CN105854929A - Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method - Google Patents
Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method Download PDFInfo
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- CN105854929A CN105854929A CN201510031604.7A CN201510031604A CN105854929A CN 105854929 A CN105854929 A CN 105854929A CN 201510031604 A CN201510031604 A CN 201510031604A CN 105854929 A CN105854929 A CN 105854929A
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Abstract
The invention discloses a hydrocarbon oil desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method. The hydrocarbon oil desulfurization catalyst comprises, by total weight, a) 5-35 wt% of heat-resistant inorganic oxide, 2) 10-70 wt% of metal oxide, 3) 2-40 wt% of silicon nitride, 4) 3-30 wt% of a metal promoter, 5) 0.5-10 wt% of rare earth metal oxide ( calculated by the rare earth oxide), and 6) 1-20 wt% of molecular sieve with BEA or FAU structure. The hydrocarbon oil desulfurization catalyst has better stability, higher desulfurization activity, better wear resistance and long service life.
Description
Technical field
The method that the present invention relates to a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil, specifically
Ground, relates to a kind of desulfurization of hydrocarbon oil catalyst, prepares the method for desulfurization of hydrocarbon oil catalyst and obtained by the method
Desulfurization of hydrocarbon oil catalyst, and use the method that this desulfurization of hydrocarbon oil catalyst carries out desulfurization of hydrocarbon oil.
Background technology
The oxysulfide produced after combustion of sulfur in vehicle fuel, that can suppress in vehicle exhaust converter is expensive
Metallic catalyst activity and can be allowed to occur irreversibly to be poisoned.So that containing unburned in vehicle exhaust
The non-methane hydrocarbon burnt and nitrogen oxide and carbon monoxide, these discharge gas are by hydrophilic dye then easy shape
Becoming photochemical fog, cause acid rain, the oxysulfide in air itself is also the main of formation acid rain simultaneously
One of reason.Along with people's pay attention to day by day to environmental conservation, environmental regulation is the strictest, and reduces
The sulfur content of gasoline and diesel oil is considered as one of most important measure improving air quality.
Existing gasoline products standard GB 17930-2011 " motor petrol " of China required by 2013
December 31 days, sulfur content in gasoline must drop to 50 μ g/g；And gasoline quality standard can be more in the future
Add strict.In this case, catalytically cracked gasoline have to pass through deep desulfuration just can meet environmental protection want
Ask.
At present, the process for deep desulphurization of oil product mainly has hydrofinishing and adsorbs two kinds of methods of desulfurization, but
China makes hydrorefined relatively costly due to the problem of hydrogen source.S Zorb absorption desulfurization belongs to faces
Hydrogen desulfurization technology, realizes the adsorbing and removing of sulfide under the conditions of certain temperature and pressure.Due to this skill
Art sulfur-containing compound in removing gasoline has a hydrogen low feature of consumption, and to the purity requirement of hydrogen not
High to have broad application prospects in terms of this technology sulfur-containing compound in removing fuel oil.
The method that desulfurization often uses fixed bed from liquid traditionally, but the reaction uniformity of the method and
Regeneration all has obvious inferior position.Fluidized-bed process has preferably heat transfer and pressure drop compared with fixed-bed process
Etc. the advantage of aspect, therefore have broad application prospects.Fluidized-bed reactor typically uses granular reaction
Thing, but for great majority react, the typically no enough wearabilities of reactant used.Therefore, look for
The adsorbent the most simultaneously having preferable desulfurization performance to anti-wear performance is significant.
CN1355727A discloses a kind of be applicable to the suction removing sulfur from cracking gasoline and diesel fuel
Attached dose of compositions, is made up of zinc oxide, silicon oxide, oxidation al and ni, and wherein nickel is with substantially also original cost
State exists, and its amount can be from the cracking vapour contacted with described nickeliferous adsorbent composition under desulfurization conditions
Oil or diesel fuel stream remove sulfur.Said composition is by being formed zinc oxide, silicon oxide and aluminium oxide
Compound particles granulation form granule, be dried, impregnate with nickel or nickel compound containing after roasting, then be dried,
Roasting, reduction obtain.
CN1382071A discloses a kind of be applicable to the suction removing sulfur from cracking gasoline and diesel fuel
Attached dose of compositions, is made up of zinc oxide, silicon oxide, aluminium oxide and cobalt, and wherein cobalt is with substantially also original cost
State exists, and its amount can be from the cracking vapour contacted with the described adsorbent composition containing cobalt under desulfurization conditions
Oil or diesel fuel stream remove sulfur.CN1355727A and CN1382071A is only referred to desulfurization
Activity, does not the most introduce for adsorbent physical and chemical performance (such as abrasion strength resistance) and stability.
Adsorbent disclosed in US6150300, CN1130253C and CN1258396C is: comprise oxidation
The granular adsorbent compositions of the mixture of zinc, silicon oxide, aluminium oxide, reduction valence state nickel or cobalt.System
Preparation Method mainly uses the methods such as shearing that silicon oxide, aluminium oxide and zinc oxide are mixed merga pass comminutor
Prepare solid particle, impregnate nickel after drying and roasting thus prepare adsorbent.Although these patents are introduced
Adsorbent has a preferable desulfurization performance, but for its physical and chemical performance, mainly tear strength in the patent
Do not introduce.
CN1208124C discloses employing promoter metals such as cobalt and nickel dipping and comprises zinc oxide, expands treasure
Zhu Yan and the adsorbing agent carrier of aluminium oxide, reduce this accelerator the most at appropriate temperatures, and preparation is used for taking off
Except the adsorbent of sulfide in cracking gasoline.
CN1627988A discloses one and is suitable for from cracking gasoline and diesel fuel removing elementary sulfur
With the adsorbent composition of sulphur compound, described adsorbent composition comprises: zinc oxide, expanded perlite,
Aluminate and promoter metals, wherein said promoter metals with when make cracking gasoline or diesel fuel stream with
The amount of desulfurization from the stream of cracking gasoline or diesel fuel will be caused to deposit when it contacts under desulfurization conditions
, and at least part of described promoter metals exists with 0 valence state.
CN1856359A discloses a kind of method producing compositions, including: a) mix liquid, contain
Zinc compound, containing earth silicon material, aluminium oxide and promoter, to form its mixture；B) dry
This mixture dry, to form the mixture of drying；C) mixture of this drying is calcined, to be formed
Mixture through calcining；D) with suitable reducing agent under suitable condition by this mixture through calcining
Reduction, to have the compositions of the promoter content of reduction valence state in producing it, and e) reclaims
Reorganization compound.Promoter contains selected from various metals such as nickel.
CN1871063A discloses a kind of method producing compositions, and the method includes: a) by liquid,
Zinc compound, containing earth silicon material, aluminium oxide mix to form its mixture；B) by described
Mixture is dried this mixing to form the first drying mixture；C) by described first drying mixture
Calcine to form first through calcining mixt；D) accelerator is attached to described first through calcining mixt
Within or on to form promoted mixture；E) make described promoted mixture with selected from citric acid,
The acid contact of tartaric acid and combinations thereof is to be formed through contact mixture；F) do described through contact mixture
Dry to form the second drying mixture；G) described second drying mixture is calcined to form second
Through calcining mixt；H) use applicable reducing agent reduction described second through calcining under suitable condition
Mixture wherein contains the compositions of reduction valence state accelerator content to produce, and i) reclaims described group
Compound.
CN101816918A discloses a kind of desulfuration adsorbent, and this adsorbent consists of alkali metal, oxidation
Aluminum, silicon oxide, accelerator and one or more metal-oxides selected from IIB, VB and VIB
Adsorbent.This adsorbent has preferable abrasion strength resistance and desulphurizing activated.
These methods, while the adsorbent of preparation has preferable desulfurization performance, but there is also and significantly lack
Point.Above-mentioned adsorbent all uses zinc oxide active component, and the temperature that zinc oxide absorbs sulfur and oxidation regeneration is equal
Relatively higher, when desulphurization reaction and oxidation regeneration easily with the sial component generation zinc silicate in carrier and
23K-S, causes adsorbent activity to reduce.As can be seen here, it is desirable to provide one has more high desulfurization activity
New catalyst with abrasion resistance properties.
Summary of the invention
The invention aims to overcome desulphurizing activated low, the structural instability of adsorbent of prior art and
The defect of abrasion resistance properties difference, it is provided that a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
Method.
To achieve these goals, the present invention provides a kind of desulfurization of hydrocarbon oil catalyst, urges with this desulfurization of hydrocarbon oil
On the basis of the gross weight of agent, this desulfurization of hydrocarbon oil catalyst contains: the 1) heat resistant inorganic of 5-35 weight %
Oxide, described heat-resistant inorganic oxide is selected from aluminium oxide, titanium dioxide, zirconium dioxide and tin ash
In at least one；2) metal-oxide of 10-70 weight %, described metal-oxide selected from IIB,
At least one in the metal-oxide of VB and group vib element；3) silicon nitride of 2-40 weight %；4)
The metallic promoter agent of 3-30 weight %, described metallic promoter agent is selected from least in cobalt, nickel, ferrum and manganese
Kind；5) rare-earth oxide of 0.5-10 weight % in terms of rare earth oxide；6) 1-20 weight %
The molecular sieve with BEA and/or FAU structure.
Present invention also offers a kind of method preparing the desulfurization of hydrocarbon oil catalyst that the present invention provides, the method
Including: (1) is by heat-resistant inorganic oxide binding agent, silicon nitride, metal-oxide, rare earth metal chemical combination
Thing, water and acidic liquid are mixed to get mixed serum, then with there is the molecule of BEA and/or FAU structure
Sieve contact forms carrier pulp；Described carrier pulp is shaped, first be dried and the first roasting,
To carrier；(2) on described carrier, introduce the precursor of metallic promoter agent, and it is dry with second to carry out second
Roasting, obtains catalyst precarsor；(3) described catalyst precarsor is reduced under hydrogen atmosphere, obtain
Desulfurization of hydrocarbon oil catalyst.
The present invention also provides for the desulfurization of hydrocarbon oil catalyst that method provided by the present invention prepares.
A kind of method that present invention also offers desulfurization of hydrocarbon oil, the method includes: in a hydrogen atmosphere, will
The desulfurization of hydrocarbon oil catalyst that hydrocarbon oil containing surphur provides with the present invention contacts, and the temperature of described contact is 350-500
DEG C, the pressure of described contact is 0.5-4MPa.
Containing stable silicon nitride in the composition of the desulfurization of hydrocarbon oil catalyst that the present invention provides, decrease and oxygen
Change the dependent interaction of the metal-oxide such as zinc, it is to avoid the formation of zinc silicate material, such as Fig. 1 show
There is not silicon in the XRD spectra after the hydrothermal aging of the desulfurization of hydrocarbon oil catalyst A1 that embodiment 1 obtains
The characteristic peak of acid zinc.The desulfurization of hydrocarbon oil catalyst that the present invention provides has more preferable stability and higher de-
Sulfur activity, it is possible to more effectively the sulfur in hydrocarbon ils is adsorbed onto during desulfurization of hydrocarbon oil desulfurization of hydrocarbon oil catalysis
In agent, obtain the hydrocarbon ils that sulfur content is lower.And the desulfurization of hydrocarbon oil catalyst that the present invention provides has more preferably
Abrasion resistance properties, in sweetening process, catalyst attrition is lower, and service life is longer.
Containing rare earth oxide in the desulfurization of hydrocarbon oil catalyst that the present invention provides, activity can be efficiently reduced
Metal-oxide and the effect of sial component in carrier, reduce and generate silicate and aluminate, so that should
Desulfurization of hydrocarbon oil catalyst can absorb sulfur and at lower temperatures through reaction and regenerative process are repeated,
Still there is the most desulphurizing activated and activity stability.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the desulfurization of hydrocarbon oil catalyst A1 that obtains of embodiment 1 XRD figure before and after hydrothermal aging
Spectrum；
Fig. 2 is the desulfurization of hydrocarbon oil catalyst B1 that obtains of comparative example 1 XRD figure before and after hydrothermal aging
Spectrum.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of desulfurization of hydrocarbon oil catalyst, with the gross weight of this desulfurization of hydrocarbon oil catalyst as base
Standard, this desulfurization of hydrocarbon oil catalyst contains: the 1) heat-resistant inorganic oxide of 5-35 weight %, described heat-resisting
At least one in aluminium oxide, titanium dioxide, zirconium dioxide and tin ash of inorganic oxide；2)
The metal-oxide of 10-70 weight %, described metal-oxide is selected from IIB, VB and group vib element
At least one in metal-oxide；3) silicon nitride of 2-40 weight %；4) metal of 3-30 weight %
Accelerator, at least one in cobalt, nickel, ferrum and manganese of described metallic promoter agent；5) with rare earth oxygen
The rare-earth oxide of 0.5-10 weight % of compound meter；6) 1-20 weight % have BEA and/
Or the molecular sieve of FAU structure.
Preferably, on the basis of the gross weight of this desulfurization of hydrocarbon oil catalyst, described heat-resistant inorganic oxide
Content is 10-25 weight %, and the content of described metal-oxide is 25-60 weight %, described silicon nitride
Content be 5-25 weight %, the content of described metallic promoter agent is 10-20 weight %, described rare earth gold
Belonging to content that oxide counts with rare earth oxide for 1-5 weight %, the content of described molecular sieve is 2-10 weight
Amount %.
According to the present invention, silicon nitride is white powder, and silicon nitride can be α phase silicon nitride and/or β phase
Silicon nitride, under preferable case, silicon nitride is α phase silicon nitride.The particle diameter of alpha-silicon nitride powders can be preferably
Between 2000-500 mesh (i.e. 6.5-25 μm).
The desulfurization of hydrocarbon oil catalyst that the present invention provides contains silicon nitride, can be effectively prevented from carrying out hydrocarbon ils
Sweetening process forms in the composition of this catalyst zinc silicate, it is ensured that this catalyst has more preferable desulfurization to live
Property.Preferably, in described desulfurization of hydrocarbon oil catalyst XRD spectra after hydrothermal aging 2 θ be 22.0,
25.54, there is no the characteristic peak of zinc silicate at 48.9 and 59.4.Described hydrothermal aging is temperature 500-700
DEG C, steam partial pressure be 10-30kPa, the process time is 10-24h.
According to the present invention, described metal-oxide is the metal-oxide with storage sulfur performance, it is preferable that
Described metal-oxide is zinc oxide, Aska-Rid., vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, oxygen
Change at least one in molybdenum and tungsten oxide；It is highly preferred that described metal-oxide is zinc oxide, molybdenum oxide
With at least one in vanadium oxide；The most described metal-oxide is zinc oxide.
According to the present invention, described heat-resistant inorganic oxide can be each component in described desulfurization of hydrocarbon oil catalyst
Between provide cementation.Described heat-resistant inorganic oxide is selected from aluminium oxide, titanium dioxide, zirconium dioxide
With at least one in tin ash.Wherein, described aluminium oxide can be gama-alumina, η-aluminium oxide,
At least one in θ-aluminium oxide and χ-aluminium oxide；Preferably, described aluminium oxide is gama-alumina；Described
Titanium dioxide can be anatase titanium dioxide.
According to the present invention, described metallic promoter agent can be any oxidation state sulfur can be reduced to hydrogen sulfide
Metal, it is preferable that described metallic promoter agent can be nickel.
According to the present invention, described rare-earth oxide can be stablized the skeleton of heat-resistant inorganic oxide, subtract
Few metal-oxide and silicon, the effect of al composition in carrier, reduce and generate silicate and aluminate, improve
The activity of desulfurization and stability.Preferably, described rare-earth oxide is the oxide of lanthanum, cerium and neodymium
In at least one.
In the present invention, described FAU structure molecular screen is faujasite-type molecular sieve.The type molecular sieve
Having three-dimensional twelve-ring duct, aperture isFAU structure molecular screen be mainly X-type and
The molecular sieve of Y type, in general SiO2: Al2O3Mol ratio be 2.2-3.0 for X-type molecular sieve, SiO2:
Al2O3Mol ratio more than 3.0 for Y type molecular sieve.The framing structure of X-type and Y type molecular sieve all belongs to
In hexagonal crystal system, space group structure is Fd3m, the cell parameter of X-type molecular sieve
The cell parameter of Y type molecular sieve
In the present invention, the molecular sieve with FAU structure also includes this modified molecular sieve analog.Modified
Method can include hydro-thermal method, method of chemical treatment (such as mineral acid logos, hexafluosilicic acid aluminium-eliminating and silicon-replenishing
Method and SiC14Vapor phase method) or hydro-thermal combine with chemical treatment, modified obtain molecular sieve include but not
It is limited to super-stable Y molecular sieves (USY), containing REUSY, REHY, REY of rare earth element, with
And phosphorous PUSY, PREHY, PREY etc..Rare earth can be the carbonate of rare earth metal, carbonic acid
At least one in hydrogen salt, nitrate, chloride, formates and acetate；Preferably, described rare earth
Metallic compound can be in the carbonate of rare earth metal, bicarbonate, formates and acetate at least
A kind of.Wherein, at least one during described rare earth metal is preferably lanthanum, cerium and neodymium.Described have FAU
The SiO of the molecular sieve of structure2: Al2O3Mol ratio be 2.6-10:1；Preferably, there is described in FAU
The SiO of the molecular sieve of structure2: Al2O3Mol ratio be 2.8-9:1.
In the present invention, BEA structure molecular screen is mainly beta-molecular sieve, and its structural formula is
(Nan[AlnSi64-nO128], n < 7), it is that two structures are different but polymorph A that is closely related and B
Mixed crystal, both there is twelve-ring 3 D pore canal system: polymorph A forms a pair enantiomer, empty
Between group be P4122 and P4322, cell parameter isPolymorph B belongs to non-hands
Property space group C2/c, cell parameterβ=114.5 °.BEA
In structure molecular screen, twelve-ring pore size is<100 direction>and<001
Direction >.The SiO of the described molecular sieve with BEA structure2: Al2O3Mol ratio be 10-50:1；
Preferably, there is described in the SiO of the molecular sieve of BEA structure2: Al2O3Mol ratio be 15-30:1.
In the case of according to the invention it is preferred to, described in have the molecular sieve of FAU and/or BEA structure be X
Type molecular sieve, Y type molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY,
At least one in PREY and beta-molecular sieve.
In the present invention, addition has the molecular sieve of FAU and/or BEA structure can be improved gasoline products
The effect of octane number or effect.
Present invention also offers a kind of method preparing the desulfurization of hydrocarbon oil catalyst that the present invention provides, the method
Including: (1) is by heat-resistant inorganic oxide binding agent, silicon nitride, metal-oxide, rare earth metal chemical combination
Thing, water and acidic liquid are mixed to get mixed serum, then with there is the molecule of BEA and/or FAU structure
Sieve contact forms carrier pulp；Described carrier pulp is shaped, first be dried and the first roasting,
To carrier；(2) on described carrier, introduce the precursor of metallic promoter agent, and it is dry with second to carry out second
Roasting, obtains catalyst precarsor；(3) described catalyst precarsor is reduced under hydrogen atmosphere, obtain
Desulfurization of hydrocarbon oil catalyst.
In the present invention, under preferable case, described rare earth compound can be rare earth metal carbonate,
At least one in bicarbonate, nitrate, chloride, formates and acetate；Preferably, described
Rare earth compound can be in the carbonate of rare earth metal, bicarbonate, formates and acetate
At least one.Wherein, at least one during described rare earth metal is preferably lanthanum, cerium and neodymium.
In the present invention, under preferable case, described heat-resistant inorganic oxide binding agent can be heat resistant inorganic oxygen
Compound or the material of heat-resistant inorganic oxide can be changed under conditions of described first roasting.Preferably
Ground, described heat-resistant inorganic oxide binding agent is alumina binder and non-al binder, non-al binder
At least one in zirconium dioxide binding agent, titanium dioxide binding agent and tin ash binding agent can be included
Kind.It is highly preferred that described alumina binder can be hydrated alumina and/or Alumina gel, wherein, institute
State hydrated alumina selected from boehmite (boehmite), false boehmite (boehmite),
At least one in Alumina hydrate and amorphous hydroted alumina；Described zirconium dioxide binding agent can be
At least one in Zirconium tetrachloride., zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide；
Described tin ash binding agent can be butter of tin, four isopropanol stannum, tin acetate, aqua oxidation stannum and
At least one in tin ash；Described titanium dioxide binding agent can be titanium tetrachloride, tetraethyl titanate,
At least one in isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.
In the present invention, the precursor of described metallic promoter agent can be can under conditions of described second roasting
It is changed into the material of the oxide of metallic promoter agent.Under preferable case, the precursor of described metallic promoter agent can
Think in the acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide
At least one.
In the present invention, described metal-oxide, silicon nitride and have FAU and/or BEA structure point
Son sieve is not as it has been described above, repeat them here.
In the desulfurization of hydrocarbon oil catalyst that method provided by the present invention prepares, the content of each component is according to feeding intake
Amount calculates.
The step (1) of the preparation method of the desulfurization of hydrocarbon oil catalyst that the present invention provides is used for preparing carrier.
The process of mixing described in the preparation method step (1) of the desulfurization of hydrocarbon oil catalyst that the present invention provides
Can to the addition of silicon nitride, there is no particular limitation opportunity, a kind of detailed description of the invention is: step (1)
The process of described mixing includes: (i) is by heat-resistant inorganic oxide binding agent, silicon nitride, water and acidity
Liquid contact forms mixture: rare earth compound, metal-oxide and water are mixed by (ii), and with
The contact of described mixture obtains mixed serum.
Another kind of detailed description of the invention is: the process of step (1) described mixing includes: (a) is by heat-resisting
Inorganic oxide binder, water contact formation mixture with acidic liquid: (b) is by silicon nitride, metal oxygen
Compound, rare earth compound and water mixing, and contact with described mixture and obtain mixed serum.
In the present invention, described silicon nitride with the charged material weight ratio of described heat-resistant inorganic oxide binding agent is
0.4-2:1, preferably 0.6-1.5:1, thus can provide described desulfurization of hydrocarbon oil catalyst with more preferable each group
Caking property between Fen.
In the present invention, the addition of described metal-oxide can be oxide powder form, it is also possible to be by
Metal-oxide uses after being prepared as serosity the most as a slurry.
In the present invention, the solid content of mixture described in step (1) can be 15-30 weight %.
In the present invention, described acidic liquid is acid or aqueous acid, and described acid can be selected from water soluble
Mineral acid and/or organic acid, can be such as at least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
In step (i) and (a), under preferable case, the consumption of described acidic liquid makes described mixture
PH value is 1-5, preferably 1.5-4.Wherein, when described heat-resistant inorganic oxide binding agent be non-aluminum glue
During knot agent, the mixture of formation is colloidal sol；When described heat-resistant inorganic oxide binding agent is alumina bound
During agent, the mixture of formation is serosity.
In the present invention, the amount adding water in step (i) and (a) can be not specially limited, if energy
Access described mixture.Such as add the amount of water and heat-resistant inorganic oxide binding agent or with
The weight ratio of the weight summation of heat-resistant inorganic oxide binding agent and silicon nitride is 5-10:1.
In the present invention, molding described in step (1) described carrier pulp can be shaped to extrudate,
Sheet, pill, ball or micro-spherical particle.Such as, when described carrier pulp is dough or paste mixture,
Described mixture forming (preferably extrusion molding) can be made to form granule, preferably diameter in 1-8mm, length
Spend at the cylindrical extrudates of 2-5mm, then extrudate is dried, roasting.If gained mixes
Compound is wet mixture form, this mixture can be made to be thickened, through dried molding.More preferably carrier slurry
Liquid is slurry form, forms, by being spray-dried, the microsphere that granularity is 20-200 micron, reaches molding
Purpose.For the ease of being spray-dried, before being dried, the solid content of described carrier pulp is 10-40 weight %,
It is preferably 20-35 weight %.Can also include during obtaining described carrier pulp in step (1)
Adding water, there is no particular limitation for the addition of water, as long as the carrier pulp obtained meets above-mentioned solid content
?.
In the present invention, described first be dried and the first roasting condition can by those skilled in the art public affairs
Know, under preferable case, described first be dried temperature be 80-150 DEG C, described first be dried time be
0.5-24h；The temperature of described first roasting is 300-700 DEG C, and the time of described first roasting is at least 0.5
h.Preferably, the temperature of described first roasting is 400-500 DEG C, and the time of described first roasting is 0.5-100
H, the time of the most described first roasting is 0.5-10h.
According to the present invention, step (2) is used for adding metallic promoter agent.The precursor of described metallic promoter agent
For the material of the oxide of metallic promoter agent can be changed under the second roasting condition；Under preferable case,
The precursor of described metallic promoter agent can be selected from the acetate of metallic promoter agent, carbonate, nitrate, sulfur
At least one in hydrochlorate, rhodanate and oxide.
In the case of according to the invention it is preferred to, the method for the precursor introducing metallic promoter agent on carrier is leaching
Stain or precipitation.Described dipping can be the solution with the precursor of metallic promoter agent or suspension impregnation carrier；
Described precipitation can be solution or the suspension of the precursor of metallic promoter agent to be mixed with carrier, is subsequently adding
Ammonia by the precursor precipitation of metallic promoter agent on carrier.
In the present invention, described second be dried and the second roasting condition can by those skilled in the art public affairs
Know, under preferable case, described second be dried temperature be 50-300 DEG C, described second be dried time be
0.5-8h；The temperature of described second roasting is 300-700 DEG C, and the time of described second roasting is 0.5-4h；
Preferably, the described second temperature being dried is 100-250 DEG C, and the described second time being dried was 1-5h；
The temperature of described second roasting is 400-500 DEG C, and the time of described second roasting is 1-3h.Described second
Roasting can be carried out under with the presence of oxygen or oxygen-containing gas, until volatile material is removed and gold
Belong to accelerator and be converted into the form of metal-oxide, obtain catalyst precarsor.
According to the present invention, in step (3), by the oxidation of the metallic promoter agent in described catalyst precarsor
Thing is changed into metal simple-substance, can be reduced by described catalyst precarsor, make gold under hydrogen atmosphere
Belong to accelerator substantially to exist with reduction-state, obtain catalyst of the present invention.The condition of described reduction is only by institute
State the oxide of the metallic promoter agent in catalyst precarsor and be changed into metal simple-substance, and the gold in described carrier
Belong to oxide will not change.Under preferable case, the temperature of described reduction is 300-600 DEG C, described reduction
Time be 0.5-6h, in described hydrogen atmosphere, hydrogen content is 10-60 volume %；Preferably, institute
The temperature stating reduction is 350-450 DEG C, and the time of described reduction is 1-3h.
In the present invention, step (3) can after prepared catalyst precarsor immediately by catalyst precarsor reduction
Carry out, it is also possible to carry out (i.e. before desulfurization is adsorbed) before use.Due to the easy oxygen of metallic promoter agent
Change, and the metallic promoter agent in catalyst precarsor exists in the form of an oxide, therefore for ease of transport, excellent
Step (3) is selected catalyst precarsor reduction to be carried out before carrying out desulfurization absorption.Described being reduced to makes metal
Metal in the oxide of accelerator substantially exists with reduction-state, obtains the desulfurization of hydrocarbon oil catalysis of the present invention
Agent.
The preparation method provided according to the present invention, described heat-resistant inorganic oxide binding agent, metal-oxide
Precursor, silicon nitride, rare earth compound, have the molecular sieve of FAU and/or BEA structure with
And the addition of the precursor of metallic promoter agent so that in the desulfurization of hydrocarbon oil catalyst obtained, take off with this hydrocarbon ils
On the basis of the gross weight of sulfur catalyst, the heat-resistant inorganic oxide containing 5-35 weight %, 10-70 weight
The metal-oxide of %, the silicon nitride of 2-40 weight %, the metallic promoter agent of 3-30 weight %, with rare earth
The rare-earth oxide of 0.5-10 weight % of oxide meter and 1-20 weight % have FAU and/
Or the molecular sieve of BEA structure.
Preferably, on the basis of the gross weight of this desulfurization of hydrocarbon oil catalyst, described heat-resistant inorganic oxide
Content is 10-25 weight %, and the content of described metal-oxide is 25-60 weight %, described silicon nitride
Content be 5-25 weight %, the content of described metallic promoter agent is 10-20 weight %, described rare earth gold
Belong to content that oxide counts with rare earth oxide for 1-5 weight %, described in there is FAU and/or BEA knot
The content of the molecular sieve of structure is 2-10 weight %.
The present invention also provides for the desulfurization of hydrocarbon oil catalyst that method provided by the present invention prepares.
A kind of method that the invention provides desulfurization of hydrocarbon oil, the method includes: in a hydrogen atmosphere, will contain
The desulfurization of hydrocarbon oil catalyst that sulfur hydrocarbon ils provides with the present invention contacts, and the temperature of described contact is 350-500 DEG C,
The pressure of described contact is 0.5-4MPa；Preferably, the temperature of described contact is 400-450 DEG C, described
The pressure of contact is 1-2MPa.Sulfur in hydrocarbon ils is adsorbed on catalyst in the process, thus
Hydrocarbon ils to low sulfur content.
The method of the desulfurization of hydrocarbon oil that the present invention provides is carried out the most in a fluidized bed reactor, the most described contact
Carry out the most in a fluidized bed reactor.
In the present invention, reacted catalyst can be reused after regeneration.Described regeneration is at oxygen gas
Carrying out under atmosphere, the condition of regeneration includes: the pressure of regeneration is normal pressure, and the temperature of regeneration is 400-700 DEG C,
It is preferably 500-600 DEG C.
In the present invention, the catalyst after regeneration is before re-starting desulfurization of hydrocarbon oil, in addition it is also necessary at hydrogen gas
Reducing under atmosphere, the reducing condition of the catalyst after regeneration includes: temperature is 350-500 DEG C, is preferably
400-450℃；Pressure is 0.2-2MPa, preferably 0.2-1.5MPa.
In the present invention, described hydrocarbon ils includes cracking gasoline and diesel fuel, wherein " cracking gasoline " meaning
Refer to hydrocarbon or its any fraction that boiling range is 40 DEG C to 210 DEG C, be from making bigger hydrocarbon molecule be cracked into relatively
The heat of little molecule or the product of catalytic process.The example of the catalytic cracking process being suitable for includes but not limited to stream
Change bed catalytic cracking and RFCC etc. and combinations thereof.Therefore, the catalytically cracked gasoline being suitable for includes
But it is not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and weight
Oil cracking gasoline and combinations thereof.In some cases, can be when being used as hydrocarbon-containifluids fluids in the methods of the invention
By described cracking gasoline fractional distillation and/or hydrotreating before desulfurization.
Term used herein " diesel fuel " means the hydrocarbon mixture that boiling range is 170 DEG C to 450 DEG C
Or the liquid of its any fractional composition.This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight
Evaporate diesel oil and hydroprocessed diesel etc. and combinations thereof.
Term used herein " sulfur " represent any type of element sulphur such as hydrocarbon-containifluids fluids such as cracking gasoline or
The organosulfur compound being commonly present in diesel fuel.Present in hydrocarbon-containifluids fluids of the present invention sulfur include but not
Be limited to carbonyl sulfide (COS), Carbon bisulfide (CS2), mercaptan or other thiophenes etc. and
Combination, especially includes thiophene, benzothiophene, alkylthrophene, alkyl benzothiophenes and alkyl diphenyl thiophene
The thiophenes that the molecular weight that is commonly present in fen, and diesel fuel is bigger.
Containing silicon nitride component in the composition of the desulfurization of hydrocarbon oil catalyst that the present invention provides, this component is in catalysis
Many secondary responses of agent and regenerative process are difficult to and the zinc oxide component effect of reacting, silicic acid will not be produced
Zinc material makes this desulfurization of hydrocarbon oil catalyst reduce desulphurizing activated because losing zinc oxide.Catalyst of the present invention has
Have the highest desulphurizing activated, the most also there is the character significantly increasing catalyst abrasion strength resistance, can fit
For catalytically cracked gasoline or the sweetening process repeatedly reacted and regenerate of diesel fuel.
Hereinafter will be described the present invention by embodiment.
The desulfurization of hydrocarbon oil catalyst that embodiment and comparative example obtain uses X-ray diffractometer, and (Siemens is public
Department's D5005 type) obtain XRD spectra, carry out structure determination, Cu target, K α radiation, solid detects
Device, tube voltage 40kV, tube current 40mA.
In the following Examples and Comparative Examples, the composition of desulfurization of hydrocarbon oil catalyst calculates according to feeding intake.
Embodiment 1
The present embodiment is for illustrating the method preparing desulfurization of hydrocarbon oil catalyst of the present invention.
(1) carrier is prepared.By the zinc oxide (traditional Chinese medicines chemical reagents corporation, analytical pure) of 3.14kg, 2.45kg
Silicon nitride (purity > 99.0%, Qinhuangdao one promise new high-tech material development corporation, Ltd.) and the carbon of 430g
Acid lanthanum (traditional Chinese medicines chemical reagents corporation, lanthanum oxide content 45 weight %) mix and blend in the water of 8.5kg
Uniformly, the mixed serum containing zinc oxide, silicon nitride and lanthana is obtained；
By boehmite (catalyst Nanjing branch company, containing butt 1.80kg) and the 7.0kg of 2.40kg
Deionized water under agitation mix homogeneously, add 200g concentrated nitric acid (Beijing Chemical Plant, chemical pure)
Stirring makes pH=1.8, and is warming up to more than 60 DEG C acidifying 1h.When temperature is reduced to below 40 DEG C, add
Enter above-mentioned mixed serum and 1.0kg beta-molecular sieve (catalyst Nanjing branch company, containing butt 0.70kg,
SiO2:Al2O3Mol ratio=20:1), stir after 1h after mixing and obtain carrier pulp；
Described carrier pulp is used Niro Bowen Nozzle TowerTMThe spray dryer of model enters
Row is spray-dried, and being spray-dried pressure is 8.5 to 9.5MPa, inlet temperature less than 500 DEG C, outlet temperature
Degree is about 150 DEG C.The microsphere obtained by spray drying is first dried 1h at 150 DEG C, then at 480 DEG C
Lower roasting 1h obtains carrier；
(2) Nickelous nitrate hexahydrate of the carrier 7.0kg of 6.4kg and the deionization of 1.10kg are formed
Aqueous solution impregnates at twice, the mixture obtained through 150 DEG C of dry 4h followed by 480 DEG C of roastings 1
H, obtains catalyst precarsor；
(3) reduction.By catalyst precarsor reductase 12 h at 425 DEG C in hydrogen atmosphere, obtain hydrocarbon ils and take off
Sulfur catalyst A1.
The chemical composition of A1 is: zinc oxide content is 31.0 weight %, and silicon nitride content is 24.0 weight
%, alumina content is 18.0 weight %, and the content of beta-molecular sieve is 7 weight %, and nickel content is 18.0
Weight %, lanthanum oxide content is 2.0 weight %.
Embodiment 2
The present embodiment is for illustrating the method preparing desulfurization of hydrocarbon oil catalyst of the present invention.
By the Zinc oxide powder (Beijing Chemical Plant produces, containing butt 4.8kg) of 4.85kg, the nitrogen of 0.60kg
SiClx powder (purity > 99.0%, Qinhuangdao one promise new high-tech material development corporation, Ltd.) and 1.261kg
Cerous nitrate (traditional Chinese medicines chemical reagents corporation, purity is more than 99.0 weight %) is in the deionized water of 7.1kg
Mixing, obtains the serosity containing zinc oxide, silicon nitride and cerous nitrate after stirring 30 minutes；
Zirconium tetrachloride. (Beijing Chemical Plant, analytical pure) by 4.30kg is slowly added into the concentration of 4.9kg
The salpeter solution of 5 weight % makes pH=2.0, and is slowly stirred and avoids crystal of zirconium oxide to separate out, obtain nothing
The zirconium colloidal sol that color is transparent；
By the beta-molecular sieve of above-mentioned serosity, zirconium colloidal sol and 0.43kg, (catalyst Nanjing branch company, containing butt
0.3kg, SiO2:Al2O3Mol ratio=40:1) be mixed together 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,
Desulfurization of hydrocarbon oil catalyst A2 is obtained after reduction.
The chemical composition of A2 is: zinc oxide content is 48.0 weight %, and silicon nitride content is 6.0 weight %,
Zirconium dioxide content is 25.0 weight %, and beta-molecular sieve content is 3.0 weight %, and nickel content is 15.0 weights
Amount %, cerium-oxide contents is 3.0 weight %.
Embodiment 3
The present embodiment is for illustrating the method preparing desulfurization of hydrocarbon oil catalyst of the present invention.
By the Zinc oxide powder of 4.86kg, 0.6kg silicon nitride (purity > 99.0%, Qinhuangdao one promise is high
New material development corporation, Ltd.) and the lanthana (traditional Chinese medicines chemical reagents corporation, analytical pure) of 400g exist
The deionized water of 5kg mixes, obtains containing zinc oxide, silicon nitride and lanthana after stirring 30 minutes
Serosity；
By hydrated alumina (catalyst Nanjing branch company, containing butt 2.5kg) and the 12.5kg of 3.3kg
Deionized water under agitation mix homogeneously after, add 230g concentrated nitric acid stirring make pH=1.8 and heat up
To more than 60 DEG C acidifying 1h.When temperature is reduced to below 40 DEG C, after adding above-mentioned serosity, process
(catalyst Nanjing branch company, containing butt 0.5kg, SiO for the USY molecular sieve of kieselguhr and 0.6kg2:Al2O3
Mol ratio=8.5:1) mixing, stirring 1h after obtain carrier pulp.
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel,
Desulfurization of hydrocarbon oil catalyst A3 is obtained after reduction.
The chemical composition of A3 is: zinc oxide content is 48.0 weight %, and silicon nitride content is 6.0 weight %,
Alumina content is 25.0 weight %, and the content of USY molecular sieve is 5.0 weight %, and nickel content is 12.0
Weight %.Lanthanum oxide content is 4.0 weight %.
Embodiment 4
The present embodiment is for illustrating the method preparing desulfurization of hydrocarbon oil catalyst of the present invention.
By the Zinc oxide powder (Beijing Chemical Plant, containing butt 4.0kg) of 4.04kg, the silicon nitride of 1.50kg
Powder (purity > 99.0%, Qinhuangdao one promise new high-tech material development corporation, Ltd.) and the nitric acid of 0.648kg
Lanthanum (traditional Chinese medicines chemical reagents corporation, purity is more than 99.0 weight %, lanthanum oxide content 45 weight %) exists
The deionized water of 12.5kg mixes, after stirring 30 minutes, obtains zinc oxide, silicon nitride and Lanthanum (III) nitrate
Serosity；
The titanium tetrachloride (Beijing Chemical Plant, analytical pure) of 6.05kg is slowly added into going of 8.00kg
In ionized water, and it is slowly stirred and avoids titanium oxide crystal to separate out, obtain the titanium colloidal sol of pale yellow transparent,
PH=1.0；
By above-mentioned serosity, titanium colloidal sol and REHY molecular sieve, (Qilu Petrochemical Company's catalyst plant, containing butt
0.7kg, SiO2:Al2O3Mol ratio=7.2:1) be mixed together after stir 1h obtain carrier pulp.
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel,
Desulfurization of hydrocarbon oil catalyst A4 is obtained after reduction.
The chemical composition of A4 is: zinc oxide content is 40.0 weight %, and silicon nitride content is 15.0 weight
%, content of titanium dioxide is 25.0 weight %, and nickel content is 14.0 weight %, and lanthanum oxide content is 3.0
Weight %, REHY molecular sieve content is 3.0 weight %.
Comparative example 1
The mixing and stirring in the water of 12.5kg by the zinc oxide of 4.94kg and the lanthanum carbonate of 430g,
To containing zinc oxide and the serosity of lanthana；
By thin for the plan of the Kaolin (catalyst asphalt in Shenli Refinery, containing butt 2.4kg) of 2.88kg, 2.40kg
The deionized water of diaspore (catalyst Nanjing branch company, containing butt 1.80kg) and 7.0kg is under agitation
Mix homogeneously, concentrated nitric acid (chemical pure, the Beijing Chemical Plant produces) stirring adding 200g makes pH=1.8,
And it is warming up to more than 60 DEG C acidifying 1h.When temperature is reduced to below 40 DEG C, add above-mentioned mixed serum
And the beta-molecular sieve of 1.0kg (catalyst Nanjing branch company, containing butt 0.70kg, SiO2:Al2O3's
Mol ratio=20:1), obtain carrier pulp 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,
Desulfurization of hydrocarbon oil catalyst B1 is obtained after reduction.
The chemical composition of B1 is: zinc oxide content is 31.0 weight %, and alumina content is 18.0 weight
%, Kaolin content is 24.0 weight %, and the content of beta-molecular sieve is 7 weight %, and nickel content is 18.0
Weight %, lanthanum oxide content is 2.0 weight %.
Comparative example 2
The mixing and stirring in the water of 12.5kg by the zinc oxide of 4.94kg and the silicon nitride of 1.45kg,
Obtain the serosity containing zinc oxide and silicon nitride；
By boehmite (catalyst Nanjing branch company, containing butt 1.20kg) and the 7.0kg of 1.60kg
Deionized water under agitation mix homogeneously, add 200g concentrated nitric acid (chemical pure, Beijing Chemical Plant
Produce) stirring makes pH=1.8, and is warming up to more than 60 DEG C acidifying 1h.Treat that temperature is reduced to less than 40 DEG C
Time, (catalyst Nanjing branch company, containing butt to add the beta-molecular sieve of above-mentioned mixed serum and 1.0kg
0.70kg, SiO2:Al2O3Mol ratio=20:1), stir after 1h after mixing and obtain carrier pulp；
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel,
Desulfurization of hydrocarbon oil catalyst B2 is obtained after reduction.
The chemical composition of B2 is: zinc oxide content is 49.0 weight %, and silicon nitride content is 14.0 weight
%, alumina content is 12.0 weight %, and the content of beta-molecular sieve is 7 weight %, and nickel content is 18.0
Weight %.
Comparative example 3
By the lanthanum carbonate of the zinc oxide of 4.94kg, the silicon nitride of 1.45kg and 430g in the water of 12.5kg
Mixing and stirring, obtains the mixed serum containing zinc oxide, silicon nitride and lanthana；
By boehmite (catalyst Nanjing branch company, containing butt 1.70kg) and the 7.0kg of 2.26kg
Deionized water under agitation mix homogeneously, add 200g concentrated nitric acid (chemical pure, Beijing Chemical Plant
Produce) stirring makes pH=1.8, and is warming up to more than 60 DEG C acidifying 1h.Treat that temperature is reduced to less than 40 DEG C
Time, add above-mentioned mixed serum, after stirring 1h after mixing, obtain carrier pulp；
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel,
Desulfurization of hydrocarbon oil catalyst B3 is obtained after reduction.
The chemical composition of B3 is: zinc oxide content is 49.0 weight %, and silicon nitride content is 14.0 weight
%, alumina content is 17.0 weight %, and nickel content is 18.0 weight %, and lanthanum oxide content is 2.0 weights
Amount %.
Embodiment 5
Abrasion strength resistance is evaluated.Desulfurization of hydrocarbon oil catalyst A1-A4 and B1-B3 is carried out abrasion strength resistance
Test.Using straight tube abrasion method, method is with reference to " Petrochemical Engineering Analysis method (RIPP) experimental technique "
Middle RIPP 29-90, the results are shown in Table 1.The numerical value that test obtains is the least, shows that abrasion strength resistance is the highest.
The percent that when what in table 1, abrasion index was corresponding is abrasion under certain condition, fine powder generates.
In order to more preferably represent desulfurization of hydrocarbon oil catalyst activity during commercial Application, at sulfuration
After reason, desulfurization of hydrocarbon oil catalyst is also carried out intensity analysis, and concrete processing method is: weigh the hydrocarbon of appropriate mass
Oil desulphurization catalyst is positioned in fluid bed, is passed through hydrogen sulfide (50 volume %) and nitrogen (50 volume %)
Gaseous mixture, and be heated to 400 DEG C of vulcanizing treatment 1h, obtain desulfurization of hydrocarbon oil catalyst after vulcanizing treatment,
And carry out abrasion strength resistance evaluation.The results are shown in Table 1.
Embodiment 6
Desulfurization performance is evaluated.Desulfurization of hydrocarbon oil catalyst A1-A4 and B1-B3 is used the micro-anti-reality of fixed bed
Experiment device carries out HDS evaluation experiment, by the desulfurization of hydrocarbon oil Catalyst packings of 16 grams internal diameter be 30mm,
In the fixed bed reactors of a length of 1m.Raw material hydrocarbon ils is the catalytically cracked gasoline of sulphur concentration 960ppm,
Reaction pressure is 1.38MPa, and hydrogen flowing quantity is 6.3L/h, and gasoline flow is 80mL/h, and reaction temperature is
380 DEG C, the weight space velocity of raw material hydrocarbon ils is 4h-1, carry out the desulphurization reaction of hydrocarbon oil containing surphur.With product vapour
In oil, sulfur content is weighed desulphurizing activated.In product gasoline, sulfur content passes through off-line chromatogram analysis method, uses
The GC6890-SCD instrument of An Jielun company is measured.In order to accurate characterization goes out desulfurization of hydrocarbon oil catalyst
Activity in industry actual motion, HDS evaluation tested after catalyst at the air gas of 480 DEG C
Regeneration Treatment is carried out under atmosphere.Desulfurization of hydrocarbon oil catalyst is carried out HDS evaluation experiment, after regenerating 6 circulations
Its activity settles out substantially, and the catalyst after 6 circulations takes out the content surveying wherein zinc silicate,
The activity of catalyst is represented with the sulfur content in the product gasoline after the 6th stable circulation of catalyst, stable
In rear product gasoline, sulfur content is as shown in table 1.
Product gasoline is weighed simultaneously and calculate its yield.
It is respectively adopted before GB/T 503-1995 and GB/T 5487-1995 measures reaction and the 6th circulation is steady
The motor octane number (MON) of fixed rear gasoline and research octane number (RON) (RON), the results are shown in Table 1.
Table 1
| A1 | A2 | A3 | A4 | B1 | B2 | B3 | |
| Abrasion index | 2.4 | 3.1 | 3.5 | 3.1 | 6.8 | 2.6 | 2.5 |
| Yield of gasoline/% | 99.8 | 99.9 | 99.8 | 99.9 | 98.3 | 98.1 | 98.8 |
| Product sulfur content | 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:
1, the sulfur content of feed gasoline be 960ppm, RON be 93.7, MON is 83.6.
2, △ MON represents the value added of product MON；
3, △ RON represents the value added of product RON；
4, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
From the result data of table 1 it can be seen that the desulfurization of hydrocarbon oil catalyst of present invention offer contains nitridation
Silicon components, desulfurization of hydrocarbon oil catalyst has the most desulphurizing activated and activity stability.Possibly together with rare earth oxygen
Compound, can enable this desulfurization of hydrocarbon oil catalyst absorb sulfur at lower temperatures and through repeatedly further
Carry out reacting and regenerative process, still there is the most desulphurizing activated and activity stability.And this hydrocarbon ils takes off
Sulfur catalyst has more preferable abrasion strength resistance, so that desulfurization of hydrocarbon oil catalyst has the longer use longevity
Life.
Embodiment 7
Carrying out aging to desulfurization of hydrocarbon oil catalyst A1-A4 and B1-B3, condition is: catalyst is placed
In 600 DEG C, steam partial pressure be 20kPa atmosphere under process 16h.
A1-A4 and B1-B3 before and after aging is carried out XRD spectra analysis, and Fig. 1 is that A1 hydro-thermal is old
XRD spectra before and after change, Fig. 2 is the XRD spectra before and after B1 hydrothermal aging.A2-A4 and A1
There is similar XRD spectra, do not show；B2-B3 to B1 has similar XRD spectra, does not shows.
In FIG, the XRD spectra after A1 hydrothermal aging does not occur 2 θ=22.0 of zinc silicate, 25.54,
The characteristic peak of 48.9 and 59.4；In fig. 2, the XRD spectra after B1 hydrothermal aging occurs in that silicic acid
The features described above peak of zinc.The zinc silicate in the XRD spectra of crystal content quantitative analysis B1-B3 is used to contain
Amount, the results are shown in Table 2.
With evaluation methodology same as in Example 6 evaluate aging after the desulphurizing ability of A1-A4 and B1-B3
Can, the results are shown in Table 2.
Table 2
| Catalyst | A1 | A2 | A3 | A4 | B1 | B2 | B3 |
| Zinc silicate content/weight % | 0 | 0 | 0 | 0 | 13.4 | 0 | 0 |
| Product gasoline sulfur content/ppm | 9 | 11 | 13 | 9 | 30 | 36 | 35 |
| △MON | 0.59 | 0.40 | 0.35 | 0.45 | -0.45 | -0.40 | -0.60 |
| △RON | 0.55 | 0.30 | 0.40 | 0.35 | -0.40 | -0.35 | -0.54 |
| △(RON+MON)/2 | 0.57 | 0.35 | 0.38 | 0.40 | -0.43 | -0.38 | -0.57 |
From the results shown in Table 2, after ageing process, the desulfurization of hydrocarbon oil catalyst of embodiment does not has
There is a generation zinc silicate, and the catalyst in comparative example, zinc oxide can generate silicic acid with the material of silicon oxide-containing
Zinc, so that the desulphurizing activated reduction of catalyst.
Claims (15)
1. a desulfurization of hydrocarbon oil catalyst, on the basis of the gross weight of this desulfurization of hydrocarbon oil catalyst, this hydrocarbon
Oil desulphurization catalyst contains:
1) heat-resistant inorganic oxide of 5-35 weight %, described heat-resistant inorganic oxide selected from aluminium oxide,
At least one in titanium dioxide, zirconium dioxide and tin ash；
2) metal-oxide of 10-70 weight %, described metal-oxide is selected from IIB, VB and VIB
At least one in the metal-oxide of race's element；
3) silicon nitride of 2-40 weight %；
4) metallic promoter agent of 3-30 weight %, described metallic promoter agent is in cobalt, nickel, ferrum and manganese
At least one；
5) rare-earth oxide of 0.5-10 weight % in terms of rare earth oxide；
6) molecular sieve with BEA or FAU structure of 1-20 weight %.
Desulfurization of hydrocarbon oil catalyst the most according to claim 1, wherein, is catalyzed with this desulfurization of hydrocarbon oil
On the basis of the gross weight of agent, the content of described heat-resistant inorganic oxide is 10-25 weight %, described metal
The content of oxide is 25-60 weight %, and the content of described silicon nitride is 5-25 weight %, described metal
The content of accelerator is 10-20 weight %, described rare-earth oxide content in terms of rare earth oxide
For 1-5 weight %, the content of described molecular sieve is 2-10 weight %.
Desulfurization of hydrocarbon oil catalyst the most according to claim 1, wherein, described rare earth metal aoxidizes
Thing is at least one in the oxide of lanthanum, cerium and neodymium.
Desulfurization of hydrocarbon oil catalyst the most according to claim 1, wherein, described metal-oxide is
In zinc oxide, Aska-Rid., vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide
At least one.
Desulfurization of hydrocarbon oil catalyst the most according to claim 1, wherein, silicon nitride is that α phase nitrogenizes
Silicon.
Desulfurization of hydrocarbon oil catalyst the most according to claim 1, wherein, described molecular sieve is X-type
Molecular sieve, Y type molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY, PREY
With at least one in beta-molecular sieve.
7. the side of the hydrocarbon ils desulfurization of hydrocarbon oil catalyst prepared in claim 1-6 described in any one
Method, the method includes:
(1) by heat-resistant inorganic oxide binding agent, silicon nitride, metal-oxide, rare earth metal chemical combination
Thing, water and acidic liquid are mixed to get mixed serum, then with there is the molecule of BEA and/or FAU structure
Sieve contact forms carrier pulp；Described carrier pulp is shaped, first be dried and the first roasting,
To carrier；
(2) on described carrier, introduce the precursor of metallic promoter agent, and carry out second dry and the second roasting
Burn, obtain catalyst precarsor；
(3) described catalyst precarsor is reduced under hydrogen atmosphere, obtain desulfurization of hydrocarbon oil catalyst.
Method the most according to claim 7, wherein, described heat-resistant inorganic oxide binding agent is
Heat-resistant inorganic oxide or heat-resistant inorganic oxide can be changed under conditions of described first roasting
Material.
Method the most according to claim 7, wherein, described rare earth compound is rare earth gold
At least one in the carbonate, bicarbonate, nitrate, chloride, formates and the acetate that belong to.
Method the most according to claim 7, wherein, the precursor of described metallic promoter agent is metal
In the acetate of accelerator, carbonate, nitrate, sulfate, rhodanate and oxide at least one
Kind.
11. methods according to claim 7, wherein, the described first temperature being dried is 80-120 DEG C,
Described first time being dried was 0.5-24h；The temperature of described first roasting is 300-700 DEG C, described
The time of one roasting is at least 0.5h.
12. methods according to claim 7, wherein, the described second temperature being dried is 50-300 DEG C,
Described second time being dried was 0.5-8h；The temperature of described second roasting is 300-700 DEG C, described
The time of two roastings is 0.5-4h.
13. methods according to claim 7, wherein, the temperature of described reduction is 300-600 DEG C,
The time of described reduction is 0.5-6h, and in described hydrogen atmosphere, hydrogen content is 10-60 volume %.
The hydrocarbon ils desulfurization of hydrocarbon oil that in 14. claim 7-13, preparation method described in any one prepares is urged
Agent.
The method of 15. 1 kinds of desulfurization of hydrocarbon oil, the method includes: in a hydrogen atmosphere, by hydrocarbon oil containing surphur with
In claim 1-6 and 14, the hydrocarbon ils desulfurization of hydrocarbon oil catalyst described in any one contacts, described contact
Temperature be 350-500 DEG C, the pressure of described contact is 0.5-4MPa.
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