CN109423326A - A kind of hydrodesulfurizationprocess process of FCC gasoline - Google Patents
A kind of hydrodesulfurizationprocess process of FCC gasoline Download PDFInfo
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- CN109423326A CN109423326A CN201710768200.5A CN201710768200A CN109423326A CN 109423326 A CN109423326 A CN 109423326A CN 201710768200 A CN201710768200 A CN 201710768200A CN 109423326 A CN109423326 A CN 109423326A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of hydrodesulfurizationprocess process of FCC gasoline, using fixed bed reactors；The catalyst is support type cobaltmolybdate catalyst, and the composition of catalyst includes cobalt oxide and molybdenum oxide, and carrier is the aluminium oxide with macroporous structure.Hydrodesulfurization condition are as follows: 180-320 DEG C of reaction temperature, reaction pressure 1.1-2.8MPa, volume space velocity 1.2-3.5h‑1, hydrogen to oil volume ratio 180-400:1.Hydrodesulfurization mild condition, adaptable to different material, loss of octane number is low, and desulfurization degree is high.
Description
Technical field
The present invention provides a kind of hydrodesulfurizationprocess process of FCC gasoline, produces gasoline for catalytic gasoline hydrogenation desulfurization
Product.
Background technique
Raw material sources of the petroleum and products thereof as the main energy and daily chemicals etc. support the warp of entire country
Ji development.Catalytic process and reaction are indispensable component parts in petroleum refining process, in order to improve petroleum refining process
In transformation efficiency, effective catalyst exploitation be always researcher common pursuit.In order to improve the conversion of catalyst
Efficiency, macroporous catalyst carrier material are widely used in the performance for improving catalyst from the angle for improving mass transfer rate.
Aluminium oxide as traditional catalyst carrier material, have technology maturation, pore structure are adjustable, use cost is low,
The characteristics of being easily worked molding is widely used in the preparation of oil-refining chemical catalyst.Important composition portion of the carrier as catalyst
Point, the dispersion effect of active component on the one hand can be improved, on the other hand, cellular structure provides reactant molecule and product
The diffusion admittance of molecule improves the utilization efficiency of metal.Macropore carrier material has the characteristics that resistance to mass tranfer is small, high-efficient, closely
Nian Lai, core component of the carrier as catalyst, aluminium oxide, molecular sieve, active carbon of macroporous structure etc. are widely ground
Study carefully, to improve the service efficiency of catalyst.Two classes can be divided into large pore material according to synthesis process: one kind is synthesis process
Directly synthesize the carrier new material with macroporous structure, another kind of is to the carrier for obtaining having macroporous structure modified after material
Material.For the research of the second class macropore carrier material synthesis method, macropore is mainly obtained by the methods of template, hydro-thermal
Structure has the advantages that simple production process, cost is relatively low, and relevant processing technique is applied in the industry.
The pertinent literature of template method macroporous aluminium oxide material is more, according to Template Types difference, can divide
Are as follows: two methods of hard mould agent and soft template.Using active carbon as the available preferable macropore oxygen of the hard mould agent method of representative
Change aluminium, US4448896 discloses a kind of carbon black as expanding agent, macropore oxidation of the available pore-size distribution in 15-300nm
Aluminium, but since the particle diameter distribution of carbon black is inhomogenous, it is more difficult to prepare the macroporous aluminium oxide of pore-size distribution concentration.
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.CN 201010509425.7 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.CN 200310103035.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.CN201410148773.4 discloses a kind of preparation method of aluminum oxide porous microballoon, comprising the following steps: 1) surface is living
Property agent be dissolved in deionized water, stir, as water phase；2) chelating agent, alumina precursor and n-octyl alcohol are mixed, is stirred, made
For 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
In 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.
The microballoon has internal closing macroporous structure, and Microsphere Size is 1 μm~100 μm, the invention using pore-foaming agent with it is molten in lotion
Glue gel process obtains the metal porous microballoon with internal closing macroporous structure.Porous microsphere is prepared using phase separation principle.
Inside closing aperture is 50nm~5 μm.Pore-foaming agent is polyvinylpyrrolidone, polyacrylamide or polyacrylic acid.The invention makes
With a large amount of surfactant, chelating agent, pore-foaming agent, prepare that raw material is more, and synthesis technology is complicated.CN201310748661.8 is public
The preparation method for having opened a kind of aluminium oxide/carbon aerogel composite material, in closed container, by water-soluble saccharides compound and
Water soluble polymer is dissolved in water, and aluminium salt or aluminium hydroxide is then added, and reacts at 140~300 DEG C, after drying 300~
Calcining obtains aluminium oxide/carbon aerogel composite material under 1500 DEG C of inert atmospheres.The invention prepares low-density, height using one kettle way
Aluminium oxide/carbon aerogel composite material of porosity, the present invention have many advantages, such as that raw material is easy to get, preparation process is simple, at low cost,
Resulting aluminium oxide/carbon aerogel composite material is light, porosity is high, can be used for catalyst carrier, gas sensor, solid electrolytic
Diaphragm, molten steel oxygen measuring probe material etc..CN201310499233.6 discloses a kind of preparation method of alumina support, including as follows
Content: alkaline precipitating agent aqueous solution and acid aluminium salt aqueous solution carry out neutralization reaction and obtain sediment slurry first；Then to precipitating
Water-soluble resin is added in slurries and aging process is carried out to it using microwave heating；Mixed material after last aging passes through
Final alumina support is made in filter, washing, dry, molding.The alumina support of this method preparation has biggish aperture sum aggregate
In pore size distribution, it is big to account for total pore volume ratio, reaches 60~80% the especially hole of 10~20nm, is suitable for heavy-oil hydrogenation catalysis
The carrier of agent.CN201310258011.5 is related to a kind of tooth spherical alumina support, tooth ball-aluminium oxide hydrotreating catalyst
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, Sodium Polyacrylate, starch
One of derivative or carbon black or mixture.The invention, which is added to anionic surfactant and reduces various auxiliary components, to be added
Specific surface area increases 246m while dosage2/ g, expanding agent Sodium Polyacrylate.Tooth spherical alumina support described in the invention,
Since containing for wherein components such as various auxiliary agents such as peptizing agent, expanding agent, dispersing agent, anionic surfactant is greatly lowered
Amount, 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, lubrication
Agent, dispersing agent, the reagents such as expanding agent, obtained alumina support are unimodal pore size distributions.
CN201110170283.0 discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The three-dimensional order is big
Porous aluminum oxide, diameter macropores are 50~1000nm, and grain diameter is 1~50mm, and mechanical strength is 80~280g/mm.This method
The following steps are included: being obtained saccharide compound and the concentrated sulfuric acid is added into monodisperse polymer micro-sphere lotion polymer-modified
Microballoon glue crystal template is subsequently filled alumina sol, then through aging and roasting, obtains three-dimensional ordered macroporous alumina.This method
The adhesion amount that aluminium oxide precursor can be increased substantially enhances the mechanical strength of material, big when removing template is removed in high-temperature roasting
Not easily broken Porous materials are subtle powder, can still keep higher integrity degree.CN201110116418.5 provides one kind
Mesoporous sphere aluminium oxide and the method that the mesoporous sphere aluminium oxide is prepared using template guiding.Using oil-drop method,
Prepare the template for being added during Aluminum sol into Aluminum sol and there is guide function, Aluminum sol in molding and ageing process,
Since the presence of the template with guide function makes to produce a large amount of meso-hole structure in alumina balls.Template is organic list
Body or linear polymer, organic monomer are one of acrylic acid, ammonium acrylate, acrylamide, allyl alcohol.The mesoporous sphere oxygen
Change aluminium specific surface is 150~300m2/ g, 0.1~5mm of particle diameter, pore volume be 0.7~1.5ml/g, bore dia be 2~
The hole of 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.It is big that CN 201010221302.3 (CN102311134A) discloses a kind of spherical integral
Porous aluminum oxide and preparation method thereof.Method includes the following steps: by polymer microballoon lotion, alumina sol and coagulant with
Certain proportion is uniformly mixed, which is scattered in oily phase, is formed w/o type drop, is then reheated above-mentioned mixed phase system,
Make the alumina sol gelling balling-up in water phase, isolates molding gel micro-ball from oily phase later, then in aqueous ammonia medium
The spherical integral macroporous alumina is obtained after aged, dry and roasting.The macropore diameter of the aluminium oxide is less than 1 μm
In the range of it is uniform controllable, the size of spheric granules is controllable, and mechanical strength is higher, and forming process is simple and easy to do, convenient for big
It is prepared by batch.Polymer microballoon 50~1000nm of diameter, the type of polymer microballoon are polystyrene microsphere, the positive fourth of polyaerylic acid
The esters microballoon such as ester microsphere, polyacrylate.Coagulant is hexamethylenetetramine, urea.Oily is mutually organic hydrocarbon.Invention master
If preparing Integral macroporous alumina, and macropore diameter is uniform controllable.Preparation process has used lipid microballoon and has promoted solidifying
Agent etc..Preparation process is complicated, and reagent raw material used is relatively more.Due to polymer microballoon make alumina support internal holes
Road structure is blind bore, that is to say, that alumina support internal gutter does not have connectivity.CN200910204238.5
(CN102040235) a kind of three-dimensional ordered macroporous alumina and preparation method thereof is disclosed.Method includes the following steps: by single
The polymer microballoon of dispersion is assembled into glue crystal template, the alumina sol of ad hoc approach preparation is then filled into template, finally
Macroporous aluminium oxide is obtained through dry and roasting.This method can be good at controlling Aluminum sol and Aluminum sol and polymer microballoon
Recombination process does not destroy the network structure of alumina gel as far as possible, and prepared aluminium oxide is made not only to have three-dimensional order
Macropore duct but also specific surface area with higher.The small fenestra that the invention is formed and the appropriateness to template is sintered, makes
Macropore in material is connected with the macropore of surrounding by 12 small fenestras.The aluminium oxide of the invention is suitable for use as mink cell focus catalysis
The adsorption and separation material of agent carrier and organic macromolecule.Be conducive to improve material in catalyst carrier material application in catalyst
In mass transfer ability, be conducive to improve catalyst activity and selectivity.CN201410148773.4 discloses a kind of aluminium oxide
The preparation method of porous microsphere, comprising the following steps: 1) surfactant is dissolved in deionized water, is stirred, as water phase；2)
Chelating agent, alumina precursor are mixed with n-octyl alcohol, stirred, as oily phase；3) Span80 and pore are added in oily phase
Agent, stirring；4) clear oil obtained by step 3) is mutually poured into water phase and continues stirring and emulsifying；5) by step 4) gains vacuum
It filters, it is dry after gained Washing of Filter Cake, obtain aluminum oxide porous microballoon.The microballoon has internal closing macroporous structure, Microsphere Size
It is 1 μm~100 μm, inside closing aperture is 50nm~5 μm.Aperture is closed inside the aluminum oxide porous microballoon, that is,
Say that alumina support internal gutter does not have connectivity.
Macroporous aluminium oxide has been successfully applied to multiple catalyst systems, to the activity, selectivity and stability of catalyst
Aspect has different degrees of improvement result.Hard mould agent although available preferable macroporous structure, but in adjustment aperture
There are certain deficiency in terms of size, the solubility of polyvinyl alcohol soft template in water is influenced by the degree of polymerization, leads to it
It is also subject to certain restrictions in the preparation of super large porous aluminum oxide.
Summary of the invention
The present invention provides a kind of hydrodesulfurizationprocess process of FCC gasoline, produces gasoline for catalytic gasoline hydrogenation desulfurization
Product.Hydrodesulfurization mild condition, adaptable to different material, loss of octane number is low, and desulfurization degree is high.
A kind of hydrodesulfurizationprocess process of FCC gasoline, using fixed bed reactors；Hydrodesulfurization condition are as follows: reaction temperature
180-320 DEG C, preferably 200-300 DEG C, reaction pressure 1.1-2.8MPa, volume space velocity 1.2-3.5h of degree-1, preferably 1.5-3.0h-1, hydrogen to oil volume ratio 180-400:1, preferably 200-300:1.Hydrobon catalyst is support type cobaltmolybdate catalyst, catalyst
Carrier is the alumina support with macroporous structure, and active component includes cobalt and molybdenum oxide.Catalyst used carrier is adopted
Use one or more of macromolecule polyacrylic acid sodium, ammonium polyacrylate, polyacrylic acid as expanding agent, the aluminium oxide synthesized
With macroporous structure.The characteristics of macroporous aluminium oxide is adjustable with pore size, and macropore ratio can be controlled effectively.
FCC gasoline hydrodesulfurizationprocess process provided by the invention, reactor can be fixed bed adiabatic reactor can also be with
It is fixed bed isothermal reactor, preferably fixed bed adiabatic reactor.
The composition of catalyst of the present invention is with oxidation material meter, including following component: cobalt oxide content 0.5-
8wt%, preferably 1.0-4.5wt%, oxidation molybdenum content are 1.0-12wt%, preferably 4-9wt%, the aluminium oxide with macroporous structure
Carrier 77-95wt%.
The catalytic cracking gasoline hydrodesulfurization catalyst preparation method includes the following steps: that cobalt will be contained and containing the solvable of molybdenum
Property salt be made into maceration extract, impregnate the alumina support with macroporous structure, 4-8 hours dry at 120-160 DEG C, 500-700
It is roasted 5-9 hours at DEG C, obtains Hydrobon catalyst.
Alumina support of the present invention with macroporous structure, 60~200nm of pore-size distribution, preferably 80~180nm, greatly
Hole ratio 1~80%, preferably 10~80%, Kong Rong 0.8~2.3ml/g, preferably 0.8~1.2ml/g or preferably 1.8~2.3ml/
G, alumina support internal gutter have connectivity.Carrier uses in macromolecule polyacrylic acid sodium, ammonium polyacrylate, polyacrylic acid
One or more as expanding agent.The mixture of expanding agent preferred ammonium polyacrylate and Sodium Polyacrylate of the present invention, either
The mixture of ammonium polyacrylate and polyacrylic acid, wherein the mass ratio of ammonium polyacrylate and Sodium Polyacrylate or polyacrylic acid is 1
~10:1.As expanding agent, alumina support is easier to produce the mixture of ammonium polyacrylate and Sodium Polyacrylate or polyacrylic acid
Raw macropore, and pore-size distribution is more concentrated, and pore-size distribution is in 120~200nm.
Alumina support of the present invention with macroporous structure, aperture can be by changing the molecular weight of expanding agent, gathering
Ammonium acrylate is adjusted with Sodium Polyacrylate or with the quality proportioning of polyacrylic acid and additional amount.Pore-size distribution can be 60
Change between~200nm, such as 60~200nm, 60~90nm, 140~180nm, the ranges such as 120~200nm.Macropore ratio is
0.1~80%, the ranges such as 10~80%, 20~80% can be tuned as.
The preparation method of alumina support of the present invention with macroporous structure, firstly, being carried out at acidification to expanding agent
Boehmite powder and sesbania powder, are then added in kneader and are uniformly mixed by reason, i.e. acid solution of the configuration containing expanding agent,
Then the acid solution containing expanding agent is added in boehmite powder and is mediated uniformly, the additional amount of the acid solution containing expanding agent
It obtains having big by extrusion-molding-drying-roasting for 0.1~10wt% of boehmite, preferably 0.5~5.0wt%
The alumina support of pore structure.
The configuration process of the acid solution containing expanding agent is as follows: deionized water being heated to 25~95 DEG C first, then
By acid dissolution into deionized water, expanding agent is added later, and dissolve completely, obtains the acid solution containing expanding agent.To expanding agent
Acidification is carried out, expanding agent good dispersion is effectively improved alumina particle and is easy the problem of reuniting, dry by extrusion-molding-
After dry-roasting, diameter of particle is more uniform, good forming effect.
Wherein, sour additional amount is 2~8wt% of boehmite, and preferably 3~5wt%, the acid used is in the art
Common various organic or inorganic acids can be acetic acid, citric acid, nitric acid, hydrochloric acid etc..The additional amount of the sesbania powder is thin to intend
0.2~8wt% of diaspore.The source of the boehmite powder and property are without restriction, can be carbonizatin method, nitre
The product of the techniques such as acid system, sulfuric acid process, ammonium method production.It is adapted to different range specific surface area, thin water aluminium is intended in Kong Rong, aperture
Stone.
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 80~200 DEG C dry 2~8 hours, 550~700 DEG C roast 4~6 hours, finally
Obtain the alumina support containing macropore.
In order to which alumina support has better performance, it is applied in FCC gasoline Hydrobon catalyst as carrier, oxygen
Change in alumina supporter and be preferably introduced auxiliary agent boron, potassium, strontium, detailed process includes the following steps: firstly, carrying out at acidification to expanding agent
Boehmite powder and sesbania powder, are then added in kneader and are uniformly mixed by reason, i.e. acid solution of the configuration containing expanding agent,
Then the aqueous solution of boronic acid containing, potassium nitrate and strontium nitrate is added；Subsequently the acid solution containing expanding agent is added to and intends thin water aluminium
It is mediated in stone powder uniformly, the additional amount of the acid solution containing expanding agent is 0.1~10wt% of boehmite, preferably 0.5~
5.0wt% obtains the alumina support that used additives potassium and strontium are modified by extrusion-molding-drying-roasting.The group of carrier
At with oxidation material meter: the aluminium oxide including 93-99wt%, the boron of 0.1-2.5wt%, the potassium of 0.1-3.8wt%, 0.1-
The strontium of 3.8wt%.
By the modification of auxiliary agent boron, potassium, strontium, which is prepared into Hydrobon catalyst, such as cobaltmolybdate catalyst, favorably
In the acidity for adjusting Hydrobon catalyst, the polymerization of alkene in feedstock oil can be reduced, inhibit catalytic inner coking deactivation,
Carbon deposition rate is low, improves the stabilized hydrogenation of Hydrobon catalyst.
The alumina support modified by auxiliary agent boron, potassium, strontium of the present invention, is further improved, preferably sharp
The carrier of boron containing auxiliary agent, potassium, strontium is surface modified with potassium and strontium, detailed process includes the following steps: configuration containing potassium nitrate
With strontium nitrate aqueous solution as maceration extract impregnated carrier, used additives potassium is obtained through drying, roasting and what strontium was surface modified answers
Close carrier.Complex carrier potassium oxide and content of strontium are controlled respectively in the range of 0.1-3.8wt% and 0.1-3.8wt%.
The surface of alumina support of the present invention makes the potassium of carrier surface and the concentration of strontium after potassium and strontium modification
Concentration difference is formed with the concentration of carrier inside potassium and strontium, and the content of carrier surface potassium and strontium is higher than containing for carrier inside potassium and strontium
Amount, the i.e. molar content or mass content of carrier surface potassium and strontium can be 2.1-2.5 times of the content of internal potassium and strontium.In this way
Carrier surface can be made to tend to equally distributed state, reduce the acidity of carrier surface, which is prepared into hydrodesulfurization catalytic
Agent can be improved the specific surface area of Hydrobon catalyst, inhibit Hydrobon catalyst surface coking deactivation, improves plus hydrogen is de-
The dispersion degree and adhesion on carrier such as sulfur catalyst active component cobalt molybdenum, active component cobalt molybdenum etc. not easily run off, have in this way
Effect solves the problems, such as to decline activity because active component cobalt molybdenum etc. is lost.The molar content or quality of carrier surface potassium and strontium contain
Amount is preferably 2.1-3.0 times of the content of internal potassium and strontium, and the acidity for adjusting carrier surface is not achieved lower than 2 times, improves activity
Dispersion degree and adhesion of the component on carrier, the purpose that inhibitory activity component is lost.
Compared with prior art, aluminium oxide of the present invention is made it is not necessary that the reagents such as coagulant, dispersing agent, chelating agent are added
Standby cost substantially reduces.Expanding agent Sodium Polyacrylate, ammonium polyacrylate, polyacrylic acid etc. belong to high molecular polymer, so that its
Solubility in water is higher, while molecular volume expands the characteristic of hundreds of times after its water suction, can reduce to a certain extent
The dosage of expanding agent reaches the same effect with other expanding agents.In addition, macromolecule polyacrylic acid sodium, ammonium polyacrylate, poly- third
Olefin(e) acid etc. be used as expanding agent, can be adjustable from thousand grades to millions according to the difference of the degree of polymerization, molecular weight so that polypropylene
Sour sodium, ammonium polyacrylate, polyacrylic acid are used for expanding agent, have the advantages that aperture can be adjusted according to molecular size range.
Expanding agent Sodium Polyacrylate, ammonium polyacrylate, polyacrylic acid have ball of string structure, so that carrier inside duct has connectivity,
Rather than blind bore structure.The alumina support of preparation contains macroporous structure, while also containing meso-hole structure, and macropore range is 5
~50nm, mesoporous ratio 20~70%, preferably 20~50%, it is a kind of containing Jie-macropore alumina support.And aperture is not
Uniform aperture structure.
The hydrodesulfurizationprocess process of gasoline of the present invention, reaction condition is mild, to the adaptable of different material；Add catalyst
Hydrogen is desulphurizing activated and selectivity is high, and loss of octane number is low, and desulfurization degree is high, and stability is good, is conducive to device long period steady running.
Detailed description of the invention
Fig. 1 is the graph of pore diameter distribution of the alumina support containing macropore prepared by embodiment 4.
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.
The specific surface area and mesoporous pore size of alumina support of the present invention with macroporous structure are public using U.S. Mike
The 3000 type automatic adsorption device of TStar II of department's production is tested.The pore volume of alumina support with macroporous structure
It is tested with pore-size distribution using the full-automatic mercury injection apparatus of AutoPore IV9520 type of Merck & Co., Inc, U.S. production.
The sulfur content of full fraction FCC gasoline raw material of the present invention and reaction product uses TSN-2000 type sulphur apparatus for nitrogen examination
It is analyzed.FCC gasoline raw material and the research octane number (RON) of reaction product are tested using octane number testing machine.FCC gasoline raw material
And the composition of reaction product is analyzed using Agilent 7890B type gas chromatograph, data processing is by HW-2000PONA points
Dedicated chromatographic work station is analysed to complete.
In embodiments, the composition content such as the cobalt oxide of catalyst, molybdenum oxide is measured with x-ray fluorescence method (referring to " stone
Oily chemical analysis method (RIPP experimental method) ", Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes).
Embodiment 1
12.0g concentration is that 68% nitric acid is add to deionized water mixing by the deionized water that 240mL is measured with beaker
It is even, it is placed in 80 DEG C of water-bath.Weigh 6.0g molecular weight be million grades Sodium Polyacrylate and be added to it is prepared go from
It in sub- aqueous nitrate solution, stirs and is completely dissolved, obtain the acid solution containing Sodium Polyacrylate.
300g boehmite powder and 15.0g sesbania powder are weighed, and is uniformly mixed, the acid solution of Sodium Polyacrylate is added
Enter into boehmite and sesbania powder, is clover shape by kneading-extruded moulding.It is 8 hours, 650 DEG C dry at 120 DEG C
Roasting 4 hours, obtains the alumina support A-1 containing macropore.Alumina support specific surface area containing macropore is shown in Table with pore-size distribution
1。
233.3g ammonium heptamolybdate, 17.32g cobalt nitrate is taken to be added in 50ml distilled water, ammonium hydroxide adjusting pH value, which is added, makes salt
It all after dissolution, then is diluted with deionized water, is made into maceration extract impregnated carrier, obtained catalyst precursor is dried at 120 DEG C
Afterwards in 600 DEG C of roasting 6h, catalyst 1 is obtained.Catalyst 1 mainly forms: cobalt oxide 4wt%, molybdenum oxide 11wt%, carrier
85wt%.
Embodiment 2
The preparation method of the acid solution of expanding agent polyacrylic acid, kneading-extrusion, dry, method of roasting according to embodiment 1 into
Row.The difference is that million grade polypropylene acid sodium are changed to millions polyacrylic acid, the alumina support containing macropore is obtained
A-2.Alumina support specific surface area and pore-size distribution containing macropore are shown in Table 1.
Ammonium molybdate, cobalt nitrate are made into maceration extract, dipping is containing macropore after addition ammonium hydroxide adjusting pH value dissolves salt all
Alumina support A-2, the specific steps are the same as those in embodiment 1.It roasts 8 hours, is catalyzed at drying 6 hours, 550 DEG C at 110 DEG C
Agent 2.Catalyst 2 mainly forms: cobalt oxide 6wt%, molybdenum oxide 8wt%, carrier 86wt%.
Hydrobon catalyst 2 is fitted into 10ml fixed bed adiabatic reactor, evaluation catalyst reaction performance is carried out.With
Sulfurized oil carries out presulfurization to catalyst, and sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, concentration 1.0wt%；Vulcanization pressure
Power is 3.0MPa, and hydrogen to oil volume ratio 350, sulfurized oil volume space velocity is 3.0h-1, vulcanization program is respectively at 230 DEG C, 270 DEG C
Vulcanizing treatment 5h.After vulcanizing treatment, it is switched to full fraction FCC gasoline replacement Treatment 6h, after pre-vulcanization process, is adjusted
It is whole to arrive reaction process condition, it is reacted into catalytically cracked gasoline.Reaction process condition are as follows: 260 DEG C of reaction temperature, reaction pressure
2.0MPa, volume space velocity 2.1h-1, hydrogen to oil volume ratio 250:1.Sampling analysis after reaction about 50h.Hydrobon catalyst 2 reacts
Performance is as shown in table 2.
Embodiment 3
The preparation method of the acid solution of expanding agent ammonium polyacrylate, kneading-extrusion, dry, method of roasting is according to embodiment 1
It carries out.The difference is that million grade polypropylene acid sodium are changed to 100,000 grade polypropylene acid ammoniums, the aluminium oxide containing macropore is obtained
Carrier A-3.Its specific surface area and pore-size distribution are shown in Table 1.
Ammonium molybdate, cobalt nitrate are made into maceration extract, dipping is containing macropore after addition ammonium hydroxide adjusting pH value dissolves salt all
Alumina support A-3, the specific steps are the same as those in embodiment 1.It roasts 7 hours, is catalyzed at drying 4 hours, 580 DEG C at 130 DEG C
Agent 3.Catalyst 3 mainly forms: cobalt oxide 2wt%, molybdenum oxide 10wt%, carrier 88wt%.
Embodiment 4
The compounding method of the acid solution of expanding agent, kneading-extrusion, dry, method of roasting are carried out according to embodiment 1.It is different
Place is million grade polypropylene acid sodium being changed to million grade polypropylene acid ammoniums and 100,000 grade polypropylene acid sodium, ammonium polyacrylate
The alumina support A-4 containing macropore is obtained with Sodium Polyacrylate mass ratio 2:1.Its specific surface area and pore-size distribution are shown in Table 1.Fig. 1
For the graph of pore diameter distribution of alumina support A-4.As shown in Figure 1, the alumina support of preparation has the structure of bimodal pore distribution.
Ammonium molybdate, cobalt nitrate are made into maceration extract, dipping is containing macropore after addition ammonium hydroxide adjusting pH value dissolves salt all
Alumina support A-4, the specific steps are the same as those in embodiment 1.It roasts 6 hours, is catalyzed at drying 5 hours, 600 DEG C at 120 DEG C
Agent 4.Catalyst 4 mainly forms: cobalt oxide 3wt%, molybdenum oxide 7wt%, carrier 90wt%.
Embodiment 5
The preparation method of the acid solution of expanding agent, kneading-extrusion, dry, method of roasting are carried out according to embodiment 1.It is different
Place is for million grade polypropylene acid sodium to be changed to million grade polypropylene acid and 100,000 grade polypropylene acid ammoniums, ammonium polyacrylate and
Polyacrylic acid mass ratio 8:1 obtains the alumina support A-5 containing macropore.Its specific surface area and pore-size distribution are shown in Table 1.
Ammonium molybdate, cobalt nitrate are made into maceration extract, dipping is containing macropore after addition ammonium hydroxide adjusting pH value dissolves salt all
Alumina support A-5, the specific steps are the same as those in embodiment 1.It roasts 8 hours, is catalyzed at drying 6 hours, 550 DEG C at 110 DEG C
Agent 5.Catalyst 5 mainly forms: cobalt oxide 7wt%, molybdenum oxide 8wt%, carrier 85wt%.
Hydrobon catalyst 5 is fitted into 10ml fixed bed adiabatic reactor, evaluation catalyst reaction performance is carried out.With
Sulfurized oil carries out presulfurization to catalyst, and sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, concentration 1.0wt%；Vulcanization pressure
Power is 3.0MPa, and hydrogen to oil volume ratio 350, sulfurized oil volume space velocity is 3.0h-1, vulcanization program is respectively at 230 DEG C, 270 DEG C
Vulcanizing treatment 5h.After vulcanizing treatment, it is switched to full fraction FCC gasoline replacement Treatment 6h, after pre-vulcanization process, is adjusted
It is whole to arrive reaction process condition, it is reacted into catalytically cracked gasoline.Reaction process condition are as follows: 280 DEG C of reaction temperature, reaction pressure
2.3MPa, volume space velocity 2.8h-1, hydrogen to oil volume ratio 290:1.Sampling analysis after reaction about 50h.Hydrobon catalyst 5 reacts
Performance is as shown in table 2.
Embodiment 6
The preparation method of the acid solution of expanding agent, kneading-extrusion, dry, method of roasting are carried out according to embodiment 1.It is different
Place is million grade polypropylene acid sodium being changed to million grade polypropylene acid sodium and million grade polypropylene acid ammoniums, ammonium polyacrylate
With Sodium Polyacrylate mass ratio 5:1, the alumina support A-6 containing macropore is obtained.Its specific surface area and pore-size distribution are shown in Table 1.
Ammonium molybdate, cobalt nitrate are made into maceration extract, dipping is containing macropore after addition ammonium hydroxide adjusting pH value dissolves salt all
Alumina support A-6, the specific steps are the same as those in embodiment 1.It roasts 6 hours, is catalyzed at drying 6 hours, 600 DEG C at 120 DEG C
Agent 6.Catalyst 6 mainly forms: cobalt oxide 2wt%, molybdenum oxide 12wt%, carrier 86wt%.
Hydrobon catalyst 6 is fitted into 10ml fixed bed adiabatic reactor, evaluation catalyst reaction performance is carried out.With
Sulfurized oil carries out presulfurization to catalyst, and sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, concentration 1.0wt%；Vulcanization pressure
Power is 3.0MPa, and hydrogen to oil volume ratio 350, sulfurized oil volume space velocity is 3.0h-1, vulcanization program is respectively at 230 DEG C, 270 DEG C
Vulcanizing treatment 5h.After vulcanizing treatment, it is switched to full fraction FCC gasoline replacement Treatment 6h, after pre-vulcanization process, is adjusted
It is whole to arrive reaction process condition, it is reacted into catalytically cracked gasoline.Reaction process condition are as follows: 220 DEG C of reaction temperature, reaction pressure
1.6MPa, volume space velocity 1.5h-1, hydrogen to oil volume ratio 220:1.Sampling analysis after reaction about 50h.Hydrobon catalyst 6 reacts
Performance is as shown in table 2.
Embodiment 7
The preparation method of the acid solution of expanding agent, kneading-extrusion, dry, method of roasting are carried out according to embodiment 1.It is different
Place is for million grade polypropylene acid sodium to be changed to million grade polypropylene acid sodium and million grade polypropylenes acid, Sodium Polyacrylate and
The mass ratio 3:1 of polyacrylic acid obtains the alumina support A-7 containing macropore.Its specific surface area and pore-size distribution are shown in Table 1.
Ammonium molybdate, cobalt nitrate are made into maceration extract, dipping is containing macropore after addition ammonium hydroxide adjusting pH value dissolves salt all
Alumina support A-7, the specific steps are the same as those in embodiment 1.It roasts 6 hours, is catalyzed at drying 5 hours, 580 DEG C at 130 DEG C
Agent 7.Catalyst 7 mainly forms: cobalt oxide 4wt%, molybdenum oxide 9wt%, carrier 87wt%.
Comparative example 1
Weigh 300g boehmite powder and 15.0g sesbania powder, and be uniformly mixed, with beaker measure 240mL go from
12.0g concentration is that 68% nitric acid is add to deionized water uniformly mixed, is then added to boehmite and sesbania by sub- water
It is clover shape by kneading-extruded moulding in powder.8 hours dry at 120 DEG C, 650 DEG C roast 4 hours, obtain containing macropore
Alumina support.Alumina support specific surface area and pore-size distribution containing macropore are shown in Table 1.The difference of comparative example and embodiment 1
It is not add expanding agent.
233.3g ammonium heptamolybdate, 17.32g cobalt nitrate is taken to be added in 50ml distilled water, ammonium hydroxide adjusting Ph value, which is added, makes salt
It all after dissolution, then is diluted with deionized water, is made into maceration extract impregnated carrier, obtained catalyst precursor is dried at 120 DEG C
Afterwards in 600 DEG C of roasting 6h, comparative catalyst D-1 is obtained.Comparative catalyst D-1 is mainly formed: cobalt oxide 4wt%, molybdenum oxide
11wt%, carrier 85wt%.
The alumina support specific surface area and pore-size distribution of 1 macropore of table
| Specific surface area, m2/g | Total pore volume, ml/g | Macropore hole holds, ml/g | Macropore diameter, nm | Mesoporous pore size, nm | |
| A-1 | 279.8 | 1.66 | 0.86 | 89 | 23 |
| A-2 | 278.7 | 1.51 | 0.95 | 143 | 15 |
| A-3 | 273.8 | 1.84 | 1.16 | 65 | 41 |
| A-4 | 276.1 | 1.69 | 1.29 | 132 | 9 |
| A-5 | 276.4 | 1.71 | 0.71 | 158 | 47 |
| A-6 | 279.8 | 2.03 | 0.78 | 187 | 31 |
| A-7 | 273.1 | 1.64 | 1.13 | 124 | 27 |
| D-1 | 253.2 | 1.12 | 0.49 | 58 | 18 |
Hydrobon catalyst 1,3,4,7 and comparative example D-1 are respectively charged into 10ml fixed bed adiabatic reactor, carried out
Evaluate catalyst reaction performance.Presulfurization is carried out to catalyst with sulfurized oil, sulfurized oil is direct steaming gasoline, vulcanizing agent CS2,
Concentration is 1.0wt%；Sulfide stress is 3.0MPa, and hydrogen to oil volume ratio 350, sulfurized oil volume space velocity is 3.0h-1, vulcanize program
For respectively in 230 DEG C, 270 DEG C of vulcanizing treatment 5h.After vulcanizing treatment, it is switched to full fraction FCC gasoline replacement Treatment 6h, to
After pre-vulcanization process, it is adjusted to reaction process condition, is reacted into catalytically cracked gasoline.Reaction process condition are as follows: reactor
250 DEG C of temperature, reaction pressure 1.4MPa, volume space velocity 3h-1, hydrogen to oil volume ratio 280.Sampling analysis after reaction about 50h.Add hydrogen de-
Sulfur catalyst 1~7 and comparative example D-1 reactivity worth are as shown in table 2.
2 Hydrobon catalyst of table and comparative example catalyst reaction performance
Embodiment 8
12.0g concentration is that 68% nitric acid is add to deionized water mixing by the deionized water that 240mL is measured with beaker
It is even, it is placed in 80 DEG C of water-bath.Weigh 6.0g molecular weight be million grades Sodium Polyacrylate and be added to it is prepared go from
It in sub- aqueous nitrate solution, stirs and is completely dissolved, obtain the acid solution containing Sodium Polyacrylate.
300g boehmite powder and 15.0g sesbania powder are weighed, and is uniformly mixed, weighs boric acid 1.89g, nitric acid respectively
Potassium 1.6g, strontium nitrate 1.16g are dissolved completely in the aqueous solution that boracic, potassium strontium are made into 60g distilled water.Then it is added and intends thin water aluminium
In mountain flour and the mixture of sesbania powder.The acid solution of Sodium Polyacrylate is added in boehmite and sesbania powder, is passed through
Kneading-extruded moulding is clover shape.8 hours dry at 120 DEG C, 650 DEG C roast 4 hours, obtain used additives potassium and strontium into
The modified alumina support A-8 of row.
Cobalt nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
Body A-8,5 hours dry at 130 DEG C, 600 DEG C roast 7 hours, obtain Hydrobon catalyst C-1.The main group of catalyst C-1
At: cobalt oxide 2.5wt%, molybdenum oxide 9.5wt% change alumina supporter A-888wt%.
Embodiment 9
12.0g concentration is that 68% nitric acid is add to deionized water mixing by the deionized water that 240mL is measured with beaker
It is even, it is placed in 80 DEG C of water-bath.Weigh 6.0g molecular weight be million grades Sodium Polyacrylate and be added to it is prepared go from
It in sub- aqueous nitrate solution, stirs and is completely dissolved, obtain the acid solution containing Sodium Polyacrylate.
300g boehmite powder and 15.0g sesbania powder are weighed, and is uniformly mixed, weighs boric acid 1.89g, nitric acid respectively
Potassium 1.6g, strontium nitrate 1.16g are dissolved completely in the aqueous solution that boracic, potassium strontium are made into 60g distilled water.Then it is added and intends thin water aluminium
In mountain flour and the mixture of sesbania powder.The acid solution of Sodium Polyacrylate is added in boehmite and sesbania powder, is passed through
Kneading-extruded moulding is clover shape.8 hours dry at 120 DEG C, 650 DEG C roast 4 hours, obtain used additives potassium and strontium into
The modified alumina support A-8 of row.
The alumina support A-8 that used additives potassium and strontium are modified is surface modified using potassium and strontium, detailed process
Include the following steps: that configuration, as maceration extract, weighs potassium nitrate 3.5g, strontium nitrate containing potassium nitrate and strontium nitrate aqueous solution respectively
2.6g is dissolved completely in 30ml distilled water, then is diluted with deionized water, is made into maceration extract oxide impregnation alumina supporter A-8, through dry
Dry, roasting obtains the aluminium oxide aluminium complex carrier A-9 that used additives potassium and strontium are surface modified.
Cobalt nitrate and ammonium molybdate are made into maceration extract, ammonium hydroxide adjusting pH value, which is added, carries oxide impregnation aluminium after salt whole dissolution
Body A-9 roasts 5 hours at 5 hours, 650 DEG C dry at 130 DEG C, obtains Hydrobon catalyst C-2.Catalyst C-2 is main
Composition: cobalt oxide 2wt%, molybdenum oxide 8.5wt% change alumina supporter A-989.5wt%.
Hydrobon catalyst C-1 and C-2 are respectively charged into 10ml fixed bed adiabatic reactor, evaluation catalyst is carried out
Reactivity worth.Presulfurization is carried out to catalyst with sulfurized oil, sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, concentration is
1.0wt%；Sulfide stress is 3.0MPa, and hydrogen to oil volume ratio 350, sulfurized oil volume space velocity is 3.0h-1, vulcanization program is difference
In 230 DEG C, 270 DEG C of vulcanizing treatment 5h.After vulcanizing treatment, it is switched to full fraction FCC gasoline replacement Treatment 6h, to presulfurization
After process, it is adjusted to reaction process condition, is reacted into catalytically cracked gasoline.Reaction process condition are as follows: temperature of reactor 250
DEG C, reaction pressure 1.4MPa, volume space velocity 3h-1, hydrogen to oil volume ratio 280.Sampling analysis after reaction about 50h.Hydrodesulfurization catalytic
Agent C-1 and C-2 product desulfurization degree is respectively 83% and 84%, and alkene drop amount is respectively 1.9 percentage points and 1.6 percentage points,
Loss of octane number is respectively 0.4 unit and 0.3 unit, and Hydrobon catalyst loss of octane number is low, and desulfurization degree is high, catalysis
Agent activity is good.Study on the stability, reaction operation 300h, Hydrobon catalyst C-1 and C-2 product desulfurization degree are carried out to catalyst
Respectively 81% and 83%, loss of octane number is respectively 0.3 unit and 0.2 unit, and carbon deposition rate 2.2 and 2.0, catalyst is anti-
Performance is answered to stablize, active component not easily runs off, and carbon deposition rate is low, illustrates that its hydrodesulfurization has good stability.
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 (13)
1. a kind of hydrodesulfurizationprocess process of FCC gasoline, which is characterized in that use fixed bed reactors；The catalyst is load
Type cobaltmolybdate catalyst, the composition of catalyst is with oxidation material meter, including following component: cobalt oxide content 0.5-8wt%, oxygen
Change molybdenum content is 1.0-12wt%, has the alumina support 77-95wt% of macroporous structure, and alumina support uses polyphosphazene polymer
One or more of sodium acrylate, ammonium polyacrylate and polyacrylic acid are used as expanding agent；Hydrodesulfurization condition are as follows: reaction
180-320 DEG C of temperature, reaction pressure 1.1-2.8MPa, volume space velocity 1.2-3.5h-1, hydrogen to oil volume ratio 180-400:1.
2. hydrodesulfurizationprocess process according to claim 1, which is characterized in that cobalt oxide content is 1.0- in the catalyst
4.5wt%, oxidation molybdenum content are 4-9wt%；200-300 DEG C of reaction temperature, reaction pressure 1.1-2.8MPa, volume space velocity 1.5-
3.0h-1, hydrogen to oil volume ratio 200-300:1.
3. hydrodesulfurizationprocess process according to claim 1, which is characterized in that the FCC gasoline Hydrobon catalyst
Preparation method includes the following steps: cobalt is contained and the soluble-salt containing molybdenum is made into maceration extract, impregnates the alumina support containing macropore,
It is roasted 5-9 hours at drying 4-8 hours, 500-700 DEG C at 120-160 DEG C, obtains Hydrobon catalyst.
4. hydrodesulfurizationprocess process according to claim 1, which is characterized in that the alumina support with macroporous structure
60~200nm of pore-size distribution, macropore ratio 1~80%, 0.8~2.3ml/g of Kong Rong.
5. hydrodesulfurizationprocess process according to claim 1, which is characterized in that the alumina support with macroporous structure
Also contain meso-hole structure simultaneously, macropore range is in 5~50nm, mesoporous ratio 20~70%.
6. hydrodesulfurizationprocess process according to claim 5, which is characterized in that the alumina support with macroporous structure
Hole holds 0.8~1.2ml/g or 1.8~2.3ml/g, the mesoporous ratio 20~50%.
7. hydrodesulfurizationprocess process according to claim 1, which is characterized in that the expanding agent is ammonium polyacrylate and poly- third
The mixture or ammonium polyacrylate of olefin(e) acid sodium and the mixture of polyacrylic acid.
8. hydrodesulfurizationprocess process according to claim 7, which is characterized in that ammonium polyacrylate and poly- third in the expanding agent
The mass ratio of olefin(e) acid sodium or polyacrylic acid is 1~10:1.
9. hydrodesulfurizationprocess process according to claim 1, which is characterized in that the alumina support with macroporous structure
Middle introducing auxiliary agent boron, potassium, strontium, the composition of the alumina support with macroporous structure is with oxidation material meter: including 93-
The aluminium oxide of 99wt%, the boron of 0.1-2.5wt%, the potassium of 0.1-3.8wt%, the strontium of 0.1-3.8wt%.
10. hydrodesulfurizationprocess process according to claim 9, which is characterized in that the carrying alumina with macroporous structure
The content of body surface face potassium and strontium is higher than the content of carrier inside potassium and strontium.
11. hydrodesulfurizationprocess process according to claim 10, which is characterized in that the carrying alumina with macroporous structure
The mass content of body surface face potassium and strontium is 2.1-3.0 times of the content of carrier inside potassium and strontium.
12. described in any item hydrodesulfurizationprocess process according to claim 1~9, which is characterized in that the oxidation with macroporous structure
The preparation method of alumina supporter includes the following steps: firstly, carrying out acidification to expanding agent obtains the acid solution containing expanding agent, so
Boehmite powder and sesbania powder are added in kneader afterwards and are uniformly mixed, is then added to the acid solution containing expanding agent
It is mediated in boehmite powder uniformly, the additional amount of the acid solution containing expanding agent is 0.1~10wt% of boehmite, warp
Extrusion-molding-drying-roasting is crossed, the alumina support with macroporous structure is obtained.
13. hydrodesulfurizationprocess process described in 0 or 11 according to claim 1, which is characterized in that the carrying alumina with macroporous structure
The preparation method of body include the following steps: firstly, to expanding agent carry out acidification obtain the acid solution containing expanding agent, then will
Boehmite powder and sesbania powder are added in kneader and are uniformly mixed, and add the water of boronic acid containing, potassium nitrate and strontium nitrate
Solution；Then the acid solution containing expanding agent is added in boehmite powder and is mediated uniformly, the acid solution containing expanding agent
Additional amount is 0.1~10wt% of boehmite, by extrusion-molding-drying-roasting, obtains used additives potassium and strontium carries out
Modified alumina support；It is reconfigured containing potassium nitrate and strontium nitrate aqueous solution impregnates used additives potassium as maceration extract and strontium is changed
Property alumina support, obtain the complex carrier that used additives potassium and strontium be surface modified through drying, roasting.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5744668A (en) * | 1995-08-08 | 1998-04-28 | Li Xing | Process of producing gasoline, diesel and carbon black with waste rubbers and/or waste plastics |
| CN106635135A (en) * | 2016-12-23 | 2017-05-10 | 兰州石化职业技术学院 | Hydrodesulfurization method of catalytic cracking gasoline |
| CN107081155A (en) * | 2017-06-02 | 2017-08-22 | 钦州学院 | A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5744668A (en) * | 1995-08-08 | 1998-04-28 | Li Xing | Process of producing gasoline, diesel and carbon black with waste rubbers and/or waste plastics |
| CN106635135A (en) * | 2016-12-23 | 2017-05-10 | 兰州石化职业技术学院 | Hydrodesulfurization method of catalytic cracking gasoline |
| CN107081155A (en) * | 2017-06-02 | 2017-08-22 | 钦州学院 | A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization |
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