CN1774407A - The preparation of titania and cobalt aluminate catalyst supports and their use in fischer-tropsch synthesis - Google Patents
The preparation of titania and cobalt aluminate catalyst supports and their use in fischer-tropsch synthesis Download PDFInfo
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Abstract
Supports for Fischer-Tropsch catalysts are formed by forming a particulate material from titania, alumina and optionally silica. A cobalt compound is incorporated into the particulate material which then is calcined to convert at least part of the alumina to cobalt aluminate.
Description
Invention field
The present invention relates to contain the support of the catalyst of titanium dioxide and Leyden blue.Also relate to this carrier and the catalyst component purposes in the fischer-tropsch hydrocarbon is synthetic, carry high alpha-value thus and improve the selectivity of this method higher hydrocarbon.
Background of invention
As being the method that hydrogen and carbon monoxide are produced hydrocarbon from synthetic gas, the fischer-tropsch process was developed in nineteen twenties.At first, this process focuses on that production is as the hydrocarbon in the gasoline boiling range of automobile fuel.Yet nowadays, the fischer-tropsch process is regarded as preparing the heavy hydrocarbon of diesel oil fuel and so on and day by day more preferably in order to the method for the waxy molecules that is converted into the clean and effective lubricant.Thereby the importance of catalyzer that be used to produce high boiling hydrocarbon more, promptly contains the product series of higher carbon number distribution improves day by day.Measuring of carbon number distribution is Shu Erci-Florey α value, and this value representative is from the given carbon number manufacturing possibility of higher carbon number thereafter.Shu Erci-flory distribution by Shu Erci-Florey formula mathematical notation is:
W
i＝(1-α)
2iα
j-1
Wherein i represents carbon number; α is Shu Erci-flory distribution factor, represents chain growth speed and chain growth speed to add the ratio of chain termination speed; W
iRepresenting carbon number is the weight fraction of the product of i.Being higher than about 0.9 the normally representative of wax production process of α number, the α number is high more-along with it is high more to the selectivity of wax molecule near this process of 1.0-.
Usually the catalyzer that is used in the fischer-tropsch process is iron and cobalt; Ruthenium has and is used for the necessary catalyst activity of this process, but its expensive and supply relative shortage.Usually also adopt promotor to improve the each side of catalytic performance, for example rhenium, zirconium, manganese etc. especially use with cobalt.
These catalyzer load on mainly on the particulate material that is made of aluminum oxide or titanium dioxide usually.
Experience shows that fischer-tropsch synthetic operational condition causes catalyzer to die down and excessive particulate forms when especially carrying out in reaction mixture in the slurry attitude.Therefore, making great efforts the improved catalyzer of exploitation.
For example in WO99/42214, disclose with being selected from the compound of Si, Zr, Cu, Mn, Ba, Co, Zn, Ni or La with aluminum oxide, titanium dioxide or magnesium oxide carrier modification.US6 has disclosed a kind of improvement carrier that mainly comprises titanium dioxide in 117,814, wherein is mixed with silica and alumina adhesive.
A target of the present invention provides further improved novel titania supports.
Another target of the present invention provides the catalyzer that is carried on this improved titania support, and this type of catalyzer is used for the synthetic gas conversion to obtain highly selective and low methane formation.
Summary of the invention
In one embodiment, the improved support of the catalyst binding agent that mainly comprises titanium dioxide and comprise Leyden blue on a small quantity.Be converted under the condition of Leyden blue and react being enough near small part, preferred basic all aluminum oxide by the cobalt compound that forms titania support with alumina binder, make alumina binder and capacity subsequently, Leyden blue is incorporated in this titania support.Thereby this carrier also can contain alumina binder, but preferred basic alumina-free.Not necessarily this carrier can also contain the silicon-dioxide as binding agent.
Another embodiment of the invention is included in and contains cobalt Fischer-Tropsch catalysts composition, the binding agent that this carrier is mainly silicon-dioxide and comprises Leyden blue on a small quantity on the carrier.
Another embodiment comprises the optionally fischer-tropsch process with improvement, and this process comprises reacts synthetic gas in the presence of Fischer-Tropsch reaction condition and supported cobalt catalysts, and wherein carrier mainly comprises titanium dioxide and minor amount of cobalt aluminate.
When reading the rest part of this specification sheets, other embodiment of the present invention will become obvious.
The accompanying drawing summary
Fig. 1,2 and 3 is figure that the data that provide among the embodiment of all respects of the present invention are provided.
Detailed Description Of The Invention
Carrier of the present invention is the granular materials of the oxide of containing element titanium, aluminium and cobalt. These oxides can be simple oxides, i.e. the oxide of single-element is such as TiO2、Al
2O
3, CoO and Co3O
4 And the oxide of more than one elements, such as CoTiO3And CoAl2O
4 In any case this carrier mainly comprises titanium dioxide (TiO2), and a small amount of cobalt aluminate. Usually, based on the gross weight of carrier, this carrier contains at least 50 % by weight titanium dioxide, the preferred about 97 % by weight titanium dioxide of 80-. The titanium dioxide of the about 20-100 % by weight of this carrier, preferred 60-80 % by weight is the rutile crystal phase, and all the other are anatase crystal phase or amorphous phase. In the binding agent amount of cobalt aluminate depend on carrier form in the amount of used cobalt and aluminium compound. Provide cobalt/al atomic ratio greater than 0.25, preferred 0.5-2, more preferably from about 1 just enough cobalt be present in the carrier. Therefore, be 0.25 for the Co/Al ratio, make an appointment with half aluminium oxide to exist as cobalt aluminate. Be 0.5 for the Co/Al ratio, the aluminium oxide of all existence exists with cobalt aluminate substantially. For the Co/Al ratio that is higher than 0.5, carrier will also contain cobalt titanate and be substantially free of aluminium oxide except cobalt aluminate.
As previously mentioned, binding agent can also comprise aluminium oxide and nonessential silica. Usually. Binding agent is lower than about 30 % by weight of carrier, preferably is lower than about 15 % by weight of carrier. Usually binding agent is higher than 3 % by weight of carrier. The amount of silica is lower than 50 % by weight of binding agent total amount, is preferably 35 % by weight of binding agent.
This carrier has about 5m usually2The about 40m of/g-2/ g, preferred 10m2/g-30m
2Surface area in the/g scope, the pore volume in the about 0.5cc/g of about 0.2cc/g-, the preferred 0.3cc/g-0.4cc/g scope.
Usually, enter an inlet temperature by the suitable aqueous slurry spray-drying with titanium dioxide, alumina binder material and nonessential silica binder material and form this carrier for the chamber of about 105 ℃-135 ℃ warm air blowoff. Spray-drying generates the granularity scope and is the ball type carrier of about 20-120 micron. Then will this spray-dired carrier at the temperature lower calcination of 400-800 ℃ of scope, preferred about 700 ℃. Then, with the aqueous solution of cobalt compound, preferred cobalt nitrate, flood the material of this calcining with the amount that is enough at least part of aluminium oxide to be converted into when the calcining cobalt aluminate. The amount of preferred used cobalt compound is enough to the aluminium oxide of 50%-99+% is converted into cobalt aluminate. Thereby the amount and 0.25 of the cobalt compound that adds during the carrier preparation: 1-2: 1, preferred 0.5: 1-1: the Co in 1 scope: the Al atomic ratio is corresponding. In fact, the carrier of particularly preferably producing is oxygen-freeization aluminium substantially.
The preferably calcining of soaking the cobalt carrier under the temperature in air, in about 700 ℃-Yue 1000 ℃ of scopes, preferred about 800 ℃-Yue 900 ℃.
When from this preparing carriers Fischer-Tropsch catalyst, it is compound to synthesize metal and this carrier with catalytic activity to fischer-tropsch.Preferred metal is those metals, particularly iron, cobalt and the ruthenium of periodic table of elements group VIII, preferred cobalt and ruthenium, most preferably cobalt.Can also adopt promotor,, and well known to a person skilled in the art other promotor as zirconium, titanium, rhenium, hafnium, cerium, thorium and uranium.Metal exists to synthesize the amount with catalytic activity for fischer-tropsch, and this amount changes with selected metal.For example, rhenium has more activity than cobalt thereby uses with the amount in about 0.5-3.0 weight % scope in this environment, and cobalt preferably with the amount of about 2-40 weight % use, more preferably 5-30 weight %, further preferred 10-25 weight %.
When adopting promotor, they use with the amount that is less than active catalytic metal, for example based on reactive metal, with the weight ratio of about 1/20-1/10.Most preferred catalyzer is those those catalyzer, particularly cobalt and rheniums of containing cobalt and rhenium, cobalt and ruthenium and cobalt and Thorotrast.
Can be with well known to a person skilled in the art that various technology prepare catalyzer, comprise dipping (perhaps flood altogether or step impregnation-or by spraying drying or by initial wetting (incipient wetness) technology) with promotor.Because being used for fixing a preferred catalyst of fischer-tropsch process is that catalytic metal is present in granules of catalyst than the catalyzer in the outside part, promptly be not deeper than 250 microns, preferably be not deeper than 200 microns the layer in, therefore the preferred method for preparing this catalyzer is a spray method, and this method is described in US5,140, in 050, be incorporated herein by reference herein, or EP0,266, in 898, be incorporated herein by reference herein.For slurry bed fischer-tropsch process, catalyzer preferably prepares by the incipient wetness impregnation of spray-dired carrier.When adopting incipient wetness impregnation technique, not necessarily adopt organic dipping auxiliary agent.This analog assistant is described in US5, in 856,260, US5,856,261 and US5,863,856, all is incorporated herein by reference herein.
The fischer-tropsch process is known process, and reaction conditions has been described in the document that can obtain.For example temperature can be about 175 ℃-Yue 400 ℃, preferred about 180 ℃-250 ℃, and pressure can be about 1-100bar, preferred about 15-40bar.Hydrogen/CO ratio can be about 4/1 for 0.5/1-, preferred about 1.7/1-2.5/1, and most preferably its stoichiometry adds deduct about 3%.The catalyzer that is made by carrier of the present invention preferably is used in slurry for example in sluny bubble column (the slurry bubble column) reactor, and wherein gas hourly space velocity can be for about 1,000-25,000.A kind of preferred slurry bubble column operation is described in USP5, in 348,982, is incorporated herein by reference herein.Follow Shu Erci-flory distribution substantially by the product that the inventive method is produced, except methane production usually above this distribute predicted.This shows that methane obviously is to be generated by other mechanism.
Usually by making all or part of C
5+Fractionation of hydrocarbon experience and/or conversion, the hydrocarbon that will generate in process as mentioned above upgrades to the product that has more value." conversion " is meant the operation that one or more change therein to the molecular structure of small part hydrocarbon, comprises non-catalytic process simultaneously, as steam cracking, with catalytic process, and for example wherein catalytic cracking that contacts with the catalyzer that suits of part or cut.If hydrogen exists as reductive agent, this class process step typically refers to hydrocracking, and be called hydroisomerizing respectively, hydrocracking, Hydrodewaxing, hydrofining etc.The so-called hydrotreatment of more violent hydrofining.These reactions in the literature to hydrocarbon feed, comprise under the condition that the hydrocracking of the hydrocarbon feed that is rich in paraffinic hydrocarbons discloses in detail and carrying out.The example that has more valuable product that obtains by this class raw material by these processes but not determinate example comprises synthetic crude, liquid fuel, emulsion, purifying alkene, solvent, monomer or polymkeric substance, lubricating oil, medicinal oil, waxy hydrocarbon, various nitrogenous or OXO products, and analogue.The example of liquid fuel comprises gasoline, diesel oil and jet fuel, and lubricating oil comprises gasoline, air-jeting oil and turbine oil and analogue.Technical oils comprises drilling fluid, agricultural oils, heat-transfer oil and analogue.
Be appreciated that various other embodiments and the scheme of the present invention in putting into practice will obviously and be easy to make for those those of ordinary skill in this area, and do not depart from scope and spirit of the present invention as mentioned above.The scope of not expecting claims is limited to definite description listed above, but wish claim is interpreted as comprising the novel feature of all patentabilities that are present among the present invention, comprise by one of ordinary skill in the art of the present invention can be used as all features and the embodiment that its equivalent is handled.Further describe the present invention with reference to following test.
Embodiment
Preparation of catalysts
Embodiment A (carrier of the present invention and catalyzer)
(a) titania support
Followingly prepare titania support by spraying drying.With 34.4 parts of (weight) Degussa P-25 pyrolysis method TiO
2, 8.8 parts of hydroxide chlorination aluminum oxide (alumina chlorhydrol) colloidal sols (contain 23.5 weight %Al
2O
3), (Nyacol 2034 DI contain 35 weight %SiO to 0.6 part of silica sol
2) and 56.2 parts of water be mixed with the slurry raw material.The speed that this mixture divides with about 13lb/ is passed through with 10, and 9 inches atomizer of 000rpm rotation is supplied with the spray-dryer of 9 ft diams.About 285 ℃ intake air temperature and about 120 ℃ temperature out operated this spray-drying chamber during with spraying.About 60 microns and have 94 weight %TiO of products by average particle size
2-5.4 weight %Al
2O
3-0.6 weight %SiO
2The solid spherical particle of forming constitutes.
Should in the rotation calcining furnace, calcine down by spray-dired carrier, generate carrier: 24% TiO with following characteristic in 732 ℃
2For rutile-type, surface-area are 48m
2/ g and water law pore volume are 0.50cc/g.
(b) cobalt improved titania support
Following with the titania support of Xiao Suangu dipping from (a), and calcining at high temperature, cobalt improved carrier formed.Mix with 18.0 parts of water and with its dilution by the cobalt nitrate aqueous solution that 41.5 weight parts is contained 15 weight %Co.In the V-stirring mixer, this solution is all added in 95 parts of titania supports from (a).Free-pouring product is calcined in the rotation calcining furnace in air, and this calcining furnace contains respectively 315 ℃, 427 ℃ and 454 ℃ of three heating zones of operating down.This calcining makes this material drying and Xiao Suangu is decomposed into Co
3O
4Should in the rotation calcining furnace, under 870 ℃, calcine again by burnt carrier then, cobalt oxide is converted into Leyden blue and cobalt titanate.Blue green end product has following characteristic: 5.9 weight %Co, 1.02Co/Al atomic ratio, 94% TiO
2For rutile-type, surface-area are 21m
2/ g, water law pore volume are 0.31cc/g.
(c) the Co-Re catalyzer on the cobalt improved titania support
Following Xiao Suangu and the perrhenic acid dipping used forms catalyzer from the cobalt improved titania support of (b).By 74.0 parts of Cobaltous nitrate hexahydrate crystal, 1.8 parts of perrhenic acid (containing 53.5 weight %Re), 5.6 parts of propanedioic acid and 18.6 parts of water are mixed, then this mixture heating up to 43 ℃ formation solution are prepared dipping solution.By weight, in the V-stirring mixer, 57.6 parts of these solution are added in 120 parts of titania supports from (b).Free-pouring product is calcined in being respectively three sections rotation calcining furnaces of 315 ℃, 371 ℃ and 454 ℃ in air.With same dipping solution, add in 128 parts of catalyzer with 53 parts of solution this calcinate is flooded for the second time, then with identical program calcining.Final catalyzer contains 15.2%Co and 0.68%Re.
In this example catalyst, before the hydrogen reduction activation, 10.1% Co is activity form Co
3O
4All the other promptly 5.1% cobalt keep being combined in the carrier as aluminate and titanate.
Embodiment B (carrier of the present invention and catalyzer)
(a) titania support
Described in embodiment A part (a), prepare titania support by spraying drying.This carrier is calcined down in 700 ℃ in the rotation calcining furnace, generated carrier: 16% TiO with following characteristic
2For rutile-type, surface-area are 44m
2/ g and water law pore volume are 0.52cc/g.
(b) cobalt improved titania support
Following with the titania support of Xiao Suangu dipping from (a), and calcining at high temperature, cobalt improved carrier formed.10.13 gram part Cobaltous nitrate hexahydrates are dissolved in the deionized water and with cumulative volume are adjusted into 51mL.This solution is all added in the titania support of 100 grams from (a) with thorough mixing with aliquot.Free-pouring product was calcined 3 hours down in 800 ℃ in the rotation calcining furnace in air.This calcining is decomposed into Co in this material drying of temperature raising period chien shih and with Xiao Suangu
3O
4And under outlet temperature, cobalt oxide is converted into Leyden blue and cobalt titanate.Blue look end product has following characteristic: 1.93 weight %Co, 0.32Co/Al atomic ratio, 66% TiO
2For rutile-type, surface-area are 21m
2/ g, water law pore volume are 0.38cc/g.
(c) the Co-Re catalyzer on the cobalt improved titania support
Following Xiao Suangu and the perrhenic acid dipping used forms catalyzer from the cobalt improved titania support of (b).Restraining the perrhenic acid that contains 53.5 weight %Re by the cobalt nitrate aqueous solution and 2.52 that 100 grams are contained 15 weight %Co mixes and prepares dipping solution.27 (27) these solution of ml are added in the carrier of 70 grams from (b) with vibration with aliquot, product was calcined 3 hours down in 300 ℃ in stove in air.Reclaim in dipping and incinerating all material for the first time by the above solution of 24.9ml is added to, carry out flooding the second time.Product was calcined 3 hours down in 300 ℃ in stove in air.Final catalyzer contains 14.82%Co and 1.17%Re.In this example catalyst, before the hydrogen reduction activation, 13.2% Co is activity form Co
3O
4All the other promptly 1.6% cobalt keep being combined in the carrier as aluminate.
Embodiment C (reference catalyst)
Following by preparing reference catalyst with Xiao Suangu and perrhenic acid dipping rutile titanium dioxide carrier.At first, as above prepare titania support described in the embodiment A part (a).This carrier is calcined contained 95%TiO down in about 1010 ℃ in the rotation calcining furnace
2Be rutile-type.The aqueous solution with perrhenic acid and Xiao Suangu floods this through the incinerating carrier, and calcines down in 454 ℃ in air.Carry out flooding the second time and calcining, generate the final catalyzer that contains 11.3%Co and 1.09%Re.Catalyst characterization
(a) in order to make the formation amount maximum of heavy hydrocarbon described in the present invention, importantly any aluminum oxide that is present in the titania support as binding agent all is converted into Leyden blue during the last calcining of cobalt improved carrier.This conversion is accompanied by obvious color and changes: compare with the titanium dioxide raw material of white, embodiment (A) (b) the final Co modified support in the part is a turquoise.A kind of facilitated method of monitoring Leyden blue and cobalt titanate generation and existence more accurately is to analyze carrier and/or catalyzer by temperature program(me) reduction technique, particularly thermogravimetry (TGA).For example, Fig. 1 represents the weight loss that (10 ℃/minute heat-up rates) are produced when in hydrogen the catalyzer of the carrier of embodiment A and catalyzer and Embodiment C being heated to 900 ℃.Such as among the figure mark because each reduces in visibly different temperature province, so titanate (CoTiO
3) and aluminate (CoAl
2O
4) existence can be easily and cobalt oxide (Co
3O
4) differentiate.Containing from embodiment A (b) partial C o modified support is enough to cobalt that all aluminum oxide are converted into aluminate and small portion titanium dioxide are converted into titanate.
(b) solubleness of cobalt improved carrier of test and basic titania support in 0.01M nitric acid.Sample was soaked 10-45 minute in the acid of 2-10 weight part, centrifugation then, and with in coupled plasma electronic spectrum (ICPES) analytical solution molten positively charged ion.The results are summarized in the table 1.For embodiment A,, make the aluminum oxide part of carrier more soluble, and make titanium dioxide part (main ingredient) more solvable by with cobalt improved.For Embodiment B,, make aluminum oxide and titanium dioxide all more solvable by sneaking into of cobalt.Attention is for carrier is carrier and cobalt improved carrier, and the solubleness of aluminum oxide and titanium dioxide all is extremely low.
The hydrocarbon compound experiment of embodiment A and C catalyzer
By in fluidized-bed with the pure hydrogen reduction of 250psig from the catalyzer of catalyst A (the present invention) and Embodiment C (reference) and with its activation.The standard gas hourly space velocity is about 10,000.Temperature rises to 371 ℃ of outlet temperatures with 11 ℃/hour, keeps 4 hours in this temperature.Under the used whole temperature, only cobalt oxide is reduced to active cobalt metal in activation in attention.Cobalt as Leyden blue and cobalt titanate existence still keeps these forms in deactivated catalyst.
In the 6 inch diameter slurry bubble column of operating under 210 ℃ and 275psig, detecting catalyst is synthetic to hydrocarbon.The selectivity of product that table 2 has gathered operational variable and the catalyzer of embodiment A (the present invention) and Embodiment C (reference) is measured.In the table, GHSV per hour is meant the synthetic gas volume in the normal conditions on every volume of catalyst.Methane selectively mol%CH
4It is the molecular fraction of the methane that forms of the CO of every mole of conversion.Measure the α value from the linear regression of the semilogarithmic plot of the C20-C50 alkane carbon number distribution that derives from gas-chromatography.The weight % that boiling point is higher than the hydrocarbon of 700 (317 ℃) passes through determination of distillation.
Known fischer-tropsch selectivity of product depends on catalyzer and depends on operational condition in this area, as temperature, pressure, H
2/ CO ratio, level of conversion etc.The simple method that the effect of the effect of catalyzer and process variable is distinguished is the figure of plot of product distribution to methane selectively.This figure is shown in table 2 and 3, based on the selective data that provides among Fig. 2.Among Fig. 2 the α value is mapped to methane selectively.Among Fig. 3 with C
5+700+cut in the hydrocarbon is mapped to methane selectively.In this case the scope of methane selectively by process variable, mainly be that level of conversion generates.Two width of cloth figure show under any given methane selectively, compare with reference catalyst, and catalyzer of the present invention is towards the remarkable conversion of heavy hydrocarbon.Observed 700+productive rate difference usually above 10%, is the raising of a highly significant, and can directly cause the higher yields of senior lubricating base oil behind the wax isomery.
The hydrocarbon compound experiment of the catalyzer of Embodiment B and C
The catalyzer of test implementation example B (the present invention) and Embodiment C (reference) in the fixed bed pilot plant.(0.75 inch 80 series pipe 304SS) operated the catalyzer of Embodiment B in tubular reactor by loading 15.0 gram catalyzer and 177.6 gram titania diluent.In hydrogen, under 375 ℃, fill is reduced, and use 2.1H
2/ Co synthetic gas is operated under the 280psig mean pressure.With 16.15 gram Embodiment C catalyzer and 101.75 gram titania diluent base catalyst is operated in the same way.Get 4 parts of hydrocarbon product samples during 10 day cycle in each running, use gas chromatographic analysis, and from C20-C45 carbon number range alpha value calculated.The results are summarized in the table 3.Catalyzer of the present invention is with than the α value of reference example high 0.02 and low about 1% the methane generation wax that compares.About 15% increase in 700+hydrocarbon of the reliability response productive rate of this α value.
Table 1
| Carrier | SA，m 2/g | The ppm of dissolved carrier | Microgram/m 2 | ||
| Al | Ti | Al | Ti | ||
| Embodiment A (the present invention) | 21 | 70 | 5.2 | 3.3 | 0.25 |
| Embodiment B (the present invention) | 21 | 534 | 27 | 25 | 1.3 |
| Embodiment C (reference) | 14 | 133 | ＜0.2 | 9.5 | ＜0.014 |
Table 2
| H 2/ CO charge ratio | GHSV | The %CO transformation efficiency | Mol％CH 4 | The α value | C 5+In 700 °F+weight % | |
| Embodiment A | ||||||
| 2.1 | 9250 | 72 | 4.4 | 0.939 | 60.3 | |
| 2.1 | 9450 | 53 | 5.3 | 0.932 | 54.9 | |
| 2.1 | 9450 | 44 | 6.0 | 0.928 | 51.9 | |
| 1.95 | 5890 | 58 | 4.3 | 0.942 | --- | |
| 1.95 | 5890 | 54 | 4.6 | 0.936 | 58.3 | |
| Embodiment C | ||||||
| 2.1 | 11650 | 50 | 5.0 | 0.928 | 46.5 | |
| 2.1 | 11600 | 50 | 5.0 | 0.927 | 47.1 | |
| 2.1 | 11760 | 43 | 6.0 | 0.921 | 44.9 | |
| 2.1 | 11750 | 35 | 6.6 | 0.916 | 40.8 |
Table 3
| Catalyzer | Embodiment B | Embodiment C |
| Temperature, ℃ | 213 | 213 |
| GHSV | 4477 | 7350 |
| The %CO transformation efficiency | 56 | 64 |
| Mole %CH 4 | 5.9 | 6.8 |
| The α value | 0.94 | 0.92 |
Claims (9)
1. catalyst support compositions comprises:
The titanium dioxide of main amount; With
The binding agent that contains Leyden blue on a small quantity,
Wherein in the composition atomic ratio of cobalt and aluminium greater than 0.25.
2. the composition described in claim 1 contains the 0 weight % aluminum oxide of having an appointment.
3. the composition described in claim 1, wherein binding agent comprises aluminum oxide, and comprises silicon-dioxide with the amount that is less than binding agent total amount 50 weight %.
4. method for preparing support of the catalyst comprises:
To contain the material spray drying of the titanium dioxide and the small amounts aluminium of main amount, form spray-dried product;
Cobalt compound is incorporated in this spray-dried product obtains cobalt-containing materials, this cobalt compound is incorporated into the amount that is enough near small part aluminum oxide when the calcining and is converted into Leyden blue; And
With this cobalt-containing materials calcining.
5. method as claimed in claim 4 is included in and is incorporated into after the cobalt compound, in air in about 700 ℃-Yue 1000 ℃ of these spray-dried products of calcining down.
6. method as claimed in claim 5, wherein the amount of the cobalt compound that is added is enough to provide 0.25: 1-2: the Co/Al atomic ratio in 1 scope.
7. method as claimed in claim 6 is wherein to be enough to that when calcining basic all aluminum oxide are converted into the amount of Leyden blue in conjunction with cobalt compound.
8. Fischer-Tropsch catalyst composition, said composition is included in the catalytic metal that is selected from cobalt, rhenium and composition thereof basically on the carrier that mainly comprises titanium dioxide and minor amount of cobalt aluminate, wherein catalytic metal is a cobalt, and in the binding agent atomic ratio of cobalt and aluminum oxide 0.25: 1-2: in 1 scope.
9. improved fischer-tropsch synthetic method of selectivity, this method comprise makes synthetic gas in reaction in the presence of the described catalyzer of claim 8 under the Fischer-Tropsch reaction condition, generates C thus
5+Hydrocarbon.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46201703P | 2003-04-11 | 2003-04-11 | |
| US60/462,017 | 2003-04-11 | ||
| US10/819,384 | 2004-04-06 | ||
| US10/819,384 US7253136B2 (en) | 2003-04-11 | 2004-04-06 | Preparation of titania and cobalt aluminate catalyst supports and their use in Fischer-Tropsch synthesis |
| PCT/US2004/011239 WO2004091775A2 (en) | 2003-04-11 | 2004-04-09 | The preparation of titania and cobalt aluminate catalyst supports and their use in fischer-tropsch synthesis |
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|---|---|
| CN1774407A true CN1774407A (en) | 2006-05-17 |
| CN1774407B CN1774407B (en) | 2011-03-02 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134164B (en) * | 2006-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Co-based fischer-tropsch synthesis catalyst and method for preparing the same |
| CN101868299B (en) * | 2007-10-26 | 2014-07-30 | 埃克森美孚研究工程公司 | Cobalt catalyst with improved activity maintenance |
| CN104053502A (en) * | 2011-12-21 | 2014-09-17 | Ifp新能源公司 | Method For Preparing A Group Viii Metal Catalyst By Impregnation Using At Least One Organic Additive, And Selective Hydrogenation Method Implementing Said Catalyst |
| CN106966438A (en) * | 2017-04-01 | 2017-07-21 | 中南大学 | A kind of spherical Co2AlO4Material and its preparation method and application |
| CN111420665A (en) * | 2020-04-26 | 2020-07-17 | 万华化学集团股份有限公司 | Modified Fenton-like catalyst, preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6117814A (en) * | 1998-02-10 | 2000-09-12 | Exxon Research And Engineering Co. | Titania catalysts their preparation and use in fischer-tropsch synthesis |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134164B (en) * | 2006-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Co-based fischer-tropsch synthesis catalyst and method for preparing the same |
| CN101868299B (en) * | 2007-10-26 | 2014-07-30 | 埃克森美孚研究工程公司 | Cobalt catalyst with improved activity maintenance |
| CN104053502A (en) * | 2011-12-21 | 2014-09-17 | Ifp新能源公司 | Method For Preparing A Group Viii Metal Catalyst By Impregnation Using At Least One Organic Additive, And Selective Hydrogenation Method Implementing Said Catalyst |
| CN104053502B (en) * | 2011-12-21 | 2016-12-07 | Ifp 新能源公司 | Prepare the method for the catalyst based on group VIII metal using at least one organic additive to prepare and use described selectivity of catalyst method of hydrotreating |
| CN106966438A (en) * | 2017-04-01 | 2017-07-21 | 中南大学 | A kind of spherical Co2AlO4Material and its preparation method and application |
| CN106966438B (en) * | 2017-04-01 | 2018-12-07 | 中南大学 | A kind of spherical shape Co2AlO4Material and its preparation method and application |
| CN111420665A (en) * | 2020-04-26 | 2020-07-17 | 万华化学集团股份有限公司 | Modified Fenton-like catalyst, preparation method and application |
| CN111420665B (en) * | 2020-04-26 | 2022-09-20 | 万华化学集团股份有限公司 | Modified Fenton-like catalyst, preparation method and application |
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| Publication number | Publication date |
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| ZA200508172B (en) | 2007-03-28 |
| CN1774407B (en) | 2011-03-02 |
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