CN107081155A - 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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- CN107081155A CN107081155A CN201710408432.XA CN201710408432A CN107081155A CN 107081155 A CN107081155 A CN 107081155A CN 201710408432 A CN201710408432 A CN 201710408432A CN 107081155 A CN107081155 A CN 107081155A
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- alumina support
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- chitosan
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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
-
- 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
Abstract
The invention discloses a kind of for catalyst of catalytic gasoline hydrogenation desulfurization and preparation method thereof, the composition of catalyst is with oxidation material gauge, including following component：The 94.0wt% of alumina support 78.0 with macroporous structure, carrier uses chitosan as expanding agent；The 10.5wt% of active component cobalt oxide 2.0, the 15.0wt% of molybdenum oxide 2.5.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 technology
Because the general sulfur content of catalytically cracked gasoline is in 100-500v%, or even also, high-sulfur, high olefin feedstock are oily, and sulphur contains
Amount is in more than 500mg/kg, and olefin(e) centent is also above 40%.Selective hydrodesulfurization technology carry out deep hydrodesulfurizationof when not
Evitable to cause hydrocarbon fraction saturation and reduce octane number, this requires to try one's best while Hydrobon catalyst desulfurization and kept away
Exempt from loss of octane number excessive.
Macroporous oxide due to larger pore passage structure, higher specific surface area, good heat endurance, using extensively
In fields such as heterogeneous catalyst, catalyst carrier, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance materials.
The carrier of aluminum oxide with macroporous structure is relatively more.CN03126434.4 discloses a kind of macropore alumina supporter,
Containing aluminum oxide, also containing a kind of halogen, on the basis of carrier total amount, the carrier contains 95-99 weight % aluminum oxide, with member
Element meter, 0.1-5 weight % halogen, its acid amount is less than 0.2 mM/gram.The preparation method of macropore alumina supporter includes will
A kind of precursor of aluminum oxide is molded and is calcined, before shaping and roasting, and the precursor of aluminum oxide is mixed with a kind of expanding agent
Close, the expanding agent includes a kind of organic expanding agent and a kind of halide, sintering temperature is 600-850 DEG C, roasting time 1-10
Hour, the consumption of each component contains final alumina support, on the basis of carrier total amount, 95-99 weight % aluminum oxide,
In terms of element, 0.1-5 weight % halogen.Organic expanding agent is in starch, synthetic cellulose, polymeric alcohol, surfactant
One or more.Synthetic cellulose is in carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxylated cellulose
It is one or more of.One or more of the polymeric alcohol in polyethylene glycol, poly- propyl alcohol, polyvinyl alcohol, surfactant is selected from fat
Fat alcohol APEO, fatty alkanol amide, molecular weight are 200-10000 acrylic copolymer, in maleic acid copolymer
It is one or more of.CN201110410339.5 provides a kind of high temperature-resistant active aluminum oxide material and preparation method thereof, described oxygen
Change aluminum to be made by following steps：After macropore boehmite, high viscous boehmite are mixed with additive with water, turning
Speed adds the dilute nitric acid reaction that concentration is 30% to be stirred under 100-1000r/min, to the peptization that pH is 2.0-5.5
During state, 3-6h is aged under the stirring of 80 DEG C of -100 DEG C of temperature, add at room temperature pore creating material stir, it is slurrying, spraying, dry
It is dry, it is calcined at 900 DEG C and aluminum oxide is made.The alumina material has the advantages that to be easy to batch production and high-ratio surface.
It can be kept for a long time than surface in 110m at a temperature of 1000-1100 DEG C2/ more than g；The work of the alumina material preparation method
Skill process is simple, with low cost.Wherein described sky agent of making is selected from polyvinyl alcohol, polyethylene glycol, polyacrylamide or methyl fibre
One kind in dimension element, its consumption is the 0-40% of oxide gross weight in alumina material.《Zhongshan University's journal》(2002,41
(2):Method 121-122) introduced is as follows：A diameter of 600nm polystyrene colloidal crystal microballoon is placed on a buchner funnel, so
The ethanol solution of aluminum nitrate and citric acid is added drop-wise under suction filtration on glue crystalline substance afterwards, allows it fully to penetrate into the gap of microballoon,
Through drying and being calcined, polystyrene moulding is removed, macroporous aluminium oxide is obtained.《Acta PhySico-Chimica Sinica》(2006,22 (7):831-
835) method that granular formwork method prepares three-dimensional ordered macroporous alumina is described, this method is as follows：Emulsion polymerization is used first
Method obtains polystyrene microsphere, and aluminum nitrate plus weak aqua ammonia are made into alumina sol, and both are then stirred into mixed by a certain percentage
Close, it is ultrasonically treated, then through drying and being calcined, obtain macroporous aluminium oxide.CN201010221302.3 (CN102311134A) is open
A kind of spherical integral macroporous alumina and preparation method thereof.This method comprises the following steps：By polymer microballoon emulsion, oxidation
Alumina gel and coagulant are well mixed with certain proportion, and the mixture is scattered in oil phase, form w/o type drop, Ran Houzai
Above-mentioned mixed phase system is heated, makes the alumina sol gelling balling-up in aqueous phase, the gel for isolating shaping from oil phase afterwards is micro-
Ball, then obtain described spherical integral macroporous alumina after aged, dry and roasting in aqueous ammonia medium.The aluminum oxide
Macropore diameter is homogeneous controllable in the range of less than 1 μm, and the size of spheric granules is controllable, and mechanical strength is higher, is molded
Journey is simple and easy to do, is easy to be prepared on a large scale.Polymer microballoon diameter 50-1000nm, the type of polymer microballoon is polystyrene
The esters microballoons such as microballoon, polyaerylic acid N-butyl microballoon, polyacrylate.Coagulant is hexamethylenetetramine, urea.Oil phase is
Organic hydrocarbon.The invention, which is mainly, prepares Integral macroporous alumina, and macropore diameter is homogeneous controllable.Preparation process is used
Lipid microballoon and coagulant etc..Preparation technology is complicated, and reagent raw material used is relatively more.Due to polymer microballoon cause
Alumina support internal gutter structure is blind bore, that is to say, that alumina support internal gutter does not have connectivity.
CN201010221297.6 discloses a kind of preparation method of Integral macroporous alumina.This method comprises the following steps：Aluminium
Source, polyethylene glycol and after low-carbon alcohol and water at least one is well mixed, will low-carbon epoxyalkane add it is described mixed
In compound, Integral macroporous alumina is obtained through aging, immersion, dry and roasting.Preparation method of the invention is simple and easy to apply, ring
Border pollution is small, and its aperture of gained Integral macroporous alumina is controllable at 0.05-10 μm.The monoblock type macropore oxidation that the present invention is provided
Thing can be applied to the fields such as macromolecular heterogeneous catalysis, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance material.
CN201410347665.X discloses a kind of big pore volume, the preparation method of high-strength alumina, by adding polyacrylamide, gathering
The expanding agents such as vinyl alcohol, alkylcellulose, sesbania powder, starch, obtain containing eurypyloue alumina support, the consumption of its expanding agent
The 10-30% of aluminum oxide is accounted for, but specific pore diameter range is not disclosed.Although hard mould agent method can obtain preferable macropore oxidation
Alumina supporter, but the consumption of its template causes processing cost to greatly improve more preferably greater than 20%, the decomposition of a large amount of templates
The demand for development of low-carbon environment-friendly is not met.CN201010509425.7 discloses the side of a kind of hydro-thermal and the common reaming of template
Method, to prepare the alumina support containing macroporous structure, is acted on, the consumption of template can be reduced by the complementary reaming of hydro-thermal
To 3-10%, but auxiliary hydro-thermal causes the rise of energy consumption.CN200310103035.X discloses a kind of macroporous aluminium oxide
Preparation method, reaming is carried out using polyvinyl alcohol, poly- propyl alcohol, polyethylene glycol soft template, by adding 1% polyethylene glycol,
The pore volume that aperture is more than 100nm accounts for the 26.2% of total pore volume.Soft template has the advantages that consumption is low, reaming effect is good, still
Solubility property of the alcohols soft template of higher molecular weight in water is poor, causes it to be used to expanding super large porous aluminum oxide and limited
System.CN200910204238.5 (CN102040235) discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The party
Method comprises the following steps：Monodispersed polymer microballoon is assembled into glue crystal template, certain party legal system is then filled into template
Standby alumina sol, most obtains macroporous aluminium oxide through dry and roasting afterwards.This method can be good at control Alumina gel and
The recombination process of Alumina gel and polymer microballoon, the network structure of alumina gel is not destroyed as far as possible, makes prepared oxidation
Aluminium not only has the macropore duct of three-dimensional order but also with higher specific surface area.The invention is burnt by the appropriateness to template
Small fenestra formed by knot, makes the macropore in material be connected with the macropore of surrounding by 12 small fenestras.The oxidation of the invention
Aluminium is suitable for use as the adsorption and separation material of mink cell focus catalyst carrier and organic macromolecule.Have in catalyst carrier material application
Beneficial to the mass transfer ability of material in the catalyst is improved, be conducive to improving the activity and selectivity of catalyst.
CN201410148773.4 discloses a kind of preparation method of aluminum oxide porous microballoon, comprises the following steps：1) by surface-active
Agent is dissolved in deionized water, stirring, is used as aqueous phase；2) chelating agent, alumina precursor and n-octyl alcohol are mixed, stirred, as
Oil phase；3) Span80 and pore-foaming agent, stirring are added in oil phase；4) by step 3) gained clarification oil phase be poured into aqueous phase
Continue stirring and emulsifying；5) by step 4) gains vacuum filtration, dry after gained Washing of Filter Cake, obtain aluminum oxide porous microballoon.Should
Microballoon has internal closing macroporous structure, and Microsphere Size is 1 μm -100 μm, and the invention is coagulated using pore-foaming agent with the colloidal sol in emulsion
Glue process obtains the metal porous microballoon with internal closing macroporous structure.Porous microsphere is prepared using phase separation principle.It is internal
It is 50nm-5 μm to close aperture.Inside closing aperture is 50nm-5 μm.Aperture is closing inside the aluminum oxide porous microballoon,
That is alumina support internal gutter does not have connectivity.Pore-foaming agent is polyvinylpyrrolidone, polyacrylamide or poly- third
Olefin(e) acid.The invention has used substantial amounts of surfactant, chelating agent, pore-foaming agent, and preparing raw material is more, and synthesis technique is complicated.
Above macroporous aluminium oxide mainly prepares macropore oxygen using cellulose, polymeric alcohol, polystyrene etc. as expanding agent
Change aluminium.
Alumina support with macropore and mesoporous i.e. composite pore structural also compares many.CN 101200297A are disclosed
The preparation method of integral macroporous alumina：Reverse 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；Monolithic devices organic/inorganic composite after filling is de- in 600 DEG C of -900 DEG C of roastings through drying
Removing template, obtains integral macroporous alumina.The advantage of this method is that preparation process is simple and easy to apply, obtained monoblock type macropore
Aluminum oxide has the macropore duct that micron order is interconnected, and aperture is 1-50 μm.This method prepares Integral macroporous alumina letter
It is single easy, but the volume fraction of aqueous phase accounts for 75%-90% in this method, and correspondingly the volume fraction of organic monomer is relatively low,
This method is while organic monomer consumption is reduced, and the preparation efficiency of prepared template is relatively low, is unfavorable for subsequent step big
It is prepared by the batch of porous aluminum oxide.A kind of preparation methods of the alumina support of composite pore structural of CN201110032234.0, including
Calorize will be contained selected from least one of aluminium isopropoxide, aluminium secondary butylate, aluminum nitrate, aluminium chloride, Alumina gel and boehmite powder
Compound and composite mould plate agent are mixed and are calcined, and the composite mould plate agent is mesoporous template and macroporous granules template, is given an account of
Hole template is selected from polyethylene glycol propane diols-polyethylene glycol triblock polymer, polyethylene glycol, lauryl amine, hexadecane
At least one of base trimethylammonium bromide, laurate, stearic acid and AEO, the macroporous granules template choosing
It is more than 50nm polystyrene microsphere, poly (methyl methacrylate) micro-sphere, particles of bioglass, pitch particle or heavy oil from particle diameter
Residue；The weight ratio of the mesoporous template, macroporous granules template and aluminum contained compound is 0.1-2:0.1-0.7:1, wherein
The weight of the aluminum contained compound is in terms of aluminum oxide.The invention also discloses have mesoporous hole while preparation by the above method
Road and the alumina support in macropore duct, its intermediary hole account for the 40%-90% of total pore volume, and macropore accounts for the 10%-60% of total pore volume.
CN201210328824.2 discloses a kind of method for preparing solid phase of gradient distribution hole gama-alumina.This method is anti-by solid phase
Precursor aluminium carbonate ammonium should be obtained, the gamma oxidation of a kind of high specific surface area, gradient distribution hole and larger pore volume is obtained after roasting
Aluminium.What the present invention was protruded the most is technically characterized in that using raw material solid phase reactive synthesis technique, as obtained by being controlled synthesis condition
The property of gama-alumina.Meanwhile, the inventive method is simple, it is easy to operate, it is not necessary to add expanding agent, cost-effective, is adapted to work
Industryization is produced in batches.The preparation process of alumina support of the present invention comprises the following steps：(1) aluminum nitrate, ammonium hydrogen carbonate and table
Face activating agent is fully ground uniformly, and ageing certain time obtains precursor aluminium carbonate ammonium in the closed container of specified temp；(2)
Aftershaping is well mixed with peptizing agent after precursor aluminium carbonate ammonium obtained by (1) is dried, can typically be squeezed using banded extruder
Bar is molded；(3) it is (2) are obtained that article shaped is dried, final alumina support is made in aerobic roasting.Luring described in step (1)
Lead the polyethylene glycol that agent is liquid form, 0.1-10.0% of the addition equivalent to aluminum nitrate weight.Carbonic acid described in step (2)
The drying process of aluminium ammonium is generally dried 1-20 hours at 50-180 DEG C.Roasting process described in step (3) is in 350-900
It is calcined 1-10 hours at DEG C.The invention prepares gama-alumina using the decomposition at a certain temperature of precursor aluminium carbonate ammonium.Aluminium carbonate
Ammonium produces gas, such as 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 thing in roasting process
Matter is slowly escaped, and carrier is not easily caused and is caved in.Method is simple, it is not necessary to add any physics expanding agent.
CN201310097588.2 discloses a kind of gama-alumina particle and preparation method thereof：1) aluminum soluble salt is dissolved in by acid
The pH value of acidifying is less than or equal in 3 aqueous solution, and the amount that the aluminum soluble salt is added causes obtained containing aluminium in aluminum water solution
The molar concentration of ion is 0.01-5mol/L；2) to step 1) it is obtained contain in aluminum water solution add alkaline precipitating agent, the alkali
Property precipitating reagent add amount cause reaction after solution ph between 5-12；3) by step 2) obtained mixed sediment solution exists
At room temperature after stirring 0.1-3h, it is put into water-bath or water heating kettle, 6-24h is aged at a temperature of 50-150 DEG C；4) by step
3) after the solution after being aged stirs, dried using spray drying process, it is 150-400 that EAT is controlled during spray drying
DEG C, leaving air temp is 60-110 DEG C, and the thermal efficiency of spray drying is more than 50%；5) by step 4) obtained dried oxidation
Aluminium precursor powder is at room temperature with the first heating rate to 250 DEG C -350 DEG C, then with the second heating rate extremely
400 DEG C -800 DEG C, insulation 0.5-20h obtains final product gama-alumina particle；Wherein, first rate of heat addition is less than the
Two rates of heat addition, and first rate of heat addition and second rate of heat addition are in the range of 0.1-10 DEG C/min.It is obtained
Gama-alumina is experiments verify that test, its specific surface area is in the range of 180m2/g-260m2/g, with high-specific surface area.It is made
Gama-alumina particle observed under ESEM with hollow foam shape pattern, it is and compound with micropore-mesopore-macropore
Aperture structure.So, when gama-alumina is as catalyst carrier, its hollow foam shape pattern can be effectively in dispersed catalyst
Active component.And hollow foam shape pattern and composite bore diameter structure, be conducive to the mass transfer in catalytic process, so as to accelerate
Rate of catalysis reaction.The composite bore diameter structure refers to both include the micropore that aperture is less than 2nm, again including aperture in 2nm-50nm
Between it is mesoporous, in addition to aperture be more than 50nm macropore.Step 1) in also include to it is obtained contain add and make in aluminum water solution
Hole agent, the molar concentration that the amount that the pore creating material is added to add pore creating material in rear solution is aluminum ions molar concentration
0.01-5 times.The pore creating material is cetyl trimethylammonium bromide (CTAB), neopelex (SDBS), polyethylene
One or more in alcohol (PVA), polyethylene glycol (PEG) and calgon.CN101863499A
(201010187094.X) provides a kind of preparation method of macroporous-mesoporous alumina.Comprise the following steps：A. first reaction is helped
Agent and aluminium salt are dissolved in organic solvent solution, reaction promoter：Two kinds of material mol ratios of aluminium ion are 3-5: 1, then by template
Add above-mentioned solution and dissolve, aluminium ion is 1: 0.015-0.025 with template mol ratio, the pH value control of final solution exists
3.5-6.0；B., a is walked to the solution prepared and carries out burin-in process, making it, progressively organic solvent and moisture are obtained greatly in removing system
Hole-meso-porous alumina presoma；C. macroporous-mesoporous alumina powder is obtained through 400-800 DEG C of calcination process.Present invention process letter
Single, duct rule, pore-size distribution is concentrated and controllable adjustment can be realized according to concrete application situation, thus many in petrochemical industry
Mutually catalysis, adsorbing separation and as having important application value in terms of catalyst carrier, energy and material.Make full use of anti-
The space frame effect and coordination of auxiliary agent and template, and intermediary's organic polymer, reaction promoter are answered to inorganic ions
Complexing so that a step prepares the adjustable macroporous-mesoporous alumina material in aperture.Prepared foramen magnum-mesoporous oxidation
The specific surface area of aluminum is up to 250-320m2/ g, duct rule, pore-size distribution in mesoporous 5-40nm, macropore 50-150nm, and
It can be realized and adjusted according to actual conditions.Reaction promoter is organic acid, and aluminium salt is inorganic aluminate.Template is triblock copolymer.
Organic solvent is anhydrous alcohols, ethers or ketones solvent.Organic acid is citric acid or laurate.Triblock copolymer is
P123 or F127.(Langmuir, 2004,20 such as Tie-Zhen Ren：1531-1534) use nonionic surfactant
The aluminium secondary butylates of Brij 56 in acid condition use hydro-thermal method and Microwave-assisted synthesis macroporous-mesoporous alumina, synthesis it is porous
0.8-2 μm of alumina powder macropore diameter, mesoporous pore size 5-8nm, the aluminum oxide of 0.4-1.4 μm of hole wall.Its deficiency is aluminium-alcohol salt
Expensive, the macroporous-mesoporous alumina pore volume of synthesis is small, duct is irregular, pore-size distribution is excessive and can not realize pore structure
Effective regulation, thus, have significant limitation in using effect and scope.Jean-Philippe Dacquin etc.
(J.Am.Chem.Soc., 2009,131：12896-12897) use sol-gel process using P123 be template in mixed solution
It is middle to be introduced into the polystyrene droplet with single dispersed phase to realize the formation of macropore in macroporous-mesoporous alumina.Deficiency
Place is that macropore diameter size (300nm or 400nm) is determined by the size of secondary introducing polystyrene drop completely, i.e. macropore diameter
Size depends on polystyrene droplet size.Organic molecule in the part change to solution itself component and system can not be passed through
Interact to realize the adjustment in aperture.(the Inorganic Chemistry, 2009,48 such as Huining Li：4421) equally adopt
The polymethyl methacrylate with single dispersed phase is introduced in mixed solution by template of F127 with sol-gel process
(PMMA) droplet realizes the formation of macropore in macroporous-mesoporous alumina, weak point be macropore diameter size also completely by
Secondary introducing polymethyl methacrylate droplet size is determined, it is impossible to changed by the part to solution system itself component come real
Show the adjustment in aperture to realize the formation of foramen magnum-mesoporous composite pore structural, thus can not also realize the controllable of foramen magnum-mesoporous aperture
Regulation, in use, in particular for during the bulky molecular catalysis of complicated ingredient by significant limitation.
Above composite holes alumina support is typically used as mould using organic polymer such as polyvinyl alcohol, polymethylacrylic acid etc.
Plate agent either expanding agent.So that the preparation of composite holes and macroporous aluminium oxide material exist template monomer have certain toxicity,
Template consumption is larger, prepare the problems such as cost is higher, preparation process is cumbersome.Meanwhile, also there is the discharge in roasting process
The problem of thing environmental pollution.Also there is the patent of the adding carbohydrate compound in polymer microballoon emulsion.
CN201310142454.8 discloses a kind of preparation method of alumina hollow ball, preparation chitosan-acetic acid-water-soluble
Liquid；By polystyrene spheres:Chitosan-acetic acid-aqueous solution is 5:1-10：1 mass ratio, by polystyrene spheres：Alpha-alumina
Body is 1:5-1:15 mass ratio takes each raw material；Polystyrene spheres and chitosan-acetic acid-aqueous solution are mixed, make polyphenyl
Ethene ball surface uniformly coats one layer of chitosan-acetic acid-aqueous solution；The polyphenyl second of chitosan-acetic acid-aqueous solution is coated with again
Alkene ball is put into ball mill device with alpha-alumina powder, with 5-30r/s rotating speed rotation cladding 2-24h, and core-shell structure copolymer ball is made；Will
After the calcining of core-shell structure copolymer ball warp, that is, the alumina hollow ball that a diameter of 0.2-2mm, wall thickness are 20-100 μm is made.
CN201110170283.0 discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The three-dimensional ordered macroporous oxidation
Aluminium, diameter macropores are 50-1000nm, and grain diameter is 1-50mm, and mechanical strength is 80-280g/mm.This method includes following step
Suddenly：Will into monodisperse polymer micro-sphere emulsion adding carbohydrate compound and the concentrated sulfuric acid, obtain the brilliant mould of polymer-modified microballoon glue
Plate, is subsequently filled alumina sol, then through aging and roasting, obtains three-dimensional ordered macroporous alumina.The polymer microballoon
A diameter of 50-1000nm, can using polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polyacrylic acid N-butyl microballoon and
One or more in the different monooctyl ester microballoon of polyacrylic acid, preferably polystyrene microsphere.Described single dispersing refers to polymer microballoon
The standard deviation of diameter is not more than 10%.The carbohydrate organic matter is the one or more in Soluble Monosaccharide and polysaccharide, preferably
For the one or more in sucrose, glucose, chitosan.This method can increase substantially the adhesion amount of aluminum oxide precursor, increase
The strong mechanical strength of material, it is trickle powder that when removing template is removed in high-temperature roasting, large pore material is not easily broken, can still be protected
Hold higher integrity degree.Chitosan is in ceramic coating sorbing material field using more.《Mesoporous chitosan-aluminium hydroxide is combined
Material Study on adsorption properties》(author：Peng Shaohua] University Of Suzhou,《Suzhou Institute of Science and Technology journal：Natural science edition》2013 30
Rolled up for 4 phases)：With chitosan and AlCl3For raw material, chitosan and α-Al (OH) are prepared for3Composite.With X-ray powder diffraction,
Transmission electron microscope, infrared, thermogravimetric and specific surface instrument have carried out sign results to it and shown：α-Al(OH)3It is in chitosan complexes
Existing typical mesoporous characteristic, BET specific surface area is 55.4m2·g-1, BJH average pore sizes are 3.3nm；Specifically preparation method is：Claim
Take 2.0g Aluminium chloride hexahydrates to be dissolved in the hydrochloric acid that 5.0mL pH value is 1, add 2.0g chitosans, then add 10.0mL distilled water
Stirring, and the pH value of solution is adjusted to 1 with watery hydrochloric acid.Still aging 30min (solution becomes pasty state), with the NaOH that pH value is 14
The pH value of solution regulation solution has white flock precipitate generation, suction filtration washes away the NaOH of residual with distilled water, is put into baking to 8
Case, product is obtained after being incubated 5h at 120 DEG C.As above step, it is respectively 1 that chitosan and aluminium chloride mass ratio are prepared respectively:2、1:3、
2:1、3:1 product.
《The preparation of chitosan/oxidized aluminium composite aerogel and sign》(Chang Xinhong；The chemicalization engineering of Luoyang Normal College
Institute,《Luoyang Normal College's journal》, 11 phases of volume 31 in 2012)：With chitosan and inorganic aluminate AlCl3.6H2O is raw material, is passed through
Sol-gel process, uses CO respectively2Supercritical drying means and freeze-drying means are prepared for new chitosan/oxidized aluminium
Composite aerogel.As a result show, the property such as specific surface area and pore volume of the content influence composite aerogel of chitosan, with shell
The increase of glycan content, the specific surface area of mixing aeroge is gradually reduced.Ratio table of the different drying means to composite aerogel
The properties such as area also have obvious influence.Composite aerogel contains micropore and mesoporous.CN201110022814.1 one kind has super
The ordered mesoporous metal oxide material of large aperture, it is characterised in that utilize the amphipathic block with ultrahigh molecular weight hydrophobic section
Copolymer is as structure directing agent, according to the principle of part assisted self assembling, before mesoporous material is made during solvent volatilizees
Drive and acted between body and structure directing agent, and microphase-separated is differently formed according to hydrophilic and hydrophobic, ultimately form to be situated between in order and see knot
Structure；Remove again after structure directing agent, form the ordered mesoporous metal oxide material with ultra-large aperture；Wherein, block copolymerization
The molecular weight of the hydrophobic block of thing is more than 10000g/mol；The ordered mesoporous metal oxide material mesoporous pore size is in 10-50nm
Between, mesoporous wall thickness of material is between 4-20nm.The hydrophilic block of the block copolymer is polyoxyethylene blocks；Institute
The hydrophobic block for stating block copolymer is polystyrene or derivatives thereof, polyacrylate or derivatives thereof, polymethylacrylic acid
One kind of ester or derivatives thereof, PLA pole or derivative, or two or more polymer described above copolymer.The invention system
Standby is meso-porous alumina, and similar also has CN101153051A, CN1631796A, CN101134567A, CN101823706A,
CN101863499A.CN201310258011.5 is related to a kind of tooth spherical alumina support, tooth ball-aluminium oxide hydrotreating and urged
Agent and preparation method thereof, including following components：Peptizing agent, 0.5-4 parts by weight；Lubricant, 0.2-2 parts by weight；Dispersant,
0.2-3 parts by weight；Expanding agent, 0.3-4 parts by weight；Aluminium hydroxide, 100 parts by weight.Expanding agent is polyvinyl alcohol, polyacrylic acid
One kind or mixture in sodium, starch derivatives or carbon black.The invention, which with the addition of anion surfactant, reduces various help
Specific surface area increases 246m while agent composition addition2/ g, expanding agent Sodium Polyacrylate.Tooth spherical alumina described in the invention
Alumina supporter, due to the wherein various auxiliary agents such as group such as peptizing agent, expanding agent, dispersant, anion surfactant is greatly lowered
Point content, not only saved cost, it is also big with specific surface area, the advantages of high mechanical strength.The invention has used peptizing agent,
Lubricant, dispersant, the reagent such as expanding agent, obtained alumina support is unimodal pore size distribution.CN201110116418.5 is carried
A kind of mesoporous sphere aluminum oxide is supplied and the method for preparing the mesoporous sphere aluminum oxide is oriented to using template.Using oil column into
Type method, is adding the template with guide function, Alumina gel is in shaping and aging into Alumina gel during preparing Alumina gel
During, because the presence of the template with guide function makes to produce substantial amounts of meso-hole structure in alumina balls.Template
For organic monomer or linear polymer, organic monomer is one kind in acrylic acid, ammonium acrylate, acrylamide, allyl alcohol.Jie
Hole spherical alumina aluminum ratio surface is 150-300m2/ g, particle diameter 0.1-5mm, pore volume is 0.7-1.5ml/g, and bore dia is
2-40nm hole is more than 97%, and heap density is 0.30-0.80g/cm3, crushing strength is 70-250N/.The invention utilizes template
Mesoporous sphere alumina pore diameter prepared by agent compares concentration, and this kind of mesoporous sphere aluminum oxide can be used for petrochemical industry and become more meticulous
Work as catalyst or catalyst carrier.
Macroporous aluminium oxide and compound porous aluminum oxide have different journeys to activity, selectivity and the stability aspect of catalyst
The improvement result of degree.Solubility of the polyvinyl alcohol template in water is influenceed by the degree of polymerization, causes it to be used for super big hole oxygen
Also it is subject to certain restrictions in the preparation for changing aluminium.
Aluminum 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, pore volume are
0.8-0.9mL/g macroporous aluminium oxide and specific surface area is 250-280m2/ g, pore volume are 0.3-0.4mL/g small porous aluminum oxide
It is composited, active component is cobalt and molybdenum, auxiliary agent is magnesium and boron.The preparation method of the catalyst includes：By macroporous aluminium oxide and
Small porous aluminum oxide mixing, adds sesbania powder and nitric acid, then after kneading, shaping, drying and being calcined, alumina composite load is made
Body, then loads auxiliary agent magnesium and boron and active component cobalt and molybdenum, then through drying and being calcined, catalyst is made successively.Catalyst
Good with gasoline selective hydrodesulfurizationmodification activity, product research method loss of octane number is low and the advantages of high liquid yield.
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, by preparing related presoma microemulsion and ammonia microemulsion, then to mix its cocurrent and reacted, 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.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 less particle, while having higher
Load capacity.The catalyst prepared by preparation method provided by the present invention shows excellent in terms of gasoline hydrodesulfurizationmethod
Catalytic performance.
The content 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.There is the macroporous aluminium oxide pore size can adjust, 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 takes off
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：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%.
It is preferred that, a kind of described catalyst for catalytic gasoline hydrogenation desulfurization 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%.
The gasoline hydrodesulfurizationcatalyst catalyst preparation method comprises the following steps：Soluble-salt containing cobalt and containing molybdenum is made into
Maceration extract, alumina support of the dipping with macroporous structure is calcined at being dried 4-8 hours, 650-800 DEG C 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, synthesizes with big
The alumina support of pore structure.
Contain adjuvant component phosphorus and magnesium, adjuvant component in alumina support of the present invention with macroporous structure, carrier
The content of phosphorus and magnesium accounts for the percentage composition respectively P of carrier quality2O50.1-2.5wt%, MgO 0.1-2.5wt%, pore-size distribution
60-180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, preferably pore volume 0.8-2.0ml/g, 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 addition and
The molecular size range of expanding agent is adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-
The scopes such as 160nm, 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, 35-50%, the model such as 55-75%
Enclose.
The preparation method of alumina support of the present invention with macroporous structure, comprises the following steps：First, it is molten with acid
Boehmite and sesbania powder, are then added in kneader and are well 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-shaping-drying-roasting
Burn, obtain 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 afterwards, until chitosan dissolving is complete, the acid solution containing expanding agent is obtained.The acid can be inorganic acid
Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The addition of acid is advisable with that can be completely dissolved chitosan.Also may be used
To select water soluble chitosan, such as carboxyl chitosan, chitosan salt, sulfated chitosan etc..Chitosan acid solution is best
With ultrasonic oscillation or magnetic agitation.More than ultrasonic oscillation 10min, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent
Ripple shakes or magnetic agitation, and expanding agent good dispersion, alumina support is more prone to macropore, and pore-size distribution more collects
In, pore-size distribution is in 70-180nm.
The addition of the sesbania powder is the 0.1-7wt% of boehmite.
Mediate or extrusion technique is that the acid solution containing expanding agent configured is added in sesbania powder and boehmite
Well mixed, extrusion, shaping afterwards is dried 3-9 hours, 650-800 DEG C is calcined 4-8 hours, finally gives by 100-160 DEG C
Alumina support with macroporous structure.
Alumina support of the present invention uses chitosan for expanding agent, and the alumina support of preparation contains macroporous structure,
Also contain meso-hole structure simultaneously, macropore range is in 2-50nm, mesoporous ratio 15-75%, preferably 15-50%, be it is a kind of containing being situated between-it is big
The alumina support in hole.And the not homogeneous aperture structure in aperture.
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 too high, and preferably configuration concentration is less than phosphoric acid and nitre when preparing complex carrier
The sour magnesium aqueous solution sprays carrier surface, and carrier surface modification is preferably carried out 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
Phosphorus pentoxide and content of magnesia are respectively in 0.1- in alumina support, alumina support of the control with macroporous structure
In the range of 2.5wt% and 0.1-2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is set to be internal five oxidation
1.05-1.6 times of two phosphorus and content of magnesia.
Compared with prior art, the present invention has advantages below：
1st, alumina support of the present invention is using chitosan as expanding agent, and expanding agent chitosan is cheap, and environmental protection
It is nontoxic, it is adapted to industrialized production.The obtained alumina support with macroporous structure, pore size can adjust, and macropore ratio can
Effectively to control.And carrier is also containing mesoporous, is a kind of Jie-macropore alumina supporter.
2nd, the present invention can also introduce phosphorus and magnesium in alumina support, the obtained carrying alumina with macroporous structure
Body, the carrier is prepared into hydrodesulfurization/mercaptan-eliminating catalyst, the catalyst such as cobalt molybdenum or nickel molybdenum, can suppress alkene saturation
Activity, catalyst desulfurizing rate is high, and alkene saturation factor (HYD) is low, with good hydrodesulfurization selectivity.
3rd, the alumina support with macroporous structure that the present invention is obtained, using phosphorus and magnesium to the oxidation with macroporous structure
Alumina supporter surface is modified, and makes the content of carrier surface phosphorus pentoxide and magnesia 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, so advantageously reduce the micropore ratio of carrier surface, improve carrier surface Jie-macropore ratio, promote carrier surface
More active sites load centres are produced, catalyst desulfurizing activity is effectively improved.Improvement to carrier surface should not use dipping
Method, impregnated carrier surface can make large quantity of moisture enter carrier, and intensity is deteriorated, and not reach raising carrier surface Jie-macropore ratio
Purpose.
4th, gasoline hydrodesulfurizationcatalyst catalyst carrier of the present invention is the alumina support with Jie-macroporous structure, and catalyst is pungent
The loss of alkane value is low, and desulfurization degree is high.
Brief description of the drawings
Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.
Embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as the limit to the present invention
System.
Primary raw material used in catalyst is prepared to originate：Source chemicals used in the present invention are commercially available prod.
Embodiment 1
8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water first, acetic acid is added dropwise afterwards, until
Chitosan dissolving is complete, obtains the acid solution containing expanding agent.Phosphatase 11 .46g, magnesium nitrate 7.35g are weighed respectively, by phosphoric acid and nitre
Sour magnesium, which is dissolved completely in 70g distilled water, is made into phosphorous, magnesium the aqueous solution.Weigh 350g boehmites powder and 20.0g sesbanias
Powder is added in kneader, and is well mixed, and adds the mixed solution of phosphoric acid and magnesium nitrate, finally by the sour molten of chitosan-containing
Liquid, which is added in boehmite powder, to be mediated uniformly, is clover shape by kneading-extruded moulding.It is small that 8 are dried at 120 DEG C
When, 700 DEG C are calcined 4 hours, obtain phosphorous and magnesium alumina support 1.Phosphorus pentoxide 0.5wt%, magnesia in carrier 1
0.8wt%.Alumina support specific surface area with macroporous structure is shown in Table 1 with pore-size distribution.
Cobalt nitrate and ammonium molybdate are made into maceration extract, adding ammoniacal liquor regulation pH value carries oxide impregnation aluminium after salt whole dissolving
Body 1, is dried 5 hours, 650 DEG C are calcined 7 hours, obtain Hydrobon catalyst 1 at 130 DEG C.Catalyst 1 is mainly constituted：Oxygen
Change cobalt 3.5wt%, molybdenum oxide 9.5wt%, change alumina supporter 87.0wt%.
Embodiment 2
8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water, acetic acid is added dropwise afterwards, until shell gathers
Sugar dissolving is complete, obtains the acid solution containing expanding agent.Phosphatase 11 .09g, magnesium nitrate 9.12g are weighed respectively, by phosphoric acid and magnesium nitrate
It is dissolved completely in 70g distilled water and is made into phosphorous, magnesium the aqueous solution.Weigh 350g boehmite powder and 20.0g sesbania powders
It is added in kneader, and is well mixed, add the mixed solution of phosphoric acid and magnesium nitrate, finally by the acid solution of chitosan-containing
It is added in boehmite powder and mediates uniformly, is clover shape by kneading-extruded moulding.It is small that 8 are dried at 120 DEG C
When, 700 DEG C are calcined 4 hours, obtain phosphorous and magnesium alumina support 1.Recycle phosphorus and magnesium to be modified carrier surface, match somebody with somebody
Alumina support 1 of the aqueous solution spray with macroporous structure of phosphoric acid and magnesium nitrate is put, is dried 8 hours, 700 DEG C 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, adding ammoniacal liquor regulation pH value carries oxide impregnation aluminium after salt whole dissolving
Body 2, is dried 6 hours, 600 DEG C are calcined 5 hours, obtain Hydrobon catalyst 2 at 110 DEG C.Catalyst 2 is mainly constituted：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.Difference is water soluble chitosan expanding agent being replaced by
Water-insoluble chitosan expanding agent, chitosan formic acid liquid magnetic stirrer 30 minutes.Obtain the oxygen with macroporous structure
Change alumina supporter 3.The content of adjuvant component phosphorus and magnesium accounts for the percentage composition respectively P of carrier quality in carrier2O51.8wt%, 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, adding ammoniacal liquor regulation pH value carries oxide impregnation aluminium after salt whole dissolving
Body 3, is dried 6 hours, 650 DEG C are calcined 5 hours, obtain Hydrobon catalyst 3 at 120 DEG C.Catalyst 3 is mainly constituted：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.Difference is water soluble chitosan expanding agent being replaced by
Water-insoluble chitosan expanding agent, chitosan acetic acid solution ultrasonic oscillation 15 minutes.Obtain the aluminum oxide with macroporous structure
Carrier.The content of adjuvant component phosphorus and magnesium accounts for the percentage composition respectively P of carrier quality in carrier2O50.8wt%, MgO
1.0wt%.Recycle phosphorus and magnesium to be modified carrier surface, obtain carrier 4, the surface phosphorus pentoxide of carrier 4 and magnesia
Content be 1.5 times of internal phosphorus pentoxide and content of magnesia.The specific surface area of alumina support 4 with macroporous structure with
Pore-size distribution is shown in Table 1.
Cobalt nitrate and ammonium molybdate are made into maceration extract, adding ammoniacal liquor regulation pH value carries oxide impregnation aluminium after salt whole dissolving
Body 4, is dried 6 hours, 580 DEG C are calcined 6 hours, obtain Hydrobon catalyst 4 at 120 DEG C.Catalyst 4 is mainly constituted：Oxygen
Change cobalt 2.2wt%, molybdenum oxide 10.3wt%, alumina support 87.5wt%.
Catalyst 1-4 is respectively charged into 10ml fixed bed reactors, carries out evaluating catalyst reaction performance.Use sulfurized oil
Presulfurization is carried out to catalyst, sulfurized oil is direct steaming gasoline, and vulcanizing agent is CS2, its concentration is 1.0wt%；Sulfide stress is
2.8MPa, hydrogen to 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 vulcanization
Handle 6h.After vulcanizing treatment terminates, full cut FCC gasoline replacement Treatment 8h is switched to, after pre-vulcanization process terminates, is adjusted to
Reaction process condition, enters catalytically cracked gasoline reaction.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.React sampling analysis, catalyst and contrast medium reactor product after 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, is selected with good hydrodesulfurization
Property.Reaction operation 500h, the product desulfurization degree of Hydrobon catalyst 4 is 82.7%, alkene drop amount 2.3%, and loss of octane number is
0.3 unit, alkene saturation factor (HYD) is 9%, and the complex carrier surface of catalyst is produced in more active sites loads
The heart, effectively improves catalyst desulfurizing activity, and catalyst reaction performance is stable.
The alumina support specific surface area and pore-size distribution of the macropore of table 1
The catalyst reaction product property of table 2
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
Protection scope of the present invention should all be belonged to.
Claims (10)
1. a kind of catalyst for catalytic gasoline hydrogenation desulfurization, it is characterised in that：
The catalytic component composition：Alumina support 78.0-94.0wt% with macroporous structure, carrier is made using chitosan
For expanding agent；Active component cobalt oxide 2.0-10.5wt%, molybdenum oxide 2.5-15.0wt%.
2. a kind of catalyst for catalytic gasoline hydrogenation desulfurization according to claim 1, it is characterised in that：It is described
Catalytic component is constituted：Alumina support 80.0-90.0wt% with macroporous structure, active component cobalt oxide 2.0-
7.5wt%, molybdenum oxide 2.5-12.0wt%.
3. a kind of catalyst for catalytic gasoline hydrogenation desulfurization according to claim 1, it is characterised in that：It is described
Containing adjuvant component phosphorus and magnesium in carrier, the content of adjuvant component phosphorus and magnesium accounts for the percentage composition respectively P of carrier quality2O5
0.1-2.5wt%, MgO 0.1-2.5wt%, pore-size distribution 60-180nm, macropore ratio 2-75%, pore volume 0.8-2.0ml/g,
Specific surface area 250-300m2/g。
4. a kind of catalyst for catalytic gasoline hydrogenation desulfurization according to claim 3, it is characterised in that：It is described
The pore-size distribution of alumina support is in 65-150nm, macropore ratio 5-65%, pore volume 0.8-1.3ml/g.
5. a kind of catalyst for catalytic gasoline hydrogenation desulfurization according to claim 1, it is characterised in that：It is described
The preparation method of catalyst comprises the following steps：Soluble-salt containing cobalt and containing molybdenum is made into maceration extract, dipping has macropore knot
The alumina support of structure, is calcined 5-9 hours at being dried 4-8 hours, 650-800 DEG C at 120-160 DEG C, obtains hydrodesulfurization and urge
Agent.
6. a kind of catalyst for catalytic gasoline hydrogenation desulfurization according to claim 1, it is characterised in that：It is described
Alumina support also contains meso-hole structure simultaneously, and macropore range is in 5-50nm, mesoporous ratio 15-75%.
7. a kind of catalyst for catalytic gasoline hydrogenation desulfurization according to claim 1, it is characterised in that：It is described
The preparation method of alumina support comprises the following steps：First, acid solution acidified chitosan is used, then by boehmite and field
Cyanines powder is added in kneader and is well mixed, and the mixed solution of phosphoric acid and magnesium nitrate is added, finally by the sour molten of chitosan-containing
Liquid, which is added in boehmite powder, to be mediated uniformly, and the addition of the acid solution containing expanding agent is the 0.1- of boehmite
8wt%, by extrusion-shaping-drying-roasting, obtains the alumina support with macroporous structure.
8. a kind of catalyst for catalytic gasoline hydrogenation desulfurization according to claim 1, it is characterised in that：It is described
The process of acid solution acidified chitosan is as follows：Chitosan expanding agent is added in 30-95 DEG C of deionized water first, dripped afterwards
Acid adding, until chitosan dissolving is complete, obtains the acid solution containing expanding agent；The acid is in acetic acid, formic acid, malic acid or lactic acid
One or more, chitosan acid solution ultrasonic oscillation or magnetic agitation.
9. a kind of catalyst for catalytic gasoline hydrogenation desulfurization according to claim 1, it is characterised in that：It is described
The content of carrier surface phosphorus pentoxide and magnesia is 1.05-1.6 times of internal phosphorus pentoxide and content of magnesia.
10. a kind of catalyst for catalytic gasoline hydrogenation desulfurization according to claim 3, it is characterised in that：It is right
The alumina support with macroporous structure that claim 3 is obtained, is modified using phosphorus and magnesium to carrier surface：Configuration is phosphorous
Alumina support of the aqueous solution spray with macroporous structure of acid and magnesium nitrate, through drying, roasting obtains used additives phosphorus and magnesium enters
Phosphorus pentoxide and content of magnesia point in the alumina support that row surface is modified, alumina support of the control with macroporous structure
Not in the range of 0.1-2.5wt% and 0.1-2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is set to be interior
1.05-1.6 times of portion's phosphorus pentoxide and content of magnesia.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109423324A (en) * | 2017-08-31 | 2019-03-05 | 中国石油天然气股份有限公司 | A kind of method of FCC gasoline removal of mercaptans |
| CN109420504A (en) * | 2017-08-31 | 2019-03-05 | 中国石油天然气股份有限公司 | A kind of catalytic cracking gasoline hydrodesulfurization catalyst and preparation method |
| CN109420507A (en) * | 2017-08-31 | 2019-03-05 | 中国石油天然气股份有限公司 | A kind of Hydrobon catalyst and preparation method thereof containing macropore alumina supporter |
| CN109423325A (en) * | 2017-08-31 | 2019-03-05 | 中国石油天然气股份有限公司 | A kind of desulfuration processing method of catalytically cracked gasoline |
| CN109423326A (en) * | 2017-08-31 | 2019-03-05 | 中国石油天然气股份有限公司 | A kind of hydrodesulfurizationprocess process of FCC gasoline |
| CN109894122A (en) * | 2017-12-07 | 2019-06-18 | 中国石油天然气股份有限公司 | A kind of FCC gasoline Hydrobon catalyst and preparation method thereof |
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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 |
-
2017
- 2017-06-02 CN CN201710408432.XA patent/CN107081155B/en active Active
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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