CN104511301B

CN104511301B - A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil

Info

Publication number: CN104511301B
Application number: CN201310461450.6A
Authority: CN
Inventors: 林伟; 田辉平; 王振波; 徐志成; 王磊; 张萍
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-09-30
Filing date: 2013-09-30
Publication date: 2016-08-24
Anticipated expiration: 2033-09-30
Also published as: CN104511301A

Abstract

The invention discloses a desulfurization catalyst. Based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains 5-30% by weight of silicon oxide source, 5-30% by weight of aluminum oxide, and 30-70% by weight of zinc oxide , 2-15% by weight of lead oxide, 0.5-10% by weight of phosphorus oxide based on P ₂ O ₅ , 1-20% by weight of molecular sieves with BEA structure and/or molecular sieves with FAU structure and 5-30% by weight % active metal; and at least part of the lead oxide exists in the form of a zinc-lead solid solution represented by the general formula Pb _x Zn _1-x O with the zinc oxide, wherein x satisfies 0<x≤0.12, and x represents an atomic mole Ratio; the active metal is at least one of cobalt, nickel, iron and manganese. The invention also provides a preparation method of the desulfurization catalyst and a method for desulfurization of hydrocarbon oil. The desulfurization catalyst provided by the invention has better desulfurization activity and activity stability.

Description

A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil

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 are more high desulfurization activity and abrasion resistance properties, and the new catalytic of product gasoline octane number can be improved Agent.

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 %, with P₂O₅Meter 0.5-10 weight % Phosphorous oxides, the molecular sieve with BEA structure of 1-20 weight % and/or have FAU structure point Son sieve and the active metal of 5-30 weight %；And at least part of described lead oxide with described zinc oxide shape Become uses formula Pb_xZn_1-xThe zinc lead solid solution thereof that O represents exists, and wherein x meets 0 ＜ x≤0.12, 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, 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, phosphorus-containing compound, have BEA structure molecular sieve and/or have FAU structure molecular sieve, Water contacts formation serosity with acid solution, and is mixed with described serosity by the precipitated product that step (1) obtains, Form 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) will step Suddenly the desulphurization catalyst precursor that (3) obtain reduces under hydrogen atmosphere, obtains 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 Pb_xZn_1-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 composition_0.044Zn_0.956The zinc lead solid solution of O, abrasion index is 4.4；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 8 μ g/g, and regeneration temperature is 480 DEG C.Although and comparative example 4 obtaining containing lead oxide and oxidation The desulphurization catalyst B4 of zinc, but it is formed without zinc lead solid solution, at 380 DEG C, process the product that raw material obtains 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 %, with P₂O₅The meter phosphorous oxides of 0.5-10 weight %, 1-20 The molecular sieve with BEA structure of weight % and/or there is molecular sieve and the 5-30 weight of FAU structure The active metal of amount %；And at least part of described lead oxide is to use formula with described zinc oxide is formed Pb_xZn_1-xThe zinc lead solid solution thereof that O represents exists, and wherein x meets 0 ＜ x≤0.12, and x represents atom Mol ratio；Described active metal is at least one in cobalt, nickel, ferrum and manganese.

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 Pb_xZn_1-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 %, with P₂O₅Meter 1-5 weight % phosphorous oxides, The molecular sieve with BEA structure of 2-10 weight % and/or there is molecular sieve and the 8-20 of FAU structure The active metal of weight %.

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.

In the case of according to the invention it is preferred to, described phosphorous oxides contains P₂O₅、P₂O₃With poly phosphorus oxidation At least one in compound.

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 (Na_n[Al_nSi_64-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.

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 formed_xZn_1-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 obtained_xZn_1-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, aluminium oxide, have BEA structure molecular sieve and/or have FAU structure molecular sieve, The precipitated product that phosphorus-containing compound and step (1) obtain prepares carrier.Under preferable case, described Silica source, described alumina source, described in there is the molecular sieve of BEA structure and/or there is FAU structure Molecular sieve and the addition of described phosphorus-containing compound make in the desulphurization catalyst obtained, with described de- On the basis of the gross weight of sulfur catalyst, the content of silica source is that 5-30 weight %, the content of aluminium oxide are The content of 5-30 weight %, the molecular sieve with BEA structure and/or the molecular sieve with FAU structure is 1-20 weight %, phosphorous oxides content with P₂O₅It is calculated as 0.5-10 weight %；Preferably, described oxidation Silicon source, described alumina source, described in have BEA structure molecular sieve and/or have FAU structure point The addition of son sieve and described phosphorus-containing compound makes, in the desulphurization catalyst obtained, to urge with described desulfurization On the basis of the gross weight of agent, the content of silica source is that 10-20 weight %, the content of aluminium oxide are 10-20 weight %, there is the molecular sieve of BEA structure and/or there is the content of molecular sieve of FAU structure For 2-10 weight %, phosphorous oxides content with P₂O₅It is calculated as 1-5 weight %.

In the present invention, the weight ratio of described silica source and described aluminium oxide can be 0.4-2:1；Preferably, Can be 0.6-1.5:1.

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.

According to the present invention, described phosphorus-containing compound can be under conditions of the described roasting of step (2) P can be changed into₂O₅Inorganic phosphor-contained thing or phosphorus-containing matter.Described inorganic phosphor-contained thing is phosphoric acid, phosphorus At least one in acid ammonium, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, described phosphorus-containing matter be trimethyl-phosphine, At least one in triethyl phosphine, tripropyl phosphine and tributylphosphine.

In the present invention, in step (2), the consumption of described acid solution is so that described carrier mixture PH value be 1-3.Described acid solution can be 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, when the acid in described phosphorus-containing compound and described acid solution is phosphoric acid, phosphoric acid Addition makes to contain on the basis of the gross weight of this desulphurization catalyst in the desulphurization catalyst obtained, with P₂O₅The phosphorous oxides of meter 0.5-10 weight %, preferably comprises the phosphorous oxides of 1-5 weight %.And it is described When carrier mixture can not make pH value reach 1-3 not due to acid amount, can be by adding other institute Stating acid solution makes the pH value of described carrier mixture reach 1-3.

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 the present invention, the method forming serosity described in step (2) can use various order, permissible Silica source, alumina source, phosphorus-containing compound, there is the molecular sieve of BEA structure and/or there is FAU The molecular sieve of structure, water contact formation serosity together with acid solution；Can also form serosity according to the following steps: A) silica source, phosphorus-containing compound and water are mixed to form mixture, mixture are dried and at 400-600 DEG C roasting, the silica source after being processed；B) by alumina source, the molecular sieve with BEA structure And/or there is the molecular sieve of FAU structure, water and acid solution mixing, form acidified slurries；C) will process After silica source mix homogeneously with acidified slurries, formed serosity.

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.

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 Pb_0.044Zn_0.956O。

(2) carrier is prepared.(phosphoric acid contains for traditional Chinese medicines chemical reagents corporation, analytical pure to take 290 grams of phosphoric acid Amount 95%), boehmite 1.33 kilograms (catalyst Nanjing branch company, containing butt 1.00 kilograms), 2.16 kilograms of Kaolin (catalyst asphalt in Shenli Refinery, containing butt 1.8 kilograms), 1.0 kilograms of beta-molecular sieves (catalyst Nanjing branch company, containing butt 0.7 kilogram) and 9.0 kilograms of neutral waters (pH value is 6-8) Under agitation after mix homogeneously, add 200 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant produces) stirring It is warming up to 60 DEG C after being acidified 1 hour be acidified 1 hour.When temperature is reduced to below 40 DEG C, add Precipitated product C1, after mixing, stirring obtains carrier mixture in 1 hour.

Described carrier mixture uses Niro Bowen Nozzle Tower^TMThe 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 10.0 weight %, Kaolin 18.0 weight %, beta-molecular sieve 7 weight %, nickel 18.0 Weight %, P₂O₅2.0 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

(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 Pb_0.1Zn_0.9O。

(2) carrier is prepared.Take 490 grams of ammonium dihydrogen phosphates (traditional Chinese medicines chemical reagents corporation, analytical pure 99%), Boehmite 2.27 kilograms (catalyst Nanjing branch company, containing butt 1.70 kilograms), 1.33 kilograms swollen Swollen perlite (catalyst Nanjing branch company, containing butt 1.6 kilograms), 0.43 kilogram of beta-molecular sieve (catalysis Agent Nanjing branch company, containing butt 0.3 kilogram) and 8.0 kilograms of neutral waters (pH value is 6-8) in stirring After lower mix homogeneously, add 200 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant produces) stirring acidifying 1 It is warming up to 60 DEG C after hour be acidified 1 hour.When temperature is reduced to below 40 DEG C, add precipitation and produce Thing C1, after 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 17.0 weight %, expanded perlite 13.0 weight %, beta-molecular sieve 3 weight %, Nickel 14.0 weight %, P₂O₅3.0 weight %.

Embodiment 3

(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 Pb_0.07Zn_0.93O。

(2) carrier is prepared.(catalyst Nanjing branch company, containing butt 1.0 to take 1.03 kilograms of kieselguhr Kilogram) and 670 grams of triethyl phosphines (traditional Chinese medicines chemical reagents corporation, analytical pure) at 3.0 kg water solution Middle mix homogeneously is also evaporated solution, then takes out mixture roasting at 600 DEG C and is processed for 1 hour After kieselguhr.

Take hydrated alumina 1.5 kilograms (catalyst Nanjing branch company, containing butt 1.2 kilograms), 0.6 thousand (pH value is for gram USY (catalyst Nanjing branch company, containing butt 0.5 kilogram) and 9.0 kilograms of neutral waters 6-8) under agitation mix, add 170 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant produces) stirring It is warming up to 60 DEG C after being acidified 1 hour be acidified 1 hour.When temperature is reduced to below 40 DEG C, add Kieselguhr after above-mentioned process and precipitated product C3, after mixing, stirring obtains carrier mixture in 1 hour.

(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 12.0 weight %, kieselguhr 10.0 weight %, USY molecular sieve 5.0 weight %, Nickel 12.0 weight %, P₂O₅4.0 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 (traditional Chinese medicines chemical reagents corporation, analytical pure) and 290 grams of phosphoric acid (traditional Chinese medicines Chemical reagents corporation, analytical pure, phosphorus acid content 95%) mix homogeneously in 8.5 kg water solution, stirs The mixed serum of said components is obtained after mixing 30 minutes.

Take boehmite 2.0 kilograms (catalyst Nanjing branch company, containing butt 1.50 kilograms), 2.4 thousand Gram Kaolin (catalyst asphalt in Shenli Refinery, containing butt 2.0 kilograms) and 9.0 kilograms of neutral water (pH Value is for 6-8) under agitation mix homogeneously, (chemical pure, Beijing Chemical Plant goes out to add 200 grams of concentrated nitric acids Product) stirring acidifying 1 hour after be warming up to 60 DEG C be acidified 1 hour.When temperature is reduced to below 40 DEG C, Adding the mixed serum of zinc oxide and sodium carbonate, after 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 15.0 Weight %, Kaolin 20.0 weight %, nickel 18.0 weight %, P₂O₅2.0 weight %.

Comparative example 2

By 5.05 kilograms of zinc oxide (traditional Chinese medicines chemical reagents corporation, analytical pure) and 490 grams of ammonium dihydrogen phosphates (traditional Chinese medicines chemical reagents corporation, analytical pure 99%) mix homogeneously in 9.5 kg water solution, stirs 30 The mixed serum of said components is obtained after minute.

Take boehmite 2.27 kilograms (catalyst Nanjing branch company, containing butt 1.60 kilograms), 1.63 Kilogram expanded perlite (catalyst Nanjing branch company, containing butt 1.60 kilograms) and 8.0 kilograms of neutrality Water (pH value is 6-8) under agitation mixes, and adds 200 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant Produce) stirring acidifying 1 hour after be warming up to 60 DEG C be acidified 1 hour.Treat that temperature is reduced to less than 40 DEG C Time, adding the mixed serum of zinc oxide and potassium hydroxide, after mixing, stirring obtains carrier mixing for 1 hour Thing.Method with reference to embodiment 1 carries out the spray drying of carrier mixture and impregnates introducing active component nickel, Obtain desulphurization catalyst B2.

The composition of desulphurization catalyst B2 is calculated as by inventory: zinc oxide 50.0 weight %, aluminium oxide 17.0 Weight %, expanded perlite 16.0 weight %, nickel 14.0 weight %, P₂O₅3.0 weight %.

Comparative example 3

Take 1.13 kilograms of kieselguhr (catalyst Nanjing branch company, containing butt 1.10 kilograms) and 670 grams Triethyl phosphine (traditional Chinese medicines chemical reagents corporation, analytical pure) mix homogeneously handle in 3.0 kg water solution Solution is evaporated, the kieselguhr after then taking out mixture roasting being processed for 1 hour at 600 DEG C.

Hydrated alumina 2.13 kilograms (catalyst Nanjing branch company, containing butt 1.6 kilograms) and 9.0 thousand After gram neutral water (pH value is 6-8) under agitation mix homogeneously, add 170 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant produce) stir and be warming up to more than 60 DEG C be acidified 1 hour.Treat that temperature is reduced to 40 DEG C Time below DEG C, after adding 5.47 kilograms of zinc oxide (catalyst Nanjing branch company) powder and above-mentioned process Kieselguhr, stir after 1 hour after mixing and obtain carrier mixture.

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 11.0 weight %, nickel 12.0 weight %, P₂O₅4.0 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), 490 grams of ammonium dihydrogen phosphates (traditional Chinese medicines chemistry Reagent Company, analytical pure 99%) and 7.8 kilograms of deionized water mixing, obtain oxygen after stirring 30 minutes Change zinc, lead oxide and the mixed serum of phosphorus.

Take boehmite 2.27 kilograms (catalyst Nanjing branch company, containing butt 1.60 kilograms), 1.63 Kilogram expanded perlite (catalyst Nanjing branch company, containing butt 1.60 kilograms) and 8.0 kilograms of neutrality Water (pH value is 6-8) under agitation mixes, and adds 200 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant Produce) stirring acidifying 1 hour after be warming up to 60 DEG C be acidified 1 hour.Treat that temperature is reduced to less than 40 DEG C Time, add above-mentioned mixed serum and stir 1 hour.Stir after adding zinc oxide and the mixing of lead oxide serosity Mix 1 hour and obtain carrier pulp.

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 17.0 weight %, expanded perlite 16.0 weight %, nickel 14.0 weight %, P₂O₅3.0 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

1. a desulphurization catalyst, on the basis of the gross weight of this desulphurization catalyst, this desulphurization catalyst Silica source containing 5-30 weight %, the aluminium oxide of 5-30 weight %, the zinc oxide of 30-70 weight %, The lead oxide of 2-15 weight %, with P₂O₅The meter phosphorous oxides of 0.5-10 weight %, the tool of 1-20 weight % The molecular sieve having BEA structure and/or the molecular sieve with FAU structure and the activity of 5-30 weight % Metal；And at least part of described lead oxide is to form formula Pb with described zinc oxide_xZn_1-xThe zinc that O represents Presented in lead solid solution, wherein x meets 0 ＜ x≤0.12, and x represents atomic molar ratio；Described work Property metal is at least one in cobalt, nickel, ferrum and manganese.

Desulphurization catalyst the most according to claim 1, wherein, described desulphurization catalyst meet with Lower relational expression: A₁₀₀-B₁₀₀=0.2 ° to 0.3 °, A₁₀₀And B₁₀₀It is illustrated respectively in identical XRD to survey In the XRD spectra of described desulphurization catalyst obtained under fixed condition 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 meet with Lower relational expression: A₀₀₂-B₀₀₂=0.2 ° to 0.3 °；A₀₀₂And B₀₀₂It is illustrated respectively in identical XRD to survey In the XRD spectra of described desulphurization catalyst obtained under fixed condition 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 meet with Lower relational expression: A₁₀₁-B₁₀₁=0.2 ° to 0.3 °；A₁₀₁And B₁₀₁It is illustrated respectively in identical XRD to survey In the XRD spectra of described desulphurization catalyst obtained under fixed condition 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, with this desulfurization On the basis of the gross weight of catalyst, this desulphurization catalyst contains the silica source of 10-20 weight %, 10-20 The aluminium oxide of weight %, the zinc oxide of 35-54 weight %, the lead oxide of 5-12 weight %, with P₂O₅Meter The phosphorous oxides of 1-5 weight %, the molecular sieve with BEA structure of 2-10 weight % and/or there is FAU The molecular sieve of structure and the active metal of 10-20 weight %.

6. according to the desulphurization catalyst described in any one in claim 1-4, wherein, described activity Metal is nickel.

7. according to the desulphurization catalyst described in any one in claim 1-4, wherein, described phosphorus oxygen Compound is P₂O₅、P₂O₃With at least one in poly phosphoric-oxygenic compound.

8. according to the desulphurization catalyst described in any one in claim 1-4, wherein, described oxidation Silicon 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 BEA structure point Son sieve for beta-molecular sieve, described in have the molecular sieve of FAU structure be X-type molecular sieve and/or Y type molecule Sieve.

Desulphurization catalyst the most according to claim 1, wherein, described in there is FAU structure Molecular sieve is selected from super-stable Y molecular sieves and/or Y-shaped molecular sieve containing rare earth.

11. desulphurization catalysts according to claim 1, wherein, described in there is FAU structure Molecular sieve is selected from containing rare earth superstable Y-type molecular sieve, phosphorous super-stable Y molecular sieves and phosphorous Y-type rare earth At least one in molecular sieve.

12. desulphurization catalysts according to claim 1, wherein, described in there is FAU structure Molecular sieve is selected from phosphorous and rare earth Hydrogen Y molecular sieve.

The preparation method of 13. 1 kinds of desulphurization catalysts, the method includes:

(1) mixed solution that lead-containing compounds, zinc compound and water are mixed to get is carried out precipitation anti- Should, mixture precipitation obtained carries out filtering, being dried and roasting, is precipitated product；

(2) by silica source, alumina source, phosphorus-containing compound, have BEA structure molecular sieve and / or there is the molecular sieve of FAU structure, water and acid solution contact formation serosity, and step (1) is obtained Precipitated product mix with described serosity, formed carrier mixture；Again by described carrier mixture molding, It is dried and roasting, forms carrier；

(3) on the carrier that step (2) obtains, introduce the compound containing active metal and be dried, roast Burn, 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, taken off Sulfur catalyst；

Wherein, described lead-containing compounds and zinc compound addition make in the desulphurization catalyst obtained, On the basis of the gross weight of described desulphurization catalyst, the content of lead oxide is 2-15 weight %, zinc oxide Content is 30-70 weight %；

Described silica source, described alumina source, described phosphorus-containing compound, described in there is BEA structure Molecular sieve and/or there is the molecular sieve of FAU structure and adding of the described compound containing active metal Enter in the desulphurization catalyst that amount makes to obtain, on the basis of the gross weight of described desulphurization catalyst, silicon oxide The content in source be 5-30 weight %, the content of aluminium oxide be 5-30 weight %, phosphorous oxides content with P₂O₅It is calculated as 0.5-10 weight %, there is the molecular sieve of BEA structure and/or there is the molecule of FAU structure The content that content is 1-20 weight % and active metal of sieve is 5-30 weight %；

Described in step (1) be dried condition include: be dried temperature be 100-200 DEG C, be dried time Between be 0.5-3h；The condition of described roasting includes: the temperature of roasting is 400-700 DEG C, the time of roasting For 0.5-3h；

Described precipitated product is at least partly containing useful formula Pb_xZn_1-xThe zinc lead solid solution that O represents, wherein X meets 0 ＜ x≤0.12, and x represents atomic molar ratio.

14. preparation methoies according to claim 13, wherein, described precipitated product meet below Relational expression: A₁₀₀-B₁₀₀=0.2 ° to 0.3 °, A₁₀₀And B₁₀₀It is illustrated respectively in identical XRD determining Under the conditions of in the XRD spectra of described precipitated product that obtains and the XRD spectra of ZnO, characterize ZnO The 2 θ values of diffraction maximum in (100) face；B₁₀₀=31.55 °.

15. preparation methoies according to claim 13, wherein, described precipitated product meet below Relational expression: A₀₀₂-B₀₀₂=0.2 ° to 0.3 °；A₀₀₂And B₀₀₂It is illustrated respectively in identical XRD determining Under the conditions of in the XRD spectra of described precipitated product that obtains and the XRD spectra of ZnO, characterize ZnO The 2 θ values of diffraction maximum in (002) face；B₀₀₂=34.21 °.

16. preparation methoies according to claim 13, wherein, described precipitated product meet below Relational expression: A₁₀₁-B₁₀₁=0.2 ° to 0.3 °；A₁₀₁And B₁₀₁It is illustrated respectively in identical XRD determining Under the conditions of in the XRD spectra of described precipitated product that obtains and the XRD spectra of ZnO, characterize ZnO The 2 θ values of diffraction maximum in (101) face；B₁₀₁=36.04 °.

17. preparation methoies according to claim 13, wherein, described lead-containing compounds is nitric acid Lead and/or lead acetate.

18. preparation methoies according to claim 13, wherein, described zinc compound is acetic acid At least one in zinc, zinc chloride and zinc nitrate.

19. preparation methoies according to claim 13, wherein, described phosphorus-containing compound is phosphorous Inorganic matter and/or phosphorus-containing matter, described inorganic phosphor-contained thing is phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and phosphoric acid At least one in ammonium dihydrogen, described phosphorus-containing matter be trimethyl-phosphine, triethyl phosphine, tripropyl phosphine and At least one in tributylphosphine.

20. preparation methoies according to claim 13, wherein, described in step (1), precipitation is anti- The precipitant that should use is carbamide and/or ammonia.

21. preparation methoies according to claim 13, wherein, mixture described in step (1) PH be 9-13.

22. preparation methoies according to claim 13, wherein, described alumina source is in step (2) material of aluminium oxide can be changed under conditions of described roasting.

23. preparation methoies according to claim 22, wherein, described alumina source is hydration oxygen Change aluminum and/or Alumina gel；Described hydrated alumina is boehmite, false boehmite, three hydration oxygen Change at least one in aluminum and amorphous hydroted alumina.

24. preparation methoies according to claim 13, wherein, containing living described in step (3) The compound of property metal is the acetate of active metal, carbonate, nitrate, sulfate, rhodanate With at least one in oxide.

25. desulphurization catalysts obtained by the preparation method described in any one in claim 13-24.

The method of 26. 1 kinds of desulfurization of hydrocarbon oil, the method includes: by hydrocarbon oil containing surphur and hydrodesulfurization catalyst Reaction, it is characterised in that described desulphurization catalyst is in claim 1-12 and 25 described in any one Desulphurization catalyst.