CN106607055A - Shell-distributed catalyst, and preparation method and applications thereof - Google Patents
Shell-distributed catalyst, and preparation method and applications thereof Download PDFInfo
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- CN106607055A CN106607055A CN201510707785.0A CN201510707785A CN106607055A CN 106607055 A CN106607055 A CN 106607055A CN 201510707785 A CN201510707785 A CN 201510707785A CN 106607055 A CN106607055 A CN 106607055A
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Abstract
The invention belongs to the field of catalyst, and more specifically provides a shell-distributed catalyst, and a preparation method and applications thereof. The shell-distributed catalyst comprises a carrier, and a modification accessory ingredient and an active ingredient loaded on the carrier; the modification accessory ingredient comprises a first part and a second part; the first part of the modification accessory ingredient are uniformly distributed on the carrier; the active ingredient and the second part of the modification accessory ingredient are distributed on the carrier in a shell manner; the particle size of the carrier ranges from 0.1 to 1.5mm. The shell-distributed catalyst possesses relatively high C<5+> selectivity and relatively low methane selectivity, and relatively high hydrothermal stability, and is especially suitable for Fischer-Tropsch synthesis used for producing middle and heavy alkanes. The shell-distributed catalyst is especially suitable for microchannel reactors; in application of the shell-distributed catalyst in microchannel reactors, reaction activity is high, reaction pressure drop is low, catalyst strength is high, and it is beneficial for loading and unloading of the shell-distributed catalyst.
Description
Technical field
The present invention relates to a kind of shell distribution catalyst, a kind of preparation method of shell distribution catalyst and
The shell is distributed application of the catalyst in Fischer-Tropsch synthesis.
Background technology
In fixed bed reactors, Fischer-Tropsch synthesis are a gas-solid-liquid multiphase reaction systems.It is fixed
Although bed F- T synthesis are considered as " gas phase reaction ", but the generation because of F- T synthesis medium high carbon product and hair
Thin condensation effects, the heavy hydrocarbon product generated in course of reaction is generally filled in the form of liquid phase wax urges
In catalyst particles duct, and it is covered in the surface of catalyst.So, when catalyst granules is more than a scale
When very little, each reactive component of F- T synthesis will have a strong impact on chemical reaction rate in the diffusion of intragranular liquid phase
With the selectivity of product, spread impact of the control to catalytic performance and be difficult to avoid that.In the internal diffusion of reactant
During, H2Diffusion velocity it is faster than the diffusion velocity of CO, therefore, CO is inside catalyst granules
Diffusion-restricted effect be significantly stronger than H2.As the particle diameter of catalyst granules is different, result in inside granule
The difference of CO Concentraton gradient, have impact on the combination of CO and metal active centres position so that in activity
The H/C for adsorbing in the heart is reduced than increase, carbon chain growth probability, thus reduces C5+Selectivity.
US4599481 discloses a kind of method for reacting production hydrocarbon with hydrogen catalysis by carbon monoxide, the method
Under conditions of being included in temperature and being 5-100 bars (bar) for 125-350 DEG C and pressure, by carbon monoxide with
Hydrogen and catalyst contact, the catalyst contain carrier and load cobalt on this carrier, and the cobalt exists
Distribution on carrier meets (∑ Vp/ ∑ Vc) ＜ 0.85, wherein, ∑ Vc represents the totality of catalyst granules
Product, ∑ Vp are shell volume in catalyst.The preparation method of the catalyst is first to use water treatment carrier, it
After impregnate cobalt nitrate solution, then be dried and roasting.Research shows, when the cobalt in shell content about
For 90% when, catalyst has high activity and selectivity.
The prior art indicate that, for the catalyst that active component is evenly distributed, non-uniform Distribution
Catalyst (as eggshell type distribution catalyst), as diffusion-restricted is little, can significantly increase such as expense
C in this kind of reaction of support synthesis5+Selectivity, and the selectivity of methane is reduced, it is particularly suited for Fischer-Tropsch conjunction
Into this kind of reaction.
Between 1-10 millimetres longer, micro passage reaction has mass-and heat-transfer speed to the internal diameter of micro passage reaction
Hurry up, the focus such as reaction efficiency height is obtaining application in petrochemical industry.Fischer-Tropsch synthesis have
Strongly exothermic, product molecular carbon chain length is difficult to the features such as diffusing out reaction environment, and micro passage reaction can
Fischer-Tropsch synthesis are applied to as process intensification means, improve reaction efficiency.
The checking device runed by the member Velocys companies of the U.S. of SGCE and Oxford catalyst group jointly
Employ Fischer-Tropsch microchannel reactor (the single microchannel plate being made up of the microchannel of more than 900 total lengths
Device combination block size is answered to be 60cm X 60cm X 60cm), the reactor was run from July, 2010, mat
Help I L catalyst and can produce the Fischer-Tropsch liquids synthesized more than 0.75kg/h high-quality, its production efficiency is than normal
Rule system is high 4-8 times, the characteristics of the checking device is：It is close to the temperature of reactor distribution of isothermal, pressure drop
It is low, high-quality synthetic fuel (a values can be produced>0.9), shutting down is convenient.Using by Oxford catalyst collection
Group exploitation new fischer-tropsch catalysts, the conversion per pass of Velocys microchannels fischer-tropsch reactor up to 70%,
And the typical conversion per pass of Fischer Tropsch Facility of routine is below 50%.
CN1906271A is disclosed using the Fiscber-Tropscb synthesis and new catalyst of microchannel and micro-
Channel reactor, the invention are related to a kind of for will be including H2Bag is converted into the response composite of CO
At least one method with least about product of the aliphatic hydrocarbon of 5 carbon atoms is included, it is described
Method includes：The response composite is flow through micro passage reaction and is contacted with Fischer-Tropsch catalyst, by institute
State response composite and change into product, the micro passage reaction includes that the process in a large number containing catalyst is micro-
Passage；Heat is transferred to into heat exchanger from the process microchannel；And by the product from described micro- logical
Road reactor is removed；Every gram of catalyst of methods described produces at least about 0.5 gram per hour with least about 5
The aliphatic hydrocarbon of individual carbon atom；In the product, the selectivity of methane is below about 25%.
The invention further relates to a kind of loaded catalyst comprising Co, and including an at least process microchannel and
The micro passage reaction of at least one adjacent heat exchange zone.
As F- T synthesis can generate substantial amounts of water, during real reaction, catalyst is in similar hydro-thermal
Under conditions of, through the operating of a period of time, the physical property and structure of catalyst is it may happen that change, urges
The mechanical strength of agent may be deteriorated.For the catalyst of non-uniform Distribution, due to catalyst difference position
The hydrothermal stability put is different, is likely to result in the rupture and crushing of catalyst.This phenomenon may urged
The regeneration of agent easily occurs when drawing off.Therefore, it is necessary to seek a kind of with higher hydro-thermal
Stability and C5+Selectivity the fischer-tropsch reaction catalyst with relatively low methane selectively.
The content of the invention
The invention aims to overcome using existing non-uniform Distribution fischer-tropsch synthetic catalyst not
Higher hydrothermal stability and C can be had concurrently5+The defect of selectivity and relatively low methane selectively, and carry
For a kind of new shell distribution catalyst, a kind of preparation method of shell distribution catalyst and the shell
Distribution application of the catalyst in Fischer-Tropsch synthesis.
To realize object defined above, according to the first aspect of the invention, the invention provides a kind of distribution of shell
Catalyst, the shell distribution catalyst include carrier and load modified additive on the carrier and work
Property component, the modified additive include Part I and Part II, and the Part I modified additive exists
It is evenly distributed on the carrier, the active component and the Part II modified additive are in the carrier
Upper to be distributed in shell, the particle diameter of the carrier is 0.1-1.5mm.
According to the second aspect of the invention, the invention provides a kind of shell distribution catalysis of the present invention
The preparation method of agent, the method are comprised the following steps：
(1) by the first solution impregnating carrier containing Part I modified additive source, then it is dried
And roasting, wherein, the species for controlling the condition and the first solution of dipping causes Part I modified additive equal
Even distribution on the carrier, obtains being loaded with the carrier of Part I modified additive；
(2) will bear described in the second solution impregnation containing active component source and Part II modified additive source
The carrier of Part I modified additive is loaded with, is then dried and roasting, wherein, control the bar of dipping
The species of part and the second solution causes active component and Part II modified additive to exist with shell formal distribution
On the carrier.
According to the third aspect of the invention we, the invention provides shell of the present invention distribution catalyst exists
Application in Fischer-Tropsch synthesis.
The present inventor has found that through further investigation coordinating the modified additive and active component makes
With, and Part I modified additive is evenly distributed on carrier, while by Part II modified additive with
With shell formal distribution on carrier, the catalyst for enabling to both had had higher the active component
C5+Selectivity and relatively low methane selectively, and with higher hydrothermal stability, be particularly suitable for
By the Fischer-Tropsch synthesis in production, for the purpose of heavy paraffins.
The catalyst of the present invention is particularly suitable for micro passage reaction, used in micro passage reaction
The catalyst of the present invention, not only high reactivity, and, catalyst strength little with reaction pressure drop
It is good, be conducive to the filling of catalyst and the advantage such as draw off.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is that the shell that embodiment 5 is obtained is distributed catalyst A5, the shell of the reference that comparative example 3 is obtained
The XRD spectra of layer distribution catalyst DA3 and gamma-aluminium oxide carrier.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
As it was previously stated, the invention provides a kind of shell distribution catalyst, the shell is distributed catalyst to be included
Carrier and load modified additive on the carrier and active component, the modified additive include first
Part and Part II, the Part I modified additive are evenly distributed on the carrier, the work
Property component and the Part II modified additive on the carrier in shell be distributed, the granule of the carrier
A diameter of 0.1-1.5mm.
In the present invention, the modified additive and active component can be present with oxidation state or simple substance, in this regard,
Those skilled in the art know that the present invention is not explained in detail.
" shell distribution catalyst " is generally also referred to as eggshell type non-uniform Distribution and is urged by those skilled in the art
Agent, abbreviation egg-shell catalyst, its definition are known to the skilled person, for example, may refer to (Zhu
What big vast method was write《Catalyst carrier is prepared and application technology》The 199-200 page (petroleum industry in book
Publishing house's May in 2002 the 1st edition) in definition.Due to scanning electron microscope-X-ray energy spectrum (SEM-EDX)
Counting rate in characterization result along carrier radial direction every bit is mutually corresponding with the constituent content, although numeration
The size of rate may not represent the real content of the element, but counting rate be sized to reflect the point
Constituent content height.Therefore, in order to represent active component along carrier radial direction the regularity of distribution introduce distribution because
Sub- σ, σ be active component in the catalyst at the heart at concentration and a certain position concentration ratio.In general,
" egg-shell catalyst " is referred to：The distribution factor σ of catalyst is a class catalyst of 0≤σ ＜ 0.95,
Wherein, on a certain position, concentration is certain point neighbouring (position deviation≤20nm) 20 in addition to central point
The meansigma methodss of numerical point counting rate；(position deviation≤20nm) 20 nearby are put centered on the concentration of center
The meansigma methodss of numerical point counting rate.Shell distribution catalyst of the present invention refers to the work in catalyst
Property component and Part II modified additive are mainly distributed on shell, wherein, shell thickness refers to the activity
The distribution factor of component is the thickness of 0≤σ ＜, 0.95 parts.Shell is commonly referred to as according to this area shell
The higher part of concentration of component in the conventional definition of distribution.
Catalyst according to the invention, preferably in terms of oxide, the Part I modified additive with it is described
The weight ratio of Part II modified additive is (0.1-1000):1, preferably (1-500):1, more preferably
For (2-100):1.Using aforesaid weight ratio, the hydrothermal stability of catalyst can be further improved.
Catalyst according to the invention, is preferably counted with oxide and with the gross weight of the catalyst as base
Standard, the content of the active component is 1-60 weight %, preferably 2-50 weight %, more preferably 10-50
Weight %；The content of the Part I modified additive is 0.1-20 weight %, preferably 0.2-15 weight
%, more preferably 0.5-5 weight %；The content of the Part II modified additive is 0.001-1 weight %,
Preferably 0.005-0.8 weight %, more preferably 0.01-0.5 weight %.
The present invention is not particularly limited to the shape of the carrier, can be existing variously-shaped, example
Such as, can be preferably spherical for spherical, piece dosage form, bar shaped etc..The particle diameter of the carrier is preferred
For 0.2-0.5mm, most preferably 0.25-0.3mm.
Catalyst according to the invention, the shell thickness of preferably described shell distribution is 0.01-0.6mm,
More preferably 0.03-0.5mm, most preferably 0.05-0.3mm.Wherein, the shell thickness refers to described
The distribution factor σ of active component is the thickness of 0≤σ ＜, 0.95 parts.
In the present invention, the thickness of the shell is measured using SEM-EDX, specifically：Randomly select
30 shell distribution catalyst simultaneously measure its cross-sectional view and particle diameter with SEM, are distinguished with EDX afterwards
Obtain the radial distribution of active component and obtain 0≤σ ＜ 0.95 along each shell distribution catalyst radial scan
Partial thickness, the arithmetic mean of instantaneous value for taking above-mentioned thickness are the thickness of shell of the present invention.
According to catalyst of the present invention, wherein, as long as shell distribution catalyst has the present invention
Foregoing features there is the little advantage of good hydrothermal stability and diffusion-restricted, which can be each
Plant the catalyst of purposes, for example, Hydrobon catalyst, catalytic reforming catalyst, the catalysis of aromatic hydrocarbons saturation
One or more in agent and fischer-tropsch synthetic catalyst.
One kind of the invention preferred embodiment, urge for F- T synthesis by the shell distribution catalyst
Agent, the modified additive are fischer-tropsch synthetic catalyst modified additive, and the active component is that Fischer-Tropsch is closed
Into catalyst active component.
The present invention is not particularly limited to the species of the modified additive, and reaction that can be as needed is entered
Row is selected.For example, for shell distribution catalyst is fischer-tropsch synthetic catalyst, the modified additive
The Ith A races metallic element, the IIth A races metallic element, group IIIA metallic element, the IVth A can be selected from
Race's element, the Vth A races element, the Ith B races metallic element, the IVth B races metallic element, group VIB
Metallic element, the VIIth B races metallic element, group VIII metal element, the Vth race's metallic element and group of the lanthanides gold
Category element in one or more, be preferably selected from lithium, potassium, magnesium, calcium, strontium, copper, molybdenum, thallium, tungsten,
In zirconium, titanium, rhenium, silicon, phosphorus, lanthanum, cerium, manganese, zinc, vanadium, platinum, palladium, ruthenium, rhodium and iridium at least
It is a kind of.Namely first modified additive and second modified additive each can be selected from the Ith A races gold
Category element, the IIth A races metallic element, group IIIA metallic element, the IVth A races element, the Vth A races
Element, the Ith B races metallic element, the IVth B races metallic element, group VIB metallic element, the VIIth B
One kind in race's metallic element, group VIII metal element, the Vth race's metallic element and lanthanide element or
It is various, each preferably be selected from lithium, potassium, magnesium, calcium, strontium, copper, molybdenum, thallium, tungsten, zirconium, titanium, rhenium,
At least one in silicon, phosphorus, lanthanum, cerium, manganese, zinc, vanadium, platinum, palladium, ruthenium, rhodium and iridium.
A preferred embodiment of the invention, the Part I modified additive and Part II change
Property auxiliary agent it is different, can each be selected from the Ith A races metallic element, the IIth A races metallic element, the IIIth A
Race's metallic element, the IVth A races element, the Vth A races element, the Ith B races metallic element, the IVth B races
Metallic element, group VIB metallic element, the VIIth B races metallic element, group VIII metal element, the Vth
One or more in race's metallic element and lanthanide element, each preferably be selected from lithium, potassium, magnesium, calcium,
Strontium, copper, molybdenum, thallium, tungsten, zirconium, titanium, rhenium, silicon, phosphorus, lanthanum, cerium, manganese, zinc, vanadium, platinum, palladium,
At least one in ruthenium, rhodium and iridium.
A preferred embodiment of the invention, the Part I modified additive and Part II change
Property auxiliary agent it is different, the Part I modified additive is in titanium, zirconium, lanthanum, cerium, tungsten, phosphorus and silicon
One or more, one or more in platinum, palladium, ruthenium and rhenium of the Part II modified additive.
The present invention is not particularly limited to the species of the active component, and reaction that can be as needed is entered
Row is selected.For example, for shell distribution catalyst is fischer-tropsch synthetic catalyst, the active component
Can be ferrum and/or cobalt.
The present invention is not particularly limited to the species of the carrier, as long as with certain intensity and can
Load the modified additive and active component.For example, close for Fischer-Tropsch when the shell is distributed catalyst
During into catalyst, the carrier can selected from aluminium oxide, silica-alumina, aluminium silicate, silicon oxide,
One or more in titanium oxide, zirconium oxide and activated carbon.
It is of the invention it is a kind of preferred embodiment, the modified additive selected from lithium, potassium, magnesium, calcium,
Strontium, copper, molybdenum, thallium, tungsten, zirconium, titanium, rhenium, silicon, phosphorus, lanthanum, cerium, manganese, zinc, vanadium, platinum, palladium,
At least one in ruthenium, rhodium and iridium, namely first modified additive and second modified additive are each
Can selected from lithium, potassium, magnesium, calcium, strontium, copper, molybdenum, thallium, tungsten, zirconium, titanium, rhenium, silicon, phosphorus, lanthanum,
At least one in cerium, manganese, zinc, vanadium, platinum, palladium, ruthenium, rhodium and iridium；The active component be ferrum and
/ or cobalt；The support selected from alumina, silica-alumina, aluminium silicate, silicon oxide, titanium oxide,
At least one in zirconium oxide and activated carbon.
The catalyst for meeting aforementioned claim of the present invention can realize the purpose of the present invention, and the present invention is made to which
, without particular/special requirement, for the present invention, shell distribution catalyst preferably of the present invention is by as follows for Preparation Method
It is prepared by step：
(1) by the first solution impregnating carrier containing Part I modified additive source, then it is dried
And roasting, wherein, the species for controlling the condition and the first solution of dipping causes Part I modified additive equal
Even distribution on the carrier, obtains being loaded with the carrier of Part I modified additive；
(2) will bear described in the second solution impregnation containing active component source and Part II modified additive source
The carrier of Part I modified additive is loaded with, is then dried and roasting, wherein, control the bar of dipping
The species of part and the second solution causes active component and Part II modified additive to exist with shell formal distribution
On the carrier.
In concrete preparation process, in order to obtain the shell distribution catalyst, those skilled in the art's energy
Enough know that the species that how control condition and the first solution for impregnating causes Part I modified additive
It is uniformly distributed on the carrier, and the condition and the second solution that how control dipping can be known
Species cause Part II modified additive and active component with shell formal distribution on the carrier.
For example, typically saturation dipping is impregnated described in step (1), i.e. the bar of the dipping
Part should generally meet：VL0/VC0>=1, wherein, VL0For the volume of the first solution, VC0For the load
The pore volume of body so that the amount of first solution is enough to the pore filling in the carrier completely, from
And the Part I modified additive is uniformly distributed on the carrier.
And for example, typically unsaturated dipping is impregnated described in step (2), i.e. the dipping
Condition should generally meet：VL/VC=0.01-0.99, preferred VL/VC=0.1-0.8, more preferably
VL/VC=0.1-0.6, more preferably VL/VC=0.4-0.6, wherein, VLFor the volume of the second solution, VCFor
It is loaded with the pore volume of the carrier of the Part I modified additive.Wherein, the VCBy being loaded with
The vehicle weight of a part of modified additive is multiplied by the water absorption rate of the carrier for being loaded with Part I modified additive
Obtain, what the water absorption rate for being loaded with the carrier of Part I modified additive referred to Unit Weight is loaded with
The water absorption (ml/g) of the carrier of a part of modified additive, its assay method are to be loaded with first
The carrier (g) of point modified additive dipping 2 hours in water (mL), are loaded with that Part I is modified to be helped
The carrier (g) of agent is 1 with the amount ratio of water (mL):3, afterwards by water suction after be loaded with first
The carrier of modified additive is divided to be separated from water, computational load has the carrier water-absorbing body of Part I modified additive
Product, is loaded with the load of the carrier water absorption rate of Part I modified additive=be loaded with Part I modified additive
The vehicle weight of body water suction volume/be loaded with Part I modified additive.
It is distributed in the preparation process of catalyst in the shell, the shell thickness can pass through the second solution
Consumption be controlled by, the condition impregnated described in the step (2) meets：VL1/VC1=0.01-0.99,
It is preferred that VL1/VC1=0.1-0.8, more preferably VL1/VC1=0.1-0.6, more preferably VL1/VC1During=0.4-0.6,
The respective thickness of the shell for obtaining is usually 0.01-0.6mm, more preferably 0.03-0.5mm, most preferably
0.05-0.3mm。
The present invention is not particularly limited to the species of solvent in first solution, can be existing each
Kind can by the Part I modified additive source dissolve inertia liquid, for example, can selected from water,
At least one in alcohol, ether, aldehyde and ketone.
A preferred embodiment of the invention, on the basis of the gross weight of first solution, institute
The content for stating Part I modified additive source in the first solution can be for 0.1-20 weight %, preferably 4-15
Weight %.
The present invention is also not particularly limited to the species of solvent in second solution, can be existing
The various inertia liquids that the active component source and Part II modified additive source can be dissolved, but
In order to be more beneficial for the active component and Part II modified additive with shell formal distribution in the load
On body, the solvent in second solution is preferably included：At least one in water, alcohol, ether, aldehyde and ketone
With surfactant, more preferably include：Water and surfactant.
The method according to the invention, further, on the basis of the gross weight of the second solution, described second
In solution, the content in active component source can be 5-90 weight %, preferably 10-85 weight %；Second
The content for dividing modified additive source can be 0.01-10 weight %, preferably 0.03-5 weight %；The table
The content of face activating agent can be 0.01-25 weight %, preferably 0.1-20 weight %.
The method according to the invention, the surfactant can be existing various ionic surfactants
One or more in agent, nonionic surfactant and amphoteric surfactant.Wherein, it is described from
Subtype surfactant generally includes anion surfactant and cationic surfactant.It is described it is cloudy from
The example of sub- surfactant is included but is not limited to：Examples of carboxylic anionic's surfactant is (such as soap, oil
Sour potassium etc.), Sulfonateses anion surfactant (such as sodium alkyl benzene sulfonate etc.), sulfuric ester salt it is cloudy
Ionic surface active agent (such as sodium lauryl sulphate etc.) and phosphate ester salt analog anion surfactants are (such as
C16H33OPO3Na2Deng) in one or more.The example of the cationic surfactant include but
It is not limited to：Ammonium salt cationoid surfactant and/or quaternary cationic surfactant (such as 16
Alkyl trimethyl ammonium chloride etc.).The example of the nonionic surfactant is included but is not limited to：Poly- second
Diol type nonionic surfactant is (such as fatty alcohol-polyoxyethylene ether, polyoxyethylene alkylphenol ether, fat
Fat acid polyoxyethylene ether, polyoxyethylene fatty amine and polyoxyethanyl alkylamide etc., and preferably Polyethylene Glycol
The polymerization degree n of type nonionic surfactant is 5-15, preferably 5-9) and/or polyol type nonionic
Surfactant (such as derivant of sucrose, Sorbitol, glyceryl alcohol etc.).The amophoteric surface active
The example of agent is included but is not limited to：Glycine betaine and aminoacid two types.
A preferred embodiment of the invention, the surfactant are non-ionic surfactant
Agent.
The carrier of the present invention is had been described in description catalyst prod, specific as follows：The present invention is right
The species of the carrier is not particularly limited, as long as with certain intensity and can load described modified
Auxiliary agent and active component.For example, when shell distribution catalyst is fischer-tropsch synthetic catalyst,
The carrier can be selected from aluminium oxide, silica-alumina, aluminium silicate, silicon oxide, titanium oxide, oxygen
Change one or more in zirconium and activated carbon., to the shape of the carrier without particular/special requirement, which can for the present invention
To make various easily operated molded bodys, and generally regular shape according to different requirements, for example can be with
Shaping carrier for spherical, piece dosage form or bar shaped etc., it is preferably spherical.Additionally, the granule of the carrier
Diameter is preferably 0.1-1.5mm, most preferably more preferably 0.2-0.5mm, 0.25-0.3mm.
In the present invention, the modified additive include Part I modified additive and Part II modified additive with
And active component is described in detail in description catalyst prod, here does not carry out repetition one by one and repeats.
In the present invention, the species in the modified additive source can be to provide any of the modified additive
Compound, such as when the modified additive can be selected from the Ith A races metallic element, the IIth metal unit of A races
Element, group IIIA metallic element, the IVth A races element, the Vth A races element, the Ith B races metallic element,
IVth B races metallic element, group VIB metallic element, the VIIth B races metallic element, group VIII metal unit
One or more in element, the Vth race's metallic element and lanthanide element, be preferably selected from lithium, potassium, magnesium,
Calcium, strontium, copper, molybdenum, thallium, tungsten, zirconium, titanium, rhenium, silicon, phosphorus, lanthanum, cerium, manganese, zinc, vanadium, platinum,
During at least one in palladium, ruthenium, rhodium and iridium；Correspondingly, the modified additive source can be existing each
Plant containing the Ith A races metallic element, the IIth A races metallic element, group IIIA metallic element, the IVth A
Race's element, the Vth A races element, the Ith B races metallic element, the IVth B races metallic element, group VIB
Metallic element, the VIIth B races metallic element, group VIII metal element, the Vth race's metallic element and group of the lanthanides gold
Category element at least one compound, preferably containing lithium, potassium, magnesium, calcium, strontium, copper, molybdenum,
Thallium, tungsten, zirconium, titanium, rhenium, silicon, phosphorus, lanthanum, cerium, manganese, zinc, vanadium, platinum, palladium, ruthenium, rhodium and iridium
In at least one compound.
And for example, a preferred embodiment of the invention, the Part I modified additive and second
Partially modified auxiliary agent is different, each can selected from the Ith A races metallic element, the IIth A races metallic element,
Group IIIA metallic element, the IVth A races element, the Vth A races element, the Ith B races metallic element,
IV B races metallic element, group VIB metallic element, the VIIth B races metallic element, group VIII metal element,
One or more in Vth race's metallic element and lanthanide element, each preferably be selected from lithium, potassium, magnesium,
Calcium, strontium, copper, molybdenum, thallium, tungsten, zirconium, titanium, rhenium, silicon, phosphorus, lanthanum, cerium, manganese, zinc, vanadium, platinum,
During at least one in palladium, ruthenium, rhodium and iridium；Correspondingly, the Part I modified additive source and second
Partially modified auxiliary agent source can be each existing various containing the Ith A races metallic element, the IIth A races gold
Category element, group IIIA metallic element, the IVth A races element, the Vth A races element, the Ith B races metal
Element, the IVth B races metallic element, group VIB metallic element, the VIIth B races metallic element, the VIIIth race
At least one compound in metallic element, the Vth race's metallic element and lanthanide element, preferably
Each containing lithium, potassium, magnesium, calcium, strontium, copper, molybdenum, thallium, tungsten, zirconium, titanium, rhenium, silicon, phosphorus, lanthanum,
At least one compound in cerium, manganese, zinc, vanadium, platinum, palladium, ruthenium, rhodium and iridium.
In the present invention, the species in the active component source can be to provide any of the active component
Compound, such as, when described active component can be ferrum and/or cobalt, correspondingly, the active component source can
Think the existing various compounds containing ferrum and/or cobalt.Wherein, the compound containing ferrum can be
Ferric nitrate, the compound containing cobalt can be selected from cobalt nitrate, cobalt acetate and citric acid cobalt etc.
Plant or various.
In the present invention, the preferably Part I modified additive source and Part II modified additive source and work
Property component source consumption the shell that obtains is distributed in catalyst, be distributed in terms of oxide and with the shell
On the basis of the gross weight of catalyst, the content of the active component is 1-60 weight %, preferably 2-50
Weight %, more preferably 10-50 weight %；The content of the Part I modified additive is 0.1-20 weights
Amount %, preferably 0.2-15 weight %, more preferably 0.5-5 weight %；The Part II modified additive
Content be 0.001-1 weight %, preferably 0.005-0.8 weight %, more preferably 0.01-0.5
Weight %.
The consumption in more preferably described Part I modified additive source and Part II modified additive source causes institute
The weight ratio that Part I modified additive is stated with the Part II modified additive is (0.1-1000):1,
Preferably (1-500):1, more preferably (2-100):1.
In the present invention, the described first purpose for being dried (described in step (1) be dried) is in order to will be attached
The solvent in the first solution on carrier is removed, and second drying (is done described in step (2)
It is dry) purpose be in order to will be attached to the solvent in the second solution on carrier removal.Described first is dried
It is dried with second and can be dried for drying or be vacuum dried, and this condition being dried twice can be this
The conventional selection in field, for example, includes independently of one another：Baking temperature can be 50-300 DEG C, preferably
For 100-250 DEG C；Drying time can be 1-48 hours, preferably 1-12 hours.
The purpose of first roasting (roasting described in step (1)) is in order that Part I changes
Property auxiliary agent source be converted into Part I modified additive (generally in the form of the oxide exist), described second
The purpose of roasting (roasting described in step (2)) is in order that active component source and Part II change
Property auxiliary agent source be converted into active component and Part II modified additive (generally existing in the form of the oxide).
First roasting can be with identical with the condition of the second roasting, it is also possible to different, and includes independently of one another：
Sintering temperature can be 300-600 DEG C, preferably 350-550 DEG C；Roasting time can be 1-48h, excellent
Elect 2-12h as.
According to the method that the present invention is provided, step (2) carrier and containing active component source and second
The immersive contact of second solution in modified additive source can be once, or repeatedly.When for it is multiple when,
Be dried after contacting every time, roasting or not roasting.
In a kind of embodiment being more highly preferred to, described in step (1) and step (2), rolling is immersed in
Carry out in cartridge type (or converter type) spray equipment.Including the rolling that carrier is placed in spray equipment at room temperature
In cylinder (or converter type), start cylinder (or converter type) device, carrier is with cylinder (or converter type)
Roll, by dipping solution Jing atomizers spray and carrier under carrier rolling condition.
Additionally, present invention also offers shell distribution application of the catalyst in Fischer-Tropsch synthesis.
Before the above-mentioned shell distribution catalyst that the present invention is provided is used for Fischer-Tropsch synthesis, it usually needs
In presence of hydrogen, the active component of oxidation state is carried out into reduction activation first.Wherein, the reduction activation
Condition can include：Reduction temperature is 200-1000 DEG C, preferably 200-800 DEG C；Recovery time is
1-96 hours, preferably 2-24 hours.Additionally, the reduction activation can be carried out in pure hydrogen,
Can carry out in the mixed gas of hydrogen and noble gases, wherein, Hydrogen Vapor Pressure can be 0.1-4MPa, excellent
Elect 0.1-2MPa as.In the present invention, the pressure refers both to gauge pressure.The noble gases can be ability
It is various under the conditions of above-mentioned reduction activation known to field technique personnel, the gas of chemical reaction is not involved in, such as
Nitrogen and/or zero group gas.
Additionally, the improvements of the Fischer-Tropsch synthesis are only that has used a kind of new catalyst, and
Reaction raw materials and reaction condition etc. can be the conventional selection in this area, and therefore not to repeat here.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example, the particle diameter of carrier adopts scanning electron microscope (SEM)
It is measured.Part II modified additive, the distribution of active component and shell thickness adopt SEM-EDX
Method is analyzed, wherein, shell thickness refers to that the distribution factor σ of the active component is 0≤σ ＜ 0.95
Partial thickness.
Embodiment 1-8
Embodiment 1-8 is used to illustrate shell distribution catalyst of present invention offer and preparation method thereof.
In embodiment, 1-4 used carriers are that (content of aluminium oxide is 70 to spherical silica-alumina particle
Weight %, particle diameter are 0.25 millimeter), in embodiment, 5-8 used carriers are spherical gamma-aluminium oxide granule
Grain (particle diameter is 0.3 millimeter), the consumption of carrier is 10 grams.
The first solution of preparation using saturation impregnation carrier of feeding intake listed according to table 1 respectively, soaks
The stain time is 5 minutes, prior to 140 DEG C of dryings 4 hours after dipping, then at 450 DEG C of roastings 4 hours,
Obtain being loaded with the carrier of Part I modified additive.
The second solution of preparation bear using unsaturated impregnation is above-mentioned according to the feeding intake of listing of table 2 respectively
It is loaded with the carrier of Part I modified additive, co-impregnation four times, prior to 140 DEG C of dryings 4 after impregnating every time
Hour, then at 400 DEG C of roastings 4 hours, obtain shell distribution catalyst A1-A8.Wherein, shell point
Cloth catalyst A1-A8 includes carrier and loads modified additive on the carrier and active component.Jing
SEM-EDX is characterized, and the Part I modified additive is evenly distributed on the carrier, the work
Property component and the Part II modified additive on the carrier in shell be distributed.Wherein, the activity
The shell thickness of component distribution is as shown in table 3.
Table 1
Table 2
Note：Ratio in table 2 is volume ratio, for example, water:Ethanol=1:2 refer to that water is 1 with the volume ratio of ethanol:2.
Comparative example 1
The comparative example is used to illustrate shell distribution catalyst of reference and preparation method thereof.
Method according to embodiment 1 prepare shell distribution catalyst, except for the difference that, the method do not include by
The step of the first solution of spherical silica-alumina particle carries out saturation and impregnates, but directly will be spherical
The second solution of silica-alumina granule carries out unsaturated dipping, adjusts the use of auxiliary agent in the second solution
Amount obtains the catalyst of the auxiliary agent of target content, and remaining condition is constant, obtains the shell distribution of reference
Catalyst DA1.Wherein, the shell distribution catalyst DA1 of reference includes carrier and is supported on the load
Active component and modified additive on body.Jing SEM-EDX are characterized, the active component, modified additive
It is distributed in shell on the carrier.Wherein, the shell thickness of the Active components distribution such as 3 institute of table
Show.
Comparative example 2
The comparative example is used to illustrate shell distribution catalyst of reference and preparation method thereof.
Method according to embodiment 5 prepare shell distribution catalyst, except for the difference that, the method do not include by
The step of the first solution of spherical gamma-alumina particle carries out saturation and impregnates, but directly by spherical gamma oxidation
The second solution of alumina particles carries out unsaturated dipping, and the consumption for adjusting auxiliary agent in the second solution causes to obtain mesh
The catalyst of the auxiliary agent of mark content, remaining condition are constant, obtain the shell distribution catalyst DA2 of reference.
Wherein, the shell distribution catalyst DA2 of reference includes carrier and load activearm on the carrier
Divide and modified additive.Jing SEM-EDX are characterized, and the active component and modified additive are on the carrier
It is distributed in shell.Wherein, the shell thickness of the Active components distribution is as shown in table 3.
Comparative example 3
The comparative example is used to illustrate shell distribution catalyst of reference and preparation method thereof.
Method according to embodiment 5 prepares shell distribution catalyst, except for the difference that, loads described first
Unsaturated infusion process is adopted when dividing modified additive, and the consumption of first solution causes VL0/VC0=0.8,
Wherein, VL0For the volume of the first solution, VC0For the pore volume of the carrier, the shell point of reference is obtained
Cloth catalyst DA3.Wherein, the shell distribution catalyst DA3 of reference includes carrier and is supported on described
Modified additive and active component on carrier.Jing SEM-EDX are characterized, and modified additive and active component exist
It is distributed in shell on carrier.Wherein, shell thickness D (mm) such as table 3 of the Active components distribution
It is shown.
Comparative example 4
The comparative example is used to illustrate shell distribution catalyst of reference and preparation method thereof.
Method according to embodiment 7 prepares shell distribution catalyst, except for the difference that, loads described second
Saturation infusion process is adopted when dividing modified additive, the shell distribution catalyst DA4 of reference is obtained.Wherein, join
The shell distribution catalyst DA4 of ratio includes carrier and loads modified additive on the carrier and activity
Component.Jing SEM-EDX are characterized, and active component is distributed in shell on carrier, and Part I is modified
Auxiliary agent and Part II modified additive are evenly distributed.Wherein, the shell thickness of the Active components distribution
As shown in D (mm) table 3.
Table 3
Note：D represents the shell thickness of active component.
Test case
Test case is used to illustrate the test that shell is distributed catalyst performance.
(1) shell is distributed the hydrothermal stability of catalyst：
Respectively by shell be distributed catalyst A1-A8, reference shell distribution catalyst DA1-DA4 and
Gamma-aluminium oxide carrier carries out hydrothermal treatment consists, wherein, hydrothermal conditions are as follows：Respectively by 10g above-mentioned shell
Layer distribution catalyst A1-A8, the shell distribution catalyst DA1-DA4 of reference and gamma-aluminium oxide carrier
It is scattered in 50mL deionized waters, and is transferred in 100mL hydrothermal reaction kettles, the hydro-thermal at 200 DEG C
Reaction 24h, then characterizes the change of crystal structure before and after hydro-thermal reaction by XRD, finds the present invention
Catalyst A1-A8 hydro-thermals after there is not the characteristic peak of boehmite, and reference catalyst DA1-DA4
And gamma-aluminium oxide carrier occurs in that the characteristic peak of boehmite near 14 °.Specifically, for example pass through
Shell distribution the catalyst DA3 and γ of shell distribution catalyst A5, reference after above-mentioned hydrothermal treatment consists-
The XRD spectra of alumina support is as shown in figure 1, from the graph, it is apparent that the shell of reference point
Cloth catalyst DA3 and gamma-aluminium oxide carrier occur in that the characteristic peak of boehmite near 14 °, and shell
Do not occur the characteristic peak of boehmite after layer distribution catalyst A5 hydro-thermals.As can be seen here, shell of the invention
The structure of layer distribution catalyst A5 is highly stable.
(2) shell distribution performance of the catalyst in Fischer-Tropsch synthesis：
Respectively the shell distribution catalyst DA1-DA4 that shell is distributed catalyst A1-A8 and reference is filled out
It is mounted in the fixed bed reactors of microchannel, Fischer-Tropsch synthesis is carried out in micro passage reaction.It is described micro-
Channel reactor includes a process microchannel.The process microchannel is 0.51mm deeply, and width is 0.7cm,
And length is 5.1cm.Catalyst is loaded in microprocessor passage.The amount of fill of catalyst is 0.5
Gram.
Then, (represented relative to every gram of catalyst flow hourly as 1000 with 1000NL/g-cat/h
Standard liter) flow injection hydrogen, and be warming up to 400 DEG C with 4 DEG C/min of heating rate, Ran Hou
Kept for 5 hours at this temperature.
Then, under 220 DEG C, 2.5MPa, with 20000h-1Gas hourly space velocity (GHSV) to described
H is injected in fixed bed reactors2With the mixed gas (H of CO2/ CO mol ratios are 2), so as to carry out
Fischer-Tropsch synthesis.The conversion ratio of CO is evaluated by the product in the fixed bed reactors
(XCO)、C5The above (C5+) hydro carbons selectivityCH4SelectivityWith
CO2SelectivityIts result is as shown in table 4 below.Specifically, XCO、SC5+、WithIt is calculated by following formula respectively：
Wherein, V1、V2It is illustrated respectively under the status of criterion, in certain time period, enters the raw material of response system
The exhaust gas volumes of the volume and outflow response system of gas；c1,CO、c2,COUnstripped gas and tail gas are represented respectively
The content of middle CO.nconThe molal quantity of the CO for reaction is participated in by reaction bed in certain time period,To generate CO2CO molal quantity,To generate CH4CO molal quantity,For
Generate CH4、C2Hydrocarbon, C3Hydrocarbon and C4The molal quantity sum of the CO of hydrocarbon, as a result as shown in table 4.
Table 4
| Catalyst | XCO | SC5+ | SCH4 | SCO2 |
| A1 | 56.03 | 88.01 | 6.36 | 0.21 |
| A2 | 55.66 | 88.91 | 6.77 | 0.11 |
| A3 | 54.22 | 86.21 | 6.03 | 0.26 |
| A4 | 53.41 | 85.95 | 6.11 | 0.29 |
| A5 | 53.32 | 85.03 | 6.09 | 0.40 |
| A6 | 55.85 | 87.87 | 6.12 | 0.33 |
| A7 | 55.21 | 87.35 | 6.33 | 0.27 |
| A8 | 45.00 | 86.25 | 6.56 | 0.30 |
| DA1 | 47.23 | 83.26 | 7.96 | 0.38 |
| DA2 | 46.53 | 83.61 | 7.97 | 0.37 |
| DA3 | 52.87 | 83.59 | 7.73 | 0.35 |
| DA4 | 54.01 | 86.21 | 6.39 | 0.29 |
The shell distribution catalyst that present invention offer be can be seen that by the result of table 4 and Fig. 1 not only has
Higher hydrothermal stability, and the catalyst has higher C in Fischer-Tropsch synthesis5+Hydro carbons is selected
Property, CO conversion and relatively low carbon dioxide and methane selectively, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of shell is distributed catalyst, and the shell distribution catalyst includes carrier and is supported on described
Modified additive and active component on carrier, it is characterised in that the modified additive include Part I and
Part II, the Part I modified additive are evenly distributed on the carrier, the active component
And the Part II modified additive is distributed in shell on the carrier, the particle diameter of the carrier is
0.1-1.5mm。
2. catalyst according to claim 1, wherein, in terms of oxide, the Part I
Modified additive is (0.1-1000) with the weight ratio of the Part II modified additive:1, preferably
(1-500):1, more preferably (2-100):1.
3. catalyst according to claim 1 and 2, wherein, urge in terms of oxide and with described
On the basis of the gross weight of agent, the content of the active component is 1-60 weight %, and preferably 10-50 is again
Amount %；The content of the Part I modified additive is 0.1-20 weight %, preferably 0.5-5 weight %；
The content of the Part II modified additive is 0.001-1 weight %, preferably 0.01-0.5 weight %.
4. catalyst according to claim 1 and 2, wherein, the shell of the shell distribution is thick
Spend for 0.01-0.4mm, preferably 0.05-0.3mm.
5. catalyst according to claim 1 and 2, wherein, the shell distribution catalyst is
Fischer-tropsch synthetic catalyst, the modified additive be fischer-tropsch synthetic catalyst modified additive, the activearm
It is divided into fischer-tropsch synthetic catalyst active component.
6. catalyst according to claim 1 and 2, wherein, the Part I modified additive
With the Part II modified additive each be selected from lithium, potassium, magnesium, calcium, strontium, copper, molybdenum, thallium, tungsten,
In zirconium, titanium, rhenium, silicon, phosphorus, lanthanum, cerium, manganese, zinc, vanadium, platinum, palladium, ruthenium, rhodium and iridium at least
It is a kind of；The active component is ferrum and/or cobalt；The support selected from alumina, silica-alumina,
At least one in aluminium silicate, silicon oxide, titanium oxide, zirconium oxide and activated carbon.
7. catalyst according to claim 6, wherein, the Part I modified additive and institute
State Part II modified additive different, each be selected from lithium, potassium, magnesium, calcium, strontium, copper, molybdenum, thallium, tungsten,
In zirconium, titanium, rhenium, silicon, phosphorus, lanthanum, cerium, manganese, zinc, vanadium, platinum, palladium, ruthenium, rhodium and iridium at least
It is a kind of；It is preferred that the Part I modified additive in titanium, zirconium, lanthanum, cerium, tungsten, phosphorus and silicon
Plant or various, one or more in platinum, palladium, ruthenium and rhenium of the Part II modified additive.
8. the shell in a kind of claim 1-7 described in any one is distributed the preparation method of catalyst,
The method is comprised the following steps：
(1) by the first solution impregnating carrier containing Part I modified additive source, then it is dried
And roasting, wherein, the species for controlling the condition and the first solution of dipping causes Part I modified additive equal
Even distribution on the carrier, obtains being loaded with the carrier of Part I modified additive；
(2) will bear described in the second solution impregnation containing active component source and Part II modified additive source
The carrier of Part I modified additive is loaded with, is then dried and roasting, wherein, control the bar of dipping
The species of part and the second solution causes active component and Part II modified additive to exist with shell formal distribution
On the carrier.
9. method according to claim 8, wherein, dipping described in step (1) is saturation leaching
Stain；Dipping described in step (2) is unsaturated dipping, and the condition impregnated described in step (2) is full
Foot：VL/VC=0.01-0.99, preferred VL/VC=0.4-0.6；Wherein, VLFor the volume of the second solution,
VCTo be loaded with the pore volume of the carrier of Part I modified additive.
10. method according to claim 8 or claim 9, wherein, the solvent choosing in first solution
At least one from water, alcohol, ether, aldehyde and ketone.
11. methods according to claim 10, wherein, the gross weight with first solution is
Benchmark, the content in Part I modified additive source is 0.1-20 weight %, preferably 4-15 weight %.
12. methods according to claim 8 or claim 9, wherein, the solvent bag in second solution
Include：At least one and surfactant in water, alcohol, ether, aldehyde and ketone.
13. methods according to claim 12, wherein, the gross weight with second solution is
Benchmark, the content in active component source is 5-90 weight %, preferably 10-85 weight %；Part II changes
Property auxiliary agent source content be 0.01-10 weight %, preferably 0.03-5 weight %；Surfactant contains
Measure as 0.01-25 weight %, preferably 0.1-20 weight %.
14. methods according to claim 12, wherein, the surfactant is nonionic
Surfactant.
Shell in 15. claim 1-7 described in any one is distributed catalyst in Fischer-Tropsch synthesis
Application.
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| 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 |
| CN109395729A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Condensed-nuclei aromatics selective hydrogenation mononuclear aromatics catalyst |
| CN110961096A (en) * | 2018-09-30 | 2020-04-07 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
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| 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 |
| CN109395729A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Condensed-nuclei aromatics selective hydrogenation mononuclear aromatics catalyst |
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| CN110961096A (en) * | 2018-09-30 | 2020-04-07 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
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