CN104511284B - Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurizing method - Google Patents

Abstract

The invention discloses a desulfurization catalyst which includes following components, on the basis of the total weight of the desulfurization catalyst, by weight: 5-35% of a silicon oxide source, 5-35% of aluminum oxide, 30-70% of zinc oxide, 2-15% of lead oxide, 0.5-10% of an alkaline-earth metal oxide and 5-30% of an active metal. At least partial lead oxide and the zinc oxide are formed into a zinc-lead solid solution with a general formula being Pb＜x＞Zn＜1-x＞O, wherein 0＜x≤0.12 and the x refers to atom molar 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 hydrocarbon oil desulfurizing method. The desulfurization catalyst is better in 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, in particular it relates to a kind of Desulphurization catalyst, the preparation method of a kind of desulphurization catalyst and the desulphurization catalyst obtained by the method, and desulphurization catalyst The method of application 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 reduces the sulfur of gasoline and diesel oil Content is considered as one of most important measure improving air quality, because the sulfur in fuel can be to the property of vehicle catalytic converter Can have adverse effect on.Present in automobile engine tail gas, sulfur can suppress the noble metal in converter and can be allowed to occur not Reversibly it is poisoned, reduces the converter effect to purifying vehicle exhaust.Non-purified vehicle exhaust contains unburned non-methane Hydrocarbon, nitrogen oxide and carbon monoxide, 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 catalytically cracked gasoline.Therefore In hot-working petroleum, the minimizing of sulfur content contributes to reducing the sulfur content of China's gasoline products.The gasoline products standard that China is existing GB17930-2011 " motor petrol " requirement to 2013 on December 31, 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 the degree of depth Desulfurization just can make gasoline products meet 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 keep away as far as possible Exempt from olefin(e) centent in gasoline to change and make its octane number (including ROM and MON) reduce.Affect olefin(e) centent to be typically due to Remove the same of thiophenes (including thiophene, benzothiophene, alkylthrophene, alkyl benzothiophenes and methyldibenzothiophene) Shi Yinfa hydrogenation reaction causes.In addition it is also necessary to avoid desulfurization condition to make the aromatic hydrocarbons of catalytically cracked gasoline to be saturated and Loss.The most 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 desulfurization two kinds of methods, wherein hydrofinishings Relatively costly.S Zorb absorption desulfurization belongs to absorption desulfurization technology, and this technology is in certain temperature, pressure and the condition facing hydrogen Sulfur compounds adsorption in hydrocarbon ils is removed by lower realization.This technology has the advantages that hydrogen consumption is low and the highest to the purity requirement of hydrogen, This technology is had broad application prospects in terms of fuel desulfuration.

CN1355727A discloses a kind of be applicable to the combination of adsorbents removing sulfur from cracking gasoline and diesel fuel Thing, is made up of zinc oxide, silicon oxide, oxidation al and ni, and wherein nickel is substantially to reduce valence state existence, and its amount can be from de- The cracking gasoline contacted with described nickeliferous adsorbent composition under the conditions of sulfur or diesel fuel stream remove sulfur.Said composition is led to Cross compound particles granulation zinc oxide, silicon oxide and aluminium oxide formed and form granule, be dried, after roasting with nickel or nickeliferous chemical combination Thing impregnates, then be dried, roasting, reduction obtain.

CN1382071A discloses a kind of be applicable to the combination of adsorbents removing sulfur from cracking gasoline and diesel fuel Thing, is made up of zinc oxide, silicon oxide, aluminium oxide and cobalt, and wherein cobalt is substantially to reduce valence state existence, and its amount can be from de- The cracking gasoline contacted with the described adsorbent composition containing cobalt under the conditions of sulfur or diesel fuel stream remove sulfur.

US6150300 discloses a kind of method preparing adsorbent, including preparing spheroidal particle: (a) will contain silicon dioxide Compositions, the compositions containing dispersion metal-oxide in an aqueous medium and the compositions mixing shape containing zinc oxide Become the first mixture and do not extrude described first mixture；B described first mixture globulate is formed by () has diameter 10- The granule of 1000mm.Wherein step (a) also includes mixing with metallic promoter agent.

CN1422177A discloses a kind of be applicable to the combination of adsorbents removing sulfur from cracking gasoline and diesel fuel Thing, is made up of zinc oxide, expanded perlite, aluminium oxide and promoter metals, and wherein said promoter metals is substantially to reduce Valence state and the amount of sulfur can be removed when contacting under desulfurization conditions from cracking gasoline or diesel fuel stream exist.

CN1627988A discloses one and is suitable for from cracking gasoline and diesel fuel removing elementary sulfur and sulfuration conjunction The adsorbent composition of thing, described adsorbent composition comprises: zinc oxide, expanded perlite, aluminate and promoter metals, its Described in promoter metals will cause from cracking when making cracking gasoline or diesel fuel stream contacts under desulfurization conditions with it The amount of desulfurization in the stream of gasoline or diesel fuel exists, and at least part of described promoter metals exists with 0 valence state.

CN1856359A discloses a kind of method producing compositions, including: a) mixing liquid, zinc compound, containing two Silica material, aluminium oxide and promoter, to form its mixture；B) it is dried this mixture, to form the mixing of drying Thing；C) mixture of this drying is calcined, to form the mixture through calcining；D) with suitable reducing agent under suitable condition This is reduced through the mixture of calcining, to have the compositions of the promoter content of reduction valence state in producing it, and e) Reclaim 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, Mix to form its mixture containing earth silicon material, aluminium oxide；B) described mixture is dried this mixing to form first Drying mixture；C) by described first drying mixture calcining to form first through calcining mixt；D) accelerator is tied Close to described first within calcining mixt or on to form promoted mixture；E) described promoted mixture and choosing are made From the acid contact of citric acid, tartaric acid and combinations thereof to be formed through contact mixture；F) by described through contact mixture be dried with Form the second drying mixture；G) by described second drying mixture calcining to form second through calcining mixt；H) exist Applicable reducing agent reduction described second is used wherein to contain reduction valence state rush through calcining mixt to produce under conditions of Shi Dang Enter the compositions of agent content, and i) reclaim described compositions.

Although published adsorbent has certain desulfurization performance, but owing to being desulfurization under facing hydrogen state, can not keep away The generation hydrogenation of olefins exempted from, thus cause loss of octane number.And along with the raising of gasoline quality standard, product gasoline sulfur is contained Amount requires also the strictest.As can be seen here, it is desirable to provide one has more high desulfurization activity and abrasion resistance properties, and can change The new catalyst of kind product gasoline octane number.

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 desulfurization 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, with the gross weight of this desulphurization catalyst as base Standard, this desulphurization catalyst contain the silica source of 5-35 weight %, the aluminium oxide of 5-35 weight %, the zinc oxide of 30-70 weight %, The lead oxide of 2-15 weight %, the alkaline earth oxide of 0.5-10 weight % and the active metal of 5-30 weight %；And at least partly Described lead oxide is to use formula Pb with described zinc oxide is formed_xZn_1-xThe zinc lead solid solution thereof that O represents exists, and wherein x is full Foot 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) by lead-containing compounds, contain The mixed solution that zinc compound and water are mixed to get carries out precipitation, and mixture precipitation obtained carries out filtering, doing Dry and roasting, is precipitated product；(2) silica source, alumina source, alkaline earth metal compound, water are contacted shape with acid solution Become serosity, and the precipitated product that step (1) obtains is mixed with described serosity, form carrier mixture；Again described carrier is mixed Compound molding, dry and roasting, form carrier；(3) on the carrier that step (2) obtains, the compound containing active metal is introduced 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: connect with desulphurization catalyst by hydrocarbon oil containing surphur Touch reaction, 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 part of lead oxide is to be formed with zinc oxide Use formula Pb_xZn_1-xThe zinc lead solid solution thereof that O represents exists, and absorbs constituent element as sulfur, so that present invention offer is de- Sulfur catalyst has the most desulphurizing activated and activity stability.And this desulphurization catalyst also have more preferable wear-resistant by force Degree, can improve the service life of desulphurization catalyst.In addition this desulphurization catalyst can also absorb sulfur also at lower temperatures Carrying out oxidation regeneration, it is 410 DEG C that prior art carries out absorbing the temperature of sulfur, and the temperature of oxidation regeneration is 550 DEG C.In embodiment 1 Desulphurization catalyst A1 to have chemical composition be Pb_0.044Zn_0.956The zinc lead solid solution of O, abrasion index is 4.8；Desulphurization catalyst Make the sulfur content of product gasoline be 9 μ g/g as long as A1 can process raw material in example 4 at 380 DEG C, and regeneration temperature is 480 DEG C.Although and comparative example 4 obtains the desulphurization catalyst B4 containing lead oxide and zinc oxide, but being formed without zinc lead Solid solution, the sulfur content processing the product gasoline that raw material obtains at 380 DEG C 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 following tool Body embodiment is used for explaining the present invention together, but is not intended that limitation of the present invention.In the accompanying drawings:

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 values A of the diffraction maximum in (100) face of ZnO, (002) face and (101) face in sign C1₁₀₀、A₀₀₂And A₁₀₁Respectively It is 31.75 °, 34.42 ° and 36.24 °,

2 θ values A of the diffraction maximum in (100) face of ZnO, (002) face and (101) face in sign C2₁₀₀、A₀₀₂And A₁₀₁Respectively It is 31.80 °, 34.45 ° and 36.28 °,

2 θ values A of the diffraction maximum in (100) face of ZnO, (002) face and (101) face in sign C3₁₀₀、A₀₀₂And A₁₀₁Respectively It is 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 described herein specifically Embodiment 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, and on the basis of the gross weight of this desulphurization catalyst, this desulphurization catalyst contains Have the silica source of 5-35 weight %, the aluminium oxide of 5-35 weight %, the zinc oxide of 30-70 weight %, the lead oxide of 2-15 weight %, The alkaline earth oxide of 0.5-10 weight % and the active metal of 5-30 weight %；And at least part of described lead oxide is with described What zinc oxide was formed uses formula Pb_xZn_1-xThe zinc lead solid solution thereof that O represents exists, and 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.

According to the present invention, described desulphurization catalyst contains lead oxide and zinc oxide, and described desulphurization catalyst can contain There is the zinc lead solid solution that lead oxide and zinc oxide are formed.Described zinc lead solid solution can stablize the lattice structure of zinc oxide, keeps The activity of zinc oxide constituent element.The amount of the lead oxide that described desulphurization catalyst contains and the amount of zinc oxide contained can make described de- Sulfur catalyst contains the zinc lead solid solution represented with above-mentioned formula.Described desulphurization catalyst can be containing lead oxide and Zinc oxide all forms the zinc lead solid solution represented with above-mentioned formula；Can also be except containing the zinc lead represented with above-mentioned formula Solid solution is outer possibly together with lead oxide and/or zinc oxide, and whole lead oxide forms zinc lead solid solution with most zinc oxide Body, outer possibly together with a small amount of zinc oxide containing zinc lead solid solution in desulphurization catalyst.The oxygen that the most described desulphurization catalyst contains Change lead and zinc oxide all forms 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 not destroyed, But enter in lattice, so the XRD spectra of described desulphurization catalyst characterizes the feature of ZnO owing to lead ion replaces zinc ion The angle of diffraction at peak can change, and therefore be may determine that at described desulphurization catalyst by desulphurization catalyst described in XRD determining In there is zinc lead solid solution.The XRD spectra of the desulphurization catalyst A1 obtained under the conditions of same XRD determining as shown in Fig. 2 XRD spectra with ZnO.In fig. 2, the single characteristic peak of lead oxide and zinc oxide does not occur, but occurs in that peak position is inclined The characteristic peak of the cubic crystal characterizing zinc oxide moved, illustrates that lead oxide and zinc oxide have been completely formed zinc lead solid solution.Preferably In the case of, described desulphurization catalyst meets relationship below: 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 desulphurization catalyst that obtains and the XRD spectra of ZnO, characterize (100) face of ZnO 2 θ values of diffraction maximum.

In the case of according to the invention it is preferred to, described desulphurization catalyst meets relationship below: A₀₀₂-B₀₀₂=0.2 ° extremely 0.3°；A₀₀₂And B₀₀₂The XRD spectra of the described desulphurization catalyst obtained under the conditions of being illustrated respectively in identical XRD determining and ZnO XRD spectra in, characterize the 2 θ values of diffraction maximum in (002) face of ZnO.

In the case of according to the invention it is preferred to, described desulphurization catalyst meets relationship below: A₁₀₁-B₁₀₁=0.2 ° extremely 0.3°；A₁₀₁And B₁₀₁The XRD spectra of the described desulphurization catalyst obtained under the conditions of being illustrated respectively in identical XRD determining and ZnO XRD spectra in, characterize the 2 θ values of diffraction maximum in (101) face of ZnO.

According to the present invention, may determine that described desulphurization catalyst contains lead oxide and zinc oxide shape by above-mentioned XRD determining The zinc lead solid solution become, in this zinc lead solid solution, mol ratio x of lead and zinc can pass through elementary analysis such as spectrofluorimetry Measure, 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 former Sub-mol ratio.

According to the present invention, described desulphurization catalyst preferably, on the basis of the gross weight of this desulphurization catalyst, urge by this desulfurization Agent contains the silica source of 10-25 weight %, the aluminium oxide of 10-25 weight %, the zinc oxide of 35-54 weight %, 5-12 weight % Lead oxide, the alkaline earth oxide of 1-5 weight % and the active metal of 10-20 weight %.

According to the present invention, described desulphurization catalyst is possibly together with the molecular sieve of 1-20 weight %, and described molecular sieve is phosphorus aluminum molecule At least one in the molecular sieve sieving, having BEA structure and the molecular sieve with FAU structure.I.e. total with this desulphurization catalyst On the basis of weight, this desulphurization 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 alkaline earth oxide of 0.5-10 weight %, the molecular sieve of 1-20 weight % and 5-30 The active metal of weight %.

In accordance with the present invention it is preferred that, on the basis of the gross weight of this desulphurization catalyst, this desulphurization catalyst contains 10-25 The silica source of weight %, the aluminium oxide of 10-25 weight %, the zinc oxide of 35-54 weight %, the lead oxide of 5-12 weight %, 1-5 weight The amount alkaline earth oxide of %, the molecular sieve of 2-10 weight % and the active metal of 10-20 weight %.

According to the present invention, described phosphate aluminium molecular sieve (abbreviation SAPO molecular sieve) is nearly body silicoaluminophosphate, is to be introduced by silicon Obtaining in aluminum phosphate skeleton, its skeleton is by PO⁴⁺、AlO^4-And SiO₂Tetrahedron forms, including 13 kinds of three-dimensional microporous framework structures. Under preferable case, the hole size of described phosphate aluminium molecular sieve isPore volume is 0.18-0.48cm³/g.Preferably, described phosphorus Aluminum molecular screen is at least one in SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieve.SAPO-5、 The hole size of SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieve is respectively(12 ring),(10 Yuans rings)(10 Yuans rings),(8 Yuans rings) and(6 Yuans rings), pore volume is respectively 0.31,0.18,0.42,0.42 and 0.40cm³/g.It is highly preferred that described phosphate aluminium molecular sieve is at least in SAPO-11, SAPO-31 and SAPO-34 molecular sieve Kind.

According to the present invention, described in have the molecular sieve of FAU structure be faujasite-type molecular sieve, the type molecular sieve has Three-dimensional twelve-ring duct, aperture isThe molecular sieve of the described FAU of having structure is mainly X-type and Y type Molecular sieve, in general SiO₂/Al₂O₃Mol ratio be 2.2-3.0 for X-type molecular sieve, SiO₂/Al₂O₃Mol ratio is more than 3.0 For Y type molecular sieve.The framing structure of X-type and Y type molecular sieve broadly falls into hexagonal crystal system, and space group structure is Fd3m, X-type molecular sieve Cell 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 the modified molecular sieve with FAU 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 SiC1₄Gas Phase method) or hydro-thermal combine with chemical treatment.The modified molecular sieve obtained includes but not limited to super-stable Y molecular sieves (USY), Containing REUSY, REHY, REY of rare earth element, 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 is (Na_n[Al_nSi_{64- n}O₁₂₈], n < 7), it is different by two structures but the mixed crystal that formed of polymorph A that is closely related and B, both there is twelve-ring 3 D pore canal system, polymorph A forms a pair enantiomer, and space group is P4₁22 and P4₃22, cell parameter is Polymorph B belongs to achirality space group C2/c, cell parameter In BEA structure molecular screen, twelve-ring pore size is

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, described in there is FAU knot The molecular sieve of structure is at least in X-type molecular sieve, Y type molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY and PREY Kind；Preferably, the molecular sieve described in FAU structure is at least one in USY, REUSY, REY, PUSY and PREY.

According to the present invention, described active metal can be any metal that the sulfur of oxidation state can be reduced to hydrogen sulfide, Preferably, described active metal is nickel.

According to the present invention, described silica source can be to provide cementation in described desulphurization catalyst between each component. Under preferable case, described silica source can be the natural crystal that silicon oxide or silica content are more than 45 weight %.Preferably, Described silica source can be laminated clay column, kieselguhr, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silicon At least one in glue.

According to the present invention, described aluminium oxide can be to provide cementation in described desulphurization catalyst between each component.Excellent In the case of choosing, described aluminium oxide can be at least one in gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-aluminium oxide.

According to the present invention, described alkaline earth oxide can increase the effect of catalyst abrasion strength resistance.Preferable case Under, described alkaline earth oxide is the oxide of magnesium and/or calcium.

Present invention also offers the preparation method of a kind of desulphurization catalyst, the method includes: (1) by lead-containing compounds, contain The mixed solution that zinc compound and water are mixed to get carries out precipitation, and mixture precipitation obtained carries out filtering, doing Dry and roasting, is precipitated product；(2) silica source, alumina source, alkaline earth metal compound, water are contacted shape with acid solution Become serosity, and the precipitated product that step (1) obtains is mixed with described serosity, form carrier mixture；Again described carrier is mixed Compound molding, dry and roasting, form carrier；(3) on the carrier that step (2) obtains, the compound containing active metal is introduced 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.

In the preparation method of the desulphurization catalyst of present invention offer, step (1) can form zinc lead solid solution.

According to the present invention, described in step (1), the addition of lead-containing compounds and zinc compound can be at wider model Enclose interior selection, formula Pb can be used as long as can be formed_xZn_1-xThe zinc lead solid solution that O represents.Under preferable case, step (1) lead-containing compounds described in and zinc compound addition make in the desulphurization catalyst obtained, with described desulphurization catalyst Gross weight on the basis of, the content of lead oxide is 2-15 weight %, and the content of zinc oxide is 30-70 weight %；Preferably, described contain Lead compound and zinc compound addition make in the desulphurization catalyst obtained, with the gross weight of described desulphurization catalyst as base Standard, 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, according to elementary analysis Can be determined that in this precipitated product containing zinc lead solid solution with XRD determining result.Specifically, first this precipitated product is carried out unit Element is analyzed and is judged 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, root According to the characteristic peak of the hexagonal crystal system of the sign ZnO occurred in XRD spectra, 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 is brilliant Body structure without, so in the XRD spectra of zinc lead solid solution, still have the architectural feature of ZnO crystal, and there is no lead oxide The architectural feature of crystal.But the position at the crystalline phase peak of ZnO is subjected to displacement in zinc lead solid solution.Therefore, by precipitated product XRD spectra can be determined that in precipitated product containing zinc lead solid solution.

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 XRD spectra of the described precipitated product obtained under the conditions of being illustrated respectively in identical XRD determining and the XRD spectrum of ZnO In figure, characterize 2 θ values of the diffraction maximum in (100) face of ZnO.

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 XRD spectra of the described precipitated product obtained under the conditions of being illustrated respectively in identical XRD determining and the XRD spectrum of ZnO In figure, characterize 2 θ values of the diffraction maximum in (002) face of ZnO.

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 XRD spectra of the described precipitated product obtained under the conditions of being illustrated respectively in identical XRD determining and the XRD spectrum of ZnO In figure, characterize 2 θ values of the diffraction maximum in (101) face of ZnO.

In the present invention, in the XRD spectra of described precipitated product, 2 θ values of the diffraction maximum of the ZnO crystal of appearance meet State relational expression.Can be determined that in the precipitated product that the preparation method that the present invention provides obtains 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 the zinc lead solid solution of formation Middle lead and the mol ratio of zinc.Under preferable case, containing useful formula in XRD determining analysis, the precipitated product that step (1) obtains Pb_xZn_1-xThe zinc lead solid solution that O represents, wherein x meets 0 ＜ x≤0.12, and x represents atomic molar ratio.Formed uses above-mentioned formula In the zinc lead solid solution represented, lead and zinc are according to above-mentioned atomic molar ratio coupling, it is provided that ZnO crystal is absorbing sulfur and oxidation More preferable crystal structural stability is had, such that it is able to be further ensured that containing zinc lead solid solution under the hot environment of regenerative process Desulphurization catalyst has the most desulphurizing activated.

According to the present invention, lead-containing compounds described in step (1) can be various water solublity lead-containing compounds, preferable case Under, described lead-containing compounds is plumbi nitras and/or lead acetate.The described lead-containing compounds used in the present invention can also be for containing The form of the hydrated compound of water of crystallization.

According to the present invention, zinc compound described in step (1) can be various water solublity zinc compound, preferable case Under, described zinc compound is at least one in zinc acetate, zinc chloride and zinc nitrate.Use in the present invention is described containing zinc impregnation Compound can also be the form of the hydrated compound containing water of crystallization.

According to the present invention, precipitation described in step (1) is for being co-precipitated out lead and zinc from described mixed solution Obtain the mixture containing lead and zinc.Under preferable case, the precipitant that precipitation described in step (1) uses can be carbamide And/or ammonia.Use above-mentioned precipitant that described precipitation can be made to carry out more complete, and the life of beneficially zinc lead solid solution Become.

In the case of according to the invention it is preferred to, described in step (1), the pH of mixture is 9-13.Precipitation in step (1) When the described mixture obtained is above-mentioned pH scope, it is ensured that the lead contained in described mixed solution and zinc are total to more completely It is settled out, and the generation of beneficially zinc lead solid solution.

According to the present invention, described being dried can play the described mixture transformation being co-precipitated out in step (1) with roasting For zinc lead solid solution.In order to obtain the zinc lead solid solution that can represent with above-mentioned formula, under preferable case, described in step (1) The condition being dried 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: roasting The temperature burnt is 400-700 DEG C, and the time of roasting is 0.5-3h.

According to the present invention provide desulphurization catalyst preparation method in step (2), this step for by silica source, The precipitated product that alumina source, alkaline earth metal compound and step (1) obtain prepares carrier.Under preferable case, described oxygen The addition of SiClx source, described alumina source and described alkaline earth metal compound makes in the desulphurization catalyst obtained, with described On the basis of the gross weight of desulphurization catalyst, the content of silica source be 5-35 weight %, the content of aluminium oxide be 5-35 weight %, alkali The content of soil metal oxide is 0.5-10 weight %；Preferably, described silica source, described alumina source and described alkaline earth gold The addition belonging to compound makes in the desulphurization catalyst obtained, on the basis of the gross weight of described desulphurization catalyst, and silicon oxide The content in source be 10-25 weight %, the content of aluminium oxide be 10-25 weight %, the content of alkaline earth oxide be 1-5 weight %.

A kind of preferred implementation in the present invention, step (2) is for by silica source, alumina source, molecular sieve and step (1) precipitated product obtained prepares carrier.Described molecular sieve is phosphate aluminium molecular sieve, has molecular sieve and the tool of BEA structure There is at least one in the molecular sieve of FAU structure.Under preferable case, described silica source, described alumina source and described molecule The addition of sieve makes in the desulphurization catalyst obtained, on the basis of the gross weight of described desulphurization catalyst, and containing of silica source Amount is 5-30 weight %, the content of aluminium oxide is 5-30 weight %, the content of molecular sieve is 1-20 weight %；Preferably, described oxidation The addition of silicon source, described alumina source and described molecular sieve makes in the desulphurization catalyst obtained, with described desulphurization catalyst Gross weight on the basis of, the content of silica source be 10-25 weight %, the content of aluminium oxide be 10-25 weight %, the containing of molecular sieve Amount is 2-10 weight %.

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

In the case of according to the invention it is preferred to, described alumina source can be energy under conditions of the described roasting of step (2) Enough it is changed into the material of aluminium oxide.Preferably, described alumina source is hydrated alumina and/or Alumina gel；Described aqua oxidation Aluminum is at least one in boehmite, false boehmite, Alumina hydrate and amorphous hydroted alumina.

According to the present invention, described silica source can be to provide cementation in described desulphurization catalyst between each component. Under preferable case, described silica source is the natural crystal that silicon oxide or silica content are more than 45 weight %.Preferably, described Silica source can be in laminated clay column, kieselguhr, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel At least one.

Although it should be noted that aluminium oxide may be contained in above-mentioned silica source, but the content of aluminium oxide in the present invention Not including the amount of aluminium oxide contained in above-mentioned silica source, the content of aluminium oxide only includes the oxidation formed by alumina source The amount of aluminum.The amount of aluminium oxide contained in silica source still can be regarded as the amount of silica source.The phosphorus aluminum added in step (2) divides Son sieve, there is the molecular sieve of BEA structure and to have the molecular sieve of FAU structure same as above, do not repeat them here.Although described phosphorus Aluminum molecular screen, there is the molecular sieve of BEA structure and there is the molecular sieve of FAU structure in containing aluminium oxide, but described phosphorus aluminum divides Son sieves, has the molecular sieve of BEA structure and has the amount of the aluminium oxide each contained respectively in the molecular sieve of FAU structure, still Each can be regarded as respectively described phosphate aluminium molecular sieve, described in there is the molecular sieve of BEA structure and the described molecular sieve with FAU structure Amount, is not counted in aluminium oxide.In the desulphurization catalyst that method the most provided by the present invention prepares, the content of each component is according to feeding intake Amount calculates.

In the case of according to the invention it is preferred to, described alkaline earth metal compound be the carbonate of alkaline-earth metal, bicarbonate, At least one in nitrate, chloride, formates, hydroxide and acetate；Described alkaline-earth metal is magnesium and/or calcium.

In the present invention, in step (2), the consumption of described acid solution so that the pH value of described carrier mixture is 1-5, It is preferably 1.5-4.Described acid solution can be selected from water-soluble mineral acid and/or organic acid, such as, can be hydrochloric acid, nitre At least one in 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 institute in step (1) can be obtained State mixed solution.Such as adding the amount of water with the weight ratio of lead-containing compounds and zinc compound 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 institute in step (2) can be obtained The serosity stated.Such as adding the amount of water makes the solid content of the described serosity obtained be 15-40 weight %.

In the present invention, the method forming serosity described in step (2) can use various order, can be with silica source, oxygen Change aluminum source, alkaline earth metal compound, water and contact formation serosity together with acid solution；Serosity can also be formed according to the following steps: a) Silica source, alkaline earth metal compound and water are mixed to form mixture, mixture are dried and 400-600 DEG C of roasting, Silica source after process；B) alumina source, water and acid solution are mixed, form acidified slurries；C) oxidation after processing Mixing homogeneously with acidified slurries in silicon source, forms serosity.

A kind of preferred implementation in the present invention, the method forming serosity described in step (2) can use various order, Formation serosity can be contacted together with acid solution with molecular sieve, silica source, alumina source, alkaline earth metal compound, water；Can also Form serosity according to the following steps: a) silica source, alkaline earth metal compound and water are mixed to form mixture, mixture is dried And in 400-600 DEG C of roasting, the silica source after being processed；B) molecular sieve, alumina source, water and acid solution are mixed, shape Become acidified slurries；C) silica source after processing is mixed homogeneously with acidified slurries, forms serosity.

In step of the present invention (2), described carrier mixture can be wet mixture, paste mixture, dough or serosity Etc. form.By described molding, described carrier mixture can be shaped to extrudate, sheet, pill, ball or micro-spherical particle. Such as, when described carrier mixture is dough or paste mixture, described carrier mixture molding can be made (to be preferably extruded into Type) form granule, preferably diameter at 1.0-8.0mm, length, at the cylindrical extrudates of 2.0-5.0mm, then makes squeezing of gained Go out thing 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, forms, by being spray-dried, the microsphere that granularity is 20-200 micron, Reach the purpose of molding.For the ease of being spray-dried, before being dried, the solid content of serosity can be 10-50 weight %, preferably 20- 50 weight %.

In the present invention, drying means and the condition of described carrier mixture are known to those skilled in the art, such as, dry Dry method can be dry, dry, forced air drying.Under preferable case, in step (2), be dried temperature can be room temperature extremely 400 DEG C, preferably 100-350 DEG C；The described dry time is at least 0.5 hour, preferably 0.5-60 hour.

In the present invention, the roasting condition of described carrier mixture can also be known to those skilled in the art, typically comes Saying, the temperature of described roasting is 400-700 DEG C, preferably 450-650 DEG C；The time of described roasting is at least 0.5 hour, preferably For 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 in the desulphurization catalyst obtained, 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 %.Its In, described can be the material of the oxide being converted into active metal under the roasting condition of step (3) containing active metal.Institute State the compound containing active metal and can be selected from the acetate of active metal, carbonate, nitrate, sulfate, rhodanate With at least one in oxide.Described active metal can be at least one in cobalt, nickel, ferrum and manganese；The most described work Property metal can be nickel.

In the present invention, on described carrier, introduce the compound containing active metal can pass through accomplished in many ways.Such as, Can use and well known to a person skilled in the art that dipping method or intermediate processing realize.Described dipping method is with containing active metal The solution of compound or suspension impregnation described in carrier；Described intermediate processing be by the solution of the compound containing active metal or Suspension mixes with described carrier, is subsequently adding ammonia and is deposited on carrier by active metal.Preferably dipping method.

It is dried described in step of the present invention (3) and roasting can be the carrier being introduced into the compound containing active metal On volatile material remove and be changed into by active metal the oxide of active metal, obtain desulphurization catalyst precursor.Institute Stating dry condition can include, the temperature being dried is about 50-300 DEG C, preferably 100-250 DEG C, and the time being dried is about 0.5-8 hour, preferably about 1-5 hour.The condition of described roasting can be included in the condition with the presence of oxygen or oxygen-containing gas Under carry out, the temperature of described roasting can be about 300-800 DEG C, preferably 400-750 DEG C, and the time of roasting may be about 0.5- 4 hours, preferably 1-3 hour.

The reduction of desulphurization catalyst precursor can be entered after prepared desulphurization catalyst precursor by step of the present invention (4) immediately OK, it is also possible to carry out (i.e. before desulfurization is adsorbed) before use.Owing to active metal easily aoxidizes, and desulphurization catalyst precursor In active metal exist in the form of an oxide, therefore for ease of transport, preferred steps (4) by desulphurization catalyst precursor reduction exist Carry out before carrying out desulfurization absorption.Described being reduced to makes the metal in the oxide of active metal substantially exist with reduction-state, Desulphurization catalyst to the present invention.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 For 400-500 DEG C, 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 desulphurization catalyst has The composition of aforementioned desulphurization catalyst, content and structure of feature, do not repeat them here.

A kind of method that present invention also offers desulfurization of hydrocarbon oil, the method includes: connect with desulphurization catalyst by hydrocarbon oil containing surphur Touch reaction, 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 be at hydrogen Reacting under gas atmosphere, the condition of reaction includes: the temperature of reaction can be 350-500 DEG C, preferably 360-430 DEG C；Reaction Pressure 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 the desulphurization catalyst through reaction after reaction Regenerate.The condition of regeneration includes: regenerate under oxygen atmosphere (oxygen content can be 10-80 volume %)；Regeneration Temperature is 450-600 DEG C, preferably 480-520 DEG C；The pressure of regeneration is normal pressure.

In the present invention, the method for described desulfurization of hydrocarbon oil can also include: the desulphurization catalyst after regeneration is before reuse Reduce.The condition of reduction includes: reduce under hydrogen atmosphere (hydrogen content can be 30-60 volume %)；Reduction Temperature can be 350-500 DEG C, preferably 400-450 DEG C；The pressure of reduction can be 0.2-2MPa, preferably 0.2-1.5MPa.

In the present invention, described hydrocarbon ils includes cracking gasoline and diesel fuel, and wherein " cracking gasoline " means that boiling range is 40 To the hydrocarbon of 210 DEG C or its any fraction, it is from making bigger hydrocarbon molecule be cracked into the heat of less molecule or the product of catalytic process Product.The thermal cracking process being suitable for includes, but are not limited to coking, thermal cracking and visbreaking etc. and combinations thereof.The catalysis being suitable for is split The example of change process includes but not limited to fluid catalystic cracking and RFCC etc. and combinations thereof.Therefore, be suitable for urges Change cracking gasoline and include but not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and weight Oil cracking gasoline and combinations thereof.In some cases, in the methods of the invention be used as hydrocarbon-containifluids fluids time can be by institute before desulfurization State cracking gasoline fractional distillation and/or hydrotreating.Described " diesel fuel " means the hydrocarbon mixture that boiling range is 170 DEG C to 450 DEG C Or the liquid of its any fractional composition.This type of hydrocarbon-containifluids fluids includes but not limited to that light cycle oil, kerosene, straight-run diesel oil, catalysis are split Change 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 gasoline or diesel engine The organosulfur compound being commonly present in fuel.Present in hydrocarbon-containifluids fluids of the present invention sulfur include but not limited to carbonyl sulfide (COS), Carbon bisulfide (CS₂), mercaptan or other thiophenes etc. and combinations thereof, especially include thiophene, benzothiophene, alkyl thiophene The thiophene-based that the molecular weight that is commonly present in fen, alkyl benzothiophenes and methyldibenzothiophene, and diesel fuel is bigger Compound.

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) to carry out desulfurization adsorption combined The structure determination of thing, 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 acetate trihydrate lead (traditional Chinese medicines chemical reagents corporation, analytical pure) and 18 kilograms of deionized waters mixing, complete after stir 30 minutes Dissolve.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, it is precipitated product C1.

Precipitated product C1 is carried out fluorescence analysis and XRD determining.In XRD spectra, (see figure 1) does not has the diffraction maximum of PbO, and 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 °, it is heavy to illustrate In the product C1 of shallow lake, PbO and ZnO is completely formed zinc lead solid solution, and its chemical composition is Pb_0.044Zn_0.956O。

(2) carrier is prepared.Take two water magnesium nitrate 915 grams (traditional Chinese medicines chemical reagents corporation, analytical pure), boehmite 2.0 Kilogram (catalyst Nanjing branch company, containing butt 1.50 kilograms), (catalyst asphalt in Shenli Refinery, containing butt for 2.40 kilograms of Kaolin 2.0 kilograms) and 9.0 kilograms of neutral waters (pH value is 6-8) under agitation mix, add 200 grams of concentrated nitric acids (chemical pure, Beijing Factory produce) 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, add precipitation Product C1, after mixing, stirring obtains carrier mixture in 1 hour.

Described carrier mixture uses Niro Bowen Nozzle Tower^TMThe spray dryer of model carries out spray dried Dry, being spray-dried pressure is 8.5 to 9.5MPa, and inlet temperature less than 500 DEG C, outlet temperature is about 150 DEG C.By being spray-dried The microsphere arrived first is dried 1 hour at 150 DEG C, and then at 480 DEG C, roasting obtains catalyst carrier in 1 hour.

(3) desulphurization catalyst precursor is prepared.The catalyst carrier steps of 6.4 kilograms (2) obtained is with 7.0 kilogram of six water Closing nickel nitrate, 1.10 kilograms of deionized water solution spray impregnation at twice, the mixture obtained is after 150 DEG C are dried 4 hours Then 480 DEG C of roastings 1 hour, desulphurization catalyst precursor is obtained.

(4) desulphurization catalyst is prepared.Desulphurization catalyst precursor step (3) obtained is gone back in the hydrogen atmosphere of 400 DEG C Desulphurization catalyst A1 is obtained after former 3 hours.

The composition of desulphurization catalyst A1 is calculated as by inventory: zinc oxide 40.0 weight %, lead oxide 5.0 weight %, oxidation Aluminum 15.0 weight %, Kaolin 20.0 weight %, magnesium oxide 2.0 weight %, nickel 18.0 weight %.

Desulphurization catalyst A1 is carried out fluorescence analysis and XRD determining result as shown in Figure 2.Compose with the XRD of precipitated product C1 Scheming corresponding, in the XRD spectra of desulphurization catalyst A1, the diffraction maximum of ZnO is respectively in 31.75 °, 34.42 ° and 36.24 °, this peak position With in the XRD spectra of precipitated product C1 occur ZnO peak position be consistent, illustrate use zinc lead solid solution be raw material prepare take off Sulfur catalyst exists the structure of 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 produce, analytical pure), 1.80 kilograms Plumbi nitras powder (traditional Chinese medicines chemical reagents corporation, analytical pure) and 18 kilograms of deionized water mixing, add 2.0 thousand after stirring 30 minutes Gram carbamide and be heated to 80 DEG C process 2 hours after obtain white precipitate, first dry 2 hours at 150 DEG C after filtration, then 500 DEG C roasting 1 hour, is precipitated product C2.

Precipitated product C2 is carried out fluorescence analysis and XRD determining.In XRD spectra, (see figure 1) does not has the diffraction maximum of PbO, and 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 °, explanation In precipitated product C2, PbO and ZnO is completely formed zinc lead solid solution, and its chemical composition is Pb_0.1Zn_0.9O。

(2) carrier is prepared.Take 397 grams of calcium hydroxide (traditional Chinese medicines chemical reagents corporation, analytical pure), boehmite 2.27 thousand Gram (catalyst Nanjing branch company, containing butt 1.70 kilograms), (catalyst asphalt in Shenli Refinery, containing dry for 1.33 kilograms of expanded perlites 1.3 kilograms of base), 0.43 kilogram of SAPO-11(catalyst Nanjing branch company, containing butt 0.30 kilogram) and 8.0 kilograms of neutral water (pH Value is 6-8) under agitation mix, add 200 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant produces) stirring acidifying and rise after 1 hour Temperature is acidified 1 hour to 60 DEG C.When temperature is reduced to below 40 DEG C, adding precipitated product C2, after mixing, stirring obtains for 1 hour Carrier mixture.

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.Method with reference to embodiment 1 step (3) obtains desulphurization catalyst 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 %, oxidation Aluminum 17.0 weight %, expanded perlite 13.0 weight %, SAPO-31 molecular sieve 3.0 weight %, nickel 14.0 weight %, calcium oxide 3.0 weight Amount %.

Embodiment 3

According to the method for embodiment 2, except for the difference that, in step (2), with 0.43 kilogram of beta-molecular sieve, (public affairs are divided in catalyst Nanjing Department, containing butt 0.30 kilogram), substitute 0.43 kilogram of SAPO-11(catalyst Nanjing branch company, containing butt 0.30 kilogram).

The composition of desulphurization catalyst A3 is calculated as by inventory: zinc oxide 38.0 weight %, lead oxide 12.0 weight %, oxidation Aluminum 17.0 weight %, expanded perlite 13.0 weight %, beta-molecular sieve 3.0 weight %, nickel 14.0 weight %, calcium oxide 3.0 weight %.

Embodiment 4

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 Kilogram plumbi nitras (traditional Chinese medicines chemical reagents corporation, analytical pure) and 20 kilograms of deionized waters mixing, be completely dissolved after stirring 30 minutes. After adding 2.0 kg urea and be heated to 80 DEG C and process the white precipitates obtained after 2 hours.First 2 are dried at 150 DEG C little after filtration Time, then 500 DEG C of roastings 1 hour, it is precipitated product C3.

Precipitated product C3 is carried out fluorescence analysis and XRD determining.In XRD spectra, (see figure 1) does not has the diffraction maximum of PbO, and 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 °, explanation In precipitated product C3, PbO and ZnO is completely formed zinc lead solid solution, and its chemical composition is Pb_0.07Zn_0.93O。

(2) carrier is prepared.Take 1.03 kilograms of kieselguhr (catalyst Nanjing branch company, containing butt 1.00 kilograms) and 1.83 thousand Gram two water magnesium nitrates (traditional Chinese medicines chemical reagents corporation, analytical pure) mix homogeneously solution being evaporated, so in 3.0 kg water solution Rear taking-up mixture kieselguhr after roasting is processed for 1 hour at 600 DEG C.

Take aluminium oxide 1.5 kilograms (Shandong Aluminum Plant produces, containing butt 1.2 kilograms), 0.6 kilogram of USY molecular sieve (catalyst south Capital branch company, containing butt 0.5 kilogram) and 9.0 kilograms of neutral waters (pH value is 6-8) under agitation mix, add 200 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant produces) stirring acidifying is warming up to 60 DEG C after 1 hour and is acidified 1 hour.Treat temperature be reduced to 40 DEG C with Time lower, adding the kieselguhr after above-mentioned process and precipitated product C3, 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.Method with reference to embodiment 1 step (3) obtains desulphurization catalyst precursor.

(4) desulphurization catalyst is prepared.Method with reference to embodiment 1 step (4) obtains desulphurization catalyst A3.

The composition of desulphurization catalyst A4 is calculated as by inventory: zinc oxide 50.0 weight %, lead oxide 7.0 weight %, oxidation Aluminum 12.0 weight %, kieselguhr 10.0 weight %, USY molecular sieve 5.0 weight %, nickel 12.0 weight %, magnesium oxide 4.0 weight %.

Comparative example 1

This comparative example is used for illustrating that prior art preparation method prepares desulphurization catalyst.

By 4.56 kilograms of zinc oxide (traditional Chinese medicines chemical reagents corporation, analytical pure) and two water magnesium nitrates 915 grams (traditional Chinese medicines chemistry examination Agent company, analytical pure) mix at 8.5 kilograms of deionized waters, obtain the mixed serum of zinc oxide and sodium carbonate after stirring 30 minutes.

Take boehmite 2.0 kilograms (catalyst Nanjing branch company, containing butt 1.50 kilograms), the Kaolin of 2.4 kilograms (catalyst asphalt in Shenli Refinery, containing butt 2.0 kilograms) and 9.0 kilograms of neutral water (pH value is 6-8) under agitation mix homogeneously, add Enter 200 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant produces) stirring acidifying to be warming up to 60 DEG C after 1 hour and be acidified 1 hour.Treat temperature When being reduced to less than 40 DEG C, adding the mixed serum of zinc oxide and sodium carbonate, 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, is taken off Sulfur catalyst B1.

The composition of desulphurization catalyst B1 is calculated as by inventory: zinc oxide 45.0 weight %, aluminium oxide 15.0 weight %, kaolinite Soil 20.0 weight %, nickel 18.0 weight %, magnesium oxide 2.0 weight %.

Comparative example 2

By 5.05 kilograms of zinc oxide (traditional Chinese medicines chemical reagents corporation, analytical pure) and 397 grams of calcium hydroxide (traditional Chinese medicines chemical reagent Company, analytical pure) mix at 9.5 kilograms of deionized waters, obtain the mixed serum of zinc oxide and potassium hydroxide after stirring 30 minutes.

Take boehmite 2.27 kilograms (catalyst Nanjing branch company, containing butt 1.70 kilograms), the expansion of 1.63 kilograms Perlite (catalyst Nanjing branch company, containing butt 1.60 kilograms) and 8.0 kilograms of neutral waters (pH value is 6-8) are under agitation mixed Close, add 200 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant produces) stirring acidifying and be warming up to 60 DEG C after 1 hour and be acidified 1 hour. When temperature is reduced to below 40 DEG C, adding the mixed serum of zinc oxide and potassium hydroxide, after mixing, stirring is carried for 1 hour Body mixture.

Method with reference to embodiment 1 carries out the spray drying of carrier mixture and impregnates introducing active component nickel, is taken off Sulfur catalyst B2.

The composition of desulphurization catalyst B2 is calculated as by inventory: zinc oxide 50.0 weight %, aluminium oxide 17.0 weight %, expands Perlite 16.0 weight %, nickel 14.0 weight %, calcium oxide 3.0 weight %.

Comparative example 3

By 1.13 kieselguhr (catalyst Nanjing branch company, containing butt 1.10 kilograms) and 1.83 kilogram of two water magnesium nitrate (state Medicine chemical reagents corporation, analytical pure) mix homogeneously solution is evaporated in 3.0 kg water solution, then take out mixture and exist Kieselguhr after roasting is processed for 1 hour at 600 DEG C.

(pH value is 6-to take aluminium oxide 2.13 kilograms (Shandong Aluminum Plant produce, containing butt 1.6 kilograms) and 9.0 kilograms of neutral waters 8), under agitation after mix homogeneously, add 170 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant produces) and stir and be warming up to 60 DEG C of acid Change 1 hour.When temperature is reduced to below 40 DEG C, add 5.79 kilograms of zinc oxide (catalyst Nanjing branch company) powder and on State the kieselguhr after process, after stirring 1 hour after mixing, obtain carrier mixture.

Method with reference to embodiment 1 carries out the spray drying of carrier mixture and impregnates introducing active component nickel, is taken off Sulfur catalyst B3.

The composition of desulphurization catalyst B3 is calculated as by inventory: zinc oxide 57.0 weight %, aluminium oxide 16.0 weight %, diatom Soil 11.0 weight %, nickel 12.0 weight %, magnesium oxide is 4.0 weight %.

Comparative example 4

By 3.84 kilograms of Zinc oxide powders (Beijing Chemical Plant produces, containing butt 3.8 kilograms), 1.21 kilograms of lead oxide powder (traditional Chinese medicines chemical reagents corporation, analytical pure), 397 grams of calcium hydroxide (traditional Chinese medicines chemical reagents corporation, analytical pure) and 7.8 kilograms go from Sub-water mixes, and obtains potassium hydroxide, zinc oxide and lead oxide mixed serum after stirring 30 minutes.

Take boehmite 2.27 kilograms (catalyst Nanjing branch company, containing butt 1.70 kilograms), the expansion of 1.63 kilograms Perlite (catalyst Nanjing branch company, containing butt 1.60 kilograms) and 8.0 kilograms of neutral waters (pH value is 6-8) are under agitation mixed Close, add 200 grams of concentrated nitric acids (chemical pure, Beijing Chemical Plant produces) stirring acidifying and be warming up to 60 DEG C after 1 hour and be acidified 1 hour. When temperature is reduced to below 40 DEG C, add the mixed serum of potassium hydroxide, zinc oxide and lead oxide, stir 1 after mixing little Time obtain carrier mixture.

Method with reference to embodiment 1 carries out the spray drying of carrier mixture and impregnates introducing active component nickel, is taken off Sulfur catalyst B4.

The composition of desulphurization catalyst B4 is calculated as by inventory: zinc oxide 38.0 weight %, lead oxide 12.0 weight %, oxidation Aluminum 17.0 weight %, expanded perlite 16.0 weight %, nickel 14.0 weight %, calcium oxide 3.0 weight %.

Embodiment 5

(1) abrasion strength resistance evaluation.Desulphurization catalyst A1-A4 and B1-B4 uses straight tube abrasion method be evaluated, evaluates Method is with reference to the method for RIPP29-90 in " Petrochemical Engineering Analysis method (RIPP) experimental technique ", and numerical value is the least, shows wear-resistant Intensity is the highest.The results are shown in Table 1.

(2) desulfurization performance evaluation.The micro-anti-experimental provision of fixed bed is used to comment desulphurization catalyst A1-A4 and B1-B4 Valency, adsorption reaction raw material uses sulphur concentration to be the catalytically cracked gasoline of 960ppm.The desulfurization adsorbing composition A1 of 16 grams are loaded Internal diameter be 30mm, in the fixed bed reactors of a length of 1m, reaction pressure is 1.38MPa, and hydrogen flowing quantity is 6.3L/h, gasoline stream Amount is 80mL/h, and reaction temperature is 380 DEG C, and the charging of adsorption reaction raw material is weight space velocity 4h^-1, carry out the desulfurization of hydrocarbon oil containing surphur Reaction.Weigh desulphurizing activated with sulfur content in product gasoline.In product gasoline, sulfur content passes through off-line chromatogram analysis method, uses The GC6890-SCD instrument of An Jielun company is measured.In order to accurate characterization goes out desulphurization catalyst A1 in industry actual motion Activity, reacted rear desulphurization catalyst A1 and carried out Regeneration Treatment, Regeneration Treatment is to carry out under the air atmosphere of 480 DEG C 's.After desulphurization catalyst A1 carries out reaction regeneration 6 circulation, its activity settles out substantially, produces after stablizing with desulphurization catalyst A1 Sulfur content in product gasoline represents the activity of desulphurization catalyst A1, the results are shown in Table 1.Carry out desulfurization adsorbing composition employing equally The desulfurization performance evaluation of A2-A4 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/T503-1995 and GB/T5487-1995 and measures reaction raw materials catalytically cracked gasoline and desulfurization is urged The motor octane number (MON) of agent stably rear 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 desulphurization catalyst A1-A3 of present invention offer contains Zinc lead solid solution, desulphurization catalyst has the most desulphurizing activated and activity stability.Desulphurization catalyst has the most wear-resisting Damage intensity, so that desulphurization catalyst has longer service life.

Additionally, this desulphurization catalyst can be carried out at 380 DEG C absorbing oxidation regeneration at sulfur and 480 DEG C in lower temperature.

Claims (31)

1. a desulphurization catalyst, on the basis of the gross weight of this desulphurization catalyst, this desulphurization catalyst contains 5-35 weight % Silica source, the aluminium oxide of 5-35 weight %, the zinc oxide of 30-70 weight %, the lead oxide of 2-15 weight %, 0.5-10 weight The alkaline earth oxide of amount % and the active metal of 5-30 weight %；And at least part of described lead oxide with described zinc oxide Form formula Pb_xZn_1-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；Wherein, described silica source be laminated clay column, kieselguhr, At least one in expanded perlite, silicalite and macropore silicon oxide.

Desulphurization catalyst the most according to claim 1, wherein, on the basis of the gross weight of this desulphurization catalyst, this desulfurization Catalyst contains the silica source of 10-25 weight %, the aluminium oxide of 10-25 weight %, the zinc oxide of 35-54 weight %, 5-12 The lead oxide of weight %, the alkaline earth oxide of 1-5 weight % and the active metal of 10-20 weight %.

Desulphurization catalyst the most according to claim 1, wherein, this desulphurization catalyst is possibly together with the molecule of 1-20 weight % Sieve, described molecular sieve is phosphate aluminium molecular sieve, there is the molecular sieve of BEA structure and there is the molecular sieve of FAU structure at least one Kind.

Desulphurization catalyst the most according to claim 3, wherein, on the basis of the gross weight of this desulphurization catalyst, this desulfurization Catalyst contains the silica source of 10-25 weight %, the aluminium oxide of 10-25 weight %, the zinc oxide of 35-54 weight %, 5-12 The lead oxide of weight %, the alkaline earth oxide of 1-5 weight %, the molecular sieve of 2-10 weight % and the work of 10-20 weight % Property metal.

Desulphurization catalyst the most according to claim 3, wherein, the hole size of described phosphate aluminium molecular sieve isPore volume For 0.18-0.48cm³/g。

Desulphurization catalyst the most according to claim 5, wherein, described phosphate aluminium molecular sieve is SAPO-11, SAPO-31, At least one in SAPO-34 and SAPO-20.

Desulphurization catalyst the most according to claim 3, wherein, described in have the molecular sieve of BEA structure be beta-molecular sieve, institute State have the molecular sieve of FAU structure be X-type molecular sieve, Y type molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY and At least one in PREY.

8. according to the desulphurization catalyst described in any one in claim 1-7, wherein, described desulphurization catalyst meets with ShiShimonoseki It is formula: A₁₀₀-B₁₀₀=0.2 ° to 0.3 °, A₁₀₀And B₁₀₀The described desulfurization obtained under the conditions of being illustrated respectively in identical XRD determining In the XRD spectra of catalyst and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (100) face of ZnO.

9. according to the desulphurization catalyst described in any one in claim 1-7, wherein, described desulphurization catalyst meets with ShiShimonoseki It is formula: A₀₀₂-B₀₀₂=0.2 ° to 0.3 °；A₀₀₂And B₀₀₂The described desulfurization obtained under the conditions of being illustrated respectively in identical XRD determining In the XRD spectra of catalyst and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (002) face of ZnO.

10. according to the desulphurization catalyst described in any one in claim 1-7, wherein, below described desulphurization catalyst meets Relational expression: A₁₀₁-B₁₀₁=0.2 ° to 0.3 °；A₁₀₁And B₁₀₁Obtain under the conditions of being illustrated respectively in identical XRD determining is described de- In the XRD spectra of sulfur catalyst and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (101) face of ZnO.

11. according to the desulphurization catalyst described in any one in claim 1-7, and wherein, described active metal is nickel.

12. according to the desulphurization catalyst described in any one in claim 1-7, and wherein, described alkaline earth oxide is magnesium And/or the oxide of calcium.

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, precipitation is obtained To mixture carry out filtering, be dried and roasting, be precipitated product；

(2) mixture containing silica source, alumina source, alkaline earth metal compound, water and acid solution is formed serosity, and will The precipitated product that step (1) obtains mixes with described serosity, forms carrier mixture；Again by described carrier mixture molding, do Dry and roasting, forms carrier；

(3) introduce on the carrier that step (2) obtains containing the compound of active metal and be dried, roasting, obtain desulfurization catalyst Agent 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, 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；

Wherein, during described silica source is laminated clay column, kieselguhr, expanded perlite, silicalite and macropore silicon oxide at least A kind of.

14. preparation methoies according to claim 13, wherein, described silica source, described alumina source, described alkaline earth gold The addition belonging to compound and the described compound containing active metal 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 be 5-35 weight %, the content of aluminium oxide be 5-35 weight %, alkaline earth gold The content that content is 0.5-10 weight % and active metal belonging to oxide is 5-30 weight %.

15. preparation methoies according to claim 13, wherein, described in step (2) containing silica source, alumina source, The mixture of alkaline earth metal compound, water and acid solution is possibly together with molecular sieve, and described molecular sieve is phosphate aluminium molecular sieve, has BEA The molecular sieve of structure and at least one having in the molecular sieve of FAU structure.

16. preparation methoies according to claim 15, wherein, described silica source, described alumina source, described molecular sieve Make in the desulphurization catalyst obtained with the addition of the described compound containing active metal, total with described desulphurization catalyst On the basis of weight, the content of silica source be 5-30 weight %, the content of aluminium oxide be that 5-30 weight %, the content of molecular sieve are The content of 1-20 weight % and active metal is 5-30 weight %.

17. according to the preparation method described in any one in claim 13-16, wherein, and lead-containing compounds described in step (1) Make in the desulphurization catalyst obtained with zinc compound addition, on the basis of the gross weight of described desulphurization catalyst, oxidation The content of lead is 2-15 weight %, and the content of zinc oxide is 30-70 weight %.

18. according to the preparation method described in any one in claim 13-16, and wherein, described precipitated product meets with ShiShimonoseki It is formula: 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 2 θ values of the diffraction maximum in (100) face of ZnO.

19. according to the preparation method described in any one in claim 13-16, and wherein, described precipitated product meets with ShiShimonoseki It is formula: 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 2 θ values of the diffraction maximum in (002) face of ZnO.

20. according to the preparation method described in any one in claim 13-16, and wherein, described precipitated product meets with ShiShimonoseki It is formula: 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 2 θ values of the diffraction maximum in (101) face of ZnO.

21. according to the preparation method described in any one in claim 13-16, and wherein, described precipitated product at least partly contains 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.

22. according to the preparation method described in any one in claim 13-16, and wherein, described lead-containing compounds is plumbi nitras And/or lead acetate.

23. according to the preparation method described in any one in claim 13-16, wherein, described zinc compound be zinc acetate, At least one in zinc chloride and zinc nitrate.

24. according to the preparation method described in any one in claim 13-16, and wherein, described alkaline earth metal compound is alkali At least one in the carbonate of earth metal, bicarbonate, nitrate, chloride, formates, hydroxide and acetate；Institute Stating alkaline-earth metal is magnesium and/or calcium.

25. according to the preparation method described in any one in claim 13-16, and wherein, described in step (1), precipitation makes Precipitant be carbamide and/or ammonia.

26. according to the preparation method described in any one in claim 13-16, wherein, and the pH of mixture described in step (1) For 9-13.

27. according to the preparation method described in any one in claim 13-16, and wherein, described alumina source is in step (2) Described roasting under conditions of can be changed into the material of aluminium oxide.

28. preparation methoies according to claim 27, wherein, described alumina source is hydrated alumina and/or Alumina gel； Described hydrated alumina be in boehmite, false boehmite, Alumina hydrate and amorphous hydroted alumina at least A kind of.

29. according to the preparation method described in any one in claim 13-16, wherein, containing active gold described in step (3) The compound belonged to is at least in the acetate of active metal, carbonate, nitrate, sulfate, rhodanate and oxide Kind.

30. desulphurization catalysts obtained by the preparation method described in any one in claim 13-29.

The method of 31. 1 kinds of desulfurization of hydrocarbon oil, the method includes: reacted with hydrodesulfurization catalyst by hydrocarbon oil containing surphur, and its feature exists In, described desulphurization catalyst is the desulphurization catalyst in claim 1-12 and 30 described in any one.