CN105583003A - Desulphurization catalyst and preparation method thereof as well as hydrocarbon oil desulfurizing method - Google Patents
Desulphurization catalyst and preparation method thereof as well as hydrocarbon oil desulfurizing method Download PDFInfo
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Abstract
The invention discloses a desulphurization catalyst and a preparation method thereof as well as a hydrocarbon oil desulfurizing method. The desulfurization catalyst comprises the following components, on the basis of the total weight of the desulfurization catalyst, by weight: 1) 5-35% of a heatproof inorganic oxide; 2) 5-35% of a silicon oxide source; 3) 10-70% of a first metal oxide; 4) 2-20% of a second metal oxide; 5) 3-30% of a metal promoter; 6) 0.5-10 % of a rare-earth metal oxide based on rare earth oxide; and 7) 1-20% of a phosphorous and aluminum molecular sieve. The desulphurization catalyst has better desulphurization 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 desulphurization catalyst of preparing the method for desulphurization catalyst and being obtained by the method, and use this desulphurization catalyst to carry out the method for desulfurization of hydrocarbon oil.
Background technology
The oxysulfide producing after combustion of sulfur in vehicle fuel, can suppress the activity of the noble metal catalyst in vehicle exhaust converter and can make it to occur irreversibly poisoning. Thereby make to contain in vehicle exhaust unburned non-methane hydrocarbon and nitrogen oxide and carbon monoxide, these discharge gas are easily formed photochemical fog by day photocatalysis, cause acid rain, the oxysulfide itself in atmosphere is also the one of the main reasons that forms acid rain simultaneously. Along with the pay attention to day by day of people to environmental protection, environmental regulation is also day by day strict, and the sulfur content of reduction 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 must just can meet through deep desulfuration the requirement of environmental protection.
At present, the process for deep desulphurization of oil product mainly contains hydrofinishing and two kinds of methods of adsorption desulfurize, but the problem of originating due to hydrogen in China 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 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 aspect the sulfur-containing compound removing 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 advantages of the aspects such as better heat transfer and pressure drop compared with fixed-bed process, therefore has broad application prospects. Fluidized-bed reactor is general 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 that is applicable to remove sulphur from cracking gasoline and diesel fuel, formed by zinc oxide, silica, oxidation al and ni, wherein nickel exists substantially to reduce valence state, and its amount can remove sulphur from the cracking gasoline that contacts with described nickeliferous adsorbent composition under desulfurization condition or diesel fuel stream. Said composition forms particle by the compound particles granulation that zinc oxide, silica and aluminium oxide are formed, and after dry, roasting, with nickel or nickel compound containing dipping, drier, roasting, reduction obtain.
CN1382071A discloses a kind of adsorbent composition that is applicable to remove sulphur from cracking gasoline and diesel fuel, formed by zinc oxide, silica, aluminium oxide and cobalt, wherein cobalt exists substantially to reduce valence state, and its amount can remove sulphur from flow with described cracking gasoline contact containing cobalt adsorbent composition or diesel fuel under desulfurization condition. In CN1355727A and CN1382071A, all only mention desulphurizing activatedly, all do not introduce for adsorbent physical and chemical performance (such as abrasion strength resistance) and stability.
The disclosed adsorbent of US6150300, CN1130253A and CN1258396A is: the granular adsorbent composition of the mixture that comprises zinc oxide, silica, aluminium oxide, reduction valence state nickel or cobalt. Preparation method adopts the methods such as shearing that mixed to silica, aluminium oxide and zinc oxide merga pass comminutor is prepared to solid particle, makes adsorbent thereby flood nickel after drying and roasting. Although the adsorbent of these patent Introductions has good desulfurization performance, for its physical and chemical performance, be mainly that tear strength is not introduced in patent.
CN1208124A discloses and has adopted promoter metals to flood the adsorbing agent carrier that comprises zinc oxide, expanded perlite and aluminium oxide as cobalt and nickel, then under suitable temperature, reduces this promoter, for the preparation of the adsorbent that removes cracking gasoline medium sulphide content.
CN1627988A discloses a kind of adsorbent composition that is 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 in the time that cracking gasoline or diesel fuel stream are contacted under desulfurization condition with it, amount that causes desulfurization from the material stream of cracking gasoline or diesel fuel is existed, 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) dry this mixture, to form the mixture of drying; C) calcine the mixture of this drying, to form the mixture through calcining; D) under suitable condition this mixture through calcining is reduced with suitable reducing agent, to produce the composition in it with the co-catalyst content of 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, mix to form its mixture containing earth silicon material, aluminium oxide; B) dry this of described mixture mixed to form the first drying mixture; C) described the first drying mixture is calcined to form first through calcining mixt; D) promoter is attached to described first within calcining mixt or on to form through promoting mixture; E) make described through promote mixture contact to form through contact mixture with the acid that is selected from citric acid, tartaric acid and combination thereof; F) by described dry to form the second drying mixture through contact mixture; G) described the second drying mixture is calcined to form second through calcining mixt; H) adopt under suitable condition applicable reducing agent reduce described second through calcining mixt to produce the composition that wherein contains 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 silicon, al composition in the time of desulphurization reaction and oxidation regeneration easily and in carrier generate zinc silicate and/or zinc aluminate, cause adsorbent activity to reduce. As can be seen here, need to provide a kind of more new catalyst of high desulfurization activity and abrasion resistance properties that has.
Summary of the invention
The object of the invention is desulphurizing activated low, the structural instability of adsorbent in order to overcome prior art and the poor defect of abrasion resistance properties, the method for a kind of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil is provided.
To achieve these goals, the invention provides a kind of desulphurization catalyst, taking the gross weight of this desulphurization catalyst as 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) the first metal oxide of 10-70 % by weight, described the first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element; 4) the second metal oxide of 2-20 % by weight, described the 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) phosphate aluminium molecular sieve of 1-20 % by weight.
The present invention also provides the preparation method of desulphurization catalyst of the present invention, and the method comprises: precursor and the water of rare earth compound, the first metal oxide, the second metal oxide are mixed to get slurries by (1); (2) heat-resistant inorganic oxide binding agent, silica source, water are mixed with acidic liquid, and contact formation carrier pulp with described slurries, more described carrier pulp, phosphate aluminium molecular sieve are carried out to moulding, 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 being prepared by method provided by the invention.
A kind of method that the invention provides desulfurization of hydrocarbon oil, the method comprises: under hydrogen atmosphere, hydrocarbon oil containing surphur is contacted with desulphurization 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.
In desulphurization catalyst provided by the invention, containing the first metal oxide mixes with the second metal oxide as sulphur absorption constituent element, the second metal oxide can effectively reduce the silicon in the first metal oxide and carrier, the effect of al composition, reduce the silicate and/or the aluminate that generate the first metal, thereby make this desulphurization catalyst can at lower temperature, absorb sulphur and through repeatedly reacting and regenerative process, still there is better desulphurizing activated and activity stability.
In desulphurization catalyst provided by the invention, contain rare earth oxide, can further effectively strengthen the effect that weakens that the second metal oxide acts on mutually to the first metal oxide and silicon, al composition.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, detailed description of the invention described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of desulphurization catalyst, taking the gross weight of this desulphurization catalyst as 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) the first metal oxide of 10-70 % by weight, described the first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element; 4) the second metal oxide of 2-20 % by weight, described the 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) phosphate aluminium molecular sieve of 1-20 % by weight.
Preferably, taking the gross weight of this desulphurization catalyst as 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 the first metal oxide is 35-54 % by weight, and the content of described the 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 taking the content of rare earth oxide as 1-5 % by weight, and the content of described phosphate aluminium molecular sieve is 2-10 % by weight.
According to the present invention, described the first metal oxide is the metal oxide with storage sulphur performance, and preferably, described the 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 the first metal oxide is at least one in zinc oxide, molybdenum oxide and vanadium oxide; Most preferably described the first metal oxide is zinc oxide.
According to the present invention, described the second metal oxide can suppress described the first metal oxide in the time repeatedly experiencing desulphurization reaction under high temperature and regenerative response, have an effect with the silicon, the al composition that contain in described desulphurization catalyst, reduce the loss of described the first metal oxide.
According to the present invention, described heat-resistant inorganic oxide can be for providing cementation between each component 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 be for providing cementation between each component in described desulphurization catalyst. Under preferable case, described silica source can be the natural minerals that pure silica or silica content are greater than 45 % by weight. 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. In natural minerals, can also contain other component as Al2O3、K2O、CaO、MgO、Fe2O3、TiO2Deng. In the present invention, the amount of other components that contain in described silica source still be 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 preferably, 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 improving the effect of catalyst abrasion intensity, can stablize the skeleton of heat-resistant inorganic oxide simultaneously, further weaken the interaction between the first metal oxide and silicon, al composition, improve activity and the stability of desulfurization. Preferably, described rare-earth oxide is at least one in the oxide of lanthanum, cerium and neodymium.
According to the present invention, under preferable case, described phosphate aluminium molecular sieve is selected from least one in SAPO molecular sieve and the wide-aperture SAPO molecular sieve of SAPO molecular sieve, mesoporous of small-bore. The SAPO molecular sieve of small-bore can be selected from least one in SAPO-34, SAPO-17, SAPO-18, SAPO-26, SAPO-33, SAPO-34, SAPO-35, SAPO-39, SAPO-42, SAPO-43, SAPO-44 and SAPO-47; The SAPO molecular sieve of mesoporous can be selected from least one in SAPO-11, SAPO-31 and SAPO-41; Wide-aperture SAPO molecular sieve can be selected from least one in SAPO-5, SAPO-36, SAPO-37, SAPO-40 and SAPO-46. Preferably, described phosphate aluminium molecular sieve is at least one in SAPO-5, SAPO-11, SAPO-31 and SAPO-34 molecular sieve. Described phosphate aluminium molecular sieve is nearly body silicoaluminophosphate, and silicon is introduced in aluminum phosphate skeleton and obtained, and its skeleton is by PO4 +、AlO4 -And SiO2Tetrahedron composition. Described phosphate aluminium molecular sieve comprises 13 kinds of three-dimensional microporous framework structures, and its hole size is, pore volume is 0.18-0.48cm3/ g. The hole size of SAPO-5, SAPO-11, SAPO-31 and SAPO-34 molecular sieve is respectively(12 ring),(10 ring),(10 ring) and(8 ring); Pore volume is respectively 0.31,0.18,0.42 and 0.42cm3/ g. More preferably, described phosphate aluminium molecular sieve is at least one in SAPO-11, SAPO-31 and SAPO-34. The SiO of described SAPO molecular sieve2：Al2O3Mol ratio be 0.02-3:1; Preferably, the SiO of described SAPO molecular sieve2：Al2O3Mol ratio be 0.025-2:1.
In the present invention, thereby add phosphate aluminium molecular sieve to have to promote straight-chain hydrocarbons isomerization in gasoline to improve effect or the effect of gasoline products octane number.
The present invention also provides the preparation method of desulphurization catalyst of the present invention, and the method comprises: precursor and the water of rare earth compound, the first metal oxide, the second metal oxide are mixed to get slurries by (1); (2) heat-resistant inorganic oxide binding agent, silica source, water are mixed with acidic liquid, and contact formation carrier pulp with described slurries, phosphate aluminium molecular sieve, more described carrier pulp is carried out to moulding, 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 the 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 aluminium colloidal sol, 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 be for providing cementation between each component in described desulphurization catalyst. Under preferable case, described silica source can be the natural crystal that silica or silica content are greater than 45 % by weight. Preferably, described silica source can be at least one in laminated clay column, diatomite, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel. 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 being formed by alumina source. In silica source, the amount of contained aluminium oxide still be can be regarded as the amount of silica source. In the desulphurization catalyst being made by method provided by the invention, the content of each component calculates according to inventory.
In the present invention, the precursor of described the second metal oxide is described the second metal oxide or the material that can change described the second metal oxide under the condition of described the first roasting into. Under preferable case, the precursor of described the 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 be for changing the material of the oxide of metallic promoter agent under the condition of described the second roasting. Under preferable case, the precursor of described metallic promoter agent can be at least one in acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of metallic promoter agent.
In the present invention, under preferable case, described rare earth compound can be at least one in carbonate, bicarbonate, nitrate, chloride, formates and the acetate of rare earth metal; Preferably, described rare earth compound can be at least one in carbonate, bicarbonate, formates and the acetate of rare earth metal. Wherein, described rare earth metal is preferably at least one in lanthanum, cerium and neodymium.
In the present invention, as previously mentioned, this is no longer going to repeat them for described the first metal oxide, metallic promoter agent and phosphate aluminium molecular sieve.
The preparation method's of desulphurization catalyst provided by the invention step (1) and (2) are for the preparation of carrier.
In step of the present invention (1), adding of described the first metal oxide can be oxide powder form, can be also to use with slurries form after the first metal oxide is prepared as to slurries again.
In the present invention, add the precursor of described the second metal oxide, can directly add at least one the powder in lead oxide, antimony oxide and bismuth oxide, or be added in the material that can change described the second metal oxide under the condition of described the first roasting into, as at least one in the carbonate of metallic lead, antimony and bismuth, nitrate, chloride and hydroxide; Also after at least one in lead oxide, antimony oxide and bismuth oxide can being prepared as to slurries, use with slurries form again.
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), the weight ratio that feeds intake of described silica source and described heat-resistant inorganic oxide binding agent is 0.4-2:1, 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: by heat-resistant inorganic oxide binding agent and silica source respectively water and acidic liquid carry out after acidification, then the mixture obtaining is separately mixed into described slurries; Wherein, in the time that described heat-resistant inorganic oxide binding agent is non-al binder, the mixture obtaining is colloidal sol. In addition, in the time that described heat-resistant inorganic oxide binding agent is alumina binder, described mixing can also be: by water, acidic liquid, alumina binder and silica source mixing, aging, form acidifying slurries. Preferably, the pH value of described acidifying slurries is 1-5, is preferably 1.5-4; The solid content of described acidifying 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, for example, can be at least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
In the present invention, moulding described in step (2) can be shaped to extrudate, sheet, pill, ball or micro-spherical particle by described slurries. For example, when described slurries are dough or paste mixture, can make described mixture moulding (preferably extrusion molding) form particle, preferably diameter is at 1-8mm, length is at the cylindrical extrudate of 2-5mm, then makes the extrudate of gained be dried, roasting. If gained mixture is wet mixture form, can make this mixture multiviscosisty, through super-dry aftershaping. More preferably slurries are slurries form, are the microballoon of 20-200 micron by the dry formation granularity of spraying, and reach the object of moulding. Dry for the ease of spraying, the solid content of dry front described carrier pulp is 10-40 % by weight, is preferably 20-35 % by weight. In step (2), obtain can also comprising and adding water in the process of described carrier pulp, there is no particular limitation for the addition of water, as long as the carrier pulp obtaining meets the solid content of above-mentioned carrier pulp.
In the present invention, the described first condition dry and the first roasting can be conventionally known to one of skill in the art, and under preferable case, described the first dry temperature is 80-150 DEG C, and described the first dry time is 0.5-24h; The temperature of described the first roasting is 300-700 DEG C, and the time of described the first roasting is 0.5h at least. Preferably, the temperature of described the first roasting is 400-500 DEG C, and the time of described the first roasting is 0.5-100h, and more preferably the time of described the first roasting is 0.5-10h.
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 acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of metallic promoter agent.
According to the present invention, under preferable case, the method for introducing the precursor of metallic promoter agent on carrier is dipping or precipitation. Described dipping can be solution or the suspension impregnation carrier of the precursor by metallic promoter agent; Described precipitation can be that the solution of the precursor of metallic promoter agent or suspension are mixed with carrier, then adds ammoniacal liquor that the precursor of metallic promoter agent is deposited on carrier.
In the present invention, the described second condition dry and the second roasting can be conventionally known to one of skill in the art, and under preferable case, described the second dry temperature is 50-300 DEG C, and described the second dry time is 0.5-8h; The temperature of described the second roasting is 300-700 DEG C, and the time of described the second roasting is 0.5-4h; Preferably, described the second dry temperature is 100-250 DEG C, and described the second dry time is 1-5h; The temperature of described the second roasting is 400-500 DEG C, and the time of described the second roasting is 1-3h. Described the second roasting can be carried out under having that oxygen or oxygen-containing gas 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, obtain 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 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, step (4) can be carried out catalyst precarsor reduction immediately making after catalyst precarsor, and also (for before desulfurization absorption) is carried out before use. Because metallic promoter agent is easily oxidized, and metallic promoter agent in catalyst precarsor exists with oxide form, and therefore for ease of transport, preferred steps (4) is carried out catalyst precarsor reduction carrying out before desulfurization absorption. The described metal being reduced in the oxide that makes metallic promoter agent exists with reduction-state substantially, obtains desulphurization catalyst of the present invention.
According to preparation method provided by the invention, described heat-resistant inorganic oxide binding agent, silica source, the first metal oxide, the precursor of the second metal oxide, rare earth compound, the addition of the precursor of phosphate aluminium molecular sieve and metallic promoter agent, in the desulphurization catalyst that makes to obtain, taking the gross weight of this desulphurization catalyst as benchmark, the heat-resistant inorganic oxide that contains 5-35 % by weight, the silica source of 5-35 % by weight, the first metal oxide of 10-70 % by weight, the second metal oxide of 2-20 % by weight, the metallic promoter agent of 3-30 % by weight, the phosphate aluminium molecular sieve of 1-20 % by weight and in the rare-earth oxide of the 0.5-10 % by weight of rare earth oxide.
Preferably, taking the gross weight of this desulphurization catalyst as 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 the first metal oxide is 35-54 % by weight, and the content of described the 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 taking the content of rare earth oxide as 1-5 % by weight, and the content of described phosphate aluminium molecular sieve is 2-10 % by weight.
The present invention also provides the desulphurization catalyst being 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.
A kind of method that the invention provides desulfurization of hydrocarbon oil, the method comprises: under hydrogen atmosphere, hydrocarbon oil containing surphur is contacted with desulphurization 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 this process in hydrocarbon ils is adsorbed on catalyst, thereby obtains the hydrocarbon ils of low sulfur content.
The method of desulfurization of hydrocarbon oil provided by the invention is preferably carried out in fluidized-bed reactor, i.e. described contact is preferably carried out in 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, re-starting before desulfurization of hydrocarbon oil, also need to reduce under hydrogen atmosphere, and 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.
It is hydrocarbon or its any cut of 40 to 210 DEG C that term used herein " cracking gasoline " means boiling range, is from making larger hydrocarbon molecule be cracked into the product of more micromolecular heat or catalytic process. Applicable thermal cracking process includes, but are not limited to coking, thermal cracking and visbreaking etc. and combination thereof. The example of applicable catalytic cracking process includes but not limited to fluid catalystic cracking and RFCC etc. and combination thereof. Therefore, applicable catalytically cracked gasoline includes but not limited to coker gasoline, pressure gasoline, visbreaking gasoline, fluid catalystic cracking gasoline and residual oil cracking gasoline and combination thereof. In some cases, can be by described cracking gasoline fractionation and/or hydrotreatment before desulfurization during in the methods of the invention as hydrocarbon-containifluids fluids.
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 hydrotreatment diesel oil etc. and combination thereof.
Term used herein " sulphur " represents that any type of element sulphur is if hydrocarbon-containifluids fluids is as the normal organosulfur compound existing in cracking gasoline or diesel fuel. The sulphur existing in hydrocarbon-containifluids fluids of the present invention includes but not limited to carbonyl sulfide (COS), carbon disulfide (CS2), mercaptan or other thiophenes etc. and combination thereof, especially comprise thiophene, benzothiophene, alkylthrophene, alkylbenzene bithiophene and methyldibenzothiophene, and the normal larger thiophenes of molecular weight existing in diesel fuel.
Desulphurization catalyst provided by the invention has good abrasion strength resistance and desulphurizing activated, can greatly increase the service life, and is applicable to adsorption desulfurize process.
Below will describe 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 illustrating the method for preparing desulphurization catalyst of the present invention.
(1) prepare carrier. By the zinc oxide of 3.14kg (traditional Chinese medicines chemical reagents corporation, 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 that contain zinc oxide, lead oxide and lanthana;
By the kaolin of 2.16kg (catalyst asphalt in Shenli Refinery, 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. In the time that temperature is reduced to below 40 DEG C, add above-mentioned mixed serum and 1.0kg SAPO-11 (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO2:Al2O3Mol ratio=1:1), after mixing, stir after 1h and obtain carrier pulp;
Described carrier pulp is adopted to NiroBowenNozzleTowerTMIt is dry that the spray dryer of model is sprayed, and spraying drying pressure is 8.5 to 9.5MPa, and inlet temperature is below 500 DEG C, and outlet temperature is about 150 DEG C. By first dry 1h at 150 DEG C of the dry microballoon obtaining of spraying, then at 480 DEG C, roasting 1h obtains carrier;
(2) carrier of 8.2kg is flooded at twice with the aqueous solution that the Nickelous nitrate hexahydrate of 8.91kg and the deionization of 1.10kg form, the mixture obtaining then at 480 DEG C of roasting 1h, obtains catalyst precarsor after 150 DEG C of dry 4h;
(3) reduction. 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, SAPO-11 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 illustrating the method for 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 six water cerous nitrate (the traditional Chinese medicines chemical reagents corporations of 0.794kg, purity is greater than 99.0 % by weight) in the deionized water of 7.1kg, mix, stir and after 30 minutes, obtain the slurries that contain zinc oxide, bismuth oxide and cerous nitrate;
The zirconium chloride of 3.23kg (Beijing Chemical Plant analyzes pure) is slowly joined in the salpeter solution of concentration 5 % by weight of 4.4kg and make pH=2.0, and slowly stir and avoid crystal of zirconium oxide to separate out, obtain water white zirconium colloidal sol;
Get rectorite (the Qilu Petrochemical catalyst plant of 1.62kg, containing butt 1.30kg) add deionized water 1.4kg to mix after, add the hydrochloric acid stirring of 30 % by weight of 90ml to make pH=2.0, after acidifying 1h, be warming up to 80 DEG C of aging 2h, obtain the mixture containing rectorite; Add again the SAPO-31 molecular sieve of above-mentioned slurries, zirconium colloidal sol and 0.43kg (to contain butt 0.3kg, SiO2:Al2O3Mol ratio=0.3:1) be mixed together stir 1h obtain carrier pulp.
Carry out the spray drying forming of carrier pulp and introduce active component nickel with reference to the method for embodiment 1, after reduction, obtaining desulphurization catalyst A2.
The chemical composition of A2 is: zinc oxide content is 40.0 % by weight, bismuth oxide content is 9.0 % by weight, zirconium dioxide content is 17.0 % by weight, rectorite content is 13.0 % by weight, SAPO-31 molecular sieve content is 3.0 % by weight, nickel content is 15.0 % by weight, and cerium oxide content is 3.0 % by weight.
Embodiment 3
The present embodiment is for illustrating the method for preparing desulphurization catalyst of the present invention.
The lanthana of the antimony oxide of the Zinc oxide powder of 4.86kg, 0.6kg and 400g (traditional Chinese medicines chemical reagents corporation analyzes pure) is mixed in the deionized water of 5kg, stir and after 30 minutes, obtain the slurries that contain zinc oxide, antimony oxide and lanthana;
After the diatomite of 1.03kg (catalyst Nanjing branch company, containing butt 1.00kg) is mixed in the water of 3.0kg, add the red fuming nitric acid (RFNA) of 170g to stir and make pH=2.0, and be warming up to more than 60 DEG C acidifying 1h and obtain diatomite after treatment;
After the deionized water of the hydrated alumina of 2.0kg (catalyst Nanjing branch company, containing butt 1.5kg) and 8.0kg is under agitation mixed, add the red fuming nitric acid (RFNA) stirring of 170g to make pH=1.8 and be warming up to more than 60 DEG C acidifying 1h. In the time that temperature is reduced to below 40 DEG C, add above-mentioned slurries, diatomite after treatment and 0.6kg SAPO-34 (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.5kg, SiO2:Al2O3Mol ratio=0.25:1) stir after 1h after mixing and obtain carrier pulp.
Carry out the spray drying forming of carrier pulp and introduce active component nickel with reference to the method for embodiment 1, after reduction, obtaining desulphurization catalyst A3.
The chemical composition of A3 is: zinc oxide content is 48.0 % by weight, and antimony oxide content is 6.0 % by weight, and alumina content is 15.0 % by weight, and diatomite content is 10.0 % by weight, and SAPO-34 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 illustrating the method for preparing desulphurization catalyst of the present invention.
By the Zinc oxide powder (Beijing Chemical Plant of 3.84kg, containing butt 3.8kg), the lead oxide powder of 0.90kg and the lanthanum nitrate of 0.682kg (traditional Chinese medicines chemical reagents corporation, purity is greater than 99.0 % by weight) in the deionized water of 8.3kg, mix, stir the slurries that obtain zinc oxide, lead oxide and lanthanum nitrate after 30 minutes;
The titanium tetrachloride of 4.36kg (Beijing Chemical Plant analyzes pure) is slowly joined in the deionized water of 5.76kg, and slowly stir and avoid titanium oxide crystal to separate out, obtain faint yellow transparent titanium colloidal sol, pH=1.0;
Get rectorite (the Qilu Petrochemical catalyst plant of 1.85kg, containing butt 1.50kg), after adding deionized water 2.5kg to mix, add the hydrochloric acid of 30 % by weight of 75ml to stir, after acidifying 1h, be warming up to 80 DEG C of aging 2h, obtain the mixture containing rectorite; (Shanghai Shen Tan environmental friendly material Co., Ltd contains butt 0.3kg, SiO to add above-mentioned slurries, titanium colloidal sol and 0.42kgSAPO-5 molecular sieve again2:Al2O3Mol ratio=0.15:1) be mixed together rear stirring 1h and obtain carrier pulp.
Carry out the spray drying forming of carrier pulp and introduce active component nickel with reference to the method for embodiment 1, after reduction, obtaining desulphurization catalyst A4.
The chemical composition of A4 is: zinc oxide content is 38.0 % by weight, and lead 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, and SAPO-5 molecular sieve content is 3.0 % by weight.
Comparative example 1
By the lanthanum carbonate of the zinc oxide of 3.14kg and 430g mixing and stirring in the water of 8.5kg, obtain the slurries that contain zinc oxide and lanthana;
By the kaolin of 2.16kg (catalyst asphalt in Shenli Refinery, containing butt 1.8kg), boehmite (the catalyst Nanjing branch company of 3.19kg, containing butt 2.40kg) and the deionized water of 15.0kg under agitation mix, add the red fuming nitric acid (RFNA) stirring of 500g to make pH=1.8, and be warming up to more than 60 DEG C acidifying 1h. In the time that temperature is reduced to below 40 DEG C, add above-mentioned mixed serum and 1.0kg SAPO-11 (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO2:Al2O3Mol ratio=1:1), after mixing, stir after 1h and obtain carrier pulp;
Carry out the spray drying forming of carrier pulp and introduce active component nickel with reference to the method for embodiment 1, after reduction, obtaining desulphurization catalyst B1.
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 SAPO-11 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
By the lead oxide of the zinc oxide of 3.14kg and 1.45kg mixing and stirring in the water of 8.5kg, obtain the slurries that contain zinc oxide and lead oxide;
By the kaolin of 2.16kg (catalyst asphalt in Shenli Refinery, 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, add the red fuming nitric acid (RFNA) stirring of 250g to make pH=1.8, and be warming up to more than 60 DEG C acidifying 1h. In the time that temperature is reduced to below 40 DEG C, add above-mentioned mixed serum and 1.0kg SAPO-11 (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO2:Al2O3Mol ratio=1:1), after mixing, stir after 1h and obtain carrier pulp;
Carry out the spray drying forming of carrier pulp and introduce active component nickel with reference to the method for embodiment 1, after reduction, obtaining desulphurization catalyst B2.
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 SAPO-11 molecular sieve content is 7 % by weight, and nickel content is 18.0 % by weight.
Comparative example 3
By the lanthanum carbonate of the lead oxide of the zinc oxide of 3.14kg, 1.45kg and 430g mixing and stirring in the water of 8.5kg, obtain the slurries that contain zinc oxide, lead oxide and lanthana;
By the kaolin of 2.16kg (catalyst asphalt in Shenli Refinery, 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, add the red fuming nitric acid (RFNA) stirring of 340g to make pH=1.8, and be warming up to more than 60 DEG C acidifying 1h. In the time that temperature is reduced to below 40 DEG C, add above-mentioned mixed serum, after mixing, after stirring 1h, obtain carrier pulp;
Carry out the spray drying forming of carrier pulp and introduce active component nickel with reference to the method for embodiment 1, after reduction, obtaining desulphurization catalyst B3.
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. Desulphurization catalyst A1-A4 and B1-B3 are carried out to abrasion strength resistance test. 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. The numerical value that test obtains is less, shows that abrasion strength resistance is higher. What in table 1, abrasion index was corresponding is fine powder generates while wearing and tearing under certain condition percentage.
In order better to represent the activity of adsorbent in commercial Application process, adsorbent after vulcanizing treatment is also carried out to intensive analysis, concrete processing method is: the adsorbent that takes 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 desulfurization evaluation experimental to desulphurization catalyst A1-A4 and B1-B3, it is in 30mm, the long fixed bed reactors for 1m that the desulphurization catalyst of 16 grams is seated in to internal diameter. 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, by off-line chromatogram analysis method, adopts the GC6890-SCD instrument of An Jielun company to measure. In order accurately to symbolize the activity of desulphurization catalyst in industrial actual motion, the processing of regenerating under the air atmosphere of 480 DEG C of the catalyst after desulfurization evaluation experimental completes. Desulphurization catalyst is carried out to desulfurization evaluation experimental, and after 6 circulations of regenerating, its activity settles out substantially, represents the activity of catalyst with the sulfur content in the product gasoline after the 6th stable circulation of catalyst, and in stable rear product gasoline, sulfur content is as shown in table 1.
Product gasoline is weighed and calculated its yield simultaneously.
Motor octane number (MON) and the research octane number (RON) (RON) of gasoline before adopting respectively GB/T503-1995 and GB/T5487-1995 to measure reaction and after the 6th stable circulation, the results are shown in Table 1.
Embodiment 7
Zinc aluminate assay. The crystalline phase composition of desulphurization catalyst A1-A4 after the 6th circulation in embodiment 6 and B1-B3 is analyzed, measured 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), Rietveld model (RIQASrietveldAnalysis, operation manual through revising, MaterialData, Inc., Berkley, CA (1999)), analyze different samples, and adopt the method for matching to calculate the crystalline phase composition of sample. PhilipsXRG3100 generator (40kV, 30mA drive), Philips3020 digital angle measurement instrument, Philips3710MPD control computer and the cooling silicon detector of KevexPSIPeltier that use is equipped with long fine focusing copper X-ray source carry out all X-ray diffraction measurements. Adopt Kevex4601 ionic pump controller, Kevex4608Peltier power supply, Kevex4621 detector bias, Kevex4561A pulse processor and Kevex4911-A single channel analyzer operation Kevex detector. Use PhilipsAPD4.1c version software to obtain diffraction pattern. Use MaterialData, Inc.Riqas3.1c version software (OutokumpuHSCChemistryforWindows: user's manual, OutokumpoResarchOy, Pori, Finland (1999)) carries out all Rietveld and calculates. The zinc aluminate content of different desulphurization catalysts is as shown in table 1.
Table 1
| A1 | A2 | A3 | A4 | B1 | B2 | B3 | |
| ZnAl2O4, % 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 | 98.5 | 98.3 | 98.8 |
| Product sulfur content, ppm | 6 | 9 | 10 | 8 | 23 | 27 | 35 |
| △RON | 0.62 | 0.43 | 0.45 | 0.39 | -0.38 | -0.47 | -0.63 |
| △MON | 0.60 | 0.39 | 0.40 | 0.36 | -0.40 | -0.40 | -0.55 |
| △(RON+MON)/2 | 0.61 | 0.41 | 0.42 | 0.37 | -0.39 | -0.44 | -0.59 |
Note:
1, the sulfur content of feed gasoline is 960ppm, and RON is that 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 poor of product anti-knock index and raw material anti-knock index.
Can find out 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, thereby makes desulphurization catalyst have longer service life.
Claims (18)
1. a desulphurization catalyst, taking the gross weight of this desulphurization catalyst as benchmark, this desulphurization catalystContain:
1) heat-resistant inorganic oxide of 5-35 % by weight, described heat-resistant inorganic oxide be selected from aluminium oxide,At least one in titanium dioxide, zirconium dioxide and tin ash;
2) silica source of 5-35 % by weight;
3) the first metal oxide of 10-70 % by weight, described the first metal oxide is selected from IIB, VBWith at least one in the metal oxide of group vib element;
4) the second metal oxide of 2-20 % by weight, described the second metal oxide be selected from lead oxide,At least one in antimony oxide and bismuth oxide;
5) metallic promoter agent of 3-30 % by weight, described metallic promoter agent is selected from cobalt, nickel, iron and manganeseAt least one;
6) in the rare-earth oxide of the 0.5-10 % by weight of rare earth oxide;
7) phosphate aluminium molecular sieve of 1-20 % by weight.
2. desulphurization catalyst according to claim 1, wherein, with the gross weight of this desulphurization catalystAmount is for benchmark, and the content of described heat-resistant inorganic oxide is 10-25 % by weight, the containing of described silica sourceAmount is 10-25 % by weight, and the content of described the first metal oxide is 35-54 % by weight, described secondThe content of 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 taking the content of rare earth oxide as 1-5 % by weight, described phosphate aluminium molecular sieveContent be 2-10 % by weight.
3. desulphurization catalyst according to claim 1 and 2, wherein, described rare earth metal oxidationThing is at least one in the oxide of lanthanum, cerium and neodymium.
4. desulphurization catalyst according to claim 1 and 2, wherein, described the first burningThing is zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxideIn at least one.
5. desulphurization catalyst according to claim 1 and 2, wherein, described silica source is selected fromLaminated clay column, diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, macropore oxidationAt least one in silicon and silica gel.
6. desulphurization catalyst according to claim 1, wherein, described phosphate aluminium molecular sieve is selected from littleIn the SAPO molecular sieve in aperture, the SAPO molecular sieve of mesoporous and wide-aperture SAPO molecular sieveAt least one.
7. the preparation method of the desulphurization catalyst described in any one in claim 1-6, the method bagDraw together:
(1) by the precursor of rare earth compound, the first metal oxide, the second metal oxideBe mixed to get slurries with water;
(2) heat-resistant inorganic oxide binding agent, silica source, water are mixed with acidic liquid, and withThe contact of described slurries, phosphate aluminium molecular sieve forms carrier pulp, more described carrier pulp is carried out to moulding, theOne dry and the first roasting, obtains carrier;
(3) on described carrier, introduce the precursor of metallic promoter agent, and carry out second dry and the second roastingBurn, obtain catalyst precarsor;
(4) described catalyst precarsor is reduced under hydrogen atmosphere, obtain desulphurization catalyst.
8. preparation method according to claim 7, wherein, before described the second metal oxideBody thing is at least one in lead oxide, antimony oxide and bismuth oxide; Or the carbonic acid of metallic lead, antimony and bismuthAt least one in salt, nitrate, chloride and hydroxide.
9. preparation method according to claim 7, wherein, described heat-resistant inorganic oxide bondingAgent is heat-resistant inorganic oxide or under the condition of described the first roasting, can changes heat-resisting inorganic oxygen intoThe material of compound.
10. preparation method according to claim 7, wherein, described rare earth compound is rareAt least one in carbonate, bicarbonate, nitrate, chloride, formates and the acetate of earth metalKind.
11. preparation methods according to claim 7, wherein, the precursor of described metallic promoter agent isIn acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of metallic promoter agent extremelyFew a kind of.
12. preparation methods according to claim 7 wherein, introduce described metal short on carrierThe method of entering the precursor of agent is dipping or precipitation.
13. preparation methods according to claim 7, wherein, described acidic liquid is acid or sourThe aqueous solution, described acid is selected from water-soluble inorganic acid and/or organic acid.
14. preparation methods according to claim 7, wherein, described the first dry temperature is80-120 DEG C, described the first dry time is 0.5-24h; The temperature of described the first roasting is 300-700DEG C, the time of described the first roasting is 0.5h at least.
15. preparation methods according to claim 7, wherein, described the second dry temperature is50-300 DEG C, described the second dry time is 0.5-8h; The temperature of described the second roasting is 300-700DEG C, the time of described the second roasting is 0.5-4h.
16. preparation methods according to claim 7, wherein, the temperature of described reduction is 300-600DEG C, the time of described reduction is 0.5-6h, 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 makes.
The method of 18. 1 kinds of desulfurization of hydrocarbon oil, the method comprises: under hydrogen atmosphere, by hydrocarbon oil containing surphur withClaim 1-6 contacts with the desulphurization catalyst described in any one in 17, and the temperature of described contact is350-500 DEG C, the pressure of described contact is 0.5-4MPa.
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