CN105498830A - Desulfurization catalyst, preparation method thereof and method for desulfurizing hydrocarbon oil by employing same - Google Patents
Desulfurization catalyst, preparation method thereof and method for desulfurizing hydrocarbon oil by employing same Download PDFInfo
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Abstract
The invention discloses a desulfurization catalyst, a preparation method thereof and a method for desulfurizing hydrocarbon oil by employing the same. By taking the total weight of the desulfurization catalyst as the reference, the desulfurization catalyst comprises, 1) 5-35 wt% of a heatproof inorganic oxide; 2) 5-35 wt% of a silicon oxide source; 3) 10-70 wt% of a first metal oxide; 4) 2-20 wt% of a second metal oxide; 5) 3-30 wt% of a metal promoter; 6) 0.5-10 wt% of a rare-earth metal oxide calculated in terms of a rare earth oxide; and 7) 1-20 wt% of a molecular sieve possessing a BEA or FAU structure. The desulfurization catalyst possesses relatively good desulfurization activity and activity stability.
Description
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, the method preparing desulphurization catalyst and the desulphurization catalyst obtained by the method, and use this desulphurization catalyst to carry out the method for desulfurization of hydrocarbon oil.
Background technology
The oxysulfide produced after combustion of sulfur in vehicle fuel, can suppress the activity of the noble metal catalyst in vehicle exhaust converter also can make it generation irreversibly poisoning.Thus make in vehicle exhaust containing unburned non-methane hydrocarbon and nitrogen oxide and carbon monoxide, these discharge gas are then easily formed photochemical fog by hydrophilic dye, cause acid rain, 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.
The existing gasoline products standard GB17930-2011 " motor petrol " of China required on December 31st, 2013, and sulfur content in gasoline must drop to 50 μ g/g; And gasoline quality standard can be stricter in the future.In this case, catalytically cracked gasoline has to pass through the requirement that deep desulfuration just can meet environmental protection.
At present, the process for deep desulphurization of oil product mainly contains hydrofinishing and adsorption desulfurize two kinds of methods, but in China because the problem of hydrogen source makes hydrorefined cost higher.SZorb adsorption desulfurize belongs to and faces hydrogen desulfur technology, realizes the adsorbing and removing of sulfide under certain temperature and pressure condition.Due to this technology, removing the sulfur-containing compound in gasoline, to have hydrogen consumption low, and not high to the purity requirement of hydrogen, and this technology is had broad application prospects removing in the sulfur-containing compound in fuel oil.
From liquid state, desulfurization often adopts the method for fixed bed traditionally, but the reaction uniformity of the method and regeneration all have obvious inferior position.Fluidized-bed process has the advantage of the better aspect such as heat transfer and pressure drop compared with fixed-bed process, therefore has broad application prospects.Fluidized-bed reactor generally adopts granular reactant, but for great majority reaction, reactant used does not generally have enough wearabilities.Therefore, find anti-wear performance well to have the adsorbent of better desulfurization performance significant simultaneously.
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.All only mention desulphurizing activated in CN1355727A and CN1382071A, adsorbent physical and chemical performance (such as abrasion strength resistance) and stability are not all introduced.
Adsorbent disclosed in US6150300, CN1130253A and CN1258396A is: the granular adsorbent composition comprising the mixture of zinc oxide, silica, aluminium oxide, reduction valence state nickel or cobalt.Preparation method mainly adopts the methods such as shearing that silica, aluminium oxide and zinc oxide are mixed merga pass comminutor and prepares solid particle, floods nickel thus obtained adsorbent after drying and roasting.Although the adsorbent of these patent Introductions has good desulfurization performance, for its physical and chemical performance, mainly tear strength is not introduced in the patent.
CN1208124A discloses and adopts promoter metals to comprise the adsorbing agent carrier of zinc oxide, expanded perlite and aluminium oxide as cobalt and nickel dipping, then reduces this promoter at appropriate temperatures, for the preparation of the adsorbent removing cracking gasoline medium sulphide content.
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.
CN101816918A discloses a kind of desulfuration adsorbent, and this adsorbent consists of rare earth metal, aluminium oxide, silica, promoter and is selected from the adsorbent of one or more metal oxides of IIB, VB and VIB.This adsorbent has good abrasion strength resistance and desulphurizing activated.
Although adsorbent prepared by these methods has good desulfurization performance, also there is obvious shortcoming.Above-mentioned adsorbent all adopts zinc oxide active component, and the temperature that zinc oxide absorbs sulphur and oxidation regeneration is all higher, and the silicon when desulphurization reaction and oxidation regeneration easily and in carrier, al composition generate zinc silicate and/or zinc aluminate, cause adsorbent activity to reduce.As can be seen here, need to provide a kind of new catalyst with more high desulfurization activity and abrasion resistance properties.
Summary of the invention
The object of the invention is the defect of desulphurizing activated low, the structural instability of adsorbent in order to overcome prior art and abrasion resistance properties difference, providing the method for a kind of desulphurization catalyst and preparation method thereof and 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 contains: the 1) heat-resistant inorganic oxide of 5-35 % by weight, and described heat-resistant inorganic oxide is selected from least one in aluminium oxide, titanium dioxide, zirconium dioxide and tin ash; 2) silica source of 5-35 % by weight; 3) first metal oxide of 10-70 % by weight, described first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element; 4) second metal oxide of 2-20 % by weight, described second metal oxide is selected from least one in lead oxide, antimony oxide and bismuth oxide; 5) metallic promoter agent of 3-30 % by weight, described metallic promoter agent is selected from least one in cobalt, nickel, iron and manganese; 6) in the rare-earth oxide of the 0.5-10 % by weight of rare earth oxide; 7) molecular sieve of 1-20 % by weight, described molecular sieve is the molecular sieve with BEA and/or FAU structure.
Present invention also offers the preparation method of desulphurization catalyst of the present invention, the method comprises: the precursor of rare earth compound, the first metal oxide, the second metal oxide and water are mixed to get slurries by (1); (2) heat-resistant inorganic oxide binding agent, silica source, water are mixed with acidic liquid, and form carrier pulp with described slurry liquid contacts, again described carrier pulp, the molecular sieve with BEA and/or FAU structure are carried out shaping, first dry and the first roasting, obtain carrier; (3) on described carrier, introduce the precursor of metallic promoter agent, and carry out second dry and the second roasting, obtain catalyst precarsor; (4) described catalyst precarsor is reduced under hydrogen atmosphere, obtain desulphurization catalyst.
The present invention also provides the desulphurization catalyst prepared by method provided by the invention.
The invention provides a kind of method of desulfurization of hydrocarbon oil, the method comprises: in a hydrogen atmosphere, and by hydrocarbon oil containing surphur and hydrodesulfurization catalyst provided by the invention, the temperature of described contact is 350-500 DEG C, and the pressure of described contact is 0.5-4MPa.
Mix with the second metal oxide containing the first metal oxide in desulphurization catalyst provided by the invention and absorb constituent element as sulphur, second metal oxide effectively can reduce the effect of silicon in the first metal oxide and carrier, al composition, reduce silicate and/or the aluminate of generation first metal, thus enable this desulphurization catalyst absorb sulphur at lower temperatures and through repeatedly carrying out reacting and regenerative process, still there is better desulphurizing activated and activity stability.
Containing rare earth oxide in desulphurization catalyst provided by the invention, that effectively can strengthen that the second metal oxide acts on silicon, al composition mutually to the first metal oxide further weakens effect.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
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 contains: the 1) heat-resistant inorganic oxide of 5-35 % by weight, and described heat-resistant inorganic oxide is selected from least one in aluminium oxide, titanium dioxide, zirconium dioxide and tin ash; 2) silica source of 5-35 % by weight; 3) first metal oxide of 10-70 % by weight, described first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element; 4) second metal oxide of 2-20 % by weight, described second metal oxide is selected from least one in lead oxide, antimony oxide and bismuth oxide; 5) metallic promoter agent of 3-30 % by weight, described metallic promoter agent is selected from least one in cobalt, nickel, iron and manganese; 6) in the rare-earth oxide of the 0.5-10 % by weight of rare earth oxide; 7) molecular sieve of 1-20 % by weight, described molecular sieve is the molecular sieve with BEA and/or FAU structure.
Preferably, with the gross weight of this desulphurization catalyst for benchmark, the content of described heat-resistant inorganic oxide is 10-25 % by weight, the content of described silica source is 10-25 % by weight, the content of described first metal oxide is 35-54 % by weight, and the content of described second metal oxide is 5-15 % by weight, and the content of described metallic promoter agent is 10-20 % by weight, described rare-earth oxide is in the content of rare earth oxide for 1-5 % by weight, and the content of described molecular sieve is 2-10 % by weight.
According to the present invention, described first metal oxide is the metal oxide with storage sulphur performance, and preferably, described first metal oxide is at least one in zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide; More preferably, described first metal oxide is at least one in zinc oxide, molybdenum oxide and vanadium oxide; Most preferably described first metal oxide is zinc oxide.
According to the present invention, described second metal oxide can suppress described first metal oxide when the desulphurization reaction repeatedly experienced under high temperature and regenerative response, have an effect with the silicon contained in described desulphurization catalyst, al composition, reduce the loss of described first metal oxide.
According to the present invention, described heat-resistant inorganic oxide can for providing cementation between component each in described desulphurization catalyst.Described heat-resistant inorganic oxide is selected from least one in aluminium oxide, titanium dioxide, zirconium dioxide and tin ash.Wherein, described aluminium oxide can be at least one in gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-aluminium oxide; Preferably, described aluminium oxide is gama-alumina; Described titanium dioxide can be anatase titanium dioxide.
According to the present invention, described silica source can for providing cementation between component each in described desulphurization catalyst.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 laminated clay column, diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.Can also containing other component as Al in natural minerals
2o
3, K
2o, CaO, MgO, Fe
2o
3, TiO
2deng.In the present invention, the amount of other components contained in described silica source still can be regarded as the amount of silica source.
According to the present invention, described metallic promoter agent can be any metal that oxidation state sulphur can be reduced to hydrogen sulfide, and preferred described metallic promoter agent is nickel.
According to the present invention, described rare-earth oxide can and the second metal oxide between interaction, strengthen the second metal oxide to the effect improving catalyst abrasion intensity, the skeleton of heat-resistant inorganic oxide can be stablized simultaneously, weaken the interaction between the first metal oxide and silicon, al composition further, improve activity and the stability of desulfurization.Preferably, described rare-earth oxide is at least one in the oxide of lanthanum, cerium and neodymium.
In the present invention, described FAU structure molecular screen is faujasite-type molecular sieve.The type molecular sieve has three-dimensional twelve-ring duct, and aperture is
fAU structure molecular screen is mainly the molecular sieve of X-type and Y type, in general SiO
2/ Al
2o
3mol ratio be 2.2-3 for X-type molecular sieve, SiO
2/ Al
2o
3mol ratio be greater than 3 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
In the present invention, the molecular sieve with FAU structure also comprises this modified molecular sieve analog.The method of modification 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 that obtains includes but not limited to super-stable Y molecular sieves (USY), REUSY, REHY, REY containing rare earth element, and phosphorous PUSY, PREHY, PREY etc.Rare earth can be at least one in the carbonate of rare earth metal, bicarbonate, nitrate, chloride, formates and acetate; Preferably, described rare earth compound can be at least one in the carbonate of rare earth metal, bicarbonate, formates and acetate.Wherein, described rare earth metal is preferably at least one in lanthanum, cerium and neodymium.The described SiO with the molecular sieve of FAU structure
2: Al
2o
3mol ratio be 2.6-10:1; Preferably, there is described in the SiO of the molecular sieve of FAU structure
2: Al
2o
3mol ratio be 2.8-9:1.
In the present invention, BEA structure molecular screen is mainly beta-molecular sieve, and its structural formula is (Na
n[Al
nsi
64-no
128], n<7), be two structures differences but the mixed crystal of the polymorph A be closely related and B, both have twelve-ring 3 D pore canal system: polymorph A forms a pair enantiomer, 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
<001 direction >.The described SiO with the molecular sieve of BEA structure
2: Al
2o
3mol ratio be 10-50:1; Preferably, there is described in the SiO of the molecular sieve of BEA structure
2: Al
2o
3mol ratio be 15-30:1.
According to the present invention, under preferable case, described in there is FAU and/or BEA structure molecular sieve be at least one in X-type molecular sieve, Y zeolite, USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta-molecular sieve.
In the present invention, add effect or effect that the molecular sieve with FAU and/or BEA structure can be improved gasoline products octane number.
Present invention also offers the preparation method of desulphurization catalyst of the present invention, the method comprises: the precursor of rare earth compound, the first metal oxide, the second metal oxide and water are mixed to get slurries by (1); (2) heat-resistant inorganic oxide binding agent, silica source, water are mixed with acidic liquid, and contact with described slurries, the molecular sieve with FAU and/or BEA structure and form carrier pulp, again described carrier pulp is carried out shaping, first dry and the first roasting, obtain carrier; (3) on described carrier, introduce the precursor of metallic promoter agent, and carry out second dry and the second roasting, obtain catalyst precarsor; (4) described catalyst precarsor is reduced under hydrogen atmosphere, obtain desulphurization catalyst.
In the present invention, under preferable case, described heat-resistant inorganic oxide binding agent can be heat-resistant inorganic oxide or the material that can change heat-resistant inorganic oxide under the condition of described first roasting into.Preferably, described heat-resistant inorganic oxide binding agent is at least one in alumina binder, zirconium dioxide binding agent, titanium dioxide binding agent and tin ash binding agent.More preferably, described alumina binder can be hydrated alumina and/or Alumina gel, wherein, described hydrated alumina is selected from least one in boehmite (boehmite), false boehmite (boehmite), hibbsite and amorphous hydroted alumina; Described zirconium dioxide binding agent can be at least one in zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide; Described tin ash binding agent can be at least one in butter of tin, four isopropyl alcohol tin, tin acetate, aqua oxidation tin and tin ash; Described titanium dioxide binding agent can be at least one in titanium tetrachloride, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.
In 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.Described laminated clay column can be at least one in rectorite, Yun Mengshi, bentonite, imvite and smectite.
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.Namely in the desulphurization catalyst obtained by method provided by the invention, the content of each component calculates according to inventory.
In the present invention, the precursor of described second metal oxide is described second metal oxide or the material that can change described second metal oxide under the condition of described first roasting into.Under preferable case, the precursor of described second metal oxide is at least one in lead oxide, antimony oxide and bismuth oxide; Or at least one in the carbonate of metallic lead, antimony and bismuth, nitrate, chloride and hydroxide.
In the present invention, the precursor of described metallic promoter agent can for changing the material of the oxide of metallic promoter agent under the condition of described second roasting.Under preferable case, the precursor of described metallic promoter agent can be at least one in the acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide.
In the present invention, under preferable case, described rare earth compound can be at least one in the carbonate of rare earth metal, bicarbonate, nitrate, chloride, formates and acetate; Preferably, described rare earth compound can be at least one in the carbonate of rare earth metal, bicarbonate, formates and acetate.Wherein, described rare earth metal is preferably at least one in lanthanum, cerium and neodymium.
In the present invention, described first metal oxide, metallic promoter agent and to have the molecular sieve of FAU and/or BEA structure described above, do not repeat them here.
The step (1) of the preparation method of desulphurization catalyst provided by the invention and (2) are for the preparation of carrier.
In step of the present invention (1), adding of described first metal oxide can be oxide powder form, also can be use as a slurry after the first metal oxide is prepared as slurries again.
In the present invention, add the precursor of described second metal oxide, directly can add the powder of at least one in lead oxide, antimony oxide and bismuth oxide, or change the material of described second metal oxide under being added in the condition of described first roasting into, as the one in the carbonate of metallic lead, antimony and bismuth, nitrate, chloride and hydroxide; Also use as a slurry again after at least one in lead oxide, antimony oxide and bismuth oxide can being prepared as slurries.
In the present invention, the solid content of slurries described in step (1) can be 15-30 % by weight.
In step of the present invention (2), in the present invention, described silica source is 0.4-2:1 with the charged material weight ratio of described heat-resistant inorganic oxide binding agent, is preferably 0.6-1.5:1.Caking property between the better each component of described desulphurization catalyst can be provided thus.
In step of the present invention (2), described mixing can be: after heat-resistant inorganic oxide binding agent and silica source are carried out acidification with water and acidic liquid respectively, then the mixture obtained separately is mixed into described slurries; Wherein, when described heat-resistant inorganic oxide binding agent is non-al binder, the mixture obtained is colloidal sol.In addition, when described heat-resistant inorganic oxide binding agent is alumina binder, described mixing can also be: by water, acidic liquid, alumina binder and silica source mix, aging, formed acidified slurries.Preferably, the pH value of described acidified slurries is 1-5, is preferably 1.5-4; The solid content of described acidified slurries is 15-30 % by weight.
In the present invention, described acidic liquid is acid or aqueous acid, and described acid 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, shapingly described in step (2) described slurries can be shaped to extrudate, sheet, pill, ball or micro-spherical particle.Such as, described slurries be dough or paste mixture time, described mixture shaping (preferred extrusion molding) can be made to form particle, and preferred diameter is at 1-8mm, length, at the cylindrical extrudates of 2-5mm, then makes the extrudate of gained carry out drying, roasting.If gained mixture is wet mixture form, this mixture multiviscosisty can be made, through super-dry aftershaping.More preferably slurries are slurry form, form 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 described carrier pulp is 10-40 % by weight, is preferably 20-35 % by weight.Obtain can also comprising in the process of described carrier pulp adding water in step (2), there is no particular limitation for the addition of water, as long as the carrier pulp obtained meets the solid content of above-mentioned carrier pulp.
In the present invention, the described first condition that is dry and the first roasting can be conventionally known to one of skill in the art, and under preferable case, the temperature of described first drying is 80-150 DEG C, and the time of described first drying is 0.5-24h; The temperature of described first roasting is 300-700 DEG C, and the time of described first roasting is at least 0.5 hour.Preferably, the temperature of described first roasting is 400-500 DEG C, and the time of described first roasting is 0.5-100 hour, and the time of more preferably described first roasting is 0.5-10 hour.
According to the present invention, step (3) is for adding metallic promoter agent.The precursor of described metallic promoter agent is the material that can change the oxide of metallic promoter agent under the second roasting condition into; Under preferable case, the precursor of described metallic promoter agent can be selected from least one in the acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide.
According to the present invention, under preferable case, carrier is introduced the method for the precursor of metallic promoter agent for dipping or precipitation.Described dipping can be the solution of the precursor by metallic promoter agent or suspension impregnation carrier; Described precipitation can be the solution of the precursor of metallic promoter agent or suspension are mixed with carrier, then adds ammoniacal liquor by the precursor precipitation of metallic promoter agent on carrier.
In the present invention, the described second condition that is dry and the second roasting can be conventionally known to one of skill in the art, and under preferable case, the temperature of described second drying is 50-300 DEG C, and the time of described second drying is 0.5-8h; The temperature of described second roasting is 300-700 DEG C, and the time of described second roasting is 0.5-4h; Preferably, the temperature of described second drying is 100-250 DEG C, and the time of described second drying is 1-5h; The temperature of described second roasting is 400-500 DEG C, and the time of described second roasting is 1-3h.Described second roasting can be carried out under having oxygen or oxygen-containing gas to exist, until volatile materials is removed and metallic promoter agent is converted into the form of metal oxide, obtains catalyst precarsor.
According to the present invention, in step (4), change the oxide of the metallic promoter agent in described catalyst precarsor into metal simple-substance, described catalyst precarsor can be reduced under hydrogen atmosphere, metallic promoter agent is existed with reduction-state substantially, obtains catalyst of the present invention.The condition of described reduction only changes the oxide of the metallic promoter agent in described catalyst precarsor into metal simple-substance, and the metal oxide in described carrier can not change.Under preferable case, the temperature of described reduction is 300-600 DEG C, and the time of described reduction is 0.5-6h, and in described hydrogen atmosphere, hydrogen content is 10-60 volume %; Preferably, the temperature of described reduction is 350-450 DEG C, and the time of described reduction is 1-3h.
In the present invention, catalyst precarsor reduction can be carried out immediately by step (4) after obtained catalyst precarsor, also can before use (namely for desulfurization absorption before) carry out.Because metallic promoter agent is easily oxidized, and the metallic promoter agent in catalyst precarsor exists in the form of an oxide, and therefore for ease of transport, catalyst precarsor reduction is carried out by preferred steps (4) before carrying out desulfurization absorption.Described being reduced to makes the metal in the oxide of metallic promoter agent substantially exist with reduction-state, obtains desulphurization catalyst of the present invention.
According to preparation method provided by the invention, described heat-resistant inorganic oxide binding agent, silica source, first metal oxide, the precursor of the second metal oxide, rare earth compound, there is the addition of the molecular sieve of FAU and/or BEA structure and the precursor of metallic promoter agent, make in the desulphurization catalyst obtained, with the gross weight of this desulphurization catalyst for benchmark, heat-resistant inorganic oxide containing 5-35 % by weight, the silica source of 5-35 % by weight, first metal oxide of 10-70 % by weight, second metal oxide of 2-20 % by weight, the metallic promoter agent of 3-30 % by weight and in the rare-earth oxide of the 0.5-10 % by weight of rare earth oxide, the molecular sieve with FAU and/or BEA structure of 1-20 % by weight.
Preferably, with the gross weight of this desulphurization catalyst for benchmark, the content of described heat-resistant inorganic oxide is 10-25 % by weight, the content of described silica source is 10-25 % by weight, the content of described first metal oxide is 35-54 % by weight, the content of described second metal oxide is 5-15 % by weight, the content of described metallic promoter agent is 10-20 % by weight, described rare-earth oxide in the content of rare earth oxide for 1-5 % by weight, described in there is the molecular sieve of FAU and/or BEA structure content be 2-10 % by weight.
The present invention also provides the desulphurization catalyst prepared by method provided by the invention.As previously mentioned, this is no longer going to repeat them for the composition of this desulphurization catalyst.
The invention provides a kind of method of desulfurization of hydrocarbon oil, the method comprises: in a hydrogen atmosphere, and by hydrocarbon oil containing surphur and hydrodesulfurization catalyst provided by the invention, the temperature of described contact is 350-500 DEG C, and the pressure of described contact is 0.5-4MPa; Preferably, the temperature of described contact is 400-450 DEG C, and the pressure of described contact is 1-2MPa.Sulphur in the process in hydrocarbon ils is adsorbed on catalyst, thus obtains the hydrocarbon ils of low sulfur content.
The method of desulfurization of hydrocarbon oil provided by the invention is preferably carried out in a fluidized bed reactor, and namely described contact is preferably carried out in a fluidized bed reactor.
In the present invention, reacted catalyst can be reused after regeneration.Described regeneration is carried out under oxygen atmosphere, and the condition of regeneration comprises: the pressure of regeneration is normal pressure, and the temperature of regeneration is 400-700 DEG C, is preferably 500-600 DEG C.
In the present invention, the catalyst after regeneration is before re-starting desulfurization of hydrocarbon oil, and also need to reduce under hydrogen atmosphere, the reducing condition of the catalyst after regeneration comprises: temperature is 350-500 DEG C, is preferably 400-450 DEG C; Pressure is 0.2-2MPa, is preferably 0.2-1.5MPa.
Term used herein " 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.
It is the hydrocarbon mixture of 170 to 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 abrasion strength resistance and desulphurizing activated, greatly can increase the service life, be applicable to adsorption desulfurize process.
Below will be described the present invention by embodiment.
In the following Examples and Comparative Examples, the composition of desulphurization catalyst calculates according to feeding intake.
Embodiment 1
The present embodiment is for illustration of the method preparing desulphurization catalyst of the present invention.
(1) carrier is prepared.By zinc oxide (the traditional Chinese medicines chemical reagents corporation of 3.14kg, analyze pure), lead oxide (the traditional Chinese medicines chemical reagents corporation of 1.45kg, analyze pure) and lanthanum carbonate (the traditional Chinese medicines chemical reagents corporation of 430g, lanthana content 45 % by weight) mixing and stirring in the water of 8.5kg, obtain the slurries containing zinc oxide, lead oxide and lanthana;
By kaolin (the catalyst asphalt in Shenli Refinery of 2.16kg, containing butt 1.8kg), boehmite (the catalyst Nanjing branch company of 1.33kg, containing butt 1.00kg) and the deionized water of 7.0kg under agitation mix, add the red fuming nitric acid (RFNA) (Beijing Chemical Plant of 200g, chemical pure) stir and make pH=1.8, and be warming up to more than 60 DEG C acidifying 1h.When temperature is reduced to below 40 DEG C, (catalyst Nanjing branch company, containing butt 0.70kg, SiO to add the beta-molecular sieve of above-mentioned mixed serum and 1.0kg
2: Al
2o
3mol ratio=20:1), stir after 1h after mixing and obtain carrier pulp;
Described carrier pulp is adopted NiroBowenNozzleTower
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 obtained by spraying dry is dry 1h at 150 DEG C first, and then at 480 DEG C, roasting 1h obtains carrier;
(2) flooded at twice by the aqueous solution that the deionization of the Nickelous nitrate hexahydrate of the carrier 8.94kg of 8.2kg and 1.10kg is formed, the mixture obtained then at 480 DEG C of roasting 1h, obtains catalyst precarsor after 150 DEG C of dry 4h;
(3) reduce.By catalyst precarsor reductase 12 h at 425 DEG C in hydrogen atmosphere, obtain desulphurization catalyst A1.
The chemical composition of A1 is: zinc oxide content is 31.0 % by weight, and lead oxide content is 14.0 % by weight, and alumina content is 10.0 % by weight, kaolin content is 18.0 % by weight, beta-molecular sieve content is 7 % by weight, and nickel content is 18.0 % by weight, and lanthana content is 2.0 % by weight.
Embodiment 2
The present embodiment is for illustration of the method preparing desulphurization catalyst of the present invention.
By the Zinc oxide powder of 4.05kg, (Beijing Chemical Plant produces, containing butt 4.0kg), bismuth oxide powder (the traditional Chinese medicines chemical reagents corporation of 0.90kg, analyze pure) and cerous nitrate (the traditional Chinese medicines chemical reagents corporation of 0.794kg, purity is greater than 99.0 % by weight) mix in the deionized water of 7.1kg, stir the slurries obtained after 30 minutes containing zinc oxide, bismuth oxide and cerous nitrate;
The zirconium chloride (Beijing Chemical Plant analyzes pure) of 3.23kg is slowly joined in the salpeter solution of the concentration 5 % by weight of 4.4kg and makes pH=2.0, and slowly stirring avoids crystal of zirconium oxide to separate out, and obtains water white zirconium colloidal sol;
Get rectorite (the Qilu Petrochemical catalyst plant of 1.63kg, containing butt 1.30kg) add after deionized water 1.3kg mixes, the hydrochloric acid adding 30 % by weight of 80ml stirs and makes pH=1.8, is warming up to 80 DEG C of aging 2h after acidifying 1h, obtains the mixture containing rectorite; (catalyst Nanjing branch company, containing butt 0.3kg, SiO to add the beta-molecular sieve of above-mentioned slurries, zirconium colloidal sol and 0.43kg again
2: Al
2o
3mol ratio=40:1) be mixed together stir 1h obtain carrier pulp.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulphurization catalyst A2 after reduction.
The chemical composition of A2 is: zinc oxide content is 40.0 % by weight, and bismuth oxide content is 9.0 % by weight, and zirconium dioxide content is 17.0 % by weight, rectorite content is 13.0 % by weight, beta-molecular sieve content is 3.0 % by weight, and nickel content is 15.0 % by weight, and cerium-oxide contents is 3.0 % by weight.
Embodiment 3
The present embodiment is for illustration of the method preparing desulphurization catalyst of the present invention.
The lanthana (traditional Chinese medicines chemical reagents corporation analyzes pure) of the Zinc oxide powder of 4.86kg, the lead oxide of 0.6kg and 400g is mixed in the deionized water of 5kg, stirs the slurries obtained after 30 minutes containing zinc oxide, lead oxide and lanthana;
After being mixed in the water of 3.0kg by the diatomite of 1.03kg (catalyst Nanjing branch company, containing butt 1.00kg), the red fuming nitric acid (RFNA) adding 170g stirs and makes pH=2.0, and is warming up to more than 60 DEG C acidifying 1h and obtains the diatomite after processing;
After the hydrated alumina (catalyst Nanjing branch company, containing butt 1.5kg) of 2.0kg and the deionized water of 8.5kg under agitation being mixed, the red fuming nitric acid (RFNA) adding 160g stirs and makes pH=1.8 and be warming up to more than 60 DEG C acidifying 1h.When temperature is reduced to below 40 DEG C, (catalyst Nanjing branch company, containing butt 0.5kg, SiO to add the diatomite after above-mentioned slurries, process and the USY molecular sieve of 0.6kg
2: Al
2o
3mol ratio=8.5:1) mixing, stir after 1h and obtain carrier pulp.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulphurization catalyst A3 after reduction.
The chemical composition of A3 is: zinc oxide content is 48.0 % by weight, and lead oxide content is 6.0 % by weight, and alumina content is 15.0 % by weight, and diatomite content is 10.0 % by weight, and USY molecular sieve content is 5.0 % by weight, and nickel content is 12.0 % by weight.Lanthana content is 4.0 % by weight.
Embodiment 4
The present embodiment is for illustration of the method preparing desulphurization catalyst of the present invention.
By the Zinc oxide powder (Beijing Chemical Plant of 3.84kg, containing butt 3.8kg), the antimony oxide powder of 0.90kg and lanthanum nitrate (the traditional Chinese medicines chemical reagents corporation of 0.682kg, lanthana content is greater than 44.0 % by weight) mix in the deionized water of 8.3kg, stir the slurries obtaining zinc oxide, antimony oxide and lanthanum nitrate after 30 minutes;
The titanium tetrachloride (Beijing Chemical Plant analyzes pure) of 4.36kg is slowly joined in the deionized water of 5.76kg, and slowly stirring avoids titanium oxide crystal to separate out, and obtains the titanium colloidal sol of pale yellow transparent, pH=1.0;
Get rectorite (the Qilu Petrochemical catalyst plant of 1.85kg, containing butt 1.50kg), add after deionized water 2.5kg mixes, the hydrochloric acid adding 30 % by weight of 75ml stirs and makes pH=1.8, be warming up to 80 DEG C of aging 2h after acidifying 1h, obtain the mixture containing rectorite; (Qilu Petrochemical Company's catalyst plant, containing butt 0.3kg, SiO to add the REHY molecular sieve of above-mentioned slurries, titanium colloidal sol and 0.4kg again
2: Al
2o
3mol ratio=7.2:1) be mixed together rear stirring 1h and obtain carrier pulp.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulphurization catalyst A4 after reduction.
The chemical composition of A4 is: zinc oxide content is 38.0 % by weight, and antimony oxide content is 9.0 % by weight, and content of titanium dioxide is 18.0 % by weight, rectorite content is 15.0 % by weight, nickel content is 14.0 % by weight, and lanthana content is 3.0 % by weight, REHY molecular sieve content is 3.0 % by weight.
Comparative example 1
The mixing and stirring in the water of 8.5kg by the zinc oxide of 3.14kg and the lanthanum carbonate of 430g, obtains the slurries containing zinc oxide and lanthana;
By kaolin (the catalyst asphalt in Shenli Refinery of 2.16kg, containing butt 1.8kg), boehmite (the catalyst Nanjing branch company of 3.19kg, containing butt 2.4kg) and the deionized water of 15.0kg under agitation mix, the red fuming nitric acid (RFNA) adding 500g stirs and makes pH=1.8, and is warming up to more than 60 DEG C acidifying 1h.When temperature is reduced to below 40 DEG C, (catalyst Nanjing branch company, containing butt 0.70kg, SiO to add the beta-molecular sieve of above-mentioned mixed serum and 1.0kg
2: Al
2o
3mol ratio=20:1), stir after 1h after mixing and obtain carrier pulp;
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulphurization catalyst B1 after reduction.
The chemical composition of B1 is: zinc oxide content is 31.0 % by weight, and alumina content is 24.0 % by weight, and kaolin content is 18.0 % by weight, and beta-molecular sieve content is 7 % by weight, and nickel content is 18.0 % by weight, and lanthana content is 2.0 % by weight.
Comparative example 2
The mixing and stirring in the water of 8.5kg by the zinc oxide of 3.14kg and the lead oxide of 1.45kg, obtains the slurries containing zinc oxide and lead oxide;
By kaolin (the catalyst asphalt in Shenli Refinery of 2.16kg, containing butt 1.8kg), boehmite (the catalyst Nanjing branch company of 1.60kg, containing butt 1.20kg) and the deionized water of 7.5kg under agitation mix, the red fuming nitric acid (RFNA) adding 250g stirs and makes pH=1.8, and is warming up to more than 60 DEG C acidifying 1h.When temperature is reduced to below 40 DEG C, (catalyst Nanjing branch company, containing butt 0.70kg, SiO to add the beta-molecular sieve of above-mentioned mixed serum and 1.0kg
2: Al
2o
3mol ratio=20:1), stir after 1h after mixing and obtain carrier pulp;
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulphurization catalyst B2 after reduction.
The chemical composition of B2 is: zinc oxide content is 31.0 % by weight, and lead oxide content is 14.0 % by weight, and alumina content is 12.0 % by weight, and kaolin content is 18.0 % by weight, and the content of beta-molecular sieve is 7 % by weight, and nickel content is 18.0 % by weight.
Comparative example 3
By the lanthanum carbonate of the zinc oxide of 3.14kg, the lead oxide of 1.45kg and 430g mixing and stirring in the water of 8.5kg, obtain the slurries containing zinc oxide, lead oxide and lanthana;
By kaolin (the catalyst asphalt in Shenli Refinery of 2.16kg, containing butt 1.8kg), boehmite (the catalyst Nanjing branch company of 2.26kg, containing butt 1.70kg) and the deionized water of 10.0kg under agitation mix, the red fuming nitric acid (RFNA) adding 340g stirs and makes pH=1.8, and is warming up to more than 60 DEG C acidifying 1h.When temperature is reduced to below 40 DEG C, add above-mentioned mixed serum, after stirring 1h after mixing, obtain carrier pulp;
Method with reference to embodiment 1 is carried out the spray drying forming of carrier pulp and introduces active component nickel, obtains desulphurization catalyst B3 after reduction.
The chemical composition of B3 is: zinc oxide content is 31.0 % by weight, and lead oxide content is 14.0 % by weight, and alumina content is 17.0 % by weight, and kaolin content is 18.0 % by weight, and nickel content is 18.0 % by weight, and lanthana content is 2.0 % by weight.
Embodiment 5
Abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulphurization catalyst A1-A4 and B1-B3.Adopt straight tube wearing and tearing method, method, with reference to RIPP29-90 in " Petrochemical Engineering Analysis method (RIPP) experimental technique ", the results are shown in Table 1.Test the numerical value obtained less, show that abrasion strength resistance is higher.What in table 1, abrasion index was corresponding is fine powder generates when wearing and tearing under certain condition percentage.
In order to the activity of adsorbent in commercial Application process better can be represented, also intensive analysis is carried out to adsorbent after vulcanizing treatment, concrete processing method is: the adsorbent taking appropriate mass is positioned in fluid bed, pass into the gaseous mixture of hydrogen sulfide (50 volume %) and nitrogen (50 volume %), and be heated to 400 DEG C of vulcanizing treatment 1h.The results are shown in Table 1.
Embodiment 6
Desulfurization performance is evaluated.Adopt the micro-anti-experimental provision of fixed bed to carry out HDS evaluation experiment to desulphurization catalyst A1-A4 and B1-B3, the desulphurization catalyst of 16 grams being seated in internal diameter is in 30mm, the long fixed bed reactors for 1m.Raw material hydrocarbon ils is the catalytically cracked gasoline of sulphur concentration 960ppm, and reaction pressure is 1.38MPa, and hydrogen flowing quantity is 6.3L/h, and gasoline flow is 80mL/h, and reaction temperature is 380 DEG C, and the weight space velocity of raw material hydrocarbon ils is 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 in industrial actual motion, HDS evaluation tested after catalyst carry out under the air atmosphere of 480 DEG C regeneration process.Desulphurization catalyst is carried out HDS evaluation experiment, and after regenerating 6 circulations, its activity settles out substantially, represents the activity of catalyst with the sulfur content in the product gasoline after catalyst the 6th stable circulation, and after stable, in product gasoline, sulfur content is as shown in table 1.
Product gasoline is weighed simultaneously and calculate its yield.
The motor octane number (MON) of gasoline and research octane number (RON) (RON) before adopting GB/T503-1995 and GB/T5487-1995 to measure reaction respectively and after the 6th stable circulation, the results are shown in Table 1.
Embodiment 7
Zinc aluminate content measures.The crystalline phase composition of desulphurization catalyst A1-A4 and B1-B3 after the 6th circulation in embodiment 6 is analyzed, measures zinc aluminate content wherein.
Crystal phase analysis adopts X-ray diffraction and phase filtering (R.V.Siriwardane, J.A.Poston, G.Evans, Jr.Ind.Eng.Chem.Res.33 (1994) 2810-2818), through revise Rietveld model (RIQASrietveldAnalysis, operation manual, MaterialData, Inc., Berkley, CA (1999)), analyze different sample, and adopt the method for matching to calculate the crystalline phase composition of sample.Use PhilipsXRG3100 generator (40kV, 30mA drive), Philips3020 digital goniometer, Philips3710MPD computer for controlling and the KevexPSIPeltier being equipped with long fine focusing copper X-ray source to cool silicon detector to carry out all X-ray diffractions and measure.Adopt Kevex4601 ion pump controller, Kevex4608Peltier power supply, Kevex4621 detector bias, Kevex4561A pulse processor and Kevex4911-A single channel analyzer operation Kevex detector.PhilipsAPD4.1c version software is used to obtain diffraction pattern.Use MaterialData, Inc.Riqas3.1c version software (OutokumpuHSCChemistryforWindows: user's manual, OutokumpoResarchOy, Pori, Finland (1999)) to carry out all Rietveld to calculate.The zinc aluminate content of different desulphurization catalyst is as shown in table 1.
Table 1
| A1 | A2 | A3 | A4 | B1 | B2 | B3 | |
| ZnAl 2O 4, % by weight | 0 | 0 | 0 | 0 | 4.8 | 3.5 | 5.5 |
| Abrasion index | 3.0 | 3.8 | 3.8 | 3.2 | 7.8 | 7.0 | 5.0 |
| Yield of gasoline, % | 99.8 | 99.9 | 99.8 | 99.9 | 98.3 | 98.1 | 98.8 |
| Product sulfur content, ppm | 6 | 9 | 10 | 5 | 27 | 30 | 35 |
| △RON | 0.61 | 0.36 | 0.42 | 0.53 | -0.48 | -0.57 | -0.63 |
| △MON | 0.57 | 0.34 | 0.40 | 0.48 | -0.48 | -0.49 | -0.55 |
| △(RON+MON)/2 | 0.59 | 0.35 | 0.41 | 0.50 | -0.48 | -0.53 | -0.59 |
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 table 1, desulphurization catalyst provided by the invention has better desulphurizing activated and activity stability.Desulphurization catalyst has better abrasion strength resistance, thus makes desulphurization catalyst have longer service life.
Claims (18)
1. a desulphurization catalyst, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contains:
1) heat-resistant inorganic oxide of 5-35 % by weight, described heat-resistant inorganic oxide is selected from least one in aluminium oxide, titanium dioxide, zirconium dioxide and tin ash;
2) silica source of 5-35 % by weight;
3) first metal oxide of 10-70 % by weight, described first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element;
4) second metal oxide of 2-20 % by weight, described second metal oxide is selected from least one in lead oxide, antimony oxide and bismuth oxide;
5) metallic promoter agent of 3-30 % by weight, described metallic promoter agent is selected from least one in cobalt, nickel, iron and manganese;
6) in the rare-earth oxide of the 0.5-10 % by weight of rare earth oxide;
7) molecular sieve of 1-20 % by weight, described molecular sieve is the molecular sieve with BEA and/or FAU structure.
2. desulphurization catalyst according to claim 1, wherein, with the gross weight of this desulphurization catalyst for benchmark, the content of described heat-resistant inorganic oxide is 10-25 % by weight, the content of described silica source is 10-25 % by weight, the content of described first metal oxide is 35-54 % by weight, the content of described second metal oxide is 5-15 % by weight, the content of described metallic promoter agent is 10-20 % by weight, described rare-earth oxide is in the content of rare earth oxide for 1-5 % by weight, and the content of described molecular sieve is 2-10 % by weight.
3. desulphurization catalyst according to claim 1 and 2, wherein, described rare-earth oxide is at least one in the oxide of lanthanum, cerium and neodymium.
4. desulphurization catalyst according to claim 1 and 2, wherein, described first metal oxide is at least one in zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide.
5. desulphurization catalyst according to claim 1 and 2, wherein, described silica source is selected from least one in laminated clay column, diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
6. desulphurization catalyst according to claim 1 and 2, wherein, described molecular sieve is at least one in X-type molecular sieve, Y zeolite, USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta-molecular sieve.
7. the preparation method of the desulphurization catalyst in claim 1-6 described in any one, the method comprises:
(1) precursor of rare earth compound, the first metal oxide, the second metal oxide and water are mixed to get slurries;
(2) heat-resistant inorganic oxide binding agent, silica source, water are mixed with acidic liquid, and contact with described slurries, the molecular sieve with BEA and/or FAU structure and form carrier pulp, again described carrier pulp is carried out shaping, first dry and the first roasting, obtain carrier;
(3) on described carrier, introduce the precursor of metallic promoter agent, and carry out second dry and the second roasting, obtain catalyst precarsor;
(4) described catalyst precarsor is reduced under hydrogen atmosphere, obtain desulphurization catalyst.
8. preparation method according to claim 7, wherein, the precursor of described second metal oxide is at least one in lead oxide, antimony oxide and bismuth oxide; Or at least one in the carbonate of metallic lead, antimony and bismuth, nitrate, chloride and hydroxide.
9. preparation method according to claim 7, wherein, described heat-resistant inorganic oxide binding agent is heat-resistant inorganic oxide or the material that can change heat-resistant inorganic oxide under the condition of described first roasting into.
10. preparation method according to claim 7, wherein, described rare earth compound is at least one in the carbonate of rare earth metal, bicarbonate, nitrate, chloride, formates and acetate.
11. preparation methods according to claim 7, wherein, the precursor of described metallic promoter agent is at least one in the acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide.
12. preparation method according to claim 7, wherein, carrier is introduced the method for the precursor of described metallic promoter agent for dipping or precipitation.
13. preparation method according to claim 7, wherein, described acidic liquid is acid or aqueous acid, and described acid is selected from water-soluble inorganic acid and/or organic acid.
14. preparation methods according to claim 7, wherein, the temperature of described first drying is 80-120 DEG C, and the time of described first drying is 0.5-24h; The temperature of described first roasting is 300-700 DEG C, and time of described first roasting is at least 0.5h.
15. preparation methods according to claim 7, wherein, the temperature of described second drying is 50-300 DEG C, and the time of described second drying is 0.5-8h; The temperature of described second roasting is 300-700 DEG C, and the time of described second roasting is 0.5-4h.
16. preparation methods according to claim 7, wherein, the temperature of described reduction is 300-600 DEG C, and the time of described reduction is 0.5-6h, and in described hydrogen atmosphere, hydrogen content is 10-60 volume %.
The desulphurization catalyst that preparation method in 17. claim 7-16 described in any one obtains.
The method of 18. 1 kinds of desulfurization of hydrocarbon oil, the method comprises: in a hydrogen atmosphere, and by the hydrodesulfurization catalyst in hydrocarbon oil containing surphur and claim 1-6 and 17 described in any one, the temperature of described contact is 350-500 DEG C, and the pressure of described contact is 0.5-4MPa.
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| CN110252323B (en) * | 2019-05-31 | 2021-08-17 | 南京工业大学 | Denitration and demercuration double-effect catalyst and preparation method thereof |
| CN112742385A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Catalyst for gasoline catalytic conversion, preparation method thereof and gasoline catalytic conversion method |
| CN112742385B (en) * | 2019-10-31 | 2023-11-10 | 中国石油化工股份有限公司 | Catalyst for catalytic conversion of gasoline, preparation method thereof and catalytic conversion method of gasoline |
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