CN104415778A - Desulfurization catalyst, preparation method thereof and sulfur-containing fuel oil desulfurization method - Google Patents
Desulfurization catalyst, preparation method thereof and sulfur-containing fuel oil desulfurization method Download PDFInfo
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- CN104415778A CN104415778A CN201310389122.XA CN201310389122A CN104415778A CN 104415778 A CN104415778 A CN 104415778A CN 201310389122 A CN201310389122 A CN 201310389122A CN 104415778 A CN104415778 A CN 104415778A
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Abstract
The invention discloses a desulfurization catalyst. The catalyst comprises a core and a coating layer, wherein the core contains aluminium oxide, silicon oxide, molecular sieves with an MFI structure and reactive metals; the coating layer contains aluminium oxide, silicon oxide and zinc oxide. The invention also discloses a preparation method of the desulfurization catalyst, the desulfurization catalyst obtained by the method and a sulfur-containing fuel oil desulfurization method. The desulfurization catalyst provided by the invention has a lamellar structure, can have better desulfurization performance and has better abrasive resistance.
Description
Technical field
The present invention relates to the sulfur method of a kind of desulphurization catalyst and preparation method thereof and sulfurous fuels oil, particularly, relate to a kind of desulphurization catalyst with layer structure, a kind of preparation method with the desulphurization catalyst of layer structure, and the desulphurization catalyst with layer structure to be prepared by the method, and a kind of sulfur method of sulfurous fuels oil.
Background technology
The oxysulfide produced after combustion of sulfur in vehicle fuel, the activity of the noble metal catalyst in vehicle exhaust converter can be suppressed also can to make it generation irreversibly poisoning, thus unburned non-methane hydrocarbon, nitrogen oxide and the carbon monoxide emission contained in vehicle exhaust is increased.These emission gases are then easily formed photochemical fog by hydrophilic dye, cause acid rain, and the oxysulfide itself simultaneously in air is also the one of the main reasons forming acid rain.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.
Sulphur great majority in China's motor petrol come from hot-working petroleum, are mainly catalytically cracked gasoline blending component.Therefore the minimizing of Sulfur Content in Catalytic Cracking Gasoline contributes to the sulfur content reducing motor petrol.The existing gasoline products standard of China is GB 17930-2011 " motor petrol ", and this standard restricts further to sulfur content in gasoline, and require on December 31st, 2013, sulfur content in gasoline drops to 50ppm.In this case, catalytically cracked gasoline has to pass through the requirement that deep desulfuration just can meet environmental protection.
CN1151333A discloses a kind of method preparing adsorbent composition, comprise (a) by following component contacts: at least one zinc component (comprising the compound that zinc oxide maybe can be converted into zinc oxide), at least one silica component (comprising the compound that silica maybe can be converted into silica), at least one colloidal oxide component and at least one pore generating agent component, to form a kind of wet composition (there is the moisture being about 22-33 % by weight with described wet composition weight meter), b () extrudes described wet composition to form a kind of crushed wet composition, wherein said crushed, wet composition has the moisture being about 22-33 % by weight with its weighing scale, (c) by described crushed, wet composition is made spherical spherical to be formed, crushed wet composition, the particle diameter of said composition is about 0.5-15 millimeter.The particle that this preparation method obtains is 100-300 micron, and this is not best for fluid mapper process.And the method improves pore volume by adding inflammable pore creating material, make particle easily broken pure, intensity is poor.
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.
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.
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.Zinc compound and co-catalyst are mixed together with production combination thing by the method, and both Monodisperseds are in whole particle.
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.The method first prepares the mixture containing zinc compound, then adds promoter.
The grain structure that the desulfuration adsorbent obtained by the existing method preparing desulfuration adsorbent has, being unfavorable for that this desulfuration adsorbent for more removing sulphur to the degree of depth from cracking gasoline and diesel fuel, being difficult to make cracked-gasoline products or diesel fuel meet national standard.
Therefore, in order to overcome the defect of existing desulfuration adsorbent, need to provide new can have better desulphurizing activated, promote the desulphurization catalyst that desulphurization reaction carries out.
Summary of the invention
The object of the invention is the defect existed to overcome existing desulfuration adsorbent, providing a kind of for the sulfur method of desulphurization catalyst with layer structure removing sulphur from cracking gasoline and diesel fuel and preparation method thereof with sulfurous fuels oil.
In order to realize foregoing invention object, the invention provides a kind of desulphurization catalyst, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contains the active metal of the aluminium oxide of 5-35 % by weight, the silica of 5-35 % by weight, the zinc oxide of 10-70 % by weight, the molecular sieve with MFI structure of 1-10 % by weight and 5-30 % by weight; This desulphurization catalyst comprises kernel and is attached to the clad at least part of surface of described kernel: 1) kernel contains aluminium oxide, silica, the molecular sieve with MFI structure and active metal; 2) clad contains aluminium oxide, silica and zinc oxide; And the weight ratio of the active metal in described clad and the active metal in desulphurization catalyst is less than 0.3, the weight ratio of the zinc oxide in described clad and the zinc oxide in desulphurization catalyst is for being greater than 1.5; Described active metal is selected from least one in group VIII metal.
The present invention also provides a kind of preparation method of desulphurization catalyst, the method comprises: binding agent, silica source, the molecular sieve with MFI structure, active metal precursor.In, water and the first acid solution are carried out the first mixing by (1), obtain mixed serum, mixed serum is shaping, dry and roasting, obtains inner core particles; (2) binding agent, silica source, zinc oxide source, water and the second acid solution are carried out the second mixing, form clad slurries; The inner core particles that step (1) obtains is added in described clad slurries, again carry out shaping, dry and roasting, obtain catalyst precarsor; (3) catalyst precarsor that step (2) obtains is reduced under hydrogen atmosphere, obtain desulphurization catalyst; Described first acid solution and described second acid solution are identical or different, are inorganic acid and/or the organic acid aqueous solution separately.
Present invention also offers the desulphurization catalyst prepared by method provided by the invention.
Present invention also offers a kind of sulfur method of sulfurous fuels oil, the method comprises: by sulfurous fuels oil and hydrodesulfurization catalyst, wherein, described desulphurization catalyst is desulphurization catalyst provided by the invention.
Desulphurization catalyst provided by the invention has layer structure, can have better desulfurization performance, and desulphurization catalyst has better abrasion strength resistance.The desulphurization catalyst A1 that such as embodiment 1 obtains consists of aluminium oxide 22.7 % by weight, silica 15.3 % by weight, zinc oxide 36.0 % by weight, ZSM-5 molecular sieve 8 % by weight, nickel 20.0 % by weight; And the weight ratio of the Ni in Ni and the A1 in clad is 0.31, the weight ratio of the zinc oxide in clad and the zinc oxide in A1 is 1.5; The Thickness Ratio of kernel and clad is 1:0.32; In the clad recorded by XPS, the mol ratio of Ni:Zn is 1:7.The FBAT index of desulphurization catalyst A1 is 4.6, and the product gasoline sulfur content obtained for 6 times that circulates is 14 μ g/g.And although desulphurization catalyst B1 that comparative example 1 obtains forms identical with A1, with prior art by active metal nickel all by the surface of dipping method load at desulphurization catalyst B1.Adopt XPS to measure, the mol ratio of B1 Ni:Zn is on the surface 1.7:1; Measured by fluorescence analysis and XPS, the weight ratio of the Ni in Ni and the B1 in B1 clad is 1.45, and the weight ratio of the zinc oxide in clad and the zinc oxide in B1 is 0.75.B1 is not formed as kernel in desulphurization catalyst A1 is rich in the layer structure that nickel and clad are rich in zinc oxide.The FBAT index of desulphurization catalyst B1 is 5.0, and the product gasoline sulfur content obtained for 6 times that circulates is 38 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 TPR spectrogram of desulphurization catalyst A1;
Fig. 2 is the layer structure schematic diagram of desulphurization catalyst.
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 desulfurizing agent for benchmark, this desulphurization catalyst contains the active metal of the aluminium oxide of 5-35 % by weight, the silica of 5-35 % by weight, the zinc oxide of 10-70 % by weight, the molecular sieve with MFI structure of 1-10 % by weight and 5-30 % by weight; This desulphurization catalyst comprises kernel and is attached to the clad at least part of surface of described kernel: 1) kernel contains aluminium oxide, silica source, the molecular sieve with MFI structure and active metal; 2) clad contains aluminium oxide, silica source and zinc oxide; And the weight ratio of the active metal in described clad and the active metal in desulphurization catalyst is less than 0.3, the weight ratio of the zinc oxide in described clad and the zinc oxide in desulphurization catalyst is for being greater than 1.5; Described active metal is selected from least one in group VIII metal; Preferably, with desulphurization catalyst gross weight for benchmark, described desulphurization catalyst contains the active metal of the aluminium oxide of 12-30 % by weight, the silica of 15-30 % by weight, the zinc oxide of 30-55 % by weight, the molecular sieve with MFI structure of 4-8 % by weight and 10-25 % by weight.
In the present invention, although the molecular sieve with MFI structure represents the composition of molecular sieve usually with the content of aluminium oxide and silica, but the content of silica, aluminium oxide does not comprise the amount of aluminium oxide and silica in the molecular sieve with MFI structure in the present invention, and refer to the amount of silica except in the molecular sieve with MFI structure and aluminium oxide.Above-mentioned composition calculates according to feeding intake.
According to the present invention, under preferable case, the Thickness Ratio of described kernel and described clad is 1:0.2-0.6.
According to the present invention, as shown in Figure 2, described desulphurization catalyst comprises kernel and clad, and active metal is mainly included in kernel, and zinc oxide is mainly included in clad, namely forms the layer structure that kernel is rich in active metal, clad is rich in zinc oxide.The desulphurization catalyst with this spline structure more can be conducive to carrying out active metal reduction-oxidation state sulphur and zinc oxide adsorption storage sulphur in desulphurization reaction process; And the content of each component that described desulphurization catalyst contains is in above-mentioned scope, can have better desulfurized effect.
In the present invention, active metal in clad and zinc oxide respectively with the weight ratio of the active metal in desulphurization catalyst and zinc oxide, in the clad that in the desulphurization catalyst that can be obtained by fluorescence analysis, active metal and zinc oxide component content and X-ray photoelectron spectroscopic analysis (XPS) determination and analysis obtain, active metal and zinc oxide component content are determined.
In the present invention, the kernel of shown desulphurization catalyst and the Thickness Ratio of clad, the data that can be measured by SEM and energy disperse spectroscopy (i.e. SEM-EDX) are calculated.Particularly, the cross section of desulphurization catalyst is scanned by SEM-EDX, measure active metal and Zn-ef ficiency along content everywhere on this diameter of section by EDX, obtain active metallic element and the Zn-ef ficiency content distribution along the radial direction in described desulphurization catalyst cross section, distribution obtains above-mentioned Thickness Ratio thus.Described Thickness Ratio is the ratio between the radius of the particle forming described kernel and the thickness of described clad.
According to the present invention, the clad of described desulphurization catalyst contains zinc oxide, and kernel contains active metal.Also a small amount of active metal can be had to move in clad when described desulphurization catalyst experiences the roasting in preparation process, but the active metal in described desulphurization catalyst is still mainly present in kernel; The zinc oxide component that described desulphurization catalyst contains is produced the clad being mainly present in described desulphurization catalyst.The amount of the zinc therefore existed in clad is higher than the amount of active metal.Under preferable case, described clad is with X-ray photoelectron spectroscopic analysis (XPS), and the mol ratio of described active metal and zinc is at below 1:3; Preferably, described clad is with X-ray photoelectron spectroscopic analysis, and the mol ratio of described active metal and zinc is at below 1:5.
According to the present invention, described active metal can for being reduced to the metal of hydrogen sulfide by oxidation state sulphur, more preferably, described active metal can be cobalt and/or nickel; Further preferably, described active metal can be nickel.
According to the present invention, under preferable case, described in there is MFI structure molecular sieve be there is two ten-ring intersect the molecular sieve in duct.Can be such as ZSM-5 molecular sieve analog, can also be this molecular sieve analog containing phosphorus and/or iron modification, as ZRP, ZSP Series Molecules sieve.
The present invention also provides a kind of preparation method with the desulphurization catalyst of layer structure, the method comprises: binding agent, silica source, the molecular sieve with MFI structure, active metal precursor.In, water and the first acid solution are carried out the first mixing by (1), obtain mixed serum, mixed serum is shaping, dry and roasting, obtains inner core particles; (2) binding agent, silica source, zinc oxide source, water and the second acid solution are carried out the second mixing, form clad slurries; The inner core particles that step (1) obtains is added in described clad slurries, again carry out shaping, dry and roasting, obtain catalyst precarsor; (3) catalyst precarsor that step (2) obtains is reduced under hydrogen atmosphere, obtain desulphurization catalyst; Described first acid solution and described second acid solution are identical or different, are inorganic acid and/or the organic acid aqueous solution separately.
According to the present invention, under preferable case, described binding agent, silica source, zinc oxide source, the addition of molecular sieve and active metal precursor.In with MFI structure make in the desulphurization catalyst obtained, with this desulphurization catalyst gross weight for benchmark, the content of aluminium oxide is 5-35 % by weight, the content of silica is 5-35 % by weight, the content of zinc oxide is 10-70 % by weight, have that the content of the molecular sieve of MFI structure is 1-10 % by weight, the content of active metal is 5-30 % by weight.Preferably, described binding agent, silica source, zinc oxide source, the addition of molecular sieve and active metal precursor.In with MFI structure make in the desulphurization catalyst obtained, with this desulphurization catalyst gross weight for benchmark, the content of aluminium oxide is 12-30 % by weight, the content of silica is 15-30 % by weight, the content of zinc oxide is 30-55 % by weight, have that the content of the molecular sieve of MFI structure is 4-8 % by weight, the content of active metal is 10-25 % by weight.
Preparing the raw material that described desulphurization catalyst uses in the present invention can be chemical pure material, also can use the industrial materials that generally can be commercially available.When using industrial materials, in the desulphurization catalyst of acquisition, can partial impurities be contained, but as long as the key component of desulphurization catalyst and content are still in above-mentioned limited range, just not affect the performance of desulphurization catalyst.The composition content of the desulphurization catalyst obtained listed in embodiments of the invention and comparative example is the content of the key component that desulphurization catalyst contains.These content add and are less than or equal to 100 % by weight, and the content differed with 100 % by weight is the content of impurity.Impurity due to above-mentioned content does not affect the performance of desulphurization catalyst, and therefore the present invention does not specifically list the composition of impurity.
According to the present invention, described active metal precursor.In is the material that can be converted into metal oxide under the roasting condition of step (1), under preferable case, described active metal can be selected from least one in the acetate of group VIII metal, carbonate, nitrate, sulfate, rhodanate and oxide.
According to the present invention, under preferable case, described zinc oxide source can be zinc oxide and/or the zinc oxide precursor that can be converted into zinc oxide under the condition of the described roasting of step (2); Described zinc oxide precursor can be at least one in zinc sulphide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate and zinc nitrate.
According to the present invention, under preferable case, the natural minerals that described silica source can be greater than 45 % by weight for pure silica or silica content.Preferably, described silica source can be selected from least one in diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
According to the present invention, can form the material of heat-resistant inorganic oxide after described binding agent refers to roasting, wherein heat-resistant inorganic oxide can be one or more in aluminium oxide, silica and amorphous silicon aluminium, preferential oxidation aluminium.Under preferable case, described binding agent can be at least one in hydrated alumina, Alumina gel, boehmite (boehmite), false boehmite (boehmite), hibbsite and amorphous hydroted alumina.Can with γ-Al after the roasting of these multi-form binding agents in step (1) or (2)
2o
3form exist.Particularly, the binding agent used in the present invention can for known in those skilled in the art.
According to the present invention, particularly, prepare desulphurization catalyst can carry out in accordance with the following methods:
In step (1), described first mixing can there is no particular limitation, can be described binding agent, described silica source and described active metal precursor.In add in described water and obtain slurries, and then add described first acid solution and obtain mixed serum.There is no particular limitation for the order that described binding agent, described silica source and described active metal precursor.In add in described water, preferably, after other component adds, adds described active metal again.Each component adds fashionable needs and fully stirs.The consumption of described first acid solution can be without particular limitation of, and preferably the consumption of described first acid solution makes the pH value of slurries be 2-5, is preferably 2-4.If described active metal precursor.In is originally as acidity, and the pH value of the slurries obtained after can ensureing mixing is the preferred 2-4 of 2-5() time, can separately add the first acid solution.Described first acid solution can be inorganic acid and/or the organic acid aqueous solution, preferably, can be hydrochloric acid and/or nitric acid.The described mixed serum obtained can carry out aging further, and can be the aging method that this area routine uses, preferably, described aging temperature can be about 60-90 DEG C, and the described aging time can be about 1-4 hour.
In step (1), under preferable case, with the described binding agent of 100 weight portions for benchmark, add the water of the described silica source of 40-250 weight portion, the molecular sieve with MFI structure of 10-80 weight portion, the active metal precursor.In of 50-400 weight portion and 500-1000 weight portion.
In step (1), described shaping mode can according to the formal character of described mixed serum.Described mixed serum can be the forms such as dough, paste mixture, wet mixture or slurries, and described shaping mode can be selected for described mixed serum is shaped to extrudate, sheet, pill, ball or micro-spherical particle.Such as, described mixed serum be dough or paste mixture form time, described mixed serum shaping (preferred extrusion molding) can be made to be 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.When described mixed serum is wet mixture form, this mixture multiviscosisty can be made, through super-dry aftershaping.When described mixed serum is slurry form, can form by spraying dry the microballoon that average grain diameter (diameter) is 20-100 micron, be preferably the microballoon of 40-60 micron, reach shaping object.For the ease of spraying dry, before dry, the solid content of slurries is 10-60 % by weight, is preferably 20-50 % by weight.
The drying of step (1) and the method for roasting and condition can be conventionally known to one of skill in the art, such as dry method can be dry, dry, forced air drying.Dry temperature can be room temperature to 400 DEG C, can be preferably 100-350 DEG C.The dry time can be about 0.5-8 hour, more preferably can be about 1-5 hour.After drying, carry out roasting having under oxygen or oxygen-containing gas existent condition, the temperature of roasting can be about 300-800 DEG C, more preferably 450-750 DEG C can be about, the time of roasting can be about 0.5-4 hour, preferably be about 1-3 hour, until volatile materials is removed and active metal is converted into metal oxide.
In step (2), described second mixing can there is no particular limitation, can be described binding agent, described silica source and described zinc oxide source add in described water and obtain mixed serum, and then add described second acid solution and obtain clad slurries.Described clad slurries can carry out aging further, and can be the aging method that this area routine uses, preferably, described aging temperature can be about 60-90 DEG C, and the described aging time can be about 1-4 hour.The consumption of described second acid solution can be without particular limitation of, preferably the consumption of described second acid solution make described clad slurries through described aging after pH value be 2-5.Described second acid solution can be inorganic acid and/or the organic acid aqueous solution, preferably, can be hydrochloric acid and/or nitric acid.
In step (2), under preferable case, with the described binding agent of 100 weight portions for benchmark, add the water of the described silica source of 40-250 weight portion, the zinc oxide source of 80-600 weight portion and 500-1000 weight portion.
In the present invention, described first acid solution and described second acid solution can be identical or different; Preferably identical.
Shaping in step (2) can be realize making described clad slurry package be rolled in the object of described inner core particles.Described clad slurries are carried out shaping method to select according to the inner core particles shape obtained in step (1).What such as, obtain in step (2) is microballoon, described clad slurries can be carried out spray drying forming, and the coating thickness forming microballoon is 5-25 micron, preferred 8-20 micron.For the ease of spraying dry, before dry, the solid content of slurries is 20-60 % by weight, is preferably 30-50 % by weight.When what step (1) obtained is bar, sheet or bead, can when stirring and heat, moisture in described clad slurries is evaporated, to complete described clad slurries object shaping in described inner core particles on the surface that the solid constituent in clad slurries can be attached to inner core particles.
Drying means in step (2) and condition can be conventionally known to one of skill in the art, such as dry method can be dry, dry, forced air drying.Dry temperature can be room temperature to 400 DEG C, can be preferably 100-350 DEG C.The dry time can be about 0.5-8 hour, more preferably can be about 1-5 hour.
Step (2) if in method of roasting and condition can be the oxide form of each component by each constitutional changes forming integument slurries in step (2), and nickel in kernel is less moves in integument.Roasting is carried out having under oxygen or oxygen-containing gas existent condition, and the temperature of roasting can be about 300-800 DEG C, more preferably can be about 450-750 DEG C, and the time of roasting can be about 0.5-4 hour, is preferably about 1-3 hour.
In the present invention, the binding agent added in step (1) and (2) and the total amount of silica source make in the desulphurization catalyst obtained, and with this desulphurization catalyst gross weight for benchmark alumina content is for 5-35 % by weight, silica content is 5-35 % by weight; Preferably, alumina content is 12-30 % by weight, and silica content is 15-30 % by weight.
In step (3), by catalyst precarsor reduction can carry out immediately after obtained desulphurization catalyst precursor, also can before use (namely for before desulfurization catalyst) carry out.Due to active metal solution oxide, and the active metal in desulphurization catalyst precursor exists in the form of an oxide, therefore for ease of transport and storage, catalyst precarsor reduction is carried out before carrying out desulfurization catalyst in preferred steps (3).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.Described hydrogen atmosphere can be the atmosphere of 10-60 volume % for hydrogen content, and the temperature of reduction is 300-600 DEG C, and the time of reduction can be 0.5-6 hour; Preferably, the temperature of reduction is 400-500 DEG C, and the time of reduction is 1-3 hour.
Can measure from employing H2-TPR method the H2-TPR spectrogram obtained to desulphurization catalyst in the present invention, if the active metal in Fig. 1 desulphurization catalyst A1 is nickel, judge that in desulphurization catalyst kernel, active metal changes metal into from oxide through hydrogen reducing.In FIG, abscissa carries out reducing experienced temperature for desulphurization catalyst, and ordinate is in H2-TPR method, the TCD signal corresponding to the reducing atmosphere through desulphurization catalyst surface that corresponding each temperature spot adopts TCD detector to detect.Amounts of hydrogen in the corresponding initial reduction atmosphere of TCD signal base line, TCD signal departs from baseline and illustrates that in the reducing atmosphere measured, amounts of hydrogen there occurs change than time initial.Go out peak from TCD signal can judge temperature range corresponding to peak, the hydrogen in reducing atmosphere is consumed the reduction reaction that take part in certain monoxide.After the reduction reaction of this oxide terminates, TCD signal returns baseline.First in desulphurization catalyst A1, silica, aluminium oxide are by the temperature of hydrogen reducing all more than 1000 DEG C, and zinc oxide is known is difficult to reduction by hydrogen, and therefore Fig. 1 display is the process that nickel oxide is reduced to nickel, and the temperature of nickel oxide reduction is at 200-300 DEG C.It can be said that the reduction in bright step (3) to make the active metal of desulphurization catalyst kernel exist with reduction-state.
Present invention also offers a kind of desulphurization catalyst with layer structure prepared by method provided by the invention.
According to the present invention, this desulphurization catalyst as previously mentioned, does not repeat them here.
Present invention also offers a kind of sulfur method of sulfurous fuels oil, the method comprises: by sulfurous fuels oil and hydrodesulfurization catalyst, wherein, described desulphurization catalyst is desulphurization catalyst provided by the invention.
According to the present invention, in the sulfur method of described sulfurous fuels oil, described contact can be carried out in a hydrogen atmosphere, and the condition of described contact comprises: the temperature of contact can be 350-500 DEG C, and the pressure of contact can be 0.5-4MPa; The temperature of preferred contact is 400-450 DEG C, and the pressure of contact is 1-3MPa.Sulfurous fuels oil is made fully to contact with desulphurization catalyst provided by the invention under these conditions.Sulphur in the process in sulfurous fuels oil is catalyzed on catalyst, thus obtains the product of low sulfur content.
According to the present invention, the sulfur method of described sulfurous fuels oil can also comprise: regenerated by the desulphurization catalyst through contact after contact.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 sulfur method of described sulfurous fuels 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, the desulphurization catalyst after regeneration-reduction can re-start the desulfurization of sulfurous fuels oil.
In the present invention, described contact is preferably carried out in fluid bed.
Term used herein " cracking gasoline " means hydrocarbon or its any cut that boiling range is 40-210 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.
It is the hydrocarbon mixture of 170-450 DEG C or the liquid of its any fractional composition that term used herein " diesel fuel " means boiling range.This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight-run diesel oil and hydroprocessed diesel etc. and combination thereof.
Term used herein " 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.
Desulphurization catalyst provided by the invention has good desulphurizing activated, and the abrasion strength resistance of this desulphurization catalyst is better, greatly can extend the service life of desulphurization catalyst.
The invention will be further described by the following examples.
In the following Examples and Comparative Examples, the composition of desulphurization catalyst calculates according to feeding intake.
Fluorescence analysis adopts Rigaku company 3271E type Xray fluorescence spectrometer to measure.
SEM-EDX measures and adopts FDAC S4800 ESEM.In advance catalyst microspheres is fixed in resin, obtains its section by cutting, adopt SEM to observe and the composition analyzing diverse location element in conjunction with EDX, record the thickness of kernel and clad.
XPS measures and adopts the test of Britain VG company MK II type photoelectron spectrograph, and incident light is AlK alpha ray, and incident light electron energy is 1486.6eV, by being 50eV.Be interior mark with C1s, BE=285.0eV after correcting.
TPR analyzes the 2950 High Pressure Absorption instrument adopting Micromeritics company of the U.S., under 1.5MPa pressure, adopts 30 volume %H
2+ 70 volume %Ar are reducing atmosphere, from 100 DEG C to 500 DEG C with the ramp of 10 DEG C/min, by the change of amounts of hydrogen in reducing atmosphere during the reduction of TCD record.
Embodiment 1
The present embodiment is for illustration of the preparation method of desulphurization catalyst of the present invention.
(1) kernel preparation.1.33 kilograms of kaolin (Kaolin of Suzhou factory, S1, containing butt 1.0 kilograms; In butt, silica content is 50 % by weight, alumina content is 45 % by weight), hydrated alumina 0.56 kilogram of (boehmite, Shandong Aluminum Plant produces, containing butt 0.45 kilogram), 9.9 kilogram of six water nickel nitrate (is analyzed pure, traditional Chinese medicines chemical reagents corporation) and after under agitation mixing with 5.0 kilograms of neutral waters, and aging 1 hour.Add after 1.0 kilograms of ZEM-5 molecular sieves (Shandong catalyst branch company, containing butt 0.8 kilogram) stir and obtain mixed serum, its pH value is 3.0.
Described mixed serum adopts Niro Bowen Nozzle Tower
tMthe spray dryer of model carries out spraying dry: the nozzle adopting 1.4mm, spraying dry pressure is 8.5-9.5 MPa, and inlet temperature less than 500 DEG C, outlet temperature is about 150 DEG C.The microballoon that obtained by spraying dry first at 180 DEG C dry 1 hour, then at 635 DEG C, roasting obtains kernel microballoon in 1 hour.The average grain diameter (radius) measuring the kernel microballoon obtained is 28 microns.
(2) clad preparation.(Beijing chemical reagent factory, containing butt 1.65 kilograms to get 1.70 kilograms of diatomite; In butt, silica content is 91 % by weight, alumina content is 6 % by weight), hydrated alumina 0.63 kilogram of (boehmite, Shandong Aluminum Plant produces, containing butt 0.5 kilogram) and 7.0 kilograms of deionized waters, be uniformly mixed, the nitric acid (chemical pure, Beijing Chemical Plant produces) adding 120 gram 30 % by weight stirs acidifying 1 hour.Add 3.6 kilograms of Zinc oxide powders, stir 0.5 hour, then add the kernel microballoon obtained in step (1), after stirring, obtain clad slurries.
Clad slurries adopt Niro Bowen Nozzle Tower
tMthe spray dryer of model carries out spraying dry: the nozzle adopting 2.0mm, spraying dry pressure is 2.0-2.5 MPa, and inlet temperature less than 500 DEG C, outlet temperature is about 150 DEG C.The microballoon that obtained by spraying dry first at 180 DEG C dry 1 hour, then at 635 DEG C, roasting obtains catalyst precarsor in 1 hour.Measure the average grain diameter (radius) of catalyst precarsor, subtracting each other with the average grain diameter (radius) measuring the kernel microballoon obtained in step (1) thickness obtaining clad is 9 microns.
(3) reduce.Catalyst precarsor reductase 12 hour in the hydrogen atmosphere (hydrogen content is 30 volume %) of 425 DEG C can obtain desulphurization catalyst, is designated as desulphurization catalyst A1.In addition desulphurization catalyst A1 is carried out H2-TPR test, obtain H2-TPR spectrogram, as shown in Figure 1.The nickel oxide that in Fig. 1, TCD signal goes out in peak explanation desulphurization catalyst A1 is reduced to metallic nickel.
The chemical composition of desulphurization catalyst A1 is calculated as by feeding intake: aluminium oxide 15.0 % by weight, silica 20.0 % by weight, zinc oxide 36.0 % by weight, ZSM-5 molecular sieve 8 % by weight, nickel 20.0 % by weight.
Desulphurization catalyst A1 is carried out SEM-EDX determination and analysis, according to the nickel obtained, zinc along the content distribution of A1 cross-section radial, show that the Thickness Ratio of kernel and clad is 1:0.32.
Desulphurization catalyst A1 carries out XPS mensuration, and in clad, the mol ratio of Ni:Zn is 1:7.
Measured by fluorescence analysis and XPS, the weight ratio of the Ni in Ni and the A1 in desulphurization catalyst A1 clad is 0.31, and the weight ratio of the zinc oxide in clad and the zinc oxide in A1 is 1.50.
Embodiment 2
The present embodiment is for illustration of the preparation method of desulphurization catalyst of the present invention.
(1) kernel preparation.1.02 kilograms of expanded perlites (Global Mining Industry company, M27, containing butt 1.00 kilograms; In butt, silica content is 72 % by weight, alumina content is 18 % by weight), hydrated alumina 0.86 kilogram of (boehmite, Shandong Aluminum Plant produces, containing butt 0.69 kilogram), 6.95 kilogram of six water nickel nitrate (is analyzed pure, traditional Chinese medicines chemical reagents corporation) and 4.8 kilograms of neutral waters are under agitation evenly, and aging 1 hour.Then add 0.75 kilogram of ZRP-1 molecular sieve (Shandong catalyst branch company, containing butt 0.6 kilogram), obtain mixed serum, its pH value is 2.6.
Carry out spraying dry according to the method in embodiment 1 step (1), obtain kernel microballoon.The average grain diameter (radius) measuring the kernel microballoon obtained is 27 microns.
(2) clad preparation.Get 1.23 kilograms of expanded perlites (Global Mining Industry company, M27, containing butt 1.21 kilograms; In butt, silica content is 72 % by weight, alumina content is 18 % by weight), hydrated alumina 0.75 kilogram of (boehmite, Shandong Aluminum Plant produces, containing butt 0.6 kilogram) and 9.0 kilograms of deionized waters, be uniformly mixed, the hydrochloric acid (chemical pure, Beijing Chemical Plant produces) adding 130 gram 30 % by weight stirs acidifying 1 hour.Add 4.5 kilograms of Zinc oxide powders, stir 0.5 hour, then add the kernel microballoon obtained in step (1), after stirring, obtain clad slurries.
Carry out the spray drying forming of clad slurries and calcination process according to the method in embodiment 1 step (2), obtain catalyst precarsor.Measure the average grain diameter (radius) of catalyst precarsor, subtracting each other with the average grain diameter (radius) measuring the kernel microballoon obtained in step (1) thickness obtaining clad is 11 microns.
(3) reduce.Carry out the reduction of catalyst precarsor according to the method in embodiment 1 step (3), obtain desulphurization catalyst A2.Carry out H2-TPR test according to method in embodiment 1, the nickel oxide in display desulphurization catalyst A2 is reduced to metallic nickel.
The chemical composition of desulphurization catalyst A2 is calculated as by feeding intake: aluminium oxide 16.9 % by weight, silica 15.9 % by weight, zinc oxide 45.0 % by weight, ZRP-1 molecular sieve 6.0 % by weight, nickel 14.0 % by weight.
Carry out SEM-EDX determination and analysis according to method in embodiment 1, show that the Thickness Ratio of kernel and clad is 1:0.41.Desulphurization catalyst A2 carries out XPS mensuration, and in clad, the mol ratio of Ni:Zn is 1:10.Measured by fluorescence analysis and XPS, the weight ratio of the Ni in Ni and the A2 in desulphurization catalyst A2 clad is 0.25, and the weight ratio of the zinc oxide in skin and the zinc oxide in A2 is 1.68.
Embodiment 3
The present embodiment is for illustration of the preparation method of desulphurization catalyst of the present invention.
(1) kernel preparation.(Beijing chemical reagent factory, containing butt 0.95 kilogram for 0.98 kilogram of diatomite; In butt, silica content is 91 % by weight, alumina content is 6 % by weight), hydrated alumina 0.75 kilogram of (boehmite, Shandong Aluminum Plant produces, containing butt 0.6 kilogram), the hydrochloric acid of 120 gram 30 % by weight (chemical pure, Beijing Chemical Plant produces) and 4.5 kilograms of neutral waters under agitation even.Then add 1.28 kilograms of nickel oxide (analyzing pure, traditional Chinese medicines chemical reagents corporation) and 0.50 kilogram of ZSP-3 molecular sieve (Shandong catalyst branch company, containing butt 0.40 kilogram), obtain mixed serum after stirring, its pH value is 3.1.
Carry out spraying dry according to the method in embodiment 1 step (1), obtain kernel microballoon.The average grain diameter (radius) measuring the kernel microballoon obtained is 26 microns.
(2) clad preparation.(Kaolin of Suzhou factory, containing butt 1.25 kilograms to get 1.50 kilograms of carclazytes; In butt, silica content is 50 % by weight, alumina content is 45 % by weight), hydrated alumina 0.75 kilogram of (boehmite, Shandong Aluminum Plant produces, containing butt 0.6 kilogram) and 8.0 kilograms of deionized waters, be uniformly mixed, the hydrochloric acid (chemical pure, Beijing Chemical Plant produces) adding 140 gram 30 % by weight stirs acidifying 1 hour.Add 5.2 kilograms of Zinc oxide powders, stir 0.5 hour, then add the kernel microballoon obtained in step (1), after stirring, obtain clad slurries.
Carry out the spray drying forming of clad slurries and calcination process according to the method in embodiment 1 step (2), obtain catalyst precarsor.Measure the average grain diameter (radius) of catalyst precarsor, subtracting each other with the average grain diameter (radius) measuring the kernel microballoon obtained in step (1) thickness obtaining clad is 15 microns.
(3) reduce.Carry out the reduction of catalyst precarsor according to the method in embodiment 1 step (3), obtain desulphurization catalyst A3.Carry out H2-TPR test according to method in embodiment 1, the nickel oxide in display desulphurization catalyst A3 is reduced to metallic nickel.
The chemical composition of desulphurization catalyst A3 is calculated as by feeding intake: aluminium oxide 18.2 % by weight, silica 14.9 % by weight, zinc oxide 52.0 % by weight, ZSP-3 molecular sieve 4.0 % by weight, nickel 10.0 % by weight.
Carry out SEM-EDX determination and analysis according to method in embodiment 1, show that the Thickness Ratio of kernel and clad is 1:0.58.
Desulphurization catalyst A3 carries out XPS mensuration, and in clad, the mol ratio of Ni:Zn is 1:15.
Measured by fluorescence analysis and XPS, the weight ratio of the Ni in Ni and the A3 in desulphurization catalyst A3 clad is 0.20, and the weight ratio of the zinc oxide in kernel and the zinc oxide in A3 is 1.80.
Comparative example 1
(Beijing chemical reagent factory, containing butt 1.65 kilograms to get 1.70 kilograms of diatomite; In butt, silica content is 91 % by weight, and alumina content is 6 % by weight), 1.33 kilograms of kaolin (Kaolin of Suzhou factory, S1, containing butt 1.0 kilograms; In butt, silica content is 50 % by weight, alumina content is 45 % by weight), hydrated alumina 1.19 kilograms of (boehmites, Shandong Aluminum Plant produces, containing butt 0.95 kilogram), and after 14.0 kilograms of neutral waters under agitation mix, the nitric acid (chemical pure, Beijing Chemical Plant produces) adding 210 gram 30 % by weight stirs acidifying 1 hour.Stir after adding 3.6 kilograms of Zinc oxide powders and 1.0 kilograms of ZSM-5 molecular sieve (Shandong catalyst branch company, containing butt 0.8 kilogram) mixing and obtain carrier pulp in 1 hour.
Described carrier pulp adopts Niro Bowen Nozzle Tower
tMthe spray dryer of model carries out spraying dry: the nozzle adopting 2.0mm, spraying dry pressure is 8.5-9.5 MPa, and inlet temperature less than 500 DEG C, outlet temperature is about 150 DEG C.The microballoon that obtained by spraying dry first at 180 DEG C dry 1 hour, then at 635 DEG C, roasting obtains catalyst carrier in 1 hour.
The catalyst carriers of 4.10 kilograms (butt 4.0 kilograms) are flooded at twice with 4.98 kilograms of Nickelous nitrate hexahydrates, 2.1 kilograms of deionized water solutions, the mixture obtained after 4 hours, 1 hour can obtain catalyst precarsor in air atmosphere 635 DEG C of roastings through 180 DEG C of dryings.Catalyst precarsor reductase 12 hour in the hydrogen atmosphere of 425 DEG C can obtain desulphurization catalyst, is designated as desulphurization catalyst B1.
The chemical composition of desulphurization catalyst B1 is calculated as by feeding intake: aluminium oxide 15.0 % by weight, silica 20.0 % by weight, zinc oxide 36.0 % by weight, ZSM-5 molecular sieve 8.0 % by weight, nickel 20.0 % by weight.
Desulphurization catalyst B1 carries out XPS mensuration, and on the surface of desulphurization catalyst B1, the mol ratio of Ni:Zn is 1.70:1.
Measured by fluorescence analysis and XPS, the weight ratio of the Ni in Ni and the B1 on desulphurization catalyst B1 surface is 1.50, and the weight ratio of the zinc oxide in surperficial zinc oxide and B1 is 0.75.
Comparative example 2
4.5 kilograms of Zinc oxide powders (Beijing Chemical Plant's product), 0.75 kilogram of ZRP-1(Shandong catalyst branch company, containing butt 0.6 kilogram) and 7.2 kilograms of deionized water mixing, stir 30 minutes, obtain zinc oxide slurries.
Get 2.24 kilograms of expanded perlites (Global Mining Industry company, M27, containing butt 2.21 kilograms; In butt, silica content is 72 % by weight, alumina content is 18 % by weight), hydrated alumina 1.61 kilograms (Shandong Aluminum Plant produce, containing butt 1.29 kilograms) and after 6.8 kilograms of neutral waters under agitation mix, add the nitric acid (chemical pure of 260 gram 30 % by weight, Beijing Chemical Plant produces) stir acidifying after 1 hour, add above-mentioned zinc oxide slurries, and stir and obtain carrier pulp in 1 hour.
Carry out the spray drying forming of carrier according to the method for comparative example 1 and introduce active component nickel, obtaining desulphurization catalyst B2.
The chemical composition of desulphurization catalyst B2 is calculated as by feeding intake: aluminium oxide 16.9 % by weight, silica 15.9 % by weight, zinc oxide 45.0 % by weight, ZRP-1 molecular sieve 6.0 % by weight, nickel 14.0 % by weight.
Desulphurization catalyst B2 carries out XPS mensuration, and on the surface of desulphurization catalyst B2, the mol ratio of Ni:Zn is 1.50:1.
Measured by fluorescence analysis and XPS, the weight ratio of the Ni in Ni and the B2 on desulphurization catalyst B2 surface is 1.42, and the weight ratio of the zinc oxide in surperficial zinc oxide and B2 is 0.84.
Comparative example 3
(Beijing chemical reagent factory, containing butt 0.95 kilogram to get 0.98 kilogram of diatomite; In butt, silica content is 91 % by weight, and alumina content is 6 % by weight), (Kaolin of Suzhou factory, containing butt 1.25 kilograms for 1.50 kilograms of carclazytes; In butt, silica content is 50 % by weight, alumina content is 45 % by weight), (Shandong Aluminum Plant produces hydrated alumina 1.60 kilograms, containing butt 1.20 kilograms) and after 12.0 kilograms of neutral waters (pH value is 6-8) under agitation mix, the hydrochloric acid (chemical pure, Beijing Chemical Plant produce) adding 225 gram 30 % by weight stir acidifying be warming up to after 2 hours 80 DEG C aging 2 hours.When temperature is reduced to below 40 DEG C, add 5.4 kilograms of Zinc oxide powders and 0.50 kilogram of ZSP-3 molecular sieve (Shandong catalyst branch company, containing butt 0.40 kilogram), stir after mixing and obtain carrier pulp in 1 hour.
Carry out the spray drying forming of carrier according to the method for comparative example 1 and introduce active component nickel, obtaining desulphurization catalyst B3.
The chemical composition of desulphurization catalyst B3 is calculated as by feeding intake: aluminium oxide 18.2 % by weight, silica 14.9 % by weight, zinc oxide 52.0 % by weight, ZSP-3 molecular sieve 4.0 % by weight, nickel 10.0 % by weight.
Desulphurization catalyst B3 carries out XPS mensuration, and on the surface of desulphurization catalyst B3, the mol ratio of Ni:Zn is 1.15:1.
Measured by fluorescence analysis and XPS, the weight ratio of the Ni in Ni and the B3 on desulphurization catalyst B3 surface is 1.28, and the weight ratio of the zinc oxide in surperficial zinc oxide and B3 is 0.90.
Test case
Measure abrasion strength resistance and the desulfurization performance of desulphurization catalyst A1-A3 and B1-B3.
Abrasion strength resistance adopts straight tube wearing and tearing method to evaluate, and its evaluation method is with reference to enterprise mark Q/SH3360212-2009, and numerical value is less, shows that abrasion strength resistance is higher.The abrasion index (FBAT) of different desulphurization catalyst is as shown in table 1.
The desulfurization performance of desulphurization catalyst adopts the micro-anti-experimental provision of fixed bed to evaluate.Evaluate the raw material that uses for sulfur content be the catalytically cracked gasoline of 796 μ g/g.The desulphurization catalyst of 16 grams being seated in internal diameter is in 30mm, the long fixed bed reactors for 1m.Evaluation procedure adopts hydrogen atmosphere (hydrogen content is 30 volume %), and reaction temperature is 410 DEG C, and the weight space velocity evaluating the charging of the raw material used is 4h-1.
After evaluation completes, desulphurization catalyst carries out regeneration process, and regeneration process is what to carry out under the air atmosphere of 550 DEG C.Altogether carry out 6 circulations to evaluate, represent the activity of catalyst with the sulfur content in product gasoline, sulfur content adopts off-line chromatography, adopts the GC6890-SCD instrument of An Jielun company to measure.
The sulfur content that desulphurization catalyst carries out the product gasoline that desulfurization performance evaluation obtains is as shown in table 2.
The change that desulphurization catalyst carries out the octane number of the product gasoline that desulfurization performance evaluation obtains is as shown in table 3.
Table 1
| Catalyst | A1 | A2 | A3 | B1 | B2 | B3 |
| FBAT index | 4.6 | 4.9 | 5.3 | 5.0 | 5.2 | 5.5 |
Table 2
Table 3
Note: the difference that [Δ (RON+MON)/2] is product gasoline anti-knock index and raw material anti-knock index.
As can be seen from embodiment and the experimental result of comparative example and the data result of table 1 and table 2, desulphurization catalyst provided by the invention is because form the layer structure with kernel and clad, wherein contain zinc oxide in clad, kernel is rich in active metal, so desulphurization catalyst provided by the invention has better desulfurization performance and abrasion strength resistance.
Claims (21)
1. a desulphurization catalyst, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contains the active metal of the aluminium oxide of 5-35 % by weight, the silica of 5-35 % by weight, the zinc oxide of 10-70 % by weight, the molecular sieve with MFI structure of 1-10 % by weight and 5-30 % by weight;
This desulphurization catalyst comprises kernel and is attached to the clad at least part of surface of described kernel:
1) described kernel contains aluminium oxide, silica, the molecular sieve with MFI structure and active metal;
2) described clad contains aluminium oxide, silica and zinc oxide;
And the weight ratio of the active metal in described clad and the active metal in desulphurization catalyst is less than 0.3, the weight ratio of the zinc oxide in described clad and the zinc oxide in desulphurization catalyst is for being greater than 1.5;
Described active metal is selected from least one in group VIII metal.
2. desulphurization catalyst according to claim 1, wherein, the Thickness Ratio of described kernel and described clad is 1:0.2-0.6.
3. desulphurization catalyst according to claim 1 and 2, wherein, with X-ray photoelectron spectroscopic analysis, described in described clad, the mol ratio of active metal and zinc is at below 1:3.
4. desulphurization catalyst according to claim 3, wherein, with X-ray photoelectron spectroscopic analysis, described in described clad, the mol ratio of active metal and zinc is at below 1:5.
5. desulphurization catalyst according to claim 1, wherein, with the gross weight of described desulphurization catalyst for benchmark, described desulphurization catalyst contains the active metal of the aluminium oxide of 12-30 % by weight, the silica of 15-30 % by weight, the zinc oxide of 30-55 % by weight, the molecular sieve with MFI structure of 4-8 % by weight and 10-25 % by weight.
6. desulphurization catalyst according to claim 1, wherein, described active metal is cobalt and/or nickel.
7. disengaging catalyst according to claim 1, wherein, described in there is MFI structure molecular sieve be there is two ten-ring intersect the molecular sieve in duct.
8. a preparation method for desulphurization catalyst, the method comprises:
(1) binding agent, silica source, the molecular sieve with MFI structure, active metal precursor.In, water and the first acid solution are carried out the first mixing, obtain mixed serum, mixed serum is shaping, dry and roasting, obtains inner core particles;
(2) binding agent, silica source, zinc oxide source, water and the second acid solution are carried out the second mixing, form clad slurries; The inner core particles that step (1) obtains is added in described clad slurries, again carry out shaping, dry and roasting, obtain catalyst precarsor;
(3) catalyst precarsor that step (2) obtains is reduced under hydrogen atmosphere, obtain desulphurization catalyst;
Described first acid solution and described second acid solution identical or different, is separately inorganic acid and/or the organic acid aqueous solution.
9. preparation method according to claim 8, wherein, described binding agent, silica source, zinc oxide source, the addition of molecular sieve and active metal precursor.In with MFI structure make in the desulphurization catalyst obtained, with this desulphurization catalyst gross weight for benchmark, the content of aluminium oxide is 5-35 % by weight, the content of silica is 5-35 % by weight, the content of zinc oxide is 10-70 % by weight, have the content of the molecular sieve of MFI structure be the content of 1-10 % by weight and active metal is 5-30 % by weight.
10. preparation method according to claim 8, wherein, described binding agent, silica source, zinc oxide source, the addition of molecular sieve and active metal precursor.In with MFI structure make in the desulphurization catalyst obtained, with this desulphurization catalyst gross weight for benchmark, the content of aluminium oxide is 12-30 % by weight, the content of silica is 15-30 % by weight, the content of zinc oxide is 30-55 % by weight, have the content of the molecular sieve of MFI structure be the content of 4-8 % by weight and active metal is 10-25 % by weight.
11. preparation methods according to claim 8, wherein, in step (1) with the described binding agent of 100 weight portions for benchmark, add the water of the described silica source of 40-250 weight portion, the molecular sieve with MFI structure of 10-80 weight portion, the active metal precursor.In of 50-400 weight portion and 500-1000 weight portion; In step (2) with the described binding agent of 100 weight portions for benchmark, add the water of the described silica source of 40-250 weight portion, the zinc oxide source of 80-600 weight portion and 500-1500 weight portion.
12. preparation methods according to Claim 8 in-11 described in any one, wherein, the consumption of described first acid solution makes the pH value of the mixed serum obtained be 2-5.
13. preparation methods according to Claim 8 in-11 described in any one, wherein, the consumption of described second acid solution makes the pH value of the clad slurries obtained be 2-5.
14. preparation methods according to Claim 8 in-11 described in any one, wherein, described active metal precursor.In is be selected from least one in the acetate of group VIII metal, carbonate, nitrate, sulfate, rhodanate and oxide.
15. preparation methods according to Claim 8 in-11 described in any one, wherein, described zinc oxide source is zinc oxide and/or zinc oxide precursor, and described zinc oxide precursor is the material that can be converted into zinc oxide under the condition of the described roasting of step (2).
16. preparation methods according to claim 15, wherein, described zinc oxide precursor is at least one in zinc sulphide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate and zinc nitrate.
17. preparation methods according to Claim 8 in-11 described in any one, wherein, described binding agent is at least one in hydrated alumina, Alumina gel, boehmite, false boehmite, hibbsite and amorphous hydroted alumina.
18. preparation methods according to Claim 8 in-11 described in any one, wherein, described silica source is the natural crystal that silica or silica content are greater than 45 % by weight.
19. preparation methods according to claim 8, wherein, the condition of the described roasting of step (2) comprising: temperature is 300-800 DEG C, and the time is 0.5-4 hour.
20. desulphurization catalysts prepared by the method in claim 8-19 described in any one.
The sulfur method of 21. 1 kinds of sulfurous fuels oil, the method comprises: by sulfurous fuels oil and hydrodesulfurization catalyst, it is characterized in that, described desulphurization catalyst is the desulphurization catalyst in claim 1-7 and 20 described in any one.
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