CN109833872A - The cobalt oxide bulk phase catalyst and its preparation method and application of controllable product distribution - Google Patents
The cobalt oxide bulk phase catalyst and its preparation method and application of controllable product distribution Download PDFInfo
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Abstract
The invention belongs to bulk phase catalyst technical fields, disclose a kind of cobalt oxide bulk phase catalyst and its preparation method and application of controllable product distribution, the catalyst series are with cobalt oxide for main body catalyst；When preparation, the different hydro-thermal times are taken to synthesize cobalt oxide catalyst using hydro-thermal method, drying and roasting obtains a series of Co3O4- xh catalyst, wherein x indicates hydro-thermal time 0-3h.Catalyst prepared by the present invention is suitable for hydrogenation of carbon dioxide carbon monoxide and methane reaction, using Co as active component, a series of catalyst by adjusting the preparation of hydro-thermal time realize the gradient regulation of 95% carbon monoxide selective to 90% methane selectively, it is simple with structure, preparation is convenient, the low feature of operating pressure, the catalyst series while also remaining stable over property.
Description
Technical field
The present invention relates to bulk phase catalyst technical fields, are to be related to a kind of cobalt oxide for exposing different crystal faces specifically
The application of bulk phase catalyst and preparation method thereof and the catalyst in regulation hydrogenation of carbon dioxide product distribution.
Background technique
Hydrogenation of carbon dioxide not only contributes to reduce atmospheric carbon dioxide levels, moreover it is possible to generate carbon monoxide, methane, first
The efficient fuel such as alcohol, dimethyl ether, ethyl alcohol, hydro carbons, convenient for storage and transport.Wherein, carbon monoxide and methane are generated in heating power
It learns and is kinetically relatively easy to, and carbon monoxide is to prepare petrol and diesel oil, C by Fischer-Tropsch reaction2-C4The raw material of higher alcohol, again
It is the important source material for preparing many fine chemical products such as medicine, cosmetics, polyester；Furthermore methane is a kind of combustion of clean and effective
Material, therefore catalysis transform of carbon dioxide is that a carbon products such as carbon monoxide or methane are got more attention.
Due to CO2Chemical property is stable, activation is difficult, causes the conversion ratio of the reaction generally lower；On the other hand, an oxygen
Change carbon and methane two kinds of products that be hydrogenation of carbon dioxide degree different, due to adding the bad control of hydrogen degree under rich hydrogen condition,
The two is often accompanied, to cause the selectivity of the two not high；Therefore how to design effective catalyst and carry out dynamics
Control promotes CO2Activating conversion simultaneously adjusts selectivity of product, so as to be efficiently obtained carbon monoxide or methane is one
Urgent problem to be solved.
Currently, generally accepted CO2Following several control paths are distributed in hydrogenation products.First is that adjusting load type gold
The partial size of metallic particles on metal catalyst；Second is that adjusting active metal and oxide carrier interface by changing carrier
The carbon dioxide adsorption property at place, to achieve the purpose that change product distribution.Both the above method, due to the knot of catalyst
Structure is complicated, and reaction site is indefinite, so that preparation method complexity is not easy to repeat, while interfering vulnerable to environmental factor, catalytic effect
It can not achieve gradient adjusting.Co base catalyst is widely used in carbon dioxide hydrogenation reaction.How catalysis is further improved
Agent makes it have stronger CO2Activation capacity and higher carbon monoxide or methane selectively, especially stability are CO2
Add the research emphasis of hydrogen.
Summary of the invention
The present invention is to solve in carbon dioxide hydrogenation reaction, the single selectivity of product such as carbon monoxide or methane compared with
The technical issues of poor (< 60%), provides a kind of cobalt oxide bulk phase catalyst and preparation method thereof of controllable product distribution,
With the application in hydrogenation of carbon dioxide, carbon dioxide hydrogenation reaction product complexity is overcome, single selectivity of product is low to be lacked
It falls into, by the hydro-thermal time in adjusting preparation process, realizes carbon monoxide selective > 90% and arrive methane selectively > 90%, from
And realize the controllable adjustment to product distribution.
In order to solve the above-mentioned technical problem, the present invention is achieved by technical solution below:
A kind of cobalt oxide bulk phase catalyst of controllable product distribution, the cobalt oxide bulk phase catalyst is by following preparation method
It obtains:
(1) cobalt acetate is dissolved in and forms the mixed solution that concentration is 0.5-1.5M/L in ethylene glycol, which is added
Heat is to 150-200 DEG C；
(2) configuration concentration is the wet chemical of 0.5-1M/L, by wet chemical with 20-50 drop/minute speed
Degree is added dropwise in the mixed solution of cobalt acetate and ethylene glycol, solution of potassium carbonate used and cobalt acetate used and ethylene glycol
The mass ratio of mixed solution is 1:5-1:3；
(3) at 150-200 DEG C after hydro-thermal reaction 0-3h, gained suspension is centrifuged and is washed, and at 80-100 DEG C
Vacuum drying, then roasts 2-6h at 400-500 DEG C, obtains a series of Co3O4- xh cobalt oxide bulk phase catalyst, wherein x table
Show the hydro-thermal time.
Preferably, the concentration of the mixed solution of cobalt acetate described in step (1) and ethylene glycol is 1M/L.
Preferably, the heating temperature in step (1) is 180 DEG C.
Preferably, the concentration of wet chemical is 0.5M/L in step (2).
Preferably, vacuum drying temperature is 80 DEG C in step (3).
Preferably, the vacuum drying in step (3) carries out in vacuum drying oven.
Preferably, the maturing temperature in step (3) is 450 DEG C, calcining time 4h.
A kind of preparation method of the cobalt oxide bulk phase catalyst, this method follow the steps below:
(1) cobalt acetate is dissolved in and forms the mixed solution that concentration is 0.5-1.5M/L in ethylene glycol, which is added
Heat is to 150-200 DEG C；
(2) configuration concentration is the wet chemical of 0.5-1M/L, by wet chemical with 20-50 drop/minute speed
Degree is added dropwise in the mixed solution of cobalt acetate and ethylene glycol, solution of potassium carbonate used and cobalt acetate used and ethylene glycol
The mass ratio of mixed solution is 1:5-1:3；
(3) at 150-200 DEG C after hydro-thermal reaction 0-3h, gained suspension is centrifuged and is washed, and at 80-100 DEG C
Vacuum drying, then roasts 2-6h at 400-500 DEG C, obtains a series of Co3O4- xh cobalt oxide bulk phase catalyst, wherein x table
Show the hydro-thermal time.
A kind of application of the cobalt oxide bulk phase catalyst prepares a carbon product for hydrogenation of carbon dioxide.
Further, it follows the steps below:
(1) the cobalt oxide bulk phase catalyst is subjected to compressing tablet process, obtains the pellet type catalyst of 20-40 mesh；
(1) pellet type catalyst of above-mentioned preparation is packed into fixed bed reactors, fixed bed reactors are warming up to reaction temperature
250-350 DEG C of degree, is passed through reaction gas and is reacted, and wherein the molar ratio of hydrogen and carbon dioxide is 2-3, and Balance Air is nitrogen,
Reaction velocity based on carbon dioxide is 1-10h-1。
The beneficial effects of the present invention are:
The present invention using body phase oxidation cobalt as main component, by change the hydro-thermal time, can prepare a series of different-shapes,
The Co of the different crystal faces of exposure3O4Catalyst.
On the one hand, without the Co of hydro-thermal3O4Grain structure, main exposure (111) crystal face, also is presented in -0h catalyst
It is easier to be reduced in originality atmosphere；The catalyst is suitable under lower pressure, has to carbon dioxide hydrogenation reaction good
Effect, specifically Co3O4- 0h can promote catalytic activity well, while can promote C-O scission of link, and it is raw to be conducive to methane
At finally methane selectively being made to reach 90%.
On the other hand, the hydro-thermal time is the Co of 2h3O4Club shaped structure, main exposure (110) crystal face is presented in -2h catalyst；
For carbon dioxide hydrogenation reaction, carbon dioxide conversion is higher than 10%, Co3O4The carbon monoxide selective of -2h reaches
95%, and it is with good stability.
Therefore, the present invention provides the Co of the different crystal faces of exposure3O4With different reproducibilities, with adding for hydro-thermal time
Long, catalyst, which is reduced degree in reduction atmosphere, gradually to be weakened, wherein Co3O4- 0h reproducibility is significantly stronger than Co3O4- 2h,
The Co of different crystal faces during carbon dioxide hydrogenation reaction3O4Show carbon monoxide selective or the methane selection of gradient
Property, promote the activation of carbon dioxide in reaction process.Simultaneously as Co3O4It is cheap, small toxicity, and relatively low
It can be realized the adjusting of one carbon product of hydrogenation of carbon dioxide under pressure by straightforward procedure, therefore there is certain industrial significance.
Detailed description of the invention
Fig. 1 is Co prepared by embodiment 1,12,13,14,153O4Catalyst hydrogenation of carbon dioxide products therefrom point
Cloth change over time figure (350 DEG C, 30bar, air speed=3h-1, CO2/N2/H2=1/1/3)；
Fig. 2 is Co prepared by embodiment 1,12,143O4Catalyst H-TPR figure；
Fig. 3 is Co prepared by embodiment 1,143O4Catalyst TEM figure；Wherein a is Co3O4The conventional TEM of -0h schemes, b
For Co3O4The conventional TEM of -2h schemes, c Co3O4The high power TEM of -0h schemes, d Co3O4The high power TEM of -2h schemes, e Co3O4-0h
Illustraton of model, f Co3O4The illustraton of model of -2h；
Fig. 4 is Co prepared by embodiment 1,12,143O4Catalyst hydrogenation of carbon dioxide at different temperatures gained
Carbon monoxide selective and carbon dioxide conversion with reaction temperature variation diagram (300-350 DEG C, 30bar, air speed=3h-1,
CO2/N2/H2=1/1/3).
Specific embodiment
Below by specific embodiment, the present invention is described in further detail, and following embodiment can make this profession
The present invention, but do not limit the invention in any way is more completely understood in technical staff.
Embodiment 1
(1) 4.8g cobalt acetate ((CH is taken3COO)2Co) it is added to 60ml ethylene glycol ((CH2OH)2) in, it is formed by solution
Concentration is 1M/L, and above-mentioned solution is heated to 180 DEG C, stands stirring；
(2) by potassium carbonate (K2CO3) be dissolved in deionized water, being formed by solution concentration is 0.5M/L；
(3) solution of potassium carbonate is added in the cobalt acetate of (1) and the mixed solution of ethylene glycol dropwise (20 drops/minute),
Solution of potassium carbonate used is that 20ml is finally centrifuged suspension and washs four times then in 180 DEG C of difference hydro-thermal reaction 0h；
(4) 80 DEG C of solid dry 12h for obtaining (3)；
(5) solid that (4) obtain is roasted into 4h at 450 DEG C, obtains cobalt oxide catalyst.
It (6) is the pellet type catalyst of 20-40 mesh by above-mentioned fine catalyst tabletting；
(7) cobalt oxide catalyst after tabletting is packed into fixed bed reactors, is passed through N2, when reaching 350 DEG C of reaction temperature,
Reaction gas is switched to, wherein carbon dioxide and hydrogen molar ratio are 3:1, and Balance Air is nitrogen (CO2=10ml/min, H2=
30mL/min, N2=10mL/min), the reaction velocity based on carbon dioxide is 3h-1。
Catalyst activity is indicated with produced carbon monoxide and methane (mL/min) and selectivity, below selectivity of product
Formula is calculated:
Conversion ratio:
Selectivity:
Wherein, FCO2,inRepresent the volume flow rate of carbon dioxide at reactor inlet, FCO2,outRepresent reactor exit two
The gas volume flow velocity of carbonoxide, i represent reaction product, including CH4, CO, n represents carbon number contained in these substances.
Reaction product uses gas chromatograph on-line analysis, and Product Rate and selectivity are as shown in table 1 with the relationship of time.
Table 1, the selectivity of product of differential responses time
Seen from table 1, catalyst activity with higher, and stability is fine, and it is basic to react 5 hour response datas
It is unchanged.
Embodiment 2:
It is reacted using 1 method of embodiment, distinguishing the addition cobalt acetate quality being only that in step (1) is 2.4g,
Being formed by solution concentration is 0.5M/L.
Embodiment 3:
It is reacted using 1 method of embodiment, distinguishing the addition cobalt acetate quality being only that in step (1) is 7.2g,
Being formed by solution concentration is 1.5M/L.
Embodiment 4:
It is reacted using 1 method of embodiment, difference is only that the hydrothermal temperature of step (1) and step (3) is 150
℃。
Embodiment 5:
It is reacted using 1 method of embodiment, difference is only that the hydrothermal temperature of step (1) and step (3) is 200
℃。
Embodiment 6:
It is reacted using 1 method of embodiment, difference is only that in step (2) that solution of potassium carbonate concentration is 0.75M/L.
Embodiment 7:
It is reacted using 1 method of embodiment, difference is only that in step (2) that solution of potassium carbonate concentration is 1M/L.
Embodiment 8:
It is reacted using 1 method of embodiment, difference is only that the drop rate of the solution of potassium carbonate of step (3) is 35
Drop/minute.
Embodiment 9:
It is reacted using 1 method of embodiment, difference is only that the drop rate of the solution of potassium carbonate of step (3) is 50
Drop/minute.
Embodiment 10:
It is reacted using 1 method of embodiment, difference is only that the dripping quantity of the solution of potassium carbonate of step (3) is
12ml。
Embodiment 11:
It is reacted using 1 method of embodiment, difference is only that the dripping quantity of the solution of potassium carbonate of step (3) is
15ml。
Embodiment 12:
It is reacted using 1 method of embodiment, difference is only that the hydro-thermal time of step (3) is 0.5h.
Embodiment 13:
It is reacted using 1 method of embodiment, difference is only that the hydro-thermal time of step (3) is 1h.
Embodiment 14:
It is reacted using 1 method of embodiment, difference is only that the hydro-thermal time of step (3) is 2h.
Embodiment 15:
It is reacted using 1 method of embodiment, difference is only that the hydro-thermal time of step (3) is 3h.
Embodiment 16:
It is reacted using 1 method of embodiment, difference is only that the drying temperature of step (4) is 90 DEG C.
Embodiment 17:
It is reacted using 1 method of embodiment, difference is only that the drying temperature of step (4) is 100 DEG C.
Embodiment 18:
It is reacted using 1 method of embodiment, difference is only that the maturing temperature of step (5) is 400 DEG C.
Embodiment 19:
It is reacted using 1 method of embodiment, difference is only that the maturing temperature of step (5) is 500 DEG C.
Embodiment 20:
It is reacted using 1 method of embodiment, difference is only that the calcining time of step (5) is 2h.
Embodiment 21:
It is reacted using 1 method of embodiment, difference is only that the calcining time of step (5) is 6h.
Embodiment 22:
It is reacted using 1 method of embodiment, difference is only that the reaction temperature of step (7) is 250 DEG C.
Embodiment 23:
It is reacted using 1 method of embodiment, difference is only that the reaction temperature of step (7) is 300 DEG C.
Embodiment 24:
It is reacted using 1 method of embodiment, difference is only that the reaction temperature of step (7) is 330 DEG C.
Embodiment 25:
It is reacted using 1 method of embodiment, difference is only that the reaction temperature of step (7) is 340 DEG C.
Embodiment 26:
It is reacted using 1 method of embodiment, difference is, the hydro-thermal time of step (3) is 0.5h, step (7)
Reaction temperature is 250 DEG C.
Embodiment 27:
It is reacted using 1 method of embodiment, difference is, the hydro-thermal time of step (3) is 0.5h, step (7)
Reaction temperature is 300 DEG C.
Embodiment 28:
It is reacted using 1 method of embodiment, difference is, the hydro-thermal time of step (3) is 0.5h, step (7)
Reaction temperature is 330 DEG C.
Embodiment 29:
It is reacted using 1 method of embodiment, difference is, the hydro-thermal time of step (3) is 0.5h, step (7)
Reaction temperature is 340 DEG C.
Embodiment 30:
Reacted using 1 method of embodiment, difference is, hydro-thermal time of step (3) is 2h, step (7) it is anti-
Answering temperature is 250 DEG C.
Embodiment 31:
Reacted using 1 method of embodiment, difference is, hydro-thermal time of step (3) is 2h, step (7) it is anti-
Answering temperature is 300 DEG C.
Embodiment 32:
Reacted using 1 method of embodiment, difference is, hydro-thermal time of step (3) is 2h, step (7) it is anti-
Answering temperature is 330 DEG C.
Embodiment 33:
Reacted using 1 method of embodiment, difference is, hydro-thermal time of step (3) is 2h, step (7) it is anti-
Answering temperature is 340 DEG C.
Embodiment 34:
It is reacted using 1 method of embodiment, difference is only that the carbon dioxide volume space velocity of step (7) is 1h-1。
Embodiment 35:
It is reacted using 1 method of embodiment, difference is only that the carbon dioxide volume space velocity of step (7) is 5h-1。
Embodiment 36:
It is reacted using 1 method of embodiment, difference is only that the carbon dioxide volume space velocity of step (7) is 10h-1。
Embodiment 37:
It is reacted using 1 method of embodiment, difference is only that the hydro-thermal time of step (3) is 2h, step (7)
Carbon dioxide volume space velocity is 1h-1。
Embodiment 38:
It is reacted using 1 method of embodiment, difference is only that the hydro-thermal time of step (3) is 2h, step (7)
Carbon dioxide volume space velocity is 5h-1。
Embodiment 39:
It is reacted using 1 method of embodiment, difference is only that the hydro-thermal time of step (3) is 2h, step (7)
Carbon dioxide volume space velocity is 10h-1。
Embodiment 40:
It is reacted using 1 method of embodiment, distinguish the hydrogen being only that in step (7) is with carbon dioxide molar ratio
2:1。
About above-described embodiment result and data, activity data when being all made of reaction 4h is compared, to investigate different ginsengs
The influence of several pairs of catalyst reaction performances.In addition to the condition of following special instruction, the change of conditions above can prepare me
Catalyst, and the similar performance shown in carbon dioxide hydrogenation reaction.
(1) the hydro-thermal reaction time is on the active influence of catalyst reaction, referring to table 2 and attached drawing 1.Reaction condition is the same as implementation
Example 1,12,13,14,15.
Table 2, different hydro-thermal times are on the active influence of hydrogenation of carbon dioxide
As can be seen from the table, the cobalt oxide catalyst of the series shows preferable hydrogenation of carbon dioxide system activity,
Specifically, as the increase of hydro-thermal time, carbon dioxide conversion and methane selectively are gradually reduced and carbon monoxide selection
Property gradually rises, and methane selectively is by Co3O4The 88% of -0h is reduced to Co3O4The 5% of -2h, and carbon monoxide selective by
Co3O4The 12% of -0h is increased to Co3O4The 95% of -2h.As shown in Fig. 1, can be maintained there are five the reactivity worth of sample
At least four hour does not reduce, and illustrates that catalyst is with good stability.
As shown in attached drawing 2,3, with the increase of hydro-thermal time, the pattern of cobalt oxide is presented to be turned by particle to corynebacterium
Become, it can be seen that exposure crystal face is changed into (110) by (111), by hydrogen temperature programmed reduction figure from transmission electron microscope picture TEM
H-TPR can be seen that reduction temperature gradually rises, and reproducibility gradually weakens.
(2) reaction temperature is to Co3O4The influence of -0h catalytic reaction activity, referring to table 3.Reaction condition with embodiment 1,
22、23、24、25。
Table 3, reaction temperature are on the active influence of hydrogenation of carbon dioxide
As can be seen from the table, with the raising of reaction temperature, the conversion ratio of hydrogenation of carbon dioxide is obviously increased, that is, is reacted
Activity gradually rises；For Co3O4- 0h catalyst, selectivity of product are very sensitive to reaction temperature variation, with reaction temperature
The raising of degree, carbon monoxide selective are gradually reduced, and methane selectively gradually rises, when reaction temperature is 350 DEG C, first
Alkane selectively reaches maximum value.
(3) reaction temperature is to Co3O4The influence of -0.5h catalytic reaction activity, referring to table 4 and attached drawing 4.Reaction condition is same
Embodiment 1,26,27,28,29.
Table 4, reaction temperature are on the active influence of hydrogenation of carbon dioxide
As can be seen from the table, with the raising of reaction temperature, the conversion ratio of hydrogenation of carbon dioxide is obviously increased, that is, is reacted
Activity gradually rises；For Co3O4- 0.5h catalyst, selectivity of product is more sensitive to temperature change, with reaction temperature
It increasing, carbon monoxide selective is gradually reduced, and methane selectively gradually rises, when reaction temperature is 350 DEG C, methane choosing
Selecting property reaches maximum value, but still has a certain amount of carbon monoxide to generate at this time；Under any reaction temperature, Co3O4-
The methane selectively of 0.5h is below Co3O4-0h。
(4) reaction temperature is to Co3O4The influence of -2h catalytic reaction activity, referring to table 5.Reaction condition with embodiment 1,
30、31、32、33。
Table 5, reaction temperature are on the active influence of hydrogenation of carbon dioxide
As can be seen from the table, with the raising of reaction temperature, the conversion ratio of hydrogenation of carbon dioxide is obviously increased, that is, is reacted
Activity gradually rises；For Co3O4- 2h catalyst, selectivity of product is insensitive to temperature change, with the liter of reaction temperature
Height, carbon monoxide selective does not change substantially, and methane selectively is also basically unchanged, and is 300-350 DEG C in reaction temperature
Range in, be nearly free from methane, namely for methane selectivity is very low, but carbon monoxide selective is always held at 95% at this time
More than, i.e., product is based on carbon monoxide.
As shown in figure 4, to be distributed the trend changed with reaction temperature consistent for the conversion ratio of three samples and product, but they it
Between selectivity of product difference clearly, and it is generally existing to vary with temperature this difference, does not change.
(5) influence of the carbon dioxide volume space velocity to catalyst activity, referring to table 6.Reaction condition with embodiment 1,
34、35、36、37、38、39。
The influence of table 6, carbon dioxide volume space velocity to catalytic activity
As can be seen from the table, with the raising of carbon dioxide volume space velocity, carbon dioxide conversion is constantly reduced, still
The selectivity of methane and carbon monoxide is basically unchanged, air speed 1h-1And 3h-1It is not much different, therefore best carbon dioxide volume space velocity
It is 3h-1。
Although the preferred embodiment of the present invention is described above in conjunction with attached drawing, the invention is not limited to upper
The specific embodiment stated, the above mentioned embodiment is only schematical, be not it is restrictive, this field it is general
Logical technical staff under the inspiration of the present invention, without breaking away from the scope protected by the purposes and claims of the present invention, goes back
The specific transformation of many forms can be made, within these are all belonged to the scope of protection of the present invention.
Claims (10)
1. a kind of cobalt oxide bulk phase catalyst of controllable product distribution, which is characterized in that the cobalt oxide bulk phase catalyst by with
Lower preparation method obtains:
(1) cobalt acetate is dissolved in and forms the mixed solution that concentration is 0.5-1.5M/L in ethylene glycol, which is heated to
150-200℃；
(2) configuration concentration be 0.5-1M/L wet chemical, by wet chemical with 20-50 drop/minute speed by
It is added dropwise in the mixed solution of cobalt acetate and ethylene glycol, the mixing of solution of potassium carbonate used and cobalt acetate used and ethylene glycol is molten
The mass ratio of liquid is 1:5-1:3；
(3) at 150-200 DEG C after hydro-thermal reaction 0-3h, gained suspension is centrifuged and is washed, and the vacuum at 80-100 DEG C
It is dry, 2-6h then is roasted at 400-500 DEG C, obtains a series of Co3O4- xh cobalt oxide bulk phase catalyst, wherein x indicates water
The hot time.
2. a kind of cobalt oxide bulk phase catalyst of controllable product distribution according to claim 1, which is characterized in that step
(1) concentration of the mixed solution of cobalt acetate and ethylene glycol described in is 1M/L.
3. a kind of cobalt oxide bulk phase catalyst of controllable product distribution according to claim 1, which is characterized in that step
(1) heating temperature in is 180 DEG C.
4. a kind of cobalt oxide bulk phase catalyst of controllable product distribution according to claim 1, which is characterized in that step
(2) concentration of wet chemical is 0.5M/L in.
5. a kind of cobalt oxide bulk phase catalyst of controllable product distribution according to claim 1, which is characterized in that step
(3) vacuum drying temperature is 80 DEG C in.
6. a kind of cobalt oxide bulk phase catalyst of controllable product distribution according to claim 1, which is characterized in that step
(3) vacuum drying in carries out in vacuum drying oven.
7. a kind of cobalt oxide bulk phase catalyst of controllable product distribution according to claim 1, which is characterized in that step
(3) maturing temperature in is 450 DEG C, calcining time 4h.
8. a kind of preparation method of the cobalt oxide bulk phase catalyst as described in any one of claim 1-7, which is characterized in that the party
Method follows the steps below:
(1) cobalt acetate is dissolved in and forms the mixed solution that concentration is 0.5-1.5M/L in ethylene glycol, which is heated to
150-200℃；
(2) configuration concentration be 0.5-1M/L wet chemical, by wet chemical with 20-50 drop/minute speed by
It is added dropwise in the mixed solution of cobalt acetate and ethylene glycol, the mixing of solution of potassium carbonate used and cobalt acetate used and ethylene glycol is molten
The mass ratio of liquid is 1:5-1:3；
(3) at 150-200 DEG C after hydro-thermal reaction 0-3h, gained suspension is centrifuged and is washed, and the vacuum at 80-100 DEG C
It is dry, 2-6h then is roasted at 400-500 DEG C, obtains a series of Co3O4- xh cobalt oxide bulk phase catalyst, wherein x indicates water
The hot time.
9. a kind of application of the cobalt oxide bulk phase catalyst as described in any one of claim 1-7, which is characterized in that be used for dioxy
Changing carbon adds hydrogen to prepare carbon monoxide and/or methane.
10. a kind of application of the cobalt oxide bulk phase catalyst as described in any one of claim 1-7, which is characterized in that according to
Lower step carries out:
(1) the cobalt oxide bulk phase catalyst is subjected to compressing tablet process, obtains the pellet type catalyst of 20-40 mesh；
(1) pellet type catalyst of above-mentioned preparation is packed into fixed bed reactors, fixed bed reactors are warming up to reaction temperature
It 250-350 DEG C, is passed through reaction gas and is reacted, wherein the molar ratio of hydrogen and carbon dioxide is 2-3, and Balance Air is nitrogen, base
In carbon dioxide reaction velocity be 1-10h-1。
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| CN110787822A (en) * | 2019-09-24 | 2020-02-14 | 青岛大学 | Cobaltosic oxide catalyst, preparation method and application thereof |
| CN113426472A (en) * | 2020-03-23 | 2021-09-24 | 中国科学院山西煤炭化学研究所 | Cobalt-based catalyst and CO2Method for preparing CO by catalytic hydrogenation |
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