CN104511299B - A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil - Google Patents
A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil Download PDFInfo
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Abstract
The invention discloses a kind of desulphurization catalyst, on the basis of the gross weight of this desulphurization catalyst, this desulphurization catalyst contains the silica source of 5 30 weight %, the aluminium oxide of 5 30 weight %, the zinc oxide of 30 70 weight %, the lead oxide of 2 15 weight %, the molecular sieve with BEA structure of 1 20 weight % and/or has molecular sieve and the active metal of 5 30 weight % of FAU structure；And at least part of described lead oxide is to form formula Pb with described zinc oxidexZn1‑xPresented in the zinc lead solid solution that O represents, wherein x meets 0 ＜ x≤0.12, and x represents atomic molar ratio；Described active metal is at least one in cobalt, nickel, ferrum and manganese.Present invention also offers the preparation method of a kind of desulphurization catalyst and the method for desulfurization of hydrocarbon oil.The desulphurization catalyst that the present invention provides has the most desulphurizing activated and activity stability.
Description
Technical field
The method that the present invention relates to a kind of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil, specifically,
Relating to a kind of desulphurization catalyst, preparation method and the desulfurization obtained by the method for a kind of desulphurization catalyst are urged
Agent, and the method that desulphurization catalyst is applied in desulfurization of hydrocarbon oil.
Background technology
Along with people's pay attention to day by day to environmental conservation, environmental regulation is the strictest, and reduce gasoline and
The sulfur content of diesel oil is considered as one of most important measure improving air quality, because the sulfur meeting in fuel
The performance of vehicle catalytic converter is had adverse effect on.Present in automobile engine tail gas, sulfur can press down
Noble metal in converter processed also can be allowed to occur irreversibly to be poisoned, and reduces converter clean to vehicle exhaust
The effect changed.Non-purified vehicle exhaust contains unburned non-methane hydrocarbon, nitrogen oxide and an oxidation
Carbon, these gases are formed photochemical fog by hydrophilic dye.
Most of sulfur in China's gasoline products come from hot-working petroleum blending component, such as catalytic cracking vapour
Oil.Therefore in hot-working petroleum, the minimizing of sulfur content contributes to reducing the sulfur content of China's gasoline products.I
Existing gasoline products standard GB 17930-2011 " motor petrol " of state requires to December 31 in 2013
Day, in gasoline products, sulfur content must drop to 50 μ g/g.And the gasoline product quality standard in future
Will be stricter.In this case, catalytically cracked gasoline has to pass through deep desulfuration and just can make gasoline
Product meets the requirement of environmental protection.
In order to ensure the combustibility of motor vehicle fuel, while reducing the sulfur content of motor vehicle fuel, also should
This is avoided olefin(e) centent in gasoline to change and make its octane number (including ROM and MON) as far as possible
Reduce.Affect olefin(e) centent be typically due to remove thiophenes (include thiophene, benzothiophene,
Alkylthrophene, alkyl benzothiophenes and methyldibenzothiophene) while cause hydrogenation reaction to cause.
In addition it is also necessary to avoid desulfurization condition to make the aromatic hydrocarbons of catalytically cracked gasoline may be saturated and lose.Therefore
Optimal method be realize desulfurization while keep the combustibility of gasoline products.
At present, the process for deep desulphurization of oil product mainly has hydrofinishing and absorption two kinds of methods of desulfurization, wherein
Hydrorefined relatively costly.S Zorb absorption desulfurization belongs to absorption desulfurization technology, and this technology is certain
Temperature, pressure and realize under conditions of facing hydrogen removing the sulfur compounds adsorption in hydrocarbon ils.This technology has hydrogen
Consume low and the highest to the purity requirement of hydrogen feature so that this technology has wide in terms of fuel desulfuration
Application prospect.
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.
US6150300 discloses a kind of method preparing adsorbent, including preparing spheroidal particle: (a) will
Silica containing compositions, compositions containing dispersion metal-oxide in an aqueous medium and contain
The compositions having zinc oxide is mixed to form the first mixture and does not extrude described first mixture；(b) by institute
State the first mixture globulate and form the granule with diameter 10-1000mm.Wherein step (a) is also wrapped
Include and mix with metallic promoter agent.
CN1422177A 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, expanded perlite, aluminium oxide and promoter metals, wherein said
Can be from cracking gasoline when promoter metals with the valence state substantially reduced and contacts under desulfurization conditions
Or the amount removing sulfur in diesel fuel stream exists.
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.
Although published adsorbent has certain desulfurization performance, but due to be under facing hydrogen state de-
, inevitably there is hydrogenation of olefins, thus cause loss of octane number in sulfur.And along with quality of gasoline mark
Accurate raising, requires also the strictest to product gasoline sulfur content.As can be seen here, it is desirable to provide a kind of tool
There is more high desulfurization activity, and the new catalyst of product gasoline octane number can be improved.
Summary of the invention
The problem that the invention aims to the adsorbent activity reduction overcoming prior art to exist, it is provided that
A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil.
To achieve these goals, the present invention provides a kind of desulphurization catalyst, total with this desulphurization catalyst
On the basis of weight, this desulphurization catalyst contains the silica source of 5-30 weight %, the oxidation of 5-30 weight %
Aluminum, the zinc oxide of 30-70 weight %, the lead oxide of 2-15 weight %, 1-20 weight % there is BEA
The molecular sieve of structure and/or there is molecular sieve and the active metal of 5-30 weight % of FAU structure；And
At least part of described lead oxide is to use formula Pb with described zinc oxide is formedxZn1-xThe zinc lead that O represents is solid
Solution exists, and wherein x meets 0 ＜ x≤0.12, and x represents atomic molar ratio；Described active metal
For at least one in cobalt, nickel, ferrum and manganese.
Present invention also offers the preparation method of a kind of desulphurization catalyst, the method includes: (1) is by leaded
The mixed solution that compound, zinc compound and water are mixed to get carries out precipitation, precipitation is obtained
To mixture carry out filtering, be dried and roasting, be precipitated product；(2) by silica source, oxidation
Aluminum source, there is the molecular sieve of BEA structure and/or there is the molecular sieve of FAU structure, water and acid solution connect
Touch and form serosity, and the precipitated product that step (1) obtains is mixed with described serosity, form carrier and mix
Compound；Again by described carrier mixture molding, it is dried and roasting, forms carrier；(3) to step (2)
Introduce on the carrier obtained containing the compound of active metal and be dried, roasting, before obtaining desulphurization catalyst
Body；Described active metal is at least one in cobalt, nickel, ferrum and manganese；(4) step (3) is obtained
Desulphurization catalyst precursor reduce under hydrogen atmosphere, obtain desulphurization catalyst.
Present invention also offers the desulphurization catalyst that preparation method provided by the present invention obtains.
A kind of method that present invention also offers desulfurization of hydrocarbon oil, the method includes: by hydrocarbon oil containing surphur and desulfurization
Catalyst haptoreaction, wherein, the desulphurization catalyst that described desulphurization catalyst provides for the present invention.
By technique scheme, in the desulphurization catalyst that the present invention provides at least partly lead oxide with oxygen
That changes zinc formation uses formula PbxZn1-xThe zinc lead solid solution thereof that O represents exists, and absorbs constituent element as sulfur,
The desulphurization catalyst making the present invention provide has the most desulphurizing activated and activity stability.And this desulfurization
Catalyst also has more preferable abrasion strength resistance, can improve the service life of desulphurization catalyst.In addition should
Desulphurization catalyst can also absorb sulfur at lower temperatures and carry out oxidation regeneration, and prior art is inhaled
The temperature receiving sulfur is 410 DEG C, and the temperature of oxidation regeneration is 550 DEG C.Desulphurization catalyst in embodiment 1
It is Pb that A1 has chemical composition0.044Zn0.956The zinc lead solid solution of O, abrasion index is 5.6；Desulfurization catalyst
The sulfur content of product gasoline is made to be as long as agent A1 can process raw material in example 4 at 380 DEG C
10 μ g/g, and regeneration temperature is 480 DEG C.Although and comparative example 4 obtaining containing lead oxide and oxygen
Change the desulphurization catalyst B4 of zinc, but be formed without zinc lead solid solution, at 380 DEG C, process what raw material obtained
The sulfur content of product gasoline to be up to 28 μ g/g.
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 XRD spectra of precipitated product C1-C3, ZnO and PbO；Wherein
Characterize 2 θ values B of the diffraction maximum in (100) face of ZnO, (002) face and (101) face100、
B002And B101It is respectively 31.55 °, 34.21 ° and 36.04 °,
2 θ of the diffraction maximum in (100) face of ZnO, (002) face and (101) face in sign C1
Value A100、A002And A101It is respectively 31.75 °, 34.42 ° and 36.24 °,
2 θ of the diffraction maximum in (100) face of ZnO, (002) face and (101) face in sign C2
Value A100、A002And A101It is respectively 31.80 °, 34.45 ° and 36.28 °,
2 θ of the diffraction maximum in (100) face of ZnO, (002) face and (101) face in sign C3
Value A100、A002And A101It is respectively 31.78 °, 34.43 ° and 36.26 °；
Fig. 2 is the XRD spectra of desulphurization catalyst A1.
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 desulphurization catalyst, on the basis of the gross weight of this desulphurization catalyst, this desulfurization
Catalyst contains the silica source of 5-30 weight %, the aluminium oxide of 5-30 weight %, 30-70 weight %
Zinc oxide, the lead oxide of 2-15 weight %, the molecular sieve with BEA structure of 1-20 weight % and/or
There is molecular sieve and the active metal of 5-30 weight % of FAU structure；And at least part of described oxidation
Lead is to use formula Pb with described zinc oxide is formedxZn1-xThe zinc lead solid solution thereof that O represents exists, its
Middle x meets 0 ＜ x≤0.12, and x represents atomic molar ratio；Described active metal is cobalt, nickel, ferrum and manganese
In at least one.
According to the present invention, described desulphurization catalyst contains lead oxide and zinc oxide, and described desulfurization catalyst
The zinc lead solid solution that agent can be formed containing lead oxide and zinc oxide.Described zinc lead solid solution can be with Stable Oxygen
Change the lattice structure of zinc, keep the activity of zinc oxide constituent element.The lead oxide that described desulphurization catalyst contains
The amount of the zinc oxide measured and contain can make described desulphurization catalyst contain the zinc lead represented with above-mentioned formula
Solid solution.Described desulphurization catalyst can be containing lead oxide and zinc oxide all formed and use
State the zinc lead solid solution that formula represents；Can also be in addition to containing the zinc lead solid solution represented with above-mentioned formula
Possibly together with lead oxide and/or zinc oxide, it is solid that whole lead oxide and most zinc oxide form zinc lead
Solution, outer possibly together with a small amount of zinc oxide containing zinc lead solid solution in desulphurization catalyst.The most described desulfurization
Lead oxide and zinc oxide that catalyst contains all form the zinc lead solid solution represented with above-mentioned formula.
After forming zinc lead solid solution according to the present invention, lead oxide and zinc oxide, the lattice structure of zinc oxide is also
Do not destroy, but enter in lattice owing to lead ion replaces zinc ion, so described desulphurization catalyst
The angle of diffraction of the characteristic peak characterizing ZnO in XRD spectra can change, and is therefore surveyed by XRD
Fixed described desulphurization catalyst may determine that and there is zinc lead solid solution in described desulphurization catalyst.In Fig. 2
The XRD spectra of the desulphurization catalyst A1 obtained under the conditions of same XRD determining of display and ZnO's
XRD spectra.In fig. 2, the single characteristic peak of lead oxide and zinc oxide does not occur, but goes out
Show the characteristic peak of the hexagonal crystal system characterizing zinc oxide of peak position skew, illustrated that lead oxide and zinc oxide are whole
Define zinc lead solid solution.Under preferable case, described desulphurization catalyst meets relationship below:
A100-B100=0.2 ° to 0.3 °, A100And B100Obtain under the conditions of being illustrated respectively in identical XRD determining
To the XRD spectra of described desulphurization catalyst and the XRD spectra of ZnO in, characterize ZnO (100)
2 θ values of the diffraction maximum in face.
In the case of according to the invention it is preferred to, described desulphurization catalyst meets relationship below:
A002-B002=0.2 ° to 0.3 °；A002And B002Obtain under the conditions of being illustrated respectively in identical XRD determining
To the XRD spectra of described desulphurization catalyst and the XRD spectra of ZnO in, characterize ZnO (002)
2 θ values of the diffraction maximum in face.
In the case of according to the invention it is preferred to, described desulphurization catalyst meets relationship below:
A101-B101=0.2 ° to 0.3 °；A101And B101Obtain under the conditions of being illustrated respectively in identical XRD determining
To the XRD spectra of described desulphurization catalyst and the XRD spectra of ZnO in, characterize ZnO (101)
2 θ values of the diffraction maximum in face.
According to the present invention, may determine that described desulphurization catalyst contains lead oxide by above-mentioned XRD determining
The zinc lead solid solution formed with zinc oxide, in this zinc lead solid solution, mol ratio x of lead and zinc can be by unit
Element is analyzed such as spectrofluorimetry and is measured, it may be determined that described zinc lead solid solution can use formula
PbxZn1-xO represents, wherein x meets 0 ＜ x≤0.12, and x represents atomic molar ratio.
According to the present invention, described desulphurization catalyst preferably, on the basis of the gross weight of this desulphurization catalyst,
This desulphurization catalyst contains the silica source of 10-20 weight %, the aluminium oxide of 10-20 weight %, 35-54
The zinc oxide of weight %, the lead oxide of 5-12 weight %, the molecule with BEA structure of 2-10 weight %
Sieve and/or have molecular sieve and the active metal of 10-20 weight % of FAU structure.
According to the present invention, described active metal can be any the sulfur of oxidation state can be reduced to hydrogen sulfide
Metal, it is preferable that described active metal is nickel.
According to the present invention, described silica source can be to provide viscous in described desulphurization catalyst between each component
Knot effect.Under preferable case, described silica source can be that silicon oxide or silica content are more than 45 weights
The natural crystal of amount %.Preferably, described silica source can be laminated clay column, kieselguhr, expansion treasure
At least one in Zhu Yan, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
According to the present invention, described aluminium oxide can be to provide bonding in described desulphurization catalyst between each component
Effect.Under preferable case, described aluminium oxide can be gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-
At least one in aluminium oxide.
According to the present invention, described in have the molecular sieve of FAU structure be faujasite-type molecular sieve, such
Type molecular sieve has three-dimensional twelve-ring duct, and aperture isDescribed have FAU structure
Molecular sieve be mainly X-type and the molecular sieve of Y type, in general SiO2/Al2O3Mol ratio is 2.2-3.0
For X-type molecular sieve, SiO2/Al2O3Mol ratio more than 3.0 for Y type molecular sieve.X-type and Y type
The framing structure of molecular sieve broadly falls into hexagonal crystal system, and space group structure is Fd3m, the crystalline substance of X-type molecular sieve
Born of the same parents' parameterThe cell parameter of Y type molecular sieve
According to the present invention, described in there is the molecular sieve of FAU structure also include modified there is FAU knot
The molecular sieve of structure.Method of modifying 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 limited to super-stable Y molecular sieves (USY), REUSY containing rare earth element,
REHY, REY, and phosphorous PUSY, PREHY, PREY etc..
According to the present invention, described in there is the molecular sieve of BEA structure be mainly beta-molecular sieve, its structural formula
For (Nan[AlnSi64-nO128], n < 7), it is polymorph A that is different by two structures but that be closely related
The mixed crystal formed with B, both has twelve-ring 3 D pore canal system, and polymorph A is formed a pair
Enantiomer, space group is P4122 and P4322, cell parameter isPolymorph
B belongs to achirality space group C2/c, cell parameterβ=114.5
°.In BEA structure molecular screen, twelve-ring pore size is<100 direction>and <001 direction>.
In the case of according to the invention it is preferred to, described in have the molecular sieve of BEA structure be beta-molecular sieve,
The molecular sieve of the described FAU of having structure be X-type molecular sieve, Y type molecular sieve, USY, REUSY,
At least one in REHY, REY, PUSY, PREHY and PREY；Preferably, have described in
The molecular sieve of FAU structure is at least one in USY, REUSY, REY, PUSY and PREY.
Present invention also offers the preparation method of a kind of desulphurization catalyst, the method includes: (1) is by leaded
The mixed solution that compound, zinc compound and water are mixed to get carries out precipitation, precipitation is obtained
To mixture carry out filtering, be dried and roasting, be precipitated product；(2) by silica source, oxidation
Aluminum source, the molecular sieve with BEA structure and/or the molecular sieve of FAU structure, water contact shape with acid solution
Become serosity, and the precipitated product that step (1) obtains is mixed with described serosity, form carrier mixture；
Again by described carrier mixture molding, it is dried and roasting, forms carrier；(3) obtain to step (2)
Carrier on introduce containing the compound of active metal and be dried, roasting, obtain desulphurization catalyst precursor；
Described active metal is at least one in cobalt, nickel, ferrum and manganese；(4) step (3) obtained is de-
Sulfur catalyst precursor reduces under hydrogen atmosphere, obtains desulphurization catalyst.
In the preparation method of the desulphurization catalyst of present invention offer, it is solid that step (1) can form zinc lead
Solution.
According to the present invention, described in step (1), the addition of lead-containing compounds and zinc compound is permissible
Select in wider scope, formula Pb can be used as long as can be formedxZn1-xThe zinc lead solid solution that O represents
Body.Under preferable case, described in step (1), lead-containing compounds and zinc compound addition make
In the desulphurization catalyst that must obtain, on the basis of the gross weight of described desulphurization catalyst, the content of lead oxide
For 2-15 weight %, the content of zinc oxide is 30-70 weight %；Preferably, described lead-containing compounds and
Zinc compound addition makes in the desulphurization catalyst obtained, and with the gross weight of described desulphurization catalyst is
Benchmark, the content of lead oxide is 5-12 weight %, and the content of zinc oxide is 35-54 weight %.
According to the present invention, the precipitated product that step (1) obtains is carried out elementary analysis and XRD determining,
Can be determined that in this precipitated product containing zinc lead solid solution according to elementary analysis and XRD determining result.Tool
Body ground, first carries out this precipitated product elementary analysis and judges wherein to contain lead element and zinc element.Secondly
This precipitated product is carried out XRD determining analysis, as it is shown in figure 1, according to the table occurred in XRD spectra
Levy the characteristic peak of the hexagonal crystal system of ZnO, and there is no the characteristic peak of lead oxide, may infer that formation zinc lead
Solid solution.Because forming zinc lead solid solution is that lead replaces in the lattice structure that zinc enters zinc oxide, independent
Lead oxide crystal structure without, so in the XRD spectra of zinc lead solid solution, still have ZnO brilliant
The architectural feature of body, and there is no the architectural feature of lead oxide crystal.But ZnO in zinc lead solid solution
The position at crystalline phase peak is subjected to displacement.Therefore, can be determined that precipitation is produced by the XRD spectra of precipitated product
Containing zinc lead solid solution in thing.
In the case of according to the invention it is preferred to, described precipitated product meets relationship below: A100-B100=0.2
° to 0.3 °, A100And B100The described precipitation obtained under the conditions of being illustrated respectively in identical XRD determining
In the XRD spectra of product and the XRD spectra of ZnO, characterize the diffraction maximum in (100) face of ZnO
2 θ values.
In the case of according to the invention it is preferred to, described precipitated product meets relationship below: A002-B002=0.2
° to 0.3 °；A002And B002The described precipitation obtained under the conditions of being illustrated respectively in identical XRD determining
In the XRD spectra of product and the XRD spectra of ZnO, characterize the diffraction maximum in (002) face of ZnO
2 θ values.
In the case of according to the invention it is preferred to, described precipitated product meets relationship below: A101-B101=0.2
° to 0.3 °；A101And B101The described precipitation obtained under the conditions of being illustrated respectively in identical XRD determining
In the XRD spectra of product and the XRD spectra of ZnO, characterize the diffraction maximum in (101) face of ZnO
2 θ values.
In the present invention, according to the diffraction maximum of the ZnO crystal occurred in the XRD spectra of described precipitated product
2 θ values meet above-mentioned relation formula.Can be determined that the precipitated product that the preparation method that the present invention provides obtains
In containing zinc lead solid solution.
According to the present invention it is possible to carry out elementary analysis and XRD determining by precipitated product, determine formation
Zinc lead solid solution in lead and the mol ratio of zinc.Under preferable case, through XRD determining analysis, step (1)
Containing useful formula Pb in the precipitated product obtainedxZn1-xThe zinc lead solid solution that O represents, wherein x meets 0
＜ x≤0.12, x represents atomic molar ratio.In the zinc lead solid solution represented with above-mentioned formula formed, lead
With zinc according to above-mentioned atomic molar than coupling, it is provided that ZnO crystal is absorbing sulfur and oxidation regeneration mistake
More preferable crystal structural stability is had, such that it is able to be further ensured that containing zinc lead solid under the hot environment of journey
The desulphurization catalyst of solution has the most desulphurizing activated.
According to the present invention, lead-containing compounds described in step (1) can be the leaded chemical combination of various water solublity
Thing, under preferable case, described lead-containing compounds is plumbi nitras and/or lead acetate.The institute used in the present invention
Stating lead-containing compounds can also be for the form of the hydrated compound containing water of crystallization.
According to the present invention, zinc compound described in step (1) can be that various water solublity closes containing zinc impregnation
Thing, under preferable case, described zinc compound is at least one in zinc acetate, zinc chloride and zinc nitrate.
The described zinc compound used in the present invention can also be the form of the hydrated compound containing water of crystallization.
According to the present invention, precipitation described in step (1) for from described mixed solution by lead and
Zinc is co-precipitated out the mixture obtained containing lead and zinc.Under preferable case, precipitate described in step (1)
The precipitant that reaction uses can be carbamide and/or ammonia.Use above-mentioned precipitant that described precipitation can be made anti-
Should carry out more complete, and the generation of beneficially zinc lead solid solution.
In the case of according to the invention it is preferred to, described in step (1), the pH of mixture is 9-13.Step
Suddenly when the described mixture that in (1), precipitation obtains is above-mentioned pH scope, it is ensured that by described mixed
Close in solution the lead contained and zinc is co-precipitated out more completely, and the generation of beneficially zinc lead solid solution.
According to the present invention, described being dried can be played described by be co-precipitated out in step (1) with roasting
Mixture is changed into zinc lead solid solution.In order to obtain the zinc lead solid solution that can represent with above-mentioned formula, excellent
In the case of choosing, the condition being dried described in step (1) includes: the temperature being dried is 100-200 DEG C, dry
The dry time is 0.5-3h；The condition of described roasting includes: the temperature of roasting is 400-700 DEG C, roasting
Time be 0.5-3h.
Step (2) in the preparation method of the desulphurization catalyst according to present invention offer, this step is used for will
Silica source, alumina source, there is the molecular sieve of BEA structure and/or there is the molecular sieve of FAU structure
The precipitated product obtained with step (1) prepares carrier.Under preferable case, described silica source,
Described alumina source and described in there is the molecular sieve of BEA structure and/or there is the molecular sieve of FAU structure
Addition make in the desulphurization catalyst obtained, on the basis of the gross weight of described desulphurization catalyst, oxygen
The content in SiClx source is that 5-30 weight %, the content of aluminium oxide are 5-30 weight %, have BEA structure
Molecular sieve and/or the content of the molecular sieve with FAU structure be 1-20 weight %；Preferably, described
Silica source, described alumina source and described in have BEA structure molecular sieve and/or have FAU knot
The addition of the molecular sieve of structure makes in the desulphurization catalyst obtained, with the gross weight of described desulphurization catalyst
On the basis of, the content of silica source be 12-25 weight %, the content of aluminium oxide be 10-25 weight %,
The content of the molecular sieve with BEA structure and/or the molecular sieve with FAU structure is 2-10 weight %.
In the case of according to the invention it is preferred to, described alumina source can be the described roasting in step (2)
The material of aluminium oxide can be changed under conditions of burning.Preferably, described alumina source is hydrated alumina
And/or Alumina gel；Described hydrated alumina is boehmite, false boehmite, Alumina hydrate
With at least one in amorphous hydroted alumina.
According to the present invention, described silica source can be to provide viscous in described desulphurization catalyst between each component
Knot effect.Under preferable case, described silica source is that silicon oxide or silica content are more than 45 weight %
Natural crystal.Preferably, described silica source can be laminated clay column, kieselguhr, expanded perlite,
At least one in silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
Although it should be noted that above-mentioned silica source may contain aluminium oxide, but the present invention aoxidizes
The content of aluminum does not include the amount of aluminium oxide contained in above-mentioned silica source, and the content of aluminium oxide only includes
The amount of the aluminium oxide formed by alumina source.The amount of aluminium oxide contained in silica source still can be regarded as oxygen
The amount in SiClx source.The molecular sieve with BEA structure that adds in step (2) and/or there is FAU knot
The molecular sieve of structure is same as above, does not repeats them here.Have described in although BEA structure molecular sieve and/
Or have in the molecular sieve of FAU structure containing aluminium oxide, but have BEA structure molecular sieve and/
Or the amount with the aluminium oxide contained in the molecular sieve of FAU structure still can be regarded as have BEA structure point
The amount of the molecular sieve that son sieves and/or has FAU structure is not counted in aluminium oxide.The most provided by the present invention
In the desulphurization catalyst that method prepares, the content of each component calculates according to inventory.
In the present invention, in step (2), the consumption of described acid solution is so that described carrier mixture
PH value be 1-5, preferably 1.5-4.Described acid solution can selected from water-soluble mineral acid and/or
Organic acid, such as, can be at least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
In the present invention, the amount adding water in step (1) can be not specially limited, as long as can obtain
Mixed solution described in step (1).Such as add amount and the lead-containing compounds of water and close containing zinc impregnation
The weight ratio of thing weight summation is 5-10:1.
In the present invention, the amount adding water in step (2) can be not specially limited, as long as can obtain
Serosity described in step (2).The amount such as adding water makes the solid content of the described serosity obtained
For 15-40 weight %.
In step of the present invention (2), described carrier mixture can be wet mixture, paste mixture,
The form such as dough or serosity.By described molding, described carrier mixture can be shaped to extrudate,
Sheet, pill, ball or micro-spherical particle.Such as, described carrier mixture is dough or paste mixture
Time, described carrier mixture molding (preferably extrusion molding) can be made to form granule, preferably diameter is at 1.0-8.0
Mm, length at the cylindrical extrudates of 2.0-5.0mm, then make the extrudate of gained be dried,
Roasting.If described carrier mixture is wet mixture form, this mixture can be made to be thickened, through being dried
Aftershaping.The most described carrier mixture is slurry form, by being spray-dried formation granularity is
The microsphere of 20-200 micron, reaches the purpose of molding.For the ease of being spray-dried, before being dried, serosity consolidates
Content can be 10-50 weight %, preferably 20-50 weight %.
In the present invention, public affairs that the drying means of described carrier mixture and condition are those skilled in the art
Know, such as, the method being dried can be dry, dry, forced air drying.Under preferable case, step (2)
In, be dried temperature can be room temperature to 400 DEG C, preferably 100-350 DEG C；The described dry time
At least 0.5 hour, preferably 0.5-60 hour.
In the present invention, the roasting condition of described carrier mixture can also by those skilled in the art public affairs
Knowing, in general, the temperature of described roasting is 400-700 DEG C, preferably 450-650 DEG C；Described roasting
Time be at least 0.5 hour, preferably 0.5-100 hour, more preferably 0.5-10 hour.
In step of the present invention (3), the addition of the described compound containing active metal makes obtain to take off
In sulfur catalyst, on the basis of the gross weight of desulphurization catalyst, the content of described active metal is 5-30
Weight %；It is preferably 10-20 weight %.Wherein, described can be in step (3) containing active metal
Roasting condition under be converted into the material of oxide of active metal.The described compound containing active metal
The acetate of active metal, carbonate, nitrate, sulfate, rhodanate and oxide can be selected from
In at least one.Described active metal can be at least one in cobalt, nickel, ferrum and manganese；Preferably
Described active metal can be nickel.
In the present invention, introducing the compound containing active metal on described carrier can be real by multiple method
Existing.It is for instance possible to use well known to a person skilled in the art that dipping method or intermediate processing realize.Described
Dipping method is carrier described in the solution with the compound containing active metal or suspension impregnation；Described precipitation
Method is solution or the suspension of the compound containing active metal to be mixed with described carrier, is subsequently adding ammonia
Active metal is deposited on carrier by water.Preferably dipping method.
It is dried described in step of the present invention (3) and roasting can be to be introduced into the change containing active metal
Volatile material on the carrier of compound is removed and active metal is changed into the oxide of active metal,
Obtain desulphurization catalyst precursor.Described dry condition can include, the temperature being dried is about 50-300
DEG C, preferably 100-250 DEG C, the time being dried is about 0.5-8 hour, preferably about 1-5 hour.Institute
State under conditions of the condition of roasting can be included in oxygen or oxygen-containing gas and carry out, described roasting
Temperature can be about 300-800 DEG C, preferably 400-750 DEG C, the time of roasting may be about 0.5-4
Hour, preferably 1-3 hour.
Can be at prepared desulphurization catalyst precursor by the reduction of desulphurization catalyst precursor in step of the present invention (4)
After carry out immediately, it is also possible to (i.e. for desulfurization adsorb before) is carried out before use.Owing to active metal holds
Oxidizable, and the active metal in desulphurization catalyst precursor exists in the form of an oxide, therefore for ease of fortune
Defeated, the reduction of desulphurization catalyst precursor is carried out before carrying out desulfurization absorption by preferred steps (4).Described also
Originally it was that the metal in the oxide making active metal substantially exists with reduction-state, obtained the desulfurization of the present invention
Catalyst.Under preferable case, the condition that desulphurization catalyst precursor reduces in a hydrogen atmosphere is included: hydrogen
Gas content is 10-60 volume %, and the temperature of reduction is 300-600 DEG C, and the time of reduction is 0.5-6 hour；
The temperature preferably reduced is 400-500 DEG C, and the time of reduction is 1-3 hour.
Present invention also offers the desulphurization catalyst that preparation method provided by the present invention obtains.This desulfurization is urged
Agent has the composition of aforementioned desulphurization catalyst, content and structure of feature, does not repeats them here.
A kind of method that present invention also offers desulfurization of hydrocarbon oil, the method includes: by hydrocarbon oil containing surphur and desulfurization
Catalyst haptoreaction, wherein, the desulphurization catalyst that described desulphurization catalyst provides for the present invention.
According to the present invention, in the method for described desulfurization of hydrocarbon oil, described hydrocarbon oil containing surphur and described desulphurization catalyst
Can react in a hydrogen atmosphere, the condition of reaction includes: the temperature of reaction can be 350-500 DEG C,
It is preferably 360-430 DEG C；The pressure of reaction can be 0.5-4MPa；It is preferably 1-2MPa.
According to the present invention, the method for described desulfurization of hydrocarbon oil can also include: by taking off through reaction after reaction
Sulfur catalyst regenerates.The condition of regeneration includes: at oxygen atmosphere, (oxygen content can be 10-80
Volume %) under regenerate；The temperature of regeneration is 450-600 DEG C, preferably 480-520 DEG C；Regeneration
Pressure is normal pressure.
In the present invention, the method for described desulfurization of hydrocarbon oil can also include: the desulphurization catalyst after regeneration is at weight
Reduce before new use.The condition of reduction includes: at hydrogen atmosphere, (hydrogen content can be 30-60
Volume %) under reduce；The temperature of reduction can be 350-500 DEG C, preferably 400-450 DEG C；Reduction
Pressure can be 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 to 210 DEG C, be less from making bigger hydrocarbon molecule be cracked into
The heat of molecule or the product of catalytic process.The thermal cracking process being suitable for includes, but are not limited to coking, hot tearing
Change and visbreaking etc. and combinations thereof.The example of the catalytic cracking process being suitable for includes but not limited to fluid bed
Catalytic cracking and RFCC etc. and combinations thereof.Therefore, be suitable for catalytically cracked gasoline include but not
It is limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and heavy oil to split
Change gasoline and combinations thereof.In some cases, in the methods of the invention be used as hydrocarbon-containifluids fluids time can be in desulfurization
Before by described cracking gasoline fractional distillation and/or hydrotreating.Described " diesel fuel " means that boiling range is
The hydrocarbon mixture of 170 DEG C to 450 DEG C or the liquid of its any fractional composition.This type of hydrocarbon-containifluids fluids include but not
It is limited to light cycle oil, kerosene, straight-run diesel oil, catalytic cracking diesel oil and hydroprocessed diesel etc. and combinations thereof.
In the present invention, term used " sulfur " represents any type of element sulphur such as hydrocarbon-containifluids fluids such as cracking vapour
The organosulfur compound being commonly present in oil or diesel fuel.Present in hydrocarbon-containifluids fluids of the present invention, sulfur includes
But it is not limited to carbonyl sulfide (COS), Carbon bisulfide (CS2), mercaptan or other thiophenes etc.
And combinations thereof, especially include thiophene, benzothiophene, alkylthrophene, alkyl benzothiophenes and alkyl diphenyl
The thiophenes that the molecular weight that is commonly present in bithiophene, and diesel fuel is bigger.
In the present invention, the pressure related to is gauge pressure.
Hereinafter will be described the present invention by embodiment.
In the following Examples and Comparative Examples, the composition of desulfurization adsorbing composition calculates according to feeding intake.
Polycrystal X ray diffraction (XRD) uses X-ray diffractometer (Siemens company D5005 type)
Carry out the structure determination of desulfurization adsorbing composition, Cu target, K α radiation, solid probe, tube voltage 40kV,
Tube current 40mA.
Embodiment 1
The present embodiment is for illustrating the preparation method of the desulphurization catalyst of the present invention.
(1) precipitated product is prepared.By 10.9 kilograms of acetate dihydrate zinc powders (Beijing Chemical Plant produce,
Analytical pure), 0.86 kilogram of acetate trihydrate lead (traditional Chinese medicines chemical reagents corporation, analytical pure) and 18 kilograms go
Ionized water mixes, and is completely dissolved after stirring 30 minutes.Add the precipitated product that 1.8 kilograms of ammonia obtains,
First dry 2 hours at 150 DEG C after filtration, then 500 DEG C of roastings 1 hour, be precipitated product C1.
Precipitated product C1 is carried out fluorescence analysis and XRD determining.XRD spectra does not has (see Fig. 1)
There is the diffraction maximum of PbO, and moving to right occurs in the standard diffraction peak of ZnO, wherein A100-B100=0.2 °,
A002-B002=0.21 °, A101-B101=0.2 °, the whole shape of PbO and ZnO in precipitated product C1 is described
Becoming zinc lead solid solution, its chemical composition is Pb0.044Zn0.956O。
(2) carrier is prepared.Take aluminium oxide 1.60 kilograms (Shandong Aluminum Plant produce, containing butt 1.20 kilograms),
The Kaolin (containing butt 1.80 kilograms) (deriving from Qilu Petrochemical catalyst plant) and 1.0 thousand of 2.16 kilograms
Gram beta-molecular sieve (catalyst Nanjing branch company, containing butt 0.7 kilogram) under agitation mixes, and then adds
After entering 3.6 kilograms of mix homogeneously of deionized water, add 300 milliliter of 30 weight % hydrochloric acid (chemical pure,
Beijing Chemical Plant produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours.Add precipitation to produce
After thing C1 mixing, stirring obtains carrier mixture in 1 hour.
Described carrier mixture uses 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 1 hour at 150 DEG C, then 480
At DEG C, roasting obtains catalyst carrier in 1 hour.
(3) desulphurization catalyst precursor is prepared.The catalyst carrier that the steps of 6.4 kilograms (2) are obtained
With 7.0 kilograms of Nickelous nitrate hexahydrates, 1.10 kilograms of deionized water solution spray impregnation at twice, obtain
Mixture through 150 DEG C be dried 4 hours followed by 480 DEG C of roastings 1 hour, obtain desulphurization catalyst
Precursor.
(4) desulphurization catalyst is prepared.Desulphurization catalyst precursor step (3) obtained is at 400 DEG C
Desulphurization catalyst A1 is obtained after hydrogen atmosphere reduces 3 hours.
The composition of desulphurization catalyst A1 is calculated as by inventory: zinc oxide 40.0 weight %, lead oxide 5.0
Weight %, aluminium oxide 12.0 weight %, Kaolin 18.0 weight %, beta-molecular sieve 7 weight %, nickel 18.0
Weight %.
Desulphurization catalyst A1 is carried out fluorescence analysis and XRD determining result as shown in Figure 2.With precipitation
The XRD spectra of product C1 is corresponding, the diffraction maximum of ZnO in the XRD spectra of desulphurization catalyst A1
Respectively 31.75 °, 34.42 ° and 36.24 °, in the XRD spectra of this peak position and precipitated product C1
The ZnO peak position occurred is consistent, and illustrates that using zinc lead solid solution is the desulphurization catalyst that raw material is prepared
The middle structure that there is zinc lead solid solution.
Embodiment 2
The present embodiment is for illustrating the preparation method of the desulphurization catalyst of the present invention.
(1) precipitated product is prepared.By 14.0 kilograms of zinc nitrate hexahydrates, (Beijing Chemical Plant produces, and analyzes
Pure), 1.80 kilograms of plumbi nitras powder (traditional Chinese medicines chemical reagents corporation, analytical pure) and 18 kilograms of deionizations
Water mixes, and obtains after adding 2.0 kg urea and being heated to 80 DEG C of process 2 hours after stirring 30 minutes
White precipitate, first dries 2 hours at 150 DEG C after filtration, then 500 DEG C of roastings 1 hour, obtains
Precipitated product C2.
Precipitated product C2 is carried out fluorescence analysis and XRD determining.XRD spectra does not has (see Fig. 1)
There is the diffraction maximum of PbO, and moving to right occurs in the standard diffraction peak of ZnO, wherein A100-B100=0.25 °,
A002-B002=0.24 °, A101-B101=0.24 °, the whole shape of PbO and ZnO in precipitated product C2 is described
Becoming zinc lead solid solution, its chemical composition is Pb0.1Zn0.9O。
(2) carrier is prepared.Take aluminium oxide 2.40 kilograms (Shandong Aluminum Plant produce, containing butt 1.8 kilograms),
The expanded perlite (catalyst Nanjing branch company, containing butt 1.50 kilograms) of 1.54 kilograms and 0.43 thousand
Gram beta-molecular sieve (catalyst Nanjing branch company, containing butt 0.3 kilogram) under agitation mixes, and then adds
After entering 4.8 kilograms of mix homogeneously of deionized water, add 275 milliliter of 30 weight % hydrochloric acid (chemical pure,
Beijing Chemical Plant produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours.Add precipitation to produce
After thing C2 mixing, stirring obtains carrier mixture in 1 hour.
Carry out the spray drying forming of carrier mixture with reference to the method for embodiment 1 and roasting obtains carrier.
(3) desulphurization catalyst precursor is prepared.Obtain desulfurization with reference to the method for embodiment 1 step (3) to urge
Agent precursor.
(4) desulphurization catalyst is prepared.Method with reference to embodiment 1 step (4) obtains desulphurization catalyst
A2。
The composition of desulphurization catalyst A2 is calculated as by inventory: zinc oxide 38.0 weight %, lead oxide 12.0
Weight %, aluminium oxide 18.0 weight %, expanded perlite 15.0 weight %, beta-molecular sieve 3 weight %,
Nickel 14.0 weight %.
Embodiment 3
The present embodiment is for illustrating the preparation method of the desulphurization catalyst of the present invention.
(1) precipitated product is prepared.By 13.6 kilograms of acetate dihydrate zinc powders (Beijing Chemical Plant produce,
Analytical pure), 1.05 kilograms of plumbi nitrass (traditional Chinese medicines chemical reagents corporation, analytical pure) and 20 kilograms of deionizations
Water mixes, and is completely dissolved after stirring 30 minutes.After adding 2.0 kg urea and be heated to 80 DEG C process 2
The white precipitate obtained after hour.First dry 2 hours at 150 DEG C after filtration, then 500 DEG C of roastings 1
Hour, it is precipitated product C3.
Precipitated product C3 is carried out fluorescence analysis and XRD determining.XRD spectra does not has (see Fig. 1)
There is the diffraction maximum of PbO, and moving to right occurs in the standard diffraction peak of ZnO, wherein A100-B100=0.23 °,
A002-B002=0.22 °, A101-B101=0.22 °, the whole shape of PbO and ZnO in precipitated product C3 is described
Becoming zinc lead solid solution, its chemical composition is Pb0.07Zn0.93O。
(2) carrier is prepared.Take aluminium oxide 2.13 kilograms (Shandong Aluminum Plant produce, containing butt 1.6 kilograms),
The kieselguhr (catalyst Nanjing branch company, containing butt 1.0 kilograms) of 1.03 kilograms and 0.6 kilogram of USY
(catalyst Nanjing branch company, containing butt 0.5 kilogram) under agitation mixes, and is subsequently adding deionized water
After 4.8 kilograms of mix homogeneously, add hydrochloric acid (chemical pure, the Beijing Chemical Plant of 275 milliliter of 30 weight %
Produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours.Add precipitated product C3 mixing
Rear stirring obtains carrier mixture in 1 hour.
Carry out the spray drying forming of carrier mixture with reference to the method for embodiment 1 and roasting obtains carrier.
(3) desulphurization catalyst precursor is prepared.Obtain desulfurization with reference to the method for embodiment 1 step (3) to urge
Agent precursor.
(4) desulphurization catalyst is prepared.Method with reference to embodiment 1 step (4) obtains desulphurization catalyst
A3。
The composition of desulphurization catalyst A3 is calculated as by inventory: zinc oxide 50.0 weight %, lead oxide 7.0
Weight %, aluminium oxide 16.0 weight %, kieselguhr 10.0 weight %, USY molecular sieve 5.0 weight %,
Nickel 12.0 weight %.
Comparative example 1
This comparative example is used for illustrating that prior art preparation method prepares desulphurization catalyst.
By 4.55 kilograms of Zinc oxide powders (Beijing Chemical Plant produces, containing butt 4.5 kilograms) and 6.9 thousand
The mixing of gram deionized water, obtains zinc oxide serosity after stirring 30 minutes.
Take aluminium oxide 1.60 kilograms (Shandong Aluminum Plant produces, containing butt 1.20 kilograms) and the height of 3.0 kilograms
Ridge soil (containing butt 2.50 kilograms) (deriving from Qilu Petrochemical catalyst plant) under agitation mixes, then adds
After entering 3.6 kilograms of mix homogeneously of deionized water, add 300 milliliter of 30 weight % hydrochloric acid (chemical pure,
Beijing Chemical Plant produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours.Add zinc oxide
After serosity mixing, stirring obtains carrier mixture in 1 hour.
Method with reference to embodiment 1 carries out the spray drying of carrier mixture and impregnates introducing active component
Nickel, obtains desulphurization catalyst B1.
The composition of desulphurization catalyst B1 is calculated as by inventory: zinc oxide 45.0 weight %, aluminium oxide 12.0
Weight %, Kaolin 25.0 weight %, nickel 18.0 weight %.
Comparative example 2
By 5.06 kilograms of Zinc oxide powders (Beijing Chemical Plant produces, containing butt 5.0 kilograms) and 7.8 thousand
The mixing of gram deionized water, obtains zinc oxide serosity after stirring 30 minutes.
Take the swollen of aluminium oxide 2.40 kilograms (Shandong Aluminum Plant produce, containing butt 1.8 kilograms) and 1.85 kilograms
Swollen perlite (catalyst Nanjing branch company, containing butt 1.80 kilograms) under agitation mixes, and is subsequently adding
After 4.8 kilograms of mix homogeneously of deionized water, add hydrochloric acid (chemical pure, the north of 275 milliliter of 30 weight %
Chemical plant, capital produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours.Add zinc oxide paste
After liquid mixing, stirring obtains carrier mixture in 1 hour.
Method with reference to embodiment 1 carries out the spray drying of carrier mixture and impregnates introducing active component
Nickel, obtains desulphurization catalyst B2.
The composition of desulphurization catalyst B2 is calculated as by inventory: zinc oxide 50.0 weight %, aluminium oxide 18.0
Weight %, expanded perlite 18.0 weight %, nickel 14.0 weight %.
Comparative example 3
By 5.76 kilograms of Zinc oxide powders (Beijing Chemical Plant produces, containing butt 5.7 kilograms) and 7.8 thousand
The mixing of gram deionized water, obtains zinc oxide serosity after stirring 30 minutes.
Take aluminium oxide 2.13 kilograms (Shandong Aluminum Plant produces, containing butt 1.6 kilograms) and the silicon of 1.55 kilograms
Diatomaceous earth (catalyst Nanjing branch company, containing butt 1.50 kilograms) under agitation mixes, be subsequently adding from
After 4.8 kilograms of mix homogeneously of sub-water, add hydrochloric acid (chemical pure, Beijing of 275 milliliter of 30 weight %
Factory produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours.Add zinc oxide serosity to mix
After conjunction, stirring obtains carrier mixture in 1 hour.
Method with reference to embodiment 1 carries out the spray drying of carrier mixture and impregnates introducing active component
Nickel, obtains desulphurization catalyst B3.
The composition of desulphurization catalyst B3 is calculated as by inventory: zinc oxide 57.0 weight %, aluminium oxide 16.0
Weight %, kieselguhr 15.0 weight %, nickel 12.0 weight %.
Comparative example 4
By 3.84 kilograms of Zinc oxide powders (Beijing Chemical Plant produce, containing butt 3.8 kilograms), 1.21 thousand
Gram lead oxide powder (traditional Chinese medicines chemical reagents corporation, analytical pure) and 7.8 kilograms of deionized waters mixing, stir
Zinc oxide and lead oxide mixed serum is obtained after mixing 30 minutes.
Take the swollen of aluminium oxide 2.40 kilograms (Shandong Aluminum Plant produce, containing butt 1.8 kilograms) and 1.85 kilograms
Swollen perlite (catalyst Nanjing branch company, containing butt 1.80 kilograms) under agitation mixes, and is subsequently adding
After 4.8 kilograms of mix homogeneously of deionized water, add hydrochloric acid (chemical pure, the north of 275 milliliter of 30 weight %
Chemical plant, capital produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours.Add zinc oxide and
After the mixing of lead oxide serosity, stirring obtains carrier mixture in 1 hour.
Method with reference to embodiment 1 carries out the spray drying of carrier mixture and impregnates introducing active component
Nickel, obtains desulphurization catalyst B4.
The composition of desulphurization catalyst B4 is calculated as by inventory: zinc oxide 38.0 weight %, lead oxide 12.0
Weight %, aluminium oxide 18.0 weight %, expanded perlite 18.0 weight %, nickel 14.0 weight %.
Embodiment 4
(1) abrasion strength resistance evaluation.Desulphurization catalyst A1-A3 and B1-B4 is used straight tube abrasion method
Being evaluated, evaluation methodology is with reference to RIPP 29-90 in " Petrochemical Engineering Analysis method (RIPP) experimental technique "
Method, numerical value is the least, shows that abrasion strength resistance is the highest.The results are shown in Table 1.
(2) desulfurization performance evaluation.Desulphurization catalyst A1-A3 and B1-B4 is used the micro-anti-reality of fixed bed
Experiment device is evaluated, and adsorption reaction raw material uses sulphur concentration to be the catalytically cracked gasoline of 960ppm.Will
The desulfurization adsorbing composition A1 of 16 grams be seated in internal diameter be 30mm, the fixed bed reactors of a length of 1m
In, reaction pressure is 1.38MPa, and hydrogen flowing quantity is 6.3L/h, and gasoline flow is 80mL/h, reaction temperature
Degree is 380 DEG C, and the charging of adsorption reaction raw material is weight space velocity 4h-1, the desulfurization carrying out hydrocarbon oil containing surphur is anti-
Should.Weigh desulphurizing activated with sulfur content in product gasoline.In product gasoline, sulfur content is divided by off-line chromatograph
Analysis method, uses the GC6890-SCD instrument of An Jielun company to be measured.In order to accurate characterization goes out de-
Sulfur catalyst A1 activity in industry actual motion, has reacted rear desulphurization catalyst A1 and has carried out
Raw process, Regeneration Treatment is to carry out under the air atmosphere of 480 DEG C.Desulphurization catalyst A1 is carried out instead
After should regenerating 6 circulations, its activity settles out substantially, with desulphurization catalyst A1 stably rear product gasoline
In sulfur content represent the activity of desulphurization catalyst A1, the results are shown in Table 1.Carry out desulfurization absorption group equally
Compound uses the desulfurization performance evaluation of A2-A3 and B1-B4, the results are shown in Table 1.
Product gasoline is weighed simultaneously and calculate its yield.The results are shown in Table 1.
It is respectively adopted GB/T 503-1995 and GB/T 5487-1995 and measures reaction raw materials catalytically cracked gasoline
And desulphurization catalyst stably after the motor octane number (MON) of product gasoline and research octane number (RON)
(RON), the results are shown in Table 1.
Table 1
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 embodiment 1-4 and table 1 it can be seen that the present invention provide desulphurization catalyst
Containing zinc lead solid solution in A1-A3, desulphurization catalyst has the most desulphurizing activated and activity stability.
Desulphurization catalyst has more preferable abrasion strength resistance, so that desulphurization catalyst has longer service life.
Additionally, this desulphurization catalyst can be carried out at 380 DEG C absorbing at sulfur and 480 DEG C in lower temperature
Oxidation regeneration.
Claims (24)
1. a desulphurization catalyst, on the basis of the gross weight of this desulphurization catalyst, this desulphurization catalyst contains the silica source of 5-30 weight %, the aluminium oxide of 5-30 weight %, the zinc oxide of 30-70 weight %, the lead oxide of 2-15 weight %, the molecular sieve with BEA structure of 1-20 weight % and/or has molecular sieve and the active metal of 5-30 weight % of FAU structure；And at least part of described lead oxide is to form formula Pb with described zinc oxidexZn1-xPresented in the zinc lead solid solution that O represents, wherein x meets 0 ＜ x≤0.12, and x represents atomic molar ratio；Described active metal is at least one in cobalt, nickel, ferrum and manganese.
Desulphurization catalyst the most according to claim 1, wherein, described desulphurization catalyst meets relationship below: A100-B100=0.2 ° to 0.3 °, A100And B100In the XRD spectra of described desulphurization catalyst obtained under the conditions of being illustrated respectively in identical XRD determining and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (100) face of ZnO；B100=31.55°。
Desulphurization catalyst the most according to claim 1, wherein, described desulphurization catalyst meets relationship below: A002-B002=0.2 ° to 0.3 °；A002And B002In the XRD spectra of described desulphurization catalyst obtained under the conditions of being illustrated respectively in identical XRD determining and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (002) face of ZnO；B002=34.21°。
Desulphurization catalyst the most according to claim 1, wherein, described desulphurization catalyst meets relationship below: A101-B101=0.2 ° to 0.3 °；A101And B101In the XRD spectra of described desulphurization catalyst obtained under the conditions of being illustrated respectively in identical XRD determining and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (101) face of ZnO；B101=36.04°。
5. according to the desulphurization catalyst described in any one in claim 1-4, wherein, on the basis of the gross weight of this desulphurization catalyst, this desulphurization catalyst contains the silica source of 10-20 weight %, the aluminium oxide of 10-20 weight %, the zinc oxide of 35-54 weight %, the lead oxide of 5-12 weight %, the molecular sieve with BEA structure of 2-10 weight % and/or has molecular sieve and the active metal of 10-20 weight % of FAU structure.
6. according to the desulphurization catalyst described in any one in claim 1-4, wherein, described active metal is nickel.
7. according to the desulphurization catalyst described in any one in claim 1-4, wherein, described silica source is the natural crystal that silicon oxide or silica content are more than 45 weight %.
Desulphurization catalyst the most according to claim 1, wherein, described in have the molecular sieve of BEA structure be beta-molecular sieve, described in have the molecular sieve of FAU structure be X-type molecular sieve and/or Y type molecular sieve.
Desulphurization catalyst the most according to claim 1, wherein, described in there is the molecular sieve of FAU structure selected from super-stable Y molecular sieves and/or rare earth Y type molecular sieve.
Desulphurization catalyst the most according to claim 1, wherein, described in there is the molecular sieve of FAU structure selected from containing at least one in rare earth superstable Y-type molecular sieve, phosphorous super-stable Y molecular sieves and phosphorous rare earth Y type molecular sieve.
11. desulphurization catalysts according to claim 1, wherein, described in there is the molecular sieve of FAU structure selected from phosphorous rare earth superstable Y-type molecular sieve.
The preparation method of 12. 1 kinds of desulphurization catalysts, the method includes:
(1) mixed solution that lead-containing compounds, zinc compound and water are mixed to get being carried out precipitation, mixture precipitation obtained carries out filtering, being dried and roasting, is precipitated product；
(2) by silica source, alumina source, there is the molecular sieve of BEA structure and/or there is the molecular sieve of FAU structure, water and acid solution contact formation serosity, and the precipitated product that step (1) obtains being mixed with described serosity, formation carrier mixture；Again by described carrier mixture molding, it is dried and roasting, forms carrier；
(3) introduce on the carrier that step (2) obtains containing the compound of active metal and be dried, roasting, obtain desulphurization catalyst precursor；Described active metal is at least one in cobalt, nickel, ferrum and manganese；
(4) the desulphurization catalyst precursor that step (3) obtains is reduced under hydrogen atmosphere, obtain desulphurization catalyst；
Wherein, described lead-containing compounds and zinc compound addition make in the desulphurization catalyst obtained, and on the basis of the gross weight of described desulphurization catalyst, the content of lead oxide is 2-15 weight %, and the content of zinc oxide is 30-70 weight %；
Described silica source, described alumina source, described in there is BEA structure molecular sieve and/or the addition of the molecular sieve and the described compound containing active metal with FAU structure make in the desulphurization catalyst obtained, on the basis of the gross weight of described desulphurization catalyst, the content of silica source be 5-30 weight %, the content of aluminium oxide be 5-30 weight %, the content that content is 1-20 weight % and active metal of the molecular sieve with BEA structure and/or the molecular sieve with FAU structure be 5-30 weight %；
The condition being dried described in step (1) includes: the temperature being dried is 100-200 DEG C, and the time being dried is 0.5-3h；The condition of described roasting includes: the temperature of roasting is 400-700 DEG C, and the time of roasting is 0.5-3h；
Described precipitated product is at least partly containing useful formula PbxZn1-xThe zinc lead solid solution that O represents, wherein x meets 0 ＜ x≤0.12, and x represents atomic molar ratio.
13. preparation methoies according to claim 12, wherein, described precipitated product meets relationship below: A100-B100=0.2 ° to 0.3 °, A100And B100In the XRD spectra of described precipitated product obtained under the conditions of being illustrated respectively in identical XRD determining and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (100) face of ZnO；B100=31.55°。
14. preparation methoies according to claim 12, wherein, described precipitated product meets relationship below: A002-B002=0.2 ° to 0.3 °；A002And B002In the XRD spectra of described precipitated product obtained under the conditions of being illustrated respectively in identical XRD determining and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (002) face of ZnO；B002=34.21°。
15. preparation methoies according to claim 12, wherein, described precipitated product meets relationship below: A101-B101=0.2 ° to 0.3 °；A101And B101In the XRD spectra of described precipitated product obtained under the conditions of being illustrated respectively in identical XRD determining and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (101) face of ZnO；B101=36.04°。
16. preparation methoies according to claim 12, wherein, described lead-containing compounds is plumbi nitras and/or lead acetate.
17. preparation methoies according to claim 12, wherein, described zinc compound is at least one in zinc acetate, zinc chloride and zinc nitrate.
18. preparation methoies according to claim 12, wherein, the precipitant that precipitation described in step (1) uses is carbamide and/or ammonia.
19. preparation methoies according to claim 12, wherein, described in step (1), the pH of mixture is 9-13.
20. preparation methoies according to claim 12, wherein, described alumina source is the material that can be changed into aluminium oxide under conditions of the described roasting of step (2).
21. preparation methoies according to claim 20, wherein, described alumina source is hydrated alumina and/or Alumina gel；Described hydrated alumina is at least one in boehmite, false boehmite, Alumina hydrate and amorphous hydroted alumina.
22. preparation methoies according to claim 12, wherein, described in step (3), the compound containing active metal is at least one in the acetate of active metal, carbonate, nitrate, sulfate, rhodanate and oxide.
23. desulphurization catalysts obtained by the preparation method described in any one in claim 12-22.
The method of 24. 1 kinds of desulfurization of hydrocarbon oil, the method includes: reacted with hydrodesulfurization catalyst by hydrocarbon oil containing surphur, it is characterised in that described desulphurization catalyst is the desulphurization catalyst in claim 1-11 and 23 described in any one.
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