CN107096552B - A kind of catalyst and preparation method for FCC gasoline removal of mercaptans - Google Patents
A kind of catalyst and preparation method for FCC gasoline removal of mercaptans Download PDFInfo
- Publication number
- CN107096552B CN107096552B CN201710412089.6A CN201710412089A CN107096552B CN 107096552 B CN107096552 B CN 107096552B CN 201710412089 A CN201710412089 A CN 201710412089A CN 107096552 B CN107096552 B CN 107096552B
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- China
- Prior art keywords
- alumina support
- catalyst
- magnesium
- cerium
- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000003502 gasoline Substances 0.000 title claims abstract description 41
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 58
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011777 magnesium Substances 0.000 claims abstract description 31
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 27
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
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- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 27
- 230000000694 effects Effects 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 239000011733 molybdenum Substances 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 239000002671 adjuvant Substances 0.000 claims abstract description 11
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 30
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000395 magnesium oxide Substances 0.000 claims description 23
- 229910052684 Cerium Inorganic materials 0.000 claims description 22
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 19
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 11
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- 150000001993 dienes Chemical class 0.000 abstract description 13
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- 238000000034 method Methods 0.000 description 43
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- 239000000463 material Substances 0.000 description 34
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- 229910052717 sulfur Inorganic materials 0.000 description 31
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- 239000002243 precursor Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
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Classifications
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
The present invention relates to a kind of catalyst for FCC gasoline removal of mercaptans, catalyst includes the alumina support and the metal active constituent nickel being carried on carrier and molybdenum with macroporous structure, by weight percentage, alumina support with macroporous structure is 66-91wt%, contain adjuvant component phosphorus and magnesium, pore-size distribution 60-180nm, macropore ratio 2-75% in carrier, hole holds 0.8-2.0ml/g, specific surface area 250-300m2/g.Nickel oxide content is 5-19wt%, and oxidation molybdenum content is 2-15wt%.Catalyst has removal of mercaptans activity height, and diolefin hydrogenation selectivity is high, and loss of octane number is low.
Description
Technical field
The present invention relates to one kind to be used for FCC gasoline mercaptan-eliminating catalyst and preparation method.
Background technique
Increasingly strict with environmental regulation, countries in the world, which propose the quality of refinery products, to be increasingly stringenter
It is required that being especially increasingly stringenter to the limitation of refinery products sulfur content.Vulcanize owner contained in oils
It to be mercaptan (RSH), thioether (RSR) etc., wherein influence of the mercaptan to product quality is maximum, not only has foul smell, very strong
Corrosivity also will affect the stability of product.
CN1229838A discloses a kind of method for transformation of hydrocarbon ils, and this method is to be catalyzed feedstock oil and a kind of hydrofinishing
Agent removal of mercaptans under the process conditions of hydro-sweetening, the Hydrobon catalyst contain the oxygen of load on the alumina support
Change tungsten (molybdenum), nickel oxide and cobalt oxide, wherein the content of tungsten oxide (molybdenum) is 4-10wt%, and the content of nickel oxide is 1-5wt%,
The content of cobalt oxide is 0.01-0.1wt%, and the total atom number and the ratio between nickel, cobalt, the total atom number of tungsten (molybdenum) of nickel and cobalt are 0.3-
0.9.CN102451694A discloses a kind of hydrodesulfurization alcohol catalyst and its preparation method and application.The catalyst is with aluminium oxide
Or silicon-containing alumina is carrier, and using phosphorus as adjuvant component, using copper and zinc as active component, on the basis of catalyst quality, auxiliary agent
The content of phosphorus is 0.5-3.0wt%, and the content of zinc oxide is 3-15wt%, and the content of copper oxide is 5-30wt%.Because of the catalysis
Agent has very strong hydrogenation activity, for when handling full fraction FCC gasoline, mercaptans content to be reduced to 3 μ g/g by 38 μ g/g, together
When olefin(e) centent 20v% is also reduced to by 25v%, RON loss is up to 1.3 units.CN00136870.2 provides a kind of use
The selectively mercaptan-eliminating catalyst and preparation method thereof of mercaptan sulfur in removing aviation fuel.Catalyst includes according to parts by weight
Following component: 1. molybdenum oxide 7-20；2. cobalt oxide 0.1-5；3. nickel oxide 0-5 4. silica 0-10；5. phosphorus or boron or fluorine 0-
4；6. aluminium oxide 0-40；7. titanium dioxide 60-100.The preparation method of catalyst is that catalyst carrier maceration extract is impregnated 1-2
Hour, it is then dry at 100-130 DEG C；Finally catalyst is obtained within roasting 2-6 hours at 400-550 DEG C.This catalyst pair
Mercaptan sulfur in jet fuel has good removal effect and preferable low temperature active.CN201210393263.4 is related to a kind of new
The preparation method and application of type demercaptaning for gasoline adsorbent.The preparation method of the demercaptaning for gasoline adsorbent the following steps are included:
Solvent, metal ion presoma, mesoporous material are uniformly mixed, are aged, organic ligand is added, carries out hydrothermal crystallizing processing；So
Afterwards, the product of hydrothermal crystallizing processing filtered, washed, dried, it is compound to obtain zeolite imidazole class framework material/mesoporous material
Object；Compression molding, crushing and screening are carried out to the zeolite imidazole class framework material/mesoporous material compound, obtain gasoline desulfurization
Alcohol adsorbent.In zeolite imidazole class framework material/mesoporous material compound provided by the invention, zeolite imidazole class framework material
Specific surface area is high, while being in high dispersion state on mesoporous material, efficiently solves and spreads limitation caused by reunion.It is described molten
Agent is the combination of one or more of deionized water, methanol, ethyl alcohol and n,N-Dimethylformamide；The metal ion is
Zn2+、Cu2+And Co2+One or more of combination；The metal ion presoma is the nitrate and/or second of metal ion
The combination of one or more of hydrochlorate；The organic ligand is in imidazoles, 2-methylimidazole, 2- nitroimidazole and benzimidazole
One or more；The mesoporous material is modified ordered mesoporous molecular sieve.CN200910082945.1 is related to one kind and urges
Change cracking gasoline selective hydrocatalyst and preparation method thereof.Catalyst of the present invention is by Al2O3-TiO2Composite oxide carrier
It is formed with reactive metal oxides, based on the weight percent to catalyst, the NiO content in reactive metal oxides is
10-20w%, MoO3Content is 5-12w%；Wherein carrier Al2O3-TiO2Oxide TiO2: Al2O3Weight ratio be 0.01-1:
1.Catalyst of the present invention is in low temperature (100-200 DEG C), low pressure (1-3.0MPa), low hydrogen/gasoline ratio (hydrogen to oil volume ratio 5:1-100:1)
Under conditions of, catalytically cracked gasoline is handled, very high de- diolefin and removal of mercaptans activity, selectivity and stability are shown.
CN200910187903.4 discloses a kind of hydrodesulfurization alcohol catalyst and its preparation method and application.The catalyst is with HZSM-5
Molecular sieve is main carrier component, using copper and zinc as active component.In terms of oxide weight, the content of copper oxide is active component
5%-27%, the content of zinc oxide are 3%-15%, using saturation total immersion technology preparation.Catalyst of the invention is suitable for light
Matter oil product carries out the reaction of selective hydrodesulfurization alcohol, has the characteristics that removal of mercaptans activity is high, hydrogenation of olefins activity is low, and after reaction
Liquid yield is high, loss of octane number is seldom.It is de- that CN201610187374.8 provides the light hydrocarbons regulated and controled based on aluminium oxide crystal face
Mercaptan catalyst and its preparation method, the catalyst are using the gama-alumina after hydro-thermal process of the present invention regulation as carrier, with nickel
And molybdenum is active metal.Light hydrocarbons mercaptan-eliminating catalyst of the present invention is high activity and high-selectivity catalyst, be can be used
Mercaptan and alkadienes effect generate macromolecular sulfide in catalysis light hydrocarbons, and the selectivity that can be also catalyzed diolefin adds
Hydrogen saturation, compared with existing catalyst, catalyst desulfurizing alcohol activity provided by the present invention is high, diolefin hydrogenation selectivity is high,
And active component is not lost, not easy in inactivation, thus the catalyst runs period is long, has preferable prospects for commercial application.The invention
Gama-alumina after hydro-thermal process regulation, as described above, the gama-alumina is characterized in that it with highly exposed (111)
(110) crystal face, so that the active metal nickel (Ni) and molybdenum (Mo) in catalyst of the present invention can be in the gama-alumina crystal faces
Upper realization crystal face selection preferably loads, and W metal is preferentially supported on newly (111) crystal face of exposure, and metal Mo is preferentially supported on
Newly on (110) crystal face of exposure.Meanwhile two kinds of active metals also by respectively with modified gama-alumina (111) and
(110) effect of crystal face forms two different active crystal faces, to obtain high activity and highly selective light hydrocarbons
Mercaptan-eliminating catalyst.The catalyst can be in efficient removal liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and coker gasoline etc.
In the case where mercaptan and/or alkadienes in light fraction, retain the alkene in raw material, the octane number RON of gasoline only reduces by 0.3
Point or so, to realize the high value added utilization of light hydrocarbons.
The composition and comparision contents of above-mentioned catalyst are more, and preparation process is complicated, and produce catalyst prod matter in enormous quantities
Amount is difficult to control.
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.CN101200297A discloses whole
The preparation method of figure macroporous aluminium oxide: use reversed concentrated emulsions method big as monomer preparation monoblock type using styrene and divinylbenzene
Hole organic formwork；Al is prepared using aluminium isopropoxide or boehmite as predecessor2O3The hydrosol；By Al2O3The hydrosol is filled into whole
In body formula macropore organic formwork；Filled monolithic devices organic/inorganic composite is removed through drying in 600 DEG C of -900 DEG C of roastings
Template obtains integral macroporous alumina.The advantages of this method is that preparation process is simple and easy, monoblock type macropore oxygen obtained
Change the macropore duct that there is aluminium micron order to interconnect, aperture is 1-50 μm.It is simple that this method prepares Integral macroporous alumina
It is easy, but the volume fraction of water phase accounts for 75%-90% in this method, and correspondingly the volume fraction of organic monomer is relatively low, this
For method while reducing organic monomer consumption, the preparation efficiency of prepared template is relatively low, is unfavorable for subsequent step macropore
It is prepared by the batch of aluminium oxide.A kind of preparation method of the alumina support of composite pore structural of CN201110032234.0, including will
Closing containing calorize selected from least one of aluminium isopropoxide, aluminium secondary butylate, aluminum nitrate, aluminium chloride, Aluminum sol and boehmite powder
Object and composite mould plate agent are mixed and are roasted, the composite mould plate agent be mesoporous template and macroporous granules template, it is described mesoporous
Template is selected from polyethylene glycol propylene glycol-polyethylene glycol triblock polymer, polyethylene glycol, lauryl amine, cetyl
At least one of trimethylammonium bromide, lauric acid, stearic acid and fatty alcohol polyoxyethylene ether, the macroporous granules template are selected from
Partial size is residual greater than the polystyrene microsphere of 50nm, poly (methyl methacrylate) micro-sphere, particles of bioglass, pitch particle or heavy oil
Slag；The weight ratio of the mesoporous template, macroporous granules template and aluminum contained compound is 0.1-2:0.1-0.7:1, wherein institute
The weight of aluminum contained compound is stated in terms of aluminium oxide.The invention also discloses have mesopore orbit while preparation by the above method
With the alumina support in macropore duct, intermediary hole accounts for the 40%-90% of total pore volume, and macropore accounts for the 10%-60% of total pore volume.
CN201210328824.2 discloses a kind of method for preparing solid phase of gradient distribution hole gama-alumina.This method is anti-by solid phase
Precursor aluminium carbonate ammonium should be obtained, the gamma oxidation that a kind of high specific surface area, gradient distribution hole and large hole are held is obtained after roasting
Aluminium.The present invention is the most outstanding to be technically characterized in that using raw material solid phase reactive synthesis technique, as obtained by synthesis condition control
The property of gama-alumina.Meanwhile the method for the present invention is simple, and it is easily operated, addition expanding agent is not needed, save the cost is suitble to work
Industryization batch production.The preparation process of alumina support of the present invention the following steps are included: (1) aluminum nitrate, ammonium hydrogen carbonate and table
Face activating agent is fully ground uniformly, and certain time is aged in the closed container of specific temperature and obtains precursor aluminium carbonate ammonium；(2)
It will form after mixing after the drying of precursor aluminium carbonate ammonium obtained by (1) with peptizing agent, can generally be squeezed using banded extruder
Item molding；(3) (2) are obtained that final alumina support is made in molding drying, aerobic roasting.Step lures described in (1)
The polyethylene glycol that agent is liquid form is led, additional amount is equivalent to the 0.1-10.0% of aluminum nitrate weight.Carbonic acid described in step (2)
The drying process of aluminium ammonium is 1-20 hours dry generally at 50-180 DEG C.Roasting process described in step (3) is in 350-900
It is roasted 1-10 hours at DEG C.The invention prepares gama-alumina using the decomposition at a certain temperature of precursor aluminium carbonate ammonium.Aluminium carbonate
Ammonium generates gas, such as NH in decomposable process3And CO2, the generation and evolution of these gases can manufacture some macropores.Simultaneous oxidation
The pattern of aluminium is transformed by the pattern topology of aluminium carbonate ammonium.Slower heating rate is conducive to gas object in roasting process
Matter slowly escapes, and does not easily cause carrier to collapse.Method is simple, does not need to add any physics expanding agent.
CN201310097588.2 discloses a kind of gama-alumina particle and preparation method thereof: 1) aluminum soluble salt being dissolved in by acid
In aqueous solution of the pH value of acidification less than or equal to 3, the amount that the aluminum soluble salt is added makes obtained containing aluminium in aluminum water solution
The molar concentration of ion is 0.01-5mol/L；2) obtained containing alkaline precipitating agent, the alkali is added in aluminum water solution to step 1)
Property precipitating reagent be added amount make reaction after solution ph between 5-12；3) the mixed sediment solution that step 2) obtains is existed
At room temperature stir 0.1-3h after, be put into water-bath or water heating kettle, 50-150 DEG C at a temperature of be aged 6-24h；4) by step
3) solution after being aged is after mixing evenly, dry using spray drying process, and control inlet air temperature is 150-400 when spray drying
DEG C, leaving air temp is 60-110 DEG C, and the thermal efficiency of spray drying is 50% or more；5) oxidation after the drying for obtaining step 4)
Aluminium precursor powder is heated to 250 DEG C -350 DEG C at room temperature with first rate of heat addition, is then heated to second rate of heat addition
400 DEG C -800 DEG C, heat preservation 0.5-20h obtains final product gama-alumina particle；Wherein, first rate of heat addition is less than
Two rates of heat addition, and first rate of heat addition and second rate of heat addition are in the range of 0.1-10 DEG C/min.It is obtained
Gama-alumina is experiments verify that test, specific surface area have high-specific surface area within the scope of 180m2/g-260m2/g.It is made
Gama-alumina particle observed under scanning electron microscope have hollow foam shape pattern, and have micropore-mesopore-macropore it is compound
Aperture structure.In this way, when gama-alumina is as catalyst carrier, hollow foam shape pattern can be effectively in dispersed catalyst
Active component.And hollow foam shape pattern and composite bore diameter structure, be conducive to the mass transfer in catalytic process, to accelerate
Rate of catalysis reaction.The composite bore diameter structure refers to not only include micropore of the aperture less than 2nm, but also including aperture in 2nm-50nm
Between it is mesoporous, further include aperture be greater than 50nm macropore.It further include making to obtained containing being added in aluminum water solution in step 1)
Hole agent, the amount that the pore creating material is added that the molar concentration of pore creating material in rear solution is added to be aluminum ions molar concentration
0.01-5 times.The pore creating material is cetyl trimethylammonium bromide (CTAB), neopelex (SDBS), polyethylene
One or more of alcohol (PVA), polyethylene glycol (PEG) and calgon.CN101863499A
(201010187094.X) provides a kind of preparation method of macroporous-mesoporous alumina.The following steps are included: a. first helps reaction
Agent and aluminium salt are dissolved in organic solvent solution, reaction promoter: two kinds of material mol ratios of aluminium ion are 3-5:1, then by template
Above-mentioned solution is added and dissolves, aluminium ion and template molar ratio are 1:0.015-0.025, and the pH value control of final solution exists
3.5-6.0；B. the solution by a step preparation carries out aging process, so that it is gradually removed organic solvent and moisture in system and obtains greatly
Hole-meso-porous alumina presoma；C. macroporous-mesoporous alumina powder is obtained through 400-800 DEG C of calcination process.Present invention process letter
Single, duct rule, pore-size distribution is concentrated and can realize controllable adjustment according to concrete application situation, thus more in petrochemical industry
Mutually catalysis, adsorbing separation and have important application value as catalyst carrier, energy and material etc..It makes full use of anti-
The space frame effect and coordination and intermediary's organic polymer, reaction promoter for answering auxiliary agent and template are to inorganic ions
Complexing, so that a step prepares the adjustable macroporous-mesoporous alumina material in aperture.Prepared foramen magnum-mesoporous oxidation
The specific surface area of aluminum material is up to 250-320m2/ g, duct rule, pore-size distribution in mesoporous 5-40nm, macropore 50-150nm, and
Adjusting can be realized according to the actual situation.Reaction promoter is organic acid, and aluminium salt is inorganic aluminate.Template is triblock copolymer.
Organic solvent is anhydrous alcohols, ethers or ketones solvent.Organic acid is citric acid or lauric acid.Triblock copolymer is
P123 or F127.Tie-Zhen Ren etc. (Langmuir, 2004,20:1531-1534) uses nonionic surfactant
56 aluminium secondary butylate of Brij uses hydro-thermal method and Microwave-assisted synthesis macroporous-mesoporous alumina in acid condition, synthesis it is porous
0.8-2 μm of alumina powder macropore diameter, mesoporous pore size 5-8nm, 0.4-1.4 μm of hole wall of aluminium oxide.Its deficiency is aluminium-alcohol salt
Expensive, the macroporous-mesoporous alumina Kong Rong little of synthesis, duct is irregular, pore-size distribution is excessive and cannot achieve pore structure
Effective adjusting thus have significant limitation in using effect and range.Jean-Philippe Dacquin etc.
It using P123 is template in mixed solution that (J.Am.Chem.Soc., 2009,131:12896-12897), which uses sol-gel method,
It is middle to be introduced into the polystyrene droplet with single dispersed phase to realize the formation of macropore in macroporous-mesoporous alumina.Deficiency
Place is that macropore diameter size (300nm or 400nm) is determined by the secondary size for introducing polystyrene drop completely, i.e. macropore diameter
Size depends on polystyrene droplet size.Organic molecule in the change of the part to solution itself component and system can not be passed through
It interacts to realize the adjustment in aperture.Huining Li et al. (Inorganic Chemistry, 2009,48:4421) is equally adopted
The polymethyl methacrylate with single dispersed phase is introduced in mixed solution with sol-gel method by template of F127
(PMMA) droplet realizes the formation of macropore in macroporous-mesoporous alumina, shortcoming be macropore diameter size also completely by
Secondary introducing polymethyl methacrylate droplet size determines, can not be changed by the part to solution system itself component come real
The adjustment in existing aperture also cannot achieve the controllable of foramen magnum-mesoporous aperture to realize the formation of foramen magnum-mesoporous composite pore structural
Adjust, in use, in particular for complicated ingredient bulky molecular catalysis during by significant limitation.
The above composite holes alumina support generally uses organic polymer such as polyvinyl alcohol, polymethylacrylic acid etc. as mould
Plate agent either expanding agent.So that the preparation of composite holes and macroporous aluminium oxide material there are the monomer of template have certain toxicity,
The problems such as template consumption is larger, preparation cost is higher, preparation process is cumbersome.Meanwhile there is also the discharges in roasting process
The problem of object environmental pollution.Also there is the patent that saccharide compound is added in polymer microballoon lotion.
CN201310142454.8 discloses a kind of preparation method of alumina hollow ball, and it is water-soluble to prepare chitosan-acetic acid-
Liquid；By polystyrene spheres: chitosan-acetic acid-aqueous solution be 5:1-10:1 mass ratio, press polystyrene spheres: alpha-alumina
Body is that the mass ratio of 1:5-1:15 takes each raw material；Polystyrene spheres and chitosan-acetic acid-aqueous solution are mixed, polyphenyl is made
Ethylene ball surface uniformly coats one layer of chitosan-acetic acid-aqueous solution；It is coated with chitosan-acetic acid-aqueous solution polyphenyl second again
In alkene ball and alpha-alumina powder investment ball-milling device, with the revolving speed rotation cladding 2-24h of 5-30r/s, obtained core-shell structure copolymer ball；It will
After the calcining of core-shell structure copolymer ball warp, the alumina hollow ball that diameter is 0.2-2mm, wall thickness is 20-100 μm is obtained.
CN201110170283.0 discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The three-dimensional ordered macroporous oxidation
Aluminium, diameter macropores 50-1000nm, grain diameter 1-50mm, mechanical strength 80-280g/mm.This method includes following step
It is rapid: saccharide compound and the concentrated sulfuric acid will to be added into monodisperse polymer micro-sphere lotion, obtain polymer-modified microballoon glue crystalline substance mould
Plate is subsequently filled alumina sol, then through aging and roasting, obtains three-dimensional ordered macroporous alumina.The polymer microballoon
Diameter is 50-1000nm, can be used polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polyacrylic acid N-butyl microballoon and
One of different monooctyl ester microballoon of polyacrylic acid is a variety of, preferably polystyrene microsphere.The monodisperse refers to polymer microballoon
The standard deviation of diameter is not more than 10%.The carbohydrate organic matter be one of Soluble Monosaccharide and polysaccharide or a variety of, preferably
For one of sucrose, glucose, chitosan or a variety of.This method can increase substantially the adhesion amount of aluminium oxide precursor, increase
The strong mechanical strength of material, it is subtle powder that when removing template is removed in high-temperature roasting, large pore material is not easily broken, can still be protected
Hold higher integrity degree.Chitosan is in ceramic coating adsorbent material field using more." mesoporous chitosan-aluminium hydroxide is compound
Material Study on adsorption properties " (author: Peng Shaohua] University Of Suzhou, " Suzhou Institute of Science and Technology journal: natural science edition " 2013 30
Rolled up for 4 phases): with chitosan and AlCl3For raw material, it is prepared for chitosan and α-Al (OH)3Composite material.With X-ray powder diffraction,
Transmission electron microscope, infrared, thermogravimetric and specific surface instrument characterization has been carried out to it the result shows that: α-Al (OH)3It is in chitosan complexes
Now typical mesoporous characteristic, BET specific surface area 55.4m2g-1, BJH average pore size is 3.3nm；Specifically the preparation method comprises the following steps: claiming
It takes 2.0g Aluminium chloride hexahydrate to be dissolved in the hydrochloric acid that 5.0mL pH value is 1,2.0g chitosan, then plus 10.0m L 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.
The prior art changes support chemistry composition and type, and addition coagent mainly to promote catalyst performance
Energy.Influence due to mercaptan to oil product product quality is maximum, not only has foul smell, and very strong corrosivity also will affect
The stability of product.Therefore mercaptan-eliminating catalyst is needed to have catalyst desulfurizing alcohol activity high, diolefin hydrogenation selectivity is high, pungent
Alkane value loses low characteristic.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of FCC gasoline mercaptan-eliminating catalyst, the catalyst is living with removal of mercaptans
Property it is high, diolefin hydrogenation selectivity is high, the low feature of loss of octane number.Catalyst using aluminium oxide as carrier, adopt by alumina support
It uses chitosan as expanding agent, synthesizes the alumina support with macroporous structure.Macroporous aluminium oxide has pore size adjustable
The characteristics of section, macropore ratio can be controlled effectively.
The present invention provides one kind for FCC gasoline mercaptan-eliminating catalyst, which includes the oxidation with macroporous structure
Alumina supporter and the metal active constituent nickel and molybdenum being carried on carrier, by weight percentage, the aluminium oxide with macroporous structure
Carrier is 66-91wt%, and alumina support is used as expanding agent using chitosan, contains adjuvant component phosphorus and magnesium, auxiliary agent in carrier
The percentage composition that the content of component phosphorus and magnesium accounts for carrier quality is respectively P2O50.1-2.5wt%, MgO 0.1-2.5wt%, hole
Diameter is distributed 60-180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, Kong Rong 0.8-2.0ml/g, preferably
0.8-1.3ml/g or preferred 1.6-2.0ml/g, specific surface area 250-300m2/g.Nickel oxide content is 5-19wt%, molybdenum oxide
Content is 2-15wt%.
Preferably, adjuvant component cerium, adjuvant component cerium oxide are also contained in the alumina support with macroporous structure
Content account for carrier quality percentage composition be 0.1-2.5wt%.
Preferably, by weight percentage, the alumina support with macroporous structure is 71-88wt% to the catalyst,
Nickel oxide content is 6-17wt%.Oxidation molybdenum content is 5-12wt%.
The mercaptan-eliminating catalyst preparation method includes the following steps: cobalt is contained and the soluble-salt containing molybdenum is made into dipping
Liquid impregnates the alumina support with macroporous structure, and it is small to roast 5-9 at 4-8 hours, 650-800 DEG C dry at 120-160 DEG C
When, obtain mercaptan-eliminating catalyst.
The present invention has the alumina support of macroporous structure, and aperture can pass through the additional amount and reaming of variation expanding agent
The molecular size range of agent is adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-160nm,
The ranges such as 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, the ranges such as 35-50%, 55-75%.
The present invention also provides a kind of preparation methods of alumina support with macroporous structure, firstly, being acidified with acid solution
Chitosan, then by boehmite and sesbania powder be added in kneader be uniformly mixed, add phosphoric acid, magnesium nitrate mixing it is molten
The acid solution of chitosan-containing is finally added in boehmite and mediates uniformly by liquid, the additional amount of the acid solution containing expanding agent
It is obtained by extrusion-molding-drying-roasting with macropore for the 0.1-8wt% of boehmite, preferably 0.2-5.0wt%
The alumina support of structure.
The preparation method of alumina support with macroporous structure may be incorporated into cerium, such as by cerous nitrate and magnesium nitrate one
It plays mixing to be added in carrier, obtains the alumina support of phosphorous, magnesium, cerium.
The process of the acid solution acidified chitosan is as follows: first by chitosan expanding agent be added to 30-95 DEG C go from
In sub- water, acid is added dropwise later, until chitosan dissolution is completely, obtains the acid solution containing expanding agent.The acid can be inorganic acid
Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The additional amount of acid is advisable with that can be completely dissolved chitosan.It can also
To select water soluble chitosan, such as carboxyl chitosan, chitosan salt, sulfated chitosan etc..Chitosan acid solution is best
With ultrasonic oscillation or magnetic agitation.Ultrasonic oscillation 10min or more, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent
Wave concussion or magnetic agitation, expanding agent good dispersion, alumina support is more prone to produce macropore, and pore-size distribution more collects
In, pore-size distribution is in 70-180nm.The additional amount of the sesbania powder is the 0.1-7wt% of boehmite.
Extrusion technique is that 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.
Alumina support of the present invention uses chitosan for expanding agent, and the alumina support of preparation contains macroporous structure, simultaneously
Also contain meso-hole structure, macropore range is a kind of containing Jie-macropore in 2-50nm, mesoporous ratio 15-75%, preferably 15-50%
Alumina support.And aperture is not uniform aperture structure.
The alumina support with macroporous structure obtained using preparation method of the present invention can also utilize phosphorus and magnesium
Carrier surface is modified, the concentration of phosphorus and magnesium is unsuitable excessively high, and preferably configuration concentration is 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,
Catalyst is not easy coking and deactivation, and stability is good.
2, the present invention can also in alumina support and carrier surface introduce cerium, make carrier surface cerium content be higher than carry
Internal portion, there is the alumina support of macroporous structure to be prepared into mercaptan-eliminating catalyst for this, be able to suppress olefinic polymerization, improve diene
Hydrogenation selectivity.
3, the alumina support with macroporous structure that the present invention obtains is big to having using phosphorus and magnesium or phosphorus, magnesium and cerium
The alumina carrier surface of pore structure is modified, and make carrier surface phosphorus pentoxide, magnesia, cerium oxide content be interior
Portion's phosphorus pentoxide, magnesia, 1.1-1.6 times of cerium-oxide contents.Carrier surface is modified by the way of spray, energy
The partial pore of enough effective peptization carrier surfaces, advantageously reduces the micropore ratio of carrier surface in this way, improves carrier surface Jie-
Macropore ratio promotes carrier surface to produce more active sites load centres, improves removal of mercaptans activity.And in this carrier
Outer concentration of component different structure is not easily accessed alkadienes inside duct and polymerization reaction blocking duct occurs.To carrier surface
Improvement should not use dipping method, impregnated carrier surface can make large quantity of moisture enter carrier, be not achieved improve carrier surface be situated between-it is big
The purpose of hole ratio.
4, mercaptan-eliminating catalyst of the present invention be suitable for removing liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/
Or mercaptan and/or alkadienes in coker gasoline；Or for being catalyzed diolefin selective hydrogenation.That is catalyst is to raw material
In alkene be not added hydrogen, in the light hydrocarbons such as removing liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/or coker gasoline
Mercaptan and/or alkadienes, catalyst choice are good.Octane number RON loss 0.3-0.4 point of gasoline or so.Catalyst desulfurizing alcohol
Active high, diolefin hydrogenation selectivity is high, and loss of octane number is low.
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.
Nickel nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
Body 1,6 hours dry at 130 DEG C, 680 DEG C roast 8 hours, obtain catalyst 1.Catalyst 1 mainly forms: having macropore knot
The alumina support of structure is 79wt%, and nickel oxide content 12wt%, oxidation molybdenum content is 9wt%.
Embodiment 2
8.0g water soluble chitosan expanding 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.
Nickel nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
Body 2,6 hours dry at 130 DEG C, 720 DEG C roast 5 hours, obtain catalyst 2.Catalyst 2 mainly forms: having macropore knot
The alumina support of structure is 79.5wt%, and nickel oxide content 10.5wt%, oxidation molybdenum content is 10wt%.
Embodiment 3
The preparation method of carrier is carried out according to embodiment 1.The difference is that adjuvant component also contains cerium in carrier, by water
Soluble chitosan expanding agent is changed to water-insoluble chitosan expanding agent, and chitosan formic acid liquid magnetic stirrer 30 is divided
Clock obtains the alumina support 3 with macroporous structure.The content of adjuvant component phosphorus, magnesium and cerium accounts for the hundred of carrier quality in carrier
Point content is respectively 1.8wt%, 2.0wt%, 0.6wt%.Its specific surface area and pore-size distribution are shown in Table 1.
Nickel nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
Body 3,6 hours dry at 130 DEG C, 750 DEG C roast 5 hours, obtain catalyst 3.Catalyst 3 mainly forms: having macropore knot
The alumina support of structure is 81.5wt%, and nickel oxide content 6wt%, oxidation molybdenum content is 12.5wt%.
Embodiment 4
The preparation method of carrier is carried out according to embodiment 3.The difference is that water soluble chitosan expanding agent is changed to
Water-insoluble chitosan expanding agent, chitosan acetic acid solution 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.
Nickel nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
Body 4,6 hours dry at 130 DEG C, 750 DEG C roast 5 hours, obtain catalyst 4.Catalyst 4 mainly forms: having macropore knot
The alumina support of structure is 77.5wt%, and nickel oxide content 16wt%, oxidation molybdenum content is 6.5wt%.
Embodiment 5
The preparation method of carrier is carried out according to embodiment 2, except that carrier surface phosphorus pentoxide and magnesia
Content is 1.4 times of internal phosphorus pentoxide and content of magnesia.Catalyst 5 mainly forms: the aluminium oxide with macroporous structure
Carrier is 80.5wt%, and nickel oxide content 5.5wt%, oxidation molybdenum content is 14wt%.
Embodiment 6
The preparation method of carrier is carried out according to embodiment 4, except that surface phosphorus pentoxide, cerium oxide and magnesia
Content be 1.3 times of internal phosphorus pentoxide, cerium oxide and content of magnesia.Catalyst 6 mainly forms: having macroporous structure
Alumina support be 78wt%, nickel oxide content 13.5wt%, oxidation molybdenum content be 8.5wt%.
The alumina support specific surface area and pore-size distribution of 1 macropore of table
Catalyst 1-4 is loaded into fixed bed reactors respectively, carries out evaluation catalyst reaction performance.With sulfurized oil pair
Catalyst carries out presulfurization, and sulfide stress 3.2MPa, hydrogen to oil volume ratio 300, sulfurized oil volume space velocity is 3.5h-1, vulcanization
Program is respectively in 240 DEG C, 280 DEG C of vulcanizing treatment 6h.After to vulcanizing treatment, it is switched at full fraction FCC gasoline displacement
6h is managed, reaction process condition is then adjusted to, carries out sweetening reaction.FCC feedstock content of sulfur in gasoline 556 μ g/g, 35 μ of mercaptan sulfur
G/g, olefin(e) centent 47.35v%, RON 88.36.Reaction process condition are as follows: 115 DEG C of temperature of reactor, volume space velocity 3.3h-1,
Hydrogen to oil volume ratio 11:1, reaction pressure 2.1MPa.Sampling analysis after reaction about 55h.Catalyst 1-4 reaction result is as follows: catalysis
1 sulfur content of agent, 544 μ g/g, mercaptan sulfur 5 μ g/g, olefin(e) centent 46.59v%, RON 87.93, yield of gasoline 97.8wt%；Catalysis
2 sulfur content of agent, 547 μ g/g, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.83v%, RON 87.95, yield of gasoline 98.2wt%；Catalysis
3 sulfur content of agent, 545 μ g/g, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.85v%, RON 88.01, yield of gasoline 98.0wt%；Catalysis
4 sulfur content of agent, 548 μ g/g, mercaptan sulfur 2 μ g/g, olefin(e) centent 46.82v%, RON 88.03, yield of gasoline 98.5wt%；Catalysis
Agent product mercaptan sulfur is lower than 4 μ g/g, and olefin(e) centent is basically unchanged, and for reaction loss of octane number in 0.3-0.4, catalyst activity is high,
Selectivity is good, and loss of octane number is low.Stability test, reaction operation 400h, 1 sulfur content of catalyst, 542 μ g/ are carried out to catalyst
G, mercaptan sulfur 4 μ g/g, olefin(e) centent 46.56v%, RON 7.91, yield of gasoline 97.9wt%；2 sulfur content of catalyst, 546 μ g/
G, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.82v%, RON 7.94, yield of gasoline 98.0wt%；3 sulfur content of catalyst, 545 μ g/
G, mercaptan sulfur 3 μ g/g, olefin(e) centent 46.84v%, RON 7.98, yield of gasoline 98.1wt%；4 sulfur content of catalyst, 547 μ g/
G, mercaptan sulfur 2 μ g/g, olefin(e) centent 46.83v%, RON 8.04, yield of gasoline 98.4wt%；Catalyst runs product after 400h
Mercaptan sulfur is lower than 4 μ g/g, and olefin(e) centent is basically unchanged, and catalyst is not easy coking and deactivation, and stability is good.
Catalyst 5-6 is loaded into fixed bed reactors respectively, carries out evaluation catalyst reaction performance.With sulfurized oil pair
Catalyst carries out presulfurization, and sulfide stress 3.2MPa, hydrogen to oil volume ratio 300, sulfurized oil volume space velocity is 3.5h-1, vulcanization
Program is respectively in 240 DEG C, 280 DEG C of vulcanizing treatment 6h.After to vulcanizing treatment, it is switched at full fraction FCC gasoline displacement
6h is managed, reaction process condition is then adjusted to, carries out sweetening reaction.FCC feedstock content of sulfur in gasoline 733 μ g/g, 28 μ of mercaptan sulfur
G/g, olefin(e) centent 44.68v%, RON 9.24.Reaction process condition are as follows: 145 DEG C of temperature of reactor, volume space velocity 2.2h-1, hydrogen
Oil volume ratio 14:1, reaction pressure 2.7MPa.Sampling analysis after reaction about 55h, 5 sulfur content of catalyst 724 μ g/g, 2 μ of mercaptan sulfur
G/g, olefin(e) centent 43.95v%, RON 8.95, yield of gasoline 98.3wt%；6 sulfur content of catalyst 725 μ g/g, 2 μ of mercaptan sulfur
G/g, olefin(e) centent 44.19v%, RON 9.01, yield of gasoline 98.6wt%.Catalyst activity is high, and selectivity is good, octane number damage
Lose low, for catalyst to different sulfur contents, the oil product of mercaptan sulfur content and olefin(e) centent is adaptable.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding 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 (3)
1. a kind of catalyst for FCC gasoline removal of mercaptans, it is characterised in that:
Catalyst includes the alumina support and the metal active constituent nickel being carried on carrier and molybdenum with macroporous structure, with weight
Percentages are measured, the alumina support with macroporous structure is 71-88wt%, and alumina support is using chitosan as reaming
Agent, adjuvant component phosphorus, magnesium and cerium are contained in carrier, and the content of adjuvant component phosphorus, magnesium and cerium accounts for the percentage composition point of carrier quality
It Wei not P2O50.1-2.5wt%, MgO 0.1-2.5wt%, CeO20.1-2.5wt%；
The alumina support pore-size distribution 60-180nm, macropore ratio 2-75%, Kong Rong 0.8-2.0ml/g, specific surface area
250-300m2/g；
The alumina support macropore range is in 5-50nm, mesoporous ratio 15-75%；
The catalyst activity component nickel oxide content is 6-17wt%, and oxidation molybdenum content is 5-12wt%；
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 all in the range of 0.1-2.5wt%, and makes carrier surface phosphorus pentoxide, magnesia and oxidation
The content of cerium is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
2. a kind of preparation method of catalyst for FCC gasoline removal of mercaptans described in claim 1, it is characterised in that: including
Following steps:
Nickeliferous and containing molybdenum soluble-salt is made into maceration extract, the alumina support with macroporous structure is impregnated, at 120-160 DEG C
It is roasted 5-9 hours at lower dry 4-8 hours, 650-800 DEG C, obtains mercaptan-eliminating catalyst；
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 all in the range of 0.1-2.5wt%, and makes carrier surface phosphorus pentoxide, magnesia and oxidation
The content of cerium is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
3. a kind of preparation method of catalyst for FCC gasoline removal of mercaptans according to claim 2, it is characterised in that:
It is described to be with acid solution acidified chitosan: chitosan expanding agent being added in 30-95 DEG C of deionized water first, is added dropwise later
Acid obtains the acid solution containing expanding agent until chitosan dissolution is completely.
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| CN109423324B (en) * | 2017-08-31 | 2021-01-29 | 中国石油天然气股份有限公司 | Method for removing mercaptan from FCC gasoline |
| CN109420506B (en) * | 2017-08-31 | 2021-07-30 | 中国石油天然气股份有限公司 | Catalyst for removing mercaptan from gasoline and preparation method thereof |
| CN109894122B (en) * | 2017-12-07 | 2021-06-01 | 中国石油天然气股份有限公司 | FCC gasoline hydrodesulfurization catalyst and preparation method thereof |
| CN109897663B (en) * | 2017-12-07 | 2021-07-02 | 中国石油天然气股份有限公司 | FCC gasoline desulfurization treatment method |
| CN109364966B (en) * | 2018-10-14 | 2021-10-29 | 上海光华供应链管理有限公司 | Catalyst for removing mercaptan from gasoline and preparation method thereof |
| CN110201637B (en) * | 2019-06-13 | 2021-11-26 | 中石化中原石油工程设计有限公司 | Preparation method of adsorbent for removing organic sulfide in natural gas |
| CN114433108B (en) * | 2020-10-31 | 2023-10-10 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst with core-shell structure |
| CN113578337B (en) * | 2021-08-26 | 2023-05-02 | 青岛中瑞泰丰新材料有限公司 | Residual oil hydrogenation catalyst and preparation method and application thereof |
| CN113663684A (en) * | 2021-09-22 | 2021-11-19 | 山东京博石油化工有限公司 | Liquefied gas sweetening catalyst, preparation method and application thereof |
| CN116020417B (en) * | 2022-09-07 | 2024-08-20 | 沈阳三聚凯特催化剂有限公司 | Metal organic porous desulfurizing agent and preparation method and application thereof |
| CN115739104A (en) * | 2022-11-30 | 2023-03-07 | 山东海科创新研究院有限公司 | M-xylylenediamine catalyst, and preparation method and application thereof |
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