CN105582974A - 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, a preparation method of the desulphurization catalyst and the desulphurization catalyst obtained by the method, and an application of the desulphurization catalyst in sulfur-containing hydrocarbon oil desulphurization. The desulphurization catalyst contains a non-aluminum oxide, a silicon oxide source, a first metal oxide, lead oxide, a rare-earth metal oxide, a molecular sieve and active metal; and an XRD spectrum of the desulphurization catalyst has a characteristic peak of a rare earth-lead composite oxide. 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 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. S-Zorb 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, non-aluminum oxide and nickel, and wherein nickel is substantially to go backFormer valence state exists, its amount can under desulfurization condition with splitting that described nickeliferous adsorbent composition contactsChange in gasoline or diesel fuel stream and remove sulphur. Said composition is passed through zinc oxide, silica and non-aluminaThe compound particles granulation that compound forms forms particle, after dry, roasting with nickel or nickel compound containing dipping,Dry, roasting again, 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, non-aluminum oxide and cobalt, and wherein cobalt is substantially to go backFormer valence state exists, its amount can under desulfurization condition with described splitting of contacting containing cobalt adsorbent compositionChange in gasoline or diesel fuel stream and remove sulphur. In CN1355727A and CN1382071A, all only mentionDesulphurizing activated, 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: comprise oxidationThe granular adsorbent composition of the mixture of zinc, silica, non-aluminum oxide, reduction valence state nickel or cobalt.Preparation method adopts the methods such as shearing by mixed to silica, non-aluminum oxide and zinc oxide merga passComminutor is prepared solid particle, makes adsorbent thereby flood nickel after drying and roasting. Although these patentsThe adsorbent of introducing has good desulfurization performance, but for its physical and chemical performance, is mainly that tear strength existsIn patent, do 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 non-aluminum oxide then reduces this promoter under suitable temperature, and preparation is usedIn the adsorbent that removes 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, non-aluminum 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, with shapeBecome the mixture through calcining; D) with suitable reducing agent under suitable condition by this through calcining mixingThing reduction, to produce the composition in it with the co-catalyst content of reduction valence state, and e) returnsReceive 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, non-aluminum oxide; B) willDry this of described mixture mixes to form the first drying mixture; C) described the first drying is mixedCompound calcines to form first through calcining mixt; D) promoter is attached to described first mixed through calciningWithin compound or on form through promote mixture; E) make described through promoting mixture and being selected from lemonThe acid of acid, tartaric acid and combination thereof contacts to form through contact mixture; F) mix through contact describedThing is dry to form the second drying mixture; G) described the second drying mixture is calcined to formSecond through calcining mixt; H) adopt under suitable condition applicable reducing agent to reduce described the second warpCalcining mixt wherein contains the composition of reduction valence state promoter content with production, and i) reclaims instituteState composition.
CN101816918A discloses a kind of desulfuration adsorbent, and this adsorbent consists of rare earth metal, non-Aluminum oxide, silica, promoter and be selected from one or more metal oxygens of IIB, VB and VIBThe adsorbent of compound. 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: 1) the non-aluminum oxide of 3-35 % by weight, described non-aluminiumOxide is at least one in titanium dioxide, zirconium dioxide and tin ash; 2) 5-30 % by weightSilica source; 3) the first metal oxide of 10-80 % 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) lead oxide of 2-20 % by weight; 5)The active metal of 5-30 % by weight, described active metal is selected from least one in cobalt, nickel, iron and manganese;6) in the rare-earth oxide of the 0.5-15 % by weight of rare earth oxide; 7) dividing of 1-30 % by weightSon sieve, described molecular sieve is at least one in X-type molecular sieve, Y zeolite and beta-molecular sieve; InstituteState the characteristic peak that has rare earth-plumbum composite oxide in the XRD spectra of desulphurization catalyst.
The present invention also provides the preparation method of desulphurization catalyst provided by the invention, and the method comprises: (1)The precursor of lead oxide, rare earth compound, water and acidic liquid are mixed to get to rare earth-alucol;(2) by non-al binder, silica source, the first metal oxide, molecular sieve, water and acidic liquidBe mixed to form slurries, and contact and obtain carrier mixture with described rare earth-alucol, described carrier is mixedCompound carries out moulding, first dry and the first roasting, obtains carrier; (3) on described carrier, introduce and liveProperty metal precursor, and carry out second dry and the second roasting, obtain catalyst precarsor; (4) described in inciting somebody to actionCatalyst precarsor reduces under hydrogen atmosphere, obtains desulphurization catalyst.
The present invention also provides the desulphurization catalyst being obtained by preparation method provided by the invention.
The present invention also provides a kind of method of desulfurization of hydrocarbon oil, and the method comprises: under hydrogen atmosphere, and willHydrocarbon oil containing surphur contacts with desulphurization catalyst provided by the invention, and the temperature of described contact is 350-500 DEG C,The pressure of described contact is 0.5-4MPa.
In desulphurization catalyst provided by the invention, containing the first metal oxide mixes as sulphur with lead oxideAbsorb constituent element, lead oxide can effectively reduce the silicon in the first metal oxide and carrier, the work of al compositionWith, reduce and generate silicate and/or the aluminate of the first metal, thereby make this desulphurization catalyst can be moreAt low temperature, absorb sulphur and through repeatedly reacting and regenerative process, still have better desulphurizing activated andActivity stability.
In desulphurization catalyst provided by the invention, contain rare-earth oxide, and become rare with lead oxideSoil-plumbum composite oxide can be further effectively oxidation reinforced lead to the first metal oxide and silicon, aluminiumOrganize the effect that weakens of phase separation.
By desulphurization catalyst provided by the invention, this desulphurization catalyst carries out repeatedly desulfurization regeneration and reactedAfter journey, still can have better desulphurizing activatedly, desulfurization stability is better. And this desulphurization catalyst carries out hydrocarbonOil desulphurization reaction can have green coke amount still less, and yield of gasoline is higher. Different in the product gasoline composition obtainingStructure component is more, and sulfur content is lower, and the octane number of product gasoline improves, product gasoline better quality.This desulphurization catalyst can obtain better mar proof in addition.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, withDetailed description of the invention one is below used from explanation the present invention, but is not construed as limiting the invention. ?In accompanying drawing:
Fig. 1 is the XRD spectra of the desulphurization catalyst A1 that contains lanthanum, and wherein 2 θ are 28.3 °, 32.8°, 47.1 ° and 55.8 ° markPeak be the feature of the cubic system of lanthanum plumbum composite oxidePeak;
Fig. 2 is the XRD spectra of the desulphurization catalyst A2 that contains cerium, and wherein 2 θ are 28.5 °, 33.1°, 47.4 °, 56.3 ° and 59.0 ° markPeak be the cubic crystal of cerium plumbum composite oxideThe characteristic peak of system;
Fig. 3 is the XRD spectra of the desulphurization catalyst A3 that contains neodymium, and wherein 2 θ are 28.3 °, 32.8°, 47.0 °, 55.8 ° and 58.5 ° markPeak be the cubic crystal of neodymium plumbum composite oxideThe characteristic peak of system;
Fig. 4 is the XRD spectra of desulphurization catalyst B2, wherein do not have 2 θ be 28.3 °, 32.8 °,The characteristic peak of the lanthanum plumbum composite oxide of 47.1 ° and 55.8 °, wherein 2 θ are 22.1 °, 25.5 °, 31.5°, 38.8 °, 45.0 °, 47.0 °, 48.9 °, 57.6 °, 59.5 °, 65.6 °, 65.8 ° and 68.7° and the peak of mark " ■ " be the characteristic peak of zinc silicate.
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: 1) the non-aluminum oxide of 3-35 % by weight, described non-aluminum oxide be titanium dioxide,At least one in zirconium dioxide and tin ash; 2) silica source of 5-30 % by weight; 3) 10-80The first metal oxide of % by weight, described the first metal oxide is selected from IIB, VB and group vib elementMetal oxide at least one; 4) lead oxide of 2-20 % by weight; 5) work of 5-30 % by weightProperty metal, described active metal is selected from least one in cobalt, nickel, iron and manganese; 6) with rare-earth oxidationThe rare-earth oxide of the 0.5-15 % by weight of thing meter; 7) molecular sieve of 1-30 % by weight, described pointSon sieve is at least one in X-type molecular sieve, Y zeolite and beta-molecular sieve; Described desulphurization catalystXRD spectra in there is the characteristic peak of rare earth-plumbum composite oxide.
Preferably, taking the gross weight of described desulphurization catalyst as benchmark, the content of described non-aluminum oxide is5-25 % by weight, the content of described silica source is 10-20 % by weight, described the first metal oxideContent is 25-70 % by weight, and the content of lead oxide is 2-20 % by weight, and the content of described active metal is8-25 % by weight, described rare-earth oxide is taking the content of rare earth oxide as 0.5-10 % by weight,The content of described molecular sieve is 2-25 % by weight.
In the present invention, the content of described desulphurization catalyst middle rare earth metal oxide and lead oxide can be favourableIn forming rare earth-plumbum composite oxide structure, thereby be more conducive to oxidation reinforced lead to the first burningWhat thing and silicon, al composition acted on mutually weakens effect, to improve abrasion resistance properties, the desulfurization of desulphurization catalystActivity and product gasoline quality.
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, the rare-earth oxide containing in described desulphurization catalyst can with lead oxide phaseIn conjunction with, make desulphurization catalyst can there is the crystal structure of rare earth-plumbum composite oxide. Preferable caseUnder, the rare earth element in described rare-earth oxide be selected from La, Ce, Pr, Nd, Pm, Sm,At least one in Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; Preferred described rare earthRare earth element in metal oxide is at least one in La, Ce, Pr and Nd.
According to the present invention, under preferable case, as shown in Figure 1, when rare earth element is lanthanum, described desulfurization is urgedIn the XRD spectra of agent, having 2 θ is that the lanthanum lead of 28.3 °, 32.8 °, 47.1 ° and 55.8 ° is compoundThe characteristic peak (JCPDSNo.52-0318) of the cubic system of oxide; Not having 2 θ is 28.6 °, 31.8°, the characteristic peak (JCPDS of the tetragonal crystal system of the lead oxide of 35.7 °, 48.6 °, 54.8 ° and 59.9 °No.5-0561), do not exist 2 θ be 27.0 °, 31.4 °, 44.8 ° and 53.2 ° lanthana cubeThe characteristic peak (JCPDSNo.4-0856) of crystallographic system.
According to the present invention, under preferable case, as shown in Figure 2, and in the time that rare earth element is cerium, described desulfurizationIn the XRD spectra of catalyst, having 2 θ is 28.5 °, 33.1 °, 47.4 °, 56.3 ° and 59.0 °The characteristic peak (JCPDSNo.48-0059) of cubic system of cerium plumbum composite oxide; Do not exist 2 θ to beThe spy of the tetragonal crystal system of the lead oxide of 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 °Levy peak, not having 2 θ is the cubic system of the cerium oxide of 28.5 °, 33.1 °, 47.5 ° and 56.3 °Characteristic peak (JCPDSNo.03-065-2975).
According to the present invention, under preferable case, as shown in Figure 3, and in the time that rare earth element is neodymium, described desulfurizationIn the XRD spectra of catalyst, having 2 θ is 28.3 °, 32.8 °, 47.0 °, 55.8 ° and 58.5 °The characteristic peak (JCPDSNo.47-0875) of cubic system of neodymium plumbum composite oxide; Do not exist 2 θ to beThe spy of the tetragonal crystal system of the lead oxide of 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 °Levy peak, not having 2 θ is 26.8 °, 29.8 °, 30.8 °, 40.5 °, 47.4 °, 53.4 °, 57.0° and the characteristic peak (JCPDSNo.6-0408) of the cubic system of the neodymia of 57.6 °.
In the present invention, in desulphurization catalyst, form rare earth-plumbum composite oxide structure, can promote oxygenWhat change lead acted on mutually to the first metal oxide and silicon, al composition weakens effect, increases the activity of zinc oxidePhase, thus the desulphurizing activated of desulphurization catalyst further promoted. Also can overcome desulphurization catalyst wearing and tearing strongDegree declines, the problem that the life cycle causing shortens. In addition, the rare earth-plumbum composite oxide of formation,Can improve gasoline and diesel fuel desulfurization activity. The desulphurization catalyst that use contains rare earth-plumbum composite oxideIsomerization product content in the desulfurization product gasoline obtaining can also be improved, the pungent of product gasoline can be improvedAlkane value.
In the present invention, in described desulphurization catalyst, lead oxide can reduce desulphurization catalyst absorption withIn regenerative process, the silicon in the first metal oxide and carrier, the effect of al composition, reduce and generate firstThe silicate of metal and/or aluminate, thus the activity of maintenance the first metal oxide improves desulfurization catalysisAgent desulphurizing activated.
According to the present invention, described active metal for promote hydrocarbon oil containing surphur sulfur-containing compound absorption andCracking, for being reduced to the sulphur of oxidation state the metal of hydrogen sulfide. Described active metal can be selected from cobalt,At least one in nickel, iron and manganese, more preferably cobalt and/or nickel.
According to the present invention, described non-aluminum oxide can be for providing between each component in described desulphurization catalystCementation, and avoid described desulphurization catalyst in the time of experience desulphurization reaction and regenerative process, al binderThe defect that forms spinel structure with the first metal oxide and the performance of described desulphurization catalyst is reduced.
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, under preferable case, the sial atomic molar of described X-type molecular sieve is than being 1-3:1; The sial atomic molar ratio of described Y zeolite can be 3-25:1. Described Y zeolite alsoCan include but not limited to super-stable Y molecular sieves (USY), HY and phosphorous USY (PUSY);The sial atomic molar ratio of described beta-molecular sieve can be 10-40:1.
In the present invention, add at least one in X-type molecular sieve, Y zeolite and beta-molecular sieve passableThere are the effect or the effect that promote aromatization of hydrocarbons to improve gasoline products octane number by increasing the content of aromatic hydrocarbons.
The present invention also provides the preparation method of desulphurization catalyst provided by the invention, and the method comprises: (1)The precursor of lead oxide, rare earth compound, water and acidic liquid are mixed to get to rare earth-alucol;(2) by non-al binder, silica source, the first metal oxide, molecular sieve, water and acidic liquidBe mixed to form slurries, and contact and obtain carrier mixture with described rare earth-alucol, described carrier is mixedCompound carries out moulding, first dry and the first roasting, obtains carrier; (3) on described carrier, introduce and liveProperty metal precursor, and carry out second dry and the second roasting, obtain catalyst precarsor; (4) described in inciting somebody to actionCatalyst precarsor reduces under hydrogen atmosphere, obtains desulphurization catalyst.
According to the present invention, the precursor of described lead oxide is lead oxide or the condition in described the first roastingCan change down the material of lead oxide into. Under preferable case, the precursor of described lead oxide is selected from tetrachloroPlumbous, oxychlorination is plumbous, lead acetate, aqua oxidation are plumbous and amorphous oxidation lead at least one.
According to the present invention, under preferable case, described rare earth compound can be selected from the vinegar of rare earth elementAt least one in hydrochlorate, carbonate, nitrate, sulfate, oxalates, chloride and oxide;Preferably, described rare earth compound can be carbonate, bicarbonate, the formates of rare earth elementWith at least one in acetate. Wherein, described rare earth element is described above, repeats no longer one by one.
In the present invention, under preferable case, described non-al binder can be zirconium dioxide binding agent, dioxyChange at least one in titanium binding agent and tin ash binding agent. Described non-al binder can be titanium dioxideZirconium, titanium dioxide or tin ash, or can change titanium dioxide under the condition of described the first roastingThe material of zirconium, titanium dioxide or tin ash. Particularly, described zirconium dioxide binding agent can be tetrachloroChange at least one in zirconium, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide; InstituteStating tin ash binding agent can be butter of tin, four isopropyl alcohol tin, tin acetate, aqua oxidation tin and twoAt least one in tin oxide; The precursor of described titanium dioxide can be the condition in described the first roastingCan change down the material of anatase titanium dioxide into, described titanium dioxide binding agent can be tetrachloroIn titanium, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxideAt least one. Wherein anatase titanium dioxide still can generate anatase after hydrolysis and the first roastingType titanium dioxide.
In the present invention, the precursor of described active metal can be for can turn under the condition of described the second roastingBecome the material of the oxide of active metal. Under preferable case, the precursor of described active metal can be selected fromAt least one in acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of metal.
In the present invention, described the first metal oxide, silica source, molecular sieve and active metal are as front instituteState, this is no longer going to repeat them.
According to the present invention, the preparation method's of described desulphurization catalyst step (1), by prepare rare earth-Alucol, to form rare earth-plumbum composite oxide structure by step (2). Contain the de-of this structureSulfur catalyst is conducive to realize object of the present invention.
In the present invention, in step (1), obtaining described rare earth-alucol can have several different methods, Ke YiweiMethod one, comprises the following steps: (a) precursor of lead oxide and acidic liquid are mixed to get to alucol;(b) described alucol and rare earth compound are mixed and contact with ammonia spirit again that to obtain rare earth-lead moltenGlue. Can also be method two, comprise the following steps: (a) by mixed to the precursor of lead oxide and acidic liquidClose and obtain alucol; (b) aqueous solution of described alucol and rare earth compound is obtained to rare earth-alucol. Also can be method three, comprise: by the precursor of lead oxide, rare earth compound andAcidic liquid is mixed to get rare earth-alucol.
In said method, described acidic liquid is acid or aqueous acid, and described acid is selected from water-solubleInorganic acid and/or organic acid; Described acid can be in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid at leastOne, it is 1-5 that the consumption of described acidic liquid makes the pH value of rare earth-alucol, is preferably 1.5-4. InstituteThe concentration of stating acidic liquid can be 5-30 % by weight. The concentration of described ammonia spirit can be heavy for 10-30Amount %.
In the present invention, in step (2), forming slurries can have several different methods, a kind of preferred concrete realThe mode of executing comprises: (A) non-al binder, water are contacted and obtain glue with acidic liquid; (B) shouldGlue and the first metal oxide, molecular sieve are mixed to form slurries. Another kind of preferred detailed description of the inventionComprise: (I) by non-al binder, silica source respectively water contact with acidic liquid and obtain non-aluminium bondingAgent glue and silica source after treatment, then be mixed into acidifying slurries; (II) by described acidifying slurries andOne metal oxide, molecular sieve are mixed to form slurries. Wherein said acidic liquid is described above, described acidThe consumption of property liquid makes the pH value of described glue or described acidifying slurries be less than 6, is preferably less than 4.
According to the present invention, moulding described in step (2) can be shaped to described carrier mixture to extrudeThing, sheet, pill, ball or micro-spherical particle. For example, described carrier mixture is that dough or paste are mixedWhen compound, can make described carrier mixture moulding (preferably extrusion molding) form particle, preferably diameter exists1-8mm, length is at the cylindrical extrudate of 2-5mm, then make the extrudate of gained be dried,Roasting. If gained carrier mixture is wet mixture form, can make this mixture multiviscosisty, through super-dryAftershaping. More preferably carrier mixture is slurries form, and by spraying, dry formation granularity is 20-200The microballoon of micron, reaches the object of moulding. Dry for the ease of spraying, dry front described carrier mixtureSolid content be 10-50 % by weight, be preferably 20-50 % by weight. In step (2), obtain described carryingIn the process of body mixture, can also comprise and add water, there is no particular limitation for the addition of water, as long asTo carrier mixture meet above-mentioned solid content.
In the present invention, adding of described the first metal oxide can be oxide powder form, also canTo use with slurries form again after the first metal oxide is prepared as to slurries.
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; Preferable caseUnder, the precursor of described metallic promoter agent can be selected from metallic promoter agent acetate, carbonate, nitrate,At least one in sulfate, 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 liveProperty metal is converted into the form of metal oxide, obtains 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. Because active metal is easily oxidized,And active metal in catalyst precarsor exists with oxide form, therefore for ease of transport, preferred steps(4) catalyst precarsor reduction is carried out before desulfurization absorption carrying out. Described being reduced to makes active metalMetal in oxide exists with reduction-state substantially, obtains desulphurization catalyst of the present invention.
In the desulphurization catalyst being made by method provided by the invention, the content of each component is according to inventory meterDraw.
Preparation in accordance with the present invention, described non-al binder, the precursor of lead oxide, rare earth metalThe addition of the precursor of compound, silica source, the first metal oxide, molecular sieve and active metalIn the desulphurization catalyst that makes to obtain, taking the gross weight of this desulphurization catalyst as benchmark, described non-aluminum oxideContent be 3-25 % by weight, the content of described silica source is 5-30 % by weight, described the first metalThe content of oxide is 10-80 % by weight, and the content of lead oxide is 2-20 % by weight, described active metalContent be 5-30 % by weight, described rare-earth oxide is taking the content of rare earth oxide as 0.5-15% by weight, the content of described molecular sieve is 1-30 % by weight.
Preferably, taking the gross weight of this desulphurization catalyst as benchmark, the content of described non-aluminum oxide is5-25 % by weight, the content of described silica source is 10-20 % by weight, described the first metal oxideContent is 25-70 % by weight, and the content of lead oxide is 2-20 % by weight, and the content of described active metal is8-25 % by weight, described rare-earth oxide is taking the content of rare earth oxide as 0.5-10 % by weight,The content of described molecular sieve is 2-25 % by weight.
The present invention also provides the desulphurization catalyst being obtained by preparation method provided by the invention. This desulfurization is urgedAs previously mentioned, this is no longer going to repeat them for the composition of agent.
The present invention also provides a kind of method of desulfurization of hydrocarbon oil, and the method comprises: under hydrogen atmosphere, and willHydrocarbon oil containing surphur contacts with desulphurization catalyst provided by the invention, and the temperature of described contact is 350-500 DEG C,The pressure of described contact is 0.5-4MPa; Preferably, the temperature of described contact is 400-450 DEG C, described inThe pressure of contact is 1-2MPa. Sulphur in this process in hydrocarbon ils is adsorbed on catalyst, therebyTo 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 contactPreferably in fluidized-bed reactor, carry out.
According to the present invention, the method for described desulfurization of hydrocarbon oil can also comprise: taking off process reaction after reactionSulfur catalyst is regenerated. The condition of regeneration comprises: at oxygen atmosphere, (oxygen content can be 10-80Volume %) under regenerate; The temperature of regeneration is 450-600 DEG C, is preferably 480-520 DEG C; RegenerationPressure is normal pressure.
In the present invention, the method for described desulfurization of hydrocarbon oil can also comprise: the desulphurization catalyst after regeneration is heavyBefore new use, need under hydrogen atmosphere, reduce, the condition of reduction comprises: at hydrogen atmosphere, (hydrogen containsAmount can be for 30-60 volume %) under reduce; The temperature of reduction can be 350-500 DEG C, preferably400-450 DEG C; The pressure of reduction can be 0.2-2MPa, is preferably 0.2-1.5MPa.
In the present invention, described hydrocarbon ils comprises cracking gasoline and diesel fuel, wherein " cracking gasoline " meaningReferring to that boiling range is hydrocarbon or its any cut of 40 to 210 DEG C, is less from larger hydrocarbon molecule is cracked intoThe heat of molecule or the product of catalytic process. Applicable thermal cracking process includes, but are not limited to coking, hot tearingChange and visbreaking etc. and combination thereof. The example of applicable catalytic cracking process includes but not limited to fluid bedCatalytic cracking and RFCC etc. and combination thereof. Therefore, applicable catalytically cracked gasoline comprises but notBeing limited to coker gasoline, pressure gasoline, visbreaking gasoline, fluid catalystic cracking gasoline and heavy oil splitsChange gasoline and combination thereof. In some cases, can be in desulfurization during in the methods of the invention as hydrocarbon-containifluids fluidsBefore by described cracking gasoline fractionation and/or hydrotreatment. Described " diesel fuel " means boiling rangeThe hydrocarbon mixture of 170 DEG C to 450 DEG C or the liquid of its any fractional composition. This type of hydrocarbon-containifluids fluids comprises but notBe limited to light cycle oil, kerosene, straight-run diesel oil, catalytic cracking diesel oil and hydrotreatment diesel oil etc. and combination thereof.
In the present invention, term used " sulphur " represents that any type of element sulphur is if hydrocarbon-containifluids fluids is as catalytic cracking petrolThe normal organosulfur compound existing in oil or diesel fuel. The sulphur existing in hydrocarbon-containifluids fluids of the present invention comprisesBut be not limited to carbonyl sulfide (COS), carbon disulfide (CS2), mercaptan or other thiophenes etc.And combination, especially comprise thiophene, benzothiophene, alkylthrophene, alkylbenzene bithiophene and alkyl diphenylBithiophene, and the normal larger thiophenes of molecular weight existing in diesel fuel.
The invention will be further described by the following examples.
In the following Examples and Comparative Examples, the composition of desulphurization catalyst calculates according to feeding intake.
Polycrystal X ray diffraction (XRD) adopts X-ray diffractometer (D5005 of Siemens company type)Carry out the structure determination of desulphurization catalyst, Cu target, K α radiation, solid probe, tube voltage 40kV,Tube current 40mA.
Embodiment 1
The present embodiment is for illustrating the preparation method of desulphurization catalyst of the present invention.
(1) prepare rare earth-alucol. By the lead tetrachloride of 0.783kg (Beijing Chemical Plant analyzes pure)Join in nitric acid (Beijing Chemical Plant, the chemical pure) solution of 5 % by weight of 1.0kg and stir 1h,Obtain water white alucol. By the lanthana of 0.5kg (traditional Chinese medicines chemical reagents corporation analyzes pure)After being dissolved in the deionized water solution of 0.2kg and alucol be mixed to get lanthanum alucol.
(2) prepare carrier. The zirconium chloride of 2.28kg (Beijing Chemical Plant analyzes pure) is slowly addedEnter in the salpeter solution of concentration 5 % by weight of 3.1kg and make pH=2.0, and slowly stir and avoid zirconiaCrystal is separated out, and obtains water white zirconium colloidal sol;
By 1.73kg expanded perlite (catalyst Nanjing branch company, containing butt 1.3kg) joinIn the salpeter solution of 2 % by weight of 0.5kg, add thermal agitation in the time that temperature is reduced to below 40 DEG C, addThe Zinc oxide powder (Headhorse company, purity 99.7 % by weight) of 4.05kg, the USY of 0.8kg dividesSon sieve (catalyst asphalt in Shenli Refinery, containing butt 0.7kg, sial atomic molar is than being 9.5:1) and 3.5kgDeionized water mix, then add above-mentioned zirconium colloidal sol, then add above-mentioned lanthanum alucol, after mixing, stir 1After hour, obtain carrier mixture.
This carrier mixture is adopted to NiroBowenNozzleTowerTMThe spray dryer of model entersRow spraying is dry, and spraying drying pressure is 8.5-9.5MPa, and inlet temperature is below 500 DEG C, outlet temperatureBe about 150 DEG C. By first dry 1h at 150 DEG C of the dry microballoon obtaining of spraying, then at 650 DEG CRoasting 0.5h obtains carrier.
(3) introduce active metal. The carrier of 8.2kg is used to 8.92kg Nickelous nitrate hexahydrate (BeijingLearn reagent company, purity is greater than 98.5 % by weight) and the aqueous solution of 1.6kg deionized water flood, obtainMixture after 250 DEG C of dry 5h, at air atmosphere, 450 DEG C of roasting 1h can make catalystPrecursor.
(4) reduction. 3h that catalyst precarsor is reduced in the hydrogen atmosphere of 400 DEG C can obtain desulfurizationCatalyst A 1.
The chemical composition of A1 is: zinc oxide content is 40.0 % by weight, and lead oxide content is 5.0 % by weight,Zirconium dioxide content is 12 % by weight, expanded perlite 13.0 % by weight, and nickel content is 18.0 % by weight,Lanthana content is 5.0 % by weight, USY molecular sieve 7.0 % by weight.
A1 carries out polycrystal X ray diffraction (XRD) and characterizes, and spectrogram is shown in Fig. 1. In spectrogram, be 28.3 at 2 θ°, 32.8 °, 47.1 ° and the 55.8 ° characteristic peaks of locating the cubic system that has lanthanum plumbum composite oxide,Be 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 ° at 2 θ and locate not exist lead oxideThe characteristic peak of tetragonal crystal system, and be 27.0 °, 31.4 °, 44.8 ° and 53.2 ° at 2 θ and locate not depositAt the characteristic peak of the cubic system of lanthana. Lead oxide and lanthana formation in desulphurization catalyst A1 are describedLanthanum plumbum composite oxide structure.
Embodiment 2
The present embodiment is for illustrating the preparation method of desulphurization catalyst of the present invention.
(1) prepare rare earth-alucol. By the oxychlorination lead of 1.17kg (Aldrich company, analyze pure,98.5 % by weight) join in the hydrochloric acid solution of 15 % by weight of 2.0kg and stir acidifying 1h, formWater white alucol. The cerium oxide of 0.3kg (traditional Chinese medicines chemical reagents corporation analyzes pure) is addedIn alucol, be uniformly mixed rear dropping 25 % by weight ammonia spirits until become cerium alucol.
(2) prepare carrier. The titanium tetrachloride of 3.09kg (Beijing Chemical Plant analyzes pure) is slowly addedEnter in the salpeter solution of concentration 5 % by weight of 2.2kg and make pH=2.0, and slowly stir and avoid titanium oxideCrystal is separated out, and obtains water white titanium colloidal sol;
The deionized water of the diatomite of 1.2kg (silicon oxide-containing 1.00kg) and 8.0kg is under agitation mixedAfter closing evenly, add the red fuming nitric acid (RFNA) stirring of 200g to make pH=2.0, and it is little to be warming up to more than 60 DEG C acidifying 1Time. In the time that temperature is reduced to below 40 DEG C, add 5.06kg zinc oxide (traditional Chinese medicines chemical reagents corporation,Analyze pure), (Nanjing catalyst branch company, containing butt 0.20kg, sial is former for the beta-molecular sieve of 0.24kgSub-mol ratio is 20:1) and after the deionized water of 5.0kg mixes, then add above-mentioned titanium colloidal sol to form slurryLiquid, then add above-mentioned cerium alucol, after mixing, stir after 1 hour and obtain carrier mixture.
Spray drying forming and the roasting of carrying out carrier mixture with reference to the method for embodiment 1 obtain carrier.
(3) introduce active metal. Nickelous nitrate hexahydrate (Beijing by the carrier of 8.6kg with 6.93kgChemical reagents corporation, purity is greater than 98.5 % by weight) and the aqueous solution dipping of 0.8kg deionized water, soMake catalyst precarsor with reference to method dry in embodiment 1 step (3) and roasting afterwards.
(4) reduction. Method reduction with reference to embodiment 1 step (4) obtains desulphurization catalyst A2.
The chemical composition of A2 is: zinc oxide content is 50.0 % by weight, and lead oxide content is 8.0 % by weight,Content of titanium dioxide is 13.0 % by weight, and diatomite content is 10.0 % by weight, and nickel content is 14.0 weightsAmount %, cerium oxide content is 3.0 % by weight, beta-molecular sieve 2.0 % by weight.
A2 carries out polycrystal X ray diffraction (XRD) and characterizes, and spectrogram is shown in Fig. 2. In spectrogram, at 2 θ beLocate to exist the cubic system of cerium plumbum composite oxide for 28.5 °, 33.1 °, 47.4 °, 56.3 ° and 59.0 °Characteristic peak, be 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 ° at 2 θ and locate notThere is the characteristic peak of the tetragonal crystal system of lead oxide, and be 28.5 °, 33.1 °, 47.5 ° and 56.3 at 2 θ° locate the characteristic peak of the cubic system that does not have cerium oxide. Lead oxide and oxygen in desulphurization catalyst A2 are describedChange the structure that cerium has formed cerium plumbum composite oxide.
Embodiment 3
The present embodiment is for illustrating the preparation method of desulphurization catalyst of the present invention.
(1) prepare rare earth-alucol. By the six nitric hydrate neodymiums of the lead oxide of 0.6kg and 0.651kg(traditional Chinese medicines chemical reagents corporation, content is greater than 99.0 % by weight) joins 15 % by weight rare of 2.7kgIn nitric acid and stir acidifying 1h, obtain transparent neodymium alucol;
(2) prepare carrier. By the crystallization butter of tin (SnCl of 3.73kg4·5H2O，AlfaAesarCompany, 99 % by weight) slowly join in the hydrochloric acid solution of concentration 3 % by weight of 5.0kg and make pH=1.5,And slowly stir and avoid tin oxide crystal to separate out, obtain water white tin oxide sol;
The expanded perlite of 1.59kg (catalyst Nanjing branch company, containing butt 1.20kg) is added to 0.6kg2 % by weight nitric acid stir make pH=2.0, after acidifying 1h, be warming up to 80 DEG C of aging 2h, everywhereExpanded perlite after reason;
Above-mentioned plumbous neodymium colloidal sol, tin oxide sol and expanded perlite after treatment are mixed to form to slurries, addThe Zinc oxide powder (Headhorse company, purity 99.7 % by weight) of 4.56kg, the X molecule of 0.6kgSieve (Nanjing catalyst branch company, containing butt 0.5kg, sial atomic molar is than being 3:1) and 4.65kgDeionized water mix, then add above-mentioned neodymium alucol, after mixing, stir and after 1 hour, obtain carrier and mixThing.
Spray drying forming and the roasting of carrying out carrier mixture with reference to the method for embodiment 1 obtain carrier.
(3) introduce active metal. Nickelous nitrate hexahydrate (traditional Chinese medicines by the carrier of 8.8kg with 5.94kgChemical reagents corporation, analyzes pure)) and the aqueous solution dipping of 0.8kg deionized water, then with reference to embodimentIn 1 step (3), method dry and roasting makes catalyst precarsor.
(4) reduction. Method reduction with reference to embodiment 1 step (4) obtains desulphurization catalyst A3.
The chemical composition of A3 is: zinc oxide content is 45.0 % by weight, and lead oxide content is 6.0 % by weight,Tin ash content is 16.0 % by weight, and expanded perlite content is 12.0 % by weight, and nickel content is 12.0% by weight, neodymia is 4.0 % by weight, X molecular sieve 5.0 % by weight.
A3 carries out polycrystal X ray diffraction (XRD) and characterizes, and spectrogram is shown in Fig. 3. In spectrogram, at 2 θ beLocate to exist the cubic system of neodymium plumbum composite oxide for 28.3 °, 32.8 °, 47.0 °, 55.8 ° and 58.5 °Characteristic peak, be 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 ° at 2 θ and locate notThere is the characteristic peak of the tetragonal crystal system of lead oxide, and be 26.8 °, 29.8 °, 30.8 °, 40.5 at 2 θ°, 47.4 °, 53.4 °, 57.0 ° and the 57.6 ° characteristic peaks of locating the cubic system that does not have neodymia.Illustrate that lead oxide and neodymia in desulphurization catalyst A3 have formed the structure of neodymium plumbum composite oxide.
Comparative example 1
The zirconium chloride of 3.23kg is slowly joined in the salpeter solution of concentration 5 % by weight of 4.4kg and makePH=2.0, and slowly stir and avoid crystal of zirconium oxide to separate out, water white zirconium colloidal sol obtained;
By 1.76kg expanded perlite (catalyst Nanjing branch company, containing butt 1.30kg) joinIn the salpeter solution of 2 % by weight of 0.5kg, add thermal agitation in the time that temperature is reduced to below 40 DEG C, addThe Zinc oxide powder (Headhorse company, purity 99.7 % by weight) of 4.05kg, the USY of 0.80kgMolecular sieve (Shandong catalyst branch company, containing butt 0.7kg, sial atomic molar is than being 9.5:1) andThe deionized water of 3.5kg is mixed, then adds above-mentioned zirconium colloidal sol, then adds the lanthana (traditional Chinese medicines of 0.5kgLearn reagent company, analyze pure) slurries of the deionized water formation of powder and 0.2kg, mix and blend 1 is littleTime after obtain carrier mixture.
Carry out spray drying forming the dipping of carrier mixture with reference to the method for embodiment 1 and introduce active goldBelong to nickel, after reduction, obtain desulphurization catalyst B1.
The chemical composition of B1 is: zinc oxide content is 40.0 % by weight, and zirconium dioxide content is 17.0 weightsAmount %, expanded perlite 13.0 % by weight, nickel content is 18.0 % by weight, lanthana content is 5.0 weightsAmount %, USY molecular sieve 7.0 % by weight.
Comparative example 2
The zirconium chloride of 2.27kg is slowly joined in the salpeter solution of concentration 5 % by weight of 2.6kg and makePH=2.0, and slowly stir and avoid crystal of zirconium oxide to separate out, water white zirconium colloidal sol obtained;
By 1.73kg expanded perlite (catalyst Nanjing branch company, containing butt 1.3kg) joinIn the salpeter solution of 2 % by weight of 0.5kg, add thermal agitation in the time that temperature is reduced to below 40 DEG C, addThe Zinc oxide powder (Headhorse company, purity 99.7 % by weight) of 4.05kg, the USY of 0.8kg dividesSon sieve (catalyst asphalt in Shenli Refinery, containing butt 0.7kg, sial atomic molar is than being 9.5:1) and 3.5kgDeionized water mix, then add above-mentioned zirconium colloidal sol, then add lanthanum oxide powder and the 0.2kg of 0.5kgDeionized water form the lead tetrachloride of slurries and 0.783kg, mix and blend obtains carrier after 1 hour mixedCompound.
Carry out spray drying forming the dipping of carrier mixture with reference to the method for embodiment 1 and introduce active groupMetallic nickel, obtains desulphurization catalyst B2 after reduction.
The chemical composition of B2 is: zinc oxide content is 40.0 % by weight, and lead oxide content is 5.0 % by weight,Zirconium dioxide content is 12.0 % by weight, expanded perlite 13.0 % by weight, and nickel content is 18.0 % by weight,Lanthana content is 5.0 % by weight, USY molecular sieve 7.0 % by weight.
Comparative example 3
The lead tetrachloride of 0.783kg joined in the salpeter solution of 5 % by weight of 1.0kg and stir 1h,Obtain water white alucol;
The zirconium chloride of 3.23kg is slowly joined in the salpeter solution of concentration 5 % by weight of 3.7kg and makePH=2.0, and slowly stir and avoid crystal of zirconium oxide to separate out, water white zirconium colloidal sol obtained;
By 1.73kg expanded perlite (catalyst Nanjing branch company, containing butt 1.3kg) joinIn the salpeter solution of 2 % by weight of 0.5kg, add thermal agitation in the time that temperature is reduced to below 40 DEG C, addThe Zinc oxide powder (Headhorse company, purity 99.7 % by weight) of 4.05kg, the USY of 0.8kg dividesSon sieve (catalyst asphalt in Shenli Refinery, containing butt 0.7kg, sial atomic molar is than being 9.5:1) and 3.5kgDeionized water mix,, then add above-mentioned zirconium colloidal sol, then add above-mentioned alucol, mix and blend 1 is littleTime after obtain carrier mixture.
Carry out spray drying forming the dipping of carrier mixture with reference to the method for embodiment 1 and introduce active goldBelong to nickel, after reduction, obtain desulphurization catalyst B3.
The chemical composition of B3 is: zinc oxide content is 40.0 % by weight, and lead oxide content is 5.0 % by weight,Zirconium dioxide content is 17.0 % by weight, expanded perlite 13.0 % by weight, and nickel content is 18.0 % by weight,USY molecular sieve 7.0 % by weight.
Comparative example 4
The lead tetrachloride of 2.85kg joined in the salpeter solution of 5 % by weight of 3.5kg and stir 1h,Obtain water white alucol. The lanthanum nitrate of 1.261kg is dissolved in the deionized water solution of 0.2kgBe mixed to get lanthanum alucol with alucol afterwards;
The zirconium chloride of 3.59kg is slowly joined in the salpeter solution of concentration 5 % by weight of 4.12kg and makePH=2.0, and slowly stir and avoid crystal of zirconium oxide to separate out, water white zirconium colloidal sol obtained;
By 1.73kg expanded perlite (catalyst Nanjing branch company, containing butt 1.3kg) joinIn the salpeter solution of 2 % by weight of 0.5kg, add thermal agitation in the time that temperature is reduced to below 40 DEG C, addThe Zinc oxide powder (Headhorse company, purity 99.7 % by weight) of 4.05kg and 3.5kg go fromSub-water mixes, then adds above-mentioned zirconium colloidal sol, then adds above-mentioned lanthanum alucol, and mix and blend obtained after 1 hourTo carrier mixture.
Carry out spray drying forming the dipping of carrier mixture with reference to the method for embodiment 1 and introduce active goldBelong to nickel, after reduction, obtain desulphurization catalyst B4.
The chemical composition of B4 is: zinc oxide content is 40.0 % by weight, and lead oxide content is 5.0 % by weight,Zirconium dioxide content is 19.0 % by weight, and kaolin content is 13.0 % by weight, and nickel content is 18.0 weightsAmount %, lanthana content is 5.0 % by weight.
Embodiment 4
Abrasion strength resistance is evaluated. Desulphurization catalyst A1-A3 and B1-B4 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 5
Desulfurization performance is evaluated. Desulphurization catalyst A1-A3 and B1-B4 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 16 grams 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 6
Zinc silicate assay. By in embodiment 5 the 6th time circulation after desulphurization catalyst A1-A3 andThe crystalline phase composition of B1-B4 is analyzed, and measures zinc silicate 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 silicate content of different desulphurization catalysts is as shown in table 1.
Wherein, B2 is carried out to polycrystal X ray diffraction (XRD) and characterize, spectrogram is shown in Fig. 4. In figure2 θ be 22.1 °, 25.5 °, 31.5 °, 38.8 °, 45.0 °, 47.0 °, 48.9 °, 57.6 °,59.5 °, 65.6 °, 65.8 ° and 68.7 ° of characteristic peaks of locating to occur zinc silicate, but do not exist lanthanum plumbous multipleClose the characteristic peak of oxide, illustrate and in desulphurization catalyst B2, do not form lanthanum plumbum composite oxide structure,And form zinc silicate component.
Table 1
| A1 | A2 | A3 | B1 | B2 | B3 | B4 | |
| Zn2SiO4, % by weight | 0 | 0 | 0 | 3.4 | 3.0 | 4.1 | 0 |
| Abrasion index (before sulfuration) | 4.3 | 4.4 | 4.4 | 5.2 | 4.8 | 5.3 | 4.3 |
| Abrasion index (after sulfuration) | 4.0 | 4.2 | 4.2 | 5.0 | 4.7 | 5.1 | 4.0 |
| Yield of gasoline, % | 99.8 | 99.9 | 99.7 | 98.9 | 99.0 | 98.3 | 99.8 |
| Product sulfur content, ppm | 4 | 4 | 6 | 24 | 22 | 26 | 6 |
| △RON | 0.65 | 0.61 | 0.58 | 0.36 | 0.45 | 0.32 | 0.26 |
| △MON | 0.60 | 0.60 | 0.54 | 0.32 | 0.40 | 0.30 | 0.24 |
| △(RON+MON)/2 | 0.62 | 0.60 | 0.56 | 0.34 | 0.42 | 0.31 | 0.25 |
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 (20)
1. a desulphurization catalyst, taking the gross weight of this desulphurization catalyst as benchmark, this desulphurization catalystContain:
1) the non-aluminum oxide of 3-35 % by weight, described non-aluminum oxide is titanium dioxide, zirconium dioxideWith at least one in tin ash;
2) silica source of 5-30 % by weight;
3) the first metal oxide of 10-80 % by weight, described the first metal oxide is selected from IIB, VBWith at least one in the metal oxide of group vib element;
4) lead oxide of 2-20 % by weight;
5) active metal of 5-30 % by weight, described active metal is selected from cobalt, nickel, iron and manganese extremelyFew a kind of;
6) in the rare-earth oxide of the 0.5-15 % by weight of rare earth oxide;
7) molecular sieve of 1-30 % by weight, described molecular sieve is X-type molecular sieve, Y zeolite and βAt least one in molecular sieve;
In the XRD spectra of described desulphurization catalyst, there is the characteristic peak of rare earth-plumbum composite oxide.
2. desulphurization catalyst according to claim 1, wherein, total with described desulphurization catalystWeight is benchmark, and the content of described non-aluminum oxide is 5-25 % by weight, and the content of described silica source is10-20 % by weight, the content of described the first metal oxide is 25-70 % by weight, the content of lead oxide is2-20 % by weight, the content of described active metal is 8-25 % by weight, described rare-earth oxide is with rareThe content of soil oxide meter is 0.5-10 % by weight, and the content of described molecular sieve is 2-25 % by weight.
3. desulphurization catalyst according to claim 1, wherein, in described rare-earth oxideRare earth element be selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er,At least one in Tm, Yb and Lu.
4. desulphurization catalyst according to claim 3, wherein, in described rare-earth oxideRare earth element be at least one in La, Ce, Pr and Nd.
5. according to the desulphurization catalyst described in any one in claim 1-4, wherein, rare earth elementFor lanthanum, in the XRD spectra of described desulphurization catalyst, exist 2 θ be 28.3 °, 32.8 °, 47.1 ° andThe characteristic peak of the cubic system of the lanthanum plumbum composite oxide of 55.8 °; Do not exist 2 θ be 28.6 °, 31.8 °,, there are not 2 θ in the characteristic peak of the tetragonal crystal system of the lead oxide of 35.7 °, 48.6 °, 54.8 ° and 59.9 °It is the characteristic peak of the cubic system of the lanthana of 27.0 °, 31.4 °, 44.8 ° and 53.2 °.
6. according to the desulphurization catalyst described in any one in claim 1-4, wherein, rare earth elementFor cerium, in the XRD spectra of described desulphurization catalyst, exist 2 θ be 28.5 °, 33.1 °, 47.4 °,The characteristic peak of the cubic system of the cerium plumbum composite oxide of 56.3 ° and 59.0 °; Not having 2 θ is 28.6°, the characteristic peak of the tetragonal crystal system of the lead oxide of 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 °,Not having 2 θ is the characteristic peak of the cubic system of the cerium oxide of 28.5 °, 33.1 °, 47.5 ° and 56.3 °.
7. according to the desulphurization catalyst described in any one in claim 1-4, wherein, rare earth elementFor neodymium, in the XRD spectra of described desulphurization catalyst, exist 2 θ be 28.3 °, 32.8 °, 47.0 °,The characteristic peak of the cubic system of the neodymium plumbum composite oxide of 55.8 ° and 58.5 °; Not having 2 θ is 28.6°, the characteristic peak of the tetragonal crystal system of the lead oxide of 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 °,Not having 2 θ is 26.8 °, 29.8 °, 30.8 °, 40.5 °, 47.4 °, 53.4 °, 57.0 ° and 57.6° the characteristic peak of cubic system of neodymia.
8. 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.
9. desulphurization catalyst according to claim 1, wherein, the sial of described X-type molecular sieveAtomic molar is than being 1-3:1; The sial atomic molar of described Y zeolite is than being 3-25:1; DescribedThe sial atomic molar of beta-molecular sieve is than being 10-40:1.
10. the preparation method of the desulphurization catalyst described in any one in claim 1-9, the method bagDraw together:
(1) precursor of lead oxide, rare earth compound, water and acidic liquid are mixed to get rareSoil-alucol;
(2) by non-al binder, silica source, the first metal oxide, molecular sieve, water and acidityLiquid was mixed to form slurries, and contacts and obtain carrier mixture with described rare earth-alucol, by described yearBody mixture carries out moulding, first dry and the first roasting, obtains carrier;
(3) on described carrier, introduce the precursor of active metal, and carry out second dry and the second roasting,Obtain catalyst precarsor;
(4) described catalyst precarsor is reduced under hydrogen atmosphere, obtain desulphurization catalyst.
11. preparation methods according to claim 10, wherein, the precursor choosing of described lead oxideAt least one in lead tetrachloride, oxychlorination lead, lead acetate, aqua oxidation lead and amorphous oxidation lead.
12. preparation methods according to claim 10, wherein, described rare earth compound choosingFrom acetate, carbonate, nitrate, sulfate, oxalates, chloride and the oxide of rare earth metalIn at least one.
13. preparation methods according to claim 10, wherein, the precursor of described active metal canTo be selected from acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of metal extremelyFew a kind of.
14. preparation methods according to claim 10, wherein, described non-al binder is dioxyChange zirconium, titanium dioxide or tin ash, or can change dioxy under the condition of described the first roastingChange the material of zirconium, titanium dioxide or tin ash.
15. preparation methods according to claim 10, wherein, described acidic liquid is acid or sourThe aqueous solution, described acid is selected from water-soluble inorganic acid and/or organic acid.
16. preparation methods according to claim 10, 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.
17. preparation methods according to claim 10, 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.
18. preparation methods according to claim 10, 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 %.
Desulphurization catalyst prepared by the method in 19. claim 10-18 described in any one.
The method of 20. 1 kinds of desulfurization of hydrocarbon oil, the method comprises: under hydrogen atmosphere, by hydrocarbon oil containing surphur withClaim 1-9 contacts with the desulphurization catalyst described in any one in 19, and the temperature of described contact is350-500 DEG C, the pressure of described contact is 0.5-4MPa.
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| CN1355727A (en) * | 1999-08-25 | 2002-06-26 | 菲利浦石油公司 | Sorbent composition, process for producing same and use in desulfurization |
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| CN102895940A (en) * | 2011-07-28 | 2013-01-30 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof |
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| US6150300A (en) * | 1996-08-14 | 2000-11-21 | Phillips Petroleum Company | Process to produce sorbents |
| CN1355727A (en) * | 1999-08-25 | 2002-06-26 | 菲利浦石油公司 | Sorbent composition, process for producing same and use in desulfurization |
| CN101773815A (en) * | 2009-01-08 | 2010-07-14 | 中国石油化工股份有限公司 | silicate-resistant desulfurization sorbent |
| CN102895940A (en) * | 2011-07-28 | 2013-01-30 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof |
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