CN105582940B - 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 and desulfurization of hydrocarbon oil.On the basis of the total 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.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 and 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 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.To make to contain the oxygen of unburned non-methane hydrocarbon and nitrogen in vehicle exhaust
Compound and carbon monoxide, and these discharge gas are then easy to form photochemical fog by hydrophilic dye, cause acid rain, while in air
Oxysulfide itself be also one of the main reason for forming acid rain.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 improving one of the most important measure of 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 just, can meet the requirement of environmental protection.
Currently, 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, makes the cost of hydrofinishing 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 removing gasoline has hydrogen
Low feature is consumed, and not high to the purity requirement of hydrogen 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
Apparent disadvantage.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, it finds wear-resisting property well while to have the adsorbent of preferable desulfurization performance to have 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 restore valence state presence, amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted with the nickeliferous adsorbent composition under the conditions of sulphur.The composition is logical
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 restore valence state presence, amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted with the adsorbent composition containing cobalt under the conditions of sulphur.CN1355727A
Be all only referred in CN1382071A it is desulphurizing activated, all for adsorbent physical and chemical performance (such as abrasion strength resistance) and stability
Do not introduce.
Adsorbent disclosed in US6150300, CN1130253A and CN1258396A is：Including zinc oxide, silica, oxidation
The granular adsorbent composition of the mixture of aluminium, reduction valence state nickel or cobalt.Preparation method mainly will using the methods of shearing
Silica, aluminium oxide and zinc oxide mix merga pass comminutor and prepare solid particle, and dipping nickel is to be made after drying and roasting
Adsorbent.Although there is the adsorbent of these patent introductions preferable desulfurization performance its physical and chemical performance is mainly worn
Intensity is not described in the patent.
It includes zinc oxide, expanded perlite and oxidation that CN1208124A, which is disclosed using promoter metals such as cobalt and nickel dipping,
Then the adsorbing agent carrier of aluminium restores the accelerating agent at appropriate temperatures, prepare the suction for removing sulfide in cracking gasoline
Attached dose.
CN1627988A discloses one kind suitable for the removing elementary sulfur from cracking gasoline and diesel fuel and vulcanization conjunction
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 be contacted 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 producing composition, including：A) mixing liquid, zinc compound, contain 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) under suitable condition with reducing agent appropriate
By mixture reduction through calcining, to produce the composition and e) of the co-catalyst content in it with reduction valence state
Recycling changes composition.Co-catalyst contains selected from various metals such as nickel.
CN1871063A discloses a kind of method producing composition, and this method includes：A) by liquid, zinc compound,
It is 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 through drying composite to form first through calcining mixt；D) by accelerating agent knot
Close described first through within calcining mixt or on to form promoted mixture；E) make the promoted mixture and choosing
It is 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 dry with
Second is formed through drying composite；G) described second is calcined through drying composite to form second through calcining mixt；H) exist
Suitable reducing agent reduction described second is used wherein to contain reduction valence state rush through calcining mixt to produce under the conditions of appropriate
Into agent content composition and i) recycle the composition.
CN101816918A discloses a kind of desulfuration adsorbent, which becomes 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 adsorbent prepared by these methods has preferable desulfurization performance, there is also apparent disadvantages.Above-mentioned suction
Attached dose is all made of zinc oxide active component, and the temperature for aoxidizing zinc-iron alloy solution sulphur and oxidation regeneration is relatively high, in desulphurization reaction and
It is easy to generate zinc silicate and/or zinc aluminate with the silicon in carrier, aluminium component when oxidation regeneration, adsorbent activity is caused to reduce.By
This is visible, it is desirable to provide a kind of new catalyst with more high desulfurization activity and abrasion resistance properties.
Invention content
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 difference defect, the method for providing a kind of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil.
To achieve the goals above, 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 5-35 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 for measuring %, 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.
The present invention also provides the preparation method of the desulphurization catalyst of the present invention, this method includes：(1) by rare earth metal
It closes object, the first metal oxide, the precursor of the second metal oxide and water and is mixed to get slurries；(2) heat resistant inorganic is aoxidized
Object binder, silica source, water are mixed with acidic liquid, and form carrier pulp with the slurry liquid contacts, then by the carrier
Slurries are molded, the first drying and first roasts, and obtain carrier；(3) precursor of metallic promoter agent is introduced on the carrier,
And the second drying and the second roasting are carried out, obtain catalyst precarsor；(4) catalyst precarsor is gone back under hydrogen atmosphere
Original obtains desulphurization catalyst.
The present invention also provides the desulphurization catalysts that method provided by the present invention is prepared.
The present invention also provides a kind of method of desulfurization of hydrocarbon oil, this method includes：In a hydrogen atmosphere, by hydrocarbon oil containing surphur with
The temperature of hydrodesulfurization catalyst provided by the invention, 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 containing the first metal oxide in desulphurization catalyst provided by the invention and is 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 for generating the first metal less, to enable the desulphurization catalyst to 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 oxide in desulphurization catalyst provided by the invention, can effectively further reinforce the second metal oxygen
The decrease effect of the first metal oxide of compound pair and silicon, aluminium group phase separation.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict 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 5-35 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 %
Object, first metal oxide are selected from least one of the 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.
Preferably, on the basis of the total weight of the desulphurization catalyst, the content of the heat-resistant inorganic oxide is 10-25 weights
% is measured, 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
Content of the metal oxide in terms of rare earth oxide is 1-5 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 undergoing 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,
Preferably, the metallic promoter agent can be nickel.
According to the present invention, the rare-earth oxide can enhance 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 the oxide of lanthanum, cerium and neodymium.
The present invention also provides the preparation method of the desulphurization catalyst of the present invention, this method includes：(1) by rare earth metal
It closes object, the first metal oxide, the precursor of the second metal oxide and water and is mixed to get slurries；(2) heat resistant inorganic is aoxidized
Object binder, silica source, water are mixed with acidic liquid, and form carrier pulp with the slurry liquid contacts, then by the carrier
Slurries are molded, the first drying and first roasts, and obtain carrier；(3) precursor of metallic promoter agent is introduced on the carrier,
And the second drying and the second roasting are carried out, obtain catalyst precarsor；(4) catalyst precarsor is gone back under hydrogen atmosphere
Original obtains desulphurization catalyst.
In the present invention, under preferable case, the heat-resistant inorganic oxide binder can be heat-resistant inorganic oxide or
The substance of heat-resistant inorganic oxide can be changed under conditions of first roasting.Preferably, the heat resistant inorganic oxidation
Object binder be alumina binder, zirconium dioxide binder, titanium dioxide binder and stannic oxide binder 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 binder can be zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and
At least one of amorphous zirconium dioxide；The stannic oxide binder can be butter of tin, four isopropanol tin, acetic acid
At least one of tin, aqua oxidation tin and stannic oxide；The titanium dioxide binder 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
Do not include the amount of the aluminium oxide contained in above-mentioned silica source, the content of aluminium oxide only includes the oxidation formed by alumina source
The amount of aluminium.The amount of aluminium oxide contained in silica source still can be regarded as the amount of 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 be at least one of 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 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.
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 and metallic promoter agent are as described above, 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 is added and is changed into second metal oxide under conditions of first roasting
Substance, such as at least one of the carbonate of metallic lead, antimony and bismuth, nitrate, chloride and hydroxide；It can also be by oxygen
Change at least one of lead, antimony oxide and bismuth oxide to be 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 present invention, the charged material weight ratio of the silica source and the heat-resistant inorganic oxide binder is 0.4-2：1,
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 binder and silica source are distinguished
After carrying out acidification with water and acidic liquid, then the mixture respectively 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, working as the heat-resistant inorganic oxide
When binder 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, preferably 1.5-4；The acidification slurry
The solid content of liquid is 15-30 weight %.
In the present invention, the acidic liquid is the aqueous solution of acid or acid, and the acid can be selected from water-soluble inorganic 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 molding described in step (2)
Shape particle.For example, when the slurries are dough or paste mixture, described mixture molding (preferably extrusion molding) shape can be made
At particle, preferably diameter in 1-8mm, length in the cylindrical extrudates of 2-5mm, be then dried the extrudate of gained,
Roasting.If gained mixture is wet mixture form, the mixture can be made to be thickened, 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 dry preceding carrier pulp is 10-40 weight %, preferably 20-35 weight %.In step (2)
To that can also include that water is added during the carrier pulp, 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, it is described first roasting time be 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 for being added metallic promoter agent.The precursor of the metallic promoter agent is can be second
The substance of the oxide of metallic promoter agent can be changed under roasting condition；Under preferable case, the precursor of the metallic promoter agent
At least one of acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of metallic promoter agent can be selected from.
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, and ammonium hydroxide is then added 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 can be restored under hydrogen atmosphere, 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 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
It is carried out (before being used for desulfurization absorption) before use.Since metallic promoter agent is easy oxidation, and the metal in catalyst precarsor promotees
Exist in the form of an oxide into agent, therefore for ease of transport, catalyst precarsor is restored 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.
According to preparation method provided by the invention, the heat-resistant inorganic oxide binder, silica source, the first metal oxygen
The addition of the precursor of compound, the precursor of the second metal oxide, rare earth compound and metallic promoter agent so that
To desulphurization catalyst in, on the basis of the total weight of the desulphurization catalyst, the heat-resistant inorganic oxide containing 5-35 weight %,
The silica source of 5-35 weight %, the first metal oxide of 10-70 weight %, 2-20 weight % the second metal oxide,
The rare-earth oxide of the metallic promoter agent of 3-30 weight % and the 0.5-10 weight % in terms of rare earth oxide.
Preferably, on the basis of the total weight of the desulphurization catalyst, the content of the heat-resistant inorganic oxide is 10-25 weights
% is measured, 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
Content of the metal oxide in terms of rare earth oxide 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, details are not described herein.
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, 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., the 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, preferably 500-600 DEG C.
In the present invention, the catalyst after regeneration is before re-starting desulfurization of hydrocarbon oil, it is also necessary to it is restored under hydrogen atmosphere,
The reducing condition of catalyst after regeneration includes：Temperature is 350-500 DEG C, preferably 400-450 DEG C；Pressure is 0.2-2MPa,
Preferably 0.2-1.5MPa.
Term used herein " cracking gasoline " means that boiling range is 40 to 210 DEG C of hydrocarbon or its any fraction, is to come to make
Larger hydrocarbon molecule is cracked into the product of 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 that fluid bed is urged
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 that boiling range is 170 to 450 DEG C of hydrocarbon mixture or its any fraction
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 include 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 is suitable for absorption 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 to illustrate the method for preparing desulphurization catalyst of the present invention.
(1) carrier is prepared.By the zinc oxide (traditional Chinese medicines chemical reagents corporation, analysis are pure) of 3.14kg, the lead oxide of 1.45kg
The lanthanum carbonate (traditional Chinese medicines chemical reagents corporation, 45 weight % of lanthanum oxide content) of (traditional Chinese medicines chemical reagents corporation, analysis are pure) and 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 contains butt 2.0kg) of 2.40kg, 2.0kg (are catalyzed
Agent Nanjing branch company, contain butt 1.50kg) and the deionized water of 9.0kg be uniformly mixed under stiring, the concentrated nitric acid of 200g is added
(Beijing Chemical Plant, chemistry are pure) stirring makes pH=1.8, and is warming up to 60 DEG C or more and is acidified 1h.Wait for that temperature is reduced to 40 DEG C or less
When, above-mentioned slurries are added, 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 500 DEG C of inlet temperature is hereinafter, 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 the 8.2kg 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) it restores.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
Amount is 15.0 weight %, and kaolin content is 20.0 weight %, and nickel content is 18.0 weight %, and lanthanum oxide content is 2.0 weights
Measure %.
Embodiment 2
The present embodiment is used to illustrate the method for preparing desulphurization catalyst of the present invention.
By the Zinc oxide powder (Beijing Chemical Plant contains butt 4.0kg) of 4.05kg, the bismuth oxide powder (traditional Chinese medicines of 0.90kg
Chemical reagents corporation, analysis are pure) and the cerous nitrate (traditional Chinese medicines chemical reagents corporation, purity more than 99.0 weight %) of 0.794kg exist
It is 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 crystal of zirconium oxide is avoided to be precipitated, obtains the zirconium colloidal sol of water white transparency；
Take the rectorite (Qilu Petrochemical catalyst plant contains butt 1.60kg) of 2.00kg that deionized water 1.6kg mixing is added
After uniformly, hydrochloric acid (Beijing Chemical Plant, chemistry are pure) stirring of the 30 weight % of 100ml, which is added, makes pH=1.8, heats up after being acidified 1h
To 80 DEG C of aging 2h, the mixture containing rectorite is obtained；It adds above-mentioned slurries and zirconium colloidal sol is mixed together stirring 1h and is carried
Somaplasm liquid.
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 16.0 weight %, and nickel content is 15.0 weight %, and cerium-oxide contents are 3.0 weights
Measure %.
Embodiment 3
The present embodiment is used to illustrate the method for preparing desulphurization catalyst of 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) it is mixed in the deionized water of 5kg, stirring obtains the slurries containing zinc oxide, lead oxide and lanthana after 30 minutes；
The diatomite of 1.24kg (catalyst Nanjing branch company, 1.20kg containing butt) is uniformly mixed in the water of 3.0kg
Afterwards, the concentrated nitric acid stirring of 170g, which is added, makes pH=2.0, and is warming up to 60 DEG C or more the acidification 1h diatomite that obtains that treated；
The hydrated alumina (catalyst Nanjing branch company contains butt 1.8kg) and the deionized water of 9.0kg of 2.4kg are existed
Under stirring after mixing, the concentrated nitric acid stirring of 170g, which is added, to be made pH=1.8 and is warming up to 60 DEG C or more to be acidified 1h.Wait for that temperature drops
When as low as 40 DEG C or less, above-mentioned slurries are added, and diatomite mixes with treated, and 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
Amount is 18.0 weight %, and diatomite content is 12.0 weight %, and nickel content is 12.0 weight %.Lanthanum oxide content is 4.0 weights
Measure %.
Embodiment 4
The present embodiment is used to illustrate the method for preparing desulphurization catalyst of the present invention.
By the Zinc oxide powder of 3.84kg (Beijing Chemical Plant contains butt 3.8kg), 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 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 contains butt 1.80kg) for taking 2.22kg, is added deionized water 3.0kg mixing
After uniformly, the hydrochloric acid stirring of the 30 weight % of 90ml, which is added, 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 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 is 38.0 weight %, and oxidation bi content is 9.0 weight %, titanium dioxide
Content is 18.0 weight %, and rectorite content is 18.0 weight %, and nickel content is 14.0 weight %, and lanthanum oxide content is 3.0 weights
Measure %.
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 contains butt 2.0kg) of 2.40kg, 3.87kg (are urged
Agent Nanjing branch company, contain butt 2.90kg) and the deionized water of 17.0kg be uniformly mixed under stiring, the dense nitre of 580g is added
Acid stirring makes pH=1.8, and is warming up to 60 DEG C or more and is acidified 1h.When temperature is reduced to 40 DEG C or less, above-mentioned slurries are added, mix
Carrier pulp is obtained after stirring 1h after conjunction；
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 29.0 weight %, and kaolin contains
Amount is 20.0 weight %, 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 contains butt 2.0kg) of 2.40kg, 2.27kg (are urged
Agent Nanjing branch company, contain butt 1.70kg) and the deionized water of 10.0kg be uniformly mixed under stiring, the dense nitre of 340g is added
Acid stirring makes pH=1.8, and is warming up to 60 DEG C or more and is acidified 1h.When temperature is reduced to 40 DEG C or less, above-mentioned slurries are added, mix
Carrier pulp is obtained after stirring 1h after conjunction；
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
Amount is 17.0 weight %, and kaolin content is 20.0 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 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 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
Valence 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 cycles, 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 calculates 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 cycle in embodiment 6
Composition is analyzed, and zinc aluminate content therein is measured.
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 quasi-
The method of conjunction calculates the crystalline phase composition of sample.It is 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 diffractions and measure.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 calculating.Different desulphurization catalysts
Zinc aluminate content is as shown in table 1.
Table 1
| A1 | A2 | A3 | A4 | B1 | B2 | |
| ZnAl2O4, weight % | 0 | 0 | 0 | 0 | 4.5 | 2.7 |
| Abrasion index | 2.5 | 3.0 | 3.5 | 3.8 | 4.7 | 4.3 |
| Yield of gasoline, % | 99.8 | 99.9 | 99.7 | 99.9 | 99.0 | 99.3 |
| Product sulfur content, ppm | 9 | 8 | 9 | 5 | 27 | 30 |
| △RON | -0.51 | -0.18 | -0.42 | -0.37 | -0.54 | -0.60 |
| △MON | -0.48 | -0.20 | -0.39 | -0.31 | -0.50 | -0.54 |
| △(RON+MON)/2 | -0.49 | -0.19 | -0.41 | -0.34 | -0.52 | -0.57 |
Note：
1, the sulfur content of feed gasoline is 960ppm, RON 93.7, MON 83.6.
2, △ MON indicate the value added of product MON；
3, △ RON indicate the value added of product RON；
4, △ (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, to make desulphurization catalyst have longer service life.
Claims (16)
1. a kind of desulphurization catalyst, on the basis of the total 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.
2. desulphurization catalyst according to claim 1, wherein described resistance on the basis of the total 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
Content for 35-54 weight %, second metal oxide is 5-15 weight %, and the content of the metallic promoter agent is 10-
20 weight %, content of the rare-earth oxide in terms of rare earth oxide are 1-5 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. the preparation method of the desulphurization catalyst described in any one of claim 1-4, 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 binder, silica source, water are mixed with acidic liquid, and is formed with the slurry liquid contacts
Carrier pulp, then the carrier pulp is molded, the first drying and the 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 is restored under hydrogen atmosphere, obtains desulphurization catalyst.
6. preparation method according to claim 5, 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.
7. preparation method according to claim 5, wherein the heat-resistant inorganic oxide binder aoxidizes for heat resistant inorganic
Object or the substance that heat-resistant inorganic oxide can be changed under conditions of first roasting.
8. preparation method according to claim 5, wherein the rare earth compound be rare earth metal carbonate,
At least one of bicarbonate, nitrate, chloride, formates and acetate.
9. preparation method according to claim 5, wherein the precursor of the metallic promoter agent is the acetic acid of metallic promoter agent
At least one of salt, carbonate, nitrate, sulfate, rhodanate and oxide.
10. preparation method according to claim 5, wherein introduce the side of the precursor of the metallic promoter agent on carrier
Method is dipping or precipitation.
11. preparation method according to claim 5, wherein the acidic liquid is the aqueous solution of acid or acid, the acid choosing
From water-soluble inorganic acid and/or organic acid.
12. preparation method according to claim 5, wherein it is described first drying temperature be 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。
13. preparation method according to claim 5, wherein it is described second drying temperature be 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.
14. preparation method according to claim 5, 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.
15. desulphurization catalyst made from the preparation method described in any one of claim 5-14.
16. a kind of method of desulfurization of hydrocarbon oil, this method include：In a hydrogen atmosphere, by hydrocarbon oil containing surphur and claim 1-4 and 15
Any one of described in hydrodesulfurization catalyst, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5-
4MPa。
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