CN109647406A - A kind of Co based Fischer-Tropsch synthesis catalyst and preparation method thereof of activity phase high degree of dispersion - Google Patents
A kind of Co based Fischer-Tropsch synthesis catalyst and preparation method thereof of activity phase high degree of dispersion Download PDFInfo
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- CN109647406A CN109647406A CN201910100900.6A CN201910100900A CN109647406A CN 109647406 A CN109647406 A CN 109647406A CN 201910100900 A CN201910100900 A CN 201910100900A CN 109647406 A CN109647406 A CN 109647406A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 84
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 84
- 239000006185 dispersion Substances 0.000 title claims abstract description 36
- 230000000694 effects Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 66
- 239000010941 cobalt Substances 0.000 claims abstract description 66
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 27
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000010189 synthetic method Methods 0.000 claims abstract description 10
- -1 2,4-pentanedione cobalt salt Chemical class 0.000 claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 6
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims description 8
- RCNBUSVJYDRQCN-UHFFFAOYSA-N cobalt(3+);pentane-2,4-dione Chemical group [Co+3].CC(=O)CC(C)=O RCNBUSVJYDRQCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011259 mixed solution Substances 0.000 abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 7
- 238000000643 oven drying Methods 0.000 abstract description 2
- 238000011056 performance test Methods 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 229960000935 dehydrated alcohol Drugs 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of the Co based Fischer-Tropsch synthesis catalyst of active phase high degree of dispersion, the catalyst is using nano carbon microsphere as carrier, the cobalt protoxide nano particle of uniform particle diameter is highly dispersed on carbon ball carrier, after tested, the dispersion degree of cobalt may be up to 15% or more in catalyst, and particle still maintains superelevation dispersion degree after reduction.The partial size of cobalt protoxide nano particle is 5~60nm, and the load capacity of cobalt is 2~30%.Its synthetic method are as follows: a certain amount of acetylacetone,2,4-pentanedione cobalt salt is dissolved in o-dichlorohenzene and benzylamine mixed solution, obtain solution A, certain mass carbon ball is added in solution A again, after room temperature is vigorously stirred lower 30~90min of ultrasonic disperse, flow back 1~5h at 170~220 DEG C.It will be used washes of absolute alcohol 3-5 times after the centrifugation of obtained solid after the reaction was completed, then at 40~120 DEG C of oven drying 5h, F- T synthesis the performance test results show that the catalyst activity obtained by means of the present invention is higher, and methane selectively is lower and light dydrocarbon adds selectivity higher.
Description
Technical field
The present invention relates to fischer-tropsch synthetic catalyst technical fields, and in particular to a kind of co-based fischer-tropsch of activity phase high degree of dispersion
Synthetic catalyst and preparation method thereof.
Background technique
Fischer-Tropsch synthesis be syngas catalytic conversion that coal, natural gas, biomass etc. are transformed be fuel oil and
The important reaction of value added chemicals.The external Dependence rate of China's oil increased year by year in recent years, and the coal resources until 2017
60% or more has been had reached in the accounting of energy-output ratio.By the synthesis gas that will be transformed by coal resources, catalysis turns
Liquid fuel and appreciation chemicals are turned to, carbon resource utilization rate can not only be greatly improved, moreover it is possible to be eliminated in coal resource from source
Pollutant, meanwhile, which also depends on petroleum import unduly for alleviation China and provides important leverage, to guarantee China's energy peace
There is great strategic significance entirely.
Fischer-Tropsch synthesis cobalt-based catalyst activity is high, heavy hydrocarbon-selective is high, stability is good, is particularly suitable for natural gas conversion
And the volume ratio H come2The synthesis gas of/CO=2, thus it is widely used in industrial production.Specify cobalt-based catalyst system structure effect
Relationship, developing performance more preferably cobalt-base catalyst of new generation has huge supporting function to industrial production.Traditional co-based fischer-tropsch synthesis
Catalyst is prepared by infusion process or the precipitation method, and usually cobalt salt is impregnated or deposited on carrier, drying, is roasted
It burns, obtains catalyst fines, to make cobalt salt sufficiently decompose generation oxide, maturing temperature is generally at 350 DEG C or more, calcining time
Generally higher than 3h, however prolonged high-temperature roasting will lead to a large amount of reunions of cobalt, and influence catalytic performance.
The catalyst of acquisition uniform particle diameter and active phase high degree of dispersion is not only to further Study of Catalyst structure-activity relationship
It is most important, and obtain the important channel of performance more preferably catalyst.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the present invention provides a kind of cobalt-baseds of active phase high degree of dispersion
The thermal decomposition method for preparing nano particle is introduced the synthesis of catalyst, allowed by fischer-tropsch synthetic catalyst and preparation method, this method
Cobalt protoxide nano particle depends on carbon ball nucleating growth, eliminates roasting process, obtained catalyst granules uniform particle diameter, can
Control, and active phase oxidation Asia cobalt is highly dispersed at carbon ball surface.
The synthetic method of the catalyst is simple, easy to operate.
Realize technical solution used by above-mentioned purpose of the present invention are as follows:
A kind of Co based Fischer-Tropsch synthesis catalyst of activity phase high degree of dispersion, the catalyst using nano carbon microsphere as carrier,
Load has the cubic phase cobalt protoxide nano particle of high degree of dispersion and uniform particle diameter, cobalt protoxide nano particle on nano carbon microsphere
Average grain diameter be (3~60) nm, the load capacity (in terms of cobalt element) of cobalt is 2%~30%.
Further, the average grain diameter of the nano carbon microsphere is 100nm~1000nm, preferably 200nm-500nm.
Further, the average grain diameter of the cobalt protoxide nano particle be (3~30) nm, the D90 of particle diameter distribution with
It is no more than 10nm with D10 difference.
Further, the average grain diameter of the cobalt protoxide nano particle is (3.4~6.1) nm, the D90 of particle diameter distribution
It is no more than 8nm with D10 difference.
The average grain diameter of the cobalt protoxide nano particle of Co based Fischer-Tropsch synthesis catalyst area load prepared by the present invention
When less than 7nm, active phase dispersion degree is up to 15% or more.
A kind of synthetic method of the Co based Fischer-Tropsch synthesis catalyst of above-mentioned active phase high degree of dispersion, includes the following steps:
A certain amount of acetylacetone,2,4-pentanedione cobalt salt is dissolved in the mixed liquor of benzylamine and o-dichlorohenzene, obtains solution A, then by certain matter
It measures carbon ball to be added in solution A, under room temperature, stirring condition after 30~90min of ultrasonic disperse, 170~220 DEG C is warming up to, 170
It flows back 1~5h (being preferably warming up to 180 DEG C, flow back 1h at 180 DEG C) at~220 DEG C, after the reaction was completed, is separated by solid-liquid separation, it will
Obtained solid in 40~120 DEG C of baking ovens dry (preferably 60 DEG C of oven drying 5h), is obtained with washes of absolute alcohol 3~5 times
To Co based Fischer-Tropsch synthesis catalyst；
The acetylacetone,2,4-pentanedione cobalt salt, benzylamine, o-dichlorohenzene and carbon ball mass ratio be 1:(10-200): (1-150):
(0.1-20), preferably 1:(30-150): (2-90): (1-10), most preferably 1:30:2:1.
Further, the acetylacetone,2,4-pentanedione cobalt salt is acetylacetone cobalt (III) or acetylacetone cobalt (II).
Further, the speed of the stirring is 10 revolutions per seconds~60 revolutions per seconds, preferably 30 revolutions per seconds.
Further, the heating rate is 2 DEG C/min.
Compared with prior art, the beneficial effects of the present invention are:
1, catalyst of the invention does not need roasting process, and the cobalt protoxide grain diameter of catalyst surface load is uniform,
Particle size is controllable, and high degree of dispersion.After tested, dispersion degree is up to 23% or more, and the cobalt activity phase obtained later through reduction
Also occur without obvious agglomeration.
2, experiments have shown that, the catalyst dispersion degree obtained through the invention is much higher than the catalyst obtained by infusion process,
F- T synthesis the performance test results show that the catalyst activity obtained by means of the present invention is higher, and methane selectively is lower
And light dydrocarbon adds selectivity higher.
3, the synthetic method of the catalyst is simple, and synthesis temperature is lower, and generated time is short, and synthesis cost is low.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram for the Co based Fischer-Tropsch synthesis catalyst that embodiment 1 synthesizes.
Fig. 2 is that the partial size for the Co based Fischer-Tropsch synthesis catalyst that embodiment 1 synthesizes counts histogram, counts 300 nanometers
Grain.
Fig. 3 is the scanning electron microscope diagram for the Co based Fischer-Tropsch synthesis catalyst that embodiment 2 synthesizes.
Fig. 4 is that the partial size for the Co based Fischer-Tropsch synthesis catalyst that embodiment 2 synthesizes counts histogram, counts 300 nanometers
Grain.
Fig. 5 is the scanning electron microscope diagram for the Co based Fischer-Tropsch synthesis catalyst that embodiment 3 synthesizes.
Fig. 6 is that the partial size for the Co based Fischer-Tropsch synthesis catalyst that embodiment 3 synthesizes counts histogram, counts 300 nanometers
Grain.
A, B are respectively the XRD spectrum for the catalyst that embodiment 2 and embodiment 3 synthesize in Fig. 7, it can be seen that area load
Particle be typical cubic cobalt protoxide particle.
Fig. 8 is the scanning electron microscope diagram for the Co based Fischer-Tropsch synthesis catalyst that embodiment 4 synthesizes.
Fig. 9 is that the partial size for the Co based Fischer-Tropsch synthesis catalyst that embodiment 4 synthesizes counts histogram, counts 300 nanometers
Grain.
Figure 10 is the catalyst that embodiment 1 synthesizes, the scanning electron microscope diagram after restoring under 350 DEG C of hydrogen atmospheres.
Figure 11 is the catalyst that embodiment 1 synthesizes, and the partial size after restoring under 350 DEG C of hydrogen atmospheres counts histogram.It can
To see, mutually there is no obvious agglomerations for metallic cobalt activity after reduction.
Figure 12 is the scanning electron microscope diagram of the synthesis cobalt-based fischer-tropsch synthetic catalyst of comparative example 1.It can be seen that due to roasting
There is agglomeration in burning process, partial particulate.
Figure 13 is the scanning electron microscope diagram of the synthesis cobalt-based fischer-tropsch synthetic catalyst of comparative example 2.It can see local
There is aggregation in grain.
Figure 14 is the scanning electron microscope diagram of carbon ball carrier used in embodiment.
Figure 15 counts histogram for the partial size of carbon ball carrier used in embodiment, counts 300 nano particles, it can be seen that
The average grain diameter of carbon ball is 339nm.
Specific embodiment
Technical solution of the present invention is described in detail combined with specific embodiments below.
Carbon ball used is reference literature ACS Catalysis, 2018,8,1591- in the embodiment of the present invention and comparative example
1600. are prepared, and scanning electron microscope diagram is shown in that Figure 14, Figure 15 are that its partial size counts histogram, count 300 nanometers
Particle, it can be seen that the average grain diameter of carbon ball is 339nm.
Embodiment 1
A kind of Co based Fischer-Tropsch synthesis catalyst of activity phase high degree of dispersion, preparation method are as follows:
In the three-neck flask equipped with reflux water-dividing device and condenser pipe, 0.5g acetylacetone cobalt (II) is dissolved in 15g benzylamine
It is added in solution in the mixed solution of 1g o-dichlorohenzene, then by 0.5g carbon ball, is stirred by ultrasonic under room temperature (25 DEG C, similarly hereinafter)
1h, mixing speed are 30 revolutions per seconds.Then three-neck flask is placed in oil bath pan, is that 2 DEG C/min is heated to 180 with heating rate
DEG C, stop heating after 1h is reacted at 180 DEG C, be cooled to room temperature, be centrifugated, remove supernatant, (is used every time with dehydrated alcohol
Measure 15mL) washing resulting black solid five times, the black solid after washing is transferred in crucible, is put into baking oven, 60
Dry 5h, obtains Co based Fischer-Tropsch synthesis catalyst at DEG C.
The present embodiment synthesis Co based Fischer-Tropsch synthesis catalyst scanning electron microscope (SEM) photograph as shown in Figure 1, it will be seen from figure 1 that
Cobalt protoxide nano particle is fairly evenly dispersed on carbon ball carrier.
The particle diameter distribution of the Co based Fischer-Tropsch synthesis catalyst of the present embodiment synthesis from Fig. 2 as shown in Fig. 2, can calculate, originally
The particle diameter distribution of cobalt protoxide nano particle is 28.7 ± 3.7nm in the resulting catalyst of embodiment.
The Co based Fischer-Tropsch synthesis catalyst of the present embodiment synthesis measures cobalt loading (in terms of cobalt element, similarly hereinafter) by ICP
It is 3.3% by the dispersion degree that chemisorption measures cobalt for 8.1wt%.
Figure 10 and Figure 11 is that the catalyst for synthesizing the present embodiment restores the scanning electricity after 3h under 350 DEG C, hydrogen atmosphere
Sub- microscope figure and partial size count histogram.It can be seen that the metallic cobalt activity phase that catalyst surface loads after reduction
There is no obvious agglomerations, compare the SEM figure of reduction front and back as can be seen that the catalyst surface after reduction still maintains
High cobalt dispersion degree.
Embodiment 2
A kind of Co based Fischer-Tropsch synthesis catalyst of activity phase high degree of dispersion, preparation method are as follows:
In the three-neck flask equipped with reflux water-dividing device and condenser pipe, 0.5g acetylacetone cobalt (II) is dissolved in 15g benzylamine
It is added in solution in the mixed solution of 15g o-dichlorohenzene, then by 0.5g carbon ball, 1h is stirred by ultrasonic under room temperature (25 DEG C), stirs
Mixing speed is 30 revolutions per seconds.Then three-neck flask is placed in oil bath pan, is that 2 DEG C/min is heated to 180 DEG C with heating rate,
Stop heating after reacting 1h at 180 DEG C, be cooled to room temperature, be centrifugated, supernatant is removed, with dehydrated alcohol (each dosage
It 15mL) washs resulting black solid five times, the black solid after washing is transferred in crucible, is put into baking oven, at 60 DEG C
Lower dry 5h, obtains Co based Fischer-Tropsch synthesis catalyst.
For the XRD of the cobalt-base catalyst of the present embodiment synthesis as shown in Fig. 7-A, obtained catalyst surface particle is typical case
The cobalt protoxide of cubic phase.
The present embodiment synthesis Co based Fischer-Tropsch synthesis catalyst scanning electron microscope (SEM) photograph as shown in figure 3, from figure 3, it can be seen that
Cobalt protoxide nano particle is fairly evenly dispersed on carbon ball carrier.
The particle diameter distribution of the Co based Fischer-Tropsch synthesis catalyst of the present embodiment synthesis from Fig. 4 as shown in figure 4, can calculate, originally
The particle diameter distribution of cobalt protoxide nano particle is 17.9 ± 4.2nm in the resulting catalyst of embodiment.
It is 8.3wt% that the Co based Fischer-Tropsch synthesis catalyst of the present embodiment synthesis, which measures cobalt loading by ICP, passes through chemistry
The dispersion degree that absorption measures cobalt is 5.5%.
Embodiment 3
A kind of Co based Fischer-Tropsch synthesis catalyst of activity phase high degree of dispersion, preparation method are as follows:
In the three-neck flask equipped with reflux water-dividing device and condenser pipe, 0.5g acetylacetone cobalt (II) is dissolved in 15g benzylamine
It is added in solution in the mixed solution of 30g o-dichlorohenzene, then by 0.5g carbon ball, 1h is stirred by ultrasonic under room temperature (25 DEG C), stirs
Mixing speed is 30 revolutions per seconds.Then three-neck flask is placed in oil bath pan, is that 2 DEG C/min is heated to 180 DEG C with heating rate,
Stop heating after reacting 1h at 180 DEG C, be cooled to room temperature, be centrifugated, supernatant is removed, with dehydrated alcohol (each dosage
It 15mL) washs resulting black solid five times, the black solid after washing is transferred in crucible, is put into baking oven, at 60 DEG C
Lower dry 5h, obtains Co based Fischer-Tropsch synthesis catalyst.
For the XRD of the cobalt-base catalyst of the present embodiment synthesis as shown in Fig. 7-B, obtained catalyst surface particle is typical case
The cobalt protoxide of cubic phase.
The present embodiment synthesis Co based Fischer-Tropsch synthesis catalyst scanning electron microscope (SEM) photograph as shown in figure 5, from fig. 5, it can be seen that
Cobalt protoxide nano particle is fairly evenly dispersed on carbon ball carrier.
The particle diameter distribution of the Co based Fischer-Tropsch synthesis catalyst of the present embodiment synthesis from Fig. 6 as shown in fig. 6, can calculate, originally
The particle diameter distribution of cobalt protoxide nano particle is 10.2 ± 4.4nm in the resulting catalyst of embodiment.
It is 7.9wt% that the Co based Fischer-Tropsch synthesis catalyst of the present embodiment synthesis, which measures cobalt loading by ICP, passes through chemistry
The dispersion degree that absorption measures cobalt is 9.5%.
Embodiment 4
A kind of Co based Fischer-Tropsch synthesis catalyst of activity phase high degree of dispersion, preparation method are as follows:
In the three-neck flask equipped with reflux water-dividing device and condenser pipe, 0.5g acetylacetone cobalt (II) is dissolved in 15g benzylamine
It is added in solution in the mixed solution of 45g o-dichlorohenzene, then by 0.5g carbon ball, 1h is stirred by ultrasonic under room temperature (25 DEG C), stirs
Mixing speed is 30 revolutions per seconds.Then three-neck flask is placed in oil bath pan, is that 2 DEG C/min is heated to 180 DEG C with heating rate,
Stop heating after reacting 1h at 180 DEG C, be cooled to room temperature, be centrifugated, supernatant is removed, with dehydrated alcohol (each dosage
It 15mL) washs resulting black solid five times, the black solid after washing is transferred in crucible, is put into baking oven, at 60 DEG C
Lower dry 5h, obtains Co based Fischer-Tropsch synthesis catalyst.
The present embodiment synthesis Co based Fischer-Tropsch synthesis catalyst scanning electron microscope (SEM) photograph as shown in figure 8, from figure 8, it is seen that
Cobalt protoxide nano particle is fairly evenly dispersed on carbon ball carrier.
The particle diameter distribution of the Co based Fischer-Tropsch synthesis catalyst of the present embodiment synthesis from Fig. 9 as shown in figure 9, can calculate, originally
The particle diameter distribution of cobalt protoxide nano particle is 6.1 ± 3.9nm in the resulting catalyst of embodiment.
It is 8.5wt% that the Co based Fischer-Tropsch synthesis catalyst of the present embodiment synthesis, which measures cobalt loading by ICP, passes through chemistry
The dispersion degree that absorption measures cobalt is 15.7%.
Embodiment 5
A kind of Co based Fischer-Tropsch synthesis catalyst of activity phase high degree of dispersion, preparation method are as follows:
In the three-neck flask equipped with reflux water-dividing device and condenser pipe, 0.5g acetylacetone cobalt (II) is dissolved in 15g benzylamine
It is added in solution in the mixed solution of 1g o-dichlorohenzene, then by 1g carbon ball, 1h, stirring speed is stirred by ultrasonic under room temperature (25 DEG C)
Degree is 30 revolutions per seconds.Three-neck flask is placed in oil bath pan, is that 2 DEG C/min is heated to 180 DEG C with heating rate, it is anti-at 180 DEG C
Stop heating after answering 1h, be cooled to room temperature, be centrifugated, removes supernatant, washed with ethyl alcohol (each dosage 15mL) resulting
Black solid five times, the black solid after washing is transferred in crucible, is put into baking oven, dry 5h, obtains cobalt at 60 DEG C
Base fischer-tropsch synthetic catalyst.
The particle diameter distribution of cobalt protoxide nano particle is 12.3 ± 3.1nm in the resulting catalyst of the present embodiment.
It is 7.4wt% that the Co based Fischer-Tropsch synthesis catalyst of the present embodiment synthesis, which measures cobalt loading by ICP, passes through chemistry
The dispersion degree that absorption measures cobalt is 7.8%.
Embodiment 6
A kind of Co based Fischer-Tropsch synthesis catalyst of activity phase high degree of dispersion, preparation method are as follows:
In the three-neck flask equipped with reflux water-dividing device and condenser pipe, 0.5g acetylacetone cobalt (II) is dissolved in 15g benzylamine
It is added in solution in the mixed solution of 1g o-dichlorohenzene, then by 2g carbon ball, 1h, stirring speed is stirred by ultrasonic under room temperature (25 DEG C)
Degree is 30 revolutions per seconds.Then three-neck flask is placed in oil bath pan, is that 2 DEG C/min is heated to 180 DEG C with heating rate, at 180 DEG C
Stop heating after lower reaction 1h, be cooled to room temperature, be centrifugated, removes supernatant, washed with dehydrated alcohol (each dosage 15mL)
It washs resulting black solid five times, the black solid after washing is transferred in crucible, is put into baking oven, it is dry at 60 DEG C
5h obtains Co based Fischer-Tropsch synthesis catalyst.
The particle diameter distribution of cobalt protoxide nano particle is 8.2 ± 2.8nm in the resulting catalyst of the present embodiment.
It is 7.2wt% that the Co based Fischer-Tropsch synthesis catalyst of the present embodiment synthesis, which measures cobalt loading by ICP, passes through chemistry
The dispersion degree that absorption measures cobalt is 11.7%.
Embodiment 7
A kind of Co based Fischer-Tropsch synthesis catalyst of activity phase high degree of dispersion, preparation method are as follows:
In the three-neck flask equipped with reflux water-dividing device and condenser pipe, 0.1g acetylacetone cobalt (III) is dissolved in 15g benzylamine
It is added in solution in the mixed solution of 3g o-dichlorohenzene, then by 1g carbon ball, 1h, stirring speed is stirred by ultrasonic under room temperature (25 DEG C)
Degree is 30 revolutions per seconds.Then three-neck flask is placed in oil bath pan, is that 2 DEG C/min is heated to 180 DEG C with heating rate, at 180 DEG C
Stop heating after lower reaction 1h, be cooled to room temperature, be centrifugated, removes supernatant, washed with dehydrated alcohol (each dosage 15mL)
It washs resulting black solid five times, black solid is transferred in crucible, is put into baking oven, dry 5h, obtains cobalt at 60 DEG C
Base fischer-tropsch synthetic catalyst.The cobalt protoxide nano particle diameter of gained catalyst is distributed as 3.4 ± 2.3nm, is measured by ICP
Cobalt loading is 9.3wt%, is 23.3% by the dispersion degree that chemisorption measures cobalt.
Embodiment 8
A kind of Co based Fischer-Tropsch synthesis catalyst of activity phase high degree of dispersion, preparation method are as follows:
In the three-neck flask equipped with reflux water-dividing device and condenser pipe, 0.3g acetylacetone cobalt (III) is dissolved in 15g benzylamine
It is added in solution in the mixed solution of 3g o-dichlorohenzene, then by 1g carbon ball, 1h, stirring speed is stirred by ultrasonic under room temperature (25 DEG C)
Degree is 30 revolutions per seconds.Then three-neck flask is placed in oil bath pan, is that 2 DEG C/min is heated to 180 DEG C with heating rate, at 180 DEG C
Stop heating after lower reaction 1h, be cooled to room temperature, be centrifugated, removes supernatant, washed with dehydrated alcohol (each dosage 15mL)
It washs resulting black solid five times, the black solid after washing is transferred in crucible, is put into baking oven, it is dry at 60 DEG C
5h obtains Co based Fischer-Tropsch synthesis catalyst.Cobalt protoxide nano particle diameter in gained catalyst is distributed as 5.2 ± 1.9nm,
Measuring cobalt loading by ICP is 8.6wt%, is 19.7% by the dispersion degree that chemisorption measures cobalt.
Comparative example 1
2.0g carbon ball is weighed, cabaltous nitrate hexahydrate is dissolved in 1.5mL deionized water and prepares nitre by 1.1g cabaltous nitrate hexahydrate
The carbon ball for being impregnated with cobalt nitrate solution after being impregnated into cobalt nitrate solution on carbon ball dropwise, is transferred to revolving by acidic cobalt solution
Instrument, in the dry 2h of 90 DEG C of revolvings, then by the reactant after revolving after 100 DEG C of dry 12h, taking-up sample in tube furnace
350 DEG C, roast 6h under nitrogen atmosphere, obtain the Co catalysts of comparative example 1.
The scanning electron microscope (SEM) photograph of the Co catalysts of the present embodiment synthesis is as shown in figure 12, as seen from Figure 12, due to passing through
More serious reunion has occurred in roasting process, cobalt oxide particle.Measuring cobalt loading in catalyst is 9.9wt%, tests institute
The dispersion degree for obtaining cobalt is 2.1%.
Comparative example 2
0.5g carbon ball is weighed, is scattered in 300mL dehydrated alcohol, weighing the average grain diameter prepared in advance is 13.3nm's
Cobalt protoxide particle 0.7g is added in above-mentioned ethyl alcohol and the mixed liquor of carbon ball, and ultrasound 2h is stirred at 25 DEG C and is sunk to without obvious solid
It forms sediment, then rotates, then at 100 DEG C of dry 12h, obtain the Co catalysts of comparative example 2.
The scanning electron microscope (SEM) photograph of the Co catalysts of the present embodiment synthesis is as shown in figure 13, as seen from Figure 13, in catalyst
The case where particle aggregations a large amount of there are part.The load capacity for measuring catalyst cobalt is 9.9wt%, and the dispersion degree of test gained cobalt is
3.4%.
The obtained catalyst of embodiment 1-8 and comparative example 1-2 is used for F- T synthesis test
Catalyst: the Co based Fischer-Tropsch synthesis catalyst of Examples 1 to 8 synthesis and the cobalt-base catalyst of comparative example 1-2 synthesis.
Experiment carries out in fixed bed reactors, first restores under pure hydrogen atmosphere, reducing condition: normal pressure, hydrogen atmosphere
Under, 3SLg-1·h-1, 350 DEG C of reduction 3h；It switches to synthesis gas after cooling to be reacted, reaction condition: air speed 2SLg-1·
h-1, 1.0MPa, 210 DEG C, H2/ CO=2:1 (volume ratio).
The performance of each catalyst F- T synthesis is as shown in table 1, and taken response data is to reach 210 DEG C of reaction temperature simultaneously
The average activity data of 100h after stabilization.
1 Co based Fischer-Tropsch synthesis catalyst catalytic performance of table
Claims (8)
1. a kind of Co based Fischer-Tropsch synthesis catalyst of activity phase high degree of dispersion, the catalyst are received using nano carbon microsphere as carrier
Load has the cubic phase cobalt protoxide nano particle of high degree of dispersion and uniform particle diameter in rice carbon ball, cobalt protoxide nano particle
Average grain diameter is 3~60nm, and the load capacity of cobalt is 2%~30%.
2. Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that: the average grain diameter of the nano carbon microsphere
For 100~1000nm.
3. a kind of synthetic method of Co based Fischer-Tropsch synthesis catalyst as claimed in claim 1 or 2, includes the following steps:
A certain amount of acetylacetone,2,4-pentanedione cobalt salt is dissolved in the mixed liquor of benzylamine and o-dichlorohenzene, obtains solution A, then by certain mass carbon
Ball is added in solution A, under room temperature, stirring condition after 30~90min of ultrasonic disperse, is warming up to 170~220 DEG C, 170~
Flow back 1~5h at 220 DEG C, after the reaction was completed, is separated by solid-liquid separation, will be dry after the washing of obtained solid, obtains co-based fischer-tropsch synthesis
Catalyst；
The acetylacetone,2,4-pentanedione cobalt salt, benzylamine, o-dichlorohenzene and carbon ball mass ratio be 1:(10-200): (1-150): (0.1-
20)。
4. synthetic method according to claim 3, which is characterized in that the acetylacetone,2,4-pentanedione cobalt salt, benzylamine, o-dichlorohenzene with
The mass ratio of carbon ball is 1:(30-150): (2-90): (1-10).
5. synthetic method according to claim 4, it is characterised in that: the drying are as follows: dry at 40~120 DEG C.
6. synthetic method according to claim 5, it is characterised in that: the acetylacetone,2,4-pentanedione cobalt salt is acetylacetone cobalt
(III) or acetylacetone cobalt (II).
7. synthetic method according to claim 6, it is characterised in that: the speed of the stirring be 10 revolutions per seconds~60 turns/
Second.
8. synthetic method according to claim 7, it is characterised in that: the heating rate is 2 DEG C/min.
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| CN107670666A (en) * | 2017-09-30 | 2018-02-09 | 中南民族大学 | A kind of Co based Fischer-Tropsch synthesis catalyst and its synthetic method |
| CN110639549A (en) * | 2019-09-19 | 2020-01-03 | 北京工业大学 | Universal method for preparing high-stability noble metal monatomic catalyst |
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| CN104925871A (en) * | 2015-06-12 | 2015-09-23 | 中南民族大学 | Synthetic method for monodispersed cobalt dioxide nanocrystalline |
| CN106925265A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院过程工程研究所 | A kind of transition metal composite oxide catalytic agent |
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