CN105582957A - A cobalt-based Fischer-Tropsch synthesis catalyst supported by a spherical carrier and a preparing method thereof - Google Patents
A cobalt-based Fischer-Tropsch synthesis catalyst supported by a spherical carrier and a preparing method thereof Download PDFInfo
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Abstract
A cobalt-based Fischer-Tropsch synthesis catalyst supported by a spherical carrier is disclosed. The catalyst comprises 1-50% by weight of cobaltous oxide, 50-99% by weight of mixed oxide spherical carrier particles the particle size of which is 10-100 mum, and less than 0.1% by weight of a precious metal selected from Pd, Pt, Au, Ag, Rh, Ru or a mixture thereof. The mixed oxide spherical carrier particles comprise microspheres and an auxiliary agent. The microspheres are microspheres made of materials selected from silicon oxide, aluminum oxide, zirconium oxide or a mixture thereof. The auxiliary agent is an oxide of an element selected from Ni, Ca, Mg, La, Zr, Ce, Ti, Mn, V, Nb, or a mixture thereof. A method of preparing the catalyst is also provided.
Description
Technical field
The present invention relates to catalyze and synthesize field, specifically, the invention provides one, to be applicable to Fischer-Tropsch syntheticLoad type cobalt-base catalyst of reaction and preparation method thereof.
Background technology
Fischer-Tropsch (F-T) is synthetic is synthesis gas (CO+H2) mistake of reaction generation hydro carbons under the effect of catalystJourney, the main hydrocarbon products and the titanium dioxide that comprise gasoline, diesel oil, wax, naphtha, low-carbon alkene of generatingThe accessory substances such as carbon, water and oxygen-containing organic compound. Fischer-Tropsch is synthetic to be widely used for coal, natural gas or living beingsFirst be converted into synthesis gas, and then be converted into liquid fuel. The synthetic main catalyst using of Fischer-Tropsch comprises ironCatalyst based and cobalt-base catalyst. Compare ferrum-based catalyst, cobalt-base catalyst has high activity, low water because of itGas shift reaction, long service life and the feature such as natural gas base synthesis gas that is applicable to high hydrogen-carbon ratio becomeOne of catalyst of tool industrial application value. And paste state bed reactor is also because of good heat conductivity, lessPressure Drop, high target hydrocarbon-selective, can be online more catalyst changeout, easily realize the advantages such as large-scale production,Becoming and replace traditional most promising technique of F-T synthetic technology, is also the developing direction of synthetic liquid fuel.Paste state bed reactor is a gas-liquid-solid reaction device, and in course of reaction, catalyst granules will stand insteadAnswer between temperature fluctuation, catalyst granules, the reaction environment such as sharp impacts between catalyst and reactor wall.Not only to there be high specific area, uniform size distribution, regular for starching the cobalt-base catalyst of state bed systemSpherical morphology, also should possess suitable density and stronger abrasion resistance properties simultaneously, anti-to adapt to starching state bedAnswer in device comparatively harsh operating environment, make catalyst keep comparatively ideal catalytic activity, selectivity of product withProduce high valuable chemicals and reduce subsequent machining cost. Simultaneously catalyst also should keep relative stabilityParticle shape shape, increases mechanical strength, the mar proof of cobalt-base catalyst particle, to effectively synthesize with F-TThe heavy wax generating in process separates, and extends the service life of cobalt-base catalyst. Along with cobalt-based slurry state bedDevelopment and the popularization of the application of F-T synthesis technique, people have higher requirement to the research and development of cobalt-base catalyst.
Co/ZrO2Catalyst is the catalyst that research is at present comparatively extensive and deep. Although Co/ZrO2CatalysisAgent shows high activity, low CH in fixed bed F-T is synthetic4Selective and long running life-span, but forUtilize the precipitation method and the spray drying process Co/ZrO for the preparation of slurry state bed2The situation of catalyst, findsThe catalyst making by the way has poor processability, gained rough, and particle diameter is notEvenly, yield rate is low, is easy to efflorescence at high temperature, high pressure and in there is the slurry state bed F-T building-up process of steam,This can cause follow-up oily wax separation difficulty. In addition, the fine grained after efflorescence easily stops up gas distributor and causesSynthesis gas diffusion is uneven, and catalyst loss rate is high. For improving slurry state bed cobalt-base catalyst abrasion resistance properties,In the preparation process of catalyst, often add wherein some structural promoters, as Al2O3Carrier. But,Due to Co-Al2O3Between there is strong interaction, in course of reaction, easily form difficult reduction and do not possess and urgeChange active CoAl2O4Material, and then can reduce to a certain extent its catalytic activity, improve methane selectivelyAnd the service life of shortening catalyst, these phenomenons are all that this area researcher does not wish to see.
Chinese patent application CN1395992A and CN1583259A disclose respectively for Fischer-Tropsch synthetic anti-The preparation method of the ferrum-based catalyst of answering, the theory of its technique is all Kaolinite Preparation of Catalyst active component and helping in advanceThe suspension slurry of agent presoma, then maybe can form the molten of silica by these slurries and silica solidLiquid system is mixed, afterwards this mixture sprayed dry, thus synthesizing spherical ferrum-based catalyst. But,These two disclosed process for synthetic catalyst of patent equally easily cause very strong carrier-active component mutually to be doneWith, and carrier easily covers activated centre, and above-mentioned phenomenon all can cause the catalytic activity of catalyst to reduce. This, owing to utilizing iron-based as active component, make it not be suitable for natural gas base synthesis gas outward, reactivity worth andStability is not as cobalt-base catalyst. And SiO2Carrier is also too late aspect mechanical strength and abrasion resistance propertiesAl2O3Carrier. Therefore the mechanical performance problems that solves catalyst carrier is a key in paste state bed reactorProblem, and key is wherein the carrier of catalyst.
Problem to be solved by this invention is a kind of load type cobalt-base that is suitable for Fischer-Tropsch synthesis of exploitationCatalyst, its carrier not only has good mechanical strength properties, can not occur strong with active catalytic compositionInteract, nor can cover catalytic active center, make this catalyst be applicable to paste state bed reactor,And there is high activity, high target selection, high mechanical properties and wear resistance.
Summary of the invention
First the present invention applies auxiliary agent coating on the part or all of surface of microballoon, obtains mixed oxide ballShape carrier granular, is then combined in cobalt on this mixed oxide spherical carrier particle, thereby has made thisThe bright cobalt-base catalyst with good catalytic performance and mechanical performance.
It is a kind of for entering at paste state bed reactor or stirred reactor that first aspect of the present invention providesThe cobalt-base catalyst of row Fischer-Tropsch synthesis, taking the gross weight of this catalyst as benchmark, described catalyst bagContaining the cobalt oxide of 1-50 % by weight, the particle diameter of 50-99 % by weight is 10-100 micron, preferably 50-100 is micro-Rice, is more preferably the mixed oxide spherical carrier particle of 50-80 micron, and is less than 0.1 % by weightBe selected from the noble metal of Pd, Pt, Au, Ag, Rh, Ru or its combination;
Described mixed oxide spherical carrier particle is made up of microballoon and auxiliary agent, with the gross weight of this cobalt-base catalystAmount is benchmark meter, and the content of described auxiliary agent is 1-20 % by weight, and described microballoon is by being selected from following materialThe microballoon of composition: silica, aluminium oxide, zirconia or its mixture; Described auxiliary agent is selected from followingThe oxide of element: Ni, Ca, Mg, La, Zr, Ce, Ti, Mn, V, Nb or theyCombination;
Prerequisite is to comprise zirconic time when described microballoon, and described auxiliary agent does not comprise zirconium; And described inThe metallic element kind that auxiliary agent comprises is simultaneously no more than 4 kinds;
Described cobalt-base catalyst also optionally comprises and loads on described mixed oxide spherical carrier particleThe transition metal oxide that is different from cobalt oxide, described in be different from the auxiliary agent transition metal oxide of cobalt oxideKind be identical with the kind of the oxide of the element comprising in described auxiliary agent.
Of the present invention one preferred embodiment in, described auxiliary agent covers described microballoon with the form of coatingPart or all of surface, more preferably cover all surfaces of described microballoon.
Of the present invention another preferred embodiment in, described microballoon is made up of aluminium oxide, described auxiliary agentBe selected from following material: zirconia, nickel oxide, manganese oxide or its combination.
Of the present invention another preferred embodiment in, taking the gross weight of this catalyst as benchmark, instituteThe content of stating cobalt oxide is 1-50 % by weight, is preferably 15-35 % by weight; The content of described microballoon is 50-99% by weight, is preferably 65-85 % by weight; The content of described auxiliary agent is 1-20 % by weight, is preferably 2-10% by weight.
Second aspect of the present invention provides a kind of side that is used for preparing cobalt-base catalyst of the present inventionMethod, said method comprising the steps of:
I) the auxiliary agent precursor solution that preparation comprises following element: Ni, Ca, Mg, La, Zr, Ce, Ti,Mn, V, Nb or their combination;
Ii) described auxiliary agent precursor solution is mixed with microballoon, under the condition raising in pH value, appliedMicroballoon;
Iii) microballoon of this coating is carried out to slaking and roasting, make described mixed oxide ball type carrierGrain;
Iv) precursor solution that preparation comprises cobalt, by the described precursor solution that comprises cobalt and step I ii) makeMixed oxide spherical carrier particle mix, the mixed oxide spherical carrier particle of cobalt that obtained load,Or by the presoma that comprises cobalt with solid form directly and step I ii) the mixed oxide ball type carrier that makesParticle carries out solids mixing, the mixed oxide spherical carrier particle of cobalt that obtained load;
V) then to this load the mixed oxide spherical carrier particle of cobalt carry out roasting, reduction and passivation,Make described cobalt-base catalyst.
For said method, one preferred embodiment in, described step I) in auxiliary agent presoma moltenLiquid is the salt of the following element solution in water, alcohol or organic acid: Ni, Ca, Mg, La, Zr, Ce,Ti, Mn, V, Nb or their combination; Described salt is nitrate, hydrochloride, sulfuric acid preferablySalt, phosphate, carboxylate; Described salt is more preferably nitrate, hydrochloride, acetate or itsMeaning mixture.
Of the present invention another preferred embodiment in, described step I i) in, described pH value raisesCondition represent by add alkali make pH value be elevated to 8-11; At step I ii) in, described coatingMicroballoon is at the curing in water 8-24 hour of 50-100 DEG C; Described roasting at the temperature of 300-700 DEG C,In air atmosphere, carry out 2-10 hour. Preferably, described step I i) and iii) can repeat 1-4Inferior, thus on microballoon, carry out applying of 1-4 auxiliary agent layer.
Of the present invention another preferred embodiment in, the described step I presoma that comprises cobalt v) is moltenLiquid is the soluble-salt of the cobalt solution in water or alcohol; The soluble-salt of described cobalt is cobalt acetate, nitric acid preferablyCobalt or their mixture.
Of the present invention another preferred embodiment in, described step I is v) and v) in the following mannerCarry out: by the presoma that comprises cobalt of the described precursor solution that comprises cobalt or solid form and step I ii)The mixed oxide spherical carrier particle that makes mixes, then at the temperature of normal temperature to 200 DEG C, air,Dry in nitrogen or vacuum, the mixed oxide spherical carrier particle of cobalt that obtained load; Then at 200-400DEG C temperature under, in air atmosphere to this load the mixed oxide spherical carrier particle of cobalt roastBurn; Then at the temperature of 200-500 DEG C, in hydrogen atmosphere, reduce 3-5 hour, the pressure of described hydrogenPower is 0.1-2MPa, and in hydrogen atmosphere, the concentration of hydrogen is 1-100 volume %; Then containing 1 volume %The nitrogen of oxygen in, passivation 10 minutes to 5 hours at the temperature of normal temperature to 40 DEG C, thus make instituteState cobalt-base catalyst.
The 3rd aspect of the present invention provides a kind of expense of carrying out in paste state bed reactor or stirred reactorThe method of holder reaction, the method comprises the following steps: in existing as claim 1-5 as described in any oneIn the situation of cobalt-base catalyst, carbon monoxide and hydrogen are reacted, generate hydrocarbon product, this reactionUnder following reaction condition, carry out: reaction temperature 180-270 DEG C, is preferably 180-250 DEG C, reaction pressure0.5-5MPa, the total air speed of gas is 1000-10000 hour-1, 500-8000 hour-1, carbon monoxide and hydrogenThe volume ratio of gas is 1:1 to 1:3.
In an embodiment of the invention, before fischer-tropsch reaction starts, under the following conditions to catalysisReduction pretreatment is carried out in agent: temperature is 200-500 DEG C, uses the pure hydrogen of 0.1-2MPa or comprises 1 volumeThe hydrogen of the CO of %.
Brief description of the drawings
Fig. 1 is to be the catalyst of the embodiment SEM photograph carrying out catalytic reaction after according to the present inventionSheet;
Fig. 2 is the catalyst of prior art of the example in contrast SEM photograph carrying out catalytic reaction afterSheet.
Detailed description of the invention
" scope " disclosed herein is with the form of lower limit and the upper limit. Can be respectively one or more lower limits,With one or more upper limits. Given range limits by a selected lower limit and a upper limit. ChoosingFixed lower limit and the upper limit define the border of special scope. All scopes that can limit are by this wayComprise with capable of being combined, any lower limit can be combined to form a scope with any upper limit. For example, forSpecial parameter has been listed the scope of 60-120 and 80-110, is interpreted as the scope of 60-110 and 80-120 alsoExpect. In addition, if the minimum zone value of listing 1 and 2, and if would list maximum magnitude value3,4 and 5, scope below can all expect: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless have other explanations, number range " a-b " represent a between b arbitrarilyThe breviary of real number combination represents, wherein a and b are real numbers. For example number range " 0-5 " represents hereinAll listed the whole real numbers between " 0-5 ", " 0-5 " be the contraction table of these combinations of values justShow.
If do not particularly not pointed out, this description term " two kinds " used refers to " at least two kinds ".
In the present invention, if not special explanation, all embodiment mentioned in this article and preferredEmbodiment can be combined to form new technical scheme mutually.
In the present invention, if not special explanation, all technical characterictic mentioned in this article and preferredFeature can be combined to form new technical scheme mutually.
In the present invention, if not special explanation mentioned in this article can sequentially carry out in steps,Also can carry out at random, but preferably in sequence. For example, described method comprises step (a) and (b),Representing that described method can comprise in sequence step (a) and (b) also can comprise step (b) in sequence(a). For example, described in mention described method and also can comprise step (c), represent that step (c) can random orderJoin described method, for example, described method can comprise step (a), (b) and (c), also can comprise step (a),(c) and (b), also can comprise step (c), (a) and (b) etc.
In the present invention, if not special explanation, " comprising " mentioned in this article represents open,Also can be closed. For example, described " comprising " can represent to comprise other groups of not listingPoint, also can only comprise the component of listing.
Cobalt-base catalyst of the present invention comprises the cobalt oxide loading on mixed oxide spherical carrier particle, alsoCan optionally comprise be less than 0.1 % by weight be selected from Pd, Pt, Au, Ag, Rh, Ru or its combinationNoble metal. Taking the gross weight of described cobalt-base catalyst as benchmark, the content of described cobalt oxide is that 1-50 is heavyAmount %, preferably 15-35 % by weight, more preferably 20-30 % by weight. With the gross weight of described cobalt-base catalystFor benchmark meter, the content of the described mixed oxide spherical carrier particle as carrier is 50-99 % by weight,Be preferably 65-85 % by weight, more preferably 70-80 % by weight. Described mixed oxide spherical carrier particle byInner microballoon and outside auxiliary agent layer composition, described auxiliary agent layer covers the part or all of table of described microballoonFace. The material that is used for forming described microballoon can be selected from silica, aluminium oxide, zirconia or its mixture.Described auxiliary agent be the oxide that is selected from following element: Ni, Ca, Mg, La, Zr, Ce, Ti, Mn,V, Nb or their combination. The quantity of the above-mentioned metallic element comprising in described auxiliary agent can be1-4 kind. In addition, clearly, when described microballoon comprises zirconic time, described auxiliary agent should not containZirconium. Of the present invention one preferred embodiment in, described cobalt-base catalyst is containing noble metal.
Of the present invention one preferred embodiment in, described microballoon is made up of aluminium oxide, described auxiliary agent isZirconia. Of the present invention another preferred embodiment in, described microballoon is made up of silica, described inAuxiliary agent is nickel oxide. Of the present invention another preferred embodiment in, described microballoon is made up of aluminium oxide,The coating that zirconia auxiliary agent forms covers the surface of this microballoon completely, and load in described auxiliary agent coatingThe oxide of Co and Mn.
Being used for preparing in the method for cobalt-base catalyst of the present invention, described auxiliary agent precursor solution and comprisingThe precursor solution of cobalt can be the soluble-salt of the corresponding metallic element solution in suitable solvent. InstituteStating salt can be sulfate, nitrate, phosphate, halogen acid salt, carboxylate, and described carboxylate can beFor example formates, acetate, propionate, acetyl pyruvate, benzoate etc. Described solvent is passableWater, methyl alcohol, ethanol, ether, acetone or its mixture, suitable as long as corresponding salt has thereinDissolubility. Described solution can be by corresponding slaine is dissolved in solvent and is made, for shortEnter to dissolve, can add corresponding acid. Or also can be by the oxide dissolution of corresponding metal molten in acidIn liquid, prepare the solution of described slaine. Of the present invention one preferred embodiment in, described auxiliary agentIn precursor solution and the precursor solution that comprises cobalt, the total concentration of one or more slaines is 0.1-20% by weight.
Microballoon used in the present invention can directly be buied from the market, for example silicon oxide microsphere can be purchased fromThe Q10 product of FUJI company of Japan, described aluminum oxide micro-sphere can be purchased from South Africa SASOL companySCCa product.
In the method for the invention, auxiliary agent precursor solution is mixed with microballoon before or afterwards, to thisIn mixture, progressively drip and can produce alkaline matter hydroxy, make pH value be elevated to 8-11, therebyMake the metal in precursor solution form hydroxide, on the outer surface of microballoon, form hydroxide and be coated withLayer. This operates at the temperature of room temperature to 100 DEG C and carries out. The alkaline matter using in this step can beThose materials that this area is conventional, such as ammoniacal liquor, alkali metal hydroxide, alkali metal alcoholates, urea etc.
The microballoon of the coating that above-mentioned precipitation reaction is obtained filters, washs, and is then transferred toThe curing in water 7-24 hour of 50-100 DEG C, or 8-24 hour. Solid by filtration after slaking, dryDry and roasting, obtains mixed oxide spherical carrier particle, and its shape is spherical in shape, and granularity is that 10-100 is micro-Rice.
In order to obtain the thickness of required coating effect or auxiliary agent coating, can repeat above-mentioned deposition aid,More than the sequence of operations once of slaking and roasting. For example can repeat 1-4 time, preferably be no more than four times.
The load of cobalt oxide can contain by use the solution impregnation oxide spherical carrier particle of the presoma of cobalt,Or the cobalt oxide presoma of solid is carried out with the mode that mixed oxide spherical carrier particle mixes. WhenWhen using the solution impregnation oxide spherical carrier particle containing the presoma of cobalt, containing cobalt in described solutionThe concentration of presoma can be adjusted as required. Of the present invention one preferred embodiment in, adoptCobalt is loaded on spherical carrier particle by the mode of incipient impregnation. It is specifically, so-called that " equal-volume soaksStain " concentration and the amount that refer to solution control, make the amount of solvent in solution just in time equal adoptThe maximum of mixed oxide spherical carrier particle this solvent that can absorb. Ordinary skill peopleMember can and simply measure and test by its experience and determine that any one contains the solution of the presoma of cobaltAmount, thereby guarantee that it realizes " incipient impregnation " in the oxide spherical carrier particle of particular types.
Embodiment
In following examples, specifically enumerate the preferred embodiment of the present invention, but should be appreciated that thisBright protection domain is not limited only to this.
The aluminum oxide micro-sphere body using in following examples is purchased from FUJI company, and granularity is 150-250 micron;Silicon oxide microsphere is purchased from SASOL company, and granularity is 100-200 micron. The water using is deionized water;The slaine reagent using is commercially available AR, without further processing directly and use.
Embodiment 1:
Determine the consumption of various raw materials according to the listed part by weight of following table 1. 50 grams of zirconium nitrates are dissolved inIn water, stir 2 hours, incipient impregnation, in aluminum oxide micro-sphere, specifically, adds load weighted oxygenChange aluminium microballoon and form suspension, keep stirring 2 hours, suspension adds gradually concentration under the condition stirringBe the sodium hydrate aqueous solution of 0.1 mol/L, the mol ratio of NaOH and zirconium nitrate is 4:1, little 2Time in add, the pH value of controlling this suspension in whole process is no more than 12, suspension is filtered,By deionized water, solid is washed, in washing process, pass through in ICP element analysis technology monitor wash waterNa ion, until washings are neutrality and Na ion concentration is zero, will washing after solid transferBe to carry out slaking 24 hours in the water of 70 DEG C to temperature, after the solid after slaking filters and washs,Roasting in Muffle furnace, sintering temperature is 600 DEG C, heating rate is 5 DEG C/min, keeps 5 hours, makesAs the mixed oxide spherical carrier particle of carrier. Recording its particle mean size by Malvern ParticleSizer is130 microns, measure and find to have formed zirconia on the whole outer surface of aluminum oxide micro-sphere body by SEMLayer. Take the mixed oxide spherical carrier particle that 8.0g makes by said process and be placed in mortar, putPut in the vacuum drying oven of 60 DEG C 2 hours, after shifting out, add fast wherein the ratio-dependent amount according to table 1Cobalt nitrate flood, dipping often stir with pestle, this dipping process continue 6 hours,Under normal temperature, place and spend the night, be then placed in tubular react furnace 10%H2/N2Reduce, heating rate is1 DEG C/min, reduction temperature is 350 DEG C, and the recovery time is 24 hours, and the catalyst after reduction is slowly coolingTo normal temperature, in cooling procedure, keep above-mentioned gaseous mixture, then use nitrogen blowing after 20 minutes, use 1%O2/N2Gaseous mixture carries out passivation 1 hour, then sealed storage. By the catalyst called after Cat-1 of above-mentioned preparation.
Embodiment 2:
Repeat the step of above embodiment 1, difference is, prepares mixed oxide spherical carrier particle processThe sintering temperature of middle employing is 800 DEG C, and the time is 5 hours. By the catalyst called after Cat-2 of above-mentioned preparation.
Embodiment 3:
Determine the consumption of various raw materials according to the listed part by weight of following table 1.50 grams of zirconium nitrates are dissolved inIn water, stir 2 hours, with this solution incipient impregnation aluminum oxide micro-sphere, specifically, add weighing wellAluminum oxide micro-sphere form suspension, keep stir 2 hours, suspension stir condition under add graduallyConcentration is the ammoniacal liquor of 0.1 mol/L, and the mol ratio of ammonia and zirconium nitrate is 6:1, in 2 hours, add,The pH value of controlling this suspension in whole process is no more than 12, and suspension is filtered, and uses deionized waterSolid is washed, until washings are neutral, is 50 DEG C by the solid transfer after washing to temperatureIn water, carry out slaking 12 hours, after the solid after slaking filters and washs, roasting in Muffle furnace,Sintering temperature is 500 DEG C, and heating rate is 5 DEG C/min, keeps 5 hours, makes the mixing oxygen as carrierCompound spherical carrier particle. Recording its particle mean size by Malvern ParticleSizer is 160 microns, passes through SEMMeasure and find to have formed zirconia layer on the whole outer surface of aluminum oxide micro-sphere body. Take 8.0g by upperThe mixed oxide spherical carrier particle that the process of stating makes is placed in mortar, is placed in the vacuum drying oven of 60 DEG C2 hours, after shifting out, add fast wherein according to the cobalt nitrate of the ratio-dependent amount of table 1 and flood, soakStain often stirs with pestle, and this dipping process continues 8 hours, places and spends the night at normal temperatures, thenBe placed in tubular react furnace 10%H2/N2Reduce, heating rate is 1 DEG C/min, and reduction temperature is350 DEG C, the recovery time is 24 hours, and the catalyst after reduction is slowly cooled to normal temperature, in cooling procedureKeep above-mentioned gaseous mixture, then use nitrogen blowing after 20 minutes, use 1%O2/N2Gaseous mixture carries out passivation 1Hour, then sealed storage. By the catalyst called after Cat-3 of above-mentioned preparation.
Embodiment 4:
Determine the consumption of various raw materials according to the listed part by weight of following table 1.50 grams of zirconium nitrates are dissolved inIn water, stir 2 hours, with this solution incipient impregnation aluminum oxide micro-sphere, specifically, add weighing wellAluminum oxide micro-sphere form suspension, keep stir 2 hours, suspension stir condition under add graduallyConcentration is the urea of 0.1 mol/L, and the mol ratio of urea and zirconium nitrate is 6:1, in 2 hours, add,In whole process, the temperature of suspension remains on 90 DEG C, and the pH value of controlling this suspension is no more than 12,Suspension is filtered, by deionized water, solid is washed, until washings are neutral, will washSolid transfer is afterwards to carry out slaking 36 hours in the water of 70 DEG C to temperature, and the solid after slaking carries out againAfter filtering and washing, roasting in Muffle furnace, sintering temperature is 500 DEG C, heating rate is 5 DEG C/min, protectsHold 5 hours, make the mixed oxide spherical carrier particle as carrier. Record by Malvern ParticleSizerIts particle mean size is 90 microns, is measured and is found shape on the whole outer surface of aluminum oxide micro-sphere body by SEMBecome zirconia layer. Taking the mixed oxide spherical carrier particle that 8.0g makes by said process is placed inIn mortar, be placed in the vacuum drying oven of 60 DEG C 2 hours, after shifting out, add fast according to table 1 whereinThe cobalt nitrate of ratio-dependent amount flood, dipping often stirs with pestle, this dipping process is heldContinuous 10 hours, place and spend the night at normal temperatures, be then placed in tubular react furnace 10%H2/N2Reduce,Heating rate is 1 DEG C/min, and reduction temperature is 350 DEG C, and the recovery time is 24 hours, the catalysis after reductionAgent is slowly cooled to normal temperature, keeps above-mentioned gaseous mixture in cooling procedure, then uses nitrogen blowing 20 minutesAfter, use 1%O2/N2Gaseous mixture carries out passivation 1 hour, then sealed storage. By the catalyst of above-mentioned preparationCalled after Cat-4.
Embodiment 5:
Determine the consumption of various raw materials according to the listed part by weight of following table 1. The present embodiment is to aluminum oxide micro-sphere Carry out twice coating, therefore each zirconates that uses half amount that applies.25 grams of zirconium nitrates are dissolved in water,Stir 2 hours, with this solution incipient impregnation aluminum oxide micro-sphere, specifically, add load weighted oxidationAluminium microballoon forms suspension, keeps stirring 2 hours, and suspension adds gradually concentration to be under the condition stirringThe urea of 0.1 mol/L, the mol ratio of urea and zirconium nitrate is 6:1, adds, whole in 2 hoursIn process, the temperature of suspension remains on 90 DEG C, and the pH value of controlling this suspension is no more than 12, to suspendingLiquid filters, and by deionized water, solid is washed, until washings are neutral, will wash afterwardsSolid transfer is to carry out slaking 20 hours in the water of 60 DEG C to temperature, the solid after slaking filter again andAfter washing, roasting in Muffle furnace, sintering temperature is 600 DEG C, and heating rate is 5 DEG C/min, and maintenance 5 is littleTime, make mixed oxide A.
And then take 25 grams of zirconium nitrates, and repeat above-mentioned steps, above-mentioned mixed oxide A is carried out to secondaryApply, make the mixed oxide spherical carrier particle as carrier. Recording it by Malvern ParticleSizer puts downAll granularity is 150 microns, is measured and is found to form on the whole outer surface of aluminum oxide micro-sphere body by SEMZirconia layer.
Take the mixed oxide spherical carrier particle that 6.0g makes by said process and be placed in mortar, putPut in the vacuum drying oven of 60 DEG C 2 hours, after shifting out, add fast wherein the ratio-dependent amount according to table 1Cobalt nitrate flood, dipping often stir with pestle, this dipping process continue 5 hours,Under normal temperature, place and spend the night, be then placed in tubular react furnace 10%H2/N2Reduce, heating rate is1 DEG C/min, reduction temperature is 350 DEG C, and the recovery time is 24 hours, and the catalyst after reduction is slowly coolingTo normal temperature, in cooling procedure, keep above-mentioned gaseous mixture, then use nitrogen blowing after 20 minutes, use 1%O2/N2Gaseous mixture carries out passivation 1 hour, then sealed storage. By the catalyst called after Cat-5 of above-mentioned preparation.
Embodiment 6:
By in nickel nitrate 20g dissolved water, make the aqueous solution, then in this solution, add 0.1 of urea to rubThe aqueous solution of that/L, the mol ratio of urea and nickel nitrate is 6:1, stirs after 2 hours, uses this solution impregnationSilicon oxide microsphere, specifically, adds the silicon oxide microsphere weighing according to the ratio shown in table 1, forms outstandingSupernatant liquid, is cooled to room temperature after maintaining 16 hours under the condition of vigorous stirring and 90 DEG C, cooled outstandingSupernatant liquid solid collected by filtration, washs this solid until washings are neutral by deionized water, and the solid obtaining existsRoasting in Muffle furnace, sintering temperature is 700 DEG C, heating rate is 5 DEG C/min, keeps 5 hours, makes workFor the mixed oxide spherical carrier particle of carrier. Recording its particle mean size by Malvern ParticleSizer is 110Micron, is measured and is found to have formed zirconia layer on the whole outer surface of aluminum oxide micro-sphere body by SEM.
Take the mixed oxide spherical carrier particle that 6.0g prepared by said method and be placed in mortar, putPut in the vacuum drying oven of 60 DEG C 2 hours, shift out rear adding fast according to six of the amount of ratio-dependent shown in table 1Water cobalt nitrate floods, and dipping often stirs with pestle, and this dipping process continues 7 hours,Under normal temperature, place and spend the night, be then placed in tubular react furnace 10%H2/N2Reduce, heating rate is1 DEG C/min, reduction temperature is 350 DEG C, and the recovery time is 24 hours, and the catalyst after reduction is slowly coolingTo normal temperature, in cooling procedure, keep above-mentioned gaseous mixture, then use nitrogen blowing after 20 minutes, use 1%O2/N2Gaseous mixture carries out passivation 1 hour, then sealed storage. By the catalyst called after Cat-6 of above-mentioned preparation.
Embodiment 7:
Repeating step described in embodiment 5, to carry out catalyst synthetic, and difference is, to mixed oxide ballWhen carrying out incipient impregnation, shape carrier granular uses the aqueous solution that contains cobalt nitrate Co and manganese nitrate, CoWith the mol ratio of Mn be 96:4. Mixture is natural drying after solution impregnation, evaporate with rotary evaporatorDry, then adopt the condition described in above embodiment 5 to reduce and Passivation Treatment to dry solid.By the catalyst called after Cat-7 of above-mentioned preparation.
Embodiment 8:
By in cerous nitrate 20g dissolved water, make the aqueous solution, then in this solution, add 0.1 of urea to rubThe aqueous solution of that/L, the mol ratio of urea and cerous nitrate is 6:1, stirs after 6 hours, adds according to table 1The silicon oxide microsphere that shown ratio weighs, forms suspension, under the condition of vigorous stirring and 90 DEG C, ties upHold after 16 hours and be cooled to room temperature, cooled suspension filtered is collected solid, and washing by deionized water shouldSolid is until washings are neutral, the solid obtaining roasting in Muffle furnace, and sintering temperature is 700 DEG C, risesTemperature speed is 5 DEG C/min, keeps 5 hours, makes the mixed oxide spherical carrier particle as carrier.Recording its particle mean size by Malvern ParticleSizer is 110 microns, is measured and is found at aluminium oxide by SEMOn the whole outer surface of microsphere, form zirconia layer.
Take the mixed oxide spherical carrier particle that 11.0g prepared by said method and be placed in mortar, putPut in the vacuum drying oven of 75 DEG C 4.5 hours, shift out and add fast according to the amount of ratio-dependent shown in table 1 afterwardsCobalt nitrate hexahydrate floods, and dipping often stirs with pestle, and this dipping process continues 10 hours,Place and spend the night at normal temperatures, be then placed in tubular react furnace 10%H2/N2Reduce, heating rateBe 1 DEG C/min, reduction temperature is 350 DEG C, and the recovery time is 24 hours, and the catalyst after reduction is slowly coldBut to normal temperature, in cooling procedure, keep above-mentioned gaseous mixture, then use nitrogen blowing after 20 minutes, use1％O2/N2Gaseous mixture carries out passivation 1 hour, then sealed storage. By the catalyst called after of above-mentioned preparationCat-8。
Embodiment 9:
Take the spherical carrier granular of 6.0g aluminium oxide and be placed in mortar, be placed in the vacuum drying oven of 60 DEG C 7Hour, shift out and flood rear adding fast according to the cobalt nitrate hexahydrate of the amount of ratio-dependent shown in table 1, dippingOften stir with pestle, this dipping process is held 9 hours, places and spends the night at normal temperatures, is then placed inIn tubular react furnace, use 10%H2/N2Reduce, heating rate is 1 DEG C/min, and reduction temperature is 350 DEG C,Recovery time is 24 hours, and the catalyst after reduction is slowly cooled to normal temperature, in cooling procedure, keepsState gaseous mixture, then use nitrogen blowing after 20 minutes, use 1%O2/N2Gaseous mixture carries out passivation 1 hour,Then sealed storage. By the catalyst called after Cat-9 of above-mentioned preparation.
Embodiment 10:
25 grams of zirconium nitrates are dissolved in water, stir 4 hours, with this solution, aluminum oxide micro-sphere is carried out etc.Volume dipping, adds load weighted aluminum oxide micro-sphere to form suspension, keeps stirring 3.5 hours suspensionUnder the condition stirring, adding gradually concentration is the urea of 0.1 mol/L, and the mol ratio of urea and zirconium nitrate is6:1 added in 2 hours, and in whole process, the temperature of suspension remains on 90 DEG C, and controlled that this is outstandingThe pH value of supernatant liquid is no more than 12, and suspension is filtered, and solid is washed by deionized water, straightBeing neutral to washings, is that in the water of 60 DEG C, to carry out slaking 48 little to temperature by the solid transfer after washingTime, after the solid after slaking filters and washs, roasting in Muffle furnace, sintering temperature is 600 DEG C,Heating rate is 5 DEG C/min, keeps 5 hours, makes mixed oxide A.
And then take 5 grams of niobates, and repeat above-mentioned steps, above-mentioned mixed oxide A is carried out to secondaryApply, make the mixed oxide spherical carrier particle as carrier. Recording it by Malvern ParticleSizer puts downAll granularity is 150 microns.
Take the mixed oxide spherical carrier particle that 9.0g makes by said process and be placed in mortar, putPut in the vacuum drying oven of 60 DEG C 7 hours, after shifting out, add fast wherein the ratio-dependent amount according to table 1Cobalt nitrate flood, dipping often stir with pestle, this dipping process continue 5 hours,Under normal temperature, place and spend the night, be then placed in tubular react furnace 10%H2/N2Reduce, heating rate is1 DEG C/min, reduction temperature is 350 DEG C, and the recovery time is 24 hours, and the catalyst after reduction is slowly coolingTo normal temperature, in cooling procedure, keep above-mentioned gaseous mixture, then use nitrogen blowing after 20 minutes, use 1%O2/N2Gaseous mixture carries out passivation 1 hour, then sealed storage. By the catalyst called after Cat-10 of above-mentioned preparation.
Synthetic example
Take respectively the synthetic cobalt-base catalyst of above each embodiment of 20 ml volumes, sneaked into 500In ml atoleine, stir and form suspension, and this suspension is poured in the paste state bed reactor of 1L,Seal this reactor, use nitrogen to purge 1 hour with the flow velocity of 100mL/min, then switch to hydrogen,Temperature is risen to 200 DEG C by programming rate with 1 DEG C/min, keeps reductase 12 4 hours in this temperature, then cutsChange synthesis gas into, start to carry out catalytic reaction. The condition of catalytic reaction is 230 DEG C of temperature, pressure 2.0MPa,H2/ CO volume ratio 2.0, total gas hourly space velocity 3000 hours-1. Use online gas chromatographic analysis tail gas composition,Off-line analysis oil wax composition. Catalytic reaction the results are shown in following table 1.
The cobalt group catalyst synthesized catalytic perfomance evaluation result of table 1 syrup state bed Fischer Tropsch
Can see from the data shown in upper table, compared with not containing the catalyst Cat-9 of auxiliary agent, of the present inventionCatalyst has the CO conversion ratio significantly improving.
In addition, Fig. 1 and Fig. 2 have shown that respectively catalyst Cat-1 and Cat-9 are after above-mentioned catalytic reactionSEM electromicroscopic photograph. Can see by contrasting these two electromicroscopic photographs, catalyst of the present invention is insteadShould can keep better complete ball-type pattern afterwards, this proves the mechanical strength that its tool is significantly improvedEnergy.
Claims (13)
1. urge for the cobalt-based that carries out Fischer-Tropsch synthesis at paste state bed reactor or stirred reactor for one kindAgent, taking the gross weight of this catalyst as benchmark, the cobalt oxide that described catalyst comprises 1-50 % by weight,The particle diameter of 50-99 % by weight is the mixed oxide spherical carrier particle of 10-100 micron, and is less than 0.1The noble metal that is selected from Pd, Pt, Au, Ag, Rh, Ru or its combination of % by weight;
Described mixed oxide spherical carrier particle is made up of microballoon and auxiliary agent, with the gross weight of this cobalt-base catalystAmount is benchmark meter, and the content of described auxiliary agent is 1-20 % by weight, and described microballoon is by being selected from following materialThe microballoon of composition: silica, aluminium oxide, zirconia or its mixture; Described auxiliary agent is selected from followingThe oxide of element: Ni, Ca, Mg, La, Zr, Ce, Ti, Mn, V, Nb or theyCombination;
Prerequisite is to comprise zirconic time when described microballoon, and described auxiliary agent does not comprise zirconium; And described inThe metallic element kind that auxiliary agent comprises is simultaneously no more than 4 kinds;
Described cobalt-base catalyst also optionally comprises and loads on described mixed oxide spherical carrier particleThe auxiliary agent transition metal oxide that is different from cobalt oxide, described in be different from the auxiliary agent oxo transition metal of cobalt oxideThe kind of compound is identical with the kind of the oxide of the element comprising in described auxiliary agent.
2. cobalt-base catalyst as claimed in claim 1, is characterized in that, described mixed oxide is sphericalThe particle diameter of carrier granular is 50-100 micron, preferably 50-80 micron.
3. cobalt-base catalyst as claimed in claim 1, is characterized in that, described auxiliary agent is with the shape of coatingFormula covers the part or all of surface of described microballoon.
4. cobalt-base catalyst as claimed in claim 1, is characterized in that, described microballoon is by aluminium oxide groupBecome, described auxiliary agent is selected from following material: zirconia, nickel oxide, manganese oxide or its combination;
Taking the gross weight of cobalt oxide in described cobalt-base catalyst as benchmark, described in be different from the auxiliary agent of cobalt oxideThe content of transition metal oxide is 0-5 % by weight.
5. cobalt-base catalyst as claimed in claim 1, is characterized in that, with the gross weight of this catalystFor benchmark meter, the content of described cobalt oxide is 1-50 % by weight, is preferably 15-35 % by weight; Described microballoonContent be 50-99 % by weight, be preferably 65-85 % by weight; The content of described auxiliary agent is 1-20 % by weightBe preferably 2-10 % by weight.
6. be used for preparing a method for the cobalt-base catalyst as described in any one in claim 1-5, described inMethod comprises the following steps:
I) the auxiliary agent precursor solution that preparation comprises following element: Ni, Ca, Mg, La, Zr, Ce, Ti,Mn, V, Nb or their combination;
Ii) described auxiliary agent precursor solution is mixed with microballoon, under the condition raising in pH value, appliedMicroballoon;
Iii) microballoon of this coating is carried out to slaking and roasting, make described mixed oxide ball type carrierGrain;
Iv) precursor solution that preparation comprises cobalt, by the described precursor solution that comprises cobalt and step I ii) makeMixed oxide spherical carrier particle mix, the mixed oxide spherical carrier particle of cobalt that obtained load,Or by the presoma that comprises cobalt with solid form directly and step I ii) the mixed oxide ball type carrier that makesParticle carries out solids mixing, the mixed oxide spherical carrier particle of cobalt that obtained load;
V) then to this load the mixed oxide spherical carrier particle of cobalt carry out roasting, reduction and passivation,Make described cobalt-base catalyst.
7. method as claimed in claim 6, is characterized in that, step I) in auxiliary agent precursor solution beThe solution of the salt of following element in water, alcohol or organic acid: Ni, Ca, Mg, La, Zr, Ce, Ti,Mn, V, Nb or their combination; Described salt preferably nitrate, hydrochloride, sulfate,Phosphate, carboxylate; Described salt is more preferably nitrate, hydrochloride, acetate or it is mixed arbitrarilyCompound.
8. method as claimed in claim 6, is characterized in that, step I i) in, described pH value raisesCondition represent by add alkali make pH value be elevated to 8-11; At step I ii) in, described coatingMicroballoon is at the curing in water 8-24 hour of 50-100 DEG C; Described roasting at the temperature of 300-700 DEG C,In air atmosphere, carry out 2-10 hour.
9. the method as described in claim 6 or 8, is characterized in that, described step I i) and step I ii)Repeat 1-4 time.
10. method as claimed in claim 6, is characterized in that, the described step I forerunner who comprises cobalt v)Liquid solution is the soluble-salt of the cobalt solution in water or alcohol; The soluble-salt of described cobalt preferably cobalt acetate,Cobalt nitrate or their mixture; In the described precursor solution that comprises cobalt, also optionally comprise and be different fromThe soluble-salt of the transition metal of cobalt.
11. methods as claimed in claim 6, is characterized in that, step I is v) and v) by with belowFormula is carried out: by the presoma that comprises cobalt and the step of the described precursor solution that comprises cobalt or solid formIii) the mixed oxide spherical carrier particle that makes mixes, then at the temperature of normal temperature to 200 DEG C, at skyDry in gas, nitrogen or vacuum, the mixed oxide spherical carrier particle of cobalt that obtained load; Then existAt the temperature of 200-400 DEG C, in air atmosphere to this load the mixed oxide spherical carrier particle of cobaltCarry out roasting; Then at the temperature of 200-500 DEG C, in hydrogen atmosphere, reduce 3-5 hour, described hydrogenThe pressure of gas is 0.1-2MPa, and in hydrogen atmosphere, the concentration of hydrogen is 1-100 volume %; Then containing 1In the nitrogen of the oxygen of volume %, passivation 10 minutes to 5 hours at the temperature of normal temperature to 40 DEG C, therebyMake described cobalt-base catalyst.
12. 1 kinds are carried out the method for fischer-tropsch reaction in paste state bed reactor or stirred reactor, the method bagDraw together following steps: in the case of existing the cobalt-base catalyst as described in any one in claim 1-5, makeObtain carbon monoxide and hydrogen and react, generate hydrocarbon product, this reaction is carried out under following reaction condition:Reaction temperature is 180-270 DEG C, is preferably 180-250 DEG C, reaction pressure 0.5-5MPa, the total air speed of gasFor 1000-10000 hour-1, be preferably 500-8000 hour-1, the volume ratio of carbon monoxide and hydrogen is 1:1To 1:3.
13. methods as claimed in claim 12, is characterized in that, before fischer-tropsch reaction starts,Under following condition, catalyst is carried out to reduction pretreatment: temperature is 200-500 DEG C, use 0.1-2MPa's is pureThe hydrogen of hydrogen or the CO that comprises 1 volume %.
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