CN105583002A - 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) 5-30% of a heatproof inorganic oxide; 2) 5-30% of a silicon oxide source; 3) 10-70% of a first metal oxide; 4) 2-20% of a second metal oxide; 5) 5-30% of a metal promoter; and 6) 1-20% of a rare earth-modified phosphorous and aluminum molecular sieve. The desulphurization catalyst has good 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 desulfurization catalysis of preparing the method for desulphurization catalyst and being obtained by the methodAgent, 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 expensive in vehicle exhaust converterThe activity of metallic catalyst also can make it to occur irreversibly poisoning. Thereby make not contain and do not fire in vehicle exhaustThe non-methane hydrocarbon and nitrogen oxide and the carbon monoxide that burn, these discharge gas are by easy shape of day photocatalysisBecome photochemical fog, cause acid rain, the oxysulfide itself in atmosphere is also form acid rain main simultaneouslyOne of reason. Along with the pay attention to day by day of people to environmental protection, environmental regulation is also day by day strict, and reducesThe sulfur content of 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 by 2013December 31, sulfur content in gasoline must drop to 50 μ g/g; And gasoline quality standard can be more in the futureAdd strict. In this case, catalytically cracked gasoline must just can meet wanting of environmental protection through deep desulfurationAsk.
At present, the process for deep desulphurization of oil product mainly contains hydrofinishing and two kinds of methods of adsorption desulfurize, butChina is because the problem in hydrogen source makes hydrorefined cost higher. SZorb adsorption desulfurize belongs to and facesHydrogen desulfur technology is realized the adsorbing and removing of sulfide under certain temperature and pressure condition. Due to this skillArt has hydrogen and consumes low feature removing sulfur-containing compound in gasoline, and to the purity requirement of hydrogen notHeight has broad application prospects this technology 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 andRegeneration all has obvious inferior position. Fluidized-bed process has better heat transfer and pressure drop compared with fixed-bed processEtc. the advantage of aspect, therefore have broad application prospects. The granular reaction of the general employing of fluidized-bed reactorThing, but for great majority reaction, reactant used does not generally have enough wearabilities. Therefore, look forWell there is the adsorbent of better desulfurization performance significant to anti-wear performance simultaneously.
CN1355727A discloses a kind of suction that is applicable to remove sulphur from cracking gasoline and diesel fuelAttached dose of composition, is made up of zinc oxide, silica, oxidation al and ni, and wherein nickel is substantially to go back original costState exists, and its amount can be from the catalytic cracking petrol contacting with described nickeliferous adsorbent composition under desulfurization conditionIn oil or diesel fuel stream, remove sulphur. Said composition is by forming zinc oxide, silica and aluminium oxideCompound particles granulation form particle, after dry, roasting with nickel or nickel compound containing dipping, drier,Roasting, reduction obtain.
CN1382071A discloses a kind of suction that is applicable to remove sulphur from cracking gasoline and diesel fuelAttached dose of composition, is made up of zinc oxide, silica, aluminium oxide and cobalt, and wherein cobalt is substantially to go back original costState exists, its amount can under desulfurization condition with the described catalytic cracking petrol contacting containing cobalt adsorbent compositionIn oil or diesel fuel stream, remove sulphur. In CN1355727A and CN1382071A, all only mention desulfurizationActivity, does not all introduce for adsorbent physical and chemical performance (such as abrasion strength resistance) and stability.
The disclosed adsorbent of US6150300, CN1130253A and CN1258396A is: comprise oxidationThe granular adsorbent composition of the mixture of zinc, silica, aluminium oxide, reduction valence state nickel or cobalt. SystemPreparation Method is mainly to adopt the methods such as shearing by mixed to silica, aluminium oxide and zinc oxide merga pass comminutorPrepare solid particle, make adsorbent thereby flood nickel after drying and roasting. Although these patent IntroductionsAdsorbent has good desulfurization performance, but for its physical and chemical performance, is mainly that tear strength is in patentDo not introduce.
CN1208124A discloses employing promoter metals as cobalt and nickel dipping comprises zinc oxide, the treasure of expandingThe adsorbing agent carrier of Zhu Yan and aluminium oxide then reduces this promoter under suitable temperature, for the preparation of de-Except the adsorbent of cracking gasoline medium sulphide content.
CN1627988A discloses one and has been suitable for removing elementary sulfur from cracking gasoline and diesel fuelWith the adsorbent composition of sulphur compound, described adsorbent composition comprises: zinc oxide, expanded perlite,Aluminate and promoter metals, wherein said promoter metals with when make cracking gasoline or diesel fuel stream andWhen it contacts under desulfurization condition, the amount that causes desulfurization from the material stream of cracking gasoline or diesel fuel is deposited, 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, containZinc compound, containing earth silicon material, aluminium oxide and co-catalyst, to form its mixture; B) dryDry this mixture, to form the mixture of drying; C) calcine the mixture of this drying, to formThrough the mixture of calcining; D) with suitable reducing agent under suitable condition by this through calcining mixtureReduction, to produce the composition in it with the co-catalyst content of reduction valence state, and e) reclaimsReorganization 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) described in inciting somebody to actionDry this of mixture mixes to form the first drying mixture; C) by described the first drying mixtureCalcining is to form first through calcining mixt; D) promoter is attached to described first through calcining mixtWithin or on form through promote mixture; E) make described through promote mixture be selected from citric acid,The acid of tartaric acid and combination thereof contacts to form through contact mixture; F) by described dry through contact mixtureDry to form the second drying mixture; G) described the second drying mixture is calcined to form secondThrough calcining mixt; H) adopt under suitable condition applicable reducing agent to reduce described second through calciningMixture wherein contains the composition of reduction valence state promoter content with production, and i) reclaims described groupCompound.
CN101816918A discloses a kind of desulfuration adsorbent, and this adsorbent consists of rare earth metal, oxygenChange aluminium, silica, promoter and be selected from one or more metal oxides of IIB, VB and VIBAdsorbent. This adsorbent has good abrasion strength resistance and desulphurizing activated.
Although adsorbent prepared by these methods has good desulfurization performance, also exist significantly and lackPoint. Above-mentioned adsorbent all adopts zinc oxide active component, and the temperature of zinc oxide absorption sulphur and oxidation regeneration is equalHigher, silicon, al composition in the time of desulphurization reaction and oxidation regeneration easily and in carrier generate zinc silicateAnd/or zinc aluminate, cause adsorbent activity to reduce. As can be seen here, need to provide one to there is higher desulfurizationThe new catalyst of activity and abrasion resistance properties.
Summary of the invention
The object of the invention is desulphurizing activated low, the structural instability of adsorbent in order to overcome prior art andDefect that abrasion resistance properties is poor, provides the side of a kind of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oilMethod.
To achieve these goals, the invention provides a kind of desulphurization catalyst, total with this desulphurization catalystWeight is benchmark, and this desulphurization catalyst contains: the 1) heat-resistant inorganic oxide of 5-30 % by weight, described inHeat-resistant inorganic oxide is selected from least one in aluminium oxide, titanium dioxide, zirconium dioxide and tin ash;2) silica source of 5-30 % by weight; 3) the first metal oxide of 10-70 % by weight, described firstMetal oxide is selected from least one in the metal oxide of IIB, VB and group vib element; 4) 2-20The second metal oxide of % by weight, described the second metal oxide is selected from lead oxide, antimony oxide and oxidationAt least one in bismuth; 5) metallic promoter agent of 5-30 % by weight, described metallic promoter agent be selected from cobalt,At least one in nickel, iron and manganese; 6) the rare earth modified 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: (1) willThe precursor of rare earth modified phosphate aluminium molecular sieve, the first metal oxide, the second metal oxide and water are mixedClose and obtain slurries; (2) heat-resistant inorganic oxide binding agent, silica source, water are mixed with acidic liquid,And contact with described slurries and form carrier pulp, then by described carrier pulp carry out moulding, first dry andThe first roasting, obtains carrier; (3) on described carrier, introduce the precursor of metallic promoter agent, and carry outTwo dry and the second roastings, obtain catalyst precarsor; (4) by described catalyst precarsor in hydrogen atmosphereLower reduction, obtains 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, will containSulphur hydrocarbon ils contacts with desulphurization catalyst provided by the invention, and the temperature of described contact is 350-500 DEG C, instituteThe pressure of stating contact is 0.5-4MPa.
In desulphurization catalyst provided by the invention, contain the first metal oxide and the second metal oxide mixedCooperation is sulphur absorption constituent element, and the second metal oxide can effectively reduce in the first metal oxide and carrierSilicon, the effect of al composition, reduce the silicate and/or the aluminate that generate the first metal, thereby make this de-Sulfur catalyst can absorb sulphur and through repeatedly reacting and regenerative process, still have at lower temperatureBetter desulphurizing activated and activity stability.
In desulphurization catalyst provided by the invention, contain rare earth modified phosphate aluminium molecular sieve, phosphate aluminium molecular sieve spySome skeleton structures and acid isomerization and the aromatization that is conducive to hydro carbons, increase octane numberAdd. By molecular sieve is carried out to rare earth ion modification, improve on the one hand heat and the hydrothermally stable of molecular sieveProperty, in life-span that can extending catalyst, reduce the generation of side reaction; Can reduce on the other hand molecular sieveAcid site intensity, reduce cracking and the green coke of gasoline, yield of gasoline is increased.
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, retouch in this placeThe detailed description of the invention of stating 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 desulfurizationCatalyst contains: the 1) heat-resistant inorganic oxide of 5-30 % by weight, described heat-resistant inorganic oxide is selected fromAt least one in aluminium oxide, titanium dioxide, zirconium dioxide and tin ash; 2) 5-30 % by weightSilica source; 3) the first metal oxide of 10-70 % by weight, described the first metal oxide be selected from IIB,At least one in the metal oxide of VB and group vib element; 4) the second metal oxygen of 2-20 % by weightCompound, described the second metal oxide is selected from least one in lead oxide, antimony oxide and bismuth oxide; 5)The metallic promoter agent of 5-30 % by weight, described metallic promoter agent is selected from least one in cobalt, nickel, iron and manganeseKind; 6) the rare earth modified 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 oxideFor 10-20 % by weight, the content of described silica source is 10-20 % by weight, described the first burningThe content of thing is 35-54 % by weight, and the content of described the second metal oxide is 5-15 % by weight, described inThe content of metallic promoter agent is 10-20 % by weight, and the content of described rare earth modified phosphate aluminium molecular sieve is2-20 % by weight.
According to the present invention, described the first metal oxide is the metal oxide with storage sulphur performance, preferablyGround, described the first metal oxide is zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, oxygenChange at least one in chromium, molybdenum oxide and tungsten oxide; More preferably, described the first metal oxide is oxygenChange at least one in zinc, 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 repeatedlyWhen desulphurization reaction under experience high temperature and regenerative response, with the silicon containing in described desulphurization catalyst, aluminium groupDivide and have an effect, reduce the loss of described the first metal oxide.
According to the present invention, described heat-resistant inorganic oxide can be in described desulphurization catalyst between each componentCementation is provided. Described heat-resistant inorganic oxide is selected from aluminium oxide, titanium dioxide, zirconium dioxide and twoAt least one in tin oxide. Wherein, described aluminium oxide can be gama-alumina, η-aluminium oxide, θ-oxygenChange at least one in aluminium and χ-aluminium oxide; Preferably, described aluminium oxide is gama-alumina; Described dioxyChanging titanium can be anatase titanium dioxide.
According to the present invention, described silica source can be for providing sticky between each component in described desulphurization catalystKnot effect. Under preferable case, described silica source can be greater than 45 for pure silica or silica contentThe natural minerals of % by weight. Preferably, described silica source can be selected from laminated clay column, diatomite, swollenAt least one in swollen 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 reduced to hydrogen sulfide by oxidation state sulphur for anyMetal, preferred described metallic promoter agent is nickel.
According to the present invention, under preferable case, described rare earth modified phosphate aluminium molecular sieve can be aluminate or phosphate(aluminophosphates), metallic aluminium phosphate (metalloaluminophosphates), metal knotThe silicoaluminophosphate that closes (metalintegratedsilicoaluminophosphates, MeAPSO andELAPSO) at least one and in silicoaluminophosphate (silicoaluminophosphates, SAPO).Preferably, described rare earth modified phosphate aluminium molecular sieve be SAPO-11, SAPO-31, SAPO-5 andAt least one in SAPO-34. The SiO of described rare earth modified phosphate aluminium molecular sieve2：Al2O3MoleThan can be 0.02-3:1.
According to the present invention, rare earth modified method can be ion-exchange and/or equi-volume impregnating.Under preferable case, taking the gross weight of described rare earth modified phosphate aluminium molecular sieve as benchmark, described rare earth modifiedPhosphate aluminium molecular sieve contain the rare earth of 2-15 % by weight in rare earth oxide.
In the present invention, rare earth is distributed in the inside in described rare earth modified phosphate aluminium molecular sieve duct. Preferably,Rare earth can be carbonate, bicarbonate, nitrate, chloride, formates and the acetic acid of rare earth metalAt least one in salt; Preferably, described rare earth compound can be rare earth metal carbonate,At least one in bicarbonate, formates and acetate. Wherein, described rare earth metal be preferably lanthanum,At least one in cerium and neodymium. Preferably, described rare earth modified phosphate aluminium molecular sieve for example can be selected fromLa-SAPO-11 molecular sieve (the La of 15 % by weight2O3), Ce-SAPO-31 molecular sieve (10 % by weightCeO2), (RE is the La of 2.5 % by weight to RE-SAPO-34 molecular sieve2O3With 2.5 % by weightCeO2), the Ce-SAPO-5 molecular sieve (CeO of 5 % by weight2) at least one.
In the present invention, add rare earth modified phosphate aluminium molecular sieve to have and ensureing that gasoline has higher yieldsTime, promote the isomerization of straight-chain hydrocarbons in gasoline, thereby improve isoparaffin content in gasoline, increaseThe effect of gasoline products octane number or effect.
The present invention also provides the preparation method of desulphurization catalyst of the present invention, and the method comprises: (1) willThe precursor of rare earth modified phosphate aluminium molecular sieve, the first metal oxide, the second metal oxide and water are mixedClose and obtain slurries; (2) heat-resistant inorganic oxide binding agent, silica source, water are mixed with acidic liquid,And contact with described slurries and form carrier pulp, then by described carrier pulp carry out moulding, first dry andThe first roasting, obtains carrier; (3) on described carrier, introduce the precursor of metallic promoter agent, and carry outTwo dry and the second roastings, obtain catalyst precarsor; (4) by described catalyst precarsor in hydrogen atmosphereLower reduction, obtains desulphurization catalyst.
In the present invention, under preferable case, described heat-resistant inorganic oxide binding agent can be heat-resisting inorganic oxygenCompound or can change the material of heat-resistant inorganic oxide under the condition of described the first roasting into. PreferablyGround, described heat-resistant inorganic oxide binding agent is alumina binder, zirconium dioxide binding agent, titanium dioxideAt least one in titanium binding agent and tin ash binding agent. More preferably, described alumina binder canThink hydrated alumina and/or aluminium colloidal sol, wherein, described hydrated alumina is selected from boehmite (Bao ShuiAluminium stone), in false boehmite (boehmite), hibbsite and amorphous hydroted aluminaAt least one; Described zirconium dioxide binding agent can be zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrationAt least one in zirconia and amorphous zirconium dioxide; Described tin ash binding agent can be tetrachloroAt least one in tin, four isopropyl alcohol tin, tin acetate, aqua oxidation tin and tin ash; Described dioxyChanging titanium binding agent can be titanium tetrachloride, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxideWith at least one in anatase titanium dioxide.
In the present invention, described silica source can be for providing bonding between each component in described desulphurization catalystEffect. Under preferable case, described silica source can be greater than 45 weight for silica or silica contentThe natural crystal of %. Preferably, described silica source can be laminated clay column, diatomite, expanded pearliteAt least one in rock, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel. Described laminated clay columnCan 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, be oxidizedThe content of aluminium does not comprise the amount of aluminium oxide contained in above-mentioned silica source, and the content of aluminium oxide only comprisesThe 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 oxygenThe amount in SiClx source. In the desulphurization catalyst being made by method provided by the invention the content of each component according toInventory calculates.
In the present invention, the precursor of described the second metal oxide be described the second metal oxide orUnder the condition of described the first roasting, can change the material of described the second metal oxide into; Preferable caseUnder, 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 can under the condition of described the second roastingChange the material of the oxide of metallic promoter agent into. Under preferable case, the precursor of described metallic promoter agent canThink in acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of metallic promoter agentAt least one. Wherein metallic promoter agent is selected from least one in cobalt, nickel, iron and manganese.
In the present invention, described the first metal oxide and rare earth modified phosphate aluminium molecular sieve are described above, noRepeat one by one again.
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 powderForm 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 lead oxide,The powder of at least one in antimony oxide and bismuth oxide, or be added in energy under the condition of described the first roastingEnough change the material of described the second metal oxide into, as the carbonate of metallic lead, antimony and bismuth, nitrate,At least one in chloride and hydroxide; Also can by lead oxide, antimony oxide and bismuth oxide extremelyAfter being prepared as slurries, few one uses 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), described silica source and described heat-resistant inorganic oxide binding agentThe weight ratio that feeds intake is 0.4-2:1, is preferably 0.6-1.5:1. Described desulphurization catalyst can be provided thusCaking property between better each component.
In step of the present invention (2), described mixing can be: by heat-resistant inorganic oxide binding agent andSilica source respectively water and acidic liquid is carried out after acidification, then the mixture obtaining is separately mixedFor acidifying slurries; Wherein, in the time that described heat-resistant inorganic oxide binding agent is non-al binder, obtainMixture is colloidal sol. In addition, in the time that described heat-resistant inorganic oxide binding agent is alumina binder, instituteStating 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; DescribedThe solid content of 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 solubleInorganic acid and/or organic acid, can be for example at least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
In the present invention, moulding described in step (2) described slurries can be shaped to extrudate, sheet,Pill, ball or micro-spherical particle. For example, when described slurries are dough or paste mixture, can make instituteState mixture moulding (preferably extrusion molding) and form particle, preferably diameter is at 1-8mm, and length is at 2-5The cylindrical extrudate of mm, then makes the extrudate of gained be dried, roasting. If gained mixesThing is wet mixture form, can make this mixture multiviscosisty, through super-dry aftershaping. More preferably slurries are slurryLiquid form, is the microballoon of 20-200 micron by the dry formation granularity of spraying, and reaches 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 preferably20-35 % 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, contains as long as the carrier pulp obtaining meets consolidating of above-mentioned carrier pulpAmount.
In the present invention, the condition of described first dry and the first roasting can by those skilled in the art public affairsKnow, under preferable case, described the first dry temperature is 80-150 DEG C, and described the first dry time is0.5-24h; The temperature of described the first roasting is 300-700 DEG C, and the time of described the first roasting is at least 0.5H. 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, 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 agentFor can change the material of the oxide of metallic promoter agent under the second roasting condition; Under preferable case,The precursor of described metallic promoter agent can be selected from acetate, carbonate, nitrate, the sulphur of metallic promoter agentAt least one in hydrochlorate, rhodanate and oxide.
According to the present invention, under preferable case, on carrier, introduce the method for precursor of metallic promoter agent for soakingStain 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 addsAmmoniacal liquor is deposited in the precursor of metallic promoter agent on carrier.
In the present invention, the condition of described second dry and the second roasting can by those skilled in the art public affairsKnow, under preferable case, described the second dry temperature is 50-300 DEG C, and described the second dry time is0.5-8h; 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 secondRoasting can be carried out under having that oxygen or oxygen-containing gas exist, until volatile materials is removed and goldBelong to the form that promoter is converted into metal oxide, obtain catalyst precarsor.
According to the present invention, in step (4), by the oxidation of the metallic promoter agent in described catalyst precarsorThing changes metal simple-substance into, described catalyst precarsor can be reduced under hydrogen atmosphere, makes goldBelong to promoter and substantially go up with reduction-state and exist, obtain catalyst of the present invention. The condition of described reduction is only by instituteThe oxide of stating the metallic promoter agent in catalyst precarsor changes metal simple-substance into, and gold in described carrierBelonging to oxide can not change. Under preferable case, the temperature of described reduction is 300-600 DEG C, described reductionTime be 0.5-6h, in described hydrogen atmosphere, hydrogen content is 10-60 volume %; Preferably, instituteThe temperature of stating reduction is 350-450 DEG C, and the time of described reduction is 1-3h.
In the present invention, step (4) can make catalyst precarsor reduction after catalyst precarsor immediatelyCarry out, also (for before desulfurization absorption) is carried out before use. Due to the easy oxygen of metallic promoter agentChange, and metallic promoter agent in catalyst precarsor exists with oxide form, therefore for ease of transport, excellentSelect step (4) that catalyst precarsor reduction is carried out before desulfurization absorption carrying out. Described being reduced to makes metalMetal in the oxide of promoter 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 precursor of the first metal oxide, the second metal oxide, rare earth modified phosphate aluminium molecular sieve and goldBelong to the addition of precursor of promoter, in the desulphurization catalyst that makes to obtain, total with this desulphurization catalystWeight is 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, 3-30 % by weightMetallic promoter agent and the rare earth modified phosphate aluminium molecular sieve of 0.5-10 % by weight.
Preferably, taking the gross weight of this desulphurization catalyst as benchmark, the content of described heat-resistant inorganic oxideFor 10-25 % by weight, the content of described silica source is 10-25 % by weight, described the first burningThe content of thing is 35-54 % by weight, and the content of described the second metal oxide is 5-15 % by weight, described inThe content of metallic promoter agent is 10-20 % by weight, and the content of described rare earth modified phosphate aluminium molecular sieve is 1-5% by weight.
The present invention also provides the desulphurization catalyst being prepared by method provided by the invention. This desulfurization catalysisAs previously mentioned, this is no longer going to repeat them for the composition of agent.
A kind of method that the invention provides desulfurization of hydrocarbon oil, the method comprises: under hydrogen atmosphere, will containSulphur hydrocarbon ils contacts with desulphurization catalyst provided by the invention, and the temperature of described contact is 350-500 DEG C, instituteThe pressure of stating contact is 0.5-4MPa; Preferably, the temperature of described contact is 400-450 DEG C, described in connectTactile pressure is 1-2MPa. Sulphur in this process in hydrocarbon ils is adsorbed on catalyst, thereby obtainsThe 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 contactPreferably in fluidized-bed reactor, carry out.
In the present invention, reacted catalyst can be reused after regeneration. Described regeneration is at oxygen gasUnder atmosphere, carry out, the condition of regeneration comprises: the pressure of regeneration is normal pressure, and the temperature of regeneration is 400-700 DEG C,Be preferably 500-600 DEG C.
In the present invention, the catalyst after regeneration, also need to be at hydrogen gas re-starting before desulfurization of hydrocarbon oilUnder atmosphere, reduce, the reducing condition of the catalyst after regeneration comprises: temperature is 350-500 DEG C, is preferably400-450 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,From making larger hydrocarbon molecule be cracked into the product of more micromolecular heat or catalytic process. Applicable hot tearingChange process includes, but are not limited to coking, thermal cracking and visbreaking etc. and combination thereof. Applicable catalysis is splitThe example of change process includes but not limited to fluid catalystic cracking and RFCC etc. and combination thereof. CauseThis, applicable catalytically cracked gasoline includes but not limited to coker gasoline, pressure gasoline, visbreaking vapourOil, fluid catalystic cracking gasoline and residual oil cracking gasoline and combination thereof. In some cases, at thisCan be by described cracking gasoline fractionation and/or hydrotreatment before desulfurization while being used as hydrocarbon-containifluids fluids in bright method.
Term used herein " diesel fuel " mean boiling range be 170 to 450 DEG C hydrocarbon mixture orThe liquid of its any fractional composition. This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight runDiesel oil and hydrotreatment diesel oil etc. and combination thereof.
Term used herein " sulphur " represent any type of element sulphur as hydrocarbon-containifluids fluids as cracking gasoline orThe normal organosulfur compound existing in diesel fuel. The sulphur existing in hydrocarbon-containifluids fluids of the present invention comprises but notBe limited to carbonyl sulfide (COS), carbon disulfide (CS2), mercaptan or other thiophenes etc. andCombination, especially comprises thiophene, benzothiophene, alkylthrophene, alkylbenzene bithiophene and alkyl diphenyl thiopheneFen, 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 prolongLong life, be 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 powder of 4.05kg (Beijing Chemical Plant, containing butt 4.0kg),The lead oxide powder (traditional Chinese medicines chemical reagents corporation analyzes pure) of 0.50kg, the 15 % by weight La of 1.0kg2O3The SAPO-11 molecular sieve of modification (contains butt 0.7kg, SiO2:Al2O3Mol ratio=1:1, be designated asLa-SAPO-11) and the deionized water of 6.9kg mix, stir after 30 minutes, obtain containing zinc oxide,The slurries of lead oxide and La-SAPO-11 molecular sieve;
The aluminium oxide of 1.60kg (Shandong Aluminum Plant, containing butt 1.20kg) and the kaolin of 2.16kg (are urgedAgent Nanjing branch company, containing butt 1.80kg) under agitation mix, then add deionized water 3.6kgAfter mixing, add the hydrochloric acid (Beijing Chemical Plant, chemical pure) of 30 % by weight of 300ml to stirMake pH=1.8, after acidifying 1h, be warming up to 80 DEG C of aging 2h. After adding again above-mentioned slurries to mix, stir 1hObtain carrier pulp;
Described carrier pulp is adopted to NiroBowenNozzleTowerTMThe spray dryer of model entersRow spraying is dry, and spraying drying pressure is 8.5 to 9.5MPa, and inlet temperature is below 500 DEG C, outlet temperatureDegree is about 150 DEG C. By first dry 1h at 150 DEG C of the dry microballoon obtaining of spraying, then at 480 DEG CLower roasting 1h obtains carrier;
(2) carrier of 8.2kg is formed with the Nickelous nitrate hexahydrate of 8.91kg and the deionization of 1.10kgThe aqueous solution flood at twice, the mixture obtaining after 150 DEG C of dry 4h then 480 DEG C of roastings1h, obtains catalyst precarsor;
(3) reduction. By catalyst precarsor reductase 12 h at 425 DEG C in hydrogen atmosphere, obtain desulfurization and urgeAgent A1.
The chemical composition of A1 is: zinc oxide content is 40.0 % by weight, and lead oxide content is 5.0 % by weight,Alumina content is 12.0 % by weight, and kaolin content is 18.0 % by weight, La-SAPO-11 molecular sieveContent is 7 % by weight, and nickel content is 18.0 % by weight.
Embodiment 2
The present embodiment is for illustrating the method for preparing desulphurization catalyst of the present invention.
By the bismuth oxide of the Zinc oxide powder of 3.84kg (Beijing Chemical Plant, containing butt 3.8kg), 1.21kgThe 10 % by weight CeO of powder (traditional Chinese medicines chemical reagents corporation analyzes pure), 0.43kg2The SAPO-31 of modificationMolecular sieve (containing butt 0.30kg, SiO2:Al2O3Mol ratio=0.5:1, be designated as Ce-SAPO-31) andThe deionized water of 7.8kg is mixed, stir after 30 minutes, obtain containing zinc oxide, bismuth oxide andThe slurries of Ce-SAPO-31 molecular sieve;
The zirconium chloride of 3.42kg (Beijing Chemical Plant analyzes pure) is slowly joined to the dense of 4.65kgSpend in the salpeter solution of 5 % by weight and make pH=2.0, and slowly stir and avoid crystal of zirconium oxide to separate out, obtainWater white zirconium colloidal sol;
The rectorite (Qilu Petrochemical catalyst plant, containing butt 1.50kg) of getting 1.85kg adds deionized waterAfter 1.5kg mixes, add the hydrochloric acid stirring of 30 % by weight of 95ml to make pH=2.0, acidifying 1hAfter be warming up to 80 DEG C of aging 2h, obtain the mixture containing rectorite; Add again above-mentioned slurries and zirconium colloidal solBe mixed together 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, obtain desulphurization catalyst A2.
The chemical composition of A2 is: zinc oxide content is 38.0 % by weight, and bismuth oxide content is 12.0 weight%, zirconia content is 18.0 % by weight, Ce-SAPO-31 content is 3.0 % by weight, rectorite contentBe 15.0 % by weight, nickel content is 14.0 % by weight.
Embodiment 3
The present embodiment is for illustrating the method for preparing desulphurization catalyst of the present invention.
By the plumbi nitras of the Zinc oxide powder of 5.06kg (Beijing Chemical Plant, containing butt 5.0kg), 1.05kgMishmetal (the La of 2.5 % by weight of (traditional Chinese medicines chemical reagents corporation analyzes pure), 0.6kg2O3WithThe CeO of 2.5 % by weight2) (catalyst Nanjing branch company, containing butt for the SAPO-34 molecular sieve of modification0.5kg，SiO2:Al2O3Mol ratio=0.25:1, be designated as RE-SAPO-34) and the deionization of 7.8kgWater mixes, and stirs and after 30 minutes, obtains containing zinc oxide, lead oxide and RE-SAPO-34 molecular sieveSlurries;
By the diatomite of 1.03kg (catalyst Nanjing branch company, containing butt 1.0kg) going at 4.8kgIn ionized water, mix, add the hydrochloric acid stirring of 30 % by weight of 275ml to make pH=1.5, acidifying 1h obtainsTo diatomite after treatment;
The deionized water of aluminium oxide 2.13kg (Shandong Aluminum Plant, containing butt 1.6kg) and 9.0kg is being stirredUnder mix after, add 170g red fuming nitric acid (RFNA) stir make pH=2.0 and be warming up to more than 60 DEG C acidifying 1H. In the time that temperature is reduced to below 40 DEG C, then after adding above-mentioned slurries to mix, stirring 1h obtains carrier slurryLiquid.
Carry out the spray drying forming of carrier pulp and introduce active component nickel with reference to the method for embodiment 1,After reduction, obtain desulphurization catalyst A3.
The chemical composition of A3 is: zinc oxide content is 50.0 % by weight, and lead oxide content is 7.0 % by weight,Alumina content is 16.0 % by weight, and diatomite content is 10.0 % by weight, RE-SAPO-34 molecular sieveContent is 5.0 % by weight, and nickel content is 12.0 % by weight.
Embodiment 4
The present embodiment is for illustrating the method for preparing desulphurization catalyst of the present invention.
By the antimony oxide of the Zinc oxide powder of 3.84kg (Beijing Chemical Plant, containing butt 3.8kg), 0.90kgThe 5 % by weight CeO of powder and 0.43kg2The SAPO-5 molecular sieve of modification (containing butt 0.30kg,SiO2:Al2O3Mol ratio=0.8:1, be designated as Ce-SAPO-5) in the deionized water of 8.3kg, mix,Stir the slurries that obtain zinc oxide, antimony oxide and Ce-SAPO-5 molecular sieve after 30 minutes;
The titanium tetrachloride of 4.36kg (Beijing Chemical Plant analyzes pure) is slowly joined to going of 5.76kgIn ionized water, and slowly stir and avoid titanium oxide crystal to separate out, obtain faint yellow transparent titanium colloidal sol,pH＝1.0；
The rectorite (Qilu Petrochemical catalyst plant, containing butt 1.80kg) of getting 2.22kg, adds deionizationAfter water 3.0kg mixes, add the hydrochloric acid stirring of 30 % by weight of 90ml to make pH=1.5, acidifying 1hAfter be warming up to 80 DEG C of aging 2h, obtain the mixture containing rectorite; Add again above-mentioned slurries and titanium colloidal solBe 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, obtain desulphurization catalyst A4.
The chemical composition of A4 is: zinc oxide content is 38.0 % by weight, and antimony oxide content is 9.0 % by weight,Content of titanium dioxide is 18.0 % by weight, and rectorite content is 18.0 % by weight, and nickel content is 14.0 weightsAmount %, Ce-SAPO-5 molecular sieve content is 3.0 % by weight.
Comparative example 1
The 15 % by weight La-SAPO-11 molecular sieves of the Zinc oxide powder of 4.05kg, 1.0kg (are contained dryBase 0.7kg, SiO2:Al2O3Mol ratio=1:1) and the deionized water of 6.9kg mix, stir 30 pointsAfter clock, obtain the slurries that contain zinc oxide and La-SAPO-11 molecular sieve;
The aluminium oxide of 2.27kg (Shandong Aluminum Plant, containing butt 1.70kg) and the kaolin of 2.16kg are existedStir lower mixing, after then adding deionized water 4.0kg to mix, add 30 % by weight of 400mlHydrochloric acid stir make pH=1.8, after acidifying 1h, be warming up to 80 DEG C of aging 2h. Add again above-mentioned slurries mixedClose 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, obtain desulphurization catalyst B1.
The chemical composition of B1 is: zinc oxide content is 40.0 % by weight, and alumina content is 17.0 weight%, kaolin content is 18.0 % by weight, La-SAPO-11 molecular sieve content is 7 % by weight, nickel contentBe 18.0 % by weight.
Comparative example 2
The deionized water of the lead oxide powder of the Zinc oxide powder of 4.05kg, 0.50kg and 6.9kg is mixed,Stir and after 30 minutes, obtain the slurries that contain zinc oxide and lead oxide;
The aluminium oxide of 2.53kg (Shandong Aluminum Plant, containing butt 1.90kg) and the kaolin of 2.16kg are existedStir lower mixing, after then adding deionized water 3.6kg to mix, add 30 % by weight of 450mlHydrochloric acid stir make pH=1.8, after acidifying 1h, be warming up to 80 DEG C of aging 2h. Add again above-mentioned slurries mixedClose 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, obtain desulphurization catalyst B2.
The chemical composition of B2 is: zinc oxide content is 40.0 % by weight, and lead oxide content is 5.0 % by weight,Alumina content is 19.0 % by weight, and kaolin content is 18.0 % by weight, and nickel content is 18.0 % by weight.
Embodiment 5
Abrasion strength resistance is evaluated. Desulphurization catalyst A1-A4 and B1-B2 are carried out to abrasion strength resistance test.Adopt straight tube wearing and tearing method, method is with reference to RIPP in " Petrochemical Engineering Analysis method (RIPP) experimental technique "29-90, the results are shown in Table 1. The numerical value that test obtains is less, shows that abrasion strength resistance is higher. Mill in table 1Damage index corresponding be the percentage that fine powder generates while wearing and tearing under certain condition.
In order better to represent the activity of adsorbent in commercial Application process, to adsorbing after vulcanizing treatmentIntensive analysis is also carried out in agent, and concrete processing method is: the adsorbent that takes appropriate mass is positioned over fluid bedIn, pass into the gaseous mixture of hydrogen sulfide (50 volume %) and nitrogen (50 volume %), and be heated to 400DEG C vulcanizing treatment 1h. The results are shown in Table 1.
Embodiment 6
Desulfurization performance is evaluated. Desulphurization catalyst A1-A4 and B1-B2 are adopted to the micro-anti-experiment dress of fixed bedPut and carry out desulfurization evaluation experimental, it is 30mm, the long 1m of being that the desulphurization catalyst of 16g is seated in to internal diameterFixed bed reactors in. Raw material hydrocarbon ils is the catalytically cracked gasoline of sulphur concentration 960ppm, reaction pressureFor 1.38MPa, hydrogen flowing quantity is 6.3L/h, and gasoline flow is 80mL/h, and reaction temperature is 380 DEG C,The weight space velocity of raw material hydrocarbon ils is 4h-1, carry out the desulphurization reaction of hydrocarbon oil containing surphur. Contain with sulphur in product gasolineAmount is weighed desulphurizing activated. In product gasoline, sulfur content, by off-line chromatogram analysis method, adopts An Jielun public affairsThe GC6890-SCD instrument of department is measured. In order accurately to symbolize desulphurization catalyst in the actual fortune of industryActivity in row, the catalyst after desulfurization evaluation experimental completes is regenerated under the air atmosphere of 480 DEG CProcess. Desulphurization catalyst is carried out to desulfurization evaluation experimental, after 6 circulations of regenerating its active basicly stable underCome, represent the activity of catalyst with the sulfur content in the product gasoline after the 6th stable circulation of catalyst,After stable, in product gasoline, sulfur content is as shown in table 1.
Product gasoline is weighed and calculated its yield simultaneously.
Adopt respectively GB/T503-1995 and GB/T5487-1995 to measure and react front and circulate for the 6th time steadyAfter fixed, motor octane number (MON) and the research octane number (RON) (RON) of gasoline, the results are shown in Table 1.
Embodiment 7
Zinc aluminate assay. By in embodiment 6 the 6th time circulation after desulphurization catalyst A1-A4 andThe crystalline phase composition of B1-B2 is analyzed, and 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), Rietveld model through revising(RIQASrietveldAnalysis, operation manual, MaterialData, Inc., Berkley, CA(1999)), analyze different samples, and adopt the method for matching to calculate the crystalline phase composition of sample. Use dressBe furnished with long fine focusing copper X-ray source PhilipsXRG3100 generator (40kV, 30mA drive),Philips3020 digital angle measurement instrument, Philips3710MPD control computer and KevexPSIPeltierCooling silicon detector carries out all X-ray diffractions and measures. Employing Kevex4601 ionic pump controller,Kevex4608Peltier power supply, Kevex4621 detector bias, Kevex4561A pulse processor andKevex4911-A single channel analyzer operation Kevex detector. Use PhilipsAPD4.1c version softPart obtains diffraction pattern. Use MaterialData, Inc.Riqas3.1c version software (OutokumpuHSCChemistryforWindows: user's manual, OutokumpoResarchOy, Pori, Finland (1999))Carrying out all Rietveld calculates. The zinc aluminate content of different desulphurization catalysts is as shown in table 1.
Table 1
| A1 | A2 | A3 | A4 | B1 | B2 | |
| ZnAl2O4, % by weight | 0 | 0 | 0 | 0 | 7.6 | 5.5 |
| Abrasion index | 3.0 | 3.8 | 3.8 | 3.2 | 7.6 | 5.0 |
| Yield of gasoline, % | 99.8 | 99.9 | 99.7 | 99.8 | 98.4 | 98.8 |
| Product sulfur content, ppm | 6 | 9 | 10 | 7 | 15 | 35 |
| △RON | 0.65 | 0.45 | 0.48 | 0.52 | -0.32 | -0.63 |
| △MON | 0.60 | 0.42 | 0.44 | 0.50 | -0.31 | -0.55 |
| △(RON+MON)/2 | 0.63 | 0.43 | 0.46 | 0.51 | -0.31 | -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 desulfurizationActivity and activity stability. Desulphurization catalyst has better abrasion strength resistance, thereby makes desulphurization catalystThere is longer service life.
Claims (16)
1. a desulphurization catalyst, taking the gross weight of this desulphurization catalyst as benchmark, this desulphurization catalystContain:
1) heat-resistant inorganic oxide of 5-30 % 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 5-30 % 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 oxide in group vib metal;
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 5-30 % by weight, described metallic promoter agent is selected from cobalt, nickel, iron and manganeseAt least one;
6) the rare earth modified 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 10-20 % by weight, the containing of described silica sourceAmount is 10-20 % 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,The content of described rare earth modified phosphate aluminium molecular sieve is 2-20 % by weight.
3. desulphurization catalyst according to claim 1, wherein, described rare earth modified phosphorus aluminium dividesIn the silicoaluminophosphate that son sieve is aluminate or phosphate, metallic aluminium phosphate, metal combination and silicoaluminophosphateAt least one.
4. according to the desulphurization catalyst described in any one in claim 1-3, wherein, with described rareThe gross weight of the phosphate aluminium molecular sieve of land reform is benchmark, and described rare earth modified phosphate aluminium molecular sieve contains 5-15% by weight is in the rare earth of rare earth oxide.
5. desulphurization catalyst according to claim 1, wherein, described the first metal oxide isIn zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxideAt least one.
6. desulphurization catalyst according to claim 1, wherein, described silica source is selected from a layer postClay, diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide andAt least one in silica gel.
7. the preparation method of the desulphurization catalyst described in any one in claim 1-6, the method bagDraw together:
(1) by rare earth modified phosphate aluminium molecular sieve, the first metal oxide, the second metal oxidePrecursor and water are mixed to get slurries;
(2) heat-resistant inorganic oxide binding agent, silica source, water are mixed with acidic liquid, and withThe contact of described slurries forms carrier pulp, more described carrier pulp is carried out to moulding, first dry and firstRoasting, 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. method according to claim 7, wherein,, the precursor of described the second metal oxideFor at least one in lead oxide, antimony oxide and bismuth oxide; Or the carbonate of metallic lead, antimony and bismuth,At least one in nitrate, chloride and hydroxide.
9. method according to claim 7, wherein, described heat-resistant inorganic oxide binding agent isHeat-resistant inorganic oxide or can change heat-resistant inorganic oxide under the condition of described the first roastingMaterial.
10. method according to claim 7, wherein, the precursor of described metallic promoter agent is metalAt least one in acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of promoterKind.
11. methods according to claim 7 wherein, are introduced described metallic promoter agent on carrierPrecursor method for dipping or precipitation.
12. methods according to claim 7, wherein, described the first dry temperature is 80-120DEG C, described the first dry time is 0.5-24h; The temperature of described the first roasting is 300-700 DEG C, instituteThe time of stating the first roasting is 0.5h at least.
13. methods according to claim 7, wherein, described the second dry temperature is 50-300DEG C, described the second dry time is 0.5-8h; The temperature of described the second roasting is 300-700 DEG C, instituteThe time of stating the second roasting is 0.5-4h.
14. methods according to claim 7, wherein, the temperature of described reduction is 300-600 DEG C,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 15. claim 7-14 described in any one makes.
The method of 16. 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 15, and the temperature of described contact is350-500 DEG C, the pressure of described contact is 0.5-4MPa.
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