CN109718783A - A kind of stable ultra-fine FT synthetic catalyst and its preparation method and application and Fischer-Tropsch synthesis method - Google Patents
A kind of stable ultra-fine FT synthetic 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.The catalyst is that core-shell type nano structure, wherein Co and stabilizer form 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 stable ultra-fine fischer-tropsch synthetic catalyst and its preparation method and application and F- T synthesis
Method.
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 core-shell type nano structure, wherein Co and stabilizer
Shell is formed, the oxide and/or hydroxide of Group IVB metallic element 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；
(3) stabilization processes are carried out to core-shell structure obtained by step (2).
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, catalyst provided by the invention greatly improves the utilization rate of cobalt, the stabilization of catalyst
Property and catalytic performance, are applicable to a variety of reactors such as microchannel, slurry bed system.For example, the catalyst reaction of the embodiment of the present invention 1
1 day relative activity is 1.53, methane selectively 6.0, C5+ selectivity 88.2%, and the relative activity after reaction 10 days is
1.39, and prior art comparative example 1 is under identical Co content and the identical situation of other conditions, activity is 1, methane selectively
It is 8.1, and C5+ is selectively only 84.6%, the relative activity after reaction 10 days is only 0.68.It can be seen that and the prior art
It compares, activity of the invention improves, and C5+ is selectively improved, and activity stability is also considerably higher.
Detailed description of the invention
Fig. 1 is the XPS-Co2p spectrogram of catalyst made from the embodiment of the present invention 3；
Fig. 2 is the TEM of titanium oxide colloid made from the embodiment of the present invention 3；
Fig. 3 is the TEM figure of catalyst colloid made from the embodiment of the present invention 3.
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 be the preferred 25-65 weight % of 20-80 weight % such as
21 weight %, 22 weight %, 23.2 weight %, 25 weight %, 30 weight %, 33.3 weight %, 39.5 weight %, 45 weights
Measure %, 50 weight %, 55 weight %, 60 weight %, stabilizer and the oxide of Group IVB metallic element and the total amount of hydroxide
For the preferred 35-75 weight % of 20-80 weight % such as 40 weight %, 45 weight %, 50 weight %, 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 granularity of the catalyst be 5-50nm, preferably 8-45nm, more preferably 10-35nm, such as 10,12,
18,20,25,26,27,28nm.By control catalyst granularity within the above range, can preferably provide catalytic activity,
The utilization rate of selectivity, stability and metallic cobalt, has a wide range of application in use.
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 the structure and performance of final catalyst.
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
G2F20S-TWIN type transmission electron microscope, voltage 200kV, with 10-100nm, not etc. resolution ratio bat does not take 10-15 to each sample
Photo, particle size measure picture by using Nano Measure software, and artificial to sample 150 times or more
Statistical result carries out distribution and calculates acquisition.The present invention passes through transmission electron microscope (TEM) and x-ray photoelectron spectroscopy (XPS)
To characterize its core-shell structure.The measuring instrument of the x-ray photoelectron spectroscopy is Thermo Scientific company
ESCALab250 type instrument, 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 3271 type instrument of Rigaku electric machine industry Co., Ltd.
Device, measuring condition are as follows: the molding of sample map sheet, rhodium target, laser voltage 50kV, laser current 50mA.Become by surface atom ratio
Change the structure feature of 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.
According to the present invention, which also contains stabilizer, and the stabilizer and Co are formed together the shell of core-shell structure.Institute
Stating stabilizer is preferably Zr, W, Ta, La, Ce and its one of oxide and/or hydroxide or a variety of.In the present invention, surely
Agent is determined for stable and the surface modified metal Co and the interface of Co and carrier.
Preferably, with elemental metal, the molar ratio of stabilizer and Co are the more preferable 1:4- of the preferred 1:3-300 of 1:2-500
200 be still more preferably 1:4-30 such as 1:5,1:6,1:7,1:8,1:9,1:10,1:15,1:18,1:20,1:25,1:30.
When catalyst of the invention contains oxide and/or hydroxide, the cobalt and stabilizer of Group IVB metallic element,
The oxide and/or hydroxide that the structural relation of three is Group IVB metallic element form the core of core-shell structure in most inner side,
Cobalt is coated on the oxide of Group IVB metallic element and/or the surface of hydroxide, and stabilizer is further coated on Group IVB metal
The oxide and/or hydroxide surfaces of element.
In the present invention, the content of each metal component is measured using ICP method in catalyst.
Active metal component is attached to the oxide or hydroxide of Group IVB metallic element by catalyst provided by the invention
Object surface forms core-shell structure, can greatly improve the activity and catalytic stability of catalyst.By further in core-shell structure
Surface increases stabilizer, can further improve stability and regulation selectivity.
Method of the invention forms nano Co stratum granulosum by the surface in situ in nano-colloid, obtains the Co of core-shell structure
Catalyst.
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 0.5-10 hours at 0-90 DEG C after ammonium hydroxide mixing, then aging 5-10 hours at 20-90 DEG C, then filter
Washing, obtains nano-colloid, and wherein the concentration of zirconium oxychloride can be 0.01-0.5 mol/L, zirconium oxychloride and urea and/or
The dosage of ammonium hydroxide, which is subject to, maintains reaction system pH in 8-11；(2) after titanium tetrachloride solution being mixed with urea and/or ammonium hydroxide
It is reacted 4-10 hours at -10 DEG C to 10 DEG C, then aging 5-10 hours at 0-40 DEG C, then filtration washing, obtains nanometer
Colloid, wherein the concentration of titanium tetrachloride solution is preferably 0.05-0.5 mol/L, and the dosage of urea and ammonium hydroxide is to maintain reactant
It is pH subject to 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 1-50nm, preferably 3-45nm, 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 is preferably PVP-30k.
The polyethylene glycol is preferably PEG4000, PEG6000.Methoxyl group in the polymethoxy aniline can ortho position, meta position,
One or more of 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, 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 boron hydrogenated amines, 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 stabilization processes, the mode of the stabilization processes include by core-shell structure product dispersion in liquid medium, and it is steady
Determine the soluble-salt of agent, nonmetallic alkaline matter is contacted under the conditions of stabilisation.
According to the embodiment, the nano-oxide or hydroxide colloid of Group IVB metallic element are first prepared, then in this glue
Fabricated in situ nanometer cobalt outside body, forming cobalt is shell, and the oxide or hydroxide of Group IVB metallic element are that the hud typed of core receives
Rice structure, finally carries out stabilization processes.
The stabilization reactions preferably carry out under the reducing atmosphere of the % hydrogen of volume containing 5-60 and/or CO, wherein hydrogen
The concentration of gas and/or CO can be any concentration within the scope of 5 volume % to 60 volume %, for example, about 10 volume %, 15 bodies
Product %, 20 volume %, 25 volume %, 30 volume %, 35 volume %, 40 volume %, 45 volume %, 50 volume %.Reproducibility gas
The remaining gas of atmosphere is the inert gases such as nitrogen.
The stabilisation condition may include that temperature is 0-400 DEG C of preferably 0 DEG C to 350 DEG C more preferable room temperature to 300 DEG C
Still more preferably 150-250 DEG C, pressure is the more preferable 1.5-3MPa of the preferred 0.1-3.5MPa of 0.1-4MPa and the time is 0.01-
Preferred 0.01-96 hours 144 hours 20-50 hours more preferable.
The stabilizer is preferably Zr, W, Ta, La, Ce and its one of oxide and/or hydroxide or a variety of.
The nonmetallic alkaline matter for example can be one of urea, ammonia, organic amine or a variety of.Stabilization reactions
In, nonmetallic alkaline matter plays a part of stabilization agent being deposited to catalyst surface.
Preferably, the molar ratio of the soluble-salt of stabilizer and core-shell structure product be 1:2-500 be preferably 1:3-300 more
Preferably 1:4-200, core-shell structure product: the weight ratio of nonmetallic alkaline matter is 1:1-20, and core-shell structure product is with Co member
Element meter, the soluble-salt of stabilizer is with elemental metal.
The liquid medium of stabilization reactions can be various insoluble nano-core-shell structures but can disperse nano core-shell knot
The liquid substance of structure, such as can be one of ethyl alcohol, propyl alcohol, ethylene glycol, glycerine or a variety of.
It is 10- that the dosage of liquid medium for stabilization reactions, which can be relative to every gram of nano-core-shell structure,
1000ml。
In the present invention, stabilization processes substantially by step (2) products therefrom washing or it is not washed after in above-mentioned gas
Atmosphere is placed under the conditions of.The stabilization processes preferably carry out under gas disturbance.
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.
Wherein the operation of the Fischer-Tropsch synthesis and condition are referred to prior art progress.Preferably, the Fischer-Tropsch
Synthetic reaction condition includes that temperature is 160-300 DEG C preferably 190-280 DEG C, and pressure is that 1-8MPa is preferably 1-5MPa, hydrogen
Molar ratio with carbon monoxide is that 0.4-2.5 is preferably 1-2.5, and the volume space velocity of gas is 200-40000h-1Preferably 500-
30000h-1。
In the present invention, unless otherwise indicated, 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 G2F20S-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 ICP method.The measuring instrument of the x-ray photoelectron spectroscopy is
The ESCALab250 type instrument of Thermo Scientific company, measuring condition are as follows: excitation light source is the monochromator Al of 150kW
K α X-ray, in conjunction with can using the peak C1s (284.8eV) correct；The measuring instrument of the X-ray fluorescence spectra is Rigaku electricity
3271 type instrument of machine Industrial Co., Ltd, measuring condition are as follows: the molding of sample map sheet, rhodium target, laser voltage 50kV, laser current
50mA.Change the structure feature of judgement sample by surface atom ratio.
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.TEM 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 after.
(3) it washs
After reaction, reaction solution is transferred to centrifuge tube to be centrifuged at a high speed (revolving speed 1000rpm), is then used
Distilled water carries out solid to be centrifuged-supersound washing 5 times, each dosage 400mL.Obtain nano particle.
(4) stabilization processes
It disperses above-mentioned nano particle in 500mL dehydrated alcohol, and five water zirconium nitrate of 2.41g and 1.2g urea is added,
50%H at 180 DEG C2Nitrogen in handle 40h under 2MPa pressure, with elemental metal, the molar ratio of stabilizer and cobalt is 1/5.
Gained catalyst is denoted as C1, and composition is shown in Table 1.
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 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, after 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) stabilization processes
It disperses above-mentioned nano particle in 500mL ethyl alcohol, and 1.22g cerium nitrate hexahydrate and 0.67g urea is added, 200
10 volume %H at DEG C2Nitrogen in handle for 24 hours under 2.5MPa pressure, the molar ratio of stabilizer and cobalt is 1/10.Catalyst is denoted as
C2, composition are shown in Table 1.
Embodiment 3
(1) titanium oxide colloid
By 7.24g TiCl under ice-water bath protection4It is slowly added dropwise in 750mL acetone soln, 100 DEG C of solvent thermal reactions
12h is washed with deionized 3 times, each 400mL after sample separation.It is generated so that filtrate is detected with silver nitrate solution without precipitating.
TEM display titanium oxide colloid average grain diameter (as shown in Figure 2) 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) 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) stabilization processes
It disperses above-mentioned nano particle in 400mL water-ethanol-ethylene glycol mixed solution (volume ratio 50:40:10), and
0.308g ammonium metatungstate and 0.5g urea, 10 volume %H at 220 DEG C are added2Nitrogen in handle for 24 hours under 2.5MPa pressure, surely
The molar ratio for determining agent and cobalt is 1/20.Catalyst is denoted as C3.The TEM of products therefrom is as shown in figure 3, 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 transmission electron microscopy of the XPS-Co2P figure and Fig. 2-3 of Fig. 1
Mirror (TEM) and x-ray photoelectron spectroscopy (XPS) are as can be seen that the catalyst is core-shell structure.
Embodiment 4
(1) zirconium hydroxide colloid
Zirconium hydroxide colloid preparation method is the same as embodiment 1.
(2)Co/Zr(OH)4Core-shell structure
Co/Zr(OH)4The preparation method is the same as that of Example 1 for core-shell structure.
(3) it washs
Washing methods is the same as embodiment 1.
(4) stabilization processes
It is carried out according to the method for 1 step of embodiment (4), unlike, it is added without five water zirconium nitrate of 2.41g and 1.2g urine
Element disperses above-mentioned nano particle in 500mL dehydrated alcohol, then the 50 volume %H at 180 DEG C2Nitrogen in 2MPa
Handle 40h under pressure, the molar ratio of stabilizer and cobalt is 1/5.Gained catalyst is denoted as C4, and composition is shown in Table 1.
Embodiment 5
Loaded catalyst is prepared according to the method for embodiment 1, unlike, the temperature of reduction activation is in step (2)
500 DEG C, catalyst C5 is obtained, composition is shown in Table 1.
Embodiment 6
Loaded catalyst is prepared according to the method for embodiment 1, unlike, the temperature of stabilization processes in step (4)
It is 500 DEG C, obtains catalyst C6, composition is shown in Table 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, 85 DEG C of reaction 1h are warming up to, after being cooled to 40 DEG C of aging 8h.From
Heart 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, and composition is shown in Table 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.Gained colloid catalyst is denoted as R2, and composition is shown in Table 1.
Comparative example 3
Loaded catalyst is prepared according to the method for embodiment 1, unlike, it does not include step (4) stabilization processes step
Suddenly, catalyst R3 is obtained, composition is shown in Table 1.
Table 1
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: raw
At C5The CO of+hydro carbons accounts for the mole percent for having converted CO；Stability indicates catalyst by urging after long-time successive reaction
Change active reduction degree, reduction is fewer, and stability is higher, conversely, stability is poorer.Specific evaluation result is shown in Table 2, table 3 and table
4, table 4 is the product distribution reacted 10 days.
Table 2
| Catalyst | Relative activity | Methane selectively/% | C5+ selectivity/% |
| C1 | 1.53 | 6.0 | 88.2 |
| C2 | 1.66 | 6.5 | 87.5 |
| C3 | 2.56 | 7.0 | 86.5 |
| C4 | 1.51 | 6.9 | 87.4 |
| C5 | 1.16 | 6.9 | 86.9 |
| C6 | 1.23 | 6.8 | 87.1 |
| R1 | 1.00 | 8.1 | 84.6 |
| R2 | 0.1 | 14.5 | 77.1 |
| R3 | 0.15 | 13.6 | 77.8 |
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
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；Table 3 the result shows that catalyst provided by the invention have higher stabilization
Property；Table 4 the result shows that catalyst provided by the invention can obtain the C5-C20 product and C5-C35 product of higher yield, more
The C36+ product of low 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 (19)
1. a kind of catalyst, which is characterized in that the catalyst is that core-shell type nano structure, wherein Co and stabilizer form shell, IVB
The oxide and/or hydroxide of race's 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, with elemental metal, it is preferably 1:3-300 more excellent that the molar ratio of stabilizer and Co, which are 1:2-500,
It is selected as 1:4-200, the total amount of the oxide and hydroxide of stabilizer and Group IVB metallic element is the preferred 35- of 20-80 weight %
75 weight %.
3. catalyst according to claim 1 or 2, wherein on the basis of the total weight of catalyst, the content of Co is 25-
65 weight %, with elemental metal, the molar ratio of stabilizer and Co are the preferred 1:4-200 of 1:3-300, stabilizer and Group IVB gold
The total amount of the oxide and hydroxide that belong to element is 35-75 weight %.
4. catalyst according to claim 3, wherein the granularity of the catalyst is 5-50nm, preferably 8-45nm.
5. catalyst described in any one of -4 according to claim 1, wherein the oxide and/or hydrogen of Group IVB metallic element
The average particle size of oxide core is that 1-40nm is preferably 3-40nm.
6. catalyst described in any one of -5 according to claim 1, wherein the Group IVB metallic element is Ti, Zr, Hf
One of or it is a variety of.
7. catalyst according to claim 6, wherein the stabilizer be Zr, W, Ta, La, Ce and its oxide and/or
One of hydroxide is a variety of.
8. 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；
(3) stabilization processes are carried out to core-shell structure product obtained by step (2).
9. according to the method described in claim 8, 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.
10. according to the method described in claim 9, 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.
11. method according to claim 9 or 10, 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 1-40nm, preferably 3-40nm, further preferably 5-40nm.
12. the method according to any one of claim 8-11, wherein the mode of the stabilization processes includes by institute
It states the dispersion of core-shell structure product in liquid medium, is then being stabilized with the soluble-salt of stabilizer, nonmetallic alkaline matter
Under the conditions of contacted.
13. according to the method for claim 12, wherein reduction of the contact in the % hydrogen of volume containing 5-60 and/or CO
Property atmosphere in carry out, the stabilisation condition include temperature be 0-400 DEG C of preferred room temperature to 300 DEG C more preferably 150-250 DEG C, press
Power is the more preferable 1.5-3MPa of the preferred 1-3.5MPa of 0.1-4MPa and the time is preferred 0.01-96 hours 0.01-144 hours more excellent
It selects 20-50 hours.
14. method according to claim 12 or 13, wherein the soluble-salt of the stabilizer is Zr, W, Ta, La, Ce
In one of one or more acetate, nitrate and chloride or a variety of, nonmetallic alkaline matter is urea, ammonia, has
One of machine amine is a variety of.
15. method described in any one of 2-14 according to claim 1, wherein with elemental metal, the solubility of stabilizer
The molar ratio of salt and core-shell structure product is that 1:2-500 is preferably that 1:3-300 is more preferably 1:4-200, core-shell structure product: non-
The weight ratio of metal alkaline substance is 1:1-20, and core-shell structure product is in terms of Co element.
16. catalyst made from method described in any one of claim 8-15.
17. application of the catalyst in Fischer-Tropsch synthesis described in any one of claim 1-7 and 16.
18. 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 1-7 and 16
Agent.
19. Fischer-Tropsch synthesis method according to claim 18, 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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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102695A (en) * | 1985-12-27 | 1988-11-02 | 埃克森研究工程公司 | Improved cobalt catalyst and to be used for methanol conversion be that hydrocarbon and Fischer-Tropsch process are synthetic |
| CN102337145A (en) * | 2010-07-22 | 2012-02-01 | 中国石油化工股份有限公司 | Fixed bed Fischer-Tropsch method for preparing liquid hydrocarbon |
| CN105008044A (en) * | 2012-12-04 | 2015-10-28 | 道达尔炼油化学公司 | Core-shell particles with catalytic activity |
| CN105597772A (en) * | 2014-11-04 | 2016-05-25 | 中国科学院上海高等研究院 | Cobalt-based catalyst having core-shell structure, and preparation method thereof |
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2017
- 2017-10-27 CN CN201711023990.0A patent/CN109718783B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102695A (en) * | 1985-12-27 | 1988-11-02 | 埃克森研究工程公司 | Improved cobalt catalyst and to be used for methanol conversion be that hydrocarbon and Fischer-Tropsch process are synthetic |
| CN102337145A (en) * | 2010-07-22 | 2012-02-01 | 中国石油化工股份有限公司 | Fixed bed Fischer-Tropsch method for preparing liquid hydrocarbon |
| CN105008044A (en) * | 2012-12-04 | 2015-10-28 | 道达尔炼油化学公司 | Core-shell particles with catalytic activity |
| CN105597772A (en) * | 2014-11-04 | 2016-05-25 | 中国科学院上海高等研究院 | Cobalt-based catalyst having core-shell structure, and preparation method thereof |
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