CN101757952A - Catalyst, preparation method thereof and Fischer-Tropsch method - Google Patents
Catalyst, preparation method thereof and Fischer-Tropsch method Download PDFInfo
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- CN101757952A CN101757952A CN 200810240548 CN200810240548A CN101757952A CN 101757952 A CN101757952 A CN 101757952A CN 200810240548 CN200810240548 CN 200810240548 CN 200810240548 A CN200810240548 A CN 200810240548A CN 101757952 A CN101757952 A CN 101757952A
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Abstract
The invention relates to a catalyst and a preparation method thereof. The catalyst comprises an inner core and an outer layer, wherein the inner core is of a first catalyst carrier; the outer layer is wrapped on the inner core; the outer layer comprises a second catalyst carrier and an active metal ingredient loaded on the second catalyst carrier, wherein the first catalyst carrier and the second catalyst carrier are made of the same material. The invention also provides a Fischer-Tropsch method. The catalyst provided in the invention has the closely-combined inner core-outer layer structure, and the inner core does not have the active metal ingredient basically, therefore, the catalyst has high selectivity, thereby being especially applicable for the Fischer-Tropsch reaction for preparing medium alkane and heavy alkane.
Description
Technical field
The invention relates to a kind of Catalysts and its preparation method, particularly about a kind of fischer-tropsch synthetic catalyst and preparation method thereof and Fischer-Tropsch synthesis method with kernel-layer structure.
Background technology
Fischer-Tropsch synthesis is a gas-solid-liquid heterogeneous reaction system, and in fixed bed reactors, the particle diameter of catalyst is generally several mm, and therefore, DIFFUSION CONTROLLED is difficult to avoid to the influence of catalytic activity.And load on catalyst surface with liquid state, vapour colloidal sol or slurry attitude form usually by the synthetic heavy paraffin that obtains of Fischer-Tropsch, to reactant H
2Exert an influence in the diffusion of catalyst granules inside with CO.In the interior diffusion process of reactant, H
2Diffusion velocity faster than CO, CO obviously is better than H in the diffusion-restricted effect of catalyst particles intragranular
2Because of the particle grain size difference, caused the difference of granule interior CO concentration gradient, influenced combining of CO and metal active centre bit, make the H/C that on the activated centre, adsorbs than increasing, carbochain increases probability and reduces, and has reduced C
5+Selectivity.
CN1988952A discloses a kind of layered catalyst that is used for hydrodesulfurization reaction, comprises kernel and is adhered on the kernel and contains the skin that load on it has the refractory inorganic oxide of at least a metal component that is selected from cobalt, nickel, molybdenum and tungsten.According to this invention, when kernel is made up of refractory inorganic oxide, outer refractory inorganic oxide must be different from the internal layer refractory oxides, and the internal layer refractory inorganic oxide has lower adsorption capacity with respect to outer refractory inorganic oxide to catalytic metal precursor.
Summary of the invention
The objective of the invention is to overcome in the prior art, the problem of fischer-tropsch reaction catalyst selectivity difference provides a kind of selectivity the good catalyst with kernel-layer structure.
The invention provides a kind of catalyst, this catalyst comprises kernel and skin, described kernel is first catalyst carrier, described skin is covering on described kernel, described skin contains second catalyst carrier and the active metal component that loads on described second catalyst carrier, wherein, described first catalyst carrier is identical with the material of described second catalyst carrier.
The invention provides a kind of Preparation of catalysts method, this method comprises with first catalyst support powder and/or the first catalyst carrier precursor powder preparation kernel, load there are second catalyst support powder and/or the second catalyst carrier precursor powder packets of the compound of active metal component overlay on the kernel, carry out drying and roasting then, wherein, described first catalyst support powder and/or the first catalyst carrier precursor powder are identical with the material of described second catalyst support powder and/or the second catalyst carrier precursor powder.
The invention provides a kind of Fischer-Tropsch synthesis method, this method comprises that wherein, described catalyst is a catalyst provided by the invention with synthesis gas synthesizing liquid fuel under the condition that catalyst exists.
In existing layered catalyst, kernel is different carrier materials with skin, because both there are differences on hot property, causes roasting rear catalyst carrier kernel outer in conjunction with not tight, is easy to generate the phenomenon of scaling.In addition, the preparation method of existing layered catalyst is: after making the layered catalyst carrier, the method by common dipping is loaded to metal active constituent on the catalyst carrier, and like this, when dipping, metal active constituent moves to internal layer easily.And catalyst provided by the invention has the kernel-layer structure of combining closely, and kernel do not have active metal component basically, so the selection of catalysts height, be particularly suitable for in producing, heavy paraffins is the Fischer-Tropsch synthesis of purpose.
Except the Fischer-Tropsch synthesis catalyst, Catalysts and its preparation method provided by the invention can also be applicable to other reactions, as hydrodesulfurization reaction, benzene anhydride oxidized reaction etc.
The specific embodiment
Catalyst provided by the invention comprises kernel and skin, described kernel is first catalyst carrier, described skin is coated on the described kernel, described skin contains second catalyst carrier and the active metal component that loads in described second catalyst carrier, it is characterized in that described first catalyst carrier is identical with the material of described second catalyst carrier.
Wherein, the diameter of described kernel can be 1-6mm, is preferably 1.5-4mm, and described outer field thickness can be 0.05-3mm, is preferably 0.1-1.5mm.Shell thickness can adopt to be cut ball open back and measures or carry out also measurement of section component analysis with the S-4700 type ESEM of configuration EDAX-9100 type X-ray energy spectrometer along the catalyst radial direction along the catalyst radial direction with slide measure.
Wherein, described active metal component can be selected in reaction as required.Those skilled in the art can be according to the kind and the content of the suitable active metal component of the type selecting of reacting.Generally speaking, be benchmark with the gross weight of catalyst, the content of active metal component can be 1-80 weight %, is preferably 1-60 weight %, more preferably 5-50 weight %.
When described catalyst be fischer-tropsch synthetic catalyst constantly, described active metal component is iron and/or cobalt, in oxide and with catalyst be benchmark, the content of described active metal component is 1-60 weight %, is preferably 5-50 weight %.The compound of described active metal component can be the conventional compound that can form active metal component that is used for the Fischer-Tropsch synthesis catalyst, for example, the compound that contains iron and/or cobalt, the compound of iron is selected from ferric nitrate, and the compound of cobalt is selected from one or more in cobalt nitrate, cobalt acetate, the citric acid cobalt etc.
Except Fischer-Tropsch synthesis, the present invention still is used for other reactions, as hydrodesulfurization reaction and benzene anhydride oxidized reaction etc.When described catalyst was Hydrobon catalyst, metal active constituent can be selected from one or more in the compound of cobalt, nickel, molybdenum and tungsten; Gross weight with catalyst is a benchmark, and the content of active metal component can be 5-80%.When described catalyst was benzene anhydride oxidized catalysts, metal active constituent can be vanadium; Gross weight with catalyst is a benchmark, and the content of active metal component is 4-80%.
Described skin can also contain catalyst promoter.Those skilled in the art can be according to the type of reaction and the suitable catalyst promoter component of type selecting of active metal component.For example, when described catalyst is fischer-tropsch synthetic catalyst, described active metal component is an iron, described auxiliary agent is one or more in the compound of the compound of IA family metal and I B-group metal, the content of the compound of IA family metal is 0-4 weight %, the content of the compound of I B-group metal is 0-6 weight %, and the content of the content of the compound of IA family metal and the compound of I B-group metal is not zero simultaneously; Perhaps, described active metal component is a cobalt, described auxiliary agent is one or more in the compound of the group VIII metal beyond the compound of group vib metal and deironing and the cobalt, the content of the compound of group vib metal is 0-30 weight %, the content of the compound of the group VIII metal beyond deironing and the cobalt is 0-5 weight %, and the content of the compound of the group VIII metal beyond the content of the compound of group vib metal and deironing and the cobalt is not zero simultaneously.The concrete example of auxiliary agent comprises one or more of compound of metals such as palladium, ruthenium and tungsten.
First catalyst carrier and described second catalyst carrier can be the catalyst carrier of routine, as one or more the mixture in aluminium oxide, silica, alumina silicate, titanium oxide, zirconia and the active carbon.
According to Preparation of catalysts method provided by the invention, this method comprises with first catalyst support powder and/or the first catalyst carrier precursor powder preparation kernel, load there are second catalyst support powder and/or the second catalyst carrier precursor powder packets of the compound of active metal component overlay on the kernel, wherein, described first catalyst support powder and/or the first catalyst carrier precursor powder are identical with the described second catalyst support powder material and/or the second catalyst carrier precursor powder.
Nuclear diameter is 1-6mm in described, is preferably 1.5-4mm, and the consumption of the described second carried catalyst powder makes that outer field thickness is 0.05-3mm, is preferably 0.1-1.5mm.The consumption of the compound of described active metal component makes, is benchmark with the gross weight of described catalyst, and in oxide, the content of described active metal component is 1-60%, is preferably 5-50%.
Described first catalyst support powder and/or the first catalyst carrier precursor powder and described second catalyst support powder and/or the second catalyst carrier precursor powder can be the powder that is used to prepare catalyst of routine, preferably use in boehmite, silica-alumina colloid, alumina silicate, silica, titanium oxide, zirconia, the active carbon one or more.Described powder particle diameter can be 0.1-150 μ m.According to the present invention, described first catalyst support powder and/or the first catalyst carrier precursor powder and second catalyst support powder and/or the second catalyst carrier precursor powder can be by commercially available, the CL powder that SB powder, Cl powder, the Chang Ling catalyst plant of producing as Sasol company (former German condea company) produced, the aluminum silicon powder SA40 of Research Institute of Petro-Chemical Engineering etc.
The method for preparing kernel with first catalyst support powder can be the method for the catalyst carrier moulding of routine, and for example, at first extrusion on banded extruder is extruded bar balling-up in nodulizer.When moulding, can separate and add conventional extrusion aid and/or adhesive in the powder and/or the first catalyst carrier precursor powder to first catalysis.The kind of described extrusion aid and/or adhesive and consumption are conventionally known to one of skill in the art, do not repeat them here.
Load is had second catalyst support powder of compound of active metal component and/or the second catalyst carrier precursor powder packets overlay on the described kernel method can for, second catalyst fines and/or the second catalyst carrier precursor powder impregnation made wet-milling in the solution of the compound that contains active metal component after, be coated on the described kernel with the method for spin.Wherein, the concentration of solution is generally 1-6mol/L.
Under the preferable case, load is had second catalyst support powder of compound of active metal component and/or the second catalyst carrier precursor powder packets overlay on the described kernel method can for, with second catalyst support powder and/or the second catalyst carrier precursor powder impregnation in the solution of the compound that contains active metal component; After the drying, can carry out roasting or not carry out roasting powder, the condition of this roasting comprises 120-600 ℃, is preferably 300-600 ℃, and roasting time is 1-48 hour, is preferably 2-12 hour; The step of above-mentioned dipping, drying, roasting or not roasting can repeat 1-3 time; Add entry and make wet-milling in the powder that obtains, the method with spin is coated on the described kernel again.Wherein, described second catalyst support powder and/or the second catalyst carrier precursor powder can be preferably unfired powder for through roasting or unfired powder.Wherein, described solution can be the aqueous solution, also can be preferably the aqueous solution for organic component solution.The compound concentrations that contains active metal component can be 1-6mol/L.Describedly add entry make in the step of wet-milling in the powder that obtains, the amount that adds entry can be calculated according to " saturated water absorption ", and those skilled in the art can determine saturated water absorption like a cork and calculate the amount that adds water.The condition of described drying comprises temperature 50-300 ℃, is preferably 100-250 ℃, and be 1-48 hour drying time, is preferably 1-12 hour.
The method of described spin is conventionally known to one of skill in the art, does not repeat them here.The rotating speed of the size of orifice plate and adjusting nodulizer is controlled the average diameter of kernel during for example, by the adjusting extrusion.By the weight ratio of second catalyst support powder and/or the second catalyst carrier precursor powder in first catalyst support powder in the kernel and/or the first catalyst carrier precursor powder and the skin, control outer field thickness then.
Under the preferable case, can also in skin, introduce the catalyst promoter component.The method of described introducing catalyst promoter can be the method for routine, for example, the catalyst that makes can be flooded in the aqueous solution of the compound that can form the catalyst promoter component.Under the preferable case, the compound of the catalyst promoter component compound with active metal component can be loaded on second catalyst support powder and/or the second catalyst carrier precursor powder, for example, with second catalyst fines and/or the second catalyst carrier precursor powder impregnation in the mixed solution of the compound of compound that contains the catalyst promoter component and active metal component.According to one embodiment of the present invention, catalyst of the present invention is used for Fischer-Tropsch when synthetic, the consumption of the compound of catalyst promoter component makes, gross weight with catalyst is a benchmark, in oxide, when described active metal component was iron, described auxiliary agent was one or more in the compound of the compound of IA family metal and I B-group metal, the content of the compound of IA family metal is 0-4 weight %, and the content of the compound of I B-group metal is 0-6 weight %; When described active metal component is cobalt, described auxiliary agent is one or more in the compound of the compound of group vib metal and group VIII metal, the content of the compound of group vib metal is 0-30 weight %, and the content of the compound of group VIII metal is 0-5 weight %.
After load being had second catalyst support powder of compound of active metal component and/or the second catalyst carrier precursor powder packets overlay on the kernel, can carry out drying and roasting to catalyst, described drying and method of roasting are conventional method, do not repeat them here.
According to the invention provides catalyst, before being used for Fischer-Tropsch synthesis, preferably in the presence of hydrogen, the active metal component of oxidation state is carried out reduction activation.The condition of described reduction activation can comprise: reduction temperature is 200 ℃ to 1000 ℃, be preferably 200 ℃ to 800 ℃, recovery time is 1-96 hour, be preferably 2-24 hour, described reduction activation can be carried out in pure hydrogen, also can in the mist of hydrogen and inert gas, carry out, as in the gaseous mixture of hydrogen and nitrogen, carrying out, Hydrogen Vapor Pressure is 0.1-4MPa, be preferably 0.1-2MPa, described inert gas is meant and does not participate in the gas of chemical reaction under condition of the present invention, as nitrogen and zero group gas.
According to Fischer-Tropsch synthesis method provided by the invention, this method comprises synthesis gas synthesizing liquid fuel under the condition that catalyst exists, wherein, and described catalyst catalyst provided by the invention.
Improvement of the present invention only is the catalyst that uses in the Fischer-Tropsch synthesis method, and synthetic raw material and reaction condition are conventionally known to one of skill in the art, do not repeat them here.
The present invention will be further described below by specific embodiment.
Embodiment 1
Used powder is boehmite (SB of Sasol company powder), at first uses the cylindrical orifice plate of 1.5mm extrusion on the twin-screw banded extruder, extrudes bar after the nodulizer balling-up, and the average diameter of measuring balling-up is 3mm, and the SB powder that is used for balling-up 125 restrains totally.It is in the cobalt nitrate solution of 4.9mol/L that the unfired boehmite of 28 grams is immersed in 13 milliliters of mass concentrations, dry back adds the ratio of 1 gram water according to per 3 gram boehmites, in load has the boehmite powder of cobalt nitrate, add water, powder is sprayed in the nodulizer.Afterwards, sample is in 140 ℃ of dryings 4 hours, and 300 ℃ of roastings 4 hours obtain catalyst A 1.Kernel average diameter 3mm, outer average thickness 0.10mm.
Embodiment 2
Used powder is boehmite (Chang Ling catalyst plant CL powder), at first uses the cylindrical orifice plate of 1.5mm extrusion on the twin-screw banded extruder, extrudes bar after the nodulizer balling-up, and the average diameter of measuring balling-up is 3mm, and the CL powder that is used for balling-up 125 restrains totally.It is in the iron nitrate solution of 4mol/L that the unfired boehmite of 56 grams is immersed in 30 milliliters mass concentration, dry back adds the ratio of 1 gram water according to per 2 gram boehmites, in load has the boehmite powder of ferric nitrate, add water, powder is sprayed in the nodulizer.Afterwards, sample is in 140 ℃ of dryings 4 hours, and 410 ℃ of roastings 4 hours obtain catalyst A 2.Kernel average diameter 3mm, outer average thickness 0.2mm.
Embodiment 3
Used powder is boehmite (Cl of Sasol company powder), at first uses the cylindrical orifice plate of 1.5mm extrusion on the twin-screw banded extruder, extrudes bar after the nodulizer balling-up, and the average diameter of measuring balling-up is 3mm, and the Cl powder that is used for balling-up 125 restrains totally.With 60 gram boehmite powder 600 ℃ of roastings after 4 hours, the mass concentration that is immersed in 23 liters is in the cobalt nitrate solution of 5mol/L, dry back adds the ratio of 0.8 gram water according to per 3 gram boehmites, adds water in load has the boehmite powder of cobalt nitrate, and powder is sprayed in the nodulizer.Afterwards, sample is in 140 ℃ of dryings 4 hours, and 410 ℃ of roastings 4 hours obtain catalyst A 3.Kernel average diameter 3mm, outer average thickness 0.2mm.
Embodiment 4
Used powder is boehmite powder (SB of Sasol company powder).At first use the cylindrical orifice plate of 1.5mm extrusion on the twin-screw banded extruder, extrude bar after the nodulizer balling-up, the average diameter of measuring balling-up is 3mm, and the SB powder that is used for balling-up 125 restrains totally.It is in the cobalt nitrate solution of 5mol/L that the unfired boehmite of 56 grams is immersed in 42 milliliters of mass concentrations, dry back adds the ratio of 0.8 gram water according to per 3 gram boehmites, in load has the boehmite powder of cobalt nitrate, add water, powder is sprayed in the nodulizer.。Afterwards, sample is in 140 ℃ of dryings 4 hours, and 350 ℃ of roastings 4 hours obtain catalyst A 4.Kernel average diameter 3mm, outer average thickness 0.21mm.
Embodiment 5
Used powder is aluminum silicon powder (SA40 is ground in the petrochemical industry scientific research), at first uses the cylindrical orifice plate of 1.5mm extrusion on the twin-screw banded extruder, extrudes bar after the nodulizer balling-up, and measuring into mean diameter of a ball is 3mm, and the SA40 powder that is used for balling-up 125 restrains totally.It is in the cobalt nitrate solution of 5.5mol/L that 70 grams are immersed in 40 milliliters mass concentration through the aluminum silicon powders of roasting, and then, drying does not directly spray to powder in the nodulizer.Afterwards, sample is in 180 ℃ of dryings 4 hours, and 410 ℃ of roastings 4 hours obtain catalyst A 5.Kernel average diameter 3mm, outer average thickness 0.23mm.
Embodiment 6
Used powder is boehmite (Cl of Sasol company powder), at first uses the cylindrical orifice plate of 1.5mm extrusion on the twin-screw banded extruder, extrudes bar after the nodulizer balling-up, and measuring into mean diameter of a ball is 3mm, and the Cl powder that is used for balling-up 125 restrains totally.Get the unfired Cl powder of 75 grams, get wherein 7.5 the gram 600 ℃ of roastings 4 hours, mix with the unfired Cl powder of 67.5 grams then, it is in the cobalt nitrate solution of 5.5mol/L that mixed powder is immersed in 35 milliliters of mass concentrations, dry back adds the ratio of 0.8 gram water according to per 3 gram boehmites, in load has the mixed powder of cobalt nitrate, add water, powder is sprayed in the nodulizer.Afterwards, sample is in 250 ℃ of dryings 4 hours, and 410 ℃ of roastings 4 hours obtain catalyst A 6.Kernel average diameter 3mm, outer average thickness 0.25mm.
Embodiment 7
Used powder is boehmite (Chang Ling catalyst plant CL powder), at first uses the cylindrical orifice plate of 1.5mm extrusion on the twin-screw banded extruder, extrudes bar after the nodulizer balling-up, and the average diameter of measuring balling-up is 3mm, and the CL powder that is used for balling-up 125 restrains totally.It is in the ammonium metatungstate solution of 3mol/L that the unfired boehmite of 75 grams is immersed in 50 milliliters mass concentration, dry back adds the ratio of 1 gram water according to per 2 gram boehmites, in load has the boehmite powder of ammonium metatungstate, add water, powder is sprayed in the nodulizer.Afterwards, sample is in 140 ℃ of dryings 4 hours, and 410 ℃ of roastings 4 hours obtain catalyst A 7.Kernel average diameter 3mm, outer average thickness 0.21mm.
Embodiment 8-13
Use 5 gram catalyst A 1-6 respectively.Under normal pressure catalyst is carried out reduction activation, other conditions are: hydrogen flowing quantity 1000Nl/g-cat/h, be warming up to 400 ℃ with the heating rate of 4 ℃/min, and keep 5h.
Use catalyst A 1-6 as the synthetic catalyst of Fischer-Tropsch respectively, wherein reaction temperature is 210 ℃, H
2/ CO ratio is 2, and pressure is 2.5MPa, and gas space-time speed (GHSV) is 2000h
-1Pass in and out the gas volume of reactor respectively with mass flowmenter and wet-test meter metering.On the multichannel gas chromatograph, unstripped gas and tail gas composition are carried out on-line analysis.And according to C in following formula calculating CO conversion ratio and the product
5More than (contain C
5) hydro carbons, CH
4And CO
2Selectivity.
X
COExpression CO conversion ratio, S
C5+, S
CH4, S
CO2Represent C in the product respectively
5More than (contain C
5) hydro carbons, CH
4, CO
2Selectivity.Following expression is seen in concrete definition:
CO transforms
C
5 +Hydro carbons (contains C
5) selection
CH
4Selection
CO
2Selection
Wherein, V
1, V
2Be illustrated respectively under the status of criterion, enter the volume and the exhaust gas volumes that flows out reaction system of the unstripped gas of reaction system in certain time period; c
1, c
2The content of representing tie substance in unstripped gas and the tail gas respectively.X
H2And X
CORepresent H respectively
2Conversion ratio with CO.n
ConFor participate in the molal quantity of the CO of reaction, n in certain time period by reaction bed
CO2For generating CO
2The molal quantity of CO, n
CH4For generating CH
4The molal quantity of CO, n
C4-For generating CH
4, C
2Hydrocarbon, C
3Hydrocarbon, C
4The molal quantity of the CO of hydrocarbon.The result is as shown in table 1.
Comparative Examples 1
Used powder is boehmite powder (SB of Sasol company powder).At first use the cylindrical orifice plate of 1.5mm extrusion on the twin-screw banded extruder, extrude bar after the nodulizer balling-up, measuring into mean diameter of a ball is 3mm.Afterwards, sample is in 140 ℃ of dryings 4 hours, 600 ℃ of roastings 4 hours.Weighing 10 gram average diameters are the ball-aluminium oxide particle of 3mm, and measuring its water absorption rate is 0.8 milliliter/gram.Weighing 5 gram cobalt nitrates are dissolved in water into 8 milliliters of cobalt nitrate solutions, and with this carrier of described solution impregnation.Afterwards, in 140 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained catalyst D1, and the cobalt oxide content that adopts x-ray fluorescence method to measure in the catalyst is 12%.Through perusal, active metal component is evenly distributed on catalyst D1 top layer and catalyst inside (broken back is observed).
Comparative Examples 2
According to the mode identical with embodiment 8-13, catalyst D1 is carried out reduction activation, and carry out Fischer-Tropsch synthesis according to the mode identical with embodiment 8-13, calculate C in CO conversion ratio and the product
5More than (contain C
5) hydro carbons, CH
4And CO
2Selectivity, the result is as shown in table 1.
Table 1
| Embodiment | Catalyst | ??X CO，％ | ??S C5+，％ | ??S CH4，％ | ??S CO2，％ |
| Comparative Examples 2 | ??D1 | ??50.12 | ??70.98 | ??13.78 | ??1.50 |
| ??4 | ??A4 | ??53.01 | ??75.40 | ??10.0 | ??0.50 |
| Embodiment | Catalyst | ??X CO，％ | ??S C5+，％ | ??S CH4，％ | ??S CO2，％ |
| ??6 | ??A6 | ??54.32 | ??76.32 | ??9.4 | ??0.30 |
As can be seen from Table 1, Preparation of catalysts method involved in the present invention compare with the traditional catalyst preparation method not only have simple to operation, repeatability is strong, kernel combines advantages such as firm with skin; And, the Fischer-Tropsch synthesizing activity and the C of gained catalyst
5+Hydrocarbon selective is higher, and the selectivity of carbon dioxide and methane is lower.
Claims (11)
1. catalyst, it is characterized in that, this catalyst comprises kernel and skin, described kernel is first catalyst carrier, described skin is coated on the described kernel, described skin contains second catalyst carrier and the active metal component that loads on described second catalyst carrier, and described first catalyst carrier is identical with the material of described second catalyst carrier.
2. catalyst according to claim 1, wherein, the diameter of described kernel is 1-6mm, described outer field thickness is 0.05-3mm.
3. catalyst according to claim 1, wherein, this catalyst is a fischer-tropsch synthetic catalyst, and described active metal component is iron and/or cobalt, is benchmark in oxide and with the gross weight of catalyst, and the content of described active metal component is 1-60 weight %.
4. catalyst according to claim 3, wherein, described skin also contains auxiliary agent, described active metal component is an iron, described auxiliary agent is one or more in the compound of the compound of IA family metal and I B-group metal, the content of the compound of IA family metal is 0-4 weight %, and the content of the compound of I B-group metal is 0-6 weight %, and the content of the content of the compound of IA family metal and the compound of I B-group metal is not zero simultaneously; Perhaps, described active metal component is a cobalt, described auxiliary agent is one or more in the compound of the group VIII metal beyond the compound of group vib metal and deironing and the cobalt, the content of the compound of group vib metal is 0-30 weight %, the content of the compound of the group VIII metal beyond deironing and the cobalt is 0-5 weight %, and the content of the compound of the group VIII metal beyond the content of the compound of group vib metal and deironing and the cobalt is not zero simultaneously.
5. catalyst according to claim 1, wherein, first catalyst carrier and described second catalyst carrier are one or more the mixture in aluminium oxide, silica, alumina silicate, titanium oxide, zirconia and the active carbon.
6. Preparation of catalysts method, it is characterized in that, this method comprises with first catalyst support powder and/or the first catalyst carrier precursor powder preparation kernel, load there are second catalyst support powder and/or the second catalyst carrier precursor powder packets of the compound of active metal component overlay on the kernel, carry out drying and roasting then, wherein, described first catalyst support powder and/or the first catalyst carrier precursor powder are identical with the material of described second catalyst support powder and/or the second catalyst carrier precursor powder.
7. method according to claim 6, wherein, described first catalyst support powder and described second catalyst support powder are one or more the mixture in aluminium oxide, alumina silicate, silica, titanium oxide, zirconia, the active carbon.
8. method according to claim 6, wherein, load there are second catalyst support powder of compound of active metal component and/or the method that the second catalyst carrier precursor powder packets overlays on the described kernel are, second catalyst fines and/or the second catalyst carrier precursor powder impregnation made wet-milling in the solution of the compound that contains active metal component after, be coated on the described kernel with the method for spin.
9. method according to claim 6, wherein, load is had second catalyst support powder of compound of active metal component and/or the method that the second catalyst carrier precursor powder packets overlays on the described kernel are, with second catalyst support powder and/or the second catalyst carrier precursor powder impregnation in the solution of the compound that contains active metal component; After the drying, powder is carried out roasting or do not carry out roasting; Add entry and make wet-milling in the powder that obtains, the method with spin is coated on the described kernel again.
10. according to claim 6,8 or 9 described methods, wherein, nuclear diameter is 1-6mm in described, the consumption of the described second carried catalyst powder makes that outer field thickness is 0.05-3mm, the amount of the compound of described active metal component makes, gross weight with described catalyst is a benchmark, and in oxide, the content of described active metal component is 1-60%.
11. a Fischer-Tropsch synthesis method, this method comprise synthesis gas is synthesized liquid fuel under the condition that catalyst exists, it is characterized in that any described catalyst among the described catalyst claim 1-5.
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| CN105312092A (en) * | 2014-06-20 | 2016-02-10 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and Fischer-Tropsch synthesis method |
| CN105582931A (en) * | 2014-10-22 | 2016-05-18 | 中国科学院上海高等研究院 | A cobalt-based Fischer-Tropsch synthesis catalyst supported by a mixed oxide carrier and a preparing method thereof |
| CN106582890A (en) * | 2015-10-15 | 2017-04-26 | 神华集团有限责任公司 | Carrier of Fischer-Tropsch synthesis catalyst, preparation method thereof, Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN110773176A (en) * | 2019-11-08 | 2020-02-11 | 中国石油化工股份有限公司 | Catalyst for reducing sulfur content of petroleum coke, preparation method and application thereof |
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|---|---|---|---|---|
| US6649802B1 (en) * | 2000-09-21 | 2003-11-18 | Uop Llc | Layered oligomerization catalyst system |
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