CN105498830B - 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
Originally the invention discloses the method for a kind of desulphurization catalyst and preparation method thereof He desulfurization of hydrocarbon oil.On the basis of the gross weight of the desulphurization catalyst, which contains：1) heat-resistant inorganic oxide of 5 35 weight %；2) silica source of 5 35 weight %；3) the first metal oxide of 10 70 weight %；4) the second metal oxide of 2 20 weight %；5) metallic promoter agent of 3 30 weight %；6) rare-earth oxide of the 0.5 10 weight % in terms of rare earth oxide；7) molecular sieve with BEA or FAU structures of 1 20 weight %.The desulphurization catalyst has more preferable desulphurizing activated and activity stability.
Description
Technical field
The present invention relates to the method for a kind of desulphurization catalyst and preparation method thereof He desulfurization of hydrocarbon oil, and in particular, to a kind of
Desulphurization catalyst, the desulphurization catalyst for preparing the method for desulphurization catalyst and being obtained by this method, and use the desulfurization catalyst
The method that agent carries out desulfurization of hydrocarbon oil.
Background technology
The oxysulfide produced after combustion of sulfur in vehicle fuel, can suppress 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 stringenter.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, make it 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 the purity requirement to hydrogen is not high so that 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
Obvious 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 thing.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
Thing, is made of zinc oxide, silica, oxidation al and ni, and for wherein nickel substantially to reduce valence state presence, its 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
Cross and be 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
Thing 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
Thing, is made of zinc oxide, silica, aluminium oxide and cobalt, and for wherein cobalt substantially to reduce valence state presence, its 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
The adsorbing agent carrier of aluminium, then reduces the accelerating agent at appropriate temperatures, prepares the suction for being used for removing 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 thing, the adsorbent composition include：Zinc oxide, expanded perlite, aluminate and promoter metals, its
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 be formed through dry mixing
Thing；C) this is calcined through dry mixture, 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 reorganization compound.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,
Mixed containing earth silicon material, aluminium oxide to form its mixture；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
Contacted from the acid of citric acid, tartaric acid and combinations thereof to be formed through contact mixture；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 the composition of agent content, 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 there is preferable desulfurization performance, there is also it is obvious the shortcomings that.Above-mentioned suction
Attached dose uses zinc oxide active component, and it is higher to aoxidize the temperature of zinc-iron alloy solution sulphur and oxidation regeneration, in desulphurization reaction and
Easily adsorbent activity is caused to reduce with the silicon in carrier, aluminium component generation zinc silicate and/or zinc aluminate 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, there is provided the method for 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 gross weight of the desulphurization catalyst as base
Standard, the desulphurization catalyst contain：1) heat-resistant inorganic oxide of 5-35 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 5-35 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 3-30 weight %, the metallic promoter agent is in cobalt, nickel, iron and manganese
It is at least one；6) rare-earth oxide of the 0.5-10 weight % in terms of rare earth oxide；7) molecular sieve of 1-20 weight %,
The molecular sieve is the molecular sieve with BEA and/or FAU structures.
Present invention also offers the preparation method of the desulphurization catalyst of the present invention, this method includes：(1) by rare earth metal
Compound, the first metal oxide, the precursor of the second metal oxide and water are mixed to get slurries；(2) heat resistant inorganic is aoxidized
Thing binding agent, silica source, water are mixed with acidic liquid, and form carrier pulp with the slurry liquid contacts, then by the carrier
Slurries, the molecular sieve with BEA and/or FAU structures are molded, the first drying and first roasts, and obtain carrier；(3) to institute
The precursor that metallic promoter agent is introduced on carrier is stated, and carries out the second drying and the second roasting, obtains catalyst precarsor；(4) by institute
State catalyst precarsor to reduce under hydrogen atmosphere, obtain desulphurization catalyst.
The present invention also provides the desulphurization catalyst 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.
Mixed in desulphurization catalyst provided by the invention containing the first metal oxide with the second metal oxide and be used as sulphur
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 more preferable desulphurizing activated and activity stability.
Contain rare earth oxide in desulphurization catalyst provided by the invention, can effectively further strengthen the second metal oxygen
Compound is to the first metal oxide and silicon, the decrease effect of aluminium component phase separation.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The 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 gross weight of the desulphurization catalyst, which contains
Have：1) heat-resistant inorganic oxide of 5-35 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 5-35 weight %；3) the first metal oxidation of 10-70 weight %
Thing, 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 3-30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese；6) with rare earth
The rare-earth oxide of the 0.5-10 weight % of oxide meter；7) molecular sieve of 1-20 weight %, the molecular sieve be with
The molecular sieve of BEA and/or FAU structures.
Preferably, on the basis of the gross 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 for stating the second metal oxide is 5-15 weight %, and the content of the metallic promoter agent is 10-20 weight %, the rare earth
For metal oxide using the content that rare earth oxide is counted as 1-5 weight %, the content of the molecular sieve is 2-10 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 suppress 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.
According to the present invention, the rare-earth oxide can strengthen with the interaction between the second metal oxide
Second metal oxide can stablize the skeleton of heat-resistant inorganic oxide to improving the effect of catalyst abrasion intensity, into
One step weakens the interaction between the first metal oxide and silicon, aluminium component, improves the activity and stability of desulfurization.It is preferred that
Ground, the rare-earth oxide are at least one of oxide of lanthanum, cerium and neodymium.
In the present invention, the FAU structure molecular screens are faujasite-type molecular sieve.The type molecular sieve has three-dimensional 12
Membered ring channel, aperture areFAU structure molecular screens are mainly the molecular sieve of X-type and Y types, in general SiO2/
Al2O3Molar ratio is 2.2-3 for X-type molecular sieve, SiO2/Al2O3Molar ratio is Y type molecular sieve more than 3.X-type and Y type molecules
The skeleton structure of sieve belongs to hexagonal crystal system, and space group structure is Fd3m, the cell parameter of X-type molecular sieveThe cell parameter of Y type molecular sieve
In the present invention, the molecular sieve with FAU structures further includes this modified molecular sieve analog.Modified method can wrap
Include hydro-thermal method, method of chemical treatment (such as mineral acid logos, fluosilicic acid aluminium-eliminating and silicon-replenishing method and SiC14Vapor phase method) or hydro-thermal and change
Processing is combined, and the modified molecular sieve that obtains includes but not limited to super-stable Y molecular sieves (USY), contains rare earth element
REUSY, REHY, REY, and phosphorous PUSY, PREHY, PREY etc..Rare earth can be carbonate, the bicarbonate of rare earth metal
At least one of salt, nitrate, chloride, formates and acetate；Preferably, the rare earth compound can be dilute
At least one of carbonate, bicarbonate, formates and acetate of earth metal.Wherein, the rare earth metal be preferably lanthanum,
At least one of cerium and neodymium.The SiO of the molecular sieve with FAU structures2：Al2O3Molar ratio be 2.6-10：1；It is preferred that
Ground, the SiO of the molecular sieve with FAU structures2：Al2O3Molar ratio be 2.8-9：1.
In the present invention, BEA structure molecular screens are mainly beta-molecular sieve, its structural formula is (Nan[AlnSi64-nO128], n<7),
It is two structures differences but the mixed crystal of the polymorph A and B that are closely related, both with twelve-ring 3 D pore canal system：
Polymorph A forms a pair of of enantiomer, space group P4122 and P4322, cell parameter isMultiform
Body B belongs to achirality space group C2/c, cell parameterβ=114.5 °.BEA
Twelve-ring pore size is in structure molecular screen<100 directions>With <001 direction>.
The SiO of the molecular sieve with BEA structures2：Al2O3Molar ratio be 10-50：1；Preferably, it is described with BEA structures
The SiO of molecular sieve2：Al2O3Molar ratio be 15-30：1.
In the case of, according to the invention it is preferred to, the molecular sieve with FAU and/or BEA structures is X-type molecular sieve, Y types
At least one of molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta-molecular sieve.
In the present invention, the work of gasoline products octane number can be improved by adding the molecular sieve with FAU and/or BEA structures
With or effect.
Present invention also offers the preparation method of the desulphurization catalyst of the present invention, this method includes：(1) by rare earth metal
Compound, the first metal oxide, the precursor of the second metal oxide and water are mixed to get slurries；(2) heat resistant inorganic is aoxidized
Thing binding agent, silica source, water are mixed with acidic liquid, and are connect with the slurries, the molecular sieve with FAU and/or BEA structures
Touch form carrier pulp, then the carrier pulp is molded, first drying and first roasting, obtain carrier；(3) to described
The precursor of metallic promoter agent is introduced on carrier, and carries out the second drying and the second roasting, obtains catalyst precarsor；(4) by described in
Catalyst precarsor reduces under hydrogen 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 material of heat-resistant inorganic oxide can be changed under conditions of the described first roasting.Preferably, the heat resistant inorganic oxidation
Thing 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, but in the present invention aluminium oxide content
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 obtained desulphurization catalyst.
In the present invention, the precursor of second metal oxide is for second metal oxide or described first
The material 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 material 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.
In the present invention, under preferable case, the rare earth compound can be carbonate, the bicarbonate of rare earth metal
At least one of salt, nitrate, chloride, formates and acetate；Preferably, the rare earth compound can be dilute
At least one of carbonate, bicarbonate, formates and acetate of earth metal.Wherein, the rare earth metal be preferably lanthanum,
At least one of cerium and neodymium.
In the present invention, first metal oxide, metallic promoter agent and with FAU and/or BEA structures molecular sieve such as
Upper described, details are not described herein.
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, lead oxide, antimony oxide and oxygen can be directly added into
Change the powder of at least one of bismuth, or add and be changed into second metal oxide under conditions of the described first roasting
Material, such as one kind in the carbonate of metallic lead, antimony and bismuth, nitrate, chloride and hydroxide；It will can also aoxidize
At least one of lead, antimony oxide and bismuth oxide are prepared as using as a slurry again after slurries.
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, in the present invention, the silica source and the throwing of the heat-resistant inorganic oxide binding agent
Material weight ratio is 0.4-2：1, it is preferably 0.6-1.5：1.It is possible thereby between the more preferable each component of the desulphurization catalyst is provided
Caking property.
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 the slurries；Wherein, when described resistance to
When hot inorganic oxide binder is non-al binder, obtained mixture is colloidal sol.In addition, work as 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, pill, 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 preferably 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 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 be 300-700 DEG C, the time of first roasting is when being at least 0.5 small.Preferably, the temperature of first roasting is
400-500 DEG C, when the time of first roasting is 0.5-100 small, the time of more preferably described first roasting is small for 0.5-10
When.
According to the present invention, step (3) is used to add metallic promoter agent.The precursor of the metallic promoter agent is can be second
It is changed into the material 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 or suspension impregnation carrier with the precursor of metallic promoter agent；The precipitation can be to promote metal
Solution or suspension into the precursor of agent are mixed with carrier, then add 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
Simple substance, the catalyst precarsor can be reduced, metallic promoter agent is substantially deposited with reduction-state under hydrogen atmosphere
Obtaining catalyst of the present invention.The condition of the reduction only turns the oxide of the metallic promoter agent in the catalyst precarsor
It is changed into 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 for stating reduction is 350-450 DEG C, and 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
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 catalyst precarsor is reduced and is carrying out desulfurization absorption for ease of transport, 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 compound, the molecular sieve and gold with FAU and/or BEA structures
Belong to the addition of the precursor of accelerating agent so that in obtained desulphurization catalyst, on the basis of the gross weight of the desulphurization catalyst, contain
There are the first metal oxidation of the heat-resistant inorganic oxide of 5-35 weight %, the silica source of 5-35 weight %, 10-70 weight %
Thing, the second metal oxide of 2-20 weight %, the metallic promoter agent of 3-30 weight % and the 0.5-10 in terms of rare earth oxide
The rare-earth oxide of weight %, the molecular sieve with FAU and/or BEA structures of 1-20 weight %.
Preferably, on the basis of the gross 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 for stating the second metal oxide is 5-15 weight %, and the content of the metallic promoter agent is 10-20 weight %, the rare earth
Using the content that rare earth oxide is counted as 1-5 weight %, the molecular sieve with FAU and/or BEA structures contains metal oxide
Measure as 2-10 weight %.
The present invention also provides the desulphurization catalyst that method provided by the present invention is prepared.The composition of the desulphurization catalyst
As it was previously stated, 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
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 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 cut 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 cut 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
Thing.
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 zinc oxide (traditional Chinese medicines chemical reagents corporation, analysis are pure), the lead oxide of 1.45kg of 3.14kg
(traditional Chinese medicines chemical reagents corporation, analysis are pure) and the lanthanum carbonate (traditional Chinese medicines chemical reagents corporation, 45 weight % of lanthanum oxide content) of 430g
It is mixed evenly in the water of 8.5kg, obtains the slurries containing zinc oxide, lead oxide and lanthana；
The boehmite of the kaolin (catalyst asphalt in Shenli Refinery, containing butt 1.8kg) of 2.16kg, 1.33kg (are urged
Agent Nanjing branch company, containing butt 1.00kg) and the deionized water of 7.0kg be uniformly mixed under agitation, add the dense nitre of 200g
Stirring makes pH=1.8 to acid (Beijing Chemical Plant, chemistry are pure), and is warming up to more than 60 DEG C and is acidified 1h.Treat temperature be reduced to 40 DEG C with
When lower, beta-molecular sieve (catalyst Nanjing branch company, the 0.70kg containing butt, SiO of above-mentioned mixed serum and 1.0kg are added2:
Al2O3Molar ratio=20：1) carrier pulp is obtained after, stirring 1h after 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 8.94kg and the deionization of 1.10kg
Impregnate 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 31.0 weight %, and oxidation lead content is 14.0 weight %, and aluminium oxide contains
It is 18.0 weight % to measure as 10.0 weight %, kaolin content, and beta-molecular sieve content is 7 weight %, and nickel content is 18.0 weights
% is measured, lanthanum oxide content is 2.0 weight %.
Embodiment 2
The present embodiment is used for the method for preparing desulphurization catalyst for illustrating the present invention.
By Zinc oxide powder (Beijing Chemical Plant produces, containing butt 4.0kg), the bismuth oxide powder of 0.90kg of 4.05kg
(traditional Chinese medicines chemical reagents corporation, purity are more than 99.0 weights for (traditional Chinese medicines chemical reagents corporation, analysis are pure) and the cerous nitrate of 0.794kg
Amount %) mixed in the deionized water of 7.1kg, stirring obtains the slurries containing zinc oxide, bismuth oxide and cerous nitrate after 30 minutes；
The zirconium chloride (Beijing Chemical Plant, analysis are pure) of 3.23kg is slowly added into the nitre of the 5 weight % of concentration of 4.4kg
Make pH=2.0 in acid solution, and be slowly stirred and avoid crystal of zirconium oxide from separating out, obtain the zirconium colloidal sol of water white transparency；
The rectorite (Qilu Petrochemical catalyst plant, containing butt 1.30kg) of 1.63kg is taken to add deionized water 1.3kg mixing
After uniformly, adding the hydrochloric acid stirring of the 30 weight % of 80ml makes pH=1.8, is warming up to 80 DEG C of aging 2h after being acidified 1h, is contained
The mixture of rectorite；Add beta-molecular sieve (the catalyst Nanjing branch company, containing butt of above-mentioned slurries, zirconium colloidal sol and 0.43kg
0.3kg, SiO2:Al2O3Molar ratio=40：1) it 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 40.0 weight %, and oxidation bi content is 9.0 weight %, zirconium dioxide
Content is 17.0 weight %, and rectorite content is 13.0 weight %, and beta-molecular sieve content is 3.0 weight %, and nickel content is 15.0 weights
% is measured, cerium-oxide contents are 3.0 weight %.
Embodiment 3
The present embodiment is used for the method for preparing desulphurization catalyst for illustrating the present invention.
By the lanthana of the Zinc oxide powder of 4.86kg, the lead oxide of 0.6kg and 400g, (traditional Chinese medicines chemical reagents corporation, divides
Analyse pure) mixed in the deionized water of 5kg, stirring obtains the slurries containing zinc oxide, lead oxide and lanthana after 30 minutes；
The diatomite of 1.03kg (catalyst Nanjing branch company, 1.00kg containing butt) is uniformly mixed in the water of 3.0kg
Afterwards, adding the concentrated nitric acid stirring of 170g makes pH=2.0, and is warming up to the diatomite after more than 60 DEG C acidifying 1h are handled；
The hydrated alumina (catalyst Nanjing branch company, containing butt 1.5kg) and the deionized water of 8.5kg of 2.0kg are existed
Under stirring after mixing, adding the concentrated nitric acid stirring of 160g makes pH=1.8 and is warming up to more than 60 DEG C to be acidified 1h.Treat that temperature drops
It is low to less than 40 DEG C when, add the diatomite after above-mentioned slurries, processing and USY molecular sieve (catalyst Nanjing point public affairs of 0.6kg
Department, 0.5kg containing butt, SiO2:Al2O3Molar ratio=8.5：1) mix, carrier pulp is obtained after stirring 1h.
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 48.0 weight %, and oxidation lead content is 6.0 weight %, and aluminium oxide contains
It is 10.0 weight % to measure as 15.0 weight %, diatomite content, and USY molecular sieve content is 5.0 weight %, and nickel content is 12.0 weights
Measure %.Lanthanum oxide content is 4.0 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 lanthanum nitrate (traditional Chinese medicines chemical reagents corporation, lanthanum oxide content are more than 44.0 weight %) of 0.682kg is in the deionized water of 8.3kg
Mixing, stirring obtain the slurries of zinc oxide, antimony oxide and lanthanum nitrate after 30 minutes；
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 avoids oxidation titanium crystal from separating out, obtains the titanium colloidal sol of pale yellow transparent, pH=1.0；
The rectorite (Qilu Petrochemical catalyst plant, containing butt 1.50kg) of 1.85kg is taken, adds deionized water 2.5kg mixing
After uniformly, adding the hydrochloric acid stirring of the 30 weight % of 75ml makes pH=1.8, is warming up to 80 DEG C of aging 2h after being acidified 1h, is contained
The mixture of rectorite；Add above-mentioned slurries, titanium colloidal sol and 0.4kg REHY molecular sieves (Qilu Petrochemical Company's catalyst plant,
0.3kg containing butt, SiO2:Al2O3Molar ratio=7.2:1) 1h is stirred after being mixed together 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 A4.
The chemical composition of A4 is：Zinc oxide content is 38.0 weight %, and oxidation antimony content is 9.0 weight %, titanium dioxide
Content is 18.0 weight %, and rectorite content is 15.0 weight %, and nickel content is 14.0 weight %, and lanthanum oxide content is 3.0 weights
% is measured, REHY molecular sieve contents are 3.0 weight %.
Comparative example 1
The lanthanum carbonate of the zinc oxide of 3.14kg and 430g are mixed evenly in the water of 8.5kg, obtained containing oxidation
The slurries of zinc and lanthana；
The boehmite of the kaolin (catalyst asphalt in Shenli Refinery, containing butt 1.8kg) of 2.16kg, 3.19kg (are urged
Agent Nanjing branch company, containing butt 2.4kg) and the deionized water of 15.0kg be uniformly mixed under agitation, add the dense nitre of 500g
Acid stirring makes pH=1.8, and is warming up to more than 60 DEG C and is acidified 1h.When temperature is reduced to below 40 DEG C, above-mentioned mixing slurry is added
The beta-molecular sieve of liquid and 1.0kg (catalyst Nanjing branch company, 0.70kg containing butt, SiO2：Al2O3Molar ratio=20：1),
Carrier pulp is obtained after stirring 1h after 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 31.0 weight %, and alumina content is 24.0 weight %, and kaolin contains
It is 7 weight % to measure as 18.0 weight %, beta-molecular sieve content, and nickel content is 18.0 weight %, and lanthanum oxide content is 2.0 weight %.
Comparative example 2
The lead oxide of the zinc oxide of 3.14kg and 1.45kg are mixed evenly in the water of 8.5kg, obtained containing aerobic
Change the slurries of zinc and lead oxide；
The boehmite of the kaolin (catalyst asphalt in Shenli Refinery, containing butt 1.8kg) of 2.16kg, 1.60kg (are urged
Agent Nanjing branch company, containing butt 1.20kg) and the deionized water of 7.5kg be uniformly mixed under agitation, add the dense nitre of 250g
Acid stirring makes pH=1.8, and is warming up to more than 60 DEG C and is acidified 1h.When temperature is reduced to below 40 DEG C, above-mentioned mixing slurry is added
The beta-molecular sieve of liquid and 1.0kg (catalyst Nanjing branch company, 0.70kg containing butt, SiO2：Al2O3Molar ratio=20：1),
Carrier pulp is obtained after stirring 1h after 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 31.0 weight %, and oxidation lead content is 14.0 weight %, and aluminium oxide contains
It is 18.0 weight % to measure as 12.0 weight %, kaolin content, and the content of beta-molecular sieve is 7 weight %, and nickel content is 18.0 weights
Measure %.
Comparative example 3
The lanthanum carbonate of the zinc oxide of 3.14kg, the lead oxide of 1.45kg and 430g is mixed in the water of 8.5kg
It is even, obtain the slurries containing zinc oxide, lead oxide and lanthana；
The boehmite of the kaolin (catalyst asphalt in Shenli Refinery, containing butt 1.8kg) of 2.16kg, 2.26kg (are urged
Agent Nanjing branch company, containing butt 1.70kg) and the deionized water of 10.0kg be uniformly mixed under agitation, add the dense nitre of 340g
Acid stirring makes pH=1.8, and is warming up to more than 60 DEG C and is acidified 1h.When temperature is reduced to below 40 DEG C, above-mentioned mixing slurry is added
Liquid, carrier pulp is obtained after stirring 1h after 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 B3.
The chemical composition of B3 is：Zinc oxide content is 31.0 weight %, and oxidation lead content is 14.0 weight %, and aluminium oxide contains
It is 18.0 weight % to measure as 17.0 weight %, kaolin content, and nickel content is 18.0 weight %, and lanthanum oxide content is 2.0 weights
Measure %.
Embodiment 5
Abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulphurization catalyst A1-A4 and B1-B3.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-B3 using the micro- anti-experimental provision of fixed bed to comment
Valency is tested, and 16 grams of desulphurization catalyst 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 circulations, is represented and urged with the sulfur content 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.
At the same time 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-B3 after the 6th circulation 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, G.Evans,
Jr.Ind.Eng.Chem.Res.33 (1994) 2810-2818), Rietveld models (the RIQAS rietveld that are corrected
Analysis, operation manual, Material Data, Inc., Berkley, CA (1999)), different samples are analyzed, and using plan
The method of conjunction calculates the crystalline phase composition of sample.Sent out using the Philips XRG3100 for being equipped with long fine focusing copper X-ray source
Raw device (40kV, 30mA drive), 3020 digital goniometers of Philips, Philips 3710MPD control computers and Kevex
PSI Peltier cooling silicon detectors carry out all X-ray diffraction measurements.Using 4601 ion pump controllers of Kevex,
Kevex4608Peltier power supplys, Kevex4621 detector bias, Kevex4561A pulse processors and Kevex4911-A are mono-
Channel analyser operates Kevex detectors.Diffraction pattern is obtained using 4.1c editions softwares of Philips APD.Use Material
3.1c editions softwares of Data, Inc.Riqas (Outokumpu HSC Chemistry for Windows:User's manual,
Outokumpo Resarch Oy, Pori, Finland (1999)) carry out all Rietveld and calculate.Different desulphurization catalysts
Zinc aluminate content is as shown in table 1.
Table 1
| A1 | A2 | A3 | A4 | B1 | B2 | B3 | |
| ZnAl2O4, weight % | 0 | 0 | 0 | 0 | 4.8 | 3.5 | 5.5 |
| Abrasion index | 3.0 | 3.8 | 3.8 | 3.2 | 7.8 | 7.0 | 5.0 |
| Yield of gasoline, % | 99.8 | 99.9 | 99.8 | 99.9 | 98.3 | 98.1 | 98.8 |
| Product sulfur content, ppm | 6 | 9 | 10 | 5 | 27 | 30 | 35 |
| △RON | 0.61 | 0.36 | 0.42 | 0.53 | -0.48 | -0.57 | -0.63 |
| △MON | 0.57 | 0.34 | 0.40 | 0.48 | -0.48 | -0.49 | -0.55 |
| △(RON+MON)/2 | 0.59 | 0.35 | 0.41 | 0.50 | -0.48 | -0.53 | -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 more preferable abrasion strength resistance, so that desulphurization catalyst has longer service life.
Claims (17)
1. a kind of desulphurization catalyst, on the basis of the gross weight of the desulphurization catalyst, which contains：
1) heat-resistant inorganic oxide of 5-35 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 5-35 weight %；
3) zinc oxide of 10-70 weight %；
4) the second metal oxide of 2-20 weight %, second metal oxide are selected from lead oxide, antimony oxide and bismuth oxide
At least one of；
5) metallic promoter agent of 3-30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese；
6) rare-earth oxide of the 0.5-10 weight % in terms of rare earth oxide；
7) molecular sieve of 1-20 weight %, the molecular sieve are the molecular sieve with BEA and/or FAU structures.
2. desulphurization catalyst according to claim 1, wherein, it is described resistance on the basis of the gross weight of the desulphurization catalyst
The content of hot inorganic oxide is 10-25 weight %, and the content of the silica source is 10-25 weight %, the content of zinc oxide
For 35-54 weight %, the content of second metal oxide is 5-15 weight %, and the content of the metallic promoter agent is 10-
20 weight %, the rare-earth oxide are by 1-5 weight %, the content of the molecular sieve of the content that rare earth oxide is counted
2-10 weight %.
3. desulphurization catalyst according to claim 1 or 2, wherein, the rare-earth oxide is the oxygen of lanthanum, cerium and neodymium
At least one of compound.
4. desulphurization catalyst according to claim 1 or 2, wherein, the silica source be selected from laminated clay column, diatomite,
At least one of expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
5. desulphurization catalyst according to claim 1 or 2, wherein, the molecular sieve is X-type molecular sieve, Y type molecular sieve,
At least one of USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta-molecular sieve.
6. the preparation method of the desulphurization catalyst in claim 1-5 described in any one, this method include：
(1) rare earth compound, zinc oxide, the precursor of the second metal oxide and water are mixed to get slurries；
(2) heat-resistant inorganic oxide binding agent, silica source, water are mixed with acidic liquid, and with the slurries, there is BEA
And/or the molecular sieve of FAU structures contacts to form carrier pulp, then the carrier pulp is molded, the first drying and first
Roasting, obtains carrier；
(3) to the precursor of introducing metallic promoter agent on the carrier, and the second drying and the second roasting are carried out, before obtaining catalyst
Body；
(4) catalyst precarsor is reduced under hydrogen atmosphere, obtains desulphurization catalyst.
7. preparation method according to claim 6, wherein, the precursor of second metal oxide is lead oxide, oxygen
Change at least one of antimony and bismuth oxide；Or in metallic lead, the carbonate of antimony and bismuth, nitrate, chloride and hydroxide
At least one.
8. preparation method according to claim 6, wherein, the heat-resistant inorganic oxide binding agent aoxidizes for heat resistant inorganic
Thing or the material that heat-resistant inorganic oxide can be changed under conditions of the described first roasting.
9. preparation method according to claim 6, wherein, the rare earth compound for rare earth metal carbonate,
At least one of bicarbonate, nitrate, chloride, formates and acetate.
10. preparation method according to claim 6, wherein, the precursor of the metallic promoter agent is the vinegar of metallic promoter agent
At least one of hydrochlorate, carbonate, nitrate, sulfate, rhodanate and oxide.
11. preparation method according to claim 6, wherein, the side of the precursor of the metallic promoter agent is introduced on carrier
Method is dipping or precipitation.
12. preparation method according to claim 6, wherein, the acidic liquid is acid or the aqueous solution of acid, and the acid selects
From water-soluble inorganic acid and/or organic acid.
13. preparation method according to claim 6, wherein, the temperature of first drying is 80-120 DEG C, described first
The dry time is 0.5-24h；The temperature of first roasting is 300-700 DEG C, and the time of first roasting is at least
0.5h。
14. preparation method according to claim 6, wherein, the temperature of second drying is 50-300 DEG C, described second
The dry time is 0.5-8h；The temperature of second roasting is 300-700 DEG C, and the time of second roasting is 0.5-4h.
15. preparation method according to claim 6, wherein, the temperature of the reduction is 300-600 DEG C, the reduction
Time is 0.5-6h, and hydrogen content is 10-60 volumes % in the hydrogen atmosphere.
16. desulphurization catalyst made from the preparation method in claim 6-15 described in any one.
17. 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 16
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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| CN101492608A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Method for deep desulfurization olefin hydrocarbon reduction of inferior gasoline |
| JP2013508527A (en) * | 2009-10-30 | 2013-03-07 | コリア エレクトリック パワー コーポレイション | Zinc-based desulfurization agent molded by spray drying method and method for producing the same |
| CN102895940A (en) * | 2011-07-28 | 2013-01-30 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof |
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