CN109718774A - A kind of catalyst and its preparation method and application and Fischer-Tropsch synthesis method - Google Patents
A kind of catalyst and its preparation method and application and Fischer-Tropsch synthesis method Download PDFInfo
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Abstract
A kind of catalyst and its preparation method and application and Fischer-Tropsch synthesis method, it is characterized in that, the catalyst contains the oxide and/or hydroxide of Co and Group IVB metallic element, and the catalyst is core-shell type nano structure, wherein Co forms shell, and the oxide and/or hydroxide of Group IVB metallic element form core.Catalyst provided by the invention greatly improves the utilization rate of cobalt, the stability of catalyst and catalytic performance, is applicable to the reactors such as microchannel, slurry bed system.
Description
Technical field
The present invention relates to a kind of catalyst and its preparation method and application and Fischer-Tropsch synthesis methods.
Background technique
As Global Oil resource is more and more rare, people are to environmental protection pay attention to day by day, using coal and natural gas etc.
Raw material preparation clean fuel and chemicals are increasingly valued by people.F- T synthesis technology is these coals and natural gas cleaning
One of key technology utilized.
The primary product that synthesis gas is converted to the Fischer-Tropsch synthesis of hydro carbons on a catalyst includes alkane and alkene, product
High-quality liquid fuel and high valuable chemicals can be obtained by deep processing.
Currently, load type cobalt-base catalyst is a kind of fischer-tropsch synthetic catalyst with industrial application value.General load
Type cobalt-base catalyst is prepared using infusion process, and active component Co particle size is larger, and distribution is wide, and the utilization rate of cobalt is low and inactivation is existing
As obvious.In addition, generally using noble metal auxiliary agent, this just makes to make cobalt oxide sufficiently be reduced into active metallic cobalt
At significantly improving for catalyst cost.Therefore, the utilization rate for how improving cobalt, improves catalyst at the utilization for reducing noble metal
Stability and catalytic performance are all difficult point and the direction of cobalt-base catalyst exploitation all the time.
Kou Yuan et al. (catalysis journal, the 2013, the 10th phase, 1914~1925) discloses Co nano particle synthesis in water oil
Method, this method include by CoCl2It is dissolved in THF with as protectant SB3-12, then slowly infuses under agitation
Enter reducing agent LiBEt3H、NaBH4Solution, mixed liquor illustrate that Co is reduced quickly by blue blackening, and reaction is quenched with ethyl alcohol after ten minutes
It goes out reaction, is then successively rinsed twice with second alcohol and water, gained nano particle is dispersed in water, preparing catalyst is obtained.It adopts
Although higher with the catalyst low temperature active that this method obtains, granule stability is poor.
US20140039037 disclose Ru, Fe, Co colloid of a kind of polymer stabilizing as catalyst low temperature (100~
200 DEG C) method of F- T synthesis.The catalyst contains transition metal nanoparticles and can stablize transition metal nanoparticles
Polymer stabilizer, the granularities of the transition metal nanoparticles is 1-10nm, preferably 1.4-2.2nm, the transition metal
Selected from one of Ru, Co, Ni, Fe and Rh or a variety of.The preparation method of the catalyst includes by transition metal salt and polymer
Stabilizer disperses in liquid medium, hydrogen reducing transition metal salt then to be used at 100-120 DEG C.The colloid catalyst is in reality
There are some problems for stability under the conditions of the Fischer-Tropsch synthesis of border.
Summary of the invention
The purpose of the invention is to overcome to be difficult to take into account catalytic activity existing for the fischer-tropsch synthetic catalyst of the prior art
And stability problem, a kind of new fischer-tropsch synthetic catalyst is provided, which has both higher catalytic activity, choosing
Selecting property and stability.
First aspect present invention provides a kind of catalyst, which is characterized in that the catalyst contains Co and Group IVB metallic element
Oxide and/or hydroxide, and the catalyst be core-shell type nano structure, wherein Co formed shell, Group IVB metallic element
Oxide and/or hydroxide form core.
Second aspect of the present invention provides a kind of preparation method of catalyst, method includes the following steps:
(1) oxide of Group IVB metallic element and/or the nano-colloid of hydroxide are prepared；
(2) Co is adhered on the surface of the nano-colloid obtained by step (1), and being formed by core, Co of the nano-colloid is shell
Core-shell structure.
Application the present invention also provides catalyst prepared by the above method and its in Fischer-Tropsch synthesis.
Further aspect of the present invention additionally provides a kind of Fischer-Tropsch synthesis method, and this method, which is included in catalyst, to be existed and Fischer-Tropsch conjunction
At under reaction condition, make CO and H2Fischer-Tropsch synthesis occurs for contact, which is characterized in that the catalyst is above-mentioned catalyst.
Compared with prior art, the amount that every gram of metallic cobalt of catalyst provided by the invention converts CO per hour increases, or
When catalyst composition is identical, the amount increase for the CO that every gram of catalyst converts per hour namely catalyst of the invention are greatly
The utilization rate of cobalt is improved, and the stability of catalyst is also obviously improved, it is a variety of to be applicable to microchannel, slurry bed system etc.
Reactor.For example, the relative activity of catalyst made from comparative example 1 is 1, methane selectively 9.1%, C5+ is selectively
79.6%, the relative activity of reaction 10 days is 0.68；And catalyst made from the embodiment of the present invention 1 is in identical active metal group
Divide under content and identical test condition, the relative activity of catalyst is 1.51, methane selectively 6.9%, and C5+ is selectively
87.4%, the relative activity of reaction 10 days is 1.06.It can be seen that catalyst provided by the invention has considerably higher catalysis
Activity, C5+ product selectivity and activity stability.
Detailed description of the invention
Fig. 1 is the XPS-Co2p spectrogram of catalyst made from the embodiment of the present invention 1；
Fig. 2 is the TEM of zirconium hydroxide colloid made from the embodiment of the present invention 1；
Fig. 3 is the TEM figure of catalyst colloid made from the embodiment of the present invention 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Preferably, on the basis of the total weight of catalyst, the content of Co is the preferred 25-65 weight % of 20-80 weight %, such as
25 weight %, 35 weight %, 40 weight %, 45 weight %, 50 weight %, 55 weight %, 60 weight %, Group IVB metallic element
Oxide and hydroxide total amount be the preferred 35-75 weight % of 20-80 weight % such as 40 weight %, 45 weight %, 50 weights
Measure %, 55 weight %, 60 weight %, 65 weight %, 70 weight %, 75 weight %.
In the present invention, the oxide of Group IVB metallic element and the total amount of hydroxide refer to the oxidation of Group IVB metallic element
The total content of the hydroxide of object and Group IVB metallic element, when the oxide without Group IVB metallic element or without Group IVB gold
When belonging to the hydroxide of element, the content of the substance is 0.
Preferably, the average particle size of the core-shell type nano structure is 5-50nm, preferably 8-45nm, more preferably 10-
35nm, such as 10,12,18,20,25,26,27,28nm.Within the above range by the granularity of control catalyst and active component,
The utilization rate of catalytic activity, selectivity, stability and metallic cobalt can be preferably improved, and improves the application range of catalyst.
The present invention characterizes its core-shell structure by transmission electron microscope (TEM) and x-ray photoelectron spectroscopy (XPS).
It is further preferred that the oxide of Group IVB metallic element or the average particle size of hydroxide core are 1-40nm, preferably
For 3-40nm, further preferably 3.5-30nm such as 4,4.5,5,8,10,15,17,20nm.By the granularity for controlling catalyst core
Within the above range, it can be ensured that final catalyst obtains the performances such as higher activity, selectivity, stability and higher cobalt benefit
With rate
In the present invention, the granularity refers to the size of particle.The granularity of spherical particles is indicated with diameter, cube
The granularity of grain is indicated with side length.To irregular particle, there is a certain sphere diameter of identical behavior as this for the particle
The equivalent diameter of grain.Wherein the granularity of the oxide of Group IVB metallic element or hydroxide core refers to the oxygen of Group IVB metallic element
The granularity of compound or hydroxide colloid is obtained by transmission electron microscope (TEM), specifically, using FEI Co. FEI TECNAI
G2 F20S-TWIN type transmission electron microscope, voltage 200kV, with 10-100nm, not etc. resolution ratio bat does not take 10- to each sample
15 photos, particle size measure picture by using Nano Measure software, and to sample 150 times or more people
Work statistical result carries out distribution and calculates acquisition.The measuring instrument of the x-ray photoelectron spectroscopy is Thermo Scientific public
The ESCALab250 type instrument of department, measuring condition are as follows: excitation light source is the monochromator Al K α X-ray of 150kW, in conjunction with can use
The peak C1s (284.8eV) correction；The measuring instrument of the X-ray fluorescence spectra is Rigaku electric machine industry Co., Ltd. 3271
Type instrument, measuring condition are as follows: the molding of sample map sheet, rhodium target, laser voltage 50kV, laser current 50mA.Pass through surface atom ratio
The structure feature of example variation judgement sample.
The catalyst provided according to the present invention, it is preferable that the Group IVB metallic element is one of Ti, Zr, Hf or more
Kind.
Active metal component Co is attached to the oxide of Group IVB metallic element to the present invention or hydroxide surfaces form core
Shell structure, thus obtained catalyst have obvious preferably catalyst activity, C5+ selectivity and catalytic stability.
According to the present invention it is possible to prepare the oxide and/or hydroxide of Group IVB metallic element using conventional method
Nano-colloid.Such as it can be the precipitation method, hydro-thermal method, solvent-thermal method.Be used to prepare Group IVB metallic element oxide and/or
The Group IVB metal precursor of the nano-colloid of hydroxide can be its inorganic salts or organic salt, such as nitrate, chloride.
For example, zirconium hydroxide nano-colloid can be prepared using any one in following methods: (1) by zirconyl chloride solution and urea
And/or reacted at 0-90 DEG C after ammonium hydroxide mixing 0.5-10 hours, then aging 5-10 is small at 20-90 DEG C preferably 20-50 DEG C
When, then filtration washing, obtains nano-colloid, and wherein the concentration of zirconium oxychloride can be 0.01-0.5 mol/L, zirconium oxychloride
Being subject to the dosage of urea and/or ammonium hydroxide maintains reaction system pH in 8-11；(2) by titanium tetrachloride solution and urea and/or
It is reacted 4-10 hours at -10 DEG C to 10 DEG C after ammonium hydroxide mixing, then aging 5-10 hours at 0-40 DEG C, crosses diafiltration later
It washs, obtains nano-colloid, wherein the concentration of titanium tetrachloride solution is preferably 0.05-0.5 mol/L, the dosage of urea and ammonium hydroxide
It is subject to and maintains reaction system pH in 9-11, the concentration of ammonium hydroxide can be 0.5-2 weight %.Aging is carried out by standing.
Titanium oxide colloid can be prepared using following methods: titanium tetrachloride being slowly added to acetone at -10 DEG C to 10 DEG C
In, it is then carried out solvent thermal reaction 8-20 hours at 80 DEG C to 120 DEG C, then filtration washing, obtains nano-colloid.
Preferably, the average particle size for the nano-colloid that step (1) obtains be 1-40nm, preferably 3-40nm, further it is excellent
It is selected as 3.5-30nm such as 4,4.5,5,8,10,15,17,20nm.
According to catalyst provided by the invention, there is no limit for the synthetic method of the fabricated in situ nanometer cobalt.In Group IVB gold
In the presence of the oxide or hydroxide colloid that belong to element, control reduction method preparation can be used and used that is, in the presence of protective agent
Reducing agent carries out reduction treatment to cobalt salt and obtains；Hydro-thermal method or solvent-thermal method can also be used.
A preferred embodiment of the invention, step (2) are realized by following manner: in inert gas shielding
Under, nano-colloid and protective agent are dispersed in Co salting liquid, then contacted with reducing agent.
The inert gas can be nitrogen and periodic table of elements group 0 element gas.
In the present invention, the protective agent can be various polymer, amine, phosphine, surfactant substance, preferably gather
It is vinylpyrrolidone, polyethylene glycol, linoleic acid, enuatrol, oleyl amine, tris hydroxymethyl phosphine, trimethyl cetyl ammonium bromide, four pungent
One of base ammonium bromide, polyethers, polymethoxy aniline are a variety of.Wherein the polyvinylpyrrolidone be preferably PVP-15k,
PVP-30k.The polyethylene glycol is preferably PEG4000, PEG6000.Methoxyl group in the polymethoxy aniline can be in neighbour
One or more of position, meta position, contraposition.
Protectant dosage is subject to can stable dispersion colloidal solid, it is preferable that nano-colloid: protective agent: Co salt
Weight ratio be 0.2-5:2-200:1 be preferably 0.5-3:5-20:1, wherein the amount of Co salt is in terms of Co element.The Co salt can
Think the inorganic salts and/or carboxylate of cobalt, such as can be cobalt acetate, cobalt nitrate, cobalt chloride and its hydrate such as six and be hydrated chlorine
Change one of cobalt, four acetate hydrate cobalts or a variety of.
The reducing agent can be it is various Co salt can be reduced into the substance of Co simple substance, such as can be sodium borohydride,
One of potassium borohydride, organic ammonium borohydride, hydrazine hydrate are a variety of.The organic boron hydrogenated amines are, for example, tetrabutyl hydroboration
One of ammonium, tetramethyl ammonium borohydride, tetraethyl ammonium borohydride are a variety of.
The dosage of the reducing agent is so that the Co element in Co salt is sufficiently reduced into subject to Co simple substance.
The condition of reduction reaction is determined by the type of reducing agent, specifically known to those skilled in the art, the present invention
Details are not described herein.
It can be by the oxide of the Group IVB metallic element or hydroxide nano colloidal dispersions in water or organic solvent etc.
In liquid medium, the organic solvent for example can be one of ethyl alcohol, propyl alcohol, ethylene glycol, glycerine or a variety of, preferably institute
Stating liquid medium is one of water, ethyl alcohol, ethylene glycol or a variety of.
The dosage of liquid medium is the nano-colloid relative to 1 gram, and the dosage of liquid medium is preferably for 10-1000ml
100-500ml。
A preferred embodiment of the invention, this method further include to core-shell structure product obtained by step (2) into
Row washing, so that the elementary metal impurities content in addition to cobalt and Group IVB metallic element is not more than 100ppm.Water can directly be used
Or organic solvent is eluted or is rinsed.The organic solvent for example can be ethyl alcohol, propyl alcohol, ethylene glycol, one in glycerine
Kind is a variety of.
A preferred embodiment of the invention, this method further include to the washing of loaded product obtained by step (2) or
Carry out intensive treatment after not washed, the mode of the intensive treatment include by reproducibility or inert gas atmosphere, water or
Catalyst is handled in organic solvent, enhances the binding force of active component and carrier, and keep catalyst structure more stable.
The reducing atmosphere preferably contains 5-60 volume % hydrogen and/or CO, and wherein the concentration of hydrogen and/or CO can be
Any concentration within the scope of 5 volume % to 60 volume %, for example, about 10 volume %, 15 volume %, 20 volume %, 25 volume %,
30 volume %, 35 volume %, 40 volume %, 45 volume %, 50 volume %.The remaining gas of reducing atmosphere is the inertia such as nitrogen
Gas.
The inert gas can be nitrogen, in the periodic table of elements group 0 element gas.
The water or organic solvent can be one of water, ammonium hydroxide, alcohols, carboxylic acids, amine, benzene class, alkanes etc.
Or it is a variety of, as long as under room temperature in liquid, can be with dispersed catalytic particles.
A preferred embodiment of the invention, the temperature of the intensive treatment are 150-400 DEG C of preferred 200-350
DEG C, pressure be the preferred 0.1-2MPa of 0-3MPa, the time is 1-80 hours 2-48 hours preferred.Strengthen that temperature is too high is not easy to reach,
And final catalyst structure and performance can be destroyed.
Intensive treatment is transferred after substantially washing by step (2) products therefrom or is not washed in above-mentioned atmosphere and condition
It sets.The intensive treatment preferably carries out under gas disturbance.
Compared with prior art, catalyst provided by the invention greatly improves the utilization rate of cobalt, the stabilization of catalyst
Property and catalytic performance, while selectivity is optimized, it is applicable to a variety of reactors such as microchannel, slurry bed system, fixed bed.
According to the present invention, wherein the operation of the Fischer-Tropsch synthesis and condition are referred to prior art progress.It is preferred that
Ground, the Fischer-Tropsch synthesis condition include that temperature is 160-300 DEG C preferably 190-280 DEG C, and pressure is preferably for 1-8MPa
The molar ratio of 1-5MPa, hydrogen and carbon monoxide is that 0.4-2.5 is preferably 1-2.5, and the volume space velocity of gas is 200-40000h-1
Preferably 500-30000h-1。
In the present invention, the pressure is gauge pressure.
The present invention will be described in detail by way of examples below.In following embodiment, received in nano-colloid, catalyst
The average particle size of rice cobalt is obtained by transmission electron microscope (TEM), specifically, using FEI Co. FEI TECNAI G2 F20S-TWIN
Type transmission electron microscope, voltage 200kV, with 10-100nm, not etc. resolution ratio bat does not take 10-15 photos to each sample, passes through
Picture is measured using Nano Measure software, and distribution meter is carried out to sample 150 times or more artificial statistical results
Calculation obtains average particle size.The composition of catalyst is measured using XRF method.Coreshell type structure passes through transmission electron microscope (TEM)
And x-ray photoelectron spectroscopy (XPS) characterizes.The measuring instrument of the x-ray photoelectron spectroscopy is Thermo Scientific
The ESCALab250 type instrument of company, measuring condition are as follows: excitation light source is the monochromator Al K α X-ray of 150kW, in conjunction with can adopt
It is corrected with the peak C1s (284.8eV)；The measuring instrument of the X-ray fluorescence spectra is Rigaku electric machine industry Co., Ltd.
3271 type instruments, measuring condition are as follows: the molding of sample map sheet, rhodium target, laser voltage 50kV, laser current 50mA.Pass through surface original
The structure feature of sub- ratio variation judgement sample.
Embodiment 1
(1) preparation of zirconium hydroxide colloid
The zirconium oxychloride aqueous solution that 268mL concentration is 0.05mol/L is mixed with 3.84g urea, is warming up to 85 DEG C of reactions
1h, after being cooled to 30 DEG C of aging 8h, centrifugal filtration is washed with deionized 3 times and is detected to filtrate with silver nitrate solution without precipitating
It generates.The TEM of zirconium hydroxide colloid is as shown in Figure 2.The TEM of Fig. 1 shows that zirconium hydroxide colloid average particle size is 15nm.
(2)Co/Zr(OH)4The preparation of core-shell structure
Under inert gas protection, in there-necked flask, by above-mentioned zirconium hydroxide colloidal dispersions in 350ml distilled water, so
30.8g protective agent PVP-30k (Chinese medicines group is analyzed pure) and 6.69g cobalt chloride hexahydrate (lark prestige is analyzed pure) are added afterwards,
It is kept for 15 minutes under room temperature, until 5.8g potassium borohydride will be contained using syringe after solid is slowly dissolved (Beijing reagent is analyzed pure)
Aqueous solution 80g fast injection into there-necked flask, continuation reacted 15 minutes under the conditions of stirring at normal temperature.
(3) it washs
After reaction, reaction solution is transferred to centrifuge tube and is centrifuged at a high speed (revolving speed 1000rpm, similarly hereinafter),
Then solid is carried out with distilled water being centrifuged-supersound washing 5 times, each dosage 400mL.Obtain nano particle.
(4) intensive treatment
Obtained nano particle is placed in polytetrafluoro reaction kettle liner and is scattered in 0.5L ethylene glycol, at 180 DEG C, 50
Volume %H2Nitrogen in place 40h under 2MPa pressure.The TEM of products therefrom is as shown in figure 3, TEM measures average grain diameter is
25nm, catalyst are denoted as C1.The composition of catalyst see the table below 1.The x-ray photoelectron spectroscopy of the catalyst is as shown in Figure 1.Pass through
The XPS-Co2P figure of Fig. 1 and transmission electron microscope (TEM) and the x-ray photoelectron spectroscopy (XPS) of Fig. 2-3 were as can be seen that should
Catalyst is core-shell structure.
Embodiment 2
(1) titanium hydroxide colloid
The TiCl for being 0.1mol/L by 623mL concentration under ice-water bath protection4Solution is sunk with 1.0wt% ammonia spirit
It forms sediment, maintenances pH value is 9-11, and after aging 8h, centrifugal filtration is washed 3 times and detected to filtrate with silver nitrate solution without precipitating generation.
TEM figure shows that titanium hydroxide colloid average particle size is 17nm.
(2)Co/Ti(OH)4Core-shell structure
Under inert gas protection, by above-mentioned titanium hydroxide colloidal dispersions in 410ml distilled water, 30.8g protective agent PVP-
30k (Chinese medicines group, analyze pure) and tetra- acetate hydrate cobalt of 7.0g (lark prestige, analysis are pure) are kept for 15 minutes under normal temperature condition, until
After solid is slowly dissolved, the aqueous solution 80g fast injection of 5.6g sodium borohydride (Beijing reagent is analyzed pure) will be contained using syringe
Into there-necked flask, continuation is reacted 15 minutes under the conditions of stirring at normal temperature.
(3) it washs
After reaction, reaction solution centrifuge tube is transferred to be centrifuged at a high speed, then with distilled water to sample into
Row centrifugation-supersound washing 6 times, each dosage 500mL.
(4) intensive treatment
Obtained nano particle is placed in stainless steel cauldron and is dispersed in 1L dehydrated alcohol, at 120 DEG C, 10 bodies
Product %H2Nitrogen in 40h is handled under 2MPa pressure, it is 25nm that TEM figure, which measures average grain diameter,.Catalyst is denoted as C2.Catalyst
Composition see the table below 1.Core-shell structure is characterized as by transmission electron microscope (TEM) and x-ray photoelectron spectroscopy (XPS).
Embodiment 3
(1) zirconium hydroxide colloid
Ice-water bath protection under by 496mL concentration be 0.05mol/L zirconyl chloride solution and 1.0wt% ammonia spirit into
Row precipitating, maintenances pH value is 9-11, and after aging 8h, centrifugal filtration is washed 3 times and detected to filtrate with silver nitrate solution without precipitating life
At.TEM shows that titanium hydroxide colloid average grain diameter is 20nm.
(2)Co/Zr(OH)4Core-shell structure
Under inert gas protection, by above-mentioned zirconium hydroxide colloidal dispersions in 350ml distilled water, 16.0g protective agent PEG-
6000 (Chinese medicines groups, analyze pure) and 6.69g cobalt chloride hexahydrate (lark prestige, analysis are pure) are kept for 15 minutes under normal temperature condition,
After being slowly dissolved to solid, quickly infused using the aqueous solution 80g that syringe will contain 5.6g sodium borohydride (Beijing reagent is analyzed pure)
It is mapped in there-necked flask, after continuation is reacted 15 minutes under the conditions of stirring at normal temperature.
(3) nanocatalyst washs
After reaction, reaction solution centrifuge tube is transferred to be centrifuged at a high speed, then with distilled water to sample into
Row centrifugation-supersound washing 7 times, each dosage 500mL.
(4) intensive treatment
Obtained nano cobalt granule is placed in ptfe autoclave liner and is dispersed in 0.5L ethyl alcohol.180
DEG C, 20h is handled in nitrogen under 2.5MPa pressure, it is 28nm that TEM, which measures average grain diameter,.Catalyst is denoted as C3.The composition of catalyst
It see the table below 1.Core-shell structure is characterized as by transmission electron microscope (TEM) and x-ray photoelectron spectroscopy (XPS) mode.
Embodiment 4
(1) titanium oxide colloid
By 7.24g TiCl under ice-water bath protection4It is slowly added dropwise in 750mL acetone, 100 DEG C of solvent thermal reaction 12h,
It is washed with deionized 3 times after sample separation, each 400mL.It is generated so that filtrate is detected with silver nitrate solution without precipitating.TEM
Display titanium oxide colloid average grain diameter is 4.5nm.
(2)Co/TiO2Core-shell structure
Under inert gas protection, above-mentioned titanium oxide colloid is dispersed in 120ml dehydrated alcohol while 8g oleic acid is added
Tetra- acetate hydrate cobalt of sodium and 15mL linoleic acid and 7.0g (lark prestige is analyzed pure) and 14.4g tetrabutyl hydroboration amine, 120 DEG C molten
Agent thermal response 8h.
(3) nanocatalyst washs
After reaction, reaction solution centrifuge tube is transferred to be centrifuged at a high speed, then with distilled water to sample into
Row centrifugation-supersound washing 6 times, each dosage 300mL.
(4) intensive treatment
Obtained nano particle is placed in stainless steel cauldron and is dispersed in 1L dehydrated alcohol.At 180 DEG C, pure H2Gas
12h is handled under 2.0MPa in gas atmosphere.Catalyst is denoted as C3.The composition of catalyst see the table below 1.Pass through transmission electron microscope
(TEM) and x-ray photoelectron spectroscopy (XPS) is characterized as core-shell structure.
Embodiment 5
Loaded catalyst is prepared according to the method for embodiment 1, unlike, step (4) intensive treatment step is in purity nitrogen
It is carried out in gas atmosphere, obtains catalyst C5.The composition of catalyst see the table below 1.
Embodiment 6
Loaded catalyst is prepared according to the method for embodiment 1, unlike, it does not include step (4) intensive treatment step,
Obtain catalyst C6.The composition of catalyst see the table below 1.
Embodiment 7
Loaded catalyst is prepared according to the method for embodiment 1, unlike, the temperature of intensive treatment is in step (4)
400 DEG C, obtain catalyst C7.The composition of catalyst see the table below 1.
Embodiment 8
Loaded catalyst is prepared according to the method for embodiment 1, unlike, step is added without protective agent PVP- in (2)
30k obtains catalyst C8.The composition of catalyst see the table below 1.
Comparative example 1
(1) catalyst preparation
6.69g cobalt chloride hexahydrate (lark prestige is analyzed pure) and 4.32g eight are hydrated zirconium oxychloride (Beijing reagent, analysis
It is pure) it is dissolved in 300mL deionized water, 7.6g urea is added, after being warming up to 85 DEG C of reactions 1h, cool aging 8h.Centrifugal filtration
Washing 3 times to filtrate with silver nitrate solution detection without precipitating generation.
(2) activation of catalyst
Above-mentioned powder is after 120 DEG C of dry 4h, and 400 DEG C of reduction 4h of normal pressure complete activation of catalyst in pure hydrogen atmosphere,
Gained catalyst is denoted as R1.The composition of catalyst see the table below 1.TEM shows that the average particle size of catalyst is 32nm.
Comparative example 2
(1) prepared by colloid catalyst
Under inert gas protection, 30.8g protective agent PVP-30k (Chinese medicines group, analysis are added in 350ml distilled water
It is pure) and 6.69g cobalt chloride hexahydrate (lark prestige, analyze pure), it is kept for 15 minutes under normal temperature condition, until after solid is slowly dissolved,
The aqueous solution 80g fast injection that 5.8g potassium borohydride (Beijing reagent is analyzed pure) will be contained using syringe continues into there-necked flask
After reacting 15 minutes under the conditions of stirring at normal temperature, colloid catalyst is obtained.TEM shows that the average particle size of colloid catalyst is
10nm。
(2) colloid catalyst washs
After reaction, reaction solution centrifuge tube is transferred to be centrifuged at a high speed, then with distilled water to sample into
Row centrifugation-supersound washing 5 times, each dosage 400mL.Obtain Co catalysts R2.The composition of catalyst see the table below 1.
Comparative example 3
(1) prepared by conventional supported catalyst
6.69g cobalt chloride hexahydrate (lark prestige is analyzed pure) and 4.32g eight are hydrated zirconium oxychloride (Beijing reagent, analysis
It is pure) it is dissolved in appropriate ionized water, multiple maceration is impregnated into 10.0g aluminum oxide micro-sphere (Sasol Products, average grain diameter
65 microns, 180 meters of specific surface area2/ gram), 300 DEG C of roasting 2h.
(2) activation of catalyst
Above-mentioned powder 400 DEG C of reduction 4h of normal pressure in pure hydrogen atmosphere complete activation of catalyst, are denoted as R3.The group of catalyst
Prejudice the following table 1.
Table 1
The cobalt that XPS is measured from table 1 can be seen that compared with conventional catalyst with the atomic ratio of group ivb element, this hair
There are obvious core-shell nanostructures by the catalyst Co of bright offer, i.e. Co is there are the surface of nano-colloid and covers group ivb element
The nano-colloid of formation.
Catalyst performance evaluation
Carried out in continuous stirred tank, concrete operations include: by the catalyst after activation in glove box oxygen free condition
Under be transferred in the autoclave for filling 150 grams of saualanes (Mobil, 4#), after airtight test, replaced with nitrogen, and heating up
Synthesis gas, synthesis gas composition are as follows: H are passed through when to 110 DEG C2:CO:N2=56:28:16, control pressure are 2.5MPa, reaction temperature
200-230 DEG C, 1000 revs/min of mixing speed, tail gas composition analysis is carried out using online gas-chromatography, calculates 20h reactivity worth.
Catalyst performance index includes catalysis relative activity, methane selectively, C5+ selectivity and stability, wherein being catalyzed
Relative activity is defined as: on the basis of the catalytic activity of R1, the numerical value that the catalytic activity of remaining catalyst obtains by comparison is i.e.
For the relative activity of corresponding catalyst, catalytic activity refers to the CO volume number (milli of every gram of catalyst of unit time (hour) conversion
It rises)；Methane selectively is defined as: the CO for being converted into methane accounts for the mole percent for having converted CO；C5+Selectivity is defined as: generate
C5+The CO of hydro carbons accounts for the mole percent for having converted CO；Stability indicates catalyst by being catalyzed work after long-time successive reaction
Property reduce degree, reduce it is fewer, stability is higher, conversely, stability is poorer.Evaluation result after reaction 24 hours is shown in Table 2, no
Relative activity with the reaction time is shown in Table 3, and the C5+ product distribution of reaction 10 days is shown in Table 4.
Table 2
| Catalyst | Relative activity | Methane selectively/% | C5+Selectivity/% |
| C1 | 1.51 | 6.9 | 87.4 |
| C2 | 1.64 | 7.1 | 86.9 |
| C3 | 1.46 | 7.3 | 86.5 |
| C4 | 2.53 | 7.5 | 85.8 |
| C5 | 1.05 | 7.8 | 85.1 |
| C6 | 1.06 | 8.0 | 84.6 |
| C7 | 1.16 | 7.5 | 85.7 |
| C8 | 1.01 | 7.2 | 86.8 |
| R1 | 1.00 | 9.1 | 79.6 |
| R2 | 0.1 | 14.5 | 77.1 |
| R3 | 0.28 | 8.7 | 80.1 |
Table 3
Defining deactivation rate is that catalyst activity loss accounts for the percentage of initial activity in the unit time, i.e. (1 day opposite
- 10 days relative activities of activity) ÷ 1 day relative activity ÷ 9 × 100%.
Table 4
| Catalyst | C5-C20 | C20-C35 | C36+ |
| C1 | 54.8 | 30.2 | 15.0 |
| C2 | 56.3 | 32.1 | 11.6 |
| C3 | 55.2 | 30.5 | 14.3 |
| C4 | 57.1 | 33.0 | 9.9 |
| C5 | 56.1 | 31.8 | 12.1 |
| C6 | 59.3 | 35.6 | 5.1 |
| C7 | 53.7 | 29.6 | 16.7 |
| C8 | 56.8 | 33.1 | 10.1 |
| R1 | 52.1 | 29.8 | 18.1 |
| R2 | - | - | - |
| R3 | 52.1 | 29.9 | 18.0 |
From the results shown in Table 2, compared with the catalyst that the prior art obtains, catalyst provided by the invention
Active height, methane selectively are low, C5+ selectivity is high, so that the utilization rate of cobalt of the invention is also higher；Table 3 the result shows that this
The catalyst that invention provides has higher stability；Table 4 the result shows that catalyst provided by the invention can obtain it is higher
The C5-C20 product and C5-C35 product of yield, the C36+ product of lower yield, so that product distribution is narrower.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (17)
1. a kind of catalyst, which is characterized in that the catalyst contains the oxide and/or hydroxide of Co and Group IVB metallic element
Object, and the catalyst is core-shell type nano structure, wherein Co forms shell, the oxide and/or hydroxide of Group IVB metallic element
Form core.
2. catalyst according to claim 1, wherein on the basis of the total weight of catalyst, the content of Co is 20-80 weight
The preferred 25-65 weight % of % is measured, the oxide of Group IVB metallic element and the total amount of hydroxide are 20-80 weight %, preferably
35-75 weight %.
3. catalyst according to claim 1 or 2, wherein the average particle size of the core-shell type nano structure is 5-50nm,
Preferably 8-45nm.
4. catalyst according to claim 3, wherein the oxide of Group IVB metallic element and/or putting down for hydroxide core
It is preferably 3-40nm that equal granularity, which is 1-40nm,.
5. catalyst described in any one of -4 according to claim 1, wherein the Group IVB metallic element is Ti, Zr, Hf
One of or it is a variety of.
6. a kind of preparation method of catalyst, method includes the following steps:
(1) oxide of Group IVB metallic element and/or the nano-colloid of hydroxide are prepared；
(2) Co is adhered on the surface of the nano-colloid obtained by step (1), and being formed by core, Co of the nano-colloid is the nucleocapsid of shell
Structure.
7. according to the method described in claim 6, wherein, step (2) is realized by following manner: in inert gas shielding
Under, nano-colloid and protective agent are dispersed in Co salting liquid, then contacted with reducing agent.
8. according to the method described in claim 7, wherein, the protective agent is polyvinylpyrrolidone, polyethylene glycol, sub- oil
Acid, enuatrol, oleyl amine, tris hydroxymethyl phosphine, trimethyl cetyl ammonium bromide, ammonium bromide and tetraoctyl ammonium bromide, polyethers, polymethoxy aniline
One of or it is a variety of.
9. method according to claim 7 or 8, wherein nano-colloid: protective agent: the weight ratio of Co salt is 0.2-5:2-
200:1, wherein the amount of Co salt is in terms of Co element；
Preferably, the granularity of the nano-colloid is 1-50nm, preferably 3-45nm, further preferably 3.5-40nm.
10. the method according to any one of claim 6-9, wherein the dosage of nano-colloid, Co and carrier makes,
On the basis of the total weight of catalyst, the content of Co is the preferred 25-65 weight % of 20-80 weight %, the oxygen of Group IVB metallic element
Compound and the total amount of hydroxide are the preferred 35-75 weight % of 20-80 weight %.
11. the method according to any one of claim 6-10, wherein this method further includes first right before intensive treatment
Core-shell structure product obtained by step (2) is washed, so that the elementary metal impurities content in addition to cobalt and Group IVB metallic element
No more than 100ppm.
12. the method according to any one of claim 6-11, wherein this method further includes to negative obtained by step (2)
It carries product and carries out intensive treatment.
13. according to the method for claim 12, wherein the intensive treatment is in reproducibility or inert atmosphere and solvent
Middle progress, the temperature of intensive treatment is 150 DEG C to less than 400 DEG C preferably 200-350 DEG C, pressure is the preferred 0.1- of 0-3MPa
2MPa, time are 1-80 hours 2-48 hours preferred.
14. catalyst made from method described in any one of claim 6-13.
15. application of the catalyst in Fischer-Tropsch synthesis described in any one of claim 1-6 and 14.
16. a kind of Fischer-Tropsch synthesis method, this method, which is included in catalyst, to be existed under the conditions of Fischer-Tropsch synthesis, make CO and H2It connects
Trigger raw Fischer-Tropsch synthesis, which is characterized in that the catalyst is catalysis described in any one of claim 1-6 and 14
Agent.
17. Fischer-Tropsch synthesis method according to claim 16, wherein the Fischer-Tropsch synthesis condition includes that temperature is
160-300 DEG C preferably 190-280 DEG C, pressure is that 1-8MPa is preferably 1-5MPa, and the molar ratio of hydrogen and carbon monoxide is
0.4-2.5 is preferably 1-2.5, and the volume space velocity of gas is 200-40000h-1Preferably 500-30000h-1。
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