CN105583000A - 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 discloses 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 alumina, a silicon oxide source, a first metal oxide, bismuth oxide, a rare-earth metal oxide, a SAPO molecular sieve and active metal; and an XRD spectrum of the desulphurization catalyst has a characteristic peak of a rare earth-bismuth 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. 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) aluminium oxide of 3-35 % by weight; 2) 5-30 % by weightSilica source; 3) the first metal oxide of 10-80 % by weight, described the first metal oxide is selected fromAt least one in the metal oxide of IIB, VB and group vib element; 4) oxidation of 2-20 % by weightBismuth; 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) 1-30 is heavyThe SAPO molecular sieve of amount %; In the XRD spectra of described desulphurization catalyst, there is rare earth-bismuth combined oxidationThe characteristic peak of thing.
The present invention also provides the preparation method of desulphurization catalyst provided by the invention, and the method comprises: (1)The precursor of bismuth oxide, rare earth compound, water and acidic liquid are mixed to get to rare earth-bismuth colloidal sol;(2) by alumina binder, silica source, the first metal oxide, SAPO molecular sieve, water andAcidic liquid is mixed to form slurries, and contacts and obtain carrier mixture with described rare earth-bismuth colloidal sol, by instituteState carrier mixture and carry out moulding, first dry and the first roasting, obtain carrier; (3) at described carrierThe precursor of upper introducing 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.
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 bismuth oxideAbsorb constituent element, bismuth 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 bismuth oxideSoil-bismuth composite oxide can be further effectively oxidation reinforced bismuth 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 26.9 °, 27.5°, the peak of 31.0 °, 44.9 °, 45.7 ° and 54.0 ° mark " ▼ " is lanthanum bismuth composite oxideThe characteristic peak of hexagonal crystal system;
Fig. 2 is the XRD spectra of the desulphurization catalyst A2 that contains cerium, and wherein 2 θ are 29.5 °, 31.5°, the peak of 45.0 °, 51.0 ° and 53.8 ° mark " ▼ " is the tetragonal of cerium bismuth 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 27.9 °, 32.1°, the peak of 46.2 ° and 55.0 ° mark " ▼ " is the feature of the cubic system of neodymium bismuth composite oxidePeak;
Fig. 4 is the XRD spectra of desulphurization catalyst B2, wherein do not have 2 θ be 26.9 °, 27.5 °,The characteristic peak of the lanthanum bismuth composite oxide of 31.0 °, 44.9 °, 45.7 ° and 54.0 °; But exist 2 θ to beThe peak of 8.1 °, 28.6 °, 30.7 °, 37.1 °, 59.4 ° and 65.4 ° mark " ■ " is zinc aluminateCharacteristic peak.
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.
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) aluminium oxide of 3-35 % by weight; 2) 5-30 % by weightSilica source; 3) the first metal oxide of 10-80 % by weight, described the first metal oxide is selected fromAt least one in the metal oxide of IIB, VB and group vib element; 4) oxidation of 2-20 % by weightBismuth; 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) 1-30 is heavyThe SAPO molecular sieve of amount %; In the XRD spectra of described desulphurization catalyst, there is rare earth-bismuth combined oxidationThe characteristic peak of thing.
Preferably, taking the gross weight of described desulphurization catalyst as benchmark, the content of described aluminium oxide is 5-25% by weight, the content of described silica source is 10-20 % by weight, the content of described the first metal oxideFor 25-70 % by weight, the content of bismuth oxide is 2-20 % by weight, and the content of described active metal is 8-25% by weight, described rare-earth oxide is taking the content of rare earth oxide as 0.5-10 % by weight, described inThe content of SAPO molecular sieve is 2-25 % by weight.
In the present invention, the content of described desulphurization catalyst middle rare earth metal oxide and bismuth oxide can be favourableIn forming rare earth-bismuth composite oxide structure, thereby be more conducive to oxidation reinforced bismuth 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 bismuth oxide phaseIn conjunction with, make desulphurization catalyst can there is the crystal structure of rare earth-bismuth 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, and in the time that rare earth element is lanthanum, described desulfurizationIn the XRD spectra of catalyst, exist 2 θ be 26.9 °, 27.5 °, 31.0 °, 44.9 °, 45.7 ° andThe characteristic peak (JCPDSNo.47-0474) of the hexagonal crystal system of the lanthanum bismuth composite oxide of 54.0 °; Do not exist2 θ be 24.5 °, 27.5 °, 30.1 °, 32.6 °, 41.2 °, 43.1 °, 45.0 °, 51.9 °,The characteristic peak (JCPDSNo.45-1344) of the cubic system of the bismuth oxide of 53.5 °, 55.1 ° and 61.2 °,Not having 2 θ is the characteristic peak of the cubic system of the lanthana of 27.0 °, 31.4 °, 44.8 ° and 53.2 °(JCPDSNo.4-0856)。
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 29.5 °, 31.5 °, 45.0 °, 51.0 ° and 53.8 °The characteristic peak (JCPDSNo.1-070-2454) of tetragonal crystal system of cerium bismuth composite oxide; There are not 2 θIt is 24.5 °, 27.5 °, 30.1 °, 32.6 °, 41.2 °, 43.1 °, 45.0 °, 51.9 °, 53.5°, the characteristic peak of the cubic system of the bismuth oxide of 55.1 ° and 61.2 °, not having 2 θ is 28.5 °, 33.1°, the characteristic peak (JCPDSNo.03-065-2975) of the cubic system of the cerium oxide of 47.5 ° and 56.3 °.
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 that the neodymium bismuth of 27.9 °, 32.1 °, 46.2 ° and 55.0 ° is multipleClose the characteristic peak (JCPDSNo.53-0003) of the cubic system of oxide; Do not exist 2 θ be 24.5 °,27.5°、30.1°、32.6°、41.2°、43.1°、45.0°、51.9°、53.5°、55.1°With the characteristic peak of the cubic system of the bismuth oxide of 61.2 °, not having 2 θ is 26.8 °, 29.8 °, 30.8°, the characteristic peak of the cubic system of the neodymia of 40.5 °, 47.4 °, 53.4 °, 57.0 ° and 57.6 °(JCPDSNo.6-0408)。
In the present invention, in desulphurization catalyst, form rare earth-bismuth composite oxide structure, can promote oxygenWhat change bismuth 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-bismuth composite oxide of formation,Can improve gasoline and diesel fuel desulfurization activity. The desulphurization catalyst that use contains rare earth-bismuth 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, bismuth 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 aluminium oxide can be for providing bonding between each component in described desulphurization catalystEffect. Under preferable case, described aluminium oxide is gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-oxidationAt least one in aluminium; Preferably, described aluminium oxide is gama-alumina.
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, the SAPO molecular sieve containing in desulphurization catalyst can make straight-chain hydrocarbons obtain isomeryChange, gasoline products octane number is improved, ensure the effect of higher yield of gasoline simultaneously. Described SAPOMolecular sieve be the SAPO-34,17,18,26,33,34,35,39,42,43 that is selected from small-bore,44,47, the SAPO-11,31 of mesoporous, 41 and wide-aperture SAPO-5,36,37,40,46In at least one. Under preferable case, described SAPO molecular sieve be SAPO-5, SAPO-11,At least one in SAPO-31, SAPO-34 and SAPO-20 molecular sieve.
According to the present invention, the sial atomic molar ratio of the SAPO molecular sieve containing in described desulphurization catalystThere is no particular limitation, as long as applicable acidity can be provided. Under preferable case, described SAPOThe sial atomic molar of molecular sieve is than being 0.05-1.0:1; Preferably, the sial of described SAPO molecular sieveAtomic molar is than being 0.05-0.75:1; More preferably, the sial atomic molar of described SAPO molecular sieveThan being 0.1-0.5:1.
In the present invention, add SAPO molecular sieve to have and promote aromatization of hydrocarbons by increasing containing of aromatic hydrocarbonsAmount improves effect or the effect of gasoline products octane number.
The present invention also provides the preparation method of desulphurization catalyst provided by the invention, and the method comprises: (1)The precursor of bismuth oxide, rare earth compound, water and acidic liquid are mixed to get to rare earth-bismuth colloidal sol;(2) by alumina binder, silica source, the first metal oxide, SAPO molecular sieve, water andAcidic liquid is mixed to form slurries, and contacts and obtain carrier mixture with described rare earth-bismuth colloidal sol, by instituteState carrier mixture and carry out moulding, first dry and the first roasting, obtain carrier; (3) at described carrierThe precursor of upper introducing 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.
According to the present invention, the precursor of described bismuth oxide is bismuth oxide or the condition in described the first roastingCan change down the material of bismuth oxide into. Under preferable case, the precursor of described bismuth oxide is selected from tetrachloroAt least one in bismuth, Bismuth Oxychloride, bismuth acetate, aqua oxidation bismuth and amorphous oxidation bismuth.
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 alumina binder is aluminium oxide or in described the first roastingCondition under can change the material of aluminium oxide, for example hydrated alumina and/or aluminium colloidal sol into; Wherein, instituteState hydrated alumina be selected from boehmite (boehmite), false boehmite (boehmite),At least one in hibbsite and amorphous hydroted alumina.
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, SAPO molecular sieve, silica source and active goldBelong to as previously mentioned, 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-Bismuth colloidal sol, to form rare earth-bismuth 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-bismuth colloidal sol can have several different methods, Ke YiweiMethod one, comprises the following steps: (a) precursor of bismuth oxide and acidic liquid are mixed to get to bismuth colloidal sol;(b) described bismuth colloidal sol and rare earth compound are mixed and contact with ammonia spirit again that to obtain rare earth-bismuth moltenGlue. Can also be method two, comprise the following steps: (i) by mixed to the precursor of bismuth oxide and acidic liquidClose and obtain bismuth colloidal sol; (ii) aqueous solution of described bismuth colloidal sol and rare earth compound is obtained to rare earth-bismuth colloidal sol. Also can be method three, comprise: by the precursor of bismuth oxide, rare earth compound andWater and acidic liquid are mixed to get rare earth-bismuth colloidal sol.
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-bismuth colloidal sol, 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) alumina binder, silica source, water are contacted and obtain acidifying with acidic liquidSlurries; (B) these acidifying slurries and the first metal oxide, SAPO molecular sieve are mixed to form to slurries.Another kind of preferred detailed description of the invention comprises: (I) by alumina binder, silica source water respectivelyContact with acidic liquid and obtain aluminium oxide glue and silica source after treatment, then be mixed into acidifying slurries;(II) described acidifying slurries and the first metal oxide, SAPO molecular sieve are mixed to form to slurries. ItsDescribed in acidic liquid described above, the consumption of described acidic liquid makes the pH value of described acidifying slurries littleIn 6, be preferably less than 4.
In the present invention, moulding described in step (2) described carrier mixture can be shaped to extrudate,Sheet, pill, ball or micro-spherical particle. For example, described carrier mixture is dough or paste mixtureTime, can make described carrier mixture moulding (preferably extrusion molding) form particle, preferably diameter is at 1.0-8.0Mm, length is at the cylindrical extrudate of 2.0-5.0mm, 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, the precursor of described alumina binder, bismuth oxide, silicaThe precursor of source, the first metal oxide, SAPO molecular sieve, rare earth compound and active metalThe addition desulphurization catalyst that makes to obtain in, taking the gross weight of this desulphurization catalyst as benchmark, described oxygenThe content of changing aluminium is 3-25 % by weight, and the content of described silica source is 5-30 % by weight, described firstThe content of metal oxide is 10-80 % by weight, and the content of bismuth oxide is 2-20 % by weight, described activityThe content of metal is 5-30 % by weight, described rare-earth oxide taking the content of rare earth oxide as0.5-15 % by weight, the content of described SAPO molecular sieve is 1-30 % by weight.
Preferably, taking the gross weight of this desulphurization catalyst as benchmark, the content of described aluminium oxide is 5-25% by weight, the content of described silica source is 10-20 % by weight, the content of described the first metal oxideFor 25-70 % by weight, the content of bismuth oxide is 2-20 % by weight, and the content of described active metal is 8-25% by weight, described rare-earth oxide is taking the content of rare earth oxide as 0.5-10 % by weight, described inThe content of SAPO 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-bismuth colloidal sol. The bismuth oxide of 0.5kg (Beijing Chemical Plant analyzes pure) is addedIn nitric acid (chemical pure, the Beijing Chemical Plant produces) solution of 5 % by weight of 1.0kg and stir 1h,Obtain water white bismuth colloidal sol. The lanthana (traditional Chinese medicines chemical reagents corporation analyzes pure) of 0.5kg is moltenIn the deionized water solution of 0.2kg after and bismuth colloidal sol be mixed to get lanthanum bismuth colloidal sol.
(2) prepare carrier. By 1.73kg expanded perlite (catalyst Nanjing branch company, containing dryBase 1.3kg) join and in the salpeter solution of 2 % by weight of 0.5kg, add thermal agitation and filter after 2 hours,To expanded perlite after treatment;
By the boehmite of 1.6kg (catalyst asphalt in Shenli Refinery, containing butt 1.2kg) and 0.8kgThe nitric acid mixing pH=1.8 of 5 % by weight, under agitation adds above-mentioned expanded perlite after treatment to mix,Add again by the zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) of 4.05kg, the SAPO-11 of 0.8kgMolecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO2:Al2O3MoleRatio=1:1) and the mixed serum that mixes of the deionized water of 5.25kg stir, more above-mentioned lanthanum bismuth colloidal sol is addedEnter and stir after 1 hour and 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: alumina content is 12 % by weight, and zinc oxide content is 40.0 % by weight,Expanded perlite content is 13.0 % by weight, and bismuth oxide content is 5.0 % by weight, and lanthana content is 5.0% by weight, nickel content is 18.0 % by weight, SAPO-11 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 26.9 at 2 θ°, 27.5 °, 31.0 °, 44.9 °, 45.7 ° and 54.0 ° six sides that locate to exist lanthanum bismuth composite oxideThe characteristic peak of crystallographic system, 2 θ be 24.5 °, 27.5 °, 30.1 °, 32.6 °, 41.2 °, 43.1 °,Locate the feature of the cubic system that does not have bismuth oxide for 45.0 °, 51.9 °, 53.5 °, 55.1 ° and 61.2 °Peak, and be 27.0 °, 31.4 °, 44.8 ° and the 53.2 ° cubic crystals of locating not exist lanthana at 2 θThe characteristic peak of system. Illustrate in desulphurization catalyst A1 that bismuth oxide and lanthana have formed lanthanum bismuth composite oxideStructure.
Embodiment 2
The present embodiment is for illustrating the preparation method of desulphurization catalyst of the present invention.
(1) prepare rare earth-bismuth colloidal sol. The bismuth oxide of 0.8kg is joined to 15 % by weight of 2.0kgIn hydrochloric acid solution and stir acidifying 1h, form water white bismuth colloidal sol. By the cerium oxide (state of 300gMedicine chemical reagents corporation, analyzes pure) add in bismuth colloidal sol, be uniformly mixed rear dropping 25 % by weightAmmonia spirit is until become cerium bismuth colloidal sol.
(2) prepare carrier. By the aluminium isopropoxide of 5.28kg (traditional Chinese medicines chemical reagents corporation, analyze pure,98.5 % by weight) join in the deionized water of 13kg and be hydrolyzed, be heated to react after 1 hour at 90 DEG C,Add in hydrochloric acid (chemical pure, the Beijing Chemical Plant produce) solution of 15 % by weight of 2.4kg and stir acidChange 1 hour, form water white colloidal solution, be called aluminium colloidal sol.
1.2kg diatomite (silicon oxide-containing 1.00kg), the Zinc oxide powder of 5.06kg, 0.24kgSAPO-34 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.2kg, SiO2:Al2O3Mol ratio=0.25:1), 30 points of the deionized water mix and blends of above-mentioned cerium bismuth composite oxide and 5.0kgAfter clock, obtain mixed serum, then mix with above-mentioned aluminium colloidal sol and 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: alumina content 13.0 % by weight, and zinc oxide content is 50.0 % by weight,Bismuth oxide content is 8.0 % by weight, and diatomite content is 10.0 % by weight, cerium oxide 3.0 % by weight, nickel14.0 % by weight, SAPO-34 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 tetragonal crystal system of cerium bismuth composite oxide for 29.5 °, 31.5 °, 45.0 °, 51.0 ° and 53.8 °Characteristic peak, be 24.5 °, 27.5 °, 30.1 °, 32.6 °, 41.2 °, 43.1 °, 45.0 at 2 θ°, 51.9 °, 53.5 °, 55.1 ° and the 61.2 ° characteristic peaks of locating the cubic system that does not have bismuth oxide,And be 28.5 °, 33.1 °, 47.5 ° and 56.3 ° cubic crystals of locating not exist cerium oxide at 2 θCharacteristic peak. Illustrate that bismuth oxide and cerium oxide in desulphurization catalyst A2 have formed the knot of cerium bismuth composite oxideStructure.
Embodiment 3
The present embodiment is for illustrating the preparation method of desulphurization catalyst of the present invention.
(1) prepare rare earth-bismuth colloidal sol. By the bismuth hydroxide of 0.7kg (Aldrich company, analyze pure,99 % by weight) and the six nitric hydrate neodymiums of 0.651kg (traditional Chinese medicines chemical reagents corporation, content is greater than 99.0% by weight) join in rare nitric acid (chemical pure, Beijing Chemical Plant produces) of 15 % by weight of 2.7kgAnd stir acidifying 1 hour, and obtain transparent colloidal solution, be called neodymium bismuth colloidal sol.
(2) prepare carrier. By the expanded perlite of 1.59kg, (catalyst Nanjing branch company, containing butt1.20kg) after mixing with the deionized water of 3.0kg, add the salpeter solution heating of 2 % by weight of 0.6kgStir pH=1.8 and obtain acidifying slurries, then with the Zinc oxide powder of 4.56kg (Headhorse company, pureSpend 99.7 % by weight), the SAPO-5 of 0.56kg (Nanjing catalyst branch company, containing butt 0.5kg,Sial atomic molar is than for 0.5:1) and the deionized water mix and blend of 4.65kg 30 minutes, then addAbove-mentioned neodymium bismuth colloidal sol stirring 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 (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: alumina content is 16 % by weight, and zinc oxide content is 45.0 % by weight,Expanded perlite content is 12.0 % by weight, and SAPO-5 molecular sieve content is 5.0 % by weight, bismuth oxideContent is 6.0 % by weight, and neodymium oxide content is 4.0 % by weight, and nickel content is 12.0 % 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 the characteristic peak of the cubic system that has neodymium bismuth composite oxide for 27.9 °, 32.1 °, 46.2 ° and 55.0 °,2 θ be 24.5 °, 27.5 °, 30.1 °, 32.6 °, 41.2 °, 43.1 °, 45.0 °, 51.9 °,Locate the characteristic peak of the cubic system that does not have bismuth oxide for 53.5 °, 55.1 ° and 61.2 °, and at 2 θ beLocate not exist for 26.8 °, 29.8 °, 30.8 °, 40.5 °, 47.4 °, 53.4 °, 57.0 ° and 57.6 °The characteristic peak of the cubic system of neodymia. Illustrate in desulphurization catalyst A3 that bismuth oxide and neodymia have formedThe structure of neodymium bismuth composite oxide.
Comparative example 1
1.261 lanthanum nitrate is dissolved in the deionized water solution of 0.2kg and obtains lanthanum solution;
The expanded perlite of 1.33kg (catalyst asphalt in Shenli Refinery, silicon oxide-containing 0.77kg) is joinedIn the salpeter solution of 2 % by weight of 0.5kg, add thermal agitation and filter after 2 hours, obtain expansion after treatmentPerlite;
By the boehmite of 2.27kg (catalyst asphalt in Shenli Refinery, containing butt 1.7kg) and 1.0kgThe nitric acid mixing pH=1.8 of 5 % by weight, under agitation add above-mentioned expanded perlite after treatment to mix,Add again by the zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) of 4.00kg, the SAPO-11 of 0.8kgMolecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO2:Al2O3MoleRatio=1:1) and the mixed serum that mixes of the deionized water of 5.25kg stir, more above-mentioned lanthanum solution is addedAnd stir after 1 hour and obtain carrier mixture.
Carry out spray drying forming, the roasting of carrier mixture with reference to the method for embodiment 1, introduce activeComponent nickel reduction, obtain desulphurization catalyst B1. Wherein the compound of active metal is six nitric hydratesNickel, consumption is 2.79kg.
The composition of desulphurization catalyst B1 is calculated as by inventory: alumina content is 17 % by weight, oxidationZinc content is 40.0 % by weight, and expanded perlite content is 13.0 % by weight, and lanthana content is 5.0 weightsAmount %, nickel content is 18.0 % by weight, SAPO-11 molecular sieve 7.0 % by weight.
Comparative example 2
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 and filter after 2 hours, obtain expansion after treatmentPerlite;
By the boehmite catalyst asphalt in Shenli Refinery of 1.6kg, containing butt 1.22.0kg) and 0.8kgThe nitric acid mixing pH=1.8 of 5 % by weight, under agitation adds above-mentioned expanded perlite after treatment to mix,Add again by the zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) of 4.05kg, the SAPO-11 of 0.8kgMolecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO2:Al2O3MoleRatio=1:1) and the mixed serum that mixes of the deionized water of 5.25kg stir, then add 1.261 nitric acidLanthanum is dissolved in the deionized water solution of 0.2kg and obtains cerium solution, and the bismuth oxide of 1.5kg mixes and stirsMix after 1 hour and obtain carrier mixture.
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: alumina content is 12 % by weight, and zinc oxide content is 40.0 % by weight,Expanded perlite content is 13.0 % by weight, and bismuth oxide content is 5.0 % by weight, and lanthana content is 5.0% by weight, nickel content is 18.0 % by weight, SAPO-11 molecular sieve 7.0 % by weight.
Comparative example 3
The bismuth oxide of 1.5kg joined in the salpeter solution of 5 % by weight of 3.5kg and stir 1h,To water white bismuth 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 and filter after 2 hours, obtain expansion after treatmentPerlite;
By the boehmite of 2.27kg (catalyst asphalt in Shenli Refinery, containing butt 1.7kg) and 1.0kgThe nitric acid mixing pH=1.8 of 5 % by weight, under agitation add above-mentioned expanded perlite after treatment to mix,Add again by the zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) of 4.05kg, the SAPO-11 of 0.8kgMolecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO2:Al2O3MoleRatio=1:1) and the mixed serum that mixes of the deionized water of 5.25kg stir, then add above-mentioned bismuth colloidal sol mixedMerge to stir after 1 hour and 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: alumina content is 17 % by weight, and zinc oxide content is 40.0 % by weight,Expanded perlite content is 13.0 % by weight, and bismuth oxide content is 5.0 % by weight, and nickel content is 18.0 weightsAmount %, SAPO-11 molecular sieve 7.0 % by weight.
Comparative example 4
The bismuth oxide of 0.5kg joined in the salpeter solution of 5 % by weight of 1.0kg and stir 1h,To water white bismuth colloidal sol. The lanthana (traditional Chinese medicines chemical reagents corporation analyzes pure) of 0.5kg is dissolved inIn the deionized water solution of 0.2kg after and bismuth colloidal sol be mixed to get lanthanum bismuth 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 and filter after 2 hours, obtain expansion after treatmentPerlite;
By the boehmite of 3.17kg (catalyst asphalt in Shenli Refinery, containing butt 1.9kg) and 1.5kgThe nitric acid mixing pH=1.8 of 5 % by weight, under agitation add above-mentioned expanded perlite after treatment to mix,Add again by the zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) of 4.05kg and 5.25kg go fromThe mixed serum that sub-water mixes stirs, more above-mentioned lanthanum bismuth colloidal sol is added and stir after 1 hour and obtain carrierMixture.
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: alumina content is 19 % by weight, and zinc oxide content is 40.0 % by weight,Expanded perlite content is 13.0 % by weight, and bismuth oxide content is 5.0 % by weight, and lanthana content is 5.0% by weight, nickel content is 18.0 % 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 aluminate 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 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.
Wherein, B2 is carried out to polycrystal X ray diffraction (XRD) and characterize, spectrogram is shown in Fig. 4. In figure2 θ are 8.1 °, 28.6 °, 30.7 °, 37.1 °, 59.4 ° and 65.4 ° of spies that locate to occur zinc aluminateLevy peak, but do not have the characteristic peak of lanthanum bismuth composite oxide, illustrate in desulphurization catalyst B2 and do not formLanthanum bismuth composite oxide structure, and form zinc aluminate component.
Table 1
| A1 | A2 | A3 | B1 | B2 | B3 | B4 | |
| ZnAl2O4, % by weight | 0 | 0 | 0 | 3.3 | 2.5 | 4.0 | 0 |
| Abrasion index (before sulfuration) | 4.3 | 4.5 | 4.5 | 5.3 | 4.8 | 5.4 | 4.3 |
| Abrasion index (after sulfuration) | 4.1 | 4.2 | 4.3 | 5.1 | 4.7 | 5.2 | 4.1 |
| Yield of gasoline, % | 99.8 | 99.9 | 99.7 | 99.0 | 99.1 | 98.4 | 99.8 |
| Product sulfur content, ppm | 5 | 7 | 8 | 35 | 29 | 40 | 5 |
| △RON | 0.58 | 0.45 | 0.40 | 0.28 | 0.30 | 0.15 | -0.10 |
| △MON | 0.55 | 0.40 | 0.35 | 0.24 | 0.25 | 0.10 | -0.10 |
| △(RON+MON)/2 | 0.57 | 0.43 | 0.38 | 0.26 | 0.28 | 0.13 | -0.10 |
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) aluminium oxide of 3-35 % by weight;
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) bismuth 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) the SAPO molecular sieve of 1-30 % by weight;
In the XRD spectra of described desulphurization catalyst, there is the characteristic peak of rare earth-bismuth composite oxide.
2. desulphurization catalyst according to claim 1, wherein, total with described desulphurization catalystWeight is benchmark, and the content of described aluminium oxide is 5-25 % by weight, and the content of described silica source is 10-20% by weight, the content of described the first metal oxide is 25-70 % by weight, the content of bismuth oxide is 2-20% by weight, the content of described active metal is 8-25 % by weight, described rare-earth oxide is with rare earth oxygenThe content of compound meter is 0.5-10 % by weight, and the content of described SAPO 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 26.9 °, 27.5 °, 31.0 °,The characteristic peak of the hexagonal crystal system of the lanthanum bismuth composite oxide of 44.9 °, 45.7 ° and 54.0 °; There are not 2 θIt is 24.5 °, 27.5 °, 30.1 °, 32.6 °, 41.2 °, 43.1 °, 45.0 °, 51.9 °, 53.5°, the characteristic peak of the cubic system of the bismuth oxide of 55.1 ° and 61.2 °, not having 2 θ is 27.0 °, 31.4°, the characteristic peak of the cubic system of the lanthana of 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 29.5 °, 31.5 °, 45.0 °,The characteristic peak of the tetragonal crystal system of the cerium bismuth composite oxide of 51.0 ° and 53.8 °; Not having 2 θ is 24.5°、27.5°、30.1°、32.6°、41.2°、43.1°、45.0°、51.9°、53.5°、55.1° and the characteristic peak of the cubic system of the bismuth oxide of 61.2 °, not having 2 θ is 28.5 °, 33.1 °, 47.5° and the characteristic peak of the cubic system of the cerium oxide of 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 27.9 °, 32.1 °, 46.2 ° andThe characteristic peak of the cubic system of the neodymium bismuth composite oxide of 55.0 °; Do not exist 2 θ be 24.5 °, 27.5 °,30.1 °, 32.6 °, 41.2 °, 43.1 °, 45.0 °, 51.9 °, 53.5 °, 55.1 ° and 61.2 °The characteristic peak of cubic system of bismuth oxide, not having 2 θ is 26.8 °, 29.8 °, 30.8 °, 40.5°, the characteristic peak of the cubic system of the neodymia of 47.4 °, 53.4 °, 57.0 ° and 57.6 °.
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, described SAPO molecular sieve isAt least one in SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieve.
10. the preparation method of the desulphurization catalyst described in any one in claim 1-9, the method bagDraw together:
(1) precursor of bismuth oxide, rare earth compound, water and acidic liquid are mixed to get rareSoil-bismuth colloidal sol;
(2) by alumina binder, silica source, the first metal oxide, SAPO molecular sieve,Water and acidic liquid are mixed to form slurries, and contact and obtain carrier mixture with described rare earth-bismuth colloidal sol,Described carrier mixture is carried out to moulding, first dry and the first roasting, obtain 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 bismuth oxideAt least one in four bismuth chlorides, Bismuth Oxychloride, bismuth acetate, aqua oxidation bismuth and amorphous oxidation bismuth.
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, described alumina binder is oxygenChange aluminium, or under the condition of described the first roasting, can change the material of aluminium oxide into.
14. 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.
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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