CN104511301A - 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: 5-30% of a silicon oxide source, 5-30% of aluminum oxide, 30-70% of zinc oxide, 2-15% of lead oxide, 0.5-10% of a phosphorus oxide based on the weight of P2O5, 1-20% of a molecular sieve having a BEA structure and/or a molecular sieve having an FAU structure, 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

The method of a kind of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil

Technical field

The present invention relates to the method for a kind of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil, particularly, relate to a kind of desulphurization catalyst, a kind of preparation method of desulphurization catalyst and the desulphurization catalyst obtained by the method, and the method that desulphurization catalyst is applied in desulfurization of hydrocarbon oil.

Background technology

Along with people are to the pay attention to day by day of environmental protection; environmental regulation is also day by day strict; and the sulfur content reducing gasoline and diesel oil is considered to one of most important measure improving air quality, because the sulphur in fuel can produce adverse influence to the performance of vehicle catalytic converter.It is irreversibly poisoning that the sulphur existed in automobile engine tail gas can suppress the noble metal in converter also can make it generation, reduces converter to the effect of purifying vehicle exhaust.The vehicle exhaust do not purified contains unburned non-methane hydrocarbon, nitrogen oxide and carbon monoxide, and these gases are formed photochemical fog by hydrophilic dye.

Most of sulphur in China's gasoline products come from hot-working petroleum blending component, as catalytically cracked gasoline.Therefore in hot-working petroleum, the minimizing of sulfur content contributes to the sulfur content reducing China's gasoline products.The existing gasoline products standard GB17930-2011 " motor petrol " of China required on December 31st, 2013, and 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 gasoline products just can be made to meet the requirement of environmental protection.

In order to ensure the combustibility of motor vehicle fuel, while the sulfur content reducing motor vehicle fuel, olefin(e) centent in gasoline also should be avoided to change and its octane number (comprising ROM and MON) is reduced as far as possible.Affecting olefin(e) centent is generally cause owing to causing hydrogenation reaction while removing thiophenes (comprising thiophene, benzothiophene, alkylthrophene, alkyl benzothiophenes and methyldibenzothiophene).In addition, also need to avoid desulfurization condition to make the aromatic hydrocarbons of catalytically cracked gasoline be saturated and to lose.Therefore optimal method is the combustibility keeping gasoline products while of realizing desulfurization.

At present, the process for deep desulphurization of oil product mainly contains hydrofinishing and adsorption desulfurize two kinds of methods, and wherein hydrorefined cost is higher.S Zorb adsorption desulfurize belongs to adsorption desulfurize technology, this technology certain temperature, pressure and face hydrogen condition under realize the sulfur compounds adsorption in hydrocarbon ils to remove.This technology has low and not high to the purity requirement of the hydrogen feature of hydrogen consumption, and this technology is had broad application prospects in fuel desulfuration.

CN1355727A discloses a kind of adsorbent composition being applicable to remove sulphur from cracking gasoline and diesel fuel, be made up of zinc oxide, silica, oxidation al and ni, wherein nickel is substantially to reduce valence state existence, and its amount can remove sulphur from the cracking gasoline contacted with described nickeliferous adsorbent composition under desulfurization conditions or diesel fuel stream.Said composition forms particle by compound particles granulation zinc oxide, silica and aluminium oxide formed, and with nickel or nickel compound containing dipping after dry, roasting, then drying, roasting, reduction obtain.

CN1382071A discloses a kind of adsorbent composition being applicable to remove sulphur from cracking gasoline and diesel fuel, be made up of zinc oxide, silica, aluminium oxide and cobalt, wherein cobalt exists substantially to reduce valence state, and its amount can from removing sulphur under desulfurization conditions with the described cracking gasoline that contacts containing cobalt adsorbent composition or diesel fuel stream.

US6150300 discloses a kind of method preparing adsorbent, comprises and prepares spheric granules: silica containing composition, the composition containing dispersion metal oxide in an aqueous medium and the composition containing zinc oxide are mixed to form the first mixture and do not extrude described first mixture by (a); B described first mixture globulate is formed the particle with diameter 10-1000mm by ().Wherein step (a) also comprises and mixing with metallic promoter agent.

CN1422177A discloses a kind of adsorbent composition being applicable to remove sulphur from cracking gasoline and diesel fuel, be made up of zinc oxide, expanded perlite, aluminium oxide and promoter metals, wherein said promoter metals exists with the amount that can remove sulphur when contacting with it under desulfurization conditions from cracking gasoline or diesel fuel stream with the valence state substantially reduced.

CN1627988A discloses a kind of adsorbent composition being suitable for removing elementary sulfur and sulphur compound from cracking gasoline and diesel fuel, described adsorbent composition comprises: zinc oxide, expanded perlite, aluminate and promoter metals, wherein said promoter metals is will cause the amount of desulfurization from the stream of cracking gasoline or diesel fuel to exist when making cracking gasoline or diesel fuel stream contacts under desulfurization conditions with it, and at least part of described promoter metals exists with 0 valence state.

CN1856359A discloses a kind of method of production combination thing, comprising: a) mixing material, zinc compound, containing earth silicon material, aluminium oxide and co-catalyst, to form its mixture; B) this mixture dry, to form the mixture of drying; C) mixture of this drying is calcined, to form the mixture through calcining; D) under suitable condition this mixture through calcining is reduced with suitable reducing agent, to produce in it composition of the co-catalyst content with reduction valence state, and e) reclaim reorganization compound.Co-catalyst contains various metals such as being selected from nickel.

CN1871063A discloses a kind of method of production combination thing, and the method comprises: a) by liquid, zinc compound, containing earth silicon material, aluminium oxide mixing to form its mixture; B) by this mixing dry for described mixture to form the first drying mixture; C) described first drying mixture is calcined to form first through calcining mixt; D) promoter is attached to described first within calcining mixt or on formed through promote mixture; E) make described through promote mixture and be selected from citric acid, the acid of tartaric acid and combination thereof contacts to be formed through contact mixture; F) by described dry to form the second drying mixture through contact mixture; G) described second drying mixture is calcined to form second through calcining mixt; H) adopt applicable reducing agent reduction described second under suitable condition through calcining mixt to produce the composition wherein containing reduction valence state promoter content, and i) reclaim described composition.

Although published adsorbent has certain desulfurization performance, owing to being facing desulfurization under hydrogen state, inevitably hydrogenation of olefins is occurring, thus cause loss of octane number.And along with the raising of gasoline quality standard, product gasoline sulfur content is required also constantly strict.As can be seen here, need to provide one to have more high desulfurization activity and abrasion resistance properties, and the new catalyst of product gasoline octane number can be improved.

Summary of the invention

The problem that the adsorbent activity that the object of the invention is to exist to overcome prior art reduces, provides the method for a kind of desulphurization catalyst and preparation method thereof with desulfurization of hydrocarbon oil.

To achieve these goals, the invention provides a kind of desulphurization catalyst, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contain the silica source of 5-30 % by weight, the aluminium oxide of 5-30 % by weight, the zinc oxide of 30-70 % by weight, 2-15 % by weight lead oxide, with P ₂o ₅count the phosphorous oxides of 0.5-10 % by weight, the molecular sieve with BEA structure of 1-20 % by weight and/or there is the molecular sieve of FAU structure and the active metal of 5-30 % by weight; And at least part of described lead oxide uses general formula Pb with what formed with described zinc oxide _xzn _1-xthe plumbous solid solution thereof of the zinc 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, iron and manganese.

Present invention also offers a kind of preparation method of desulphurization catalyst, the method comprises: the mixed solution that lead-containing compounds, zinc compound and water are mixed to get by (1) carries out precipitation reaction, mixture precipitation reaction obtained carries out filtering, dry 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 to contact with acid solution and form slurries, and the precipitated product that step (1) obtains is mixed with described slurries, form carrier mixture; Again by shaping for described carrier mixture, dry and roasting, form carrier; (3) carrier obtained to step (2) is introduced the compound containing active metal and dry, roasting, obtain desulphurization catalyst precursor; Described active metal is at least one in cobalt, nickel, iron and manganese; (4) the desulphurization catalyst precursor that step (3) obtains is reduced under hydrogen atmosphere, obtain desulphurization catalyst.

Present invention also offers the desulphurization catalyst obtained by preparation method provided by the invention.

Present invention also offers a kind of method of desulfurization of hydrocarbon oil, the method comprises: hydrocarbon oil containing surphur and hydrodesulfurization catalyst are reacted, and wherein, described desulphurization catalyst is desulphurization catalyst provided by the invention.

By technique scheme, in desulphurization catalyst provided by the invention, at least part of lead oxide uses general formula Pb with what formed with zinc oxide _xzn _1-xthe plumbous solid solution thereof of the zinc that O represents exists, and absorbs constituent element, make desulphurization catalyst provided by the invention have better desulphurizing activated and activity stability as sulphur.And this desulphurization catalyst also has better abrasion strength resistance, the service life of desulphurization catalyst can be improved.In addition this desulphurization catalyst can also absorb sulphur at lower temperatures and carry out oxidation regeneration, and the temperature that prior art carries out absorbing sulphur is 410 DEG C, and the temperature of oxidation regeneration is 550 DEG C.It is Pb that desulphurization catalyst A1 in embodiment 1 has chemical composition _0.044zn _0.956the plumbous solid solution of zinc of O, abrasion index is 4.4; Make the sulfur content of product gasoline be 8 μ g/g as long as desulphurization catalyst A1 can process raw material in example 4 at 380 DEG C, and regeneration temperature is 480 DEG C.Although and the desulphurization catalyst B4 obtained in comparative example 4 containing lead oxide and zinc oxide, do not form the plumbous solid solution of zinc, the sulfur content processing the product gasoline that raw material obtains at 380 DEG C will up to 28 μ g/g.

Other features and advantages of the present invention are 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 forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:

Fig. 1 is the XRD spectra of precipitated product C1-C3, ZnO and PbO; Wherein

Characterize the 2 θ value B of diffraction maximum in (100) face of ZnO, (002) face and (101) face ₁₀₀, B ₀₀₂and B ₁₀₁be respectively 31.55 °, 34.21 ° and 36.04 °,

Characterize the 2 θ value A of diffraction maximum in (100) face of the ZnO in C1, (002) face and (101) face ₁₀₀, A ₀₀₂and A ₁₀₁be respectively 31.75 °, 34.42 ° and 36.24 °,

Characterize the 2 θ value A of diffraction maximum in (100) face of the ZnO in C2, (002) face and (101) face ₁₀₀, A ₀₀₂and A ₁₀₁be respectively 31.80 °, 34.45 ° and 36.28 °,

Characterize the 2 θ value A of diffraction maximum in (100) face of the ZnO in C3, (002) face and (101) face ₁₀₀, A ₀₀₂and A ₁₀₁be respectively 31.78 °, 34.43 ° and 36.26 °;

Fig. 2 is the XRD spectra of desulphurization catalyst A1.

Detailed description of the invention

Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.

The invention provides a kind of desulphurization catalyst, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contain the silica source of 5-30 % by weight, the aluminium oxide of 5-30 % by weight, the zinc oxide of 30-70 % by weight, 2-15 % by weight lead oxide, with P ₂o ₅count the phosphorous oxides of 0.5-10 % by weight, the molecular sieve with BEA structure of 1-20 % by weight and/or there is the molecular sieve of FAU structure and the active metal of 5-30 % by weight; And at least part of described lead oxide uses general formula Pb with what formed with described zinc oxide _xzn _1-xthe plumbous solid solution thereof of the zinc 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, iron and manganese.

According to the present invention, described desulphurization catalyst contains lead oxide and zinc oxide, and the plumbous solid solution of zinc that described desulphurization catalyst can be formed containing lead oxide and zinc oxide.The plumbous solid solution of described zinc 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 desulphurization catalyst contain the plumbous solid solution of zinc represented with above-mentioned general formula.Described desulphurization catalyst can be that the lead oxide that contains and zinc oxide all form the plumbous solid solution of the zinc represented with above-mentioned general formula; Also can be also contain lead oxide and/or zinc oxide except containing except the plumbous solid solution of the zinc represented with above-mentioned general formula, such as whole lead oxide and most zinc oxide form the plumbous solid solution of zinc, also contain a small amount of zinc oxide outward in desulphurization catalyst containing the plumbous solid solution of zinc.The lead oxide that preferred described desulphurization catalyst contains and zinc oxide all form the plumbous solid solution of the zinc represented with above-mentioned general formula.

According to the present invention, after lead oxide and zinc oxide form the plumbous solid solution of zinc, the lattice structure of zinc oxide is not destroyed, but enter in lattice because lead ion replaces zinc ion, so the angle of diffraction characterizing the characteristic peak of ZnO in the XRD spectra of described desulphurization catalyst can change, therefore can determine in described desulphurization catalyst, there is the plumbous solid solution of zinc by desulphurization catalyst described in XRD determining.As the XRD spectra of desulphurization catalyst A1 obtained under same XRD determining condition that shows in Fig. 2 and the XRD spectra of ZnO.In fig. 2, there is not the independent characteristic peak of lead oxide and zinc oxide, but occurred the characteristic peak of the cubic crystal of the sign zinc oxide that peak position offsets, illustrate that lead oxide and zinc oxide all define the plumbous solid solution of zinc.Under preferable case, described desulphurization catalyst meets following relational expression: A ₁₀₀-B ₁₀₀=0.2 ° to 0.3 °, A ₁₀₀and B ₁₀₀in the XRD spectra of described desulphurization catalyst obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (100) face of ZnO.

According to the present invention, under preferable case, described desulphurization catalyst meets following relational expression: A ₀₀₂-B ₀₀₂=0.2 ° to 0.3 °; A ₀₀₂and B ₀₀₂in the XRD spectra of described desulphurization catalyst obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (002) face of ZnO.

According to the present invention, under preferable case, described desulphurization catalyst meets following relational expression: A ₁₀₁-B ₁₀₁=0.2 ° to 0.3 °; A ₁₀₁and B ₁₀₁in the XRD spectra of described desulphurization catalyst obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (101) face of ZnO.

According to the present invention, can determine that described desulphurization catalyst contains the plumbous solid solution of zinc of lead oxide and zinc oxide formation by above-mentioned XRD determining, in the plumbous solid solution of this zinc, mol ratio x that is plumbous and zinc can be measured by elementary analysis such as spectrofluorimetry, can determine that the plumbous solid solution of described zinc can use general 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, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contain the silica source of 10-20 % by weight, the aluminium oxide of 10-20 % by weight, the zinc oxide of 35-54 % by weight, 5-12 % by weight lead oxide, with P ₂o ₅count the phosphorous oxides of 1-5 % by weight, the molecular sieve with BEA structure of 2-10 % by weight and/or there is the molecular sieve of FAU structure and the active metal of 8-20 % by weight.

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

According to the present invention, described silica source can for providing cementation between component each in described desulphurization catalyst.Under preferable case, the natural crystal that described silica source can be greater than 45 % by weight for silica or silica content.Preferably, described silica source can be at least one in laminated clay column, diatomite, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.

According to the present invention, described aluminium oxide can for providing cementation between component each in described desulphurization catalyst.Under preferable case, 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, under preferable case, described phosphorous oxides contains P ₂o ₅, P ₂o ₃with at least one in poly phosphoric-oxygenic compound.

According to the present invention, described in there is FAU structure molecular sieve be faujasite-type molecular sieve, the type molecular sieve has three-dimensional twelve-ring duct, and aperture is the molecular sieve of the described FAU of having structure is mainly the molecular sieve of X-type and Y type, in general SiO ₂/ Al ₂o ₃mol ratio be 2.2-3.0 for X-type molecular sieve, SiO ₂/ Al ₂o ₃mol ratio be greater than 3.0 for Y zeolite.The skeleton structure of X-type and Y zeolite all belongs to hexagonal crystal system, and space group structure is the cell parameter of Fd3m, X-type molecular sieve the cell parameter of Y zeolite

According to the present invention, described in there is FAU structure molecular sieve also comprise the modified molecular sieve with FAU structure.Method of modifying can comprise hydro-thermal method, method of chemical treatment (such as mineral acid logos, fluosilicic acid aluminium-eliminating and silicon-replenishing method and SiC1 ₄vapor 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), REUSY, REHY, REY containing rare earth element, and phosphorous PUSY, PREHY, PREY etc.

According to the present invention, described in there is BEA structure molecular sieve be mainly beta-molecular sieve, its structural formula is (Na _n[Al _nsi _64-no ₁₂₈], n<7), be different by two structures but the mixed crystal that formed of the polymorph A be closely related and B, both have twelve-ring 3 D pore canal system, polymorph A forms a pair enantiomer, and space group is P4 ₁22 and P4 ₃22, cell parameter is polymorph B belongs to achirality space group C2/c, cell parameter β=114.5 °.In BEA structure molecular screen, twelve-ring pore size is <100 direction > and direction >.

According to the present invention, under preferable case, described in there is BEA structure molecular sieve be beta-molecular sieve, described in there is FAU structure molecular sieve be at least one in X-type molecular sieve, Y zeolite, USY, REUSY, REHY, REY, PUSY, PREHY and PREY; Preferably, the molecular sieve described in FAU structure is at least one in USY, REUSY, REY, PUSY and PREY.

Present invention also offers a kind of preparation method of desulphurization catalyst, the method comprises: the mixed solution that lead-containing compounds, zinc compound and water are mixed to get by (1) carries out precipitation reaction, mixture precipitation reaction obtained carries out filtering, dry 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 to contact with acid solution and form slurries, and the precipitated product that step (1) obtains is mixed with described slurries, form carrier mixture; Again by shaping for described carrier mixture, dry and roasting, form carrier; (3) carrier obtained to step (2) is introduced the compound containing active metal and dry, roasting, obtain desulphurization catalyst precursor; Described active metal is at least one in cobalt, nickel, iron and manganese; (4) the desulphurization catalyst precursor that step (3) obtains is reduced under hydrogen atmosphere, obtain desulphurization catalyst.

In the preparation method of desulphurization catalyst provided by the invention, step (1) can form the plumbous solid solution of zinc.

According to the present invention, the addition of lead-containing compounds and zinc compound described in step (1) can be selected in wider scope, can use general formula Pb as long as can be formed _xzn _1-xthe plumbous solid solution of the zinc that O represents.Under preferable case, described in step (1), lead-containing compounds and zinc compound addition make in the desulphurization catalyst obtained, and with the gross weight of described desulphurization catalyst for benchmark, the content of lead oxide is 2-15 % by weight, and the content of zinc oxide is 30-70 % by weight; Preferably, described lead-containing compounds and zinc compound addition make in the desulphurization catalyst obtained, and with the gross weight of described desulphurization catalyst for benchmark, the content of lead oxide is 5-12 % by weight, and the content of zinc oxide is 35-54 % by weight.

According to the present invention, the precipitated product that step (1) obtains is carried out elementary analysis and XRD determining, can judge in this precipitated product containing the plumbous solid solution of zinc according to elementary analysis and XRD determining result.Particularly, first this precipitated product is carried out elementary analysis to judge wherein containing lead element and Zn-ef ficiency.Secondly this precipitated product is carried out XRD determining analysis, as shown in Figure 1, 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, can infer and form the plumbous solid solution of zinc.Because forming the plumbous solid solution of zinc is that the plumbous zinc that replaces enters in the lattice structure of zinc oxide, independently lead oxide crystal structure without, like this in the XRD spectra of the plumbous solid solution of zinc, still have the architectural feature of ZnO crystal, and there is no the architectural feature of lead oxide crystal.But the position at the crystalline phase peak of ZnO is subjected to displacement in the plumbous solid solution of zinc.Therefore, can be judged in precipitated product containing the plumbous solid solution of zinc by the XRD spectra of precipitated product.

According to the present invention, under preferable case, described precipitated product meets following relational expression: A ₁₀₀-B ₁₀₀=0.2 ° to 0.3 °, A ₁₀₀and B ₁₀₀in the XRD spectra of described precipitated product obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (100) face of ZnO.

According to the present invention, under preferable case, described precipitated product meets following relational expression: A ₀₀₂-B ₀₀₂=0.2 ° to 0.3 °; A ₀₀₂and B ₀₀₂in the XRD spectra of described precipitated product obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (002) face of ZnO.

According to the present invention, under preferable case, described precipitated product meets following relational expression: A ₁₀₁-B ₁₀₁=0.2 ° to 0.3 °; A ₁₀₁and B ₁₀₁in the XRD spectra of described precipitated product obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (101) face of ZnO.

In the present invention, 2 θ values of the diffraction maximum of the ZnO crystal occurred in the XRD spectra according to described precipitated product meet above-mentioned relation formula.Can judge in the precipitated product that preparation method provided by the invention obtains containing the plumbous solid solution of zinc.

According to the present invention, elementary analysis and XRD determining can be carried out by precipitated product, determine mol ratio that is plumbous in the plumbous solid solution of zinc formed and zinc.Under preferable case, through XRD determining analysis, containing useful general formula Pb in the precipitated product that step (1) obtains _xzn _1-xthe plumbous solid solution of the zinc that O represents, wherein x meets 0 < x≤0.12, and x represents atomic molar ratio.In the plumbous solid solution of the zinc represented with above-mentioned general formula formed, plumbous and zinc mates according to above-mentioned atomic molar ratio, ZnO crystal can be provided under the hot environment absorbing sulphur and oxidative regeneration process to have better crystal structural stability, thus can ensure that the desulphurization catalyst containing the plumbous solid solution of zinc has better desulphurizing activated further.

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

According to the present invention, described in step (1), zinc compound can be various water-soluble zinc compound, and under preferable case, described zinc compound is zinc acetate, at least one in zinc chloride and zinc nitrate.The described zinc compound used in the present invention can also be the form of the hydrated compound containing the crystallization water.

According to the present invention, precipitation reaction described in step (1) is used for the mixture gone out to obtain by plumbous and zinc co-precipitation from described mixed solution containing plumbous and zinc.Under preferable case, the precipitating reagent that precipitation reaction described in step (1) uses can be urea and/or ammoniacal liquor.Use above-mentioned precipitating reagent that described precipitation reaction can be made to carry out more complete, and be conducive to the generation of the plumbous solid solution of zinc.

According to the present invention, under preferable case, described in step (1), the pH of mixture is 9-13.When the described mixture that precipitation reaction obtains in step (1) is above-mentioned pH scope, can ensure by the lead contained in described mixed solution and zinc more completely co-precipitation go out, and be conducive to the generation of the plumbous solid solution of zinc.

According to the present invention, described drying and roasting can be played and change the described mixture that co-precipitation in step (1) goes out into zinc plumbous solid solution.In order to obtain the plumbous solid solution of the zinc that can represent with above-mentioned general formula, under preferable case, condition dry described in step (1) comprises: dry temperature is 100-200 DEG C, and the dry time is 0.5-3h; The condition of described roasting comprises: the temperature of roasting is 400-700 DEG C, and the time of roasting is 0.5-3h.

According to the step (2) in the preparation method of desulphurization catalyst provided by the invention, this step be used for by silica source, aluminium oxide, have BEA structure molecular sieve and/or there is the precipitated product that the molecular sieve of FAU structure, phosphorus-containing compound and step (1) obtain prepare carrier.Under preferable case, described silica source, described alumina source, described in there is BEA structure molecular sieve and/or the addition of the molecular sieve and described phosphorus-containing compound with FAU structure make in the desulphurization catalyst obtained, with the gross weight of described desulphurization catalyst for benchmark, the content of silica source is 5-30 % by weight, the content of aluminium oxide is 5-30 % by weight, the content of molecular sieve that has the molecular sieve of BEA structure and/or have a FAU structure is 1-20 % by weight, the content of phosphorous oxides is with P ₂o ₅count 0.5-10 % by weight; Preferably, described silica source, described alumina source, described in there is BEA structure molecular sieve and/or the addition of the molecular sieve and described phosphorus-containing compound with FAU structure make in the desulphurization catalyst obtained, with the gross weight of described desulphurization catalyst for benchmark, the content of silica source is 10-20 % by weight, the content of aluminium oxide is 10-20 % by weight, the content of molecular sieve that has the molecular sieve of BEA structure and/or have a FAU structure is 2-10 % by weight, the content of phosphorous oxides is with P ₂o ₅count 1-5 % by 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.

According to the present invention, under preferable case, described alumina source can for changing the material of aluminium oxide under the condition of the described roasting of step (2).Preferably, described alumina source is hydrated alumina and/or Alumina gel; Described hydrated alumina is at least one in boehmite, false boehmite, hibbsite and amorphous hydroted alumina.

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

It should be noted that, although may contain aluminium oxide in above-mentioned silica source, in the present invention, the content of aluminium oxide does not comprise the amount of aluminium oxide contained in above-mentioned silica source, and the content of aluminium oxide only comprises the amount of the aluminium oxide formed by alumina source.The amount of aluminium oxide contained in silica source still can be regarded as the amount of silica source.The molecular sieve with BEA structure added in step (2) and/or the molecular sieve with FAU structure same as above, do not repeat them here.Although described in there is BEA structure molecular sieve and/or there is FAU structure molecular sieve in containing aluminium oxide, the amount that the molecular sieve with BEA structure and/or the amount with the aluminium oxide contained in the molecular sieve of FAU structure still can be regarded as the molecular sieve with BEA structure and/or the molecular sieve with FAU structure is not counted in aluminium oxide.Namely in the desulphurization catalyst obtained by method provided by the invention, the content of each component calculates according to inventory.

According to the present invention, described phosphorus-containing compound can for can change P under the condition of the described roasting of step (2) ₂o ₅inorganic phosphor-contained thing or phosphorus-containing matter.Described inorganic phosphor-contained thing is at least one in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate (ADP), and described phosphorus-containing matter is at least one in trimethyl-phosphine, triethyl phosphine, tripropyl phosphine and tributylphosphine.

In the present invention, in step (2), the consumption of described acid solution can make the pH value of described carrier mixture be 1-3.Described acid solution can be selected from water-soluble inorganic 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, the addition of phosphoric acid makes to contain with the gross weight of this desulphurization catalyst for benchmark in the desulphurization catalyst obtained, with P ₂o ₅the phosphorous oxides of meter 0.5-10 % by weight, the phosphorous oxides preferably containing 1-5 % by weight.And described carrier mixture due to acid amount pH value can not be made not to reach 1-3 time, can the pH value of described carrier mixture be made to reach 1-3 by the described acid solution adding other.

In the present invention, the amount adding water in step (1) can not limit especially, as long as can obtain mixed solution described in step (1).Such as add the amount of water and 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 not limit especially, as long as can obtain the slurries described in step (2).The amount such as adding water makes the solid content of the described slurries obtained be 15-40 % by weight.

In the present invention, the method forming slurries described in step (2) can adopt various order, can silica source, alumina source, phosphorus-containing compound, have BEA structure molecular sieve and/or there is the molecular sieve of FAU structure, water contacts formation slurries together with acid solution; Also can form slurries according to the following steps: a) silica source, phosphorus-containing compound and water are mixed to form mixture, mixture drying and 400-600 DEG C of roasting, obtain the silica source after processing; B) by alumina source, have BEA structure molecular sieve and/or there is the mixing of the molecular sieve of FAU structure, water and acid solution, form acidified slurries; C) silica source after process is mixed with acidified slurries, form slurries.

In step of the present invention (2), described carrier mixture can be the forms such as wet mixture, paste mixture, dough or slurries.By described shaping, described carrier mixture can be shaped to extrudate, sheet, pill, ball or micro-spherical particle.Such as, described carrier mixture be dough or paste mixture time, described carrier mixture shaping (preferred extrusion molding) can be made to form particle, and preferred diameter is at 1.0-8.0mm, length, at the cylindrical extrudates of 2.0-5.0mm, then makes the extrudate of gained carry out drying, roasting.If described carrier mixture is wet mixture form, this mixture multiviscosisty can be made, through super-dry aftershaping.More preferably described carrier mixture is slurry form, forms the microballoon that granularity is 20-200 micron, reach shaping object by spraying dry.For the ease of spraying dry, before dry, the solid content of slurries can be 10-50 % by weight, is preferably 20-50 % by weight.

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

In the present invention, the roasting condition of described carrier mixture also can be conventionally known to one of skill in the art, and in general, the temperature of described roasting is 400-700 DEG C, is preferably 450-650 DEG C; The time of described roasting is at least 0.5 hour, is preferably 0.5-100 hour, is 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, and with the gross weight of desulphurization catalyst for benchmark, the content of described active metal is 5-30 % by weight; Be preferably 10-20 % by weight.Wherein, described can be the material of the oxide being converted into active metal under the roasting condition of step (3) containing active metal.The described compound containing active metal can be selected from least one in the acetate of active metal, carbonate, nitrate, sulfate, rhodanate and oxide.Described active metal can be at least one in cobalt, nickel, iron and manganese; Preferably described active metal can be nickel.

In the present invention, on described carrier, the compound introduced containing active metal can pass through accomplished in many ways.Such as, can adopt and well known to a person skilled in the art that dipping method or intermediate processing realize.Described dipping method is with containing carrier described in the solution of compound of active metal or suspension impregnation; Described intermediate processing is mixed with described carrier the solution of the compound containing active metal or suspension, then adds ammoniacal liquor and be deposited on carrier by active metal.Preferred dipping method.

Drying and roasting described in step of the present invention (3) can be removed by the volatile materials on the carrier of the compound introduced containing active metal and active metal changed into the oxide of active metal, obtain desulphurization catalyst precursor.The condition of described drying can comprise, and dry temperature is about 50-300 DEG C, is preferably 100-250 DEG C, and the dry time is about 0.5-8 hour, is preferably about 1-5 hour.Carry out under the condition of described roasting can be included in oxygen or oxygen-containing gas existent condition, the temperature of described roasting can be about 300-800 DEG C, and be preferably 400-750 DEG C, the time of roasting can be about 0.5-4 hour, preferred 1-3 hour.

In step of the present invention (4), the reduction of desulphurization catalyst precursor can be carried out immediately after obtained desulphurization catalyst precursor, also can before use (namely for desulfurization absorption before) carry out.Because active metal is easily oxidized, and the active metal in desulphurization catalyst precursor exists in the form of an oxide, and therefore for ease of transport, the reduction of desulphurization catalyst precursor is carried out by preferred steps (4) before carrying out desulfurization absorption.Described being reduced to makes the metal in the oxide of active metal substantially exist with reduction-state, obtains desulphurization catalyst of the present invention.Under preferable case, the condition that desulphurization catalyst precursor reduces in a hydrogen atmosphere comprised: hydrogen content is 10-60 volume %, the temperature of reduction is 300-600 DEG C, and the time of reduction is 0.5-6 hour; The temperature of preferred reduction is 400-500 DEG C, and the time of reduction is 1-3 hour.

Present invention also offers the desulphurization catalyst obtained by preparation method provided by the invention.This desulphurization catalyst has composition, the content and structure of feature of aforementioned desulphurization catalyst, does not repeat them here.

Present invention also offers a kind of method of desulfurization of hydrocarbon oil, the method comprises: hydrocarbon oil containing surphur and hydrodesulfurization catalyst are reacted, and wherein, described desulphurization catalyst is desulphurization catalyst provided by the invention.

According to the present invention, in the method for described desulfurization of hydrocarbon oil, described hydrocarbon oil containing surphur and described desulphurization catalyst can react in a hydrogen atmosphere, and the condition of reaction comprises: the temperature of reaction can be 350-500 DEG C, is preferably 360-430 DEG C; The pressure of reaction can be 0.5-4MPa; Be preferably 1-2MPa.

According to the present invention, the method for described desulfurization of hydrocarbon oil can also comprise: regenerated by the desulphurization catalyst through reaction after reaction.The condition of regeneration comprises: regenerate under oxygen atmosphere (oxygen content can be 10-80 volume %); The temperature of regeneration is 450-600 DEG C, is 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 comprise: the desulphurization catalyst after regeneration reduces before reuse.The condition of reduction comprises: reduce under hydrogen atmosphere (hydrogen content can be 30-60 volume %); The temperature of reduction can be 350-500 DEG C, preferred 400-450 DEG C; The pressure of reduction can be 0.2-2MPa, is preferably 0.2-1.5MPa.

In the present invention, described hydrocarbon ils comprises cracking gasoline and diesel fuel, and wherein " cracking gasoline " means hydrocarbon or its any cut that boiling range is 40 to 210 DEG C, is the product from making larger crack hydrocarbon molecules become more micromolecular heat or catalytic process.The thermal cracking process be suitable for includes, but are not limited to coking, thermal cracking and visbreaking etc. and combination thereof.The example of the catalytic cracking process be suitable for includes but not limited to fluid catalystic cracking and RFCC etc. and combination thereof.Therefore, the catalytically cracked gasoline be suitable for includes but not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and heavy oil cracked gasoline and combination thereof.In some cases, be in the methods of the invention used as hydrocarbon-containifluids fluids time can by described cracking gasoline fractionation and/or hydrotreatment before desulfurization.Described " diesel fuel " means 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 includes but not limited to light cycle oil, kerosene, straight-run diesel oil, catalytic cracking diesel oil and hydroprocessed diesel etc. and combination thereof.

In the present invention, term used " sulphur " represents any type of element sulphur if hydrocarbon-containifluids fluids is as the organosulfur compound existed normal in cracking gasoline or diesel fuel.The sulphur existed in hydrocarbon-containifluids fluids of the present invention includes but not limited to carbonyl sulfide (COS), carbon disulfide (CS ₂), mercaptan or other thiophenes etc. and combination thereof, especially comprise thiophene, benzothiophene, alkylthrophene, alkyl benzothiophenes and methyldibenzothiophene, and the thiophenes that in diesel fuel, the normal molecular weight existed is larger.

In the present invention, the pressure related to is gauge pressure.

Below 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) adopts X-ray diffractometer (Siemens company D5005 type) to 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 illustration of the preparation method of desulphurization catalyst of the present invention.

(1) precipitated product is prepared.By 10.9 kilograms of acetate dihydrate zinc powders (Beijing Chemical Plant produces, and analyzes pure), 0.86 kilogram of acetate trihydrate lead (traditional Chinese medicines chemical reagents corporation analyzes pure) and 18 kilograms of deionized water mixing, stir and dissolve completely after 30 minutes.Add the precipitated product that 1.8 kilograms of ammoniacal liquor obtain, first dry 2 hours at 150 DEG C after filtering, then 500 DEG C of roastings 1 hour, be precipitated product C 1.

Precipitated product C1 is carried out fluorescence analysis and XRD determining.In XRD spectra, (see figure 1) does not have the diffraction maximum of PbO, and moving to right appears in the standard diffraction peak of ZnO, wherein A ₁₀₀-B ₁₀₀=0.2 °, A ₀₀₂-B ₀₀₂=0.21 °, A ₁₀₁-B ₁₀₁=0.2 °, illustrate that in precipitated product C1, PbO and ZnO all forms the plumbous solid solution of zinc, its chemical composition is Pb _0.044zn _0.956o.

(2) carrier is prepared.Get 290 grams of phosphoric acid (traditional Chinese medicines chemical reagents corporations, analyze pure, phosphorus acid content 95%), boehmite 1.33 kilograms (catalyst Nanjing branch company, containing butt 1.00 kilograms), 2.16 kilograms of kaolin (catalyst asphalt in Shenli Refineries, containing butt 1.8 kilograms), 1.0 kilograms of beta-molecular sieve (catalyst Nanjing branch companies, containing butt 0.7 kilogram) and after 9.0 kilograms of neutral waters (pH value is 6-8) under agitation mix, add 200 grams of red fuming nitric acid (RFNA)s (chemical pure, Beijing Chemical Plant produces) stirring acidifying and after 1 hour, be warming up to 60 DEG C of acidifyings 1 hour.When temperature is reduced to below 40 DEG C, then add precipitated product C1, stir after mixing and obtain carrier mixture in 1 hour.

Described carrier mixture adopts Niro Bowen Nozzle Tower ^tMthe spray dryer of model carries out spraying dry, and spraying dry pressure is 8.5 to 9.5MPa, and inlet temperature less than 500 DEG C, outlet temperature is about 150 DEG C.The microballoon that obtained by spraying dry first at 150 DEG C dry 1 hour, then at 480 DEG C, roasting obtains catalyst carrier in 1 hour.

(3) desulphurization catalyst precursor is prepared.Catalyst carrier 7.0 kilograms of Nickelous nitrate hexahydrates that the steps of 6.4 kilograms (2) are obtained, 1.10 kilograms of deionized water solutions spray impregnation at twice, the mixture obtained through 150 DEG C of dryings after 4 hours then 480 DEG C of roastings 1 hour, obtain desulphurization catalyst precursor.

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

The composition of desulphurization catalyst A1 is calculated as by inventory: zinc oxide 40.0 % by weight, lead oxide 5.0 % by weight, aluminium oxide 10.0 % by weight, kaolin 18.0 % by weight, beta-molecular sieve 7 % by weight, nickel 18.0 % by weight, P ₂o ₅2.0 % by weight.

Desulphurization catalyst A1 is carried out fluorescence analysis and XRD determining result as shown in Figure 2.Corresponding with the XRD spectra of precipitated product C1, in the XRD spectra of desulphurization catalyst A1, the diffraction maximum of ZnO is respectively at 31.75 °, 34.42 ° and 36.24 °, this peak position is consistent with the ZnO peak position occurred in the XRD spectra of precipitated product C1, illustrates and adopts the plumbous solid solution of zinc to be the structure that there is the plumbous solid solution of zinc in the desulphurization catalyst prepared of raw material.

Embodiment 2

The present embodiment is for illustration of the preparation method of desulphurization catalyst of the present invention.

(1) precipitated product is prepared.By 14.0 kilograms of zinc nitrate hexahydrates, (Beijing Chemical Plant produces, analyze pure), 1.80 kilograms of plumbi nitras powder (traditional Chinese medicines chemical reagents corporations, analyze pure) and 18 kilograms of deionized water mixing, stir to add 2.0 kg urea after 30 minutes and be heated to 80 DEG C of process and obtain white precipitate after 2 hours, first dry 2 hours at 150 DEG C after filtering, then 500 DEG C of roastings 1 hour, product C 2 is precipitated.

Precipitated product C2 is carried out fluorescence analysis and XRD determining.In XRD spectra, (see figure 1) does not have the diffraction maximum of PbO, and moving to right appears in the standard diffraction peak of ZnO, wherein A ₁₀₀-B ₁₀₀=0.25 °, A ₀₀₂-B ₀₀₂=0.24 °, A ₁₀₁-B ₁₀₁=0.24 °, illustrate that in precipitated product C2, PbO and ZnO all forms the plumbous solid solution of zinc, its chemical composition is Pb _0.1zn _0.9o.

(2) carrier is prepared.Get 490 grams of ammonium dihydrogen phosphate (ADP) (traditional Chinese medicines chemical reagents corporations, analyze pure 99%), boehmite 2.27 kilograms (catalyst Nanjing branch company, containing butt 1.70 kilograms), 1.33 kilograms of expanded perlite (catalyst Nanjing branch companies, containing butt 1.6 kilograms), 0.43 kilogram of beta-molecular sieve (catalyst Nanjing branch company, containing butt 0.3 kilogram) and after 8.0 kilograms of neutral waters (pH value is 6-8) under agitation mix, add 200 grams of red fuming nitric acid (RFNA)s (chemical pure, Beijing Chemical Plant produces) stirring acidifying and after 1 hour, be warming up to 60 DEG C of acidifyings 1 hour.When temperature is reduced to below 40 DEG C, then add precipitated product C1, stir after mixing and obtain carrier mixture in 1 hour.

The spray drying forming of carrier mixture is carried out and roasting obtains carrier with reference to the method for embodiment 1.

(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 % by weight, lead oxide 12.0 % by weight, aluminium oxide 17.0 % by weight, expanded perlite 13.0 % by weight, beta-molecular sieve 3 % by weight, nickel 14.0 % by weight, P ₂o ₅3.0 % by weight.

Embodiment 3

The present embodiment is for illustration of the preparation method of desulphurization catalyst of the present invention.

(1) precipitated product is prepared.By 13.6 kilograms of acetate dihydrate zinc powders (Beijing Chemical Plant produces, and analyzes pure), 1.05 kilograms of plumbi nitras (traditional Chinese medicines chemical reagents corporation analyzes pure) and 20 kilograms of deionized water mixing, stir and dissolve completely after 30 minutes.80 DEG C of process white precipitate of obtaining after 2 hours is heated to after adding 2.0 kg urea.First dry 2 hours at 150 DEG C after filtering, then 500 DEG C of roastings 1 hour, be precipitated product C 3.

Precipitated product C3 is carried out fluorescence analysis and XRD determining.In XRD spectra, (see figure 1) does not have the diffraction maximum of PbO, and moving to right appears in the standard diffraction peak of ZnO, wherein A _100-b ₁₀₀=0.23 °, A ₀₀₂-B ₀₀₂=0.22 °, A ₁₀₁-B ₁₀₁=0.22 °, illustrate that in precipitated product C3, PbO and ZnO all forms the plumbous solid solution of zinc, its chemical composition is Pb _0.07zn _0.93o.

(2) carrier is prepared.Get 1.03 kilograms of diatomite (catalyst Nanjing branch company, containing butt 1.0 kilograms,) and 670 grams of triethyl phosphine (traditional Chinese medicines chemical reagents corporations, analyze pure) mix in 3.0 kg water solution and solution evaporate to dryness, then take out mixture roasting at 600 DEG C and within 1 hour, obtain the diatomite after processing.

Get hydrated alumina 1.5 kilograms (catalyst Nanjing branch company, containing butt 1.2 kilograms), 0.6 kilogram of USY(catalyst Nanjing branch company, containing butt 0.5 kilogram) and 9.0 kilograms of neutral waters (pH value is 6-8) under agitation mix, add 170 grams of red fuming nitric acid (RFNA)s (chemical pure, Beijing Chemical Plant produces) stirring acidifying and after 1 hour, be warming up to 60 DEG C of acidifyings 1 hour.When temperature is reduced to below 40 DEG C, then the diatomite added after above-mentioned process and precipitated product C3, stir after mixing and obtain carrier mixture in 1 hour.

The spray drying forming of carrier mixture is carried out and roasting obtains carrier with reference to the method for embodiment 1.

(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 A3 is calculated as by inventory: zinc oxide 50.0 % by weight, lead oxide 7.0 % by weight, aluminium oxide 12.0 % by weight, diatomite 10.0 % by weight, USY molecular sieve 5.0 % by weight, nickel 12.0 % by weight, P ₂o ₅4.0 % by weight.

Comparative example 1

This comparative example prepares desulphurization catalyst for illustration of prior art preparation method.

4.55 kilograms of zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) and 290 grams of phosphoric acid (traditional Chinese medicines chemical reagents corporation, analyzes pure, phosphorus acid content 95%) are mixed in 8.5 kg water solution, stirs the mixed serum obtaining said components after 30 minutes.

Get boehmite 2.0 kilograms (catalyst Nanjing branch company, containing butt 1.50 kilograms), kaolin (the catalyst asphalt in Shenli Refinery of 2.4 kilograms, containing butt 2.0 kilograms) and 9.0 kilograms of neutral waters (pH value is 6-8) under agitation mix, add 200 grams of red fuming nitric acid (RFNA)s (chemical pure, Beijing Chemical Plant produces) stirring acidifying and after 1 hour, be warming up to 60 DEG C of acidifyings 1 hour.When temperature is reduced to below 40 DEG C, then add the mixed serum of zinc oxide and sodium carbonate, stir after mixing and obtain carrier mixture in 1 hour.

Method with reference to embodiment 1 carries out the spraying dry of carrier mixture and dipping introduces active component nickel, obtains desulphurization catalyst B1.

The composition of desulphurization catalyst B1 is calculated as by inventory: zinc oxide 45.0 % by weight, aluminium oxide 15.0 % by weight, kaolin 20.0 % by weight, nickel 18.0 % by weight, P ₂o ₅2.0 % by weight.

Comparative example 2

5.05 kilograms of zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) and 490 grams of ammonium dihydrogen phosphate (ADP)s (traditional Chinese medicines chemical reagents corporation analyzes pure 99%) are mixed in 9.5 kg water solution, stirs the mixed serum obtaining said components after 30 minutes.

Get boehmite 2.27 kilograms (catalyst Nanjing branch company, containing butt 1.60 kilograms), expanded perlite (the catalyst Nanjing branch company of 1.63 kilograms, containing butt 1.60 kilograms) and 8.0 kilograms of neutral waters (pH value is 6-8) under agitation mix, add 200 grams of red fuming nitric acid (RFNA)s (chemical pure, Beijing Chemical Plant produces) stirring acidifying and after 1 hour, be warming up to 60 DEG C of acidifyings 1 hour.When temperature is reduced to below 40 DEG C, then add the mixed serum of zinc oxide and potassium hydroxide, stir after mixing and obtain carrier mixture in 1 hour.Method with reference to embodiment 1 carries out the spraying dry of carrier mixture and dipping introduces active component nickel, obtains desulphurization catalyst B2.

The composition of desulphurization catalyst B2 is calculated as by inventory: zinc oxide 50.0 % by weight, aluminium oxide 17.0 % by weight, expanded perlite 16.0 % by weight, nickel 14.0 % by weight, P ₂o ₅3.0 % by weight.

Comparative example 3

Get 1.13 kilograms of diatomite (catalyst Nanjing branch company, containing butt 1.10 kilograms) and 670 grams of triethyl phosphine (traditional Chinese medicines chemical reagents corporations, analyze pure) mix in 3.0 kg water solution and solution evaporate to dryness, then take out mixture roasting at 600 DEG C and within 1 hour, obtain the diatomite after processing.

Hydrated alumina 2.13 kilograms (catalyst Nanjing branch company, containing butt 1.6 kilograms) and after 9.0 kilograms of neutral waters (pH value is 6-8) under agitation mix, add 170 grams of red fuming nitric acid (RFNA)s (chemical pure, Beijing Chemical Plant produces) stir and be warming up to more than 60 DEG C acidifyings 1 hour.When temperature is reduced to below 40oC DEG C, add the diatomite after 5.47 kilograms of zinc oxide (catalyst Nanjing branch company) powder and above-mentioned process, stir after mixing after 1 hour and obtain carrier mixture.

Method with reference to embodiment 1 carries out the spraying dry of carrier mixture and dipping introduces active component nickel, obtains desulphurization catalyst B3.

The composition of desulphurization catalyst B3 is calculated as by inventory: zinc oxide 57.0 % by weight, aluminium oxide 16.0 % by weight, diatomite 11.0 % by weight, nickel 12.0 % by weight, P ₂o ₅4.0 % by 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 corporations, analyze pure), 490 grams of ammonium dihydrogen phosphate (ADP) (traditional Chinese medicines chemical reagents corporations, analyze pure 99%) and 7.8 kilograms of deionized water mixing, stir the mixed serum obtaining zinc oxide, lead oxide and phosphorus after 30 minutes.

Get boehmite 2.27 kilograms (catalyst Nanjing branch company, containing butt 1.60 kilograms), expanded perlite (the catalyst Nanjing branch company of 1.63 kilograms, containing butt 1.60 kilograms) and 8.0 kilograms of neutral waters (pH value is 6-8) under agitation mix, add 200 grams of red fuming nitric acid (RFNA)s (chemical pure, Beijing Chemical Plant produces) stirring acidifying and after 1 hour, be warming up to 60 DEG C of acidifyings 1 hour.When temperature is reduced to below 40 DEG C, then add above-mentioned mixed serum and stir 1 hour.Stir after adding zinc oxide and the mixing of lead oxide slurries again and obtain carrier pulp in 1 hour.

Method with reference to embodiment 1 carries out the spraying dry of carrier mixture and dipping introduces active component nickel, obtains desulphurization catalyst B4.

The composition of desulphurization catalyst B4 is calculated as by inventory: zinc oxide 38.0 % by weight, lead oxide 12.0 % by weight, aluminium oxide 17.0 % by weight, expanded perlite 16.0 % by weight, nickel 14.0 % by weight, P ₂o ₅3.0 % by weight.

Embodiment 4

(1) abrasion strength resistance evaluation.Adopt straight tube wearing and tearing method to evaluate to desulphurization catalyst A1-A3 and B1-B4, evaluation method is with reference to the method for RIPP29-90 in " Petrochemical Engineering Analysis method (RIPP) experimental technique ", and numerical value is less, shows that abrasion strength resistance is higher.The results are shown in Table 1.

(2) desulfurization performance evaluation.Adopt the micro-anti-experimental provision of fixed bed to evaluate to desulphurization catalyst A1-A3 and B1-B4, adsorption reaction raw material adopts sulphur concentration to be the catalytically cracked gasoline of 960ppm.The desulfurization adsorbing composition A1 of 16 grams being seated in internal diameter is in 30mm, the long fixed bed reactors for 1m, reaction pressure is 1.38MPa, and hydrogen flowing quantity is 6.3L/h, and gasoline flow is 80mL/h, reaction temperature is 380 DEG C, and the charging of adsorption reaction raw material is weight space velocity 4h ^-1, carry out the desulphurization reaction of hydrocarbon oil containing surphur.Weigh desulphurizing activated with sulfur content in product gasoline.In product gasoline, sulfur content is by off-line chromatogram analysis method, adopts the GC6890-SCD instrument of An Jielun company to measure.In order to accurate characterization goes out the activity of desulphurization catalyst A1 in industrial actual motion, reacted rear desulphurization catalyst A1 and carried out regeneration process, regeneration process is what to carry out under the air atmosphere of 480 DEG C.After desulphurization catalyst A1 carries out reaction regeneration 6 circulation, its activity settles out substantially, represents the activity of desulphurization catalyst A1, the results are shown in Table 1 with the desulphurization catalyst A1 sulfur content stablized in rear product gasoline.Carry out the desulfurization performance evaluation that desulfurization adsorbing composition adopts A2-A3 and B1-B4 equally, the results are shown in Table 1.

Product gasoline is weighed simultaneously and calculate its yield.The results are shown in Table 1.

Adopt GB/T503-1995 and GB/T5487-1995 to measure motor octane number (MON) and the research octane number (RON) (RON) that reaction raw materials catalytically cracked gasoline and desulphurization catalyst stablize rear product gasoline respectively, the results are shown in Table 1.

Table 1

Note:

1, the sulfur content of feed gasoline is 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.

As can be seen from the result data of embodiment 1-4 and table 1, containing the plumbous solid solution of zinc in desulphurization catalyst A1-A3 provided by the invention, desulphurization catalyst has better desulphurizing activated and activity stability.Desulphurization catalyst has better abrasion strength resistance, thus makes desulphurization catalyst have longer service life.

In addition, this desulphurization catalyst can in lower temperature, carries out oxidation regeneration at absorption sulphur and 480 DEG C at 380 DEG C.

Claims (27)

1. a desulphurization catalyst, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contain the silica source of 5-30 % by weight, the aluminium oxide of 5-30 % by weight, the zinc oxide of 30-70 % by weight, 2-15 % by weight lead oxide, with P ₂o ₅count the phosphorous oxides of 0.5-10 % by weight, the molecular sieve with BEA structure of 1-20 % by weight and/or there is the molecular sieve of FAU structure and the active metal of 5-30 % by weight; And at least part of described lead oxide is to form general formula Pb with described zinc oxide _xzn _1-xthe form of the plumbous solid solution of the zinc 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, iron and manganese.

2. desulphurization catalyst according to claim 1, wherein, described desulphurization catalyst meets following relational expression: A ₁₀₀-B ₁₀₀=0.2 ° to 0.3 °, A ₁₀₀and B ₁₀₀in the XRD spectra of described desulphurization catalyst obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (100) face of ZnO.

3. desulphurization catalyst according to claim 1, wherein, described desulphurization catalyst meets following relational expression: A ₀₀₂-B ₀₀₂=0.2 ° to 0.3 °; A ₀₀₂and B ₀₀₂in the XRD spectra of described desulphurization catalyst obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (002) face of ZnO.

4. desulphurization catalyst according to claim 1, wherein, described desulphurization catalyst meets following relational expression: A ₁₀₁-B ₁₀₁=0.2 ^°to 0.3 ^°; A ₁₀₁and B ₁₀₁in the XRD spectra of described desulphurization catalyst obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (101) face of ZnO.

5. according to the desulphurization catalyst in claim 1-4 described in any one, wherein, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contain the silica source of 10-20 % by weight, the aluminium oxide of 10-20 % by weight, the zinc oxide of 35-54 % by weight, 5-12 % by weight lead oxide, with P ₂o ₅count the phosphorous oxides of 1-5 % by weight, the molecular sieve with BEA structure of 2-10 % by weight and/or there is the molecular sieve of FAU structure and the active metal of 10-20 % by weight.

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

7. according to the desulphurization catalyst in claim 1-4 described in any one, wherein, described phosphorous oxides is P ₂o ₅, P ₂o ₃with at least one in poly phosphoric-oxygenic compound.

8. according to the desulphurization catalyst in claim 1-4 described in any one, wherein, described silica source is the natural crystal that silica or silica content are greater than 45 % by weight.

9. desulphurization catalyst according to claim 1, wherein, the molecular sieve of the described BEA of having structure is beta-molecular sieve, described in there is FAU structure molecular sieve be at least one in X-type molecular sieve, Y zeolite, USY, REUSY, REHY, REY, PUSY, PREHY and PREY.

10. a preparation method for desulphurization catalyst, the method comprises:

(1) mixed solution that lead-containing compounds, zinc compound and water are mixed to get is carried out precipitation reaction, mixture precipitation reaction obtained carries out filtering, dry and roasting, be 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 to contact with acid solution and form slurries, and the precipitated product that step (1) obtains is mixed with described slurries, form carrier mixture; Again by shaping for described carrier mixture, dry and roasting, form carrier;

(3) carrier obtained to step (2) is introduced the compound containing active metal and dry, roasting, obtain desulphurization catalyst precursor; Described active metal is at least one in cobalt, nickel, iron and manganese;

(4) the desulphurization catalyst precursor that step (3) obtains is reduced under hydrogen atmosphere, obtain desulphurization catalyst.

11. preparation methods according to claim 10, wherein, described in step (1), lead-containing compounds and zinc compound addition make in the desulphurization catalyst obtained, with the gross weight of described desulphurization catalyst for benchmark, the content of lead oxide is 2-15 % by weight, and the content of zinc oxide is 30-70 % by weight.

12. preparation methods according to claim 10, wherein, described precipitated product meets following relational expression: A ₁₀₀-B ₁₀₀=0.2 ° to 0.3 °, A ₁₀₀and B ₁₀₀in the XRD spectra of described precipitated product obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (100) face of ZnO.

13. preparation methods according to claim 10, wherein, described precipitated product meets following relational expression: A ₀₀₂-B ₀₀₂=0.2 ° to 0.3 °; A ₀₀₂and B ₀₀₂in the XRD spectra of described precipitated product obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (002) face of ZnO.

14. preparation methods according to claim 10, wherein, described precipitated product meets following relational expression: A ₁₀₁-B ₁₀₁=0.2 ° to 0.3 °; A ₁₀₁and B ₁₀₁in the XRD spectra of described precipitated product obtained under being illustrated respectively in identical XRD determining condition and the XRD spectra of ZnO, characterize 2 θ values of the diffraction maximum in (101) face of ZnO.

15. according to the preparation method in claim 10-14 described in any one, and wherein, described precipitated product is at least partly containing useful general formula Pb _xzn _1-xthe plumbous solid solution of the zinc that O represents, wherein x meets 0 < x≤0.12, and x represents atomic molar ratio.

16. preparation methods according to claim 10 or 11, wherein, described lead-containing compounds is plumbi nitras and/or lead acetate.

17. preparation methods according to claim 10 or 11, wherein, described zinc compound is at least one in zinc acetate, zinc chloride and zinc nitrate.

18. preparation methods according to claim 10 or 11, wherein, described phosphorus-containing compound is inorganic phosphor-contained thing and/or phosphorus-containing matter, described inorganic phosphor-contained thing is at least one in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate (ADP), and described phosphorus-containing matter is at least one in trimethyl-phosphine, triethyl phosphine, tripropyl phosphine and tributylphosphine.

19. preparation methods according to claim 10, wherein, the precipitating reagent that precipitation reaction described in step (1) uses is urea and/or ammoniacal liquor.

20. preparation methods according to claim 10, wherein, described in step (1), the pH of mixture is 9-13.

21. preparation methods according to claim 10, wherein, condition dry described in step (1) comprises: dry temperature is 100-200 DEG C, and the dry time is 0.5-3h; The condition of described roasting comprises: the temperature of roasting is 400-700 DEG C, and the time of roasting is 0.5-3h.

22. preparation methods according to claim 10, wherein, described silica source, described alumina source, described phosphorus-containing compound, described in there is BEA structure molecular sieve and/or the addition of the molecular sieve and the described compound containing active metal with FAU structure make in the desulphurization catalyst obtained, with the gross weight of described desulphurization catalyst for benchmark, the content of silica source is 5-30 % by weight, the content of aluminium oxide is 5-30 % by weight, the content of phosphorous oxides is with P ₂o ₅the content of molecular sieve counted 0.5-10 % by weight, have the molecular sieve of BEA structure and/or have a FAU structure is the content of 1-20 % by weight and active metal is 5-30 % by weight.

23. preparation methods according to claim 10, wherein, described alumina source is the material that can change aluminium oxide under the condition of the described roasting of step (2) into.

24. preparation methods according to claim 23, wherein, described alumina source is hydrated alumina and/or Alumina gel; Described hydrated alumina is at least one in boehmite, false boehmite, hibbsite and amorphous hydroted alumina.

25. preparation methods according to claim 10, wherein, containing at least one that the compound of active metal is in the acetate of active metal, carbonate, nitrate, sulfate, rhodanate and oxide described in step (3).

26. desulphurization catalysts obtained by the preparation method in claim 10-25 described in any one.

The method of 27. 1 kinds of desulfurization of hydrocarbon oil, the method comprises: hydrocarbon oil containing surphur and hydrodesulfurization catalyst are reacted, it is characterized in that, described desulphurization catalyst is the desulphurization catalyst in claim 1-9 and 26 described in any one.