CN102202787A - Cobalt catalyst precursor - Google Patents

Cobalt catalyst precursor Download PDF

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CN102202787A
CN102202787A CN2009801436049A CN200980143604A CN102202787A CN 102202787 A CN102202787 A CN 102202787A CN 2009801436049 A CN2009801436049 A CN 2009801436049A CN 200980143604 A CN200980143604 A CN 200980143604A CN 102202787 A CN102202787 A CN 102202787A
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catalyst precarsor
catalyst
cobalt
hydrogen
reduction
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P·R·埃利斯
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Johnson Matthey PLC
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Johnson Matthey PLC
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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Abstract

A catalyst precursor is described comprising 5 to 50 % by weight of one or more oxidic cobalt compounds selected from CoO, CoO(OH) and Co3O4 and 0.05 to 10 % by weight of one or more reduction promoter selected from metals or compounds of Ru, Pt, Cu, Rh, Pd, Ir, Ag and Bi, supported on an inert support selected from alpha alumina, a metal-aluminate, silica, titania, zirconia, zinc oxide, silicon carbide, carbon or mixtures thereof, wherein the cobalt is in a highly reducible form such that at least 75 % of the cobalt is reducible by a reducing gas stream at temperatures = 24O DEG C.

Description

The Co catalysts precursor
The present invention relates to Co catalysts, particularly be suitable for the synthetic Co catalysts of Fischer-Tropsch of hydrocarbon.
The Co catalysts that is applicable to the synthetic used fischer-tropsch process of hydrocarbon carries out prereduction usually before in being installed on the Fischer-Tropsch reaction device and seals with suitable material.This is because reduction process typically at＞250 ℃, is operated under ℃ the temperature especially＞300, and this is challenging for used fixed bed or slurry attitude phase reactor.Typically use hydrogen stream to reduce in addition, this air-flow that can be used for in-situ reducing comprises the syngas mixture that contains carbon monoxide usually.Yet the in-situ reducing of cobalt Fischer-Tropsch catalysts is a desired destination, and these methods are not also used commercial obtaining up to now.
The applicant has been found that and allows the cobalt effectively inert carrier of reduction and the particular combinations of additive at low temperatures.
Therefore, the invention provides the catalyst precarsor that loads on the inert carrier that is selected from alpha-aluminium oxide, metal aluminate, silica, titanium dioxide, zirconia, zinc oxide, carborundum, carbon or their mixture, this catalyst precarsor comprises 5-50 weight % and is selected from CoO, CoO (OH) and Co 3O 4One or more oxidisability cobalt compounds (oxidic cobalt compound), and 0.05-10 weight % is selected from the metal of Ru, Pt, Cu, Rh, Pd, Ir, Ag and Bi or one or more reduction accelerators of compound, and wherein said cobalt is to make that with highly reducible form at least 75% cobalt can be with the reduction of reproducibility air-flow under≤240 ℃ temperature.Therefore, in catalyst according to the invention, thereby cobalt exists with highly reducible form the oxidisability cobalt compound can effectively be reduced by being reduced property air-flow under≤240 ℃ temperature." by effectively reducing " is meant reduction degree, i.e. amount 〉=75 weight % of being reduced of cobalt, preferred 〉=85 weight %, more preferably 〉=90 Co that exists in catalyst precarsor of weight %.
Thereby such low-temperature reduction provides chance to eliminate the prereduction that can be difficult to make and transport, the needs of encapsulated catalysts for the in-situ reducing that the commercial people of being subjected to pays close attention to.
Therefore the present invention also provides the method that makes the catalyst activation, this method comprises above-mentioned catalyst precarsor is placed the Fischer-Tropsch reaction device, and make the reducibility gas mixture pass this catalyst precarsor a period of time and be reduced to simple substance form, wherein the temperature of reducibility gas mixture≤240 ℃ in whole activation step with the cobalt that will wherein exist.
The present invention also provides the Fischer-Tropsch synthetic method of hydrocarbon, this method is included in the step that makes the admixture of gas that comprises hydrogen and carbon monoxide pass catalyst in the Fischer-Tropsch reaction device, wherein by the above-mentioned catalyst precarsor that under temperature≤240 ℃ the reducibility gas mixture is passed in the fischer-tropsch reactor described catalyst is activated.
The cobalt content of catalyst precarsor is 5-50 weight %, preferred 10-35 weight %, most preferably 12-30 weight %.The additive of catalyst precarsor or accelerator content are 0.05-10 weight %, preferred 0.1-5 weight %, most preferably 0.1-2 weight %.In the catalyst precarsor total amount of additive or promoter preferred≤10 weight %.Tenor can use known method for example ICP AES or ICP OES mensuration.
Preferred in the present invention all cobalts are with reducible form, i.e. preferred＜5 weight %, and more preferably＜1 weight %, weight % most preferably＜0.05, particularly not having cobalt is the mixed oxide form of cobalt aluminate for example of cobalt load.Reducible cobalt is with CoO, CoO (OH) and Co 3O 4In one or more existence.Preferred all basically reducible cobalts are with Co 3O 4Exist.
At least 75%, preferably at least 85%, more preferably at least 90% cobalt is reducible, promptly reduction degree (DOR) preferred 〉=75%, more preferably 〉=85%, especially 〉=90%.Can be used to estimate temperature programmed reduction (TPR) method of DOR by following use:
1. with 10 ℃/min sample temperature is stably brought up to required reduction temperature (≤240 ℃), under this temperature, keep 10 hours (TPR1).
2. do not cool off and get back to room temperature, sample temperature is brought up to 1000 ℃ and kept 10 minutes at 1000 ℃ with 10 ℃/min.(TPR2)。This provides the reduction fully of all cobalts.
3. will carry out integration (integrate) from the absorption of hydrogen amount of TPR1 to 2.TPR1/ (TPR1+TPR2) ratio is reduction degree (representing with %).
Reduction accelerator among the present invention is selected from one or more compounds or the metal of Ru, Pt, Cu, Rh, Pd, Ir, Ag and Bi, one or more among preferred Ru, Pt and the Cu, more preferably Ru.
Inert carrier among the present invention is to the cobalt inertia, promptly is not easy to form the mixed oxide of cobalt, for example the carrier of cobalt aluminate spinelle.This inert carrier is selected from alpha-aluminium oxide, metal aluminate, silica, titanium dioxide, zirconia, zinc oxide, carborundum, carbon or their mixture.
Carrier and thus obtained catalyst precarsor can be the surperficial weight-average diameter D[3 with 1-200 micron, 2] powder type.Term surface weight-average diameter D[3,2], be called husky (Sauter) average diameter in addition, by M.Alderliesten at paper " A Nomenclature for Mean Particle Diameters "; Anal.Proc., the 21st volume defines in the 167-172 page or leaf in May, 1984, and is calculated by granularmetric analysis, and described grain size analysis can for example use Malvern Mastersizer to finish easily by laser diffraction.The agglomerate of this class powder that can also use the particle diameter with 200 microns-1mm is as carrier.Perhaps, carrier and thus obtained catalyst precarsor can be forming unit for example the typical case have the particle diameter of 1-25mm and less than the form of pill, extrudate or the particle of 2 draw ratio.(particle diameter is meant smallest particles size for example width, length or diameter).Perhaps carrier can be the material all in one piece form, for example the form of honeycomb ceramics or porous material such as open celled foam (open foam) structure.Inert carrier can also be the form of the washcoated layer on pottery, metal, carbon or polymeric substrate.This class catalyst advantageously provides in-situ reducing in miniature GTL equipment.
Can use as powder, pill or granular form and carbon carrier with appropriate porosity (for example being higher than 0.1ml/g) for example active carbon, high surface graphite, carbon nano-fiber and fullerene as carrier of the present invention.Preferably do not use this class carrier in the method that adopts air calcination owing to the oxidation of carrier.Preferably, during calcining carbon the gas streams of its exposure is contained preferably＜1 volume %, more preferably＜0.1 oxygen of volume % for example when the nitrogen of oxygen-free gas, helium or argon gas, is produced the catalyst precarsor that comprises carbon carrier.
Carrier can be a silica supports.Silica supports can be by for example forming as diatomaceous natural origin, can be pyrolysis or aerosil or can synthesize, for example precipitated silica or silica dioxide gel.Can use structurized mesoporous silica for example SBA-15 as carrier.Preferred precipitated silica.Silica can be powder or moulding material, for example as extrude, the form of the titanium dioxide silicon chip piece of pillization or granulation.Suitable Powdered silica typically has surperficial weight-average diameter D[3,2] be the particle of 3-100 μ m.Moulding silica can have various type shapes and particle diameter, and this depends on used mould or punch die in they are made.For example these particles can have the transversal type shape of circle, leaf or other type shape and the about 1-length greater than 10mm.The BET surface area of suitable Powdered or pelletized silica is generally 10-500m 2/ g, preferred 100-400m 2g -1Pore volume is generally about 0.1-4ml/g, and preferred 0.2-2ml/g and average pore size are preferably the about 30nm of 0.4-.If desired, can for example titanium dioxide or zirconia mix with silica and another kind of metal oxide.Perhaps, silica can be used as the coating on the forming unit (preferred aluminium oxide), and typically the coating as 0.5-5 silica individual layer on the following carrier exists.
Carrier can be a titania support.Titania support is preferably synthetic, for example precipitated titania.Titanium dioxide for example can randomly comprise the another kind of refractory oxide material of 20 weight %, silica, aluminium oxide or zirconia typically at the most.Perhaps, titanium dioxide can be used as the coating on the carrier (preferred silica or aluminium oxide), and for example the coating as 0.5-5 titanium dioxide individual layer on following aluminium oxide or the silica supports exists.The BET surface area of suitable titanium dioxide is generally 10-500m 2/ g, preferred 100-400m 2/ g.The pore volume of titanium dioxide is preferably about 0.1-4ml/g, and more preferably 0.2-2ml/g and average pore size are preferably the about 30nm of 2-.
Similarly, Zirconia carrier can synthesize, and for example precipitates zirconia.Zirconia also can be chosen wantonly and for example comprise the another kind of refractory oxide material of 20 weight %, silica, aluminium oxide or titanium dioxide typically at the most.Perhaps, zirconia can be a stabilisation, for example the zirconia of yittrium oxide or ceria-stabilised.Perhaps, zirconia can be used as the coating on the carrier (preferred silica or aluminium oxide), and for example the coating as 0.5-5 zirconia individual layer on following aluminium oxide or the silica supports exists.
Carrier can be metal aluminate, for example calcium aluminate.
In one embodiment, inert carrier is an Alpha-alumina.Alpha-aluminium oxide can from commercial acquisition or by with transition alumina for example gamma-alumina be heated to 1000-1500 ℃, preferred 〉=temperature of 1200 ℃ is prepared.Alpha-aluminium oxide is preferably quite pure, and alkali content＜100ppm is preferred＜50ppm, and does not have the metal aluminate spinelle to exist basically.The BET surface area is preferred＜50m 2/ g.Suitable alpha-alumina powder has the surperficial weight-average diameter D[3 of 1-200 μ m, 2 usually]., advantageously use by on average preferably less than 20 μ m, for example 10 μ m or very thin particle still less as desiring to be used for the catalyst of slurry reaction in some application examples., can need to use bigger particle diameter as in fluid bed, carrying out catalyst for reaction for other application examples, be preferably 50-150 μ m.Alumina supporting material can be the form of spray-dried powders or be configured as forming unit for example ball, pill, cylinder, ring or multiple hole pill, they can be leafy shape or groove line shape, for example cloverleaf pattern cross section, or extrudate form well known by persons skilled in the art.For high filterability and wearability can advantageously be selected the alpha-aluminium oxide carrier.
The cobalt Fischer-Tropsch catalysts of Alpha-alumina load is known.WO 02/47816 has described at alpha-aluminium oxide or has contained Co catalysts on the carrier of alpha-aluminium oxide.The a series of possibility promoter that provide comprise Re, Pt, Ir or Rh.Yet,, carry out the reduction of catalyst precarsor under preferred 300-400 ℃ at 250-400 ℃.
Can also use metal aluminate carrier for example nickel aluminate, lithium aluminate or calcium aluminate carrier among the present invention.These carriers have the interactional advantage of oxidisability cobalt compound that can not be easy to and wherein form.
Catalyst precarsor can use known method to be prepared.For example catalyst can be by being prepared as follows: use dipping method, intermediate processing or deposition-precipitation method, perhaps these combination is then carried out drying steps usually to remove any solvent and calcining step to realize the transformation to their each autoxidisable substances of cobalt and additive or promoter compound.Cobalt and promoter can be evenly distributed in the carrier or can be in its surface eggshell form.
The preferred deposition precipitation method and dipping method.
Wherein heat carbonic acid cobaltammine (cobalt ammine carbonate) solution so that the deposition-precipitation method that cobalt compound deposits on the carrier is known.For example, in US 5874381, WO 01/62381, WO 01/87480, WO 04/28687 and WO 05/107942, described use carbonic acid cobaltammine formulations prepared from solutions aluminium oxide-, silica-and the suitable method of the catalyst of titanium dioxide-load.Generally speaking, can by the following method cobalt compound be deposited on the inert carrier:
(a) with carbonic acid cobaltammine solution impregnating carrier, the carrier of dipping is separated with any excessive solution, and in air or in the presence of suitable oxidant, the carrier that floods is heated to 60-110 ℃ temperature then, perhaps,
(b) in air or in the presence of suitable oxidant, the carrier slurry in the carbonic acid cobaltammine solution is heated to 60-110 ℃ temperature.
When preparation shaping carrier for example during the catalyst on extrudate or the pill first method suitable especially, and second method is appropriate to dust carrier especially.
In dipping method, can with suitable soluble metal compound for example metal nitrate or acetate for example alcohol dipping is to carrier material from water-based or non-aqueous solution, it can comprise other material, and is dried then to remove and desolvates.Can there be one or more soluble metal compounds in this solution.Can have or not have under the situation of middle drying and/or calcining step and carry out one or more impregnation steps, to improve the metal carrying capacity or the pantostrat of different metal compound is provided.The known to the skilled any method that can use catalyst to make the field is flooded, but preferred by so-called " dry type " or " beginning moistens " infusion process, because this minimizes the amount of the solvent that uses and remove in drying.Beginning profit infusion process comprises mixes carrier material with the solution that only is enough to fill the carrier hole.The dipping method that is used to prepare Co catalysts generally include with the cobalt nitrate solution of catalyst carrier and suitable concn for example cabaltous nitrate hexahydrate (II) merge.Yet can use many solvents, for example water, alcohol, ketone or these mixture, preferably, carrier uses the aqueous solution of cobalt nitrate to flood.
For example nitrate, chloride, acetate or these mixture can also make reduction accelerator include (include) in catalyst precarsor by dipping to use suitable soluble compound.Additive or promoter can be before or after cobalts or can be by in identical dipping solution cobalt and additive or promoter compound being merged and being incorporated in the catalyst precarsor simultaneously.The amount that can change the amount of cobalt and additive or promoter compound in the solution or inert carrier is to obtain required metal carrying capacity.Can carry out the single or multiple dipping in catalyst precarsor, to obtain required cobalt and additive or promoter level.In preferred embodiments, flood the preparation catalyst precarsor altogether by solution with inert carrier and ruthenium acetate and cobalt nitrate.
If desired, can before calcining catalyst precarsor be carried out drying desolvates to remove.Drying steps can be in air or inert gas for example under the nitrogen or in vacuum drying oven in 20-120 ℃, carry out under preferred 95-110 ℃.
Then can be in air the heatable catalyst precursor to realize the transformation of cobalt and additive or promoter compound to their each autoxidisable substances.Calcining heat is preferably 250-500 ℃.Calcination time is preferred≤and 24, more preferably≤16, most preferably≤8, especially≤6 hour.As the replacement scheme of in air, calcining, the catalyst precarsor of drying can contain＜for example heating under nitrogen or the argon gas of the inert gas of 5 volume % oxygen, and described inert gas can comprise that concentration is nitric oxide or the nitrous oxide of 0.001-15 volume %.Have been found that the improved cobalt dispersiveness of nitrate material production of calcining load under nitric oxide or nitrous oxide, therefore compare the reduction back and produce higher cobalt surface area with similar air calcination catalyst precarsor.
Drying and/or calcining step can intermittently or carry out continuously, and this depends on the availability and/or the scale of operation of method equipment.In preferred embodiments, the method that is used to prepare catalyst precarsor comprises the steps:
(a) 1000-1500 ℃ temperature lower calcination transition alumina for example gamma-alumina forming alpha-aluminium oxide,
(b) flood alpha-aluminium oxide altogether with the solution (in the described compound at least a for nitrate) that comprises ruthenium and cobalt compound,
(c) aluminium oxide of dry and calcining dipping, described calcining step is in air or have＜5 volume % oxygen and comprise that concentration is to carry out in the inert gas of the nitric oxide of 0.001-15 volume % or nitrous oxide, and
(d) optional repeating step (b) and (c).
If desired, catalyst precarsor can be in cobalt and Ru, Pt, Cu, Rh, Pd, Ir, Ag and Bi one or more, also to comprise the appropriate addn that one or more are used for Fischer-Tropsch catalysis.For example, this catalyst can comprise one or more and changes the additive of physical properties and/or influence the reproducibility of catalyst or activity or promoter optionally.Suitable additive is selected from the compound of the metal of selecting from molybdenum (Mo), iron (Fe), manganese (Mn), titanium (Ti), zirconium (Zr), lanthanum (La), cerium (Ce), chromium (Cr), magnesium (Mg) or zinc (Zn).Can be by using suitable compound for example acid, slaine such as metal nitrate or metal acetate, or suitable metal-organic compound such as metal alkoxide or metal acetylacetonates are incorporated into catalyst precarsor with additive.The typical amount of additive is the metal based on catalyst precarsor meter 0.1-10 weight %.If desired, the compound of other additive can be joined in the cobalt liquor with suitable amount.Perhaps, can before or after dry or calcining, they and catalyst precarsor be merged.
In order to make catalyst precarsor have catalytic activity to Fischer-Tropsch reaction, oxidisability cobalt compound that can near small part is reduced to metal.Operable reproducibility air-flow comprises the gas that contains hydrogen and/or carbon monoxide.Preferably under the temperature that improves, use the gas that contains hydrogen to reduce.In the present invention the reproducibility air-flow and therefore the temperature of catalyst precarsor during whole reduction phase≤240 ℃, preferred≤230 ℃, more preferably≤225 ℃.Preferred 90 ℃ of minimum reduction temperature, more preferably 100 ℃, though higher temperature can be quickened reduction, particularly preferred reduction temperature scope is 180-240 ℃.
Before reduction step, if desired, can use method known to those skilled in the art catalyst precarsor to be configured as the forming unit that is suitable for this catalyst expection method therefor.
Expect in the present invention catalyst original position reduction, promptly in their reactor to be used, reduce.Fischer-tropsch reactor adopts various forms, comprise fixed bed reactors, wherein make the gas streams that comprises carbon monoxide and hydrogen pass the bed of one or more particles or monolithic catalysts, described catalyst comprises and loads on washcoated pottery or the catalyst on the metal base; With slurry attitude phase reactor, wherein make the gas streams that comprises hydrogen and carbon monoxide pass the slurry of beaded catalyst in the suitable liquid medium.This class reactor comprises known slurry bubble column reactor (SBCR).
Can by under the temperature that improves, make the reproducibility air-flow for example the mixture of hydrogen, synthesis gas (admixture of gas that comprises hydrogen, carbon monoxide and/or carbon dioxide) or hydrogen and/or carbon monoxide and nitrogen or other inert gas pass oxidising composition, for example pass through at 140-240 ℃, under preferred 160-220 ℃ the temperature hydrogen-containing gas was passed catalyst precarsor 1-16 hour, preferably reduced in 1-8 hour (being also referred to as activation).Preferably, the reproducibility air-flow comprises＞25 volume %, more preferably＞50 volume %, hydrogen most preferably＞75%, the hydrogen of volume % especially＞90.Yet, in the present invention, can also be able to use the syngas mixture reducing catalyst precursor effectively that contains less hydrogen.This can be particularly useful when catalyst is wanted in-situ activation.
Preferably, reduce at≤240 ℃ of following reducible cobalts at least 90%.The cobalt surface area of the catalyst of reduction can use known method to pass through H 2Chemisorbed is measured.
Can reduce under the pressure of environmental pressure or raising, promptly the pressure of reducibility gas can be suitably 1-50, preferred 1-20, more preferably 1-10bar abs.When reducing in position, the elevated pressures of＞10bar abs may be more suitable.
The gas hourly space velocity of reproducibility air-flow (GHSV) can be 100-25000hr -1, preferred 1000-15000hr -1
When in SBCR, using catalyst, can preferably make catalyst precarsor be dispersed in suitable liquid medium for example in the chloroflo such as C6-C40 hydrocarbon mixture of fusion, and make the reproducibility air-flow pass the gained slurry.The solids content of this slurry is preferably 1-50%w/v, more preferably 3-40%w/v, most preferably 5-35%w/v.
The Fischer-Tropsch that catalyst can be used for hydrocarbon synthesizes.
Synthetic with the Fischer-Tropsch of the hydrocarbon of Co catalysts is existing.Fischer-Tropsch is synthetic to make the mixture of carbon monoxide and hydrogen be converted into hydrocarbon.The mixture of carbon monoxide and hydrogen is hydrogen typically: carbon monoxide is than being 1.6-3.0: 1, and preferred 1.7-2.5: 1 synthesis gas.This reaction can use one or more stirring arm attitude phase reactors, bubble-column reactor, circulation flow reactor or fluidized-bed reactor to be undertaken by continuous or batch process.This process can operated under the pressure of 0.1-10Mpa and under 150-350 ℃ the temperature.The gas hourly space velocity (GHSV) that is used for continued operation is 100-25000hr -1Preferred opereating specification is 1000-15000hr -1
Now by the following embodiment of reference with by further describing the present invention with reference to figure 1-5, described figure has described and with the catalyst contrast that promotes, the temperature programmed reduction (TPR) of the catalyst that operable Ru-, Pt-and Cu-promote according to the present invention is schemed.
Embodiment 1: the preparation of the catalyst precarsor of alpha-aluminium oxide load
In air, under 1400 ℃ temperature, gamma-alumina (deriving from the HP 14-150 of Sasol Condea) is calcined time enough so that it changes alpha-aluminium oxide into.
(i) prepare embodiment 1 (a)-(c) by being total to dipping method.Prepare dipping solution in the demineralized water by being dissolved in 5 weight % ruthenium acetates in the acetate and cabaltous nitrate hexahydrate being dissolved in., it was descended dry 3 hours and be heated to 400 ℃ with 2 ℃/min to calcine at 105 ℃, and remained on this temperature 1 hour with described solution-treated alpha-aluminium oxide by the dry impregnation method.Material to calcining repeats described operation then.The gained catalyst precarsor has the cobalt content of 17.8 weight % and the ruthenium content of 0.21 weight %.
Use copper nitrate (II) to prepare catalyst precarsor on the material of calcining, to obtain the cobalt content of about 18 weight % and the reduction accelerator level of about 1 weight % by identical method with platinum nitrate.(supposing when all Co are reduced that the Co content of about 18 weight % is corresponding to about 20% Co content in the catalyst of reduction in the catalyst precarsor).
Also use identical common dipping method preparation to contain and have an appointment 18 weight %Co and do not contain promoter, or comparative catalyst's precursor material of gold, lanthanum and the rhenium of different amounts.
(ii) prepare embodiment 1 (d): by the solution-treated alpha-aluminium oxide of dry impregnation method with cabaltous nitrate hexahydrate by dipping method in succession, it was descended dry 3 hours and be heated to 400 ℃ with 2 ℃/min to calcine at 105 ℃, and remained on this temperature 1 hour.Material to calcining repeats described operation then.Flood the oxidisability cobalt compound precursor that promotes the load of gained alpha-aluminium oxide by the ruthenium acetate that is used in 5 weight % in the acetate, and then that it is following dry 3 hours at 105 ℃.Do not calcine the catalyst precarsor that gained Ru promotes.Provide following catalyst precarsor analysis;
Embodiment Promoter Cobalt analysis/% Promoter analysis/%
1(a) Ru 17.8 0.21％Ru
1(b) Pt 18.9 0.89％Pt
1(c) Cu 17.9 0.92％Cu
1(d) Ru 18.8 0.71％Ru
Comparative Examples 1 Do not have 18.1 -
Comparative Examples 2 La 17.3 4.20％La
Comparative Examples 3 Re 17.8 0.46％Re
Comparative Examples 4 Au 18.5 0.04％Au
Catalyst precarsor 1 (a), uncoated alpha-aluminium oxide and comparison catalyst precarsor are carried out the measurement of BET surface area.The result is as follows:
Figure BPA00001400557100091
The catalyst that ruthenium promotes provides the highest surface area result, secondly is the catalyst that Re promotes.
Temperature programmed reduction (TPR) experiment is used in the behavior of prediction catalyst during the in-situ reducing.Use can derive from the AMI-200 instrument of Altamira Instruments along with the temperature that improves is gradually carried out the thermal conductivity measurement to the sample that is exposed to hydrogen in time.The 70-80mg catalyst precarsor of use in the quartz ampoule that is fixed on original position with quartzy tampon carries out the TPR experiment.10%H at 30ml/min 2Under the flow velocity of/Ar catalyst precarsor is heated to 1000 ℃ from environment temperature with the speed of 10 ℃/min, and remain on then 1000 ℃ following 10 minutes.
Fig. 1-4 embodiment 1 (a)-(d) has been described respectively and shown along with improve temperature and along with the time and Co 3O 4Be reduced to CoO and then CoO be reduced to the relevant thermal conductivity of Co metal and change.These figure have shown that the catalyst that contains copper, ruthenium and platinum is being lower than the reduction temperature that is reduced under 300 ℃ and fully is lower than the corresponding catalyst that does not promote.Compare with the catalyst precarsor that does not promote under these conditions, the catalyst precarsor of rhenium and lanthanum is reduced under higher temperature.The result is as follows;
Figure BPA00001400557100101
Carry out a series of two-step TPR experiment by above-mentioned, difference is in first step catalyst to be heated to 220 ℃ with 10 ℃/min, and keeps 10 hours, is heated to 1000 ℃ and kept 10 minutes with 10 ℃/min then in second step.By contrasting this twice experiment, can calculate the reduction degree under 220 ℃ then.
Use above-mentioned dipping method altogether to be used in the catalyst that makes on the gamma-alumina and carry out other Comparative Examples.Employed gamma-alumina is HP14-150.The Co content of gained precursor is 16.4%, and Ru content is 0.77%.The result is as follows;
? Embodiment Auxiliary agent Reduction degree/%
?1(a) 0.21％Ru(α-Al 2O 3) 91
?1(b) 0.89％Pt 95
?1(c) 0.92％Cu 87
?1(d) 0.71％Ru 91
Comparative Examples 1 Do not have 30，22
Comparative Examples 5 0.77％Ru(γ-Al 2O 3) 36
What can find out is, the reduction degree that obtains with Ru or Pt catalyst is better than copper catalyst or the catalyst that uses gamma-alumina to make.
Embodiment 2: the preparation of silicon dioxide carried catalyst precarsor
(i) be total to dipping method.Prepare dipping solution in the demineralized water by being dissolved in 5 weight % ruthenium acetates in the acetate and cabaltous nitrate hexahydrate being dissolved in.(has 342m by the dry impregnation method with the Powdered silica of described solution-treated 2The precipitated silica in the BET surface area of/g and the aperture of 6.6nm), it was descended dry 3 hours and be heated to 400 ℃ with 2 ℃/min to calcine at 105 ℃, and remained on this temperature 1 hour.
Use single impregnation.The gained catalyst precarsor has the estimation cobalt content of 18 weight % and the estimation ruthenium content of 1 weight %.
Use identical method to prepare the catalyst that platinum promotes, difference is to use platinum nitrate, thereby obtains to have the catalyst precarsor of the estimation Pt content of the estimation cobalt content of 18 weight % and 1 weight %.
Carry out the TPR experiment according to the method described in the embodiment 1.The TPR figure of the Co catalyst of silicon dioxide carried Ru promotion has been described among Fig. 5, and the TPR figure of the catalyst precarsor that does not promote of contrast, show that clearly the reduction temperature of catalyst precarsor of the present invention is lower.On silica, be similar to the performance of Ru as the performance classes of the Pt of reduction accelerator.Provide the result below.
Figure BPA00001400557100111
Also carry out two-step TPR experiment according to the method described in the embodiment 1, this experiment demonstrates 86% reduction degree for the catalyst precarsor of Ru promotion.
Embodiment 3: in-situ reducing test and FT reactivity
The Fischer-Tropsch that the catalyst precarsor of embodiment 1 (a) is used for hydrocarbon in laboratory scale tubular reactor is synthetic.The catalyst precarsor that about 0.1g and SiC are mixed places bed (internal diameter of about 4mm multiply by the degree of depth of 50mm) and makes the reproducibility air-flow pass this bed by three kinds of different conditions of use (regime) and reduces;
A) under hydrogen, reduced 7 hours down in 210 ℃,
B) under the synthesis gas of hydrogen that comprises 2: 1 ratios and carbon monoxide in 210 ℃ down reduction 7 hours and
C) in order to contrast, under hydrogen, reduced 7 hours down in 380 ℃.
After the reduction step, these samples are cooled to 100 ℃, (a) and air-flow (c) are changed into synthesis gas and pressure is brought up to 20barg.Then temperature is brought up to 210 ℃ and monitoring Fischer-Tropsch reaction with 1 ℃/min and continue 120 hours.Air speed is 14400hr between reduction period -1And it was remained in this up to 30 hours, it is reduced to 3600hr in this moment -1Use known gas-chromatography (GC) commercial measurement catalyst to CH 4, C2-C4 and C5+ hydrocarbon activity and selectivity.Below be given in the result of the catalyst that reduces according to different condition under 40 hours, 100 hours and 120 hours.
Under the Fischer-Tropsch condition 40 hours
Figure BPA00001400557100121
Under the Fischer-Tropsch condition 100 hours
Figure BPA00001400557100122
Under the Fischer-Tropsch condition 120 hours
Figure BPA00001400557100123
These results show that with respect to the precursor that reduces down at 380 ℃, activity is maintained, and the selection of catalysts of reducing is comparable under hydrogen or synthesis gas.

Claims (20)

1. catalyst precarsor, this catalyst precarsor comprises the 5-50 weight % that loads on the inert carrier that is selected from alpha-aluminium oxide, metal aluminate, silica, titanium dioxide, zirconia, zinc oxide, carborundum, carbon or their mixture and is selected from CoO, CoO (OH) and Co 3O 4One or more oxidisability cobalt compounds, and 0.05-10 weight % is selected from the metal of Ru, Pt, Cu, Rh, Pd, Ir, Ag and Bi or one or more reduction accelerators of compound, and wherein said cobalt is that highly reducible form makes that at least 75% cobalt can be with the reduction of reproducibility air-flow under≤240 ℃ temperature.
2. according to the catalyst precarsor of claim 1, wherein said reduction accelerator is compound or the metal of Ru, Pt or Cu.
3. according to the catalyst precarsor of claim 2, wherein said reduction accelerator is the oxide of Ru or Ru.
4. according to each catalyst precarsor of claim 1-3, wherein said inert carrier is an alpha-aluminium oxide.
5. according to each catalyst precarsor of claim 1-4, this catalyst precarsor also comprises one or more additives that is selected from the compound of the metal of selecting from molybdenum (Mo), iron (Fe), manganese (Mn), titanium (Ti), zirconium (Zr), lanthanum (La), cerium (Ce), chromium (Cr), magnesium (Mg) or zinc (Zn).
6. according to each catalyst precarsor of claim 1-5, wherein said catalyst precarsor is surperficial weight-average diameter D[3,2] and be the powder of 1-200 μ m.
7. according to each catalyst precarsor of claim 1-6, wherein said catalyst precarsor is surperficial weight-average diameter D[3,2] and by the powder of on average counting 1-20 μ m.
8. according to each catalyst precarsor of claim 1-5, wherein said carrier and thus obtained catalyst precarsor are to have the particle diameter of 1-25mm and less than the form of the forming unit of 2 draw ratio.
9. according to each catalyst precarsor of claim 1-5, wherein said carrier is the form of the washcoated layer on pottery, metal, carbon or polymeric substrate.
10. method that makes catalyst activation, this method comprises and will place the Fischer-Tropsch reaction device according to each catalyst precarsor among the claim 1-9, and make the reducibility gas mixture pass this catalyst precarsor a period of time and be reduced to simple substance form, wherein the temperature of reducibility gas mixture≤240 ℃ in whole activation step with the cobalt that will wherein exist.
11., wherein incite somebody to action reducible cobalt reduction under≤240 ℃ of at least 90% according to the method for claim 10.
12. according to the method for claim 10 or claim 11, wherein said fischer-tropsch reactor is fixed bed reactors or slurry attitude phase reactor.
13. according to each method among the claim 10-12, wherein said reducibility gas mixture is the mixture of hydrogen, synthesis gas or hydrogen and/or carbon monoxide and nitrogen or other inert gas.
14. according to the method for claim 13, wherein said reducibility gas mixture comprises＞hydrogen of 90 volume %.
15. according to the method for claim 13, wherein said reducibility gas mixture comprises syngas mixture.
16., described reducibility gas mixture was passed catalyst precarsor 1-16 hour according to each method among the claim 10-15.
17. the synthetic method of Fischer-Tropsch that is used for hydrocarbon, this method is undertaken by the catalyst that the admixture of gas that comprises hydrogen and carbon monoxide is passed in the Fischer-Tropsch reaction device, and this catalyst activates according to each method among the claim 10-16.
18. according to the method for claim 17, wherein the mixture of carbon monoxide and hydrogen is a hydrogen: carbon monoxide is than being 1.6-3.0: 1 synthesis gas.
19. according to the method for claim 17 or claim 18, the wherein described reaction of operation under the temperature of the pressure of 0.1-10Mpa and 150-350 ℃.
20. according to each method among the claim 17-19, wherein said fischer-tropsch reactor is fixed bed reactors or slurry attitude phase reactor.
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