CN105833869B - A kind of shell profile catalyst and preparation method thereof and a kind of Fischer-Tropsch synthesis method - Google Patents
A kind of shell profile catalyst and preparation method thereof and a kind of Fischer-Tropsch synthesis method Download PDFInfo
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- CN105833869B CN105833869B CN201510015265.3A CN201510015265A CN105833869B CN 105833869 B CN105833869 B CN 105833869B CN 201510015265 A CN201510015265 A CN 201510015265A CN 105833869 B CN105833869 B CN 105833869B
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Abstract
The invention discloses a kind of shell profile catalyst and preparation method thereof, this method includes：(1) porous carrier is placed in hollow container, by the solution spraying containing catalytic active component in porous carrier surface, total quantity for spray of the solution is less than the total pore volume of porous carrier, in spraying process, hollow container is vacuumized, and the bleeding point for vacuumizing is arranged in the layer formed by porous carrier；(2) porous carrier for being loaded with solution that step (1) obtains is dried and is optionally calcined.Present invention also offers a kind of Fischer-Tropsch synthesis method, it is included under the conditions of Fischer-Tropsch synthesis, synthesis gas is contacted with according to the shell profile catalyst to Fischer-Tropsch synthesis with catalytic action of the present invention.The method of the present invention can repeat stably to produce shell profile catalyst.When the shell profile catalyst of the present invention is used for Fischer-Tropsch synthesis, higher C can be obtained5+Hydrocarbon selective and relatively low methane selectively.
Description
Technical field
The present invention relates to a kind of shell profile catalyst and preparation method thereof, the invention further relates to a kind of F- T synthesis side
Method.
Background technology
In catalyst duct depths, the product molecule of reaction generation such as can not in time spread out and further react,
On the one hand the selectivity of catalyst is influenceed, on the other hand will influence the life-span of catalyst.Especially internally it is diffused as rate-determining steps
Reaction, it is desirable to reaction occur beneficial to reactant and product diffusion position, it is generally desirable to occur in catalyst coating.Separately
Outside, in the cost of catalyst, the large percentage shared by the cost of active component, if by utilization rate it is not high be distributed in duct
The component of depths is moved closer in the region of catalyst coating, can undoubtedly significantly improve the activity and selectivity of catalyst.
This kind of gas-solid-liquid multiphase reaction system, catalysis are synthesized for carrying out Fischer-Tropsch (FT) such as in fixed bed reactors
The particle size of agent is generally several mm, and therefore, influence of the diffusion control to catalytic activity is difficult to avoid that.It should be noted that：By
The heavy paraffinic waxes that FT synthesizes to obtain generally are attached to catalyst surface in the form of liquid, vapour colloidal sol or slurry, to reactant H2With
Diffusions of the CO inside catalyst granules has an impact.In the interior diffusion process of reactant, H2Diffusion velocity it is faster than CO, CO
H is significantly stronger than in the diffusion restriction effect of catalyst particles intragranular2.Because the particle diameter of particle is different, CO concentration inside particle result in
The difference of gradient, it have impact on the combination of CO and metal active centres position so that the H/C adsorbed on activated centre is than increase, carbon
Chain growth probability reduces, and reduces C5+Selectivity.The prior art indicate that the catalyst being evenly distributed relative to active component
For, the catalyst of active component non-uniform Distribution, such as shell type catalyst, because diffusion limitation is small, can significantly increase as
C in this kind of reaction of F- T synthesis5+Selectivity, reduces the selectivity of methane, is particularly suited for this kind of reaction of F- T synthesis.
US5545674 discloses a kind of method for preparing shell type catalyst, and this method spreads out carrier on a wire mesh
Open, woven wire is heated to more than 140 DEG C in heating furnace, then taken out from stove.By the solution spraying of the component containing load
In on the heat carrier on woven wire, the solution of the component containing load is evaporated in the carrier surface of heat, then by with catalyst
Woven wire is put back in heating furnace and reheated.It is so repeated multiple times, until loading enough load components.
US7087191 discloses a kind of method for preparing shell profile catalyst, and this method is by the powder containing active component
End and the powder containing refractory metal oxide make pasty state or muddy with diluent, and be then sprayed at surface becomes by processing
On coarse inert solid particle, then dry, be calcined.This method can ensure that catalyst activity component has not entered carrier
The inside of the solid particle of effect, but active component, with powdered presence, the active component inside powder particle can not be sent out completely
The effect of waving, and powder sticks together by physical action with inert solid particle surface, and this physical bonds power impregnates than solution
The adhesion of chemical bond in catalyst prepared by method between active component and carrier surface wants weak many.Therefore, with by activearm
Shell profile catalyst prepared by the solution divided will be compared, and this method prepared by powdered active ingredient reduces activearm
The utilization ratio divided, in addition, powdered active ingredient is relatively easy to from inert solid particle surface under the washing away of air-flow in
Come off.
US5545674 discloses a kind of preparation method of shell profile catalyst, and this method is by using with centre
Cobalt especially cobalt nitrate solution is impregnated on bead-type substrate by the dry or immersion of combustion step or spray method repeatedly.These sides
Method is cumbersome and time-consuming, and uses multiple dipping method, and some metals can exceed expected outer layer and penetrate into carrier.
CN101318133A discloses a kind of shell type catalyst for being used to prepare naphtha and diesel oil, and the catalyst is with work
Property charcoal be carrier, take the mode of spraying that solution is sprayed onto on the carrier of rolling, then by catalyst in inert gas dry
Or roasting.But the shell rate of the catalyst of this method preparation is not high.
US4599481 discloses a kind of method by carbon monoxide and hydrogen catalysis reaction production hydrocarbon, and this method is included in
125-350 DEG C, carbon monoxide and hydrogen are contacted with catalyst under the conditions of 5-100 bars of pressure (bar), the catalyst contains carrier
With the cobalt of load on this carrier, distribution of the cobalt on carrier meets (∑ Vp/ ∑ Vc) ＜ 0.85, wherein, ∑ Vc is represented
The cumulative volume of catalyst granules, Vp are shell volume in catalyst.When the content of cobalt is about 90% in shell, catalyst has
High activity and selectivity.The preparation method of the catalyst is first to use water treatment carrier, impregnates cobalt nitrate solution, Ran Hougan afterwards
Dry and roasting.Requirement of this preparation method to the time is very strict and cumbersome, it is not easy to large-scale production.
CN102451722A discloses a kind of preparation method of eggshell hydrogenation catalyst.This method, which uses, contains thickener
With the active metal solution impregnating carrier of active metal dispersant, wherein impregnated under conditions of air bubbling is passed through,
Again through drying and being calcined, eggshell hydrogenation catalyst is obtained.This method can effectively adjust eggshell hydrogenation catalyst surface-active,
The thickness of metal shell layer and the decentralization of active metal, active metal component that can be on stable hydrogenation catalyst reduce activity
The loss of metal component, reduce Catalyst Production cost.But requirement of this preparation method to the time is very strict, and grasp
Make cumbersome, it is not easy to large-scale production.
It can be seen that, it is still desirable to continue the method that exploration prepares shell profile catalyst.
The content of the invention
It is an object of the invention to provide a kind of shell profile catalyst and preparation method thereof, is urged by prepared by this method
Agent shell rate is high.
According to the first aspect of the invention, should the invention provides a kind of preparation method of shell profile catalyst
Method comprises the following steps：
(1) porous carrier is placed in hollow container, by the solution spraying containing catalytic active component in the porous load
Body surface face, total quantity for spray of the solution is less than the total pore volume of the porous carrier, in spraying process, to the hollow appearance
Device is vacuumized, and the bleeding point for vacuumizing is arranged in the layer formed by porous carrier；
(2) porous carrier for being loaded with solution that step (1) obtains is dried successively and is optionally calcined.
According to the second aspect of the invention, the invention provides shell profile prepared by a kind of method by the present invention
Catalyst.
According to the third aspect of the present invention, the invention provides a kind of Fischer-Tropsch synthesis method, this method to be included in Fischer-Tropsch
Under synthetic reaction condition, synthesis gas is contacted with catalyst, wherein, the catalyst is pair prepared using the method for the present invention
Fischer-Tropsch synthesis has the shell profile catalyst of catalytic action.
According to the preparation method of the shell profile catalyst of the present invention, the shell rate of the catalyst of preparation is high, can repeat
Stably produce shell profile catalyst.The reason for shell profile catalyst can stably be produced using the method for the present invention
It may is that：When by the solution spraying containing catalytic active component to porous carrier surface, porous carrier surface is attached to
Solution is during the hole of porous carrier is impregnated into, due to exotherm so that and partial solvent volatilizees to form steam, this
The presence of a little steams can cause core migration of the catalytic active component to porous carrier, destroy the shell structurre of formation；According to this
The method of invention is vacuumized during spraying, and the landfill of the bleeding point for vacuumizing is formed by porous carrier
Layer in (that is, the bleeding point for vacuumizing is arranged in the layer formed by porous carrier), by disperse between porous carrier
Solvent vapour extract out in time and fully, catalytic active component can be effectively reduced to the trend of the core migration of porous carrier,
So as to improve the shell rate of the catalyst of preparation.
According to the preparation method of the shell profile catalyst of the present invention, operating process is simple and easy to control, real suitable for scale
Apply.
The shell profile catalyst prepared by the method for the present invention is used as to the catalyst of Fischer-Tropsch synthesis, can be obtained
Higher C5+Hydrocarbon selective and relatively low methane selectively.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is the structural representation for preparing the device of the shell profile catalyst of the present invention.
Fig. 2 is the structural representation for the device that comparative example 4,6 and 8 disclosed by the invention uses.
Description of reference numerals
11：Porous carrier storage tank 21：Solution reservoir
22：Pump 31：Hollow container
32：Pedestal 33：Spray boom
34：Vacuum lines 35：Rotary shaft
36：Motor 37：Travelling gear
38：Distributing device 39 and 310：The vertex of a cone
41：Dry zone
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In the present invention, " axial direction " and " radial direction " is for hollow container, i.e., along the rotating shaft side of hollow container
The direction extended to (i.e. pivot) is axial direction, and perpendicular to the axial direction for radial direction, it is necessary to which explanation is
These nouns of locality are served only for the explanation present invention, are not intended to limit the invention.In the present invention, " optional " represent to include
With the technical characteristic " optionally " to connect, the technical characteristic with " optionally " connecting can not also be included.Occur in the present invention
Number range include form the number range two end values.
According to the first aspect of the invention, should the invention provides a kind of preparation method of shell profile catalyst
Method includes step (1)：Porous carrier is placed in hollow container, by the solution spraying containing catalytic active component described more
Hole carrier surface, in spraying process, the hollow container is vacuumized.
The method according to the invention, total quantity for spray of the solution containing catalytic active component are less than the total of the porous carrier
Pore volume.From the angle of the shell rate of the further catalyst for improving and preparing, the solution containing catalytic active component it is total
Quantity for spray is VL, the total pore volume of the porous carrier is VC, VL/VC=0.01-0.99；Preferably, VL/VC=0.1-0.8；More
Preferably, VL/VC=0.2-0.7；It is further preferred that VL/VC=0.3-0.6, such as VL/VC=0.4-0.5.In the present invention, VC
Quality equal to porous carrier (in gram) is multiplied by the water absorption rate of porous carrier (density of water is 1g/cm3), water absorption rate is unit
The water absorption of the carrier of weight.Specifically, following methods measure water absorption rate can be used：Can (weight be calculated as w by carrier1, with
Gram meter) with water using the ratio of carrier (by weight) and water (by volume) as 1：3 dippings 2 hours, after filtering, solid is dripped
Dry, then weighing the weight of the solid drained, (weight is calculated as w2, in gram), water absorption rate is calculated by below equation：
Method according to the invention it is possible to the solution spraying containing catalytic active component is existed using common various methods
Porous carrier surface.Preferably, the solution containing catalytic active component is sprayed on porous carrier table in the form of atomized drop
Face.From further improving the shell rate of catalyst and the angle of catalytic efficiency that finally prepare, the atomized drop
Size is preferably in the range of 1-600 microns, more preferably in the range of 20-400 microns, further preferably in 50-300 microns
In the range of, still more preferably in the range of 60-200 microns, such as in the range of 70-150 microns.In the present invention, mist
The size for changing drop is measured using Malvern Particle Size Analyzer, is volume average particle size.In specific operation process, Ke Yitong
Injection pressure is overregulated to adjust the size of the atomized drop of formation.
The method according to the invention, contacted from further solution of the raising containing catalytic active component with porous carrier equal
The angle of even property is set out, and during spraying, porous carrier is in the state of motion.The form of the motion can be
Combination more than one or both of vibrating, roll, stir and slide.In actual mechanical process, hollow appearance can be rotated
Device, so as to drive the porous carrier in hollow container to move.
The method according to the invention, during spraying, hollow container is vacuumized.With in spraying process not
Vacuumize comparing, by vacuumizing the shell rate for the catalyst that can significantly improve preparation, so as to realize that stabilization is repeatedly made
Standby shell profile catalyst.From the angle of the shell rate of the further catalyst for improving and preparing, the bar vacuumized
Part causes the relative degree of vacuum in hollow container in the range of -10kPa to -100kPa.It is highly preferred that the bar vacuumized
Part causes the relative degree of vacuum in hollow container in the range of -30kPa to -95kPa.Further preferably, it is described to vacuumize
Condition causes the relative degree of vacuum in hollow container in the range of -40kPa to -80kPa, the model such as in -45kPa to -75kPa
In enclosing.In the present invention, the absolute pressure (in terms of kPa) -101.3 in relative degree of vacuum=hollow container.The relative degree of vacuum
It can be determined by pressure vacuum gauge.
Method in accordance with the invention it is preferred that the condition vacuumized causes in the hollow container by containing catalysis
Partial pressure is in the range of 0-30kPa caused by solvent in the solution of active component.The condition vacuumized cause it is described in
The partial pressure as caused by the solvent in the solution containing catalytic active component is preferably not higher than 20kPa in empty container, more preferably
Not higher than 10kPa.On the premise of guaranteeing to obtain higher shell rate, go out from the further angle for reducing operating cost
Hair, the condition vacuumized is controlled as caused by the solvent in the solution containing catalytic active component to divide in the hollow container
Press as not less than 0.1kPa.The partial pressure can be determined by vacuum meter.
The method according to the invention, typically before being sprayed, the hollow container with porous carrier is carried out in advance
Vacuumize, it is preferable that within the scope of the relative degree of vacuum in the hollow container with porous carrier is in described previously, and will
The relative degree of vacuum during spraying, is taken out true as base vacuum degree according to the relative degree of vacuum adjustment in hollow container
Empty condition so that the partial pressure as caused by the solvent in the solution containing catalytic active component be in previously described scope it
It is interior.In spraying process, the difference between relative degree of vacuum and benchmark relative degree of vacuum in hollow container is used as by containing catalysis
Partial pressure caused by solvent in the solution of active component.
The method according to the invention, the bleeding point for vacuumizing are arranged in the layer formed by porous carrier, that is, are used for
The bleeding point vacuumized is landfilled in the solid particle layer formed by porous carrier.Bleeding point for vacuumizing can direction
The inwall (that is, consistent with the spraying direction of the solution containing catalytic active component) of porous carrier is carried, can also be backwards to carrying
The inwall (that is, relative with the spraying direction of the solution containing catalytic active component) of porous carrier.Preferably, the bleeding point court
To the inwall of carrying porous carrier, the shell rate further improved can be so obtained, while can also further be reduced containing catalysis
The loss amount of the solution of active component.
, can be by arranging vacuum pipeline in hollow container in actual mechanical process, and opened up on vacuum pipeline
Bleeding point, vacuumized so as to realize in spraying process.
The quantity of the bleeding point can be one or more as the case may be, can be between waiting between multiple bleeding points
Every, or unequal interval, or at equal intervals or unequal interval combination (that is, to set at equal intervals between the bleeding point of part
Put, set between remainder bleeding point for unequal interval).The form of bleeding point can be conventional selection.Can by with
In setting opening on the pipeline vacuumized, so as to form the bleeding point.The bore of the opening is preferably no greater than porous carrier
Particle diameter.Preferably, screen pack is installed on bleeding point, to avoid solid particle from entering in vacuum lines.
The pipeline edge direction hermetically passing hollow appearance parallel with the rotor shaft direction of hollow container vacuumized can be used in
Device.For being preferably to be rotatably connected between the pipeline and hollow container that vacuumize, so when hollow container rotates, for taking out
The pipeline of vacuum will not rotate with hollow container.The part being located at for the pipeline vacuumized in hollow container can be according to hollow
The interior shape of container is bent, can fill in the layer that porous carrier is formed.For the number of the pipeline vacuumized
Amount can be one or more than two.When the quantity of the pipeline for vacuumizing is one, the pipeline for vacuumizing is located at
Part in hollow container can be with serpentine-like bending, to expand the overlay area of bleeding point, so as to be formed in porous carrier
Caused steam is timely in each band of position of layer and fully aspirates away.It is more in the quantity of the pipeline for vacuumizing
During root, the more pipelines for being used to vacuumize can be to be arranged along the mode parallel with the rotor shaft direction of hollow container, be taken out with expanding
The overlay area of gas port；Can also be to intersect between more vacuum lines, as long as bleeding point can be made to be located at by porous load
The multiple bands of position for the layer that body is formed.Can be more along one or more layers vacuum lines that are radially arranged of hollow container
Can be at equal intervals between layer vacuum lines, or unequal interval, every layer of vacuum lines can have one or more
Root vacuum lines.
The method according to the invention, in spraying process, it is not particularly limited for the temperature in hollow container, Ke Yi
Carried out under ordinary temperature.Usually, can be by scope of the temperature control in hollow container at 0-70 DEG C in spraying process
It is interior, preferably by the temperature control in hollow container in the range of 20-50 DEG C.
The method according to the invention, the duration of the spraying can be selected according to the property of porous carrier.One
As, the duration of the spraying can be -200 minutes 5 minutes.The duration of the spraying be preferably 10 minutes with
On, more preferably more than 15 minutes.From the further angle for improving shell rate, the duration of the spraying is preferably
Less than 100 minutes, more preferably less than 60 minutes, more preferably less than 30 minutes.In actual mechanical process, Ke Yitong
Residence time of the control porous carrier in hollow container is spent to adjust the duration of spraying.
The method according to the invention, the porous carrier can be the common porosity for being adapted as catalyst carrier
Matter.Specifically, the porous carrier can be more than one or both of heat-resistant inorganic oxide, alumina silicate and activated carbon.
The heat-resistant inorganic oxide refers under oxygen or oxygen-containing atmosphere, decomposition temperature not less than 300 DEG C (such as：Decomposition temperature is
300-1000 DEG C) inorganic oxygen-containing compound.The instantiation of the porous carrier can include but is not limited to：Aluminum oxide, oxygen
One or both of SiClx, titanium oxide, magnesia, zirconium oxide, thorium oxide, silica-alumina, alumina silicate and activated carbon with
On.Preferably, the porous carrier is silica, aluminum oxide, silica-alumina, alumina silicate, titanium oxide, zirconium oxide and work
It is more than one or both of property charcoal.It is highly preferred that the porous carrier is aluminum oxide.
The present invention is not particularly limited to the shape of the carrier, can be conventional shape, for example, can for it is spherical,
Piece shape, bar shaped etc., preferably bar shaped.The method according to the invention, the average grain diameter of the porous carrier can be according to catalyst
Specific species selected, preferably in the range of 0.5-6mm, more preferably in the range of 1-4mm.
The solvent of the solution containing catalytic active component can be conventional selection, such as can be water, alcohol, ether, aldehyde
With mixture more than one or both of ketone.Preferably, the solvent is water and/or alcohol, in water, methanol and ethanol
One or more kinds of mixtures.From environmental protection and the angle of cost is reduced, the solvent is more preferably water.
The method according to the invention, the species of the catalytic active component can be entered according to the use occasion of expected catalyst
Row selection, is defined by that can obtain the catalyst with predetermined catalytic performance, such as group VIII metallic element and/or vib
Metallic element.In a kind of preferred embodiment of the present invention, the species of the catalytic active component causes by the present invention's
Shell profile catalyst prepared by method has catalytic action to Fischer-Tropsch synthesis.In the preferred embodiment, institute
It can be the component to Fischer-Tropsch synthesis with catalytic action to state catalytic active component, it is preferable that the catalytic active component
Selected from group VIII metallic element, it is specifically as follows more than one or both of iron, cobalt and ruthenium.
Method according to the invention it is possible to by the way that the compound containing catalytic active component is dissolved in a solvent, so as to carry
For the solution containing catalytic active component.The species of compound containing catalytic active component can be entered according to the species of solvent
Row selection, is defined by that can be dissolved in the solvent.It is described containing catalytic active component for example, when the solvent is water
Compound can be water soluble compound.In one embodiment of the invention, the catalytic active component is group VIII
During metallic element, the compound containing catalytic active component can be the water-soluble non-gold using group VIII metal as cation
Belong to oxygen-containing inorganic acid salt, using group VIII metal as the water-soluble organic acid salt of cation and using group VIII metal as cation
One or both of water-soluble halide more than.Preferably, the compound containing catalytic active component is with VIII
Race's metal is the nitrate of cation, using group VIII metal as the acetate of cation, using group VIII metal as cation
Sulfate, using group VIII metal as the subcarbonate of cation and using group VIII metal as in the chloride of cation
One or more.Specifically, the compound containing catalytic active component can be selected from, but not limited to, nickel nitrate, acetic acid
Nickel, nickel sulfate, basic nickel carbonate, cobalt nitrate, cobalt acetate, cobaltous sulfate, basic cobaltous carbonate, cobalt chloride, nickel chloride, ruthenic chloride and nitre
It is more than one or both of sour ruthenium.
The concentration of catalytic active component can live according to being catalyzed in catalyst in the solution containing catalytic active component
The anticipated load amount of property component is selected, and is not particularly limited.
The method according to the invention, the load capacity of the solution containing catalytic active component on porous support is with can
The catalyst for ensuring finally to prepare is loaded with enough catalytic active components and is defined.Usually, the catalytic active component is in institute
The load capacity on porous carrier is stated so that on the basis of the total amount of the catalyst finally prepared, the catalytic activity group in terms of oxide
The content divided is 0.5-60 weight %, preferably 1-50 weight %, such as 10-30 weight %.
The method according to the invention, the solution containing catalytic active component can also contain at least one catalyst aid
Component and/or at least one surfactant.
The catalyst aid component for example can be P elements and/or fluorine element.It is anti-to F- T synthesis in the catalyst
When should have catalytic action, the catalyst aid component can be selected from Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Ru, Zr,
One or both of Ti, Re, Hf, Ce, Mn, Fe, V and noble metal (such as more than one or both of Pt, Pd, Rh and Ir) with
On.
The catalyst aid component catalyst of content finally to prepare in the solution containing catalytic active component
On the basis of expected catalyst aid constituent content.Usually, on the basis of the total amount of the catalyst finally prepared, with oxidation
The content of the component containing catalyst aid of thing meter can be 0.1-30 weight %, preferably 0.5-15 weight %, be more preferably
1-5 weight %.
When the catalyst has catalytic action to Fischer-Tropsch synthesis, the surfactant can be ionic table
It is more than one or both of face activating agent and nonionic surface active agent.The ionic surfactant includes anion
Type surfactant, cationic surface active agent and amphoteric ionic surfactant.The anionic surfactant
Instantiation can include but is not limited to carboxylic acid type (such as soap, potassium oleate) surfactant, sulfonate type (such as alkyl
Benzene sulfonic acid sodium salt etc.) surfactant, sulfuric ester salt form (such as lauryl sodium sulfate) surfactant and phosphate salt form are (such as
C16H33OPO3Na2Deng) surfactant.The instantiation of the cationic surfactant can include but is not limited to：Ammonium salt
Type surfactant, quaternary (such as hexadecyltrimethylammonium chloride) surfactant.The amphoteric ion type surface
The instantiation of activating agent can include but is not limited to betaine type amphoteric surfactant and amino acid type surfactant.It is described non-
The instantiation of ionic surfactant can include but is not limited to polyethylene glycol type surfactant (such as fatty alcohol polyoxy second
Alkene ether, polyoxyethylene alkylphenol ether, aliphatic acid polyethenoxy ether, polyoxyethylene fatty amine and polyoxyethanyl alkylamide, its
In, the repeating segment number n of ethylene oxide repeating units can be conventional selection, usually, n=l-10) and polyol type surface
Activating agent (derivative of the derivative of such as sucrose, the derivative of D-sorbite and glyceryl alcohol).The preferably surface of the invention
Activating agent is more than one or both of nonionic surface active agent.
Concentration of the surfactant in the solution containing catalytic active component is preferably 0.01-10 weight %.
The method according to the invention, after the completion of spraying, the obtained porous carrier for being loaded with solution is dried.It is described
Dry temperature is defined by that can remove the solvent in the solution of load on porous support.Usually, the drying can be
Carry out at a temperature of 50-300 DEG C, carried out preferably at a temperature of 60-250 DEG C.The drying can be carried out at ambient pressure, also may be used
To carry out at reduced pressure.
In a kind of preferred embodiment of the present invention, the drying is under conditions of normal pressure (that is, 1 standard atmospheric pressure)
Carry out, the temperature of the drying is preferably in the range of 130-230 DEG C, more preferably in 140-160 DEG C of scope.The present invention's
In another preferred embodiment, the drying is -0.5kPa to -60kPa, is preferably -5kPa in pressure (in terms of gauge pressure)
Carried out under conditions of to -45kPa, the temperature of the drying is preferably in the range of 100-220 DEG C, more preferably at 120-160 DEG C
In the range of.It is dried under above two preferred embodiment, the catalyst of preparation has higher shell rate, and
In the shell profile catalyst of preparation, shell thickness is thinner (that is, along the radial section of catalyst, catalytic active component enrichment
On the radial section of more outer layer), its reason may is that：In the volume of the solution containing catalytic active component for spraying
Not higher than porous carrier total pore volume when, the core of porous carrier act as the role of adsorption desiccant, adsorb in porous load
Solvent in the outer layer solution of body is dissolved in a solvent due to the trend of the oriented porous carrier core migration of capillary condensation effect
Compound containing catalytic active component is also therewith to core migration, so as to influence shell rate；In the preferable embodiment party of above two
In formula, the condition of desolvation can be effectively reduced solvent to the migration trend of porous carrier core, higher so as to obtain
Shell efficiency and thinner shell thickness.
The method according to the invention, the duration of the drying can be selected according to dry temperature and pressure,
By can the solvent that loaded in solution on porous support is whole or substantially all abjection be defined.Usually, the drying
Duration can be 1-48 hours, preferably 1.5-24 hours, more preferably 2-10 hours, such as 2-5 hours.
The method according to the invention, from the angle of the shell rate of the further catalyst for improving and preparing, the spraying
Time interval between the drying is preferably no more than 30 minutes, more preferably less than 10 minutes.
The method according to the invention, catalyst can be directly used as through dry porous carrier, after can also being calcined
As catalyst.The present invention is not particularly limited for the condition of roasting, can be conventional selection.Usually, the roasting can
To be carried out at a temperature of 300-600 DEG C, preferably at a temperature of 400-500 DEG C.The duration of the roasting can be 1-
48 hours, preferably 2-12 hours, more preferably 2-4 hours.
Method according to the invention it is possible to which interval is carried out, can also be carried out continuously.Process of this invention is particularly practical for continuous
Carry out, so the shell profile catalyst with higher shell rate can be prepared with higher production efficiency.
In a kind of preferred embodiment of the present invention, the method according to the invention is implemented in a kind of preparation system,
So as to continuously prepare shell profile catalyst.The preparation system is described in detail below in conjunction with Fig. 1.
The preparation system includes porous carrier feed unit, solution feed unit, spray unit and drying unit, porous
Carrier feed unit is used to store porous carrier and provides porous carrier to spray unit, and solution feed unit contains for storage
The solution of catalytic active component simultaneously provides the solution containing catalytic active component to spray unit, and spray unit, which is used to contain, urges
Change the solution spraying of active component in porous carrier surface, drying unit is used for being loaded with of being exported by spray unit containing urging
The porous carrier for changing the solution of active component is dried.
As shown in figure 1, porous carrier feed unit includes porous carrier storage tank 11 and is arranged on porous carrier storage tank 11
On pipeline, the pipeline be used for porous carrier storage tank 11 connect with spray unit, so as to by porous carrier be sent into spray list
In member.Valve can be set on the pipeline for connected porous carrier storage tank 11 and spray unit, so as to the company of control piper
On and off is opened.
As shown in figure 1, solution feed unit includes solution reservoir 21 and for connecting solution reservoir 21 and spray unit
Pipeline.According to specific needs, pump 22 can be set on pipeline to improve the efficiency of conveying, while improve feeding spray unit
The solution containing catalytic active component pressure, for injection necessary pressure is provided.Choke valve can also be set on pipeline,
To adjust flow.
As shown in figure 1, spray unit includes rotatable hollow container 31 and the pedestal for supporting hollow container 31
32, hollow container 31 connects with porous carrier feed unit and solution feed unit respectively, will contain catalytic active component
Solution spraying is in porous carrier surface.
Hollow container 31 can have various profiles, such as the biconial of nearly elliposoidal, single taper or shared bottom surface.One
In kind preferred embodiment, as shown in figure 1, hollow container 31 is the biconial for sharing bottom surface, now, diconical two cones
Top 39 and 310 can be set respectively can close opening, and in charging, at least one opening connects with porous carrier feed unit,
Porous carrier is set to enter in hollow container 31；In discharging, at least one opening connects with drying unit, is sprayed-on surface
The porous carrier of solution containing catalytic active component, which enters in drying unit, to be dried.
As shown in figure 1, being disposed with spray boom 33 in hollow container 31, spray boom 33 connects with solution feed unit, on spray boom 33
At equal intervals or unequal interval sets multiple atomizers, for by the solution spraying containing catalytic active component in porous carrier table
Face.The bore of the atomizer can be selected according to the size of expected atomized drop, usually, the atomizer
Size the particle diameter of atomized drop in the range of 1-600 microns, preferably in the range of 20-400 microns, is more preferably existed
In the range of 50-300 microns, further preferably in the range of 60-200 microns, such as in the range of 70-150 microns.Spray boom
33 quantity can be one or more.When the quantity of spray boom 33 is one, spray boom 33 can be with serpentine-like bending, so that atomization
Nozzle can cover the surface of the layer formed by porous carrier, so as to which more uniformly the solution spraying containing catalytic active component exist
Porous carrier surface.When the quantity of spray boom 33 is more, more spray booms 33 can be to be put down along the rotor shaft direction with hollow container
Capable mode arranges, so that atomizer can cover the surface of the layer formed by porous carrier, is urged so as to will equably contain
Change the solution even application of active component in porous carrier surface.Can also be cross arrangement between more spray booms 33, as long as energy
Atomizer is set to cover the surface of the layer formed by porous carrier.Preferably, as shown in figure 1, spray boom 33 can be made in
The side wall of the rotor shaft direction hermetically passing hollow container 31 of empty container 31 enters the inside of hollow container 31, spray boom 33 and hollow appearance
The side wall of device 31 is to be rotatably connected, wherein, the atomizer, spray boom are set on the spray boom 33 inside hollow container 31
33 one end outside hollow container 31 can connect with solution feed unit, can so be rotated in hollow container 31 same
When, spray boom 33 sprays the solution containing catalytic active component in the state of not rotating.
As shown in figure 1, vacuum lines 34 are disposed with hollow container 31, during spraying, to be vacuumized.
Vacuum lines 34 are set close to the inwall of hollow container 34, by bleeding point landfill in the layer formed by porous carrier, from
And effectively steam of the disperse between porous carrier can be extracted out in time.Vacuum lines 34 can be with hermetically passing hollow container
31 side wall, and vacuum lines 34 and the side wall of hollow container 31 are to be rotatably connected, wherein, during vacuum lines 34 are located at
Part inside empty container 31 can be bent according to the inner space of hollow container 31, so that taking out in vacuum lines 34
Gas port is filled in the layer formed by porous carrier.One end that vacuum lines 34 are located at outside hollow container 31 can be with vavuum pump
Connection.Cold-trap can be set between vacuum lines 34 and vavuum pump, to capture the volatile materials being extracted, avoid it from entering
Enter in vavuum pump.Valve can also be set between vacuum lines 34 and vavuum pump, with to the vacuum in hollow container 31
It is adjusted, it is met pre-provisioning request.
As shown in figure 1, spray unit preferably also sets up rotary shaft 35 and the drive device for driving rotary shaft 35, this
Sample can rotate hollow container 31 during spraying, so that the solution containing catalytic active component sprays in which can be more uniformly distributed
In porous carrier surface.Rotary shaft 35 is preferably two, is symmetricly set on the both sides of hollow container 31, and turn along hollow container 31
Direction of principal axis extends, and is to be fixedly connected with mesopore container 31.The drive device can drive rotary shaft 35 to rotate to be various
Device.In one embodiment, as shown in figure 1, the drive device includes motor 36 and travelling gear 37, the band of motor 36
Nutating gear 37 is rotated, and rotating torque is passed into rotary shaft 35, so as to drive hollow container 31 to rotate.
As shown in figure 1, spray unit also includes distributing device 38, the feed end of distributing device 38 and the discharging opening of hollow container 31
Connection, discharge end connect with drying unit, are loaded with for receiving from what hollow container 31 exported containing catalytic active component
The porous carrier of solution, and be sent in drying unit and be dried.The cylinder of the preferably both ends open of distributing device 38, one end
Opening is towards hollow container 31, with can be relative with the discharging opening of hollow container 31, so as to receive what is exported from hollow container 31
Porous carrier through spraying；Porous carrier through spraying is transferred to drying unit by another end opening towards drying unit.
Drying unit is used to that the porous carrier for being loaded with the solution containing catalytic active component of spray unit will to be come from
It is dried.Drying unit can use conventional various drying devices to be dried.In a preferred embodiment, such as
Described in Fig. 1, drying unit includes dry zone 41, and distributing device 38 will be loaded with the porous carrier of the solution containing catalytic active component
Dry zone 41 is delivered to, is dried on dry zone 41.The material of dry zone 41 using can bear to dry required temperature as
It is accurate.
As needed, dry zone 41 can be arranged in a housing, the pipeline vacuumized is provided in the housing,
It can so be dried at reduced pressure.
According to specific needs, the preparation system can also include calciner, with to through dry porous carrier progress
Roasting.The calciner can be the conventional device that can realize roasting function, be not particularly limited.
When the method according to the invention is implemented using above-mentioned preparation system, following process can be used to carry out.
Porous carrier is placed in porous carrier storage tank 11, the solution containing catalytic active component is placed in solution reservoir 21
In.Porous carrier is sent into hollow container 31, vacuumized by vacuum lines 34, while driven by rotary shaft 35
Hollow container 31 rotates.Solution containing catalytic active component is sprayed on porous carrier by the atomizer on spray boom 33
Surface.After the completion of spraying, the porous carrier for being loaded with catalytic active component is sent on dry zone 41, is dried.Dry
After the completion of, it will alternatively be sent into calciner and be calcined through dry porous carrier.
According to the second aspect of the invention, present invention also offers the shell profile prepared by the method for the present invention to urge
Agent.
The shell profile catalyst prepared by the method for the present invention has higher shell rate.
" shell distribution catalyst " is generally also referred to as eggshell type catalyst with non-uniform distribution by those skilled in the art, referred to as
Egg-shell catalyst, its definition are known to the skilled person, such as may refer to that (Zhu Hongfa writes《Catalyst carrier
Preparation and application technology》The definition in the 199-200 pages (petroleum industry publishing house May the 1st edition in 2002) in book.The present invention
In, shell rate passes through SEM-energy spectrum analysis (i.e. SEM-EDX, Scanning Electron Microscope-
Energy Dispersive Spectrometry) method measures.Specific method includes：Randomly select 30 catalyst granules simultaneously
Catalyst granules is radially cut, the section particle diameter of catalyst granules is observed with SEM, afterwards with EDX radially cross-sectional scans
Obtain the radial distribution of catalytic active component.Due in ESEM-X-ray energy spectrum (SEM-EDX) characterization result along carrier footpath
It is mutually corresponding with the constituent content to the counting rate of every bit, although the size of counting rate may not represent the element
Real content, but counting rate be sized to reflect the constituent content height.Therefore, in order to represent catalytic active component and to urge
It is catalytic active component and the catalyst aid heart in the catalyst to change the regularity of distribution of the auxiliary agent along carrier radial direction to introduce distribution factor σ, σ
The ratio between the concentration at place and the concentration of a certain opening position in addition to center.In general, " egg-shell catalyst " refers to：Catalysis
The distribution factor σ of agent is 0≤σ ＜ 0.95 a kind of catalyst, wherein, concentration is certain point in addition to central point on a certain position
The average value of (position deviation≤20nm) 20 numerical point counting rates nearby；(position deviation nearby is put at center centered on concentration
≤ 20nm) 20 numerical point counting rates average value.Shell distribution catalyst of the present invention refers to the work in catalyst
Property metal component is mainly distributed on shell.To be shared by the particle of shell profile catalyst in 30 catalyst granules of test
Percentage be referred to as shell rate.Wherein, shell thickness refers to that the distribution factor of catalytic active component and catalyst aid meets 0≤σ
The thickness of ＜ 0.95 part.
Catalyst according to the invention is particularly suitable as the catalyst of the reaction by interior diffusion control, as F- T synthesis is anti-
The catalyst answered.
Thus, according to the third aspect of the present invention, present invention also offers a kind of Fischer-Tropsch synthesis method, this method to include
Under the conditions of Fischer-Tropsch synthesis, synthesis gas is contacted with catalyst, wherein, the catalyst is to be prepared by the method for the present invention
The shell profile catalyst to Fischer-Tropsch synthesis with catalytic action.
According to catalyst provided by the invention, before use, it is preferred that in presence of hydrogen, by the active metal group of oxidation state
Divide and carry out reduction activation.The condition of the reduction activation can include：Reduction temperature can be 200 DEG C to 1000 DEG C, be preferably
200 DEG C to 800 DEG C, the recovery time can be 1-96 hours, preferably 2-24 hours, and the reduction activation can enter in pure hydrogen
OK, it can also carry out, such as be carried out in the gaseous mixture of hydrogen and nitrogen, Hydrogen Vapor Pressure in the mixed gas of hydrogen and inert gas
Can be 0.1-4MPa, preferably 0.1-2MPa, the inert gas refers in the conditions of the invention, be not involved in chemically reacting
Gas, such as nitrogen and group 0 element gas.
According to the Fischer-Tropsch synthesis method of the present invention, it is not particularly limited for the specific reaction condition of fischer-tropsch reaction, can be with
Carry out under normal conditions.Specifically, temperature can be 170-350 DEG C, preferably 180-300 DEG C；Gross pressure can be 1-
20MPa, preferably 1.5-15MPa；Volume space velocity can be 1000-20000h during the gas of synthesis gas-1, preferably 2000-
18000h-1。
Describe the present invention in detail with reference to embodiments, but and be not so limited the present invention.
In following examples and comparative example, the composition of the catalyst prepared is determined using x-ray fluorescence spectrometry method.
In following examples and comparative example, pass through SEM-energy spectrum analysis (that is, SEM-EDX, Scanning
Electron Microscope-Energy Dispersive Spectrometry) method determines catalytic active component along porous
The distribution of carrier radial direction, and calculate shell rate.
In following examples and comparative example, the size of atomized drop is determined using Malvern Particle Size Analyzer, is put down for volume
Equal particle diameter.
In following examples and comparative example, determined in spraying process using following methods, produced in hollow container by solvent
Partial pressure using following methods determine：After porous carrier is loaded and spraying start before, hollow container vacuumize until
Relative degree of vacuum in hollow container is stable, using the relative degree of vacuum as benchmark relative degree of vacuum, will be determined in spraying process
Relative degree of vacuum and benchmark relative degree of vacuum between difference be used as caused by solvent partial pressure.
In following examples, catalyst is prepared using the preparation system shown in Fig. 1, wherein, hollow container 31 is to share bottom
The biconial in face, its axially a length of 2 meters, radial direction internal diameter is 2.7 meters).
Embodiment 1-12 is used to illustrate the present invention.
Embodiment 1
1st, (particle length is 2-4 millimeters to the butterfly gama-alumina particle extruded 200kg by 1.6mm orifice plates, determines it
Water absorption rate is 0.8 ml/g) it is used as catalyst carrier and is put into porous carrier storage tank 11.
2nd, cobalt nitrate is dissolved in the water, be configured to containing catalytic active component solution (in terms of CoO, cobalt nitrate it is dense
Spend for 330 g/l) and be placed in solution reservoir 21.
3rd, porous carrier is sent into hollow container 31, rotates hollow container 31 (velocity of rotation is 3.5 revs/min), together
Shi Qidong vavuum pumps are vacuumized to hollow container 31 (wherein, is equidistantly spaced from 3 in hollow container along rotor shaft direction
Vacuum lines, the bleeding point in every vacuum lines fills in the layer formed by porous carrier and bleeding point is edge
Vacuum lines are spacedly distributed, bleeding point is evacuated mouth down towards the inwall of carrying porous carrier), by hollow container
Relative degree of vacuum stabilize to -50kPa (that is, benchmark relative degree of vacuum).Then, the rotation condition of hollow container 31 is maintained not
Become, with vacuumizing, the solution containing catalytic active component is sent into hollow container 31, the molten of catalytic active component will be contained
Liquid is sprayed on porous carrier surface by atomizer in the form of atomized drop.Wherein, the solution containing catalytic active component
Straying quatity VLWith the total pore volume V of porous carrierCRatio meet VL/VC=0.5, the size of atomized drop is 80 μm；It is hollow
Temperature in container is 25 DEG C, in spraying process, adjusts the condition vacuumized and make it that aquagenic partial pressure is up to 3kPa；It is more
Residence time of the hole carrier in hollow container 31 is 30 minutes.
4th, after the completion of impregnating, in 5 minutes, sample after dipping is all sent on dry zone 41 and is dried, wherein, do
Dry to carry out at ambient pressure, temperature is 160 DEG C, and residence time of the sample on dry zone 41 is 4 hours after dipping.
5th, by dried sample at a temperature of 450 DEG C, it is calcined 4 hours, so as to obtain catalyst.The group of the catalyst
Into and shell rate listed in table 1, along the radial section of porous carrier by outer layer to core, the percentage contents of cobalt element
Listed in table 2.
Comparative example 1
Catalyst is prepared using method same as Example 1, unlike, in step 3, during spraying, do not open
Vavuum pump is opened, i.e., during spraying, without vacuumizing.
The composition and shell rate of the catalyst of preparation are listed in table 1.
Comparative example 2
Catalyst is prepared using method same as Example 1, unlike, in step 3, contain catalytic active component
The straying quatity V of solutionLWith the total pore volume V of porous carrierCRatio meet VL/VC=1.0, contain the molten of catalytic active component
In liquid, in terms of CoO, the concentration of cobalt nitrate is 165 g/l.
The composition and shell rate of the catalyst of preparation are listed in table 1.
Comparative example 3
Catalyst is prepared using method same as Example 1, unlike, it is not provided with vacuum-pumping tube in hollow container 31
Line 34, wherein, for being open through the position of vacuum lines 34 for one, in spraying process, the opening is unlimited.
The composition and shell rate of the catalyst of preparation are listed in table 1.
Comparative example 4
Catalyst is prepared using method same as Example 1, unlike, catalysis is prepared using the device shown in Fig. 2
Agent, the difference of the device shown in device and Fig. 1 shown in Fig. 2 are that the bleeding point in vacuum lines 34 is not filled more
In the layer that hole carrier is formed.
The composition and shell rate of the catalyst of preparation are listed in table 1.
Embodiment 2
Catalyst is prepared using method same as Example 1, unlike, in step 3, in spraying process, do not adjust
The condition vacuumized, aquagenic partial pressure are up to 20kPa.
The composition and shell rate of the catalyst of preparation are listed in table 1, along the radial section of porous carrier by outer layer extremely
Core, the percentage contents of cobalt element are listed in table 2.
Embodiment 3
Catalyst is prepared using method same as Example 1, unlike, in step 4, dry temperature is 120 DEG C.
The composition and shell rate of the catalyst of preparation are listed in table 1, along the radial section of porous carrier by outer layer extremely
Core, the percentage contents of cobalt element are listed in table 2.
Embodiment 4
Catalyst is prepared using method same as Example 1, unlike, in step 4, dry at reduced pressure
Carry out, pressure (gauge pressure) is -45kPa, and temperature is 160 DEG C.
The composition and shell rate of the catalyst of preparation are listed in table 1, along the radial section of porous carrier by outer layer extremely
Core, the percentage contents of cobalt element are listed in table 2.
Embodiment 5
1st, (particle length is 2-4 millimeters to the butterfly gama-alumina particle extruded 200kg by 1.6mm orifice plates, determines it
Water absorption rate is 1.0 mls/g) it is used as catalyst carrier and is put into carrier storage tank 11.
2nd, ammonium molybdate, ammonium metatungstate, nickel nitrate and phosphoric acid are dissolved in the water, are configured to containing the molten of catalytic active component
Liquid (MoO3Concentration be 225 g/l, WO3Concentration be 99 g/l, NiO concentration is 50 g/l, and the concentration of P elements is 39
G/l) and be placed in solution reservoir 21.
3rd, porous carrier is sent into hollow container 31, rotates hollow container 31 (velocity of rotation is 4 revs/min), simultaneously
Startup vavuum pump is vacuumized to hollow container 31 (wherein, to be equidistantly spaced from 3 and takes out in hollow container along rotor shaft direction
Vacuum pipeline, the bleeding point in every vacuum lines is filled in the layer formed by porous carrier and bleeding point is true along taking out
Blank pipe line is spacedly distributed, bleeding point is evacuated mouth down towards the inwall of carrying porous carrier), by the phase in hollow container
It is -60kPa (that is, benchmark relative degree of vacuum) to vacustat.Then, maintain the rotation condition of hollow container 31 constant, companion
With vacuumizing, the solution containing catalytic active component is sent into hollow container 31, the solution containing catalytic active component is led to
Cross atomizer and porous carrier surface is sprayed in the form of atomized drop.Wherein, the spray of the solution containing catalytic active component
Enter amount VLWith the total pore volume V of porous carrierCRatio meet VL/VC=0.5, the size of atomized drop is 120 μm；Hollow appearance
Temperature in device is 50 DEG C, in spraying process, adjusts the condition vacuumized and make it that aquagenic partial pressure is up to 10kPa；It is more
Residence time of the hole carrier in hollow container 31 is 19 minutes.
4th, after the completion of impregnating, in 10 minutes, sample after dipping is sent on dry zone 41 and is dried, wherein, dry
Carry out at ambient pressure, temperature is 140 DEG C, and residence time of the porous carrier on dry zone 41 is 5 hours.
5th, sample is calcined 4 hours, so as to obtain catalyst at a temperature of 450 DEG C after drying.
The composition and shell rate of the catalyst are listed in table 1, along the radial section of porous carrier by outer layer to core,
The percentage contents of molybdenum element are listed in table 2.
Comparative example 5
Catalyst is prepared using method same as Example 5, unlike, during spraying, vavuum pump is not turned on,
I.e. during spraying, without vacuumizing.
The composition and shell rate of the catalyst of preparation are listed in table 1.
Comparative example 6
Catalyst is prepared using method same as Example 5, unlike, catalysis is prepared using the device shown in Fig. 2
Agent, the difference of the device shown in device and Fig. 1 shown in Fig. 2 are that the bleeding point in vacuum lines 34 is not filled more
In the layer that hole carrier is formed.
The composition and shell rate of the catalyst of preparation are listed in table 1.
Embodiment 6
1st, (particle length is 2-4 millimeters to the butterfly gama-alumina particle extruded 200kg by 1.6mm orifice plates, determines it
Water absorption rate is 1.0 mls/g) it is used as catalyst carrier and is put into porous carrier storage tank 11.
2nd, ammonium metatungstate and nickel nitrate are dissolved in the water, are configured to the solution (WO containing catalytic active component3Concentration
For 402 g/l, NiO concentration is 25 g/l) and be placed in solution reservoir 21.
3rd, porous carrier is sent into hollow container 31, rotates hollow container 31 (velocity of rotation is 3.5 revs/min), together
Shi Qidong vavuum pumps are vacuumized to hollow container 31 (wherein, is equidistantly spaced from 3 in hollow container along rotor shaft direction
Vacuum lines, the bleeding point in every vacuum lines is filled in the layer formed by porous carrier and bleeding point is along taking out
Vacuum pipeline is spacedly distributed, bleeding point is evacuated mouth down towards the inwall of carrying porous carrier), by hollow container
Relative degree of vacuum stabilizes to -70kPa (that is, benchmark relative degree of vacuum).Then, maintain the rotation condition of hollow container 31 constant,
With vacuumizing, the solution containing catalytic active component is sent into hollow container 31, by the solution containing catalytic active component
Porous carrier surface is sprayed in the form of atomized drop by atomizer.Wherein, solution containing catalytic active component
Straying quatity VLWith the total pore volume V of porous carrierCRatio meet VL/VC=0.4, the size of atomized drop is 100 μm；It is hollow
Temperature in container is 50 DEG C, in spraying process, adjusts the condition vacuumized and make it that aquagenic partial pressure is up to 7kPa；It is more
Residence time of the hole carrier in hollow container 31 is 24 minutes.
4th, after the completion of impregnating, in 6 minutes, sample after dipping is all sent on dry zone 41 and is dried, wherein, do
Dry to carry out under reduced pressure, pressure is -8kPa (for gauge pressure), and temperature is 120 DEG C, residence time of the porous carrier on dry zone 41
For 2 hours.
5th, at a temperature of 500 DEG C, will be calcined 2 hours, so as to obtain catalyst through dry porous carrier.The catalyst
Composition and shell rate listed in table 1, along the radial section of porous carrier by outer layer to core, the percentage of wolfram element
Content is listed in table 2.
Comparative example 7
Catalyst is prepared using method same as Example 6, unlike, during spraying, vavuum pump is not turned on,
I.e. during spraying, without vacuumizing.
The composition and shell rate of the catalyst of preparation are listed in table 1.
Comparative example 8
Catalyst is prepared using method same as Example 6, unlike, catalysis is prepared using the device shown in Fig. 2
Agent, the difference of the device shown in device and Fig. 1 shown in Fig. 2 are that the bleeding point in vacuum lines 34 is not filled more
In the layer that hole carrier is formed.The composition and shell rate of the catalyst of preparation are listed in table 1.
Embodiment 7
Catalyst is prepared using method same as Example 6, unlike, in step 4, dry temperature is 80 DEG C.
The composition and shell rate of the catalyst of preparation are listed in table 1, along the radial section of porous carrier by outer layer extremely
Core, the percentage contents of wolfram element are listed in table 2.
Embodiment 8
Catalyst is prepared using method same as Example 6, unlike, in step 3, bleeding point is more backwards to carrying
The inwall (that is, relative with the injection direction of the solution containing catalytic active component, i.e. bleeding point upward) of hole carrier.What is prepared urges
The composition and shell rate of agent are listed in table 1, along the radial section of porous carrier by outer layer to core, wolfram element it is relative
Percentage composition is listed in table 2.
Table 1
| Numbering | CoO, wt% | WO3, wt% | MoO3, wt% | NiO, wt% | P, wt% | Shell rate, % |
| Embodiment 1 | 11.6 | / | / | / | / | 99 |
| Comparative example 1 | 11.7 | / | / | / | / | 70 |
| Comparative example 2 | 11.6 | / | / | / | / | 0 |
| Comparative example 3 | 11.7 | / | / | / | / | 72 |
| Comparative example 4 | 11.1 | / | / | / | / | 79 |
| Embodiment 2 | 11.6 | / | / | / | / | 91 |
| Embodiment 3 | 11.6 | / | / | / | / | 94 |
| Embodiment 4 | 11.6 | / | / | / | / | 98 |
| Embodiment 5 | / | 4.1 | 9.5 | 2.0 | 1.5 | 99 |
| Comparative example 5 | / | 4.2 | 9.5 | 2.1 | 1.6 | 72 |
| Comparative example 6 | / | 3.8 | 8.9 | 1.5 | 1.1 | 78 |
| Embodiment 6 | / | 13.5 | / | 0.84 | / | 99 |
| Comparative example 7 | / | 13.7 | / | 0.85 | / | 75 |
| Comparative example 8 | / | 13.1 | / | 0.80 | / | 82 |
| Embodiment 7 | / | 13.5 | / | 0.84 | / | 93 |
| Embodiment 8 | / | 13.3 | / | 0.82 | / | 97 |
From the results shown in Table 1, the catalyst prepared using the method for the present invention has higher shell rate, so as to
It can repeat stably to prepare shell profile catalyst so that the catalyst of preparation has stable catalytic activity.
By embodiment 1 and comparative example 4, embodiment 5 with comparative example 6, embodiment 6 compared with comparative example 8 as can be seen that
If the bleeding point of vacuum lines is without landfill in the layer formed by porous carrier, the shell rate of the catalyst of preparation is still
Than relatively low, its reason may is that caused solvent vapour is embedded in the layer formed by porous carrier in adsorption process, nothing
Method is extracted out in time, and even if being sucked out, steam is also required to through the layer formed by porous carrier, so that can not be timely
Eliminate resulting negative effect.
Table 2
*：Along the radial section of catalyst, with EDX, radially section is scanned from outermost layer to core, takes 5 points at equal intervals
The concentration of catalytic active component at each point is measured respectively, obtains the concentration of each catalytic active component and aluminium element concentration at the point
Ratio.
Embodiment 9-12
Using the performance of following methods test catalyst as made from embodiment 1-4.
Test process is carried out in fixed bed Fischer-Tropsch synthesis device, and catalyst amount is 5 grams.
Catalyst is using preceding being reduced.Reduction is carried out at ambient pressure, and other conditions are：Hydrogen flowing quantity is 1000NL/
(g-cath) 400 DEG C, are warming up to 4 DEG C/min heating rate, keeps 5h.
Fischer-Tropsch synthesis temperature is 220 DEG C, H2/ CO ratios are 2, pressure 2.5MPa, and gas space speed (GHSV) is
2000h-1.As a result listed in table 3.
Comparative example 9-12
Using the performance with the test of embodiment 9-12 identicals method by the comparative example 1-4 catalyst prepared.As a result in table 3
In list.
Table 3
In table 3, XCOCO conversion ratio is represented,WithC is represented respectively5(contain C above5) hydro carbons selectivity and CH4
Selectivity.It is specifically defined the expression formula seen below：
Wherein, V1And V2Be illustrated respectively under the status of criterion, enter in certain period the unstripped gas of reaction system volume and
Flow out the exhaust gas volumes of reaction system；c1And c2The content of tie substance in unstripped gas and tail gas is represented respectively.nconFor certain time
The CO of reaction molal quantity is participated in section by reaction bed,To change into CO2CO molal quantity,To change into
CH4CO molal quantity,To change into CH4、C2Hydrocarbon, C3Hydrocarbon and C4The CO of hydrocarbon molal quantity.
From the results shown in Table 3, using catalyst made from preparation method provided by the invention to C5+Hydro carbons has
Higher selectivity, it is relatively low to the selectivity of methane, while higher CO conversion ratios can also be obtained.
Claims (27)
1. a kind of preparation method of shell profile catalyst, this method comprise the following steps：
(1) porous carrier is placed in hollow container, by the solution spraying containing catalytic active component in the porous carrier table
Face, total quantity for spray of the solution are less than the total pore volume of the porous carrier, in spraying process, the hollow container are entered
Row is vacuumized, and the bleeding point for vacuumizing is arranged in the layer formed by porous carrier；
(2) porous carrier for being loaded with solution that step (1) obtains is dried and is optionally calcined.
2. according to the method for claim 1, wherein, the solution is sprayed on porous carrier table in the form of atomized drop
Face, the condition of the spraying cause the average diameter for the atomized drop to be formed in the range of 1-600 microns.
3. according to the method for claim 2, wherein, the condition of the spraying causes the average diameter for the atomized drop to be formed
In the range of 20-400 microns.
4. according to the method for claim 3, wherein, the condition of the spraying causes the average diameter for the atomized drop to be formed
In the range of 50-300 microns.
5. according to the method described in any one in claim 1-4, wherein, total quantity for spray of the solution is VL, it is described porous
The total pore volume of carrier is VC, VL/VC=0.01-0.99.
6. the method according to claim 11, wherein, VL/VC=0.1-0.8.
7. according to the method described in any one in claim 1-4, wherein, during spraying, porous carrier is in fortune
Dynamic state.
8. according to the method for claim 7, wherein, the motion is one kind or two in vibrating, roll, stir and sliding
The combination of the kind above.
9. according to the method described in any one in claim 1-4, wherein, during spraying, rotate the hollow appearance
Device.
10. according to the method for claim 1, wherein, the condition vacuumized causes the relative vacuum in hollow container
Degree is in the range of -10kPa to -100kPa.
11. according to the method for claim 10, wherein, the condition vacuumized causes the relative vacuum in hollow container
Degree is in the range of -30kPa to -95kPa.
12. according to the method for claim 11, wherein, the condition vacuumized causes the relative vacuum in hollow container
Degree is in the range of -40kPa to -80kPa.
13. according to the method described in any one in claim 1-4 and 10-12, wherein, during the degree vacuumized causes
The interior partial pressure as caused by the solvent in the solution of empty container is in the range of 0 to 30kPa.
14. according to the method for claim 13, wherein, the degree vacuumized to be produced by the solvent in the solution
Raw partial pressure is not higher than 20kPa.
15. according to the method for claim 14, wherein, the degree vacuumized to be produced by the solvent in the solution
Raw partial pressure is not higher than 10kPa.
16. according to the method for claim 1, wherein, the drying is carried out at a temperature of 50-300 DEG C.
17. according to the method for claim 16, wherein, the drying is carried out at a temperature of 60-250 DEG C.
18. according to the method described in any one in claim 1,16 and 17, wherein, temperature of the roasting at 300-600 DEG C
Degree is lower to be carried out.
19. according to the method described in any one in claim 1-3,10-12,16 and 17, wherein, the porous carrier is oxygen
It is more than one or both of SiClx, aluminum oxide, silica-alumina, alumina silicate, titanium oxide, zirconium oxide and activated carbon.
20. according to the method described in any one in claim 1-3,10-12,16 and 17, wherein, the solvent of the solution is
Water.
21. according to the method described in any one in claim 1-3,10-12,16 and 17, wherein, the shell profile is urged
Agent has catalytic action to Fischer-Tropsch synthesis.
22. according to the method for claim 21, wherein, the catalytic active component is selected from group VIII metallic element.
23. according to the method for claim 22, wherein, the catalytic active component is one kind or two in iron, cobalt and ruthenium
More than kind.
24. according to the method for claim 21, wherein, load capacity of the active component on the porous carrier causes
On the basis of the total amount of the catalyst finally prepared, the content for the catalytic active component counted using oxide is 0.5-60 weight %.
25. according to the method for claim 24, wherein, load capacity of the active component on the porous carrier causes
On the basis of the total amount of the catalyst finally prepared, the content for the catalytic active component counted using oxide is 1-50 weight %.
26. shell profile catalyst prepared by a kind of method in 1-25 as claim described in any one.
27. a kind of Fischer-Tropsch synthesis method, this method are included under the conditions of Fischer-Tropsch synthesis, synthesis gas is contacted with catalyst,
Characterized in that, the catalyst is to be urged as shell profile prepared by the method described in any one in claim 21-25
Agent.
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