CN105833869A - Shell distribution catalyst and preparation method thereof and Fischer-Tropsch synthetic method - Google Patents
Shell distribution catalyst and preparation method thereof and Fischer-Tropsch synthetic method Download PDFInfo
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- CN105833869A CN105833869A CN201510015265.3A CN201510015265A CN105833869A CN 105833869 A CN105833869 A CN 105833869A CN 201510015265 A CN201510015265 A CN 201510015265A CN 105833869 A CN105833869 A CN 105833869A
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Abstract
The invention discloses a shell distribution catalyst and a preparation method thereof. The method comprises: (1) disposing a porous support in a hollow container, and spraying a solution containing components with catalytic activity on the surface of the porous support, wherein the total spray amount of the solution is less than the total pore volume of the porous support, and during the spraying process, the hollow container is subjected to vacuum pumping, and an air-pumping port for vacuum pumping is arranged in the layer formed by the porous support; and (2) performing drying and optional roasting of the porous support loaded with the solution and obtained from the step (1). The invention further provides a Fischer-Tropsch synthetic method. In the conditions of a Fischer-Tropsch synthetic reaction, synthesis gas is connected with the shell distribution catalyst having a catalytic action on the Fischer-Tropsch synthetic reaction. Through the method, the shell distribution catalyst can be repeatedly stably produced. The shell distribution catalyst is used for the Fischer-Tropsch synthetic reaction, and is relatively high in C5+ hydrocarbon selectivity and comparatively low in methane selectivity.
Description
Technical field
The present invention relates to a kind of shell profile catalyst and preparation method thereof, the invention still further relates to a kind of expense
Torr synthetic method.
Background technology
The product molecule generated in the reaction of depths, catalyst duct is not as spread out in time and further
React, on the one hand affect selectivity of catalyst, on the other hand will affect the life-span of catalyst.Especially
It is the reaction being internally diffused as rate-determining steps, it is desirable to reaction generation is spread at beneficially reactant and product
Position, it is generally desirable to occur at catalyst coating.It addition, in the cost of catalyst, active component
Large percentage shared by cost, if moved closer to the component being distributed in depths, duct the highest for utilization rate
In the region of catalyst coating, the activity and selectivity of catalyst can be significantly improved undoubtedly.
This kind of gas-solid-liquid heterogeneous reaction is synthesized such as Fischer-Tropsch (FT) for carry out in fixed bed reactors
System, the particle size of catalyst is generally several mm, and therefore, diffusion controls the shadow to catalysis activity
Ring and be difficult to avoid that.It is noted that the heavy paraffinic waxes obtained by FT synthesis is generally with liquid, vapour colloidal sol
Or slurry form is attached to catalyst surface, to reactant H2With CO in the expansion within catalyst granules
Dissipate and produce impact.During the internal diffusion of reactant, H2Diffusion velocity faster than CO, CO is urging
Diffusion-restricted effect in catalyst particles is significantly stronger than H2.Because the particle diameter of granule is different, result in granule
The difference of portion's CO Concentraton gradient, have impact on the combination of CO and metal active centres position so that in activity
In the H/C that adsorbs in the heart than increasing, carbon chain growth probability reduces, and reduces C5+Selectivity.Existing
Technology shows, for the catalyst that active component is evenly distributed, and active component non-uniform Distribution
Catalyst, such as shell type catalyst, owing to diffusion-restricted is little, can significantly increase as F-T synthesis this
C in class reaction5+Selectivity, reduces the selectivity of methane, is particularly suited for this kind of reaction of F-T synthesis.
US5545674 discloses a kind of method preparing shell type catalyst, the method by carrier at metal
Spread out on silk screen, metal gauze is heated in heating furnace more than 140 DEG C, then take out from stove.
By on the heat carrier on metal gauze of the solution spraying containing load component, the solution containing load component is in warm
Carrier surface be evaporated, then the metal gauze with catalyst put back in heating furnace reheat.As
This is repeated multiple times, until the load component that load is enough.
US7087191 discloses a kind of method preparing shell profile catalyst, and the method will contain activity
The powder of component and the powder diluent containing refractory metal oxide make pasty state or muddy, then spray
It is applied to surface and passes through on the inert solid particle that process becomes coarse, then dry, roasting.This method
Can ensure that catalyst activity component has not entered the inside of the solid particle of carrier function, but active component
Existing with powder, the active component within powder particle can not play a role completely, and powder is by thing
Reason effect sticks together with inert solid particle surface, prepared by this physical bonds force rate solution dipping method
In catalyst, the adhesion of chemical bond between active component and carrier surface wants weak many.Therefore, with by living
Shell profile catalyst prepared by the solution of property component will compare, and this be prepared by powdered active ingredient
Method reduces the utilization ratio of active component, it addition, in Shi Yonging under the washing away of air-flow active component powder
End is relatively easy to come off from inert solid particle surface.
US5545674 discloses the preparation method of a kind of shell profile catalyst, and the method is by using
There is the middle dry or immersion of combustion step or cobalt especially cobalt nitrate solution is soaked by spray method repeatedly
Stain is on bead-type substrate.These methods are loaded down with trivial details and time-consuming, and use repeatedly dipping method, some
The outer layer that metal can surpass the expectation penetrates in carrier.
CN101318133A discloses a kind of shell type catalyst for preparing Petroleum and diesel oil, should
Catalyst, with activated carbon as carrier, takes the mode of spraying to be sprayed onto on the carrier of rolling by solution, then will
Catalyst is dried or roasting in noble gas.But, the shell rate of catalyst prepared by the method is the highest.
US4599481 discloses a kind of method reacted by carbon monoxide and hydrogen catalysis and produce hydrocarbon, the method
It is included in 125-350 DEG C, under the conditions of pressure 5-100 bar (bar), carbon monoxide and hydrogen is connect with catalyst
Touching, described catalyst contains carrier and load cobalt on this carrier, and the distribution on carrier of the described cobalt is full
Foot (∑ Vp/ ∑ Vc) ＜ 0.85, wherein, ∑ Vc represents the cumulative volume of catalyst granules, and Vp is catalysis
Shell volume in agent.When in shell, the content of cobalt is about 90%, catalyst has high activity and selection
Property.The preparation method of this catalyst is first by water treatment carrier, impregnates cobalt nitrate solution afterwards, then does
Dry and roasting.This preparation method is very strict to the requirement of time, and complex operation, it is not easy to scale
Metaplasia is produced.
CN102451722A discloses the preparation method of a kind of eggshell hydrogenation catalyst.The method uses
Active metal solution impregnating carrier containing thickening agent and active metal dispersant, is wherein being passed through air
Impregnate under conditions of bubbling, then drying and roasting, obtain eggshell hydrogenation catalyst.The method
Can effectively regulate dividing of eggshell hydrogenation catalyst surface activity, the thickness of metal shell layer and active metal
Divergence, the active metal component on energy stable hydrogenation catalyst, reduces the loss of active metal component, fall
Low catalyst production cost.But, this preparation method is very strict to the requirement of time, and operates numerous
Trivial, it is not easy to large-scale production.
Visible, it is still desirable to continue the method that shell profile catalyst is prepared in exploration.
Summary of the invention
It is an object of the invention to provide a kind of shell profile catalyst and preparation method thereof, by the method
The catalyst shell rate of preparation is high.
According to the first aspect of the invention, the invention provides the preparation of a kind of shell profile catalyst
Method, the method comprises the following steps:
(1) porous carrier is placed in hollow container, the solution spraying containing catalytic active component is existed
Described porous carrier surface, total quantity for spray of described solution is less than the total pore volume of described porous carrier,
In spraying process, described hollow container is carried out evacuation, and for the bleeding point of evacuation be arranged in by
In the layer that porous carrier is formed；
(2) porous carrier being loaded with solution that step (1) obtains is dried and optional successively
Roasting.
According to the second aspect of the invention, the invention provides a kind of shell prepared by the method for the present invention
Layer profile catalyst.
According to the third aspect of the present invention, the invention provides a kind of Fischer-Tropsch synthesis method, the method bag
Including under the conditions of Fischer-Tropsch synthesis, contacted with catalyst by synthesis gas, wherein, described catalyst is for adopting
The shell profile catalyst that Fischer-Tropsch synthesis is had catalytic action prepared by the method for the present invention.
The preparation method of the shell profile catalyst according to the present invention, the shell rate of the catalyst of preparation
Height, can repeat stably to produce shell profile catalyst.The method using the present invention can stably produce
The reason of shell profile catalyst may is that by the solution spraying containing catalytic active component to many
During the carrier surface of hole, it is attached to the solution mistake at the hole being impregnated into porous carrier on porous carrier surface
Cheng Zhong, due to exotherm so that partial solvent volatilization forms steam, and the existence of these steams can cause
Catalytic active component, to the core migration of porous carrier, destroys the shell structurre formed；According to the present invention's
Method, during spraying, carries out evacuation, and the bleeding point landfill being used for evacuation is being carried by porous
In the layer that body is formed (that is, during the bleeding point for evacuation is arranged in the layer formed by porous carrier),
Disperse solvent vapour between porous carrier is extracted out in time and fully, catalysis activity can be effectively reduced
Component is to the trend of the core migration of porous carrier, thus improves the shell rate of the catalyst of preparation.
The preparation method of the shell profile catalyst according to the present invention, operating process is simple and easy to control, is suitable to
Scale is implemented.
The shell profile catalyst prepared by the method for the present invention is used as the catalysis of Fischer-Tropsch synthesis
Agent, can obtain higher C5+Hydrocarbon selective and relatively low methane selectively.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.
Fig. 1 is the structural representation of the device of the shell profile catalyst for preparing the present invention.
Fig. 2 is the structural representation of 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
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
In the present invention, " axially " and " radially " for hollow container, i.e. along hollow
The direction that the rotor shaft direction (i.e. center of rotation) of container extends is axial direction, and is perpendicular to this axially side
To for radial direction, it should be noted that these nouns of locality are served only for the present invention is described, be not limited to
The present invention.In the present invention, " optional " represents the technology spy that can include connecting with " optional "
Levy, it is also possible to do not include the technical characteristic connected with " optional ".The numerical value model occurred in the present invention
Enclose two end values all including constituting this numerical range.
According to the first aspect of the invention, the invention provides the preparation of a kind of shell profile catalyst
Method, the method comprising the steps of (1): is placed in hollow container by porous carrier, will be containing catalysis activity
The solution spraying of component is on described porous carrier surface, in spraying process, carries out described hollow container
Evacuation.
The method according to the invention, total quantity for spray of the solution containing catalytic active component is less than described porous
The total pore volume of carrier.From the angle of the shell rate of the catalyst improving preparation further, containing urging
Total quantity for spray of the solution changing active component is VL, the total pore volume of described porous carrier is VC,
VL/VC=0.01-0.99；Preferably, VL/VC=0.1-0.8；It is highly preferred that VL/VC=0.2-0.7；Enter one
Walk preferably, VL/VC=0.3-0.6, such as VL/VC=0.4-0.5.In the present invention, VCEqual to porous carrier
Quality (in gram) be multiplied by the water absorption rate of porous carrier (density of water be 1g/cm3), water absorption rate is
The water absorption of the carrier of Unit Weight.Specifically, following methods can be used to measure water absorption rate: can be by
(weight is calculated as w to carrier1, in gram) with water with carrier (by weight) and water (by volume)
Ratio is that 1:3 impregnates 2 hours, after filtration, is drained by solid, then weighs the weight of the solid drained
(weight is calculated as w to amount2, in gram), below equation calculate water absorption rate:
Method according to the invention it is possible to use molten by containing catalytic active component of common various methods
Liquid is sprayed on porous carrier surface.Preferably, by the solution containing catalytic active component with atomized drop
Form is sprayed on porous carrier surface.From improving the shell rate of the final catalyst prepared further and urging
The angle changing efficiency is set out, and the size of described atomized drop is preferably in the range of 1-600 micron, more excellent
It is selected in the range of 20-400 micron, further preferably in the range of 50-300 micron, further
Preferably in the range of 60-200 micron, as in the range of 70-150 micron.In the present invention, atomization
The size of drop uses Malvern Particle Size Analyzer to measure, for volume average particle size.In concrete operations
Cheng Zhong, can regulate the size of the atomized drop of formation by regulation expulsion pressure.
The method according to the invention, from improving the solution containing catalytic active component and porous carrier further
The angle of the uniformity of contact is set out, and during spraying, preferably makes porous carrier be in the state of motion.
The form of described motion can be one or more the combination in vibrating, roll, stir and sliding.
In actual mechanical process, hollow container can be rotated, thus drive the porous carrier in hollow container to transport
Dynamic.
The method according to the invention, during spraying, carries out evacuation to hollow container.With spray
Do not carry out evacuation during painting to compare, the shell of the catalyst of preparation can be significantly improved by evacuation
Rate, thus realize stably repeatedly preparing shell profile catalyst.From the catalysis improving preparation further
The angle of the shell rate of agent is set out, and the condition of described evacuation makes the relative vacuum degree in hollow container exist
In the range of-10kPa to-100kPa.It is highly preferred that in the condition of described evacuation makes hollow container
Relative vacuum degree at-30kPa in the range of-95kPa.Further preferably, the condition of described evacuation
Make relative vacuum degree in hollow container in the range of-40kPa to-80kPa, as at-45kPa extremely
In the range of-75kPa.In the present invention, the absolute pressure in relative vacuum degree=hollow container is (with kPa
Meter)-101.3.Described relative vacuum degree can be measured by pressure vacuum gauge.
Method in accordance with the invention it is preferred that the condition of described evacuation make in described hollow container by
The dividing potential drop that solvent in solution containing catalytic active component produces is in the range of 0-30kPa.Described take out
The condition of vacuum is produced by the solvent in the solution containing catalytic active component in making described hollow container
Dividing potential drop be preferably not higher than 20kPa, more preferably not above 10kPa.Higher guaranteeing to obtain
Shell rate on the premise of, from the angle reducing further operating cost, control the condition of evacuation
The dividing potential drop produced by the solvent in the solution containing catalytic active component in making described hollow container is not for
Less than 0.1kPa.Described dividing potential drop can be measured by vacuum meter.
The method according to the invention, typically before spraying, in advance to the hollow with porous carrier
Container carries out evacuation, it is preferable that have before the relative vacuum degree in the hollow container of porous carrier is in
Within the scope of literary composition is described, and using this relative vacuum degree as base vacuum degree, during spraying, root
The condition of evacuation is adjusted so that by containing catalytic active component according to the relative vacuum degree in hollow container
The dividing potential drop that solvent in solution produces is within the scope of described previously.In spraying process, hollow container
The interior difference between relative vacuum degree and benchmark relative vacuum degree is as by containing catalytic active component
The dividing potential drop that solvent in solution produces.
The method according to the invention, the bleeding point for evacuation is arranged in the layer formed by porous carrier
In, i.e. the bleeding point for evacuation is landfilled in the solid particle layer formed by porous carrier.For
The bleeding point of evacuation can towards carrying porous carrier inwall (that is, with containing catalytic active component
The spraying direction of solution is consistent), it is also possible to the inwall carrying porous carrier dorsad (that is, is catalyzed with containing
The spraying direction of the solution of active component is relative).Preferably, described bleeding point is towards carrying porous carrier
Inwall, so can obtain the shell rate of further raising, can also reduce containing catalysis alive simultaneously further
The loss amount of the solution of property component.
In actual mechanical process, can pass through in hollow container, arrange vacuum pipeline, and at vacuum tube
Offer bleeding point on line, thus realize in spraying process, carry out evacuation.
The quantity of described bleeding point can be one or more as the case may be, can between multiple bleeding points
Think at equal intervals, it is also possible to for unequal interval, or be at equal intervals or combination (that is, the portion of unequal interval
Divide between bleeding point for arrange at equal intervals, arrange for unequal interval between remainder bleeding point).Bleed
The form of mouth can be conventional selection.Can pass through on the pipeline of evacuation, arranging opening, thus
Form described bleeding point.The bore of described opening is preferably no greater than the particle diameter of porous carrier.Preferably, exist
Drainage screen is installed, to avoid solid particle to enter in vacuum lines on bleeding point.
The pipeline that can be used in evacuation is worn along the direction sealing parallel with the rotor shaft direction of hollow container
Cross hollow container.For being preferably rotatably connected between the pipeline and hollow container of evacuation, so exist
When hollow container rotates, the pipeline for evacuation will not rotate with hollow container.Pipe for evacuation
Line is positioned at the part of hollow container and can bend according to the interior shape of hollow container, with can
Fill in the layer that porous carrier is formed.Quantity for the pipeline of evacuation can be one or two with
On.When the quantity of the pipeline for evacuation is one, the pipeline for evacuation is positioned at hollow container
Interior part can serpentine-like bend, to expand the overlay area of bleeding point, thus will be in porous carrier shape
The steam produced in each band of position of the layer become in time and aspirates away fully.For evacuation
The quantity of pipeline when being many, the many pipelines for evacuation can be edge and the rotating shaft of hollow container
The parallel mode in direction arranges, to expand the overlay area of bleeding point；Also may be used between many vacuum lines
Think and intersect, as long as bleeding point can be made to be positioned at multiple bands of position of the layer formed by porous carrier i.e.
Can.Can along one or more layers vacuum lines that is radially arranged of hollow container, multilamellar vacuum lines it
Between can be at equal intervals, it is also possible to for unequal interval, every layer of vacuum lines can have one or more
Vacuum lines.
The method according to the invention, in spraying process, limits the most especially for the temperature in hollow container
Fixed, can carry out at conventional temperatures.Usually, in spraying process, can be by hollow container
Temperature controls in the range of 0-70 DEG C, preferably the temperature in hollow container is controlled the model at 20-50 DEG C
In enclosing.
The method according to the invention, the persistent period of described spraying can carry out according to the character of porous carrier
Select.Usually, the persistent period of described spraying can be 5 minutes-200 minutes.Holding of described spraying
The continuous time is preferably more than 10 minutes, more preferably more than 15 minutes.From improving shell rate further
Angle is set out, and the persistent period of described spraying is preferably less than 100 minutes, more preferably 60 minutes with
Under, more preferably less than 30 minutes.In actual mechanical process, can carry by controlling porous
The body time of staying in hollow container regulates the persistent period of spraying.
The method according to the invention, described porous carrier can be common to be adapted as catalyst carrier
Porous mass.Specifically, described porous carrier can be heat-resistant inorganic oxide, aluminium silicate and activated carbon
In one or more.Described heat-resistant inorganic oxide refers under oxygen or oxygen-containing atmosphere, decomposes
Temperature is not less than the inorganic oxygen-containing compound of 300 DEG C (such as: decomposition temperature is 300-1000 DEG C).Institute
The instantiation stating porous carrier can include but not limited to: aluminium oxide, silicon oxide, titanium oxide, oxidation
In magnesium, zirconium oxide, thorium oxide, silica-alumina, aluminium silicate and activated carbon one or both with
On.Preferably, described porous carrier be silicon oxide, aluminium oxide, silica-alumina, aluminium silicate,
One or more in titanium oxide, zirconium oxide and activated carbon.It is highly preferred that described porous carrier is
Aluminium oxide.
The shape of described carrier is not particularly limited by the present invention, can be conventional shape, such as, and can
Think spherical, sheet shape, bar shaped etc., preferably bar shaped.The method according to the invention, described porous carrier
Mean diameter can select according to the concrete kind of catalyst, preferably in the scope of 0.5-6mm
In, more preferably in the range of 1-4mm.
The solvent of the described solution containing catalytic active component can be conventional selection, can be such as water,
One or more mixture in alcohol, ether, aldehyde and ketone.Preferably, described solvent be water and/
Or alcohol, such as one or more the mixture in water, methanol and ethanol.From environmental conservation and reduction
The angle of cost is set out, and described solvent is more preferably water.
The method according to the invention, the kind of described catalytic active component can making according to expection catalyst
Select by occasion, to be obtained in that the catalyst with predetermined catalytic performance is as the criterion, such as VIII
Race's metallic element and/or vib metals element.The present invention one preferred embodiment in,
The kind of described catalytic active component makes the shell profile catalyst pair prepared by the method for the present invention
Fischer-Tropsch synthesis has catalytic action.This preferred embodiment in, described catalytic active component can
Think the component that Fischer-Tropsch synthesis is had catalytic action, it is preferable that described catalytic active component is selected from
Group VIII metallic element, be specifically as follows in ferrum, cobalt and ruthenium one or more.
Method according to the invention it is possible to pass through the compound dissolution containing catalytic active component at solvent
In, thus the described solution containing catalytic active component is provided.The kind of the compound containing catalytic active component
Class can select according to the kind of solvent, is as the criterion can be dissolved in described solvent.Such as, exist
When described solvent is water, the described compound containing catalytic active component can be water soluble compound.At this
In a kind of embodiment of invention, when described catalytic active component is group VIII metallic element, described contain
The compound of catalytic active component can be that the water solublity with group VIII metal as cation is nonmetal to be contained
Oxygen inorganic acid salt, water-soluble organic acid salt with group VIII metal as cation and with group VIII gold
Belong to for one or more in the water-soluble halide of cation.Preferably, described containing catalysis activity
The compound of component is the nitrate with group VIII metal as cation, with group VIII metal as sun
The acetate of ion, the sulfate with group VIII metal as cation, with group VIII metal as sun
In the subcarbonate of ion and the chloride with group VIII metal as cation one or both with
On.Specifically, the described 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, cobaltous acetate, cobaltous sulfate, basic cobaltous carbonate, cobaltous chloride,
One or more in Nickel dichloride., ruthenic chloride and nitric acid ruthenium.
In the described solution containing catalytic active component, the concentration of catalytic active component can be according to catalyst
The anticipated load amount of middle catalytic active component selects, and is not particularly limited.
The method according to the invention, the load on porous support of the described solution containing catalytic active component
Measure to be able to ensure that the final catalyst prepared is loaded with enough catalytic active component and is as the criterion.Usually,
Described catalytic active component load capacity on described porous carrier makes the catalyst with final preparation
On the basis of total amount, the content of the catalytic active component counted with oxide is for 0.5-60 weight %, preferably 1-50
Weight %, such as 10-30 weight %.
The method according to the invention, the described solution containing catalytic active component can also contain at least one
Catalyst aid component and/or at least one surfactant.
Described catalyst aid component can be such as P elements and/or fluorine element.At described catalyst to taking
Torr synthetic reaction is when having catalytic action, described catalyst aid component can be selected from Li, Na, K, Mg,
Ca, Sr, Cu, Mo, Ta, W, Ru, Zr, Ti, Re, Hf, Ce, Mn, Fe, V and your gold
Belong in (such as one or more in Pt, Pd, Rh and Ir) one or more.
Described catalyst aid component content in the described solution containing catalytic active component is prepared with final
Catalyst there is intended catalyst aid constituent content on the basis of.Usually, with the catalysis of final preparation
On the basis of the total amount of agent, with content containing catalyst aid component described in oxide is counted can be 0.1-30 heavily
Amount %, preferably 0.5-15 weight %, more preferably 1-5 weight %.
When described catalyst has catalytic action to Fischer-Tropsch synthesis, described surfactant can be
One or more in ionic surfactant and nonionic surfactant.Described ion-type
Surfactant includes anionic surfactant, cationic surface active agent and amphoteric ion type table
Face activating agent.The instantiation of described anionic surfactant can include but not limited to carboxylic acid type
Live in (such as soap, potassium oleate etc.) surfactant, sulfonate type (such as sodium alkyl benzene sulfonate etc.) surface
Property agent, sulfuric ester salt form (such as sodium lauryl sulphate etc.) surfactant and phosphate ester salt form (as
C16H33OPO3Na2Deng) surfactant.The instantiation of described cationic surfactant can wrap
Include but be not limited to: ammonium salt type surfactant, quaternary (such as hexadecyltrimethylammonium chloride etc.)
Surfactant.The instantiation of described amphoteric ionic surfactant can include but not limited to Radix Betae
Alkaline surfactant and amino acid type surfactant.The concrete reality of described nonionic surfactant
Example can include but not limited to that polyethylene glycol type surfactant is (such as fatty alcohol-polyoxyethylene ether, alkylbenzene
Phenol polyethenoxy ether, aliphatic acid polyethenoxy ether, polyoxyethylene fatty amine and polyoxyethanyl alkylamide,
Wherein, the repeating segment number n of ethylene oxide repeating units can be conventional selection, usually, n=l-10)
With EPE polyol EPE (such as spreading out of the derivant of sucrose, the derivant of Sorbitol and glyceryl alcohol
Biological etc.).The preferred described surfactant of the present invention is the one in nonionic surfactant or two
More than Zhong.
Described surfactant concentration in the solution containing catalytic active component is preferably 0.01-10 weight
Amount %.
The method according to the invention, after having sprayed, is carried out the porous carrier being loaded with solution obtained
It is dried.Described dry temperature is as the criterion can remove the solvent in load solution on porous support.
Usually, described being dried can be carried out, preferably at a temperature of 60-250 DEG C at a temperature of 50-300 DEG C
Carry out.Described being dried can be carried out at ambient pressure, it is also possible to carries out at reduced pressure.
The present invention one preferred embodiment in, described be dried at normal pressure (that is, 1 standard atmosphere
Pressure) under conditions of carry out, described dry temperature, preferably in the range of 130-230 DEG C, more preferably exists
The scope of 140-160 DEG C.In another preferred embodiment of the present invention, described it is dried at pressure
(counting with gauge pressure) is-0.5kPa to-60kPa, is preferably-5kPa to carrying out under conditions of-45kPa, institute
State dry temperature preferably in the range of 100-220 DEG C, more preferably in the range of 120-160 DEG C.?
Above two is dried down, and the catalyst of preparation has higher shell rate, and
And preparation shell profile catalyst in, shell thickness thinner (that is, along the radial section of catalyst,
Catalytic active component is enriched on the radial section of more outer layer), its reason may is that for spraying
The volume of the solution containing catalytic active component when being not higher than the total pore volume of porous carrier, porous carrier
Core act as the role of adsorption desiccant, absorption solvent in the outer layer solution of porous carrier due to
The trend of capillary condensation effect oriented porous carrier core migration, dissolve in a solvent containing catalysis activity group
The compound divided is the most therewith to core migration, thus affects shell rate；The preferred embodiment party of above two
In formula, the condition of desolvation can be effectively reduced the solvent migration trend to porous carrier core, thus
It is obtained in that higher shell efficiency and thinner shell thickness.
The method according to the invention, the described dry persistent period can enter according to dry temperature and pressure
Row selects, being by whole for the solvent in load solution on porous support or substantially all abjection
Accurate.Usually, the described dry persistent period can be 1-48 hour, preferably 1.5-24 hour,
More preferably 2-10 hour, such as 2-5 hour.
The method according to the invention, from the angle of the shell rate of the catalyst improving preparation further,
Described spraying and described be dried between time interval be preferably no more than 30 minutes, more preferably do not surpass
Spend 10 minutes.
The method according to the invention, the porous carrier of drying can be directly used as catalyst, it is also possible to enters
As catalyst after row roasting.The present invention is not particularly limited for the condition of roasting, can be conventional choosing
Select.Usually, described roasting can be at a temperature of 300-600 DEG C, preferably the temperature of 400-500 DEG C
Under carry out.The persistent period of described roasting can be 1-48 hour, preferably 2-12 hour, more preferably
For 2-4 hour.
Method according to the invention it is possible to interval is carried out, it is also possible to be carried out continuously.The method of the present invention is special
Be not suitable to be carried out continuously, so can divide with the shell that higher production efficiency preparation has higher shell rate
Cloth type catalyst.
The present invention one preferred embodiment in, the method according to the invention is at a kind of preparation system
Middle enforcement, thus prepare shell profile catalyst continuously.Below in conjunction with Fig. 1, this preparation system is carried out
Describe in detail.
Described preparation system includes porous carrier feed unit, solution feed unit, spray unit and is dried
Unit, porous carrier feed unit is used for storing porous carrier and providing porous carrier to spray unit, molten
Liquid feed unit is for storing the solution containing catalytic active component and providing containing catalysis to spray unit
The solution of active component, spray unit is used for the solution spraying containing catalytic active component at porous carrier
Surface, drying unit is for the solution containing catalytic active component of being loaded with that will be exported by spray unit
Porous carrier is dried.
As it is shown in figure 1, porous carrier feed unit includes porous carrier storage tank 11 and is arranged on porous
Pipeline on carrier storage tank 11, described pipeline is used for connecting porous carrier storage tank 11 with spray unit,
Thus porous carrier is sent in spray unit.Can be for connected porous carrier storage tank 11 and spraying
Valve is set on the pipeline of unit, thus the connection of control piper and disconnection.
As it is shown in figure 1, solution feed unit includes solution reservoir 21 and for connecting solution reservoir 21
Pipeline with spray unit.According to specific needs, pump 22 can be set on pipeline to improve conveying
Efficiency, improves the pressure of the solution containing catalytic active component sending into spray unit simultaneously, carries for injection
For necessary pressure.Choke valve can also be set on pipeline, to regulate flow.
As it is shown in figure 1, spray unit includes rotating hollow container 31 and holds for supporting hollow
The pedestal 32 of device 31, hollow container 31 connects with porous carrier feed unit and solution feed unit respectively,
With by the solution spraying containing catalytic active component on porous carrier surface.
Hollow container 31 can have various profile, such as nearly elliposoidal, single taper or shared bottom surface
Biconial.In a preferred embodiment, as it is shown in figure 1, hollow container 31 is for sharing bottom surface
Biconial, now, diconical two vertex of a cones 39 and 310 can be respectively provided with and can close opening,
When charging, at least one opening connects with porous carrier feed unit, makes porous carrier enter hollow and holds
In device 31；When discharging, at least one opening connects with drying unit, makes surface be sprayed-on containing
The porous carrier of the solution of catalytic active component enters in drying unit and is dried.
As it is shown in figure 1, be disposed with spray boom 33 in hollow container 31, spray boom 33 is with solution feed unit even
Logical, for will be active containing catalysis on spray boom 33 at equal intervals or unequal interval arranges multiple atomizer
The solution spraying of component is on porous carrier surface.The bore of described atomizer can be according to intended atomization
The size of drop selects, and usually, the size of described atomizer makes the particle diameter of atomized drop exist
In the range of 1-600 micron, preferably in the range of 20-400 micron, more preferably at 50-300 micron
In the range of, further preferably in the range of 60-200 micron, as in the range of 70-150 micron.
The quantity of spray boom 33 can be one or more.When the quantity of spray boom 33 is one, spray boom 33 can
With serpentine-like bending, so that atomizer can cover the surface of the layer formed by porous carrier, thus more equal
Evenly by the solution spraying containing catalytic active component on porous carrier surface.Quantity at spray boom 33 is
When many, many spray booms 33 can be to arrange along the mode parallel with the rotor shaft direction of hollow container, with
Make atomizer can cover the surface of the layer formed by porous carrier, it is thus possible to will live containing catalysis equably
The solution even application of property component is on porous carrier surface.Can also be for intersecting row between many spray booms 33
Row, as long as can make atomizer cover the surface of the layer formed by porous carrier.Preferably, such as figure
Shown in 1, spray boom 33 can be made along the side of the rotor shaft direction hermetically passing hollow container 31 of hollow container 31
Wall enters the inside of hollow container 31, the sidewall of spray boom 33 and hollow container 31 for being rotatably connected,
Wherein, being positioned on the spray boom 33 within hollow container 31 and arrange described atomizer, spray boom 33 is positioned at
One end outside hollow container 31 can connect with solution feed unit, so can be at hollow container 31
While rotation, spray boom 33 sprays the solution containing catalytic active component when not rotating.
As it is shown in figure 1, hollow container 31 is disposed with vacuum lines 34, with spraying during,
Carry out evacuation.Vacuum lines 34 is arranged near the inwall of hollow container 34, to be filled by bleeding point
In the layer formed by porous carrier, it is thus possible to effectively by timely for disperse steam between porous carrier
Extract out.Vacuum lines 34 can be with the sidewall of hermetically passing hollow container 31, and vacuum lines 34
With the sidewall of hollow container 31 for being rotatably connected, wherein, vacuum lines 34 is positioned at hollow container 31
Internal part can bend according to the inner space of hollow container 31, so that vacuum lines 34
On bleeding point fill in the layer formed by porous carrier.Vacuum lines 34 is positioned at hollow container 31
Outer one end can connect with vacuum pump.Cold-trap can be set between vacuum lines 34 and vacuum pump,
The volatile material being drawn out of with capture, it is to avoid it enters in vacuum pump.In vacuum lines 34 with true
Between empty pump, valve can also be set, to be adjusted the vacuum in hollow container 31 so that it is full
The pre-provisioning request of foot.
As it is shown in figure 1, spray unit preferably also sets up rotary shaft 35 and for driving rotary shaft 35
Driving means, so can rotate hollow container 31 during spraying, so that containing catalysis activity group
The solution divided can be sprayed on porous carrier surface with being more uniformly distributed.Rotary shaft 35 is preferably two, symmetrical
It is arranged on hollow container 31 both sides, and along the rotor shaft direction extension of hollow container 31, with mesopore container 31
For fixing connection.Described driving means can be the various device that rotary shaft 35 can be driven to rotate.?
In a kind of embodiment, as it is shown in figure 1, described driving means includes motor 36 and travelling gear 37,
Motor 36 band nutating gear 37 rotates, and rotating torque passes to rotary shaft 35, thus band disorder of internal organs
Empty 31 rotates.
As it is shown in figure 1, spray unit also includes that distributing device 38, the feed end of distributing device 38 hold with hollow
The discharging opening connection of device 31, discharge end connects with drying unit, exports from hollow container 31 for receiving
The porous carrier being loaded with the solution containing catalytic active component, and be sent in drying unit carry out
It is dried.Distributing device 38 is preferably the cylinder of both ends open, and one end open is towards hollow container 31, with energy
Relative with the discharging opening of hollow container 31, thus accept from hollow container 31 output through spraying many
Hole carrier；Other end opening is towards drying unit, will be transferred to drying unit through the porous carrier of spraying.
Drying unit will be for coming from the solution containing catalytic active component of being loaded with of spray unit
Porous carrier is dried.Drying unit can use conventional various drying devices to be dried.One
In planting preferred embodiment, as described in Figure 1, drying unit includes dry zone 41, and distributing device 38 will
The porous carrier being loaded with the solution containing catalytic active component is delivered to dry zone 41, at dry zone 41
On be dried.The material of dry zone 41 is as the criterion can bear the temperature needed for being dried.
As required, dry zone 41 can be arranged in a housing, be provided for taking out in this housing
The pipeline of vacuum, so can be dried at reduced pressure.
According to specific needs, described preparation system can also include calciner, with the porous to drying
Carrier carries out roasting.Described calciner can be the conventional device being capable of roasting function, does not has
It is particularly limited to.
When the method according to the invention uses above-mentioned preparation system to implement, following operation can be used to enter
OK.
Porous carrier is placed in porous carrier storage tank 11, the solution containing catalytic active component is placed in
In solution reservoir 21.Porous carrier is sent in hollow container 31, carried out by vacuum lines 34
Evacuation, drives hollow container 31 to rotate by rotary shaft 35 simultaneously.By containing catalytic active component
Solution is sprayed on the surface of porous carrier by the atomizer on spray boom 33.After having sprayed, will
The porous carrier being loaded with catalytic active component is delivered to, on dry zone 41, be dried.After being dried,
Alternatively the porous carrier of drying is sent in calciner and carry out roasting.
According to the second aspect of the invention, present invention also offers the shell prepared by the method for the present invention
Profile catalyst.
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 non-uniform Distribution and urges by those skilled in the art
Agent, is called for short egg-shell catalyst, and it is defined as well known to those skilled in the art, such as, may refer to (Zhu
The 199-200 page (petroleum industry in " catalyst carrier preparation and application technology " book that flood method is write
Publishing house May in 2002 the 1st edition) in definition.In the present invention, shell rate is shown by scanning electron
Micro mirror-energy spectrum analysis (i.e. SEM-EDX, Scanning Electron Microscope-Energy
Dispersive Spectrometry) method records.Concrete grammar includes: randomly select 30 catalyst
Catalyst granules is also radially cut by granule, observes the cross section particle diameter of catalyst granules with SEM, it
The radial distribution of catalytic active component is obtained afterwards with EDX radially cross-sectional scans.Due to scanning electron microscope-X
Along counting rate and this element of carrier radially every bit in ray energy spectrum (SEM-EDX) characterization result
Content is the most corresponding, although the size of counting rate may not represent the real content of this element, but remembers
Being sized to of digit rate reflects this constituent content height.Therefore, in order to represent catalytic active component and urge
Change auxiliary agent to introduce distribution factor σ, σ along the carrier regularity of distribution radially and be catalytic active component and catalysis helps
Concentration at the agent heart in the catalyst with a good appetite suddenly appearing in a serious disease heart outside the ratio of concentration of a certain position.It is said that in general,
Described " egg-shell catalyst " refers to: the class catalysis that distribution factor σ is 0≤σ ＜ 0.95 of catalyst
Agent, wherein, on a certain position, concentration is near certain point in addition to central point (position deviation≤20nm)
The meansigma methods of 20 numerical point counting rates；Centered by the concentration of center near point (position deviation≤20nm)
The meansigma methods of 20 numerical point counting rates.Shell of the present invention distribution catalyst refers in catalyst
Active metal component be mainly distributed on shell.30 catalyst granules of test will be distributed for shell
Percentage ratio shared by the granule of type catalyst is referred to as shell rate.Wherein, shell thickness refers to be catalyzed activity group
Point and the distribution factor of catalyst aid meet the thickness of part of 0≤σ ＜ 0.95.
Catalyst according to the invention is particularly suitable as the catalyst of the reaction controlled by internal diffusion, as taken
The catalyst of torr synthetic reaction.
Thus, according to the third aspect of the present invention, present invention also offers a kind of Fischer-Tropsch synthesis method,
Under the conditions of the method is included in Fischer-Tropsch synthesis, synthesis gas is contacted with catalyst, wherein, described in urge
Agent is the shell profile to Fischer-Tropsch synthesis with catalytic action prepared by the method for the present invention
Catalyst.
The catalyst provided according to the present invention, before use, the most in presence of hydrogen, by oxidation state
Active metal component carries out reduction activation.The condition of described reduction activation may include that reduction temperature is permissible
Being 200 DEG C to 1000 DEG C, preferably 200 DEG C to 800 DEG C, the recovery time can be 1-96 hour, excellent
Electing as 2-24 hour, described reduction activation can be carried out in pure hydrogen, it is also possible at hydrogen and noble gas
Mixed gas in carry out, as carried out in hydrogen with the gaseous mixture of nitrogen, Hydrogen Vapor Pressure can be
0.1-4MPa, preferably 0.1-2MPa, described noble gas refers in the conditions of the invention, be not involved in
The gas of chemical reaction, such as nitrogen and group 0 element gas.
According to the Fischer-Tropsch synthesis method of the present invention, the concrete reaction condition for fischer-tropsch reaction limits the most especially
Fixed, can carry out under normal conditions.Specifically, temperature can be 170-350 DEG C, preferably 180-300
℃；Gross pressure can be 1-20MPa, preferably 1.5-15MPa；During the gas of synthesis gas, volume space velocity can
Think 1000-20000h-1, preferably 2000-18000h-1。
Describe the present invention in detail below in conjunction with embodiment, but and be not so limited the present invention.
In following example and comparative example, use the catalyst of x-ray fluorescence spectrometry method mensuration preparation
Composition.
In following example and comparative example, by scanning electron microscope-energy spectrum analysis (i.e.,
SEM-EDX, Scanning Electron Microscope-Energy Dispersive Spectrometry) side
Method determines the catalytic active component distribution along porous carrier radial direction, and calculates shell rate.
In following example and comparative example, Malvern Particle Size Analyzer is used to measure the size of atomized drop,
For volume average particle size.
In following example and comparative example, use following methods to determine in spraying process, in hollow container by
Solvent produce dividing potential drop use following methods measure: filling porous carrier after and spraying start before, centering
Empty carries out evacuation until relative vacuum degree in hollow container is stable, using this relative vacuum degree as
Benchmark relative vacuum degree, by between the relative vacuum degree measured in spraying process and benchmark relative vacuum degree
Difference is as the dividing potential drop produced by solvent.
In following example, the preparation system shown in Fig. 1 is used to prepare catalyst, wherein, hollow container
31 for sharing the biconial of bottom surface, and its most a length of 2 meters, radially internal diameter is 2.7 meters).
Embodiment 1-12 is used for the present invention is described.
Embodiment 1
1, (particle length is 2-4 to the butterfly gama-alumina granule extruded by 1.6mm orifice plate by 200kg
Millimeter, measuring its water absorption rate is 0.8 ml/g) as catalyst carrier and put into porous carrier storage tank 11
In.
2, cobalt nitrate is dissolved in the water, be configured to solution containing catalytic active component (in terms of CoO,
The concentration of cobalt nitrate is 330 grams per liters) and be placed in solution reservoir 21.
3, being sent into by porous carrier in hollow container 31, (velocity of rotation is 3.5 to rotate hollow container 31
Rev/min), start vacuum pump simultaneously and hollow container 31 is carried out evacuation (wherein, in hollow container
Along rotor shaft direction, being equidistantly spaced from 3 vacuum lines, the bleeding point in every vacuum lines is all filled out
It is embedded in the layer formed by porous carrier and bleeding point is to be spacedly distributed along vacuum lines, bleeding point
Towards the inwall of carrying porous carrier, i.e. bleeding point is down), by steady for the relative vacuum degree in hollow container
It is set to-50kPa (that is, benchmark relative vacuum degree).Then, the rotation condition of hollow container 31 is maintained not
Become, with evacuation, in hollow container 31, send into the solution containing catalytic active component, will contain
The solution of catalytic active component is sprayed on porous carrier surface by atomizer with the form of atomized drop.
Wherein, the straying quatity V of the solution containing catalytic active componentLTotal pore volume V with porous carrierCRatio
Value meets VL/VC=0.5, the size of atomized drop is 80 μm；Temperature in hollow container is 25 DEG C,
In spraying process, the condition adjusting evacuation makes aquagenic dividing potential drop be up to 3kPa；Porous carrier
The time of staying in hollow container 31 is 30 minutes.
4, after having impregnated, in 5 minutes, sample after dipping is all sent on dry zone 41 and carry out
Being dried, wherein, be dried and carry out at ambient pressure, temperature is 160 DEG C, and after dipping, sample is at dry zone 41
On the time of staying be 4 hours.
5, by dried sample at a temperature of 450 DEG C, roasting 4 hours, thus obtain catalyst.
Composition and the shell rate of this catalyst are listed in Table 1, along porous carrier radial section by outer layer extremely
Core, the percentage contents of cobalt element is listed in table 2.
Comparative example 1
Method same as in Example 1 is used to prepare catalyst, except for the difference that, in step 3, spraying
During, it is not turned on vacuum pump, i.e. during spraying, does not carry out evacuation.
Composition and the shell rate of the catalyst of preparation are listed in Table 1.
Comparative example 2
Method same as in Example 1 is used to prepare catalyst, except for the difference that, in step 3, containing urging
Change the straying quatity V of the solution of active componentLTotal pore volume V with porous carrierCRatio meet VL/VC
=1.0, in the solution containing catalytic active component, in terms of CoO, the concentration of cobalt nitrate is 165 grams per liters.
Composition and the shell rate of the catalyst of preparation are listed in Table 1.
Comparative example 3
Use method same as in Example 1 to prepare catalyst, except for the difference that, in hollow container 31 not
Vacuum lines 34 is set, wherein, is an opening for the position through vacuum lines 34, spraying
During, this opening is unlimited.
Composition and the shell rate of the catalyst of preparation are listed in Table 1.
Comparative example 4
Use method same as in Example 1 to prepare catalyst, except for the difference that, use the dress shown in Fig. 2
Putting and prepare catalyst, the device shown in Fig. 2 is with the difference of the device shown in Fig. 1, vacuum lines
Bleeding point on 34 does not fill in the layer that porous carrier is formed.
Composition and the shell rate of the catalyst of preparation are listed in Table 1.
Embodiment 2
Method same as in Example 1 is used to prepare catalyst, except for the difference that, in step 3, spray coated
Cheng Zhong, does not adjust the condition of evacuation, and aquagenic dividing potential drop is up to 20kPa.
Composition and the shell rate of the catalyst of preparation are listed, in Table 1 along the radial section of porous carrier
By outer layer to core, the percentage contents of cobalt element is listed in table 2.
Embodiment 3
Use method same as in Example 1 to prepare catalyst, except for the difference that, in step 4, be dried
Temperature is 120 DEG C.
Composition and the shell rate of the catalyst of preparation are listed, in Table 1 along the radial section of porous carrier
By outer layer to core, the percentage contents of cobalt element is listed in table 2.
Embodiment 4
Use method same as in Example 1 to prepare catalyst, except for the difference that, in step 4, be dried
Carrying out under conditions of decompression, pressure (gauge pressure) is-45kPa, and temperature is 160 DEG C.
Composition and the shell rate of the catalyst of preparation are listed, in Table 1 along the radial section of porous carrier
By outer layer to core, the percentage contents of cobalt element is listed in table 2.
Embodiment 5
1, (particle length is 2-4 to the butterfly gama-alumina granule extruded by 1.6mm orifice plate by 200kg
Millimeter, measuring its water absorption rate is 1.0 mls/g) as catalyst carrier and put in carrier storage tank 11.
2, ammonium molybdate, ammonium metatungstate, nickel nitrate and phosphoric acid are dissolved in the water, are configured to containing catalysis
Solution (the MoO of active component3Concentration be 225 grams per liters, WO3Concentration be 99 grams per liters, NiO
Concentration be 50 grams per liters, the concentration of P elements is 39 grams per liters) and be placed in solution reservoir 21.
3, being sent into by porous carrier in hollow container 31, (velocity of rotation is 4 to rotate hollow container 31
Rev/min), start vacuum pump simultaneously and hollow container 31 is carried out evacuation (wherein, in hollow container
Along rotor shaft direction, it is equidistantly spaced from 3 vacuum lines, the bleeding point landfill in every vacuum lines
In the layer formed by porous carrier and bleeding point is to be spacedly distributed along vacuum lines, bleeding point court
To the inwall of carrying porous carrier, i.e. bleeding point is down), the relative vacuum degree in hollow container is stable
For-60kPa (that is, benchmark relative vacuum degree).Then, the rotation condition maintaining hollow container 31 is constant,
With evacuation, in hollow container 31, send into the solution containing catalytic active component, will be containing catalysis
The solution of active component is sprayed on porous carrier surface by atomizer with the form of atomized drop.Its
In, the straying quatity V of the solution containing catalytic active componentLTotal pore volume V with porous carrierCRatio
Meet VL/VC=0.5, the size of atomized drop is 120 μm；Temperature in hollow container is 50 DEG C,
In spraying process, the condition adjusting evacuation makes aquagenic dividing potential drop be up to 10kPa；Porous carries
The body time of staying in hollow container 31 is 19 minutes.
4, after having impregnated, in 10 minutes, sample after dipping is sent on dry zone 41 and do
Dry, wherein, it is dried and carries out at ambient pressure, temperature is 140 DEG C, porous carrier stopping on dry zone 41
Staying the time is 5 hours.
5, by dried sample at a temperature of 450 DEG C, roasting 4 hours, thus obtain catalyst.
Composition and the shell rate of this catalyst are listed in Table 1, along the radial section of porous carrier by outward
Layer is to core, and the percentage contents of molybdenum element is listed in table 2.
Comparative example 5
Method same as in Example 5 is used to prepare catalyst, except for the difference that, during spraying, no
Open vacuum pump, i.e. during spraying, do not carry out evacuation.
Composition and the shell rate of the catalyst of preparation are listed in Table 1.
Comparative example 6
Use method same as in Example 5 to prepare catalyst, except for the difference that, use the dress shown in Fig. 2
Putting and prepare catalyst, the device shown in Fig. 2 is with the difference of the device shown in Fig. 1, vacuum lines
Bleeding point on 34 does not fill in the layer that porous carrier is formed.
Composition and the shell rate of the catalyst of preparation are listed in Table 1.
Embodiment 6
1, (particle length is 2-4 to the butterfly gama-alumina granule extruded by 1.6mm orifice plate by 200kg
Millimeter, measuring its water absorption rate is 1.0 mls/g) as catalyst carrier and put into porous carrier storage tank 11
In.
2, ammonium metatungstate and nickel nitrate are dissolved in the water, are configured to the solution containing catalytic active component
(WO3Concentration be 402 grams per liters, the concentration of NiO is 25 grams per liters) and be placed on solution reservoir
In 21.
3, being sent into by porous carrier in hollow container 31, (velocity of rotation is 3.5 to rotate hollow container 31
Rev/min), start vacuum pump simultaneously and hollow container 31 is carried out evacuation (wherein, in hollow container
Along rotor shaft direction, it is equidistantly spaced from 3 vacuum lines, the bleeding point landfill in every vacuum lines
In the layer formed by porous carrier and bleeding point is to be spacedly distributed along vacuum lines, bleeding point court
To the inwall of carrying porous carrier, i.e. bleeding point is down), the relative vacuum degree in hollow container is stable
For-70kPa (that is, benchmark relative vacuum degree).Then, the rotation condition maintaining hollow container 31 is constant,
With evacuation, in hollow container 31, send into the solution containing catalytic active component, will be containing catalysis
The solution of active component is sprayed on porous carrier surface by atomizer with the form of atomized drop.Its
In, the straying quatity V of the solution containing catalytic active componentLTotal pore volume V with porous carrierCRatio
Meet VL/VC=0.4, the size of atomized drop is 100 μm；Temperature in hollow container is 50 DEG C,
In spraying process, the condition adjusting evacuation makes aquagenic dividing potential drop be up to 7kPa；Porous carrier
The time of staying in hollow container 31 is 24 minutes.
4, after having impregnated, in 6 minutes, sample after dipping is all sent on dry zone 41 and carry out
Being dried, wherein, be dried and under reduced pressure carry out, pressure (for gauge pressure) is-8kPa, and temperature is 120 DEG C,
The porous carrier time of staying on dry zone 41 is 2 hours.
5, by the porous carrier of drying at a temperature of 500 DEG C, roasting 2 hours, thus be catalyzed
Agent.Composition and the shell rate of this catalyst are listed in Table 1, along the radial section of porous carrier by outward
Layer is to core, and the percentage contents of wolfram element is listed in table 2.
Comparative example 7
Method same as in Example 6 is used to prepare catalyst, except for the difference that, during spraying, no
Open vacuum pump, i.e. during spraying, do not carry out evacuation.
Composition and the shell rate of the catalyst of preparation are listed in Table 1.
Comparative example 8
Use method same as in Example 6 to prepare catalyst, except for the difference that, use the dress shown in Fig. 2
Putting and prepare catalyst, the device shown in Fig. 2 is with the difference of the device shown in Fig. 1, vacuum lines
Bleeding point on 34 does not fill in the layer that porous carrier is formed.The composition of the catalyst of preparation and shell
Layer rate is listed in Table 1.
Embodiment 7
Use method same as in Example 6 to prepare catalyst, except for the difference that, in step 4, be dried
Temperature is 80 DEG C.
Composition and the shell rate of the catalyst of preparation are listed, in Table 1 along the radial section of porous carrier
By outer layer to core, the percentage contents of wolfram element is listed in table 2.
Embodiment 8
Method same as in Example 6 is used to prepare catalyst, except for the difference that, in step 3, bleeding point
For carrying the inwall of porous carrier dorsad (that is, with the injection direction phase of the solution containing catalytic active component
Right, i.e. bleeding point is upward).Composition and the shell rate of the catalyst of preparation are listed in Table 1, along many
The radial section of hole carrier is listed in table 2 by outer layer to core, the percentage contents of wolfram element.
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 using the method for the present invention to prepare has higher shell
Layer rate, it is thus possible to repeat stably to prepare shell profile catalyst so that the catalyst of preparation has surely
Fixed catalysis activity.
Embodiment 1 is entered with comparative example 8 with comparative example 6, embodiment 6 with comparative example 4, embodiment 5
If row compares it can be seen that the bleeding point of vacuum lines does not fill at the layer formed by porous carrier
In, the shell rate still ratio of the catalyst of preparation is relatively low, and its reason may is that generation in adsorption process
Solvent vapour is embedded in the layer formed by porous carrier, it is impossible to extracted out in time, even and if being taken out
Sucking out, steam is also required to through the layer formed by porous carrier, thus cannot eliminate in time and thus produce
Negative effect.
Table 2
*: along the radial section of catalyst, scan to core from outermost layer with EDX radially cross section, take 5 points at equal intervals and measure respectively
The concentration of catalytic active component at each point, obtains the ratio of aluminium element concentration at the concentration of each catalytic active component and this point.
Embodiment 9-12
Following method is used to test the performance of the catalyst prepared by embodiment 1-4.
Test process is carried out in fixed bed Fischer-Tropsch synthesis device, and catalyst amount is 5 grams.
Catalyst reduces before use.Reduction is carried out at ambient pressure, and other condition is: hydrogen flowing quantity
For 1000NL/ (g-cat h), it is warming up to 400 DEG C with the heating rate of 4 DEG C/min, keeps 5h.
Fischer-Tropsch synthesis temperature is 220 DEG C, H2/ CO ratio is 2, and pressure is 2.5MPa, gas space
Speed (GHSV) is 2000h-1.Result is listed in table 3.
Comparative example 9-12
The method identical with embodiment 9-12 is used to test the performance of the catalyst prepared by comparative example 1-4.
Result is listed in table 3.
Table 3
In table 3, XCORepresent the conversion ratio of CO,WithRepresent C respectively5Above (containing C5)
The selectivity of hydro carbons and CH4Selectivity.It is specifically defined the expression formula seen below:
Wherein, V1And V2It is illustrated respectively under the status of criterion, in certain time period, enters the raw material of response system
The volume of gas and the exhaust gas volumes of outflow response system；c1And c2Represent corresponding in unstripped gas and tail gas respectively
The content of material.nconFor being participated in the molal quantity of the CO of reaction in certain time period by reaction bed,For
Change into CO2The molal quantity of CO,For changing into CH4The molal quantity of CO,For changing into
CH4、C2Hydrocarbon, C3Hydrocarbon and C4The molal quantity of the CO of hydrocarbon.
From the results shown in Table 3, the catalyst pair that the preparation method using the present invention to provide prepares
C5+Hydro carbons has higher selectivity, relatively low to the selectivity of methane, can also obtain higher CO simultaneously
Conversion ratio.
Claims (16)
1. a preparation method for shell profile catalyst, the method comprises the following steps:
(1) porous carrier is placed in hollow container, the solution spraying containing catalytic active component is existed
Described porous carrier surface, total quantity for spray of described solution is less than the total pore volume of described porous carrier,
In spraying process, described hollow container is carried out evacuation, and for the bleeding point of evacuation be arranged in by
In the layer that porous carrier is formed；
(2) porous carrier being loaded with solution that step (1) obtains is dried and optionally roasts
Burn.
Method the most according to claim 1, wherein, described solution sprays with the form of atomized drop
Being coated in porous carrier surface, the condition of described spraying makes the average diameter of the atomized drop formed exist
In the range of 1-600 micron, preferably in the range of 20-400 micron, more preferably at 50-300 micron
In the range of.
Method the most according to claim 1 and 2, wherein, total quantity for spray of described solution is VL,
The total pore volume of described porous carrier is VC, VL/VC=0.01-0.99；Preferably, VL/VC=0.1-0.8.
4. according to the method described in any one in claim 1-3, wherein, during spraying,
Porous carrier is made to be in the state of motion；During described motion is preferably vibrated, rolls, stirs and is slided
One or more combination.
5. according to the method described in any one in claim 1-3, wherein, during spraying,
Rotate described hollow container.
6. according to the method described in any one in claim 1-5, wherein, the bar of described evacuation
Part make relative vacuum degree in hollow container in the range of-10kPa to-100kPa, preferably at-30kPa
To-95kPa, more preferably in the range of-40kPa to-80kPa.
7. according to the method described in any one in claim 1-6, wherein, the journey of described evacuation
Degree make the dividing potential drop produced by the solvent in described solution in hollow container in the range of 0 to 30kPa,
Preferably so that the dividing potential drop produced by the solvent in described solution is not higher than 20kPa, more preferably make by institute
The dividing potential drop stating the solvent generation in solution is not higher than 10kPa.
Method the most according to claim 1, wherein, described is dried at a temperature of 50-300 DEG C
Carry out, preferably carry out at a temperature of 60-250 DEG C.
9. according to the method described in claim 1 or 8, wherein, described roasting is the temperature of 300-600 DEG C
Carry out under degree.
10. according to the method described in any one in claim 1-9, wherein, described porous carrier is
In silicon oxide, aluminium oxide, silica-alumina, aluminium silicate, titanium oxide, zirconium oxide and activated carbon
One or more.
11. according to the method described in any one in claim 1-10, wherein, and described solution molten
Agent is water.
12. according to the method described in any one in claim 1-11, and wherein, described shell is distributed
Type catalyst has catalytic action to Fischer-Tropsch synthesis.
13. methods according to claim 12, wherein, described catalytic active component is selected from VIII
One or more in race's metallic element, preferably ferrum, cobalt and ruthenium.
14. according to the method described in any one in claim 1,12 and 13, wherein, described work
Property component load capacity on described porous carrier make on the basis of the total amount of the catalyst of final preparation,
The content of the catalytic active component counted with oxide for 0.5-60 weight %, preferably 1-50 weight %.
The shell profile that 15. 1 kinds are prepared by the method described in any one in claim 1-14 is urged
Agent.
16. 1 kinds of Fischer-Tropsch synthesis methods, under the conditions of the method is included in Fischer-Tropsch synthesis, by synthesis gas
Contact with catalyst, it is characterised in that described catalyst is for by any one institute in claim 12-14
Shell profile catalyst prepared by the method stated.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855057A (en) * | 2017-05-16 | 2018-11-23 | 中国石油化工股份有限公司 | Shell profile catalyst and preparation method thereof and Fischer-Tropsch synthesis method |
| CN114425446A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Shell-layer distributed catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0178008A1 (en) * | 1984-10-04 | 1986-04-16 | Shell Internationale Researchmaatschappij B.V. | Catalyst preparation |
| CN1736604A (en) * | 2005-07-27 | 2006-02-22 | 北京化工大学 | Egg shell type metal catalyst, its preparing process and application method |
| CN101143325A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院大连化学物理研究所 | Method for preparing catalyst and application thereof |
| CN101462079A (en) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | Method for preparing catalyst with lamella distribution |
| WO2011028466A2 (en) * | 2009-08-24 | 2011-03-10 | University Of South Florida | Eggshell catalyst and method of its preparation |
| CN102451722A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of eggshell-type hydrogenation catalyst |
| CN103769235A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Shell distributed catalyst and application thereof |
-
2015
- 2015-01-12 CN CN201510015265.3A patent/CN105833869B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0178008A1 (en) * | 1984-10-04 | 1986-04-16 | Shell Internationale Researchmaatschappij B.V. | Catalyst preparation |
| CN1736604A (en) * | 2005-07-27 | 2006-02-22 | 北京化工大学 | Egg shell type metal catalyst, its preparing process and application method |
| CN101143325A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院大连化学物理研究所 | Method for preparing catalyst and application thereof |
| CN101462079A (en) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | Method for preparing catalyst with lamella distribution |
| WO2011028466A2 (en) * | 2009-08-24 | 2011-03-10 | University Of South Florida | Eggshell catalyst and method of its preparation |
| CN102451722A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of eggshell-type hydrogenation catalyst |
| CN103769235A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Shell distributed catalyst and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| CHUN CHEN ET AL.: ""Fischer–Tropsch synthesis over one eggshell-type Co/SiO2 catalyst in a slurry phase reactor"", 《APPLIED CATALYSIS A: GENERAL》 * |
| E. PELUSO ET AL.: ""Eggshell catalyst in Fischer-Tropsch synthesis Intrinsic reaction kinetics", 《CHEMICAL ENGINEERING SCIENCE》 * |
| SAJAD KARIMI MAZIDI ET AL.: ""Optimization of Fischer-Tropsch Process in a Fixed-Bed Reactor Using Non-uniform Catalysts"", 《CHEMICAL ENGINEERING TECHNOLOGY》 * |
| SYED ALI GARDEZI ET AL.: ""Effect of catalyst preparation conditions on the performance of eggshell cobalt/SiO2 catalysts for Fischer–Tropsch synthesis"", 《APPLIED CATALYSIS A: GENERAL》 * |
| 马春景 等: ""蛋壳型催化剂结构、制备方法及其催化性能影响因素分析"", 《化学反应工程与工艺》 * |
| 鲁丰乐 等: ""蛋壳型钴基催化剂的费托合成反应性能"", 《石油化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855057A (en) * | 2017-05-16 | 2018-11-23 | 中国石油化工股份有限公司 | Shell profile catalyst and preparation method thereof and Fischer-Tropsch synthesis method |
| CN108855057B (en) * | 2017-05-16 | 2021-01-08 | 中国石油化工股份有限公司 | Shell layer distribution type catalyst, preparation method thereof and Fischer-Tropsch synthesis method |
| CN114425446A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Shell-layer distributed catalyst and preparation method and application thereof |
| CN114425446B (en) * | 2020-09-25 | 2023-11-10 | 中国石油化工股份有限公司 | Shell distributed catalyst and preparation method and application thereof |
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