CN105583002B - A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil - Google Patents
A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil Download PDFInfo
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Abstract
The invention discloses the methods of a kind of desulphurization catalyst and preparation method thereof He desulfurization of hydrocarbon oil.On the basis of the total weight of the desulphurization catalyst, which contains：1) heat-resistant inorganic oxide of 5 30 weight %；2) silica source of 5 30 weight %；3) the first metal oxide of 10 70 weight %；4) the second metal oxide of 2 20 weight %；5) metallic promoter agent of 5 30 weight %；6) the rare earth modified phosphate aluminium molecular sieve of 1 20 weight %.The desulphurization catalyst has better desulphurizing activated and activity stability.
Description
Technical field
The present invention relates to the methods of a kind of desulphurization catalyst and preparation method thereof He desulfurization of hydrocarbon oil, and in particular, to a kind of
Desulphurization catalyst prepares the method for desulphurization catalyst and the desulphurization catalyst that is obtained by this method and uses the desulfurization catalyst
The method that agent carries out desulfurization of hydrocarbon oil.
Background technology
The oxysulfide generated after combustion of sulfur in vehicle fuel can inhibit the precious metal catalyst in vehicle exhaust converter
The activity of agent simultaneously can be allowed to occur irreversibly to be poisoned.So that the oxygen containing unburned non-methane hydrocarbon and nitrogen in vehicle exhaust
Compound and carbon monoxide, and these discharge gas are then easily formed photochemical fog by hydrophilic dye, trigger acid rain, while in air
Oxysulfide be also one of the main reason for forming acid rain in itself.As people are to the pay attention to day by day of environmental protection, environmental law
Rule are also increasingly stringent, and the sulfur content for reducing gasoline and diesel oil is considered as one of most important measure for improving air quality.
The existing gasoline products standard GB 17930-2011 in China《Motor petrol》It is required that on December 31st, 2013, vapour
Sulfur content must drop to 50 μ g/g in oil；And future, gasoline quality standard can be more stringent.In this case, catalysis is split
Change gasoline, which has to pass through deep desulfuration, can just meet the requirement of environmental protection.
At present, the process for deep desulphurization of oil product mainly have hydrofinishing and absorption two methods of desulfurization, but China due to
The problem of hydrogen source, so that the cost of hydrofinishing is higher.S Zorb absorption desulfurization, which belongs to, faces hydrogen desulfurization technology, certain
The adsorbing and removing of sulfide is realized under the conditions of temperature and pressure.Since sulfur-containing compound of the technology in gasoline is removed has hydrogen
The characteristics of low is consumed, and it is not high to the purity requirement of hydrogen so that and the technology has in terms of the sulfur-containing compound in removing fuel oil
Have broad application prospects.
The method that traditionally desulfurization often uses fixed bed from liquid, but the reaction uniformity of this method and regeneration have
Apparent inferior position.Fluidized-bed process has the advantages that preferably heat transfer and pressure drop etc. compared with fixed-bed process, therefore has
Have broad application prospects.Fluidized-bed reactor generally uses granular reactant, but for most of reactions, reaction used
The typically no enough wearabilities of object.Therefore, the adsorbent for finding wear-resisting property well while having preferable desulfurization performance has important
Meaning.
CN1355727A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Object is made of zinc oxide, silica, oxidation al and ni, and for wherein nickel substantially to reduce valence state presence, amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted under the conditions of sulphur with the nickeliferous adsorbent composition.Said composition is led to
It crosses and is granulated to form particle by the compound particles that zinc oxide, silica and aluminium oxide are formed, nickel or nickeliferous chemical combination are used after dry, roasting
Object impregnates, and re-dry, roasting, reduction obtain.
CN1382071A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Object is made of zinc oxide, silica, aluminium oxide and cobalt, and for wherein cobalt substantially to reduce valence state presence, amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted under the conditions of sulphur with the adsorbent composition containing cobalt.CN1355727A
Be all only referred in CN1382071A it is desulphurizing activated, for adsorbent physical and chemical performance (such as abrasion strength resistance) and stability all
Do not introduce.
Adsorbent is disclosed in US6150300, CN1130253A and CN1258396A：Include zinc oxide, silica, oxidation
The granular adsorbent composition of the mixture of aluminium, reduction valence state nickel or cobalt.Preparation method mainly uses the methods of shearing will
Silica, aluminium oxide and zinc oxide mix merga pass comminutor and prepare solid particle, and nickel is impregnated after drying and roasting so as to be made
Adsorbent.Although the adsorbent of these patent introductions has preferable desulfurization performance, for its physical and chemical performance, mainly wear
Intensity is not described in the patent.
CN1208124A is disclosed includes zinc oxide, expanded perlite and oxidation using promoter metals such as cobalt and nickel dipping
Then the adsorbing agent carrier of aluminium reduces the accelerating agent at appropriate temperatures, prepare to remove the suction of sulfide in cracking gasoline
Attached dose.
CN1627988A discloses one kind and is suitable for removing elementary sulfur and vulcanization conjunction from cracking gasoline and diesel fuel
The adsorbent composition of object, the adsorbent composition include：Zinc oxide, expanded perlite, aluminate and promoter metals,
Described in promoter metals will cause from cracking when making cracking gasoline or diesel fuel stream contacts under desulfurization conditions with it
The amount of desulfurization in the stream of gasoline or diesel fuel exists, and at least partly described promoter metals exist with 0 valence state.
CN1856359A discloses a kind of method for producing composition, including：A) mixing liquid, zinc compound, containing two
Silica material, aluminium oxide and co-catalyst, to form its mixture；B) dry mixture, to form dried mixing
Object；C) the dried mixture is calcined, to form the mixture through calcining；D) with appropriate reducing agent under suitable condition
The mixture through calcining is reduced, to produce the composition of the co-catalyst content in it with reduction valence state and e)
Recycling changes composition.Co-catalyst contains selected from various metals such as nickel.
CN1871063A discloses a kind of method for producing composition, and this method includes：A) by liquid, zinc compound,
It mixes to form its mixture containing earth silicon material, aluminium oxide；B) mixture is dried into the mixing to form first
Through drying composite；C) described first is calcined to form first through calcining mixt through drying composite；D) by accelerating agent knot
Close described first through within calcining mixt or on to form promoted mixture；E) the promoted mixture and choosing are made
It contacts to be formed through contact mixture from the acid of citric acid, tartaric acid and combinations thereof；F) by it is described through contact mixture drying with
Second is formed through drying composite；G) described second is calcined to form second through calcining mixt through drying composite；H) exist
Suitable reducing agent reduction described second is used wherein to promote through calcining mixt to produce containing reduction valence state under conditions of appropriate
Into agent content composition and i) recycle the composition.
CN101816918A discloses a kind of desulfuration adsorbent, and adsorbent composition is rare earth metal, aluminium oxide, oxidation
The adsorbent of silicon, accelerating agent and one or more of metal oxides selected from IIB, VB and VIB.The adsorbent has preferable
Abrasion strength resistance and desulphurizing activated.
Although these methods prepare adsorbent have preferable desulfurization performance, there is also it is apparent the shortcomings that.Above-mentioned suction
Attached dose using zinc oxide active component, it is higher to aoxidize the temperature of zinc-iron alloy solution sulphur and oxidation regeneration, in desulphurization reaction and
Easily with silicon, aluminium component generation zinc silicate and/or the zinc aluminate in carrier adsorbent activity is caused to reduce during oxidation regeneration.By
This is visible, it is desirable to provide a kind of new catalyst with more high desulfurization activity and abrasion resistance properties.
The content of the invention
The purpose of the invention is to overcome the desulphurizing activated low, structural instability of the adsorbent of the prior art and wear resistance
Can be poor the defects of, the method for providing a kind of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil.
To achieve these goals, the present invention provides a kind of desulphurization catalyst, using the total weight of the desulphurization catalyst as base
Standard, the desulphurization catalyst contain：1) heat-resistant inorganic oxide of 5-30 weight %, the heat-resistant inorganic oxide are selected from oxidation
At least one of aluminium, titanium dioxide, zirconium dioxide and stannic oxide；2) silica source of 5-30 weight %；3) 10-70 weights
The first metal oxide of % is measured, in the metal oxide of first metal oxide selected from IIB, VB and group vib element
It is at least one；4) the second metal oxide of 2-20 weight %, second metal oxide are selected from lead oxide, antimony oxide and oxygen
Change at least one of bismuth；5) metallic promoter agent of 5-30 weight %, the metallic promoter agent is in cobalt, nickel, iron and manganese
It is at least one；6) the rare earth modified phosphate aluminium molecular sieve of 1-20 weight %.
The present invention also provides the preparation method of the desulphurization catalyst of the present invention, this method includes：It (1) will be rare earth modified
Phosphate aluminium molecular sieve, the first metal oxide, the precursor of the second metal oxide and water are mixed to get slurries；(2) by heat-resisting nothing
Machine adhesive oxides, silica source, water are mixed with acidic liquid, and form carrier pulp with the slurry liquid contacts, then by institute
State carrier pulp be molded, first drying and first roasting, obtain carrier；(3) metallic promoter agent is introduced on the carrier
Precursor, and carry out second drying and second roasting, obtain catalyst precarsor；(4) by the catalyst precarsor in hydrogen gas
It is reduced under atmosphere, obtains desulphurization catalyst.
The present invention also provides the desulphurization catalysts that method provided by the present invention is prepared.
The present invention provides a kind of method of desulfurization of hydrocarbon oil, this method includes：In a hydrogen atmosphere, by hydrocarbon oil containing surphur and this
The hydrodesulfurization catalyst provided is invented, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5-4MPa.
It is mixed with the second metal oxide as sulphur containing the first metal oxide in desulphurization catalyst provided by the invention
Constituent element is absorbed, the second metal oxide can effectively reduce the effect of the first metal oxide and silicon, aluminium component in carrier, subtract
The silicate and/or aluminate of the first metal are generated less, so that the desulphurization catalyst can absorb sulphur at lower temperatures
And through reaction and regenerative process is repeated, still there is better desulphurizing activated and activity stability.
Contain rare earth modified phosphate aluminium molecular sieve, the distinctive skeleton of phosphate aluminium molecular sieve in desulphurization catalyst provided by the invention
Structure and acid isomerization and the aromatization for being conducive to hydro carbons, increase octane number.It is dilute by being carried out to molecular sieve
On the one hand native ion modification improves the heat and hydrothermal stability of molecular sieve, can extend the service life of catalyst, reduces side reaction
Generation；On the other hand the acid site intensity of molecular sieve can be reduced, cracking and the green coke of gasoline is reduced, increases yield of gasoline
Add.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of desulphurization catalyst, and on the basis of the total weight of the desulphurization catalyst, which contains
Have：1) heat-resistant inorganic oxide of 5-30 weight %, the heat-resistant inorganic oxide are selected from aluminium oxide, titanium dioxide, titanium dioxide
At least one of zirconium and stannic oxide；2) silica source of 5-30 weight %；3) the first metal oxidation of 10-70 weight %
Object, first metal oxide are selected from least one of metal oxide of IIB, VB and group vib element；4) 2-20 weights
The second metal oxide of % is measured, second metal oxide is selected from least one of lead oxide, antimony oxide and bismuth oxide；
5) metallic promoter agent of 5-30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese；6) 1-20 weights
Measure the rare earth modified phosphate aluminium molecular sieve of %.
Preferably, on the basis of the total weight of the desulphurization catalyst, the content of the heat-resistant inorganic oxide is 10-20 weights
Measure %, the content of the silica source is 10-20 weight %, and the content of first metal oxide is 35-54 weight %, institute
The content of the second metal oxide is stated as 5-15 weight %, the content of the metallic promoter agent is 10-20 weight %, the rare earth
The content of modified phosphate aluminium molecular sieve is 2-20 weight %.
According to the present invention, first metal oxide is the metal oxide with storage sulphur performance, it is preferable that described the
One metal oxide be zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide in extremely
Few one kind；It is highly preferred that first metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide；Most preferably
First metal oxide is zinc oxide.
According to the present invention, second metal oxide can inhibit first metal oxide and undergo high temperature repeatedly
Under desulphurization reaction and regenerative response when, have an effect with the silicon that contains in the desulphurization catalyst, aluminium component, reduce described the
The loss of one metal oxide.
According to the present invention, the heat-resistant inorganic oxide can be to provide bonding between each component in the desulphurization catalyst
Effect.The heat-resistant inorganic oxide is selected from least one of aluminium oxide, titanium dioxide, zirconium dioxide and stannic oxide.Its
In, the aluminium oxide can be at least one of gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-aluminium oxide；Preferably,
The aluminium oxide is gama-alumina；The titanium dioxide can be anatase titanium dioxide.
According to the present invention, the silica source can be to provide cementation between each component in the desulphurization catalyst.
Under preferable case, the silica source can be the natural minerals that pure silica or silica content are more than 45 weight %.It is preferred that
Ground, the silica source can be selected from laminated clay column, diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, big
At least one of hole silica and silica gel.Other components such as Al can also be contained in natural minerals2O3、K2O、CaO、MgO、
Fe2O3、TiO2Deng.In the present invention, the amount of the other components contained in the silica source still can be regarded as the amount of silica source.
According to the present invention, the metallic promoter agent can be any metal that oxidation state sulphur can be reduced to hydrogen sulfide,
It is preferred that the metallic promoter agent is nickel.
In the case of, according to the invention it is preferred to, the rare earth modified phosphate aluminium molecular sieve can be aluminate or phosphate
(aluminophosphates), the sial phosphoric acid that metalloaluminophosphate (metalloaluminophosphates), metal combine
Salt (metal integrated silicoaluminophosphates, MeAPSO and ELAPSO) and silicoaluminophosphate
At least one of (silicoaluminophosphates, SAPO).Preferably, the rare earth modified phosphate aluminium molecular sieve is
At least one of SAPO-11, SAPO-31, SAPO-5 and SAPO-34.The SiO of the rare earth modified phosphate aluminium molecular sieve2：
Al2O3Molar ratio can be 0.02-3：1.
According to the present invention, rare earth modified method can be ion-exchange and/or equi-volume impregnating.Preferable case
Under, on the basis of the total weight of the rare earth modified phosphate aluminium molecular sieve, the rare earth modified phosphate aluminium molecular sieve contains 2-15
Rare earths of the weight % in terms of rare earth oxide.
In the present invention, rare earth is distributed in the inside in the rare earth modified phosphate aluminium molecular sieve duct.Preferably, rare earth can be with
For at least one of the carbonate of rare earth metal, bicarbonate, nitrate, chloride, formates and acetate；Preferably,
The rare earth compound can be at least one of carbonate, bicarbonate, formates and acetate of rare earth metal.
Wherein, the rare earth metal is preferably at least one of lanthanum, cerium and neodymium.Preferably, the rare earth modified phosphate aluminium molecular sieve
Such as La-SAPO-11 molecular sieves (La of 15 weight % can be selected from2O3), Ce-SAPO-31 molecular sieves (10 weight %'s
CeO2), RE-SAPO-34 molecular sieves (RE be 2.5 weight % La2O3With the CeO of 2.5 weight %2), Ce-SAPO-5 molecular sieves
(the CeO of 5 weight %2At least one of).
In the present invention, adding in rare earth modified phosphate aluminium molecular sieve can have while ensureing that gasoline has higher yields,
Promote the isomerization of straight-chain hydrocarbons in gasoline, so as to improve isoparaffin content in gasoline, increase the effect of gasoline products octane number
Or effect.
The present invention also provides the preparation method of the desulphurization catalyst of the present invention, this method includes：It (1) will be rare earth modified
Phosphate aluminium molecular sieve, the first metal oxide, the precursor of the second metal oxide and water are mixed to get slurries；(2) by heat-resisting nothing
Machine adhesive oxides, silica source, water are mixed with acidic liquid, and form carrier pulp with the slurry liquid contacts, then by institute
State carrier pulp be molded, first drying and first roasting, obtain carrier；(3) metallic promoter agent is introduced on the carrier
Precursor, and carry out second drying and second roasting, obtain catalyst precarsor；(4) by the catalyst precarsor in hydrogen gas
It is reduced under atmosphere, obtains desulphurization catalyst.
In the present invention, under preferable case, the heat-resistant inorganic oxide binding agent can be heat-resistant inorganic oxide or
The substance of heat-resistant inorganic oxide can be changed under conditions of the described first roasting.Preferably, the heat resistant inorganic oxidation
Object binding agent be alumina binder, zirconium dioxide binding agent, titanium dioxide binding agent and stannic oxide binding agent at least
It is a kind of.It is highly preferred that the alumina binder can be hydrated alumina and/or Aluminum sol, wherein, the hydrated alumina
Selected from boehmite (boehmite), false boehmite (boehmite), hibbsite and amorphous hydroxide
At least one of aluminium；The zirconium dioxide binding agent can be zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and
At least one of amorphous zirconium dioxide；The stannic oxide binding agent can be butter of tin, four isopropanol tin, acetic acid
At least one of tin, aqua oxidation tin and stannic oxide；The titanium dioxide binding agent can be titanium tetrachloride, metatitanic acid second
At least one of ester, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.
In the present invention, the silica source can be to provide cementation between each component in the desulphurization catalyst.It is excellent
In the case of choosing, the silica source can be the natural crystal that silica or silica content are more than 45 weight %.Preferably, institute
It can be laminated clay column, diatomite, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel to state silica source
At least one of.The laminated clay column can be at least one in rectorite, Yun Mengshi, bentonite, montmorillonite and smectite
Kind.
It should be noted that although aluminium oxide may be contained in above-mentioned silica source, the content of aluminium oxide in the present invention
The amount of aluminium oxide contained in above-mentioned silica source is not included, the content of aluminium oxide only includes the oxidation formed by alumina source
The amount of aluminium.The amount of contained aluminium oxide still can be regarded as the amount of silica source in silica source.Method i.e. provided by the present invention
The content of each component is calculated according to inventory in desulphurization catalyst obtained.
In the present invention, the precursor of second metal oxide is for second metal oxide or described first
The substance of second metal oxide can be changed under conditions of roasting；Under preferable case, second metal oxide
Precursor at least one of for lead oxide, antimony oxide and bismuth oxide；Or metallic lead, the carbonate of antimony and bismuth, nitrate,
At least one of chloride and hydroxide.
In the present invention, the precursor of the metallic promoter agent can be that can be changed into gold under conditions of the described second roasting
Belong to the substance of the oxide of accelerating agent.Under preferable case, the precursor of the metallic promoter agent can be the acetic acid of metallic promoter agent
At least one of salt, carbonate, nitrate, sulfate, rhodanate and oxide.Wherein metallic promoter agent be selected from cobalt, nickel,
At least one of iron and manganese.
In the present invention, first metal oxide and rare earth modified phosphate aluminium molecular sieve as described above, no longer go to live in the household of one's in-laws on getting married one by one
It states.
The step of preparation method of desulphurization catalyst provided by the invention (1) and (2) are used to prepare carrier.
In the step (1) of the present invention, the addition of first metal oxide can be oxide powder form, can also
It is to be prepared as after slurries using as a slurry again by the first metal oxide.
In the present invention, the precursor of second metal oxide is added in, lead oxide, antimony oxide and oxygen can be directly added into
Second metal oxygen can be changed under conditions of the described first roasting by changing the powder of at least one of bismuth or adding in
The substance of compound, such as at least one of the carbonate of metallic lead, antimony and bismuth, nitrate, chloride and hydroxide；It can also
At least one of lead oxide, antimony oxide and bismuth oxide are prepared as after slurries using as a slurry again.
In the present invention, the solid content of slurries described in step (1) can be 15-30 weight %.
In the step (2) of the present invention, the silica source and the charged material weight ratio of the heat-resistant inorganic oxide binding agent
For 0.4-2：1, it is preferably 0.6-1.5：1.It is possible thereby to provide the caking property between the better each component of the desulphurization catalyst.
In the step (2) of the present invention, the mixing can be：Heat-resistant inorganic oxide binding agent and silica source are distinguished
After carrying out acidification with water and acidic liquid, then the mixture each obtained is mixed into acidified slurries；Wherein, when described resistance to
When hot inorganic oxide binder is non-al binder, obtained mixture is colloidal sol.In addition, when the heat-resistant inorganic oxide
When binding agent is alumina binder, the mixing can also be：By water, acidic liquid, alumina binder and silica source
Mixing, aging form acidified slurries.Preferably, the pH value of the acidified slurries is 1-5, is preferably 1.5-4；The acidifying slurry
The solid content of liquid is 15-30 weight %.
In the present invention, the acidic liquid can be selected from water-soluble inorganic acid for acid or the aqueous solution of acid, the acid
And/or organic acid, such as can be at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
In the present invention, the slurries can be shaped to extrudate, piece, pellet, ball or microballoon by shaping described in step (2)
Shape particle.For example, when the slurries are dough or paste mixture, described mixture shaping (preferably extrusion molding) shape can be made
Into particle, preferably diameter in 1-8mm, length in the cylindrical extrudates of 2-5mm, be then dried the extrudate of gained,
Roasting.It if gained mixture is wet mixture form, can be thickened the mixture, by dry aftershaping.More preferable slurries
For slurry form, the microballoon that granularity is 20-200 microns is formed by spray drying, reaches molding purpose.For the ease of spraying
Dry, the solid content of the carrier pulp is 10-40 weight % before drying, is preferably 20-35 weight %.In step (2)
To can also include during the carrier pulp adding in water, there is no particular limitation for the addition of water, as long as obtained load
The solid content of somaplasm hydroful above-mentioned carrier pulp enough.
In the present invention, the condition of first drying and the first roasting can be known to those skilled in the art, preferably
In the case of, the temperature of first drying is 80-150 DEG C, and the time of first drying is 0.5-24h；First roasting
Temperature for 300-700 DEG C, the time of first roasting is at least 0.5h.Preferably, the temperature of first roasting is
400-500 DEG C, the time of first roasting is 0.5-100h, and the time of more preferably described first roasting is 0.5-10h.
According to the present invention, step (3) is used to add in metallic promoter agent.The precursor of the metallic promoter agent is can be second
It is changed into the substance of the oxide of metallic promoter agent under roasting condition；Under preferable case, the precursor of the metallic promoter agent can be with
At least one of acetate, carbonate, nitrate, sulfate, rhodanate and oxide selected from metallic promoter agent.
In the case of, according to the invention it is preferred to, the method that the precursor of metallic promoter agent is introduced on carrier is dipping or precipitation.
The dipping can be the solution of precursor or suspension impregnation carrier with metallic promoter agent；The precipitation can be to promote metal
Solution or suspension into the precursor of agent are mixed with carrier, then add in ammonium hydroxide by the precursor precipitation of metallic promoter agent in carrier
On.
In the present invention, the condition of second drying and the second roasting can be known to those skilled in the art, preferably
In the case of, the temperature of second drying is 50-300 DEG C, and the time of second drying is 0.5-8h；Second roasting
Temperature is 300-700 DEG C, and the time of second roasting is 0.5-4h；Preferably, the temperature of second drying is 100-250
DEG C, the time of second drying is 1-5h；The temperature of second roasting is 400-500 DEG C, the time of second roasting
For 1-3h.Second roasting can have lower progress existing for oxygen or oxygen-containing gas, until volatile materials is removed simultaneously
And metallic promoter agent is converted into the form of metal oxide, obtains catalyst precarsor.
According to the present invention, in step (4), the oxide of the metallic promoter agent in the catalyst precarsor is changed into metal
The catalyst precarsor under hydrogen atmosphere can be reduced, metallic promoter agent made substantially to be deposited with reduction-state by simple substance
Obtaining catalyst of the present invention.The condition of the reduction only turns the oxide of the metallic promoter agent in the catalyst precarsor
Become metal simple-substance, and the metal oxide in the carrier will not change.Under preferable case, the temperature of the reduction is 300-
600 DEG C, time of the reduction is 0.5-6h, and hydrogen content is 10-60 volumes % in the hydrogen atmosphere；Preferably, institute
The temperature of reduction is stated as 350-450 DEG C, the time of the reduction is 1-3h.
In the present invention, step (4) can carry out catalyst precarsor reduction immediately after catalyst precarsor is made, can also
It is carried out before use (before being adsorbed for desulfurization).Since metallic promoter agent easily aoxidizes, and the metal in catalyst precarsor promotees
Exist in the form of an oxide into agent, therefore for ease of transport, catalyst precarsor is reduced and carrying out desulfurization absorption by preferred steps (4)
Preceding progress.It is described to be reduced to make the metal in the oxide of metallic promoter agent substantially to exist with reduction-state, obtain the present invention's
Desulphurization catalyst.
The preparation method provided according to the present invention, the heat-resistant inorganic oxide binding agent, silica source, the first metal oxygen
Compound, the precursor of the second metal oxide, rare earth modified phosphate aluminium molecular sieve and metallic promoter agent precursor addition,
So that in obtained desulphurization catalyst, on the basis of the total weight of the desulphurization catalyst, the heat resistant inorganic containing 5-35 weight %
Oxide, the silica source of 5-35 weight %, the first metal oxide of 10-70 weight %, the second metal of 2-20 weight %
The rare earth modified phosphate aluminium molecular sieve of oxide, the metallic promoter agent of 3-30 weight % and 0.5-10 weight %.
Preferably, on the basis of the total weight of the desulphurization catalyst, the content of the heat-resistant inorganic oxide is 10-25 weights
Measure %, the content of the silica source is 10-25 weight %, and the content of first metal oxide is 35-54 weight %, institute
The content of the second metal oxide is stated as 5-15 weight %, the content of the metallic promoter agent is 10-20 weight %, the rare earth
The content of modified phosphate aluminium molecular sieve is 1-5 weight %.
The present invention also provides the desulphurization catalysts that method provided by the present invention is prepared.The composition of the desulphurization catalyst
As previously mentioned, this is no longer going to repeat them.
The present invention provides a kind of method of desulfurization of hydrocarbon oil, this method includes：In a hydrogen atmosphere, by hydrocarbon oil containing surphur and this
The hydrodesulfurization catalyst provided is invented, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5-4MPa；
Preferably, the temperature of the contact is 400-450 DEG C, and the pressure of the contact is 1-2MPa.Sulphur in hydrocarbon ils in the process
It is adsorbed on catalyst, so as to obtain the hydrocarbon ils of low sulfur content.
The method of desulfurization of hydrocarbon oil provided by the invention preferably carries out in a fluidized bed reactor, i.e., described contact is preferably being flowed
It is carried out in fluidized bed reactor.
In the present invention, the catalyst after reaction can be reused after regeneration.The regeneration carries out under oxygen atmosphere,
Regenerated condition includes：Regenerated pressure is normal pressure, and regenerated temperature is 400-700 DEG C, is preferably 500-600 DEG C.
In the present invention, the catalyst after regeneration is before desulfurization of hydrocarbon oil is re-started, it is also necessary to it is reduced under hydrogen atmosphere,
The reducing condition of catalyst after regeneration includes：Temperature is 350-500 DEG C, is preferably 400-450 DEG C；Pressure is 0.2-2MPa,
Preferably 0.2-1.5MPa.
Term used herein " cracking gasoline " means the hydrocarbon or its any fraction that boiling range is 40 to 210 DEG C, is to come to make
Larger hydrocarbon molecule is cracked into the product of the heat or catalytic process compared with small molecule.Applicable thermal cracking process includes but is not limited to
Coking, thermal cracking and visbreaking etc. and combinations thereof.The example of applicable catalytic cracking process includes but not limited to fluid bed and urges
Change cracking and heavy oil catalytic cracking etc. and combinations thereof.Therefore, applicable catalytically cracked gasoline includes but not limited to coker gasoline, heat
Cracking gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and heavy oil cracked gasoline and combinations thereof.In some cases,
The cracking gasoline can be fractionated before desulfurization when being used as hydrocarbon-containifluids fluids in the methods of the invention and/or hydrotreating.
Term used herein " diesel fuel " means the hydrocarbon mixture or its any fraction that boiling range is 170 to 450 DEG C
The liquid of composition.Such hydrocarbon-containifluids fluids include but not limited to light cycle oil, kerosene, straight-run diesel oil and hydroprocessed diesel etc. and its
Combination.
Term used herein " sulphur " represents any type of element sulphur such as hydrocarbon-containifluids fluids such as cracking gasoline or diesel engine combustion
The organosulfur compound being commonly present in material.Sulphur present in hydrocarbon-containifluids fluids of the present invention includes but not limited to carbonyl sulfide (COS), two
Nitric sulfid (CS2), mercaptan or other thiophenes etc. and combinations thereof, especially including thiophene, benzothiophene, alkylthrophene,
The thiophene-based chemical combination for the molecular weight bigger being commonly present in alkyl benzothiophenes and methyldibenzothiophene and diesel fuel
Object.
Desulphurization catalyst provided by the invention has good abrasion strength resistance and desulphurizing activated, can greatly prolong using the longevity
Life, suitable for adsorbing sweetening process.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, the composition of desulphurization catalyst is calculated according to feeding intake.
Embodiment 1
The present embodiment is used for the method for preparing desulphurization catalyst for illustrating the present invention.
(1) carrier is prepared.By the oxidation of Zinc oxide powder (Beijing Chemical Plant, containing butt 4.0kg), 0.50kg of 4.05kg
Lead powder end (traditional Chinese medicines chemical reagents corporation, analysis are pure), the 15 weight %La of 1.0kg2O3Modified SAPO-11 molecular sieves (contain butt
0.7kg, SiO2:Al2O3Molar ratio=1：1, be denoted as La-SAPO-11) and 6.9kg deionized water mixing, stir 30 minutes
The slurries containing zinc oxide, lead oxide and La-SAPO-11 molecular sieves are obtained afterwards；
By the aluminium oxide (Shandong Aluminum Plant, containing butt 1.20kg) of 1.60kg and the kaolin of 2.16kg (catalyst Nanjing point
Company, containing butt 1.80kg) it mixes under stiring, it then adds in deionized water 3.6kg after mixing, adds in the 30 of 300ml
Hydrochloric acid (Beijing Chemical Plant, chemistry are pure) stirring of weight % makes pH=1.8, and 80 DEG C of aging 2h are warming up to after being acidified 1h.It adds
Stirring 1h obtains carrier pulp after above-mentioned slurries mixing；
The carrier pulp is used into Niro Bowen Nozzle TowerTMIt is dry that the spray dryer of model carries out spraying
Dry, spray drying pressure is 8.5 to 9.5MPa, and below 500 DEG C of inlet temperature, outlet temperature is about 150 DEG C.By being spray-dried
The first 1h dry at 150 DEG C of microballoon arrived, then roasts 1h at 480 DEG C and obtains carrier；
(2) aqueous solution point for forming the carrier of 8.2kg with the Nickelous nitrate hexahydrate of 8.91kg and the deionization of 1.10kg
It impregnates twice, obtained mixture followed by roasts 1h by 150 DEG C of dry 4h at 480 DEG C, obtains catalyst precarsor；
(3) reduce.By catalyst precarsor in hydrogen atmosphere reductase 12 h at 425 DEG C, obtain desulphurization catalyst A1.
The chemical composition of A1 is：Zinc oxide content is 40.0 weight %, and oxidation lead content is 5.0 weight %, and aluminium oxide contains
It measures as 12.0 weight %, kaolin content is that 18.0 weight %, La-SAPO-11 molecular sieve contents are 7 weight %, and nickel content is
18.0 weight %.
Embodiment 2
The present embodiment is used for the method for preparing desulphurization catalyst for illustrating the present invention.
By the Zinc oxide powder (Beijing Chemical Plant, containing butt 3.8kg) of 3.84kg, the bismuth oxide powder (traditional Chinese medicines of 1.21kg
Chemical reagents corporation, analysis it is pure), the 10 weight %CeO of 0.43kg2Modified SAPO-31 molecular sieves (0.30kg containing butt,
SiO2:Al2O3Molar ratio=0.5:1, be denoted as Ce-SAPO-31) and 7.8kg deionized water mixing, after stirring 30 minutes
To the slurries containing zinc oxide, bismuth oxide and Ce-SAPO-31 molecular sieves；
The zirconium chloride (Beijing Chemical Plant, analysis are pure) of 3.42kg is slowly added into the 5 weight %'s of concentration of 4.65kg
Make pH=2.0 in salpeter solution, and be slowly stirred and crystal of zirconium oxide is avoided to be precipitated, obtain the zirconium colloidal sol of water white transparency；
The rectorite (Qilu Petrochemical catalyst plant, containing butt 1.50kg) of 1.85kg is taken to add in deionized water 1.5kg mixing
After uniformly, adding in the hydrochloric acid stirring of the 30 weight % of 95ml makes pH=2.0, is warming up to 80 DEG C of aging 2h after being acidified 1h, is contained
The mixture of rectorite；It adds above-mentioned slurries and zirconium colloidal sol is mixed together stirring 1h and obtains carrier pulp.
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulphurization catalyst A2.
The chemical composition of A2 is：Zinc oxide content is 38.0 weight %, and oxidation bi content is 12.0 weight %, and zirconium oxide contains
It is 3.0 weight % to measure as 18.0 weight %, Ce-SAPO-31 contents, and rectorite content is 15.0 weight %, nickel content 14.0
Weight %.
Embodiment 3
The present embodiment is used for the method for preparing desulphurization catalyst for illustrating the present invention.
By the Zinc oxide powder (Beijing Chemical Plant, containing butt 5.0kg) of 5.06kg, plumbi nitras (the traditional Chinese medicines chemistry of 1.05kg
Reagent Company, analysis it is pure), the mischmetal (La of 2.5 weight % of 0.6kg2O3With the CeO of 2.5 weight %2) modified SAPO-
34 molecular sieves (catalyst Nanjing branch company, 0.5kg containing butt, SiO2:Al2O3Molar ratio=0.25：1, it is denoted as RE-SAPO-
34) obtained with the mixing of the deionized water of 7.8kg, stirring after 30 minutes containing zinc oxide, lead oxide and RE-SAPO-34 molecular sieves
Slurries；
The diatomite (catalyst Nanjing branch company, containing butt 1.0kg) of 1.03kg is mixed in the deionized water of 4.8kg
It closes, adding in the hydrochloric acid stirring of the 30 weight % of 275ml makes pH=1.5, acidifying 1h obtains that treated diatomite；
Aluminium oxide 2.13kg (Shandong Aluminum Plant, containing butt 1.6kg) and the deionized water of 9.0kg are uniformly mixed under stiring
Afterwards, adding in the concentrated nitric acid stirring of 170g makes pH=2.0 and is warming up to 60 DEG C or more to be acidified 1h.Treat that temperature is reduced to less than 40 DEG C
When, stirring 1h obtains carrier pulp after adding above-mentioned slurries mixing.
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulphurization catalyst A3.
The chemical composition of A3 is：Zinc oxide content is 50.0 weight %, and oxidation lead content is 7.0 weight %, and aluminium oxide contains
It measures as 16.0 weight %, diatomite content is that 10.0 weight %, RE-SAPO-34 molecular sieve contents are 5.0 weight %, nickel content
For 12.0 weight %.
Embodiment 4
The present embodiment is used for the method for preparing desulphurization catalyst for illustrating the present invention.
By the Zinc oxide powder (Beijing Chemical Plant, containing butt 3.8kg) of 3.84kg, 0.90kg antimony oxide powder and
The 5 weight %CeO of 0.43kg2Modified SAPO-5 molecular sieves (0.30kg containing butt, SiO2:Al2O3Molar ratio=0.8:1,
It is denoted as Ce-SAPO-5) it is mixed in the deionized water of 8.3kg, stirring obtains zinc oxide, antimony oxide and Ce-SAPO- after 30 minutes
The slurries of 5 molecular sieves；
The titanium tetrachloride (Beijing Chemical Plant, analysis are pure) of 4.36kg is slowly added into the deionized water of 5.76kg, and
It is slowly stirred and oxidation titanium crystal is avoided to be precipitated, obtain the titanium colloidal sol of pale yellow transparent, pH=1.0；
The rectorite (Qilu Petrochemical catalyst plant, containing butt 1.80kg) of 2.22kg is taken, adds in deionized water 3.0kg mixing
After uniformly, adding in the hydrochloric acid stirring of the 30 weight % of 90ml makes pH=1.5, is warming up to 80 DEG C of aging 2h after being acidified 1h, is contained
The mixture of rectorite；Add above-mentioned slurries and titanium colloidal sol be mixed together after stirring 1h obtain carrier pulp.
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulphurization catalyst A4.
The chemical composition of A4 is：Zinc oxide content be 38.0 weight %, oxidation antimony content be 9.0 weight %, titanium dioxide
Content is 18.0 weight %, and rectorite content is 18.0 weight %, and nickel content contains for 14.0 weight %, Ce-SAPO-5 molecular sieves
It measures as 3.0 weight %.
Comparative example 1
By the Zinc oxide powder of 4.05kg, 1.0kg 15 weight %La-SAPO-11 molecular sieves (0.7kg containing butt,
SiO2:Al2O3Molar ratio=1：1) obtained with the mixing of the deionized water of 6.9kg, stirring after 30 minutes containing zinc oxide and La-
The slurries of SAPO-11 molecular sieves；
The aluminium oxide (Shandong Aluminum Plant, containing butt 1.70kg) and the kaolin of 2.16kg of 2.27kg are mixed under stiring,
Then deionized water 4.0kg is added in after mixing, adding in the hydrochloric acid stirring of the 30 weight % of 400ml makes pH=1.8, is acidified 1h
After be warming up to 80 DEG C of aging 2h.Stirring 1h obtains carrier pulp after adding above-mentioned slurries mixing；
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulphurization catalyst B1.
The chemical composition of B1 is：Zinc oxide content is 40.0 weight %, and alumina content is 17.0 weight %, and kaolin contains
It is 7 weight % to measure as 18.0 weight %, La-SAPO-11 molecular sieve contents, and nickel content is 18.0 weight %.
Comparative example 2
The deionized water of the Zinc oxide powder of 4.05kg, the lead oxide powder of 0.50kg and 6.9kg is mixed, stirs 30 points
The slurries containing zinc oxide and lead oxide are obtained after clock；
The aluminium oxide (Shandong Aluminum Plant, containing butt 1.90kg) and the kaolin of 2.16kg of 2.53kg are mixed under stiring,
Then deionized water 3.6kg is added in after mixing, adding in the hydrochloric acid stirring of the 30 weight % of 450ml makes pH=1.8, is acidified 1h
After be warming up to 80 DEG C of aging 2h.Stirring 1h obtains carrier pulp after adding above-mentioned slurries mixing；
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulphurization catalyst B2.
The chemical composition of B2 is：Zinc oxide content is 40.0 weight %, and oxidation lead content is 5.0 weight %, and aluminium oxide contains
It measures as 19.0 weight %, kaolin content is 18.0 weight %, and nickel content is 18.0 weight %.
Embodiment 5
Abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulphurization catalyst A1-A4 and B1-B2.It is ground using straight tube
Damage method, method reference《Petrochemical Engineering Analysis method (RIPP) experimental method》Middle RIPP29-90, the results are shown in Table 1.What test obtained
Numerical value is smaller, shows that abrasion strength resistance is higher.It is that fine powder generates when wearing under certain condition that abrasion index is corresponding in table 1
Percentage.
In order to more preferably represent activity of the adsorbent during commercial Application, adsorbent after vulcanizing treatment is also carried out
Intensive analysis, specific processing method are：The adsorbent for weighing appropriate mass is positioned in fluid bed, is passed through hydrogen sulfide (50 bodies
Product %) and nitrogen (50 volume %) gaseous mixture, and be heated to 400 DEG C of vulcanizing treatment 1h.It the results are shown in Table 1.
Embodiment 6
Desulfurization performance is evaluated.Desulfurization is carried out to desulphurization catalyst A1-A4 and B1-B2 using the micro- anti-experimental provision of fixed bed to comment
Valency is tested, and the desulphurization catalyst of 16g is seated in the fixed bed reactors that internal diameter is 30mm, a length of 1m.Raw material hydrocarbon ils is sulphur
The catalytically cracked gasoline of concentration 960ppm, reaction pressure 1.38MPa, hydrogen flowing quantity 6.3L/h, gasoline flow 80mL/h,
Reaction temperature is 380 DEG C, and the weight space velocity of raw material hydrocarbon ils is 4h-1, carry out the desulphurization reaction of hydrocarbon oil containing surphur.With sulphur in product gasoline
Content is weighed desulphurizing activated.Sulfur content is by offline chromatogram analysis method in product gasoline, using the GC6890- of An Jielun companies
SCD instruments are measured.In order to which accurate characterization goes out activity of the desulphurization catalyst in industrial actual motion, HDS evaluation has been tested
Catalyst after carries out regeneration treatment under 480 DEG C of air atmosphere.Desulphurization catalyst is subjected to HDS evaluation experiment, regeneration
Its activity settles out substantially after 6 Xun Huans, is urged with the sulfur content representative in the product gasoline after the 6th stable circulation of catalyst
The activity of agent, sulfur content is as shown in table 1 in product gasoline after stablizing.
Simultaneously product gasoline weigh and calculate its yield.
GB/T 503-1995 and GB/T 5487-1995 is respectively adopted to measure before reaction and gasoline after the 6th stable circulation
Motor octane number (MON) and research octane number (RON) (RON), the results are shown in Table 1.
Embodiment 7
Zinc aluminate content measures.By the crystalline phase of desulphurization catalyst A1-A4 and B1-B2 after the 6th Xun Huan in embodiment 6
Composition is analyzed, and measures zinc aluminate content therein.
Crystal phase analysis using X-ray diffraction and phase filtering (R. V. Siriwardane, J. A. Poston,
33 (1994) 2810-2818 of G.Evans, Jr. Ind. Eng. Chem. Res.), the Rietveld models that are corrected
(RIQAS rietveld Analysis, operation manual, Material Data, Inc., Berkley, CA (1999)), point
Different samples are analysed, and the crystalline phase composition of sample is calculated using the method being fitted.Using being equipped with long fine focusing copper X-ray source
Philips XRG3100 generators (40kV, 30mA drive), 3020 digital goniometers of Philips, Philips 3710
MPD control computers and Kevex PSI Peltier cooling silicon detectors carry out all X-ray diffraction measurements.Using
4601 ion pump controllers of Kevex, Kevex4608 Peltier power supplys, Kevex4621 detector bias, Kevex4561A arteries and veins
Rush processor and Kevex4911-A single channel analyzers operation Kevex detectors.It is obtained using 4.1c editions softwares of Philips APD
Obtain diffraction pattern.Use Material Data, 3.1c editions softwares of Inc. Riqas (Outokumpu HSCChemistry for
Windows:User's manual, Outokumpo Resarch Oy, Pori, Finland (1999)) carry out all Rietveld meters
It calculates.The zinc aluminate content of different desulphurization catalysts is as shown in table 1.
Table 1
| A1 | A2 | A3 | A4 | B1 | B2 | |
| ZnAl2O4, weight % | 0 | 0 | 0 | 0 | 7.6 | 5.5 |
| Abrasion index | 3.0 | 3.8 | 3.8 | 3.2 | 7.6 | 5.0 |
| Yield of gasoline, % | 99.8 | 99.9 | 99.7 | 99.8 | 98.4 | 98.8 |
| Product sulfur content, ppm | 6 | 9 | 10 | 7 | 15 | 35 |
| △RON | 0.65 | 0.45 | 0.48 | 0.52 | -0.32 | -0.63 |
| △MON | 0.60 | 0.42 | 0.44 | 0.50 | -0.31 | -0.55 |
| △(RON+MON)/2 | 0.63 | 0.43 | 0.46 | 0.51 | -0.31 | -0.59 |
Note：
1st, the sulfur content of feed gasoline is 960ppm, RON 93.7, MON 83.6.
2nd, △ MON represent the value added of product MON；
3rd, △ RON represent the value added of product RON；
4th, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
Desulphurization catalyst provided by the invention is can be seen that with preferably desulphurizing activated and living from the result data of table 1
Property stability.Desulphurization catalyst has better abrasion strength resistance, so that desulphurization catalyst has longer service life.
Claims (15)
1. a kind of desulphurization catalyst, on the basis of the total weight of the desulphurization catalyst, which contains：
1) aluminium oxide of 5-30 weight %；
2) kaolin of 5-30 weight %；
3) the first metal oxide of 10-70 weight %, first metal oxide in IIB, VB and group vib metal extremely
A kind of few oxide；
4) lead oxide of 2-20 weight %；
5) metallic promoter agent of 5-30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese；
6) the rare earth modified phosphate aluminium molecular sieve of 1-20 weight %.
2. desulphurization catalyst according to claim 1, wherein, on the basis of the total weight of the desulphurization catalyst, aluminium oxide
Content for 10-20 weight %, kaolinic content is 10-20 weight %, and the content of first metal oxide is 35-54
Weight %, the content of lead oxide is 5-15 weight %, and the content of the metallic promoter agent is 10-20 weight %, and the rare earth changes
Property phosphate aluminium molecular sieve content be 2-20 weight %.
3. desulphurization catalyst according to claim 1, wherein, the rare earth modified phosphate aluminium molecular sieve is aluminate or phosphate,
At least one of silicoaluminophosphate and silicoaluminophosphate that metalloaluminophosphate, metal combine.
4. according to the desulphurization catalyst described in any one in claim 1-3, wherein, with the rare earth modified phosphorus aluminium molecule
On the basis of the total weight of sieve, the rare earth modified phosphate aluminium molecular sieve contains rare earths of the 5-15 weight % in terms of rare earth oxide.
5. desulphurization catalyst according to claim 1, wherein, first metal oxide is zinc oxide, cadmium oxide, oxygen
Change at least one of vanadium, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide.
6. the preparation method of the desulphurization catalyst in claim 1-5 described in any one, this method include：
(1) rare earth modified phosphate aluminium molecular sieve, the first metal oxide, the precursor of lead oxide and water are mixed to get slurries；
(2) alumina binder, kaolin, water with acidic liquid are mixed, and carrier pulp is formed with the slurry liquid contacts, then
The carrier pulp is molded, first drying and first roasting, obtain carrier；
(3) precursor of metallic promoter agent is introduced on the carrier, and carries out the second drying and the second roasting, before obtaining catalyst
Body；
(4) catalyst precarsor under hydrogen atmosphere is reduced, obtains desulphurization catalyst.
7. according to the method described in claim 6, wherein, the precursor of the lead oxide is lead oxide or the carbonic acid of metallic lead
At least one of salt, nitrate, chloride and hydroxide.
8. according to the method described in claim 6, wherein, the alumina binder is for aluminium oxide or in the described first roasting
Under conditions of can be changed into the substance of aluminium oxide.
9. according to the method described in claim 6, wherein, the precursor of the metallic promoter agent for metallic promoter agent acetate,
At least one of carbonate, nitrate, sulfate, rhodanate and oxide.
10. according to the method described in claim 6, wherein, the method that the precursor of the metallic promoter agent is introduced on carrier is
Dipping or precipitation.
11. according to the method described in claim 6, wherein, the temperature of first drying is 80-120 DEG C, and described first dries
Time be 0.5-24h；The temperature of first roasting is 300-700 DEG C, and the time of first roasting is at least 0.5h.
12. according to the method described in claim 6, wherein, the temperature of second drying is 50-300 DEG C, and described second dries
Time be 0.5-8h；The temperature of second roasting is 300-700 DEG C, and the time of second roasting is 0.5-4h.
13. according to the method described in claim 6, wherein, the temperature of the reduction is 300-600 DEG C, the time of the reduction
For 0.5-6h, hydrogen content is 10-60 volumes % in the hydrogen atmosphere.
14. desulphurization catalyst made from the preparation method in claim 6-13 described in any one.
15. a kind of method of desulfurization of hydrocarbon oil, this method include：In a hydrogen atmosphere, by hydrocarbon oil containing surphur and claim 1-5 and 14
Hydrodesulfurization catalyst described in middle any one, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5-
4MPa。
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| CN1974726A (en) * | 2005-11-29 | 2007-06-06 | 触媒化成工业株式会社 | Desulfuration catalyst for catalytic cracking of petrol and method therefor |
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| CN1974726A (en) * | 2005-11-29 | 2007-06-06 | 触媒化成工业株式会社 | Desulfuration catalyst for catalytic cracking of petrol and method therefor |
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