is not met.CN201010509425.7 discloses the side of a kind of hydro-thermal and the common reaming of template
Method is acted on, the dosage of template can be reduced with preparing the alumina support containing macroporous structure by the complementary reaming of hydro-thermal
To 3-10%, but hydro-thermal is assisted to cause the raising of energy consumption.CN200310103035.X discloses a kind of macroporous aluminium oxide
Preparation method carries out reaming using polyvinyl alcohol, poly- propyl alcohol, polyethylene glycol soft template, by the way that 1% polyethylene glycol is added,
Kong Rong of the aperture greater than 100nm accounts for the 26.2% of total pore volume.Soft template has the advantages that dosage is low, reaming effect is good, still
The solubility property of the alcohols soft template of higher molecular weight in water is poor, causes it to be used to expand super large porous aluminum oxide and is limited
System.CN200910204238.5 (CN102040235) discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The party
Then method fills certain party legal system the following steps are included: monodispersed polymer microballoon is assembled into glue crystal template into template
Standby alumina sol most obtains macroporous aluminium oxide through dry and roasting afterwards.This method can be good at control Aluminum sol and
The recombination process of Aluminum sol and polymer microballoon does not destroy the network structure of alumina gel as far as possible, makes prepared oxidation
Aluminium not only has the macropore duct of three-dimensional order but also specific surface area with higher.The invention is burnt by the appropriateness to template
The small fenestra tied and formed, makes the macropore in material be connected with the macropore of surrounding by 12 small fenestras.The oxidation of the invention
Aluminium is suitable for use as the adsorption and separation material of mink cell focus catalyst carrier and organic macromolecule.Have in catalyst carrier material application
Conducive to the mass transfer ability of material in the catalyst is improved, be conducive to the activity and selectivity for improving catalyst.
CN201410148773.4 discloses a kind of preparation method of aluminum oxide porous microballoon, comprising the following steps: 1) by surface-active
Agent is dissolved in deionized water, stirring, as water phase；2) chelating agent, alumina precursor and n-octyl alcohol are mixed, is stirred, as
Oily phase；3) Span80 and pore-foaming agent, stirring are added in oily phase；4) clear oil obtained by step 3) is mutually poured into water phase
Continue stirring and emulsifying；5) step 4) gains are filtered by vacuum, it is dry after gained Washing of Filter Cake, obtain aluminum oxide porous microballoon.It should
Microballoon has internal closing macroporous structure, and Microsphere Size is 1 μm -100 μm, and the invention is solidifying using the colloidal sol in pore-foaming agent and lotion
Glue process obtains the metal porous microballoon with internal closing macroporous structure.Porous microsphere is prepared using phase separation principle.It is internal
Closing aperture is 50nm-5 μm.Inside closing aperture is 50nm-5 μm.Aperture is closed inside the aluminum oxide porous microballoon,
That is alumina support internal gutter does not have connectivity.Pore-foaming agent is polyvinylpyrrolidone, polyacrylamide or poly- third
Olefin(e) acid.The invention has used a large amount of surfactant, chelating agent, pore-foaming agent, and it is more to prepare raw material, and synthesis technology is complicated.
The above macroporous aluminium oxide mainly uses cellulose, polymeric alcohol, polystyrene etc. to prepare macropore oxygen as expanding agent
Change aluminium.
Alumina support with macropore and mesoporous i.e. composite pore structural also compares more.CN 101200297A is disclosed
The preparation method of integral macroporous alumina: reversed concentrated emulsions method is used to prepare monoblock type using styrene and divinylbenzene as monomer
Macropore organic formwork；Al is prepared using aluminium isopropoxide or boehmite as predecessor2O3The hydrosol；By Al2O3The hydrosol is filled into
In monoblock type macropore organic formwork；Filled monolithic devices organic/inorganic composite is de- in 600 DEG C of -900 DEG C of roastings through drying
Removing template obtains integral macroporous alumina.The advantages of this method is that preparation process is simple and easy, monoblock type macropore obtained
The macropore duct that there is aluminium oxide micron order to interconnect, aperture are 1-50 μm.This method prepares Integral macroporous alumina letter
It is single easy, but the volume fraction of water phase accounts for 75%-90% in this method, and correspondingly the volume fraction of organic monomer is relatively low,
For this method while reducing organic monomer consumption, the preparation efficiency of prepared template is relatively low, and it is big to be unfavorable for subsequent step
It is prepared by the batch of porous aluminum oxide.A kind of preparation method of the alumina support of composite pore structural of CN201110032234.0, including
Calorize will be contained selected from least one of aluminium isopropoxide, aluminium secondary butylate, aluminum nitrate, aluminium chloride, Aluminum sol and boehmite powder
It closes object and composite mould plate agent is mixed and roasted, the composite mould plate agent is mesoporous template and macroporous granules template, is given an account of
Hole template is selected from polyethylene glycol propylene glycol-polyethylene glycol triblock polymer, polyethylene glycol, lauryl amine, hexadecane
At least one of base trimethylammonium bromide, lauric acid, stearic acid and fatty alcohol polyoxyethylene ether, the macroporous granules template choosing
It is greater than polystyrene microsphere, poly (methyl methacrylate) micro-sphere, particles of bioglass, pitch particle or the heavy oil of 50nm from partial size
Residue；The weight ratio of the mesoporous template, macroporous granules template and aluminum contained compound is 0.1-2:0.1-0.7:1, wherein
The weight of the aluminum contained compound is in terms of aluminium oxide.The invention also discloses have mesoporous hole while preparation by the above method
The alumina support in road and macropore duct, intermediary hole account for the 40%-90% of total pore volume, and macropore accounts for the 10%-60% of total pore volume.
CN201210328824.2 discloses a kind of method for preparing solid phase of gradient distribution hole gama-alumina.This method is anti-by solid phase
Precursor aluminium carbonate ammonium should be obtained, the gamma oxidation that a kind of high specific surface area, gradient distribution hole and large hole are held is obtained after roasting
Aluminium.The present invention is the most outstanding to be technically characterized in that using raw material solid phase reactive synthesis technique, as obtained by synthesis condition control
The property of gama-alumina.Meanwhile the method for the present invention is simple, and it is easily operated, addition expanding agent is not needed, save the cost is suitble to work
Industryization batch production.The preparation process of alumina support of the present invention the following steps are included: (1) aluminum nitrate, ammonium hydrogen carbonate and table
Face activating agent is fully ground uniformly, and certain time is aged in the closed container of specific temperature and obtains precursor aluminium carbonate ammonium；(2)
It will form after mixing after the drying of precursor aluminium carbonate ammonium obtained by (1) with peptizing agent, can generally be squeezed using banded extruder
Item molding；(3) (2) are obtained that final alumina support is made in molding drying, aerobic roasting.Step lures described in (1)
The polyethylene glycol that agent is liquid form is led, additional amount is equivalent to the 0.1-10.0% of aluminum nitrate weight.Carbonic acid described in step (2)
The drying process of aluminium ammonium is 1-20 hours dry generally at 50-180 DEG C.Roasting process described in step (3) is in 350-900
It is roasted 1-10 hours at DEG C.The invention prepares gama-alumina using the decomposition at a certain temperature of precursor aluminium carbonate ammonium.Aluminium carbonate
Ammonium generates gas, such as NH in decomposable process3And CO2, the generation and evolution of these gases can manufacture some macropores.Simultaneous oxidation
The pattern of aluminium is transformed by the pattern topology of aluminium carbonate ammonium.Slower heating rate is conducive to gas object in roasting process
Matter slowly escapes, and does not easily cause carrier to collapse.Method is simple, does not need to add any physics expanding agent.
CN201310097588.2 discloses a kind of gama-alumina particle and preparation method thereof: 1) aluminum soluble salt being dissolved in by acid
In aqueous solution of the pH value of acidification less than or equal to 3, the amount that the aluminum soluble salt is added makes obtained containing aluminium in aluminum water solution
The molar concentration of ion is 0.01-5mol/L；2) obtained containing alkaline precipitating agent, the alkali is added in aluminum water solution to step 1)
Property precipitating reagent be added amount make reaction after solution ph between 5-12；3) the mixed sediment solution that step 2) obtains is existed
At room temperature stir 0.1-3h after, be put into water-bath or water heating kettle, 50-150 DEG C at a temperature of be aged 6-24h；4) by step
3) solution after being aged is after mixing evenly, dry using spray drying process, and control inlet air temperature is 150-400 when spray drying
DEG C, leaving air temp is 60-110 DEG C, and the thermal efficiency of spray drying is 50% or more；5) oxidation after the drying for obtaining step 4)
Aluminium precursor powder is heated to 250 DEG C -350 DEG C at room temperature with first rate of heat addition, is then heated to second rate of heat addition
400 DEG C -800 DEG C, heat preservation 0.5-20h obtains final product gama-alumina particle；Wherein, first rate of heat addition is less than
Two rates of heat addition, and first rate of heat addition and second rate of heat addition are in the range of 0.1-10 DEG C/min.It is obtained
Gama-alumina is experiments verify that test, specific surface area have high-specific surface area within the scope of 180m2/g-260m2/g.It is made
Gama-alumina particle observed under scanning electron microscope have hollow foam shape pattern, and have micropore-mesopore-macropore it is compound
Aperture structure.In this way, when gama-alumina is as catalyst carrier, hollow foam shape pattern can be effectively in dispersed catalyst
Active component.And hollow foam shape pattern and composite bore diameter structure, be conducive to the mass transfer in catalytic process, to accelerate
Rate of catalysis reaction.The composite bore diameter structure refers to not only include micropore of the aperture less than 2nm, but also including aperture in 2nm-50nm
Between it is mesoporous, further include aperture be greater than 50nm macropore.It further include making to obtained containing being added in aluminum water solution in step 1)
Hole agent, the amount that the pore creating material is added that the molar concentration of pore creating material in rear solution is added to be aluminum ions molar concentration
0.01-5 times.The pore creating material is cetyl trimethylammonium bromide (CTAB), neopelex (SDBS), polyethylene
One or more of alcohol (PVA), polyethylene glycol (PEG) and calgon.CN101863499A
(201010187094.X) provides a kind of preparation method of macroporous-mesoporous alumina.The following steps are included: a. first helps reaction
Agent and aluminium salt are dissolved in organic solvent solution, reaction promoter: two kinds of material mol ratios of aluminium ion are 3-5: 1, then by template
Above-mentioned solution is added and dissolves, aluminium ion and template molar ratio are 1: 0.015-0.025, and the pH value control of final solution exists
3.5-6.0；B. the solution by a step preparation carries out aging process, so that it is gradually removed organic solvent and moisture in system and obtains greatly
Hole-meso-porous alumina presoma；C. macroporous-mesoporous alumina powder is obtained through 400-800 DEG C of calcination process.Present invention process letter
Single, duct rule, pore-size distribution is concentrated and can realize controllable adjustment according to concrete application situation, thus more in petrochemical industry
Mutually catalysis, adsorbing separation and have important application value as catalyst carrier, energy and material etc..It makes full use of anti-
The space frame effect and coordination and intermediary's organic polymer, reaction promoter for answering auxiliary agent and template are to inorganic ions
Complexing, so that a step prepares the adjustable macroporous-mesoporous alumina material in aperture.Prepared foramen magnum-mesoporous oxidation
The specific surface area of aluminum material is up to 250-320m2/ g, duct rule, pore-size distribution in mesoporous 5-40nm, macropore 50-150nm, and
Adjusting can be realized according to the actual situation.Reaction promoter is organic acid, and aluminium salt is inorganic aluminate.Template is triblock copolymer.
Organic solvent is anhydrous alcohols, ethers or ketones solvent.Organic acid is citric acid or lauric acid.Triblock copolymer is
P123 or F127.Tie-Zhen Ren etc. (Langmuir, 2004,20:1531-1534) uses nonionic surfactant
56 aluminium secondary butylate of Brij uses hydro-thermal method and Microwave-assisted synthesis macroporous-mesoporous alumina in acid condition, synthesis it is porous
0.8-2 μm of alumina powder macropore diameter, mesoporous pore size 5-8nm, 0.4-1.4 μm of hole wall of aluminium oxide.Its deficiency is aluminium-alcohol salt
Expensive, the macroporous-mesoporous alumina Kong Rong little of synthesis, duct is irregular, pore-size distribution is excessive and cannot achieve pore structure
Effective adjusting thus have significant limitation in using effect and range.Jean-Philippe Dacquin etc.
It using P123 is template in mixed solution that (J.Am.Chem.Soc., 2009,131:12896-12897), which uses sol-gel method,
It is middle to be introduced into the polystyrene droplet with single dispersed phase to realize the formation of macropore in macroporous-mesoporous alumina.Deficiency
Place is that macropore diameter size (300nm or 400nm) is determined by the secondary size for introducing polystyrene drop completely, i.e. macropore diameter
Size depends on polystyrene droplet size.Organic molecule in the change of the part to solution itself component and system can not be passed through
It interacts to realize the adjustment in aperture.Huining Li et al. (Inorganic Chemistry, 2009,48:4421) is equally adopted
The polymethyl methacrylate with single dispersed phase is introduced in mixed solution with sol-gel method by template of F127
(PMMA) droplet realizes the formation of macropore in macroporous-mesoporous alumina, shortcoming be macropore diameter size also completely by
Secondary introducing polymethyl methacrylate droplet size determines, can not be changed by the part to solution system itself component come real
The adjustment in existing aperture also cannot achieve the controllable of foramen magnum-mesoporous aperture to realize the formation of foramen magnum-mesoporous composite pore structural
Adjust, in use, in particular for complicated ingredient bulky molecular catalysis during by significant limitation.
The above composite holes alumina support generally uses organic polymer such as polyvinyl alcohol, polymethylacrylic acid etc. as mould
Plate agent either expanding agent.So that the preparation of composite holes and macroporous aluminium oxide material there are the monomer of template have certain toxicity,
The problems such as template consumption is larger, preparation cost is higher, preparation process is cumbersome.Meanwhile there is also the discharges in roasting process
The problem of object environmental pollution.Also there is the patent that saccharide compound is added in polymer microballoon lotion.
CN201310142454.8 discloses a kind of preparation method of alumina hollow ball, and it is water-soluble to prepare chitosan-acetic acid-
Liquid；By polystyrene spheres: chitosan-acetic acid-aqueous solution be 5:1-10:1 mass ratio, press polystyrene spheres: alpha-alumina
Body is that the mass ratio of 1:5-1:15 takes each raw material；Polystyrene spheres and chitosan-acetic acid-aqueous solution are mixed, polyphenyl is made
Ethylene ball surface uniformly coats one layer of chitosan-acetic acid-aqueous solution；It is coated with chitosan-acetic acid-aqueous solution polyphenyl second again
In alkene ball and alpha-alumina powder investment ball-milling device, with the revolving speed rotation cladding 2-24h of 5-30r/s, obtained core-shell structure copolymer ball；It will
After the calcining of core-shell structure copolymer ball warp, the alumina hollow ball that diameter is 0.2-2mm, wall thickness is 20-100 μm is obtained.
CN201110170283.0 discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The three-dimensional ordered macroporous oxidation
Aluminium, diameter macropores 50-1000nm, grain diameter 1-50mm, mechanical strength 80-280g/mm.This method includes following step
It is rapid: saccharide compound and the concentrated sulfuric acid will to be added into monodisperse polymer micro-sphere lotion, obtain polymer-modified microballoon glue crystalline substance mould
Plate is subsequently filled alumina sol, then through aging and roasting, obtains three-dimensional ordered macroporous alumina.The polymer microballoon
Diameter is 50-1000nm, can be used polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polyacrylic acid N-butyl microballoon and
One of different monooctyl ester microballoon of polyacrylic acid is a variety of, preferably polystyrene microsphere.The monodisperse refers to polymer microballoon
The standard deviation of diameter is not more than 10%.The carbohydrate organic matter be one of Soluble Monosaccharide and polysaccharide or a variety of, preferably
For one of sucrose, glucose, chitosan or a variety of.This method can increase substantially the adhesion amount of aluminium oxide precursor, increase
The strong mechanical strength of material, it is subtle powder that when removing template is removed in high-temperature roasting, large pore material is not easily broken, can still be protected
Hold higher integrity degree.Chitosan is in ceramic coating adsorbent material field using more." mesoporous chitosan-aluminium hydroxide is compound
Material Study on adsorption properties " (author: Peng Shaohua] University Of Suzhou, " Suzhou Institute of Science and Technology journal: natural science edition " 2013 30
Rolled up for 4 phases): 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 size is 3.3nm；Specifically the preparation method comprises the following steps: claiming
It takes 2.0g Aluminium chloride hexahydrate to be dissolved in the hydrochloric acid that 5.0mL pH value is 1,2.0g chitosan, then plus 10.0mL distilled water is added
Stirring, and the pH value of solution is adjusted to 1 with dilute hydrochloric acid.Still aging 30min (solution becomes paste), the NaOH for being 14 with pH value
Solution adjusts the pH value of solution to 8, has white flock precipitate generation, filters, wash away remaining NaOH with distilled water, be put into baking
Case obtains product after 120 DEG C of heat preservation 5h.Step as above, prepare chitosan respectively and aluminium chloride mass ratio be respectively 1:2,1:3,
The product of 2:1,3:1.
" preparation and characterization of chitosan/oxidized aluminium composite aerogel " (Chang Xinhong；The chemicalization engineering of Luoyang Normal College
Institute, " Luoyang Normal College's journal ", 11 phases of volume 31 in 2012): 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 volatilization
It drives and is acted between body and structure directing agent, and microphase-separated is differently formed according to hydrophilic and hydrophobic, ultimately form orderly to be situated between and see knot
Structure；After removing structure directing agent again, the ordered mesoporous metal oxide material with ultra-large aperture is formed；Wherein, block copolymerization
The molecular weight of the hydrophobic block of object is greater than 10000g/mol；The ordered mesoporous metal oxide material mesoporous pore size is in 10-50nm
Between, mesoporous wall thickness of material is between 4-20nm.The hydrophilic block of the block copolymer is polyoxyethylene blocks；Institute
The hydrophobic block for stating block copolymer is polystyrene or derivatives thereof, polyacrylate or derivatives thereof, polymethylacrylic acid
The copolymer of ester or derivatives thereof, one kind of polylactic acid pole or derivative or two or more polymer described above.The invention system
Standby is meso-porous alumina, similar also CN101153051A, CN1631796A, CN101134567A, CN101823706A,
CN101863499A.CN201310258011.5 is related to a kind of tooth spherical alumina support, tooth ball-aluminium oxide hydrotreating is urged
Agent and preparation method thereof, including following components: peptizing agent, 0.5-4 parts by weight；Lubricant, 0.2-2 parts by weight；Dispersing agent,
0.2-3 parts by weight；Expanding agent, 0.3-4 parts by weight；Aluminium hydroxide, 100 parts by weight.Expanding agent is polyvinyl alcohol, polyacrylic acid
One of sodium, starch derivatives or carbon black or mixture.The invention, which is added to anionic surfactant, reduces various help
Specific surface area increases 246m while agent ingredient additive amount2/ g, expanding agent Sodium Polyacrylate.The oxidation of tooth spherical shape described in the invention
Alumina supporter, since the wherein groups such as various auxiliary agents such as peptizing agent, expanding agent, dispersing agent, anionic surfactant are greatly lowered
The content divided, has not only saved cost, has also had many advantages, such as large specific surface area, high mechanical strength.The invention has used peptizing agent,
Lubricant, dispersing agent, the reagents such as expanding agent, obtained alumina support are unimodal pore size distributions.CN201110116418.5 is mentioned
It has supplied a kind of mesoporous sphere aluminium oxide and has been oriented to the method for preparing the mesoporous sphere aluminium oxide using template.Using oil column at
The template with guide function is added in type method during preparing Aluminum sol into Aluminum sol, and Aluminum sol is in molding and aging
In the process, since the presence of the template with guide function makes to produce a large amount of meso-hole structure in alumina balls.Template
For organic monomer or linear polymer, organic monomer is one of acrylic acid, ammonium acrylate, acrylamide, allyl alcohol.Jie
Hole ball-aluminium oxide specific surface is 150-300m2/ g, particle diameter 0.1-5mm, pore volume 0.7-1.5ml/g, bore dia are
The hole of 2-40nm is greater than 97%, and heap density is 0.30-0.80g/cm3, crushing strength is 70-250N/.The invention utilizes template
The mesoporous sphere alumina pore diameter of agent preparation compares concentration, this kind of mesoporous sphere aluminium oxide can be used for petrochemical industry and fining
Work is catalyst or catalyst carrier.
Macroporous aluminium oxide and compound porous aluminum oxide have different journeys to activity, selectivity and the stability aspect of catalyst
The improvement result of degree.The solubility of polyvinyl alcohol template in water is influenced by the degree of polymerization, it is caused to be used for super big hole oxygen
Change and is also subject to certain restrictions in the preparation of aluminium.
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 include: 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 successively loads auxiliary agent magnesium and boron and active component cobalt and molybdenum, then through dry and roasting, catalyst is made.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 the preparation method of a kind of gasoline deep hydrodesulfurizationcatalytic catalytic material and catalyst.Above-mentioned preparation side
Method is then to mix its cocurrent by preparing related presoma microemulsion and ammonia microemulsion and react, most flocculated afterwards,
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 for preparing gasoline hydrodesulfurizationcatalyst catalyst as carrier using the material of gained synthesis, with the multiple elements design material
Material uses microemulsion method supported active metals component, and the metal loaded not only has lesser particle, while with higher
Load capacity.The catalyst that provided preparation method is prepared through the invention shows excellent in terms of gasoline hydrodesulfurizationmethod
Catalytic performance.
Summary of the invention
The present invention provides a kind of catalyst and preparation method for gasoline hydrodesulfurizationmethod, the carrier of Hydrobon catalyst
It is the alumina support with macroporous structure, using chitosan as expanding agent, the alumina support synthesized has macropore knot
Structure.Active component includes cobalt oxide and molybdenum oxide.The macroporous aluminium oxide is adjustable with pore size, and macropore ratio can be effective
The characteristics of control.Alumina support with macroporous structure can be used for petrochemical industry and field of fine chemical.Gasoline hydrogenation is de-
Sulfur catalyst loss of octane number is low, and desulfurization degree is high.
A kind of catalyst for catalytic gasoline hydrogenation desulfurization of the present invention, it is composed of the following components: to 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: to 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%.
The gasoline hydrodesulfurizationcatalyst catalyst preparation method includes the following steps: cobalt is contained and the soluble-salt containing molybdenum is made into
Maceration extract impregnates the alumina support with macroporous structure, roasts at 4-8 hours, 650-800 DEG C dry at 120-160 DEG C
5-9 hours, obtain Hydrobon catalyst.
Alumina support of the present invention with macroporous structure, using chitosan as expanding agent, synthesizing has greatly
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%, pore-size distribution
60-180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, Kong Rong 0.8-2.0ml/g, preferably 0.8-
1.3ml/g or preferred 1.6-2.0ml/g, specific surface area 250-300m2/g.Carrier uses chitosan as expanding agent.
Alumina support of the present invention with macroporous structure, aperture can by change expanding agent additional amount and
The molecular size range of expanding agent is adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-
The ranges such as 160nm, 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, the models such as 35-50%, 55-75%
It encloses.
The preparation method of alumina support of the present invention with macroporous structure includes the following steps: firstly, 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 additional amount 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 process of the acid solution acidified chitosan is as follows: first by chitosan expanding agent be added to 30-95 DEG C go from
In sub- water, acid is added dropwise later, until chitosan dissolution is completely, obtains the acid solution containing expanding agent.The acid can be inorganic acid
Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The additional amount of acid is advisable with that can be completely dissolved chitosan.It can also
To select water soluble chitosan, such as carboxyl chitosan, chitosan salt, sulfated chitosan etc..Chitosan acid solution is best
With ultrasonic oscillation or magnetic agitation.Ultrasonic oscillation 10min or more, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent
Wave concussion or magnetic agitation, expanding agent good dispersion, alumina support is more prone to produce macropore, and pore-size distribution more collects
In, pore-size distribution is in 70-180nm.
The additional amount of the sesbania powder is the 0.1-7wt% of boehmite.
It mediates or extrusion technique is that the configured acid solution containing expanding agent is added in sesbania powder and boehmite
Be uniformly mixed, later extrusion, molding, by 100-160 DEG C drying 3-9 hours, 650-800 DEG C roasting 4-8 hours, finally obtain
Alumina support with macroporous structure.
Alumina support of the present invention uses chitosan for expanding agent, and the alumina support of preparation contains macroporous structure,
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 be using phosphorus and magnesium to carrier
Surface is modified, and the concentration of phosphorus and magnesium is unsuitable excessively high, and preferably configuration concentration is lower than phosphoric acid and nitre when preparing complex carrier
Sour magnesium aqueous solution sprays carrier surface, preferably carries out carrier surface modification as follows: configuration phosphoric acid and magnesium nitrate
Aqueous solution spray has the alumina support of macroporous structure, obtains used additives phosphorus through drying, roasting and magnesium carries out what surface was modified
Alumina support, control is with phosphorus pentoxide in the alumina support of macroporous structure 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 invention has the following advantages that
1, for alumina support of the present invention using chitosan as expanding agent, expanding agent chitosan is cheap, and environmental protection
It is nontoxic, it is suitble to industrialized production.The obtained alumina support with macroporous structure, pore size is adjustable, and macropore ratio can
Effectively to control.And carrier also contains mesoporous, is a kind of Jie-macropore alumina supporter.
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 hydrodesulfurization/mercaptan-eliminating catalyst, such as the catalyst such as cobalt molybdenum or nickel molybdenum, are able to suppress alkene saturation
Activity, catalyst desulfurizing rate 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 are not achieved and improve carrier surface Jie-macropore ratio
Purpose.
4, gasoline hydrodesulfurizationcatalyst catalyst carrier of the present invention is that have Jie-macroporous structure alumina support, and catalyst is pungent
The loss of alkane value is low, and desulfurization degree is high.
Detailed description of the invention
Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention
System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.
Embodiment 1
8.0g water soluble chitosan expanding agent is added in 50 DEG C of deionized water first, acetic acid is added dropwise later, until
Chitosan dissolution completely, obtains the acid solution containing expanding agent.Phosphatase 11 .46g, magnesium nitrate 7.35g are weighed respectively, by phosphoric acid and nitre
Sour magnesium, which is dissolved completely in 70g distilled water, is made into phosphorous, magnesium aqueous solution.Weigh 350g boehmite powder and 20.0g sesbania
Powder is added in kneader, and is uniformly mixed, and the mixed solution of phosphoric acid and magnesium nitrate is added, finally that the acid of chitosan-containing is molten
Liquid, which is added in boehmite powder, to be mediated uniformly, is clover shape by kneading-extruded moulding.It is small in 120 DEG C of dryings 8
When, 700 DEG C roast 4 hours, obtain phosphorous and magnesium alumina support 1.Phosphorus pentoxide 0.5wt%, magnesia in carrier 1
0.8wt%.Alumina support specific surface area and pore-size distribution with macroporous structure are shown in Table 1.
Cobalt nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
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%.
Embodiment 2
8.0g water soluble chitosan expanding agent is added in 50 DEG C of deionized water, acetic acid is added dropwise later, until shell is poly-
Sugar dissolution completely, obtains the acid solution containing expanding agent.Phosphatase 11 .09g, magnesium nitrate 9.12g are weighed respectively, by phosphoric acid and magnesium nitrate
It is dissolved completely in 70g distilled water and is made into phosphorous, magnesium aqueous solution.Weigh 350g boehmite powder and 20.0g sesbania powder
It is added in kneader, and is uniformly mixed, add the mixed solution of phosphoric acid and magnesium nitrate, finally by the acid solution of chitosan-containing
It is added in boehmite powder and mediates uniformly, be clover shape by kneading-extruded moulding.It is small in 120 DEG C of dryings 8
When, 700 DEG C roast 4 hours, obtain phosphorous and magnesium alumina support 1.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 modified alumina support 2 in surface, 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 adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
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%.
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 was with 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 and pore-size distribution are shown in Table 1.
Cobalt nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
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 was with 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 adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
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 1-4 is respectively charged into 10ml fixed bed reactors, evaluation catalyst reaction performance is carried out.Use sulfurized oil
Presulfurization is carried out to catalyst, sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, concentration 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, be switched to full fraction FCC gasoline replacement Treatment 8h, to pre-vulcanization process after, be adjusted to
Reaction process condition is reacted into catalytically cracked gasoline.Reaction process condition are as follows: 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, catalyst and contrast medium reactor product after reaction about 55h
Property is shown in Table 2.
Hydrobon catalyst 1-4 loss of octane number is low, and desulfurization degree is high, and activity is good, has good hydrodesulfurization selection
Property.Reaction operation 500h, 4 product desulfurization degree of Hydrobon catalyst are 82.7%, alkene drop amount 2.3%, and loss of octane number is
0.3 unit, alkene saturation factor (HYD) are 9%, and the complex carrier surface of catalyst produces in more active sites loads
The heart, effectively improves catalyst desulfurizing activity, and catalyst reaction performance is stablized.
The alumina support specific surface area and pore-size distribution of 1 macropore of table
2 catalyst reaction product property 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 changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (4)
1. a kind of catalyst for catalytic gasoline hydrogenation desulfurization, it is characterised in that:
The catalytic component composition: the alumina support 78.0-94.0wt% with macroporous structure, carrier are made using chitosan
For expanding agent；Active component cobalt oxide 2.0-10.5wt%, molybdenum oxide 2.5-15.0wt%；The oxidation with macroporous structure
Contain adjuvant component phosphorus and magnesium in alumina supporter, it is respectively P that the content of adjuvant component phosphorus and magnesium, which accounts for the percentage composition of carrier quality,2O5
0.1-2.5wt%, MgO 0.1-2.5wt%, pore-size distribution 60-180nm, macropore ratio 2-75%, Kong Rong 0.8-2.0ml/g,
Specific surface area 250-300m2/g；
The alumina support also contains meso-hole structure simultaneously, and macropore range is in 5-50nm, mesoporous ratio 15-75%；
The preparation method of the alumina support includes the following steps: that thin water then will be intended firstly, with acid solution acidified chitosan
Aluminium stone 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 and gather
The acid solution of sugar, which is added in boehmite powder, to be mediated uniformly, and the additional amount of the acid solution containing expanding agent is boehmite
0.1-8wt% obtain 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: configuration phosphoric acid
There is the alumina support of macroporous structure with the aqueous solution spray of magnesium nitrate, obtain used additives phosphorus through drying, roasting and magnesium carries out
The modified alumina support in surface 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 catalyst for catalytic gasoline hydrogenation desulfurization described in claim 1, it is characterised in that: described to have
The pore-size distribution of the alumina support of macroporous structure is in 65-150nm, macropore ratio 5-65%, Kong Rong 0.8-1.3ml/g.
3. a kind of preparation method of catalyst for catalytic gasoline hydrogenation desulfurization of any of claims 1 or 2, feature
Be: the preparation method of the catalyst includes the following steps:
Soluble-salt containing cobalt and containing molybdenum is made into maceration extract, the alumina support with macroporous structure is impregnated, at 120-160 DEG C
It is roasted 5-9 hours at lower dry 4-8 hours, 650-800 DEG C, obtains Hydrobon catalyst；
The preparation method of the alumina support includes the following steps: that thin water then will be intended firstly, with acid solution acidified chitosan
Aluminium stone 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 and gather
The acid solution of sugar, which is added in boehmite powder, to be mediated uniformly, and the additional amount of the acid solution containing expanding agent is boehmite
0.1-8wt% obtain 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: configuration phosphoric acid
There is the alumina support of macroporous structure with the aqueous solution spray of magnesium nitrate, obtain used additives phosphorus through drying, roasting and magnesium carries out
The modified alumina support in surface 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.
4. a kind of preparation method of catalyst for catalytic gasoline hydrogenation desulfurization according to claim 3, special
Sign is: it is described as follows with the process of acid solution acidified chitosan: first by chitosan expanding agent be added to 30-95 DEG C go from
In sub- water, acid is added dropwise later, until chitosan dissolution is completely, obtains the acid solution containing expanding agent；It is described acid be acetic acid, formic acid,
One or more of malic acid or lactic acid, chitosan acid solution ultrasonic oscillation or magnetic agitation.
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| CN109423326B (en) * | 2017-08-31 | 2021-07-30 | 中国石油天然气股份有限公司 | Hydrodesulfurization method of FCC gasoline |
| CN109423325B (en) * | 2017-08-31 | 2021-01-29 | 中国石油天然气股份有限公司 | Desulfurization treatment method for catalytically cracked gasoline |
| CN109420507B (en) * | 2017-08-31 | 2021-08-27 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst containing macroporous alumina carrier and preparation method thereof |
| CN109423324B (en) * | 2017-08-31 | 2021-01-29 | 中国石油天然气股份有限公司 | Method for removing mercaptan from FCC gasoline |
| CN109897663B (en) * | 2017-12-07 | 2021-07-02 | 中国石油天然气股份有限公司 | FCC gasoline desulfurization treatment method |
| CN109894122B (en) * | 2017-12-07 | 2021-06-01 | 中国石油天然气股份有限公司 | FCC gasoline hydrodesulfurization catalyst and preparation method thereof |
| CN116022865B (en) * | 2022-11-29 | 2024-07-26 | 宁波九胜创新医药科技有限公司 | Nanoscale Ni2O3Nano Ni2O3Preparation method and application of base heterogeneous catalyst |
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| CN101439288A (en) * | 2007-11-19 | 2009-05-27 | 中国石油天然气集团公司 | Combined aluminum oxide-based selective hydrodesulfurization catalyst and preparation method thereof |
| CN102335612A (en) * | 2010-07-22 | 2012-02-01 | 中国石油天然气股份有限公司 | Selective hydrodesulfurization catalyst and preparation method thereof |
| CN103706408A (en) * | 2013-12-18 | 2014-04-09 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent |
| CN106459783A (en) * | 2014-05-01 | 2017-02-22 | 国际壳牌研究有限公司 | A catalyst and its use for the selective hydrodesulfurization of an olefin containing hydrocarbon feedstock |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101439288A (en) * | 2007-11-19 | 2009-05-27 | 中国石油天然气集团公司 | Combined aluminum oxide-based selective hydrodesulfurization catalyst and preparation method thereof |
| CN102335612A (en) * | 2010-07-22 | 2012-02-01 | 中国石油天然气股份有限公司 | Selective hydrodesulfurization catalyst and preparation method thereof |
| CN103706408A (en) * | 2013-12-18 | 2014-04-09 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent |
| CN106459783A (en) * | 2014-05-01 | 2017-02-22 | 国际壳牌研究有限公司 | A catalyst and its use for the selective hydrodesulfurization of an olefin containing hydrocarbon feedstock |
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