CN107189811B - A kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method - Google Patents
A kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method Download PDFInfo
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- CN107189811B CN107189811B CN201710408116.2A CN201710408116A CN107189811B CN 107189811 B CN107189811 B CN 107189811B CN 201710408116 A CN201710408116 A CN 201710408116A CN 107189811 B CN107189811 B CN 107189811B
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- catalyst
- alumina support
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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
- C10G45/10—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 platinum group 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
Abstract
The present invention relates to a kind of full-cut fraction pyrolysis gasoline section selective hydrogenation methods, using fixed bed reactors, catalyst is restored under hydrogen atmosphere, reaction process condition is adjusted to after process to be restored, into full-cut fraction pyrolysis gasoline feedstock oil, selective hydrogenation is carried out, hydrogenation process conditions: reaction inlet temperature >=50 DEG C, reaction pressure 2.0-4.5MPa, hydrogen to oil volume ratio 60-450;Liquid volume air speed 2.5-5.0h‑1;Catalyst includes the alumina support with macroporous structure and the metal active component palladium being carried on carrier, and the content of palladium is that 0.2-0.35wt% catalyst is strong to the drippolene adaptability to raw material of different arsenic contents, different sulfur contents based on the total weight of the catalyst.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating for petroleum hydrocarbon product, it is especially adapted for use in a kind of full fraction and splits
Solve gasoline section selective hydrogenation method.
Background technique
Drippolene is the important by-product of steam cracking industrial production ethylene, propylene, including C5-C10 fraction.Drippolene
It forms very complicated, mainly there is benzene,toluene,xylene, monoolefine, diolefin, linear paraffin, cycloalkane and nitrogen, sulphur, oxygen, chlorine
With the organic compound of heavy metal etc., a component more than totally 200, wherein benzene,toluene,xylene (being referred to as BTX) about 50-90%, no
Saturated hydrocarbons 25-30%.It is the characteristics of according to a large amount of aromatic hydrocarbons are contained in drippolene, widely used, it both can be used as the tune of gasoline
And component, high-octane gasoline is produced, separation production aromatic hydrocarbons etc. can also be passed through.
Since drippolene complicated composition, thermal stability are poor, in general, first removing alkadienes and benzene through one-stage selective hydrogenation
Ethylene after Secondary hydrodesulfurization, is mainly used for Aromatics Extractive Project.Industrial catalyst for selective hydrogenation of cracked gasoline is mainly at present
(C5 hydrocarbon-does the hydrocarbon for 204 DEG C for Pd system or Ni series catalysts, midbarrel (C6-C8 hydrocarbon compound fraction) plus hydrogen or full fraction
Compound fraction) hydrogenation technique.Due to the difference of each ethylene unit cracking stock and cracking condition, each device drippolene raw material
Composition difference is larger, and especially (polymerization reaction occurs for the unsaturation component such as alkadienes and styrene for the diene of drippolene, colloid
The high molecular polymer of generation) and As, content of beary metal there are larger differences;Some device raw pyrolysis gasoline dienes, colloid
Height, and the toxic contents such as colloid and As, heavy metal are higher in some device raw pyrolysis gasoline raw materials, individual device raw pyrolysis gasoline
The toxic contents such as diene, colloid and As, heavy metal are high.
Alkadienes and alkynes in drippolene are easy polymerization collagen at high temperature, are deposited on catalyst surface, Yi Zao
At catalyst inactivation, it is necessary to frequently activation and regeneration.Pyrolysis gasoline hydrogenation catalyst mainly has Pd/Al2O3And Ni/Al2O3
Two kinds of catalyst.The advantages that Pd series catalysts have initial temperature low, and hydrogenation activity is big, and adaptation air speed is high, long service life,
The catalyst mode for having industrial application includes Pd-Cr/Al2O3, Pd/Al2O3。
Usual pyrolysis gasoline hydrogenation catalyst is using the metal salt of active component or the solution dipping of organo-metallic compound
The carrier, it is then by processes such as dry, roastings that active component is oxide carried to carrier surface, logical hydrogen is needed before use
Pyrolysis gasoline hydrogenation reaction could be used for after gas reduction.Common carrying alumina body aperture is too small, when colloid, arsenic contain in raw material
When amount, sulfur content are exceeded, the easy coking and blocking in hole on catalyst influences catalyst activity and stabilized hydrogenation.
Macroporous oxide 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;It willAl2O3The 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 ageing certain time obtains precursor aluminium carbonate ammonium in the closed container of specific temperature;(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, and specific surface area is in 180m2/g-260m2In/g range, there is high-specific surface area.It is made
Gama-alumina particle observed under scanning electron microscope 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 hole appearance of synthesis is small, duct is irregular, pore-size distribution is excessive and cannot achieve pore structure
Effective adjusting thus have significant limitation in using effect and range.Jean-Philippe Dacquin etc.
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 5.0m L pH value is 1,2.0g chitosan, then plus 10.0mL distillation is added
Water stirring, and the pH value of solution is adjusted to 1 with dilute hydrochloric acid.Still aging 30min (solution becomes paste) is 14 with pH value
NaOH 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 oven obtains product after 120 DEG C of heat preservation 5h.Step as above, preparing chitosan and aluminium chloride mass ratio respectively is 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.
CN201010622227.1 is related to a kind of catalyst for selective hydrogenation of cracked gasoline, and it includes as carrier
Magnesia-titania-alumina composite oxide, and the Metal Palladium active component being carried on the composite oxide carrier
And Group IIA and/or IIIB race metal promoter metal, wherein metal palladium content is 0.25-0.35 weight %, and promoter metal content is
0.2-3 weight %, and the content based on oxidation aluminium magnesia in carrier is 0.1-3 weight % and the content of titanium oxide is 5-20
Weight %.The catalyst can be used for selective hydrogenation of cracked gasoline, and low temperature active is high, and selectivity is high, anti-As, S, O, N impurity energy
Power is strong, and charging capacity is greatly and activity stabilized under long-term operation.Moreover, it relates to the preparation of the catalyst and select
Application in hydrocracking gasoline.Finally, preparing composite oxides used using co-precipitation method the invention further relates to a kind of
The method of carrier.CN201310379189.5 discloses a kind of pyrolysis gasoline selective hydrogenation catalyst, including carrier and is carried on
Metal active constituent on carrier, the active component containing high molecular polymer water phase without the micro- of cosurfactant
It is prepared in lotion law system;The carrier be selected from aluminium oxide, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve,
At least one of kaolin, cordierite;The active component is main active component and helps active component, wherein main active group
It is divided into palladium, content is the 0.01wt%-1.0wt% of carrier gross weight, and the high molecular polymer is water-soluble polyphosphazene polymer
Close object.The activity of the catalyst in the reaction is higher, and selectivity is more preferable, and appearance glue ability is more preferable, and preparation process is easy, catalyst
Particle shape can be controlled well.CN201110089806.9 is related to a kind of for drippolene or its fraction selective hydrogenation
Palladium-silver/alumina-silica titanium catalyst, which includes the aluminium oxide-titanium oxide compound as carrier, and negative
The active component Pd and Ag being loaded on the carrier, wherein the content of Pd is based on the total catalyst weight as 0.15-0.5 weight
% is measured, it is 0.8-4.5 weight % that the content of Ag, which is based on the total catalyst weight,.Compared with similar catalyst, present invention catalysis
Agent can be used for drippolene or its fraction plus hydrogen, low temperature hydrogenation selectivity is high, and anti-As impurity ability is strong, and charging capacity is big, and
It is activity stabilized.Moreover, it relates to the preparation method of aforementioned catalytic agent.Catalyst of the present invention can also be used for other petroleum hydrocarbons
The selective hydrogenation of the alkynes and/or diolefin of class.CN200610029962.5 is related to a kind of for full-cut fraction pyrolysis gasoline choosing
Selecting property adds the method for hydrogen, mainly solves to exist in the prior art to be difficult to the full-cut fraction pyrolysis gasoline high to colloid and free water content
The technical issues of carrying out selective hydrogenation.The present invention is by using with C5Hydrocarbon-does the cracking of the hydrocarbon compound fraction for 204 DEG C
Gasoline and hydrogen are raw material, are 30-80 DEG C, reaction pressure 2.0-3.0MPa in reaction temperature, green oil air speed is 2.5-5.0
Hour- 1, under conditions of hydrogen/oil volume ratio is 60-120:1, raw material is contacted with catalyst, is reacted, and the diene in raw material is made
Hydrocarbon and alkylene aromatic component are converted to monoolefine and alkylaromatic hydrocarbon, and wherein catalyst includes alumina support, active group parting
Belong to palladium or its oxide, the element of at least one IA in the periodic table of elements or IIA or its oxide, at least one selected from member
The element of IVA or VA or its oxide in plain periodic table, carrier specific surface area are 40-160 meters2/ gram, total pore volume 0.3-1.2
Ml/g, and carrier has the technical solution of compound pore size distribution, preferably solves the problems, such as this, can be used for full fraction cracking vapour
In the industrial production of oily selective hydrogenation.The preparation method of catalyst of the present invention is identical as common lamella catalyst dipping technique:
Carrier first can be presoaked with liquid that maceration extract dissolves each other with a kind of, then with salt solution impregnation containing palladium, the carrier after dipping is through washing
Wash, dry, in air 300-600 DEG C roast up to oxidative catalyst finished product.Finished catalyst need to only lead in the reactor
Hydrogen reducing can be used.The catalyst that the present invention uses has a composite pore structural, it is biggish can several apertures, and rich in abundant
It is mesoporous.Catalyst of the invention has good low temperature active, selection when being used for full-cut fraction pyrolysis gasoline selective hydrogenation
Property and stability, and have good anti-interference, resistance to high colloid and high-content free water performance.40 DEG C of inlet temperature,
Reaction pressure 2.7Mpa, hydrogen/oil volume ratio 80:1, under the conditions of green oil air speed 3.8 hours -1, to gum level be 150 milligrams/
Full fraction (the hydrocarbon compound fraction that C5 hydrocarbon-is done as the 204 DEG C) drippolene that 100 grams of oil, free water content are 1000ppm into
Row selective hydrogenation reaction, outlet diene average value are 0.0 gram of iodine/100 gram oil, and diolefin hydrogenation rate is 100%, are achieved preferably
Technical effect.The preparation method of the invention carrier includes mixing aluminium oxide and modifying agent, peptizing agent, water in the desired amount, squeezing
It is first 1-24 hours dry at 50-120 DEG C after item molding, it is then roasted 1-10 hours at 800-1150 DEG C, obtains aluminium oxide
Carrier.Modifying agent, peptizing agent is not expressly recited in the invention, and polyvinyl alcohol has been used in embodiment 1, thus knows that the invention has
The carrier of compound pore size distribution is obtained with polyvinyl alcohol.It mainly solves to exist in the prior art and is difficult to colloid and dissociates
The technical issues of high full-cut fraction pyrolysis gasoline of water content carries out selective hydrogenation.It is similar there are also CN200610029963.X with
And CN200610029961.0.CN02111016.6 is related to a kind of catalyst for one-stage selective hydrogenation of gasoline splitting.It is main
When solving in conventional art using one-component Metal Palladium, the selectively lower problem of diolefin hydrogenation.The present invention is by using in δ
Phase alumina supported on carriers palladium, it is 0.6-0.9 mls/g that wherein carrier hole, which holds, and specific surface area is 2/ gram of 140-170 rice, is urged
Agent shell thickness is that 0.03-0.09 millimeters of technical solution preferably solves the problems, such as this, can be used for one section of drippolene choosing
Selecting property adds in the industrial production of hydrogen.The selectively lower disadvantage of the invention diolefin hydrogenation provides a kind of new for drippolene
The catalyst of one-stage selective hydrogenation.The catalyst has hydrogenation activity moderate, and diolefin hydrogenation selectivity is high, has stronger anti-
Poisoning capability, the good feature of operational stability.Invention uses the cylindrical body carrier containing at least one hole, carrier due to carrier
Geometrical surface is larger, and reaction bed pressure drop is enable to reduce, and is conducive to react cooling, while bed temperature can be made more uniform, have
Conducive to the selectivity for improving purpose product, high-speed operating is adapted to;The dispersion for being conducive to palladium simultaneously, reduces the content of palladium.Carrier
Hole hold it is larger, the appearance coke ability of catalyst can be improved.By the control of Metal Palladium shell thickness at 0.03-0.09 millimeters, a side
Face is conducive to inhibit the side reaction of deep hydrogenation, is on the other hand also beneficial to the evenly dispersed of Metal Palladium, improves the utilization rate of palladium,
Help to achieve the purpose that improve selectivity.Catalyst produced by the present invention, tests prove that, diolefin hydrogenation is selectively reachable
38% or more, while there is preferable stability, achieve preferable technical effect.A kind of cracking vapour of CN200810102240.7
Oil distillate section selective hydrogenation method provides use after catalyst reduction, it is characterised in that add using palladium series hydrocatalyst
Hydrogen process conditions are as follows: liquid volume air speed≤5h-1, 28-120 DEG C of reactor inlet temperature, reaction pressure >=2.4MPa, hydrogen oil body
Product compares 50-500;Palladium series hydrocatalyst used, θ, α mixing crystal form alumina support with θ type aluminium oxide or based on θ type,
Using Metal Palladium as active component, in terms of catalyst weight 100%, contain active component Pd 0.2-0.5wt%, auxiliary agent 2-8wt%
Lanthanum and/or cerium, 2-8wt% alkali earth metal;It remains to provide use by regeneration after catalyst coking and deactivation.Herein using side
Under method and process conditions, catalyst has good Hydrogenation, especially when having minor amount of water, colloid in hydrogenating materials, still
With good hydrogenation activity and stability.CN200310124229.8 one kind is used for drippolene C5-C9 fraction, especially
C8-C9 double distilled component selections are hydrogenated into the catalyst of alkene, including as carrier aluminium oxide, be covered on the carrier surface
Alkaline-earth metal or its oxide and it is carried on metal Pd and Mo or Pd and W on the carrier as active component, wherein alkali
The content of earth metal is based on the content that the total catalyst weight is 1-3 ω %, Pd and is based on the total catalyst weight to be 0.24-
The weight ratio of 0.35 ω %, Pd and Mo or Pd and W is 1:0.5-2.5.Catalyst crushing strength of the present invention is greater than 18N/mm.This is urged
Agent can be used for drippolene C5-C9 fraction, especially C8-C9 heavy fractioning hydrogenation, and low temperature active is high, and anti-As, S, O, N are miscellaneous
Mass-energy power is strong, and charging capacity is big and activity stabilized.The invention alumina catalyst carrier introduces alkaline-earth metal and is modified, it is also possible to
Add hydrogen in the selection of the alkynes or diolefin of other petroleum hydrocarbons.A kind of unsaturated hydrocarbon selective hydrogenation of CN200810114744.0 is urged
Agent and preparation method thereof.The catalyst includes following components on the basis of the total weight of catalyst using aluminium oxide as carrier: with
Palladium is active component, palladium content 0.1-1.0%, rare earth metal content 0.3-8.0%, alkaline earth metal content 0.1-
5.0%, it in addition can also contain fluorine, fluorine content 0-3.0%.Catalyst carrier is θ or mixes crystal form Al2O3, based on θ crystal form.
The palladium catalyst is distributed preferably in the secondary outer layer of catalyst;The catalyst has certain anti-impurity and anticoking capability;The catalysis
Agent is suitable for full-cut fraction pyrolysis gasoline one-stage selective hydrogenation process, is also applied for unsaturated hydrocarbons in other distillates and selectively adds
Hydrogen process.
The prior art changes support chemistry composition and type, and addition coagent mainly to promote catalyst performance
Energy.Since the impurity such as As, S, O, N and gum level are higher in drippolene, catalyst is set to be easy inactivation, it is therefore desirable to crack vapour
Oily catalyst has appearance glue ability good, anti-arsenic, sulfur resistive, the characteristic for inhibiting coking ability strong.
Summary of the invention
The present invention provides a kind of one-stage selective hydrogenation of gasoline splitting method, is particularly suitable for a kind of full-cut fraction pyrolysis gasoline
Section selective hydrogenation method.The process uses load type palladium catalyst, and carrier is the carrying alumina with macroporous structure
The characteristics of body, macropore alumina supporter is adjustable with pore size, and macropore ratio can be controlled effectively.The catalyst is reacting
In activity it is higher, selectivity is more preferable, holds that glue ability is more preferable, and anti-arsenic, inhibits coking ability strong at sulfur resistive, to different arsenic contents, no
Drippolene C5-C9 adaptability to raw material with sulfur content is strong.
A kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method, using fixed bed reactors, to urging under hydrogen atmosphere
Agent is restored, and is adjusted to reaction process condition after process to be restored, into full-cut fraction pyrolysis gasoline feedstock oil, is selected
Selecting property hydrogenation reaction;Catalyst includes the alumina support with macroporous structure and the metal active constituent being carried on carrier
Palladium, the content of palladium are 0.2-0.35wt%, preferably 0.25-0.3wt%, alumina support use based on the total weight of the catalyst
Chitosan is as expanding agent;Contain adjuvant component phosphorus and magnesium in carrier, the content of adjuvant component phosphorus and magnesium accounts for the hundred of carrier quality
Point content is respectively P2O50.1-2.5wt%, MgO 0.1-2.5wt%, pore-size distribution 60-180nm, preferably 65-150nm, greatly
Hole ratio 2-75%, preferably 5-65%, hole hold 0.8-2.0ml/g, preferably 0.8-1.3ml/g or preferred 1.6-2.0ml/g, compare table
Area 250-300m2/g;Hydrogenation process conditions: reaction inlet temperature >=50 DEG C, reaction pressure 2.0-4.5MPa, hydrogen to oil volume ratio
60-450;Liquid volume air speed 2.5-5.0h-1。
The catalyst the preparation method is as follows: prepare palladium-containing solution dipping have macroporous structure alumina support, warp
110-160 DEG C drying 3-9 hours, 400-650 DEG C roasting 4-9 hours, finally obtain catalyst prod;
The alumina support with macroporous structure the preparation method is as follows: firstly, with acid solution acidified chitosan, so
Boehmite and sesbania powder are added in kneader afterwards and are uniformly mixed, phosphoric acid, magnesium nitrate mixed solution are added, finally will
The acid solution of chitosan-containing, which is added in boehmite, to be mediated uniformly, and the additional amount of the acid solution containing expanding agent is to intend thin water aluminium
The 0.1-8wt% of stone, preferably 0.2-5.0wt% obtain the oxidation with macroporous structure by extrusion-molding-drying-roasting
Alumina supporter.
Preferably, the hydrogenation process conditions: liquid volume air speed 2.5-4.0h-1, 50-100 DEG C of inlet temperature is reacted, instead
Answer pressure 2.5-4.0MPa, hydrogen to oil volume ratio 60-300.
Preferably, adjuvant component cerium, adjuvant component cerium oxide are also contained in the alumina support with macroporous structure
Content account for carrier quality percentage composition be 0.1-2.5wt%.
In the preparation method of catalyst of the present invention, palladium compound used can be any one disclosed in prior art
Suitable for the palladium compound of palladium catalyst processed, such as palladium chloride, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, four nitre
Base palladium acid sodium, acylate such as oxalic acid palladium of palladium etc..To prepare solvent used in palladium compound solution do not have it is any specifically limited,
As long as it can dissolve used palladium compound.Preferred solvent be for example water, dilute hydrochloric acid, dust technology, dilute sulfuric acid or
Their mixed liquor.
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.
Preferably, the preparation method of the alumina support with macroporous structure may be incorporated into cerium, for example, by cerous nitrate with
Magnesium nitrate, which is mixed together, to be added in carrier, and the alumina support of phosphorous, magnesium, cerium is obtained.
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 one or more of acetic acid, formic acid, malic acid, lactic acid.The additional amount of acid is poly- can be completely dissolved shell
Sugar is advisable.Water soluble chitosan, such as carboxyl chitosan, chitosan salt, sulfated chitosan etc. can also be selected.Chitosan
The most handy ultrasonic oscillation of acid solution or magnetic agitation.Ultrasonic oscillation 10min or more, magnetic agitation 0.5-2h.To reaming
Agent carries out ultrasonic oscillation or magnetic agitation, expanding agent good dispersion, alumina support are more prone to produce macropore, and aperture
Distribution is more concentrated, and 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 preparation method of the present invention can also utilize phosphorus and magnesium
Carrier surface is modified, the concentration of phosphorus and magnesium is unsuitable excessively high, and preferably configuration concentration is lower than phosphorus when preparing complex carrier
Acid and magnesium nitrate aqueous solution spray carrier surface, preferably carry out carrier surface modification as follows: configuration phosphoric acid and nitre
The aqueous solution spray of sour magnesium has the alumina support of macroporous structure, obtains used additives phosphorus through drying, roasting and magnesium carries out surface
Modified alumina support, control is with phosphorus pentoxide in the alumina support of macroporous structure and content of magnesia in 0.1-
In the range of 2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is made to be internal phosphorus pentoxide and magnesia
1.1-1.6 times of content.
The above-mentioned alumina support containing adjuvant component phosphorus, magnesium and cerium, can also using phosphorus, magnesium and cerium to carrier surface into
Row is modified, and the aqueous solution of configuration phosphoric acid, magnesium nitrate and cerous nitrate sprays carrier surface, preferably carries out carrier as follows
Surface is modified: the aqueous solution spray of configuration phosphoric acid, magnesium nitrate and cerous nitrate has the alumina support of macroporous structure, through dry
Dry, roasting obtains used additives phosphorus, magnesium and cerium and carries out the modified alumina support in surface, controls the carrying alumina with macroporous structure
The content of phosphorus pentoxide, magnesia and cerium oxide is all in the range of 0.1-2.5wt% in body, and aoxidizes carrier surface five
The content of two phosphorus, magnesia and cerium oxide is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
Compared with prior art, the invention has the following advantages that
1, for catalyst carrier of the present invention using chitosan as expanding agent, expanding agent chitosan is cheap, and environmental protection
It is nontoxic, it is suitble to industrialized production.The obtained alumina support with macroporous structure, pore size is adjustable, and macropore ratio can
Effectively to control.And carrier also contains mesoporous, is a kind of Jie-macropore alumina supporter.Catalyst carrier has macroporous structure,
It is good to hold glue ability, inhibits coking ability strong, anti-arsenic, sulfur resistive effect are good.
2, the present invention can also in alumina support and carrier surface introduce cerium, make carrier surface cerium content be higher than carry
Internal portion, there is the alumina support of macroporous structure to be prepared into one-stage selective hydrogenation of gasoline splitting catalyst, be able to suppress for this
Olefinic polymerization improves diolefin hydrogenation selectivity.
3, the alumina support with macroporous structure that the present invention obtains, using phosphorus, magnesium or phosphorus, magnesium, cerium to macropore
The alumina carrier surface of structure is modified, and make carrier surface phosphorus pentoxide, magnesia, cerium oxide content be internal
Phosphorus pentoxide, magnesia, 1.1-1.6 times of cerium-oxide contents.Carrier surface is modified by the way of spray, it can
The partial pore of effective peptization carrier surface, advantageously reduces the micropore ratio of carrier surface in this way, and it is big to improve carrier surface Jie-
Hole ratio promotes carrier surface to produce more active sites load centres, effectively improves the utilization rate of palladium, improves drippolene
Selective hydrogenation activity.And concentration of component different structure inside and outside this carrier, so that alkynes and alkadienes is not easily accessed duct
Inside occurs polymerization reaction and blocks duct.Dipping method should not be used to the improvement of carrier surface, impregnated carrier surface can make largely
Moisture enters carrier, is not achieved and improves carrier surface Jie-macropore ratio purpose.
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 the field 20.0g
Cyanines powder is added in kneader, and is uniformly mixed, and the mixed solution of phosphoric acid and magnesium nitrate is added, finally by the acid of chitosan-containing
Solution, which is added in boehmite, to be mediated uniformly, is clover shape by kneading-extruded moulding.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.
150ml water is added in palladium chloride, is added and is diluted to 1L with ionized water again after dissolving with hydrochloric acid and is made into palladium solution, according to
Required shell thickness adjusts pH value;Carrier is presoaked with ionized water again, palladium solution impregnating carrier is used after being filtered dry moisture, after being filtered dry moisture
130 DEG C of drying, 450 DEG C roast 5 hours, obtain catalyst 1.1 palladium content of catalyst is 0.27wt%.
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 and mediates uniformly, be clover shape by kneading-extruded moulding.It is 8 hours dry at 120 DEG C, 700
DEG C roasting 4 hours, obtain phosphorous and magnesium alumina support 1.It recycles phosphorus and magnesium to be modified carrier surface, configures phosphorous
The aqueous solution of acid and magnesium nitrate spray has the alumina support 1 of macroporous structure, and 8 hours dry through 120 DEG C, 700 DEG C of roastings 4 are small
When obtain used additives phosphorus and magnesium and carry out the modified alumina support 2 in surface, the content of carrier surface phosphorus pentoxide and magnesia
It is 1.2 times of internal phosphorus pentoxide and content of magnesia.Alumina support specific surface area and aperture point with macroporous structure
Cloth is shown in Table 1.
Palladium solution impregnation of alumina carrier 2 is configured, 6 hours dry at 120 DEG C, 500 DEG C roast 5 hours, are catalyzed
Agent 2.2 palladium content of catalyst is 0.31wt%.
Embodiment 3
The preparation method of carrier is carried out according to embodiment 1.The difference is that adjuvant component also contains cerium in carrier, by water
Soluble chitosan expanding agent is changed to water-insoluble chitosan expanding agent, and chitosan formic acid liquid magnetic stirrer 30 is divided
Clock obtains the alumina support 3 with macroporous structure.The content of adjuvant component phosphorus, magnesium and cerium accounts for the hundred of carrier quality in carrier
Point content is respectively 1.8wt%, 2.0wt%, 0.6wt%.Its specific surface area and pore-size distribution are shown in Table 1.
Palladium solution impregnation of alumina carrier 3 is configured, 6 hours dry at 120 DEG C, 500 DEG C roast 5 hours, are catalyzed
Agent 3.3 palladium content of catalyst is 0.29wt%.
Embodiment 4
The preparation method of carrier is carried out according to embodiment 3.The difference is that water soluble chitosan expanding agent is changed to
Water-insoluble chitosan expanding agent, chitosan acetic acid solution was with ultrasonic oscillation 15 minutes.Obtain the aluminium oxide with macroporous structure
Carrier.In carrier the content of adjuvant component phosphorus, magnesium and cerium account for the percentage composition of carrier quality be respectively 1.6wt%, 1.6wt%,
0.6wt%.It recycles phosphorus, magnesium and cerium to be modified carrier surface, obtains carrier 4,4 surface phosphorus pentoxide of carrier, oxidation
The content of cerium and magnesia is 1.5 times of internal phosphorus pentoxide, cerium oxide and content of magnesia.Oxidation with macroporous structure
4 specific surface area of alumina supporter and pore-size distribution are shown in Table 1.
Palladium solution impregnation of alumina carrier 4 is configured, 7 hours dry at 125 DEG C, 480 DEG C roast 6 hours, are catalyzed
Agent 4.4 palladium content of catalyst is 0.30wt%.
The alumina support specific surface area and pore-size distribution of 1 macropore of table
Catalyst 1-4 is respectively charged into 100ml insulation bed reaction device, at 120 DEG C of temperature, the body of hydrogen and catalyst
Product cools to 40 DEG C of laggard full-cut fraction pyrolysis gasoline (C5-C9) feedstock oils, full fraction is split than restoring 10 hours under the conditions of 200:1
Solving diene content in gasoline stocks oil is 43.41g iodine/100g oil, iodine number 141.13g iodine/100g, gum level 123mg/
100ml oil, sulfur content is 189ppm and arsenic content is 86ppb;Reaction process condition are as follows: 50 DEG C of inlet temperature, hydrogen to oil volume ratio
210:1, reaction pressure 3.2MPa, green oil air speed 3.5h-1;The average diene for operating 1 hydrogenated products of 220h catalyst is 1.92
Gram iodine/100 gram oil, iodine number 44.35g iodine/100g, diolefin hydrogenation rate 88.6%.The average diene of 2 hydrogenated products of catalyst is
1.02 grams of iodine/100 gram oil, iodine number 41.43g iodine/100g, diolefin hydrogenation rate 89.7%.The average diene of 3 hydrogenated products of catalyst
For 1.43 grams of iodine/100 gram oil, iodine number 42.12g iodine/100g, diolefin hydrogenation rate 89.2%.Average pair of 4 hydrogenated products of catalyst
Alkene is 0.73 gram of iodine/100 gram oil, iodine number 40.32g iodine/100g, diolefin hydrogenation rate 90.2%.
From the above data, the average diene of hydrogenated products is lower than 1.92 grams of iodine/100 gram oil, diolefin hydrogenation rate
88.6% or more, catalyst activity is higher, and selectivity is more preferable, and appearance glue ability is more preferable, and anti-arsenic, inhibits coking ability strong at sulfur resistive.
Catalyst 2,3 and 4 is respectively charged into 100ml insulation bed reaction device, at 120 DEG C of temperature, hydrogen and catalyst
Volume ratio 200:1 under the conditions of restore 10 hours, cool to 40 DEG C of laggard full-cut fraction pyrolysis gasoline (C5-C9) feedstock oils, evaporate entirely
Diene content is 44.53g iodine/100g oil, iodine number 146.23g iodine/100g in division solution gasoline stocks oil, and gum level is
147mg/100ml oil, sulfur content is 137ppm and arsenic content is 168ppb;Reaction process condition are as follows: 60 DEG C of inlet temperature, hydrogen oil
Volume ratio 140:1, reaction pressure 3.5MPa, green oil air speed 4.5h-1;The average diene of 2 hydrogenated products of catalyst is 0.91 gram
Iodine/100 gram oil, iodine number 43.32g iodine/100g, diolefin hydrogenation rate 90.1%.Operate the average double of 3 hydrogenated products of 220h catalyst
Alkene is 1.02 grams of iodine/100 gram oil, iodine number 41.65g iodine/100g, diolefin hydrogenation rate 89.5%.It operates 220h catalyst 4 plus hydrogen produces
The average diene of product is 0.31 gram of iodine/100 gram oil, iodine number 41.43g iodine/100g, diolefin hydrogenation rate 90.5%.Hydrogenated products
Average diene is lower than 1.02 grams of iodine/100 gram oil, and catalyst appearance glue ability is good, and anti-arsenic, inhibits coking ability strong at sulfur resistive, catalyst
It is adaptable to the feedstock oil of different sulfur contents, gum level, arsenic content.
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 (6)
1. a kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method, it is characterised in that:
Using fixed bed reactors, catalyst is restored under hydrogen atmosphere, reaction work is adjusted to after process to be restored
Skill condition carries out selective hydrogenation, hydrogenation process conditions into full-cut fraction pyrolysis gasoline feedstock oil: reaction inlet temperature >=
50 DEG C, reaction pressure 2.0-4.5MPa, hydrogen to oil volume ratio 60-450;Liquid volume air speed 2.5-5.0h-1;
Catalyst includes the alumina support with macroporous structure and the metal active component palladium being carried on carrier, the content of palladium
Total weight based on the catalyst is 0.20-0.30wt%;
The catalyst the preparation method is as follows: prepare palladium-containing solution dipping have macroporous structure alumina support, through 110-
160 DEG C drying 3-9 hours, 400-650 DEG C roasting 4-9 hours, finally obtain catalyst prod;
Alumina support using chitosan be used as expanding agent, with macroporous structure alumina support in containing adjuvant component phosphorus with
The percentage composition that the content of magnesium, adjuvant component phosphorus and magnesium accounts for carrier quality is respectively P2O50.1-2.5wt%, MgO 0.1-
2.5wt%, has and also contains adjuvant component cerium in the alumina support of macroporous structure, and the content of adjuvant component cerium oxide accounts for carrier
The percentage composition of quality is 0.1-2.5wt%;Pore-size distribution 60-180nm, macropore ratio 2-75%, hole hold 0.8-2.0ml/g,
Specific surface area 250-300m2/g;
The preparation method of the alumina support with macroporous structure includes the following steps: firstly, poly- with acid solution acidification shell
Then boehmite and sesbania powder are added in kneader and are uniformly mixed, add phosphoric acid, magnesium nitrate and cerous nitrate by sugar
The acid solution of chitosan-containing is finally added in boehmite and mediates uniformly by mixed solution, the acid solution containing expanding agent
Additional amount is that the 0.1-8wt% of boehmite obtains the oxidation with macroporous structure by extrusion-molding-drying-roasting
Alumina supporter;
To the obtained alumina support with macroporous structure, be modified using phosphorus, magnesium and cerium to carrier surface: configuration is phosphorous
The aqueous solution spray of acid, magnesium nitrate and cerous nitrate has the alumina support of macroporous structure, obtains used additives through drying, roasting
Phosphorus, magnesium and cerium carry out the modified alumina support in surface, control phosphorus pentoxide, oxygen in the alumina support with macroporous structure
Change the content of magnesium and cerium oxide in the range of 0.1-2.5wt%, and makes carrier surface phosphorus pentoxide, magnesia and oxidation
The content of cerium is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
2. a kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method according to claim 1, it is characterised in that: described
Hydrogenation process conditions are as follows: liquid volume air speed 2.5-4.0h-1, 50-100 DEG C of inlet temperature is reacted, reaction pressure 2.5-
4.0MPa, hydrogen to oil volume ratio 60-300.
3. a kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method according to claim 1, it is characterised in that: described
Alumina support also contains meso-hole structure simultaneously, and macropore range is in 2-50nm, mesoporous ratio 15-75%.
4. a kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method according to claim 1, it is characterised in that: described
It mediates or extrusion technique is, the configured acid solution containing expanding agent is added in sesbania powder and boehmite and is mixed
It is even, later extrusion, molding, by 100-160 DEG C drying 3-9 hour, 650-800 DEG C roasting 4-8 hours, finally obtain with greatly
The alumina support of pore structure.
5. a kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method according to claim 1, it is characterised in that: described
With acid solution acidified chitosan, acid is one or more of acetic acid, formic acid, malic acid or lactic acid.
6. a kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method according to claim 1, it is characterised in that: described
Chitosan acid solution ultrasonic oscillation or magnetic agitation.
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CN101121899A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Selectivity hydrogenation method for whole fraction crack petroleum |
CN101429454A (en) * | 2008-03-19 | 2009-05-13 | 中国石油天然气股份有限公司 | Full-cut fraction pyrolysis gasoline diolefin selective hydrogenation method |
CN101433841A (en) * | 2007-12-13 | 2009-05-20 | 中国石油天然气股份有限公司 | Selectively hydrogenating 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 |
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CN101121899A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Selectivity hydrogenation method for whole fraction crack petroleum |
CN101433841A (en) * | 2007-12-13 | 2009-05-20 | 中国石油天然气股份有限公司 | Selectively hydrogenating catalyst and preparation method thereof |
CN101429454A (en) * | 2008-03-19 | 2009-05-13 | 中国石油天然气股份有限公司 | Full-cut fraction pyrolysis gasoline diolefin selective hydrogenation method |
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 |
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