CN108554416A - A kind of modified cobalt-base catalyst and the preparation method and application thereof - Google Patents
A kind of modified cobalt-base catalyst and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of modified cobalt-base catalyst and its preparation and application, include the following steps：(1) glucose is dissolved in ethanol/water solution, is reacted in a kettle after ultrasonic vibration, filtered after reaction, water and absolute ethyl alcohol is used in combination alternately to wash, it is dry, obtain carbon ball carrier；(2) soluble Co salt and soluble transition metal salt are dissolved in the water, obtain mixed solution；(3) carbon ball carrier is added in mixed solution, ultrasonic vibration, ammonium hydroxide is then added dropwise, adjusted pH, be aged, be filtered, washed, dry, obtain metal hydroxides load carbon ball powder；(4) by metal hydroxides load carbon ball powder roasting to get the modified cobalt-base catalyst.Compared with prior art, the environmental protection of the present invention uses low in raw material price, preparation condition are mild, and obtained catalyst catalytic activity in catalytic reaction process is high, stability is strong, can be used for being catalyzed during a variety of environmental catalysis such as combustion degradation volatile organic matter.
Description
Technical field
The present invention relates to environmental protection technical fields, and in particular to a kind of modified cobalt-base catalyst and preparation method thereof with answer
With.
Background technology
Volatile organic compounds (VOCs) is the major pollutants in air, they can send out with the nitrogen oxides in air
Raw reaction, generates photochemical fog, to endanger urban air-quality and human health.In recent years, with China's chemical industry
Development and vehicles number increase, VOCs pollution problem getting worses.Catalytic oxidation can be at relatively low temperature
Efficiently by VOCs it is degradable be carbon dioxide and water, have become a kind of one of most promising VOCs administering methods.
Noble metal catalyst is usually used in VOCs catalysis oxidations, with excellent low-temperature catalytic activity.However, their valences
Lattice are expensive, are easy poisoning and deactivation.Transition metal oxide has low cost, higher catalytic activity and higher mithridatism etc. excellent
Point, it is considered to be one of substitute of noble metal catalyst.
In existing non-precious metal catalyst, the oxide of cobalt (Co) has outstanding catalytic activity in cold stage, by
It is widely used in various catalysis reactions, it is considered to be one of most effective catalyst of the VOCs such as complete oxidation toluene and propane.
The preparation method of existing Co catalyst includes coprecipitation, sol-gal process or solvent-thermal method, such as patent
CN103894200A, CN101791559A, CN105983408A disclose above-mentioned preparation method, but urging of preparing of these methods
Often there is agglomeration in agent, and specific surface area is relatively low, and activity is poor with stability.This is because the doping of metal ion and
The appearance structure of material is improper caused.Therefore to find the catalyst that a kind of synthesis is simple, stability is strong is to realize that VOCs is urged
Change the most important thing of oxidation.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of synthesis is simple, stablizes
The strong modification cobalt-base catalyst and the preparation method and application thereof of property.
The purpose of the present invention can be achieved through the following technical solutions：A kind of modified cobalt-base catalyst, the catalyst packet
The cobalt oxide and transition metal oxide for including carbon ball carrier and being supported in carbon ball carrier, the transition metal oxide include
The oxide and Co elements of Cu, Ce or La and these transition elements exist jointly, the cobalt oxide and transition metal oxide
Molar ratio is 4：(0~1).The presence of transition elements in the present invention has facilitation to the catalytic activity of Co elements.
A kind of preparation method of modified cobalt-base catalyst as described above, includes the following steps：
(1) glucose is dissolved in ethanol/water solution, is reacted in a kettle after ultrasonic vibration, filtered after reaction,
It is used in combination water and absolute ethyl alcohol alternately to wash, it is dry, obtain carbon ball carrier；
(2) soluble Co salt and soluble transition metal salt are dissolved in the water, obtain mixed solution, wherein is soluble
The molar ratio of Co elements and transition metal element is 4 in Co salt and soluble transition metal salt：(0~1), in the mixed solution
The total mol concentration of Co elements and transition metal element is (0.1~0.15) mol/L；
(3) the carbon ball carrier that step (1) obtains is added in the mixed solution that step (2) obtains, ultrasonic vibration, then
Ammonium hydroxide is added dropwise, adjusts pH to 7~10, then ageing is filtered, washed, dries, obtain metal hydroxides load carbon ball powder；
(4) the metal hydroxides load carbon ball powder that step (3) obtains is roasted in inert atmosphere to get institute
State modified cobalt-base catalyst.
The volume ratio of ethanol/water solution described in step (1), second alcohol and water is 1：(1~89), the glucose of addition
The ratio between volume of quality and ethanol/water solution is (5~15) g：(70~90) mL, the time of ultrasonic vibration described in step (1)
For 30~90min.
Described in step (1) reaction carried out in the reaction kettle with polytetrafluoroethylliner liner, reaction temperature be 120~
180 DEG C, the reaction time is 5~12h.The present invention uses source of the glucose as carbon ball carrier, is because glucose is poly- first
The linear or dendritic oligosaccharides molecule of long-chain is synthesized, when solution reaches hypersaturated state, these molecules crosslink reaction, most
Great amount of hydroxy group and the carbon ball of carbonyl is distributed at surface in end form, and cobalt ions is easier to be adsorbed onto these carbon balls in follow-up preparation process
Surface on, and then improve active component unit content.
In step (1) after reaction, it filters, alternately washing 3~5 times of water and absolute ethyl alcohol is used in combination, and at 60~120 DEG C
At a temperature of be dried in vacuo 6~10h.
The addition quality of carbon ball carrier and the volume ratio of mixed solution are (45~55) in step (3)：1, and in step (3)
The time of ultrasonic vibration is 1~2h.
The temperature of the ageing is 15~25 DEG C, and digestion time is 12~15h, is washed with water 3~5 times after ageing, then
In 60~120 DEG C, at a temperature of vacuum drying 12~for 24 hours.For the present invention using ammonia spirit as precipitating reagent, the material of preparation has phase
To optimal catalytic degradation activity.
The calcination temperature is 400~500 DEG C, and preferably 440~460 DEG C, roasting time is 2~4h, preferably 2~2.5h.
It roasts under this condition, crystal form is without significant change in catalyst.
The modification cobalt-base catalyst is used for the catalyst of volatile organic compounds by catalytic combustion degradation, the hair property organic matter packet
Include butane, 2- methybutanes, pentane, 2- toluene, 1,3 butadiene, methylpentane, 3- methyl hexane, methyl heptane, isopropylbenzene,
Propyl benzene, m- ethyltoluene, o- ethyltoluene, mesitylene, m- diethylbenzene, dodecane, methyl sulfide, limonene, propylene, third
One or more of mixtures of ketone, n-hexane.Due to the modification cobalt-base catalyst that is prepared of the present invention have multilevel hierarchy,
Metal oxide dispersion degree is big thereon, it is made to be more suitable for above-mentioned volatile organic matter of degrading.
Combustion degradation uses air for oxidant, and reaction temperature is 100~400 DEG C, and preferable reaction temperature is 150~225
℃。
The dosage of the catalyst is the exhaust gas of every gram of catalyst treatment volatile organic matter Han 600~18000ppm, institute
The flow for stating exhaust gas is 10~30L/h.
Compared with prior art, beneficial effects of the present invention are embodied in following several respects：
(1) activity is high, stability is good, can realize the complete of low concentration volatile organic matter at relatively low temperature
Burning；
(2) preparation process is simple, low in raw material price, environmental protection, can further industry amplification；
(3) there is potential application prospect in terms of the environmental protections such as degradation volatile organic matter.
Description of the drawings
Fig. 1 a, 1b, 1c are respectively scanning electron microscope (SEM) figure of prepared catalyst in embodiment 1,2,3；
Fig. 2 is the toluene combustibility curve tested to prepared catalyst in embodiment 1,2,3；
Fig. 3 is the toluene flameholding linearity curve that the catalyst of embodiment 3 is tested at 200 DEG C.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
6g glucose is dissolved in 90mL deionized waters, acquired solution, ultrasonic vibration 30min is evenly dispersed to glucose
In the solution.Glucose solution is poured into 100m L polytetrafluoroethylliner liners, is placed in reaction kettle and reacts 10h at 170 DEG C.It is cooling
It is filtered after to room temperature, with deionized water and absolute ethyl alcohol alternately washing 3 times, is finally dried in vacuo 6h in 80 DEG C, obtains carbon ball powder
End.
Using soluble cobalt and lanthanum salt as presoma, wherein La:The molar ratio of Co is 0:1, suitable deionization is added
Water, makes solution metal ion concentration be equal to 0.12mol/L, and stirring obtains transparent mixed solution.
0.05g carbon balls are added into acquired solution, after ultrasonic vibration 1h, carbon ball powder are made to be dispersed in solution, it
Ammonia spirit is slowly added dropwise while stirring afterwards, adjusts pH=8.5.Ageing 12h after filter, be washed with deionized several times, in
80 DEG C of vacuum drying 12h obtain metal hydroxides load carbon ball powder.Be placed on 400 DEG C of Muffle furnace roasting 2h, changed
Property cobalt-base catalyst, electron-microscope scanning is carried out to it, obtained SEM figure is as shown in Figure 1a, therefrom it will be seen that without La
Co bases catalyst material is mainly accumulated by certain thickness laminated structure, and gap is few, bad dispersibility.
Catalyst fines 0.15g is weighed, is uniformly mixed with 0.75g quartz sands, quartzy microreactor (φ=4mm) is loaded on
In.Reaction gas is toluene/air/nitrogen mixed gas, and wherein air speed is 15000h-1, O2Volume fraction 10%, volume of toluene
Score is 0.06%.Catalytic activity measurement carries out within the scope of 150~225 DEG C, using the conversion ratio of toluene as index.Catalyst is steady
Qualitative test temperature is 200 DEG C, and the reaction time is more than 10 hours.
The catalyst toluene initiation temperature prepared by embodiment 1 is measured (when 10% toluene conversion pair by above-mentioned experiment
The temperature answered) T10It is 186 DEG C, the T of toluene90It it is 210 DEG C, conversion completely can be achieved at 225 DEG C for toluene, as shown in Figure 2.
Embodiment 2：
The present embodiment is the embodiment of the preparation method of the modification cobalt-base catalyst of the present invention.
6g glucose is dissolved in 90mL deionized waters, acquired solution, ultrasonic vibration 30min is evenly dispersed to glucose
In the solution.Glucose solution is poured into 100m L polytetrafluoroethylliner liners, is placed in reaction kettle and reacts 10h at 170 DEG C.It is cooling
It is filtered after to room temperature, with deionized water and absolute ethyl alcohol alternately washing 3 times, is finally dried in vacuo 6h in 80 DEG C, obtains carbon ball powder
End.
Using soluble cobalt and lanthanum salt as presoma, wherein La:The molar ratio of Co is 1:10, suitable deionization is added
Water, makes solution metal ion concentration be equal to 0.12mol/L, and stirring obtains transparent mixed solution.
0.05g carbon balls are added into acquired solution, after ultrasonic vibration 1h, carbon ball powder are made to be dispersed in solution, it
Ammonia spirit is slowly added dropwise while stirring afterwards, adjusts pH=8.5.Ageing 12h after filter, be washed with deionized several times, in
80 DEG C of vacuum drying 12h obtain metal hydroxides load carbon ball powder.Be placed on 400 DEG C of Muffle furnace roasting 2h, changed
Property cobalt-base catalyst.Electron-microscope scanning is carried out to it, obtained SEM figures are as shown in Figure 1 b, therefrom it will be seen that containing in material
When having a small amount of La, material hole number increases, and the trend changed to " petal-shaped " occurs on the whole in structure.
Catalyst fines 0.15g is weighed, is uniformly mixed with 0.75g quartz sands, quartzy microreactor (φ=4mm) is loaded on
In.Reaction gas is toluene/air/nitrogen mixed gas, and wherein air speed is 15000h-1, O2Volume fraction 10%, volume of toluene
Score is 0.06%.Catalytic activity measurement carries out within the scope of 150~225 DEG C, using the conversion ratio of toluene as index.Catalyst is steady
Qualitative test temperature is 200 DEG C, and the reaction time is more than 10 hours.
The catalyst toluene initiation temperature prepared by embodiment 2 is measured (when 10% toluene conversion pair by above-mentioned experiment
The temperature answered) T10It is 169 DEG C, the T of toluene90It it is 205 DEG C, conversion completely can be achieved at 210 DEG C for toluene, as shown in Figure 2.
Embodiment 3：
The present embodiment is the embodiment of the preparation method of the modification cobalt-base catalyst of the present invention.
6g glucose is dissolved in 90mL deionized waters, acquired solution, ultrasonic vibration 30min is evenly dispersed to glucose
In the solution.Glucose solution is poured into 100m L polytetrafluoroethylliner liners, is placed in reaction kettle and reacts 10h at 170 DEG C.It is cooling
It is filtered after to room temperature, with deionized water and absolute ethyl alcohol alternately washing 3 times, is finally dried in vacuo 6h in 80 DEG C, obtains carbon ball powder
End.
Using soluble cobalt and lanthanum salt as presoma, wherein La:The molar ratio of Co is 1:4, suitable deionization is added
Water, makes solution metal ion concentration be equal to 0.12mol/L, and stirring obtains transparent mixed solution.
0.05g carbon balls are added into acquired solution, after ultrasonic vibration 1h, carbon ball powder are made to be dispersed in solution, it
Ammonia spirit is slowly added dropwise while stirring afterwards, adjusts pH=8.5.Ageing 12h after filter, be washed with deionized several times, in
80 DEG C of vacuum drying 12h obtain metal hydroxides load carbon ball powder.Be placed on 400 DEG C of Muffle furnace roasting 2h, changed
Property cobalt-base catalyst.Electron-microscope scanning is carried out to it, obtained SEM schemes as illustrated in figure 1 c, therefrom it will be seen that continuing growing
La contents, material laminated structure is significantly thinning, and mutually overlapping accumulation is in petal-shaped, and thin slice distribution is more uniform, has therebetween rich
Rich intergranular pore, increases the contact area of catalyst and reactant.
Catalyst fines 0.15g is weighed, is uniformly mixed with 0.75g quartz sands, quartzy microreactor (φ=4mm) is loaded on
In.Reaction gas is toluene/air/nitrogen mixed gas, and wherein air speed is 15000h-1, O2Volume fraction 10%, volume of toluene
Score is 0.06%.Catalytic activity measurement carries out within the scope of 150~225 DEG C, using the conversion ratio of toluene as index.Catalyst is steady
Qualitative test temperature is 200 DEG C, and the reaction time is more than 10 hours.
The catalyst toluene initiation temperature prepared by embodiment 3 is measured (when 10% toluene conversion pair by above-mentioned experiment
The temperature answered) T10Less than 150 DEG C, the T of toluene90It it is 178 DEG C, conversion completely can be achieved at 195 DEG C for toluene.As shown in Figure 2.
In combustion process, toluene flameholding linearity curve is as shown in figure 3, it will be seen that entire burned from figure
The stability of catalyst is very high in journey.
Embodiment 4
The present embodiment is the embodiment of the preparation method of the modification cobalt-base catalyst of the present invention.
6g glucose is dissolved in 90mL deionized waters, acquired solution, ultrasonic vibration 30min is evenly dispersed to glucose
In the solution.Glucose solution is poured into 100m L polytetrafluoroethylliner liners, is placed in reaction kettle and reacts 10h at 170 DEG C.It is cooling
It is filtered after to room temperature, with deionized water and absolute ethyl alcohol alternately washing 3 times, is finally dried in vacuo 6h in 80 DEG C, obtains carbon ball powder
End.
Using soluble cobalt and lanthanum salt as presoma, wherein La:The molar ratio of Co is 1:4, suitable deionization is added
Water, makes solution metal ion concentration be equal to 0.12mol/L, and stirring obtains transparent mixed solution.
0.05g carbon balls are added into acquired solution, after ultrasonic vibration 1h, carbon ball powder are made to be dispersed in solution, it
Ammonia spirit is slowly added dropwise while stirring afterwards, adjusts pH=8.5.Ageing 12h after filter, be washed with deionized several times, in
80 DEG C of vacuum drying 12h obtain metal hydroxides load carbon ball powder.Be placed on 400 DEG C of Muffle furnace roasting 3h, changed
Property cobalt-base catalyst.
Catalyst fines 0.15g is weighed, is uniformly mixed with 0.75g quartz sands, quartzy microreactor (φ=4mm) is loaded on
In.Reaction gas is toluene/air/nitrogen mixed gas, and wherein air speed is 15000h-1, O2Volume fraction 10%, volume of toluene
Score is 0.06%.Catalytic activity measurement carries out within the scope of 150~225 DEG C, using the conversion ratio of toluene as index.Catalyst is steady
Qualitative test temperature is 200 DEG C, and the reaction time is more than 10 hours.
The catalyst toluene initiation temperature prepared by embodiment 4 is measured (when 10% toluene conversion pair by above-mentioned experiment
The temperature answered) T10It is 168 DEG C, the T of toluene90It it is 195 DEG C, conversion completely can be achieved at 255 DEG C for toluene.
Embodiment 5：
The present embodiment is the embodiment of the preparation method of the modification cobalt-base catalyst of the present invention.
6g glucose is dissolved in 90mL deionized waters, acquired solution, ultrasonic vibration 30min is evenly dispersed to glucose
In the solution.Glucose solution is poured into 100m L polytetrafluoroethylliner liners, is placed in reaction kettle and reacts 10h at 170 DEG C.It is cooling
It is filtered after to room temperature, with deionized water and absolute ethyl alcohol alternately washing 3 times, is finally dried in vacuo 6h in 80 DEG C, obtains carbon ball powder
End.
Using soluble cobalt and lanthanum salt as presoma, wherein La:The molar ratio of Co is 1:4, suitable deionization is added
Water, makes solution metal ion concentration be equal to 0.12mol/L, and stirring obtains transparent mixed solution.
0.05g carbon balls are added into acquired solution, after ultrasonic vibration 1h, carbon ball powder are made to be dispersed in solution, it
Ammonia spirit is slowly added dropwise while stirring afterwards, adjusts pH=8.5.Ageing 12h after filter, be washed with deionized several times, in
80 DEG C of vacuum drying 12h obtain metal hydroxides load carbon ball powder.Be placed on 400 DEG C of Muffle furnace roasting 4h, changed
Property cobalt-base catalyst.
Catalyst fines 0.15g is weighed, is uniformly mixed with 0.75g quartz sands, quartzy microreactor (φ=4mm) is loaded on
In.Reaction gas is toluene/air/nitrogen mixed gas, and wherein air speed is 15000h-1, O2Volume fraction 10%, volume of toluene
Score is 0.06%.Catalytic activity measurement carries out within the scope of 150~225 DEG C, using the conversion ratio of toluene as index.Catalyst is steady
Qualitative test temperature is 200 DEG C, and the reaction time is more than 10 hours.
The catalyst toluene initiation temperature prepared by embodiment 5 is measured (when 10% toluene conversion pair by above-mentioned experiment
The temperature answered) T10It is 180 DEG C, the T of toluene90It it is 209 DEG C, conversion completely can be achieved at 270 DEG C for toluene.
Embodiment 6
5g glucose is dissolved in the mixed solution of 89mL deionized waters and 1mL absolute ethyl alcohols, acquired solution, ultrasound shake
It is evenly dispersed in the solution to glucose to swing 30min.Glucose solution is poured into 100m L polytetrafluoroethylliner liners, is placed in reaction
In kettle 20h is reacted at 120 DEG C.It filters, is alternately washed 3 times with deionized water and absolute ethyl alcohol, finally in 60 after being cooled to room temperature
DEG C vacuum drying 10h, obtain carbon ball powder.
Using soluble cobalt and lanthanum salt as presoma, wherein La:The molar ratio of Co is 1:4, suitable deionization is added
Water, makes solution metal ion concentration be equal to 0.1mol/L, and stirring obtains transparent mixed solution.
It weighs and 0.05g carbon balls is added in 2.75g solution, after ultrasonic vibration 1h, carbon ball powder is made to be dispersed in solution,
Ammonia spirit is slowly added dropwise while stirring later, adjusts pH=7.It filters, is washed with deionized 3 times after room temperature ageing 12h, in
60 DEG C of vacuum drying for 24 hours, obtain metal hydroxides load carbon ball powder, and 4h is roasted at 400 DEG C to get modified cobalt-based catalyst
Agent.
After testing, the modification cobalt-based catalyst stability that the present embodiment obtains is strong, and catalytic activity is high.
Embodiment 7
15g glucose is dissolved in the mixed solution of 35mL deionized waters and 35mL absolute ethyl alcohols, acquired solution, ultrasound
It is evenly dispersed in the solution to glucose to shake 90min.Glucose solution is poured into 100m L polytetrafluoroethylliner liners, is placed in anti-
It answers in kettle and reacts 5h at 180 DEG C.Filtered after being cooled to room temperature, with alternately washing 5 times of deionized water and absolute ethyl alcohol, finally in
120 DEG C of vacuum drying 6h, obtain carbon ball powder.
Using soluble cobalt and lanthanum salt as presoma, wherein La:The molar ratio of Co is 1:3, suitable deionization is added
Water, makes solution metal ion concentration be equal to 0.15mol/L, and stirring obtains transparent mixed solution.
It weighs 2.25g solution and 0.05g carbon balls is added, after ultrasonic vibration 1h, carbon ball powder is made to be dispersed in solution,
Ammonia spirit is slowly added dropwise while stirring later, adjusts pH=10.It filters, is washed with deionized 5 times after room temperature ageing 15h,
It is dried in vacuo 12h in 1200 DEG C, obtains metal hydroxides load carbon ball powder.2h is roasted at 500 DEG C to get modified cobalt-based
Catalyst
After testing, the modification cobalt-based catalyst stability that the present embodiment obtains is strong, and catalytic activity is high.
Claims (10)
1. a kind of modified cobalt-base catalyst, which is characterized in that the catalyst includes carbon ball carrier and is supported in carbon ball carrier
Cobalt oxide and transition metal oxide, the transition metal oxide includes the oxide of Cu, Ce or La, the cobalt oxide and
The molar ratio of transition metal oxide is 4：(0~1).
2. a kind of preparation method of modified cobalt-base catalyst as described in claim 1, which is characterized in that include the following steps：
(1) glucose is dissolved in ethanol/water solution, is reacted in a kettle after ultrasonic vibration, filtered after reaction, is used in combination
Water and absolute ethyl alcohol alternately wash, dry, obtain carbon ball carrier；
(2) soluble Co salt and soluble transition metal salt are dissolved in the water, obtain mixed solution, wherein soluble Co salt
It is 4 with the molar ratio of Co elements and transition metal element in soluble transition metal salt：(0~1), Co members in the mixed solution
The total mol concentration of element and transition metal element is (0.1~0.15) mol/L；
(3) the carbon ball carrier that step (1) obtains is added in the mixed solution that step (2) obtains, then ultrasonic vibration is added dropwise
Ammonium hydroxide adjusts pH to 7~10, then ageing is filtered, washed, dries, and obtains metal hydroxides load carbon ball powder；
(4) the metal hydroxides load carbon ball powder that step (3) obtains is roasted in inert atmosphere and is changed to get described
Property cobalt-base catalyst.
3. a kind of preparation method of modified cobalt-base catalyst according to claim 2, which is characterized in that institute in step (1)
The volume ratio of the ethanol/water solution stated, second alcohol and water is 1：(1~89), the glucose quality of addition and ethanol/water solution
The ratio between volume is (5~15) g：(70~90) mL, the time of ultrasonic vibration described in step (1) are 30~90min.
4. a kind of preparation method of modified cobalt-base catalyst according to claim 2, which is characterized in that institute in step (1)
State reaction carried out in the reaction kettle with polytetrafluoroethylliner liner, reaction temperature be 120~180 DEG C, the reaction time be 5~
12h。
5. a kind of preparation method of modified cobalt-base catalyst according to claim 2, which is characterized in that anti-in step (1)
It after answering, filters, alternately washing 3~5 times of water and absolute ethyl alcohol be used in combination, and it is dried in vacuo at a temperature of 60~120 DEG C 6~
10h。
6. a kind of preparation method of modified cobalt-base catalyst according to claim 2, which is characterized in that carbon in step (3)
The addition quality of balloon borne body and the volume ratio of mixed solution are (45~55)：1, and in step (3) ultrasonic vibration time be 1~
2h。
7. a kind of preparation method of modified cobalt-base catalyst according to claim 2, which is characterized in that the temperature of the ageing
Degree is 15~25 DEG C, and digestion time is 12~15h, is washed with water after ageing 3~5 times, then in 60~120 DEG C, at a temperature of it is true
Sky dry 12~for 24 hours.
8. a kind of preparation method of modified cobalt-base catalyst according to claim 2, which is characterized in that the calcination temperature
It it is 400~500 DEG C, roasting time is 2~4h.
9. a kind of application of modified cobalt-base catalyst as described in claim 1, which is characterized in that the modification cobalt-base catalyst is used for
The catalyst of volatile organic compounds by catalytic combustion degradation, the hair property organic matter includes butane, 2- methybutanes, pentane, 2- first
Benzene, 1,3 butadiene, methylpentane, 3- methyl hexane, methyl heptane, isopropylbenzene, propyl benzene, m- ethyltoluene, o- ethyl first
One or more of mixing of benzene, mesitylene, m- diethylbenzene, dodecane, methyl sulfide, limonene, propylene, acetone, n-hexane
Object.
10. a kind of application of modified cobalt-base catalyst according to claim 9, which is characterized in that the use of the catalyst
Amount is the exhaust gas of every gram of catalyst treatment volatile organic matter Han 600~18000ppm, and the flow of the exhaust gas is 10~30L/
h。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647417A (en) * | 2018-11-23 | 2019-04-19 | 盐城工学院 | A kind of hollow structure CuCeOx bi-metal oxide catalyst and preparation method thereof |
| CN113600219A (en) * | 2021-07-19 | 2021-11-05 | 天津大学 | Catalyst for catalytic oxidation of VOCs and preparation method thereof |
| CN114558559A (en) * | 2022-02-21 | 2022-05-31 | 西安交通大学 | Carbon sphere-oxide composite catalytic material and preparation method and application thereof |
| CN115646494A (en) * | 2022-11-16 | 2023-01-31 | 上海化工研究院有限公司 | Transition metal modified monolithic catalyst with large specific surface area, and preparation and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616151A (en) * | 2003-11-13 | 2005-05-18 | 中国科学院大连化学物理研究所 | Process for preparing high specific surface area metal oxide |
| CN102407130A (en) * | 2011-10-31 | 2012-04-11 | 南京工业大学 | Preparation method of monolithic catalyst for catalyzing combustion of compound metal oxide |
| WO2012052624A1 (en) * | 2010-10-21 | 2012-04-26 | Oulun Yliopisto | Photocatalytic material |
| CN104979551A (en) * | 2015-07-17 | 2015-10-14 | 武汉大学 | Carbon nano-sphere/NiCo2O4 composite material as well as preparation method and application thereof |
| CN105668647A (en) * | 2015-12-29 | 2016-06-15 | 重庆大学 | High-specific surface area perovskite nano-LaCoO3 porous hollow sphere material and preparation method thereof |
-
2018
- 2018-03-29 CN CN201810274407.1A patent/CN108554416B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616151A (en) * | 2003-11-13 | 2005-05-18 | 中国科学院大连化学物理研究所 | Process for preparing high specific surface area metal oxide |
| WO2012052624A1 (en) * | 2010-10-21 | 2012-04-26 | Oulun Yliopisto | Photocatalytic material |
| CN102407130A (en) * | 2011-10-31 | 2012-04-11 | 南京工业大学 | Preparation method of monolithic catalyst for catalyzing combustion of compound metal oxide |
| CN104979551A (en) * | 2015-07-17 | 2015-10-14 | 武汉大学 | Carbon nano-sphere/NiCo2O4 composite material as well as preparation method and application thereof |
| CN105668647A (en) * | 2015-12-29 | 2016-06-15 | 重庆大学 | High-specific surface area perovskite nano-LaCoO3 porous hollow sphere material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 孙忠，: ""钙钛矿催化剂催化燃烧VOCs的活性和抗氯性研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647417A (en) * | 2018-11-23 | 2019-04-19 | 盐城工学院 | A kind of hollow structure CuCeOx bi-metal oxide catalyst and preparation method thereof |
| CN113600219A (en) * | 2021-07-19 | 2021-11-05 | 天津大学 | Catalyst for catalytic oxidation of VOCs and preparation method thereof |
| CN114558559A (en) * | 2022-02-21 | 2022-05-31 | 西安交通大学 | Carbon sphere-oxide composite catalytic material and preparation method and application thereof |
| CN115646494A (en) * | 2022-11-16 | 2023-01-31 | 上海化工研究院有限公司 | Transition metal modified monolithic catalyst with large specific surface area, and preparation and application thereof |
| CN115646494B (en) * | 2022-11-16 | 2024-03-26 | 上海化工研究院有限公司 | Transition metal modified monolithic catalyst with large specific surface area and preparation and application thereof |
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| CN108554416B (en) | 2021-03-19 |
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