CN107597119B - Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof - Google Patents
Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN107597119B CN107597119B CN201710856186.4A CN201710856186A CN107597119B CN 107597119 B CN107597119 B CN 107597119B CN 201710856186 A CN201710856186 A CN 201710856186A CN 107597119 B CN107597119 B CN 107597119B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon dioxide
- zro
- dioxide reforming
- based low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses an anti-carbon deposition typeA cobalt-based low-temperature methane and carbon dioxide reforming catalyst and a preparation method thereof belong to the technical field of preparation of methane and carbon dioxide reforming catalysts. The invention takes Co nano particles as active phase, Mg (Al) O composite oxide as carrier and ZrO2Firstly synthesizing Co-Mg-Al-Zr hydrotalcite as single precursor of catalyst, uniformly combining active component, carrier and precursor of assistant into one body, then making high-temp. roasting and reduction treatment to obtain the high-dispersion load type Co/Mg (Al) O-ZrO2A catalyst. The Co nano particles in the catalyst are in a high-dispersion state and have strong interaction with a Mg (Al) O carrier, and meanwhile, the catalyst has the basic properties of Mg (Al) O and ZrO2The catalyst has redox capability, and shows good catalytic activity, stability and anti-carbon deposition performance for low-temperature methane and carbon dioxide reforming (500-600 ℃).
Description
Technical Field
The invention belongs to the technical field of preparation of methane carbon dioxide reforming catalysts, and particularly relates to an anti-carbon deposition type cobalt-based low-temperature methane carbon dioxide reforming catalyst and a preparation method thereof.
Background
In recent years, the preparation of synthesis gas by reforming methane and carbon dioxide has become one of the research hotspots at home and abroad due to the environmental benefit and the industrial application value. The methane carbon dioxide reforming reaction leads two cheap and abundant carbon-containing compounds CH in nature4And CO2Converted into chemical raw material synthesis gas with higher added value, and compared with the process for preparing synthesis gas by methane steam reforming, the synthesis gas H2the/CO ratio is close to 1, and the method is more suitable for further synthesizing oxygen-containing organic compounds or synthesizing liquid hydrocarbon products through a Fischer-Tropsch reaction and the like. Meanwhile, methane and carbon dioxide reforming reaction also comprehensively utilizes CH4And CO2The two effective ways of the greenhouse gas not only can effectively reduce the pollution to the atmospheric environment and the dependence on fossil fuel, but also can provide renewable clean energy, and has remarkable economic benefit, social benefit and environmental benefit. Because the methane and carbon dioxide reforming is a strong endothermic reaction, in order to obtain high conversion rate, the reaction is usually carried out under the condition of high temperature (more than or equal to 800 ℃), which not only puts higher requirements on reaction equipment, but also needs to consume a large amount of fuel to maintain higher reaction temperature, thereby greatly increasing the operation cost. For this reason, low temperature methane carbon dioxide reforming (< 600 ℃) is of increasing interest. It can combine membrane reactor separation technology to selectively separate H2The product makes the reaction move towards the direction of synthesis gas generation, thereby achieving high conversion rate under low temperature condition. The solar energy heat collector can be combined with the solar energy heat collector, the reaction temperature is maintained and the energy required by the reaction is provided by utilizing the solar energy, so that the energy-saving and environment-friendly effects are achieved.
At present, the methane and carbon dioxide reforming catalyst is mainly a supported metal catalyst taking VIII group transition metal as an active component. Among them, noble metal catalysts such as ruthenium and rhodium have good catalytic performance, but because noble metal resources are limited and expensive, large-scale industrial application thereof is greatly limited. Therefore, research and development of non-noble metals, especially Ni catalysts, have attracted extensive attention. The non-noble metal catalyst has the main problem of easy deactivation due to carbon deposition, sintering and oxidation. Among them, carbon deposition is the most important cause of catalyst deactivation. Especially under low temperature reaction conditions, carbon deposition becomes a very prominent problem, which poses more serious challenges for the design and preparation of the catalyst. Currently, research and development on methane and carbon dioxide reforming catalysts are mainly focused on Ni catalysts and are mostly used for high-temperature reactions, while research and reports on low-temperature methane and carbon dioxide reforming catalysts are extremely limited, and most of the catalysts are rapidly deactivated by severe carbon deposition under low-temperature reaction conditions.
In order to improve the anti-carbon deposition performance of the catalyst, researchers at home and abroad have conducted a great deal of research, including searching for a suitable carrier (such as Al)2O3、MgO、La2O3、CeO2、ZrO2Etc.), adding alkaline earth metal oxides (e.g., MgO, CaO, BaO, etc.), adding redox oxides (e.g., CeO)2、ZrO2Etc.), the addition of other transition metals (e.g., Pt, Rh, Fe, etc.), and the development of efficient production methods, etc. Al (Al)2O3Is the most commonly used carrier material of industrial catalysts, MgO can be used as a carrier and an auxiliary agent, the strong interaction between the MgO and non-noble metals Ni and Co can improve the metal dispersion degree, and the basic property of the MgO can promote CO2The adsorption and activation of the carbon composite are beneficial to inhibiting the formation of carbon deposition. Furthermore, ZrO2With Zr4+↔ Zr3+Fast modulation capability, both oxidation and reduction, ZrO2Can react with carbon species on the surface of the active metal and quickly form surface oxygen vacancies to promote CO2The formation of carbon deposition is effectively inhibited by dissociation and adsorption. Due to different influence mechanisms of different types of oxide carriers and auxiliaries on the catalytic performance of the active metal, the catalytic performance of the catalyst is hopefully and greatly improved through the synergistic coupling of the various carriers and the auxiliaries. However, the current supported catalyst is generally prepared by adopting an impregnation method, namely, the auxiliary agent and the active component are sequentially loaded on the carrier by a step impregnation method, or the auxiliary agent and the active component are simultaneously loaded on the carrier by a co-impregnation method. The catalyst prepared by the method has various problems such as uneven composition distribution, easy sintering of active metal, larger size, interaction of metal with a carrier and an auxiliary agent in different degrees and the like, and the synergistic effect of the metal, the carrier and the auxiliary agent is difficult to be fully exerted, so that the activity, the stability and the anti-carbon deposition capability of the catalyst are not greatly improved, and obviously, the requirement of low-temperature methane and carbon dioxide reforming is difficult to meet. Therefore, in order to obtain a high-performance low-temperature methane and carbon dioxide reforming catalyst, it is necessary to develop a preparation method capable of regulating the structure and performance of the metal-support-assistant.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an anti-carbon-deposition cobalt-based low-temperature methane carbon dioxide reforming catalyst and a preparation method thereof, wherein the catalyst is prepared by passing hydrotalcite-like compoundThe precursor of the active component, the carrier and the auxiliary agent are uniformly combined into a whole by the driver to prepare the high-dispersion load type Co/Mg (Al) O-ZrO2Catalyst utilizing strong interaction between Co nanoparticles and Mg (Al) O carrier and basic properties of Mg (Al) O and ZrO2The oxidation reduction capability improves the catalytic activity, stability and anti-carbon deposition performance of low-temperature methane and carbon dioxide reforming.
In order to achieve the purpose, the invention adopts the technical scheme that:
an anti-carbon deposition cobalt-based low-temperature methane carbon dioxide reforming catalyst takes Co nano particles as an active phase, Mg (Al) O composite oxide as a carrier, ZrO2Is an auxiliary agent; the mass percentage of Co in the catalyst is 12 percent, the molar ratio of (Co + Mg)/(Al + Zr) is 3, and the molar ratio of Zr/(Al + Zr) is 0.025-0.1.
The preparation method of the anti-carbon deposition cobalt-based low-temperature methane carbon dioxide reforming catalyst comprises the steps of firstly synthesizing a Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor by a coprecipitation method, and then roasting to obtain Mg (Co, Al) O-ZrO2Then the catalyst is prepared by hydrogen reduction and is marked as Co/Mg (Al) O-ZrO2The method comprises the following specific steps:
(1) synthesizing a Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor by a coprecipitation method: stirring at 800 rpm to mix Co (NO)3)2·6H2O、Mg(NO3)2·6H2O、Al(NO3)3·9H2O and Zr (NO)3)4·5H2The mixed solution of O was added to Na at a rate of 30 drops/min using a dropping funnel2CO3The NaOH solution (precipitant) was added dropwise to the solution at 35 drops/min while adding Na2CO3A solution; the whole precipitation process was performed at room temperature, maintaining pH = 10 ± 0.5; continuing stirring for 1h after the dropwise addition is finished, then standing for 24 h, filtering, washing with deionized water until the pH is = 7 +/-0.2, and drying at 100 ℃ for 12h to obtain a hydrotalcite-like precursor, which is marked as Co-Mg-Al-Zr HTlcs;
(2) placing the Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor obtained in the step (1) in a muffle furnace, and roasting at 800 ℃ to obtain Mg (Co, Al) O composite oxide and ZrO2Mixed oxides of (B) as Mg (Co, Al) O-ZrO2Then Mg (Co, Al) O-ZrO2Reducing with hydrogen at 800 ℃ to obtain Co/Mg (Al) O-ZrO2A catalyst.
Further, (Co) in the step (1)2++ Mg2+)/(Al3++ Zr4+) In a molar ratio of 3:1, Zr4+/(Al3++Zr4+) The molar ratio is 0.025 to 0.1.
Further, Na in the step (1)2CO3Na of solution2CO3Mole number of Al (NO)3)3·9H2O and Zr (NO)3)4·5H21/2, the sum of the moles of O, was dissolved in 100 mL of deionized water as a base solution.
Further, the concentration of the precipitator NaOH solution in the step (1) is 2 mol/L, and the molar number of NaOH is equal to that of Co (NO)3)2·6H2O、Mg(NO3)2·6H2O、Al(NO3)3·9H2O and Zr (NO)3)4·5H2The ratio of the sum of the moles of O is 2: 1.
Further, the roasting conditions of the Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor in the step (2) are as follows: the roasting temperature is 800 ℃, the roasting time is 5 h, the heating rate is 3 ℃/min, and the roasting atmosphere is air.
Further, Mg (Co, Al) O-ZrO in the step (2)2The reduction conditions of the composite oxide are as follows: h2The flow rate is 30mL/min, the reduction temperature is 800 ℃, the reduction time is 30 min, and the heating rate is 10 ℃/min.
The invention has the beneficial effects that:
(1) the invention adopts a coprecipitation method to synthesize uniform Co-Mg-Al-Zr HTlcs hydrotalcite as a catalyst precursor, uniformly integrates the precursors of an active component, a carrier and an auxiliary agent, and prepares the high-dispersion load type Co/Mg (Al) O-ZrO after high-temperature roasting and reduction treatment2The catalyst has simple and effective preparation method;
(2) the catalyst prepared by the method is prepared by Co nano particle active phase (8-10 nm) and Mg (Al) O composite oxygenCompound carrier (-4-6 nm) and ZrO2The auxiliary agent (3-7 nm) forms a metal/oxide nano composite structure, and has good high-temperature thermal stability;
(3) the Co nano particles prepared by the method are in a high-dispersion state and have strong interaction with a Mg (Al) O carrier, and the catalyst has the basic properties of Mg (Al) O and ZrO2The catalyst has redox capability, and shows good catalytic activity, stability and anti-carbon deposition performance for low-temperature methane and carbon dioxide reforming (500-600 ℃).
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the catalyst of example 2 of the present invention;
FIG. 2 is a hydrogen temperature programmed reduction curve for the catalyst of example 2 of the present invention;
FIG. 3 is a transmission electron micrograph of a catalyst of example 2 of the present invention;
FIG. 4 shows the results of the stability test (600 ℃) of the catalyst of example 2 of the present invention for low temperature methane carbon dioxide reforming;
FIG. 5 shows the stability test results (500 ℃) of the catalyst of example 2 of the present invention for low temperature methane carbon dioxide reforming.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Comparative example:
weighing 40 g of NaOH solid, dissolving in 500 mL of deionized water, and stirring for 10 min to prepare 2 mol/L NaOH aqueous solution. 1.7779 g of Co (NO) are weighed according to the molar ratio of (Co + Mg)/Al of 33)2·6H2O、10.9102 g Mg(NO3)2·6H2O、6.0846 g Al(NO3)3·9H2Dissolving O in 100 mL of deionized water, and stirring for 10 min to completely dissolve the nitrate to obtain a metal salt mixed solution. Weighing anhydrous Na2CO30.8532 g, dissolved in 100 mL deionized water as a base solution. The metal salt mixed solution was dropped dropwise with Na-containing solution at a rate of 30 drops/min using a dropping funnel2CO3The solution was placed in a beaker and stirred continuously. At the same timeSlowly dripping the precipitator NaOH solution into the beaker at the speed of 35 drops/min by using a peristaltic pump, maintaining the pH = 10 +/-0.5 of the precipitate, continuing stirring for 1h after finishing dripping, standing for 24 h, filtering and washing with deionized water for multiple times until the pH = 7 +/-0.2. And then drying at 100 ℃ for 12h to obtain the Co-Mg-Al HTlcs hydrotalcite-like precursor. And (3) placing the precursor in a muffle furnace, and roasting for 5 h at the temperature of 800 ℃ at the speed of 3 ℃/min to obtain the Mg (Co, Al) O composite oxide. Placing the composite oxide in a quartz reaction tube at 30mL/min H2Raising the temperature to 800 ℃ at the speed of 10 ℃/min in the airflow and keeping the temperature for 0.5 h, and then cooling to room temperature to obtain a Co/Mg (Al) catalyst which is marked as Co/MgAl.
Example 1:
weighing 40 g of NaOH solid, dissolving in 500 mL of deionized water, and stirring for 10 min to prepare 2 mol/L NaOH aqueous solution. 1.7779 g of Co (NO) were weighed according to a molar ratio of (Co + Mg)/(Al + Zr) of 3 and a molar ratio of Zr/(Al + Zr) of 0.0253)2·6H2O、10.8179 g Mg(NO3)2·6H2O、5.8886 g Al(NO3)3·9H2O、0.1728 g Zr(NO3)4·5H2Dissolving O in 100 mL of deionized water, and stirring for 10 min to completely dissolve the nitrate to obtain a metal salt mixed solution. Weighing anhydrous Na2CO30.8532 g, dissolved in 100 mL deionized water as a base solution. The metal salt mixed solution was dropped dropwise with Na-containing solution at a rate of 30 drops/min using a dropping funnel2CO3The solution was placed in a beaker and stirred continuously. And meanwhile, slowly dripping the precipitator NaOH solution into the beaker at the speed of 35 drops/min by using a peristaltic pump, maintaining the pH = 10 +/-0.5 of the precipitate, continuously stirring for 1h after finishing dripping, standing for 24 h, filtering and washing for multiple times by using deionized water until the pH = 7 +/-0.2. And then drying for 12h at 100 ℃ to obtain a Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor. Putting the precursor into a muffle furnace, heating to 800 ℃ at the speed of 3 ℃/min, and roasting for 5 h to obtain Mg (Co, Al) O-ZrO2A composite oxide. Placing the composite oxide in a quartz reaction tube at 30mL/min H2Raising the temperature in the gas flow to 800 ℃ at the speed of 10 ℃/min and keeping the temperature for 0.5 h, and then cooling the gas flow to room temperature to obtain Co/Mg (Al) -ZrO2Catalyst, recordIs Co/MgAlZr-I.
Example 2:
weighing 40 g of NaOH solid, dissolving in 500 mL of deionized water, and stirring for 10 min to prepare 2 mol/L NaOH aqueous solution. 1.7779 g of Co (NO) were weighed out respectively according to a molar ratio (Co + Mg)/(Al + Zr) of 3 and a molar ratio Zr/(Al + Zr) of 0.053)2·6H2O、10.5079 g Mg(NO3)2·6H2O、5.5939 g Al(NO3)3·9H2O、0.3370 g Zr(NO3)4·5H2Dissolving O in 100 mL of deionized water, and stirring for 10 min to completely dissolve the nitrate to obtain a metal salt mixed solution. Weighing anhydrous Na2CO30.8319 g, dissolved in 100 mL deionized water as a base solution. The metal salt mixed solution was dropped dropwise with Na-containing solution at a rate of 30 drops/min using a dropping funnel2CO3The solution was placed in a beaker and stirred continuously. And meanwhile, slowly dripping the precipitator NaOH solution into the beaker at the speed of 35 drops/min by using a peristaltic pump, maintaining the pH = 10 +/-0.5 of the precipitate, continuously stirring for 1h after finishing dripping, standing for 24 h, filtering and washing for multiple times by using deionized water until the pH = 7 +/-0.2. And then drying for 12h at 100 ℃ to obtain a Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor. Putting the precursor into a muffle furnace, heating to 800 ℃ at the speed of 3 ℃/min, and roasting for 5 h to obtain Mg (Co, Al) O-ZrO2A composite oxide. Placing the composite oxide in a quartz reaction tube at 30mL/min H2Raising the temperature in the gas flow to 800 ℃ at the speed of 10 ℃/min and keeping the temperature for 0.5 h, and then cooling the gas flow to room temperature to obtain Co/Mg (Al) -ZrO2Catalyst, noted Co/MgAlZr-II.
Example 3:
weighing 40 g of NaOH solid, dissolving in 500 mL of deionized water, and stirring for 10 min to prepare 2 mol/L NaOH aqueous solution. 1.7779 g of Co (NO) were weighed out respectively at a (Co + Mg)/(Al + Zr) molar ratio of 3 and a Zr/(Al + Zr) molar ratio of 0.13)2·6H2O、10.4612 g Mg(NO3)2·6H2O、5.2791 g Al(NO3)3·9H2O、0.6713 g Zr(NO3)4·5H2Dissolving O in 100 mL deionized water, stirring for 10 min to completely dissolve nitrateAnd (4) decomposing to obtain a metal salt mixed solution. Weighing anhydrous Na2CO30.8286g, dissolved in 100 mL deionized water as a base solution. The metal salt mixed solution was dropped dropwise with Na-containing solution at a rate of 30 drops/min using a dropping funnel2CO3The solution was placed in a beaker and stirred continuously. And meanwhile, slowly dripping the precipitator NaOH solution into the beaker at the speed of 35 drops/min by using a peristaltic pump, maintaining the pH = 10 +/-0.5 of the precipitate, continuously stirring for 1h after finishing dripping, standing for 24 h, filtering and washing for multiple times by using deionized water until the pH = 7 +/-0.2. And then drying for 12h at 100 ℃ to obtain a Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor. Putting the precursor into a muffle furnace, heating to 800 ℃ at the speed of 3 ℃/min, and roasting for 5 h to obtain Mg (Co, Al) O-ZrO2A composite oxide. Placing the composite oxide in a quartz reaction tube at 30mL/min H2Raising the temperature in the gas flow to 800 ℃ at the speed of 10 ℃/min and keeping the temperature for 0.5 h, and then cooling the gas flow to room temperature to obtain Co/Mg (Al) -ZrO2Catalyst, noted Co/MgAlZr-III.
TABLE 1 texture parameters and grain size for catalysts of examples 1-3 and comparative examples
The performance evaluation of the low-temperature methane and carbon dioxide reforming reaction of the catalyst is carried out on a normal-pressure fixed bed reaction device. Before testing, the catalyst (30-60 mesh, 50 mg) is treated with H at 800 DEG C2Reduced for 0.5 h, then in N2The gas flow is cooled to the reaction temperature, and then raw material gas (CH) is introduced4: CO2: N2= 1: 1: 2), and the gas after the reaction is detected by an online gas chromatography (shimadzu GC-2014). And (3) testing conditions are as follows: atmospheric pressure, space velocity 60,000 mL g-1h-1The stability test temperature is 500 ℃ and 600 ℃, and the test time is 25 h. Active CH of catalyst4The conversion (X) represents: x = ([ CH)4]in-[CH4]out)/[CH4]in x 100%, wherein [ CH ]4]in and [ CH4]out is CH in the raw material gas and the reaction tail gas respectively4Content, activity of catalyst for low temperature methane carbon dioxide reformingThe results of the performance, stability and carbon deposition tests are shown in fig. 4, fig. 5 and table 2.
TABLE 2 catalyst Activity during 600 ℃ stability test and carbon deposit amount after reaction
As can be seen from Table 2, the catalyst prepared by the method has good catalytic activity, stability and anti-carbon deposition performance on low-temperature methane and carbon dioxide reforming, and the carbon deposition amount after the reaction at 600 ℃ for 25 hours is only 1.2-1.7 wt.%.
As can be seen from fig. 4, the catalyst prepared by the present invention shows good activity and stability for methane carbon dioxide reforming at 600 ℃.
As can be seen from fig. 5, the catalyst prepared by the present invention shows good activity and stability for methane carbon dioxide reforming even at a low temperature of 500 ℃.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. All equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (6)
1. An anti-carbon deposition type cobalt-based low-temperature methane carbon dioxide reforming catalyst is characterized in that: the catalyst takes Co nano particles as an active phase, Mg (Al) O composite oxide as a carrier and ZrO2Is an auxiliary agent; the mass percent of Co in the catalyst is 12 percent, the molar ratio of (Co + Mg)/(Al + Zr) is 3, and the molar ratio of Zr/(Al + Zr) is 0.025-0.1;
the preparation method of the anti-carbon deposition cobalt-based low-temperature methane carbon dioxide reforming catalyst comprises the steps of firstly synthesizing a Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor by a coprecipitation method, and then roasting to obtain Mg (Co, Al) O-ZrO2And then the catalyst is prepared by hydrogen reduction, which comprises the following steps:
(1) synthesizing a Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor by a coprecipitation method: stirring at 800 rpm to mix Co (NO)3)2·6H2O、Mg(NO3)2·6H2O、Al(NO3)3·9H2O and Zr (NO)3)4·5H2The mixed solution of O was added to Na at a rate of 30 drops/min using a dropping funnel2CO3Adding NaOH solution into the solution at 35 drops/min while adding Na2CO3In solution; the whole precipitation process was performed at room temperature, maintaining pH = 10 ± 0.5; continuing stirring for 1h after the dropwise addition is finished, then standing for 24 h, filtering, washing with deionized water until the pH is = 7 +/-0.2, and drying at 100 ℃ for 12h to obtain a cobalt-magnesium-aluminum-zirconium hydrotalcite precursor, which is marked as Co-Mg-Al-Zr HTlcs;
(2) placing the Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor obtained in the step (1) in a muffle furnace, and roasting to obtain Mg (Co, Al) O composite oxide and ZrO2Mixed oxides of (B) as Mg (Co, Al) O-ZrO2(ii) a Then Mg (Co, Al) O-ZrO2Reduction with hydrogen to give the catalyst, noted Co/Mg (Al) O-ZrO2。
2. The carbon deposition resistant cobalt-based low temperature methane carbon dioxide reforming catalyst as claimed in claim 1, wherein: in the step (1), (Co)2++ Mg2+):(Al3++ Zr4+) Zr in a molar ratio of 3:14+/(Al3++ Zr4+) The molar ratio is 0.025 to 0.1.
3. The carbon deposition resistant cobalt-based low temperature methane carbon dioxide reforming catalyst as claimed in claim 1, wherein: na in the step (1)2CO3Na of solution2CO3Mole number of Al (NO)3)3·9H2O and Zr (NO)3)4·5H21/2, the sum of the moles of O, was dissolved in 100 mL of deionized water as a base solution.
4. The carbon deposition resistant cobalt-based low temperature methane carbon dioxide reforming catalyst as claimed in claim 1, wherein: the concentration of the NaOH solution in the step (1) is 2 mol/L, NaOH moles and Co (NO)3)2·6H2O、Mg(NO3)2·6H2O、Al(NO3)3·9H2O and Zr (NO)3)4·5H2The ratio of the sum of the moles of O is 2: 1.
5. The carbon deposition resistant cobalt-based low temperature methane carbon dioxide reforming catalyst as claimed in claim 1, wherein: the roasting conditions of the Co-Mg-Al-Zr HTlcs hydrotalcite-like precursor in the step (2) are as follows: the roasting temperature is 800 ℃, the roasting time is 5 h, the heating rate is 3 ℃/min, and the roasting atmosphere is air.
6. The carbon deposition resistant cobalt-based low temperature methane carbon dioxide reforming catalyst as claimed in claim 1, wherein: mg (Co, Al) O-ZrO in the step (2)2The reduction conditions of (a) are: h2The flow rate is 30mL/min, the reduction temperature is 800 ℃, the reduction time is 30 min, and the heating rate is 10 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710856186.4A CN107597119B (en) | 2017-09-21 | 2017-09-21 | Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710856186.4A CN107597119B (en) | 2017-09-21 | 2017-09-21 | Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107597119A CN107597119A (en) | 2018-01-19 |
| CN107597119B true CN107597119B (en) | 2020-05-08 |
Family
ID=61061325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710856186.4A Active CN107597119B (en) | 2017-09-21 | 2017-09-21 | Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107597119B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108380218A (en) * | 2018-03-16 | 2018-08-10 | 福州大学 | A kind of uniform nickel cobalt (alloy) catalyst of support type and preparation method thereof |
| CN109675577A (en) * | 2019-03-04 | 2019-04-26 | 福州大学 | A kind of nickel-base catalyst and preparation method thereof for carbon dioxide methanation |
| CN111558381A (en) * | 2020-05-08 | 2020-08-21 | 重庆大学 | Carbon deposition resistant Pt-Ni methane carbon dioxide reforming catalyst |
| CN112619654A (en) * | 2020-11-06 | 2021-04-09 | 上海簇睿低碳能源技术有限公司 | Catalyst for preparing synthesis gas by reforming methane and carbon dioxide and preparation method thereof |
| CN114534730B (en) * | 2022-01-19 | 2023-03-28 | 南京航空航天大学 | Photo-thermal driving nickel-based catalyst and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071504B (en) * | 2013-01-22 | 2014-12-03 | 福州大学 | Hydrotalcite loaded nickel catalyst as well as preparation method and application thereof |
| CN106607033A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof and method for preparing synthetic gas through methane dry reforming |
| CN105709724A (en) * | 2016-01-26 | 2016-06-29 | 福州大学 | Magnesium-aluminum oxide solid solution load type ruthenium catalyst for methane reforming with carbon dioxide and preparation method of magnesium-aluminum oxide solid solution load type ruthenium catalyst for methane reforming with carbon dioxide |
-
2017
- 2017-09-21 CN CN201710856186.4A patent/CN107597119B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107597119A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107597119B (en) | Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof | |
| CN107042111B (en) | Layered perovskite type catalyst for autothermal reforming of acetic acid to produce hydrogen and preparation method thereof | |
| CN110327933B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof | |
| US8642496B2 (en) | Method for forming a catalyst comprising catalytic nanoparticles and a catalyst support | |
| CN103586030A (en) | Preparation method of mesoporous confinement nickel-based methane dry reforming catalyst | |
| CN111167495B (en) | Catalyst Ni for ammonia borane hydrogen production 2-x Fe x @ CN-G and preparation method thereof | |
| CN106512999B (en) | A kind of methane dry gas reforming catalyst and preparation method thereof | |
| CN108380218A (en) | A kind of uniform nickel cobalt (alloy) catalyst of support type and preparation method thereof | |
| CN111229235A (en) | NiO/MgAl2O4Catalyst, preparation method and application thereof | |
| CN106799228B (en) | Catalyst for preparing hydrogen by reforming methanol and preparation and application thereof | |
| CN113600200A (en) | Preparation method of anti-carbon deposition methane dry gas reforming Ni-based alkaline earth metal modified catalyst | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| CN104841442A (en) | Preparation method of anti-carbon deposition mesoporous confinement methane dry reforming catalyst | |
| CN103785391B (en) | A kind of high activity fischer-tropsch synthetic catalyst and its preparation method and application | |
| CN113019410A (en) | Metal oxide-boron nitride composite catalyst for dry reforming of methane, and preparation method and application thereof | |
| CN110918097A (en) | Cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation and preparation method and application thereof | |
| CN113634256B (en) | Multi-dimensional micro-nano non-noble metal composite catalyst and preparation and application thereof | |
| CN111450834A (en) | Ceria-supported cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen | |
| CN104588022B (en) | Reduction method of Fischer-Tropsch synthesis catalyst | |
| CN114195097B (en) | Method for preparing hydrogen by reforming, nano cuprous oxide-zinc oxide composite catalyst, preparation method thereof and cyclic regeneration method | |
| CN113332992B (en) | Perovskite catalyst and preparation method thereof | |
| CN110732335A (en) | transition metals @ BO for methane dry gas reforming reactionxCore-shell structure nano catalyst and preparation method thereof | |
| CN114192180A (en) | Modified boron nitride loaded nickel-based methane dry reforming catalyst, and preparation method and application thereof | |
| CN113731422A (en) | Preparation method of slurry bed methane synthesis catalyst | |
| CN114308057B (en) | Manganese-tungsten ore type oxide-supported cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |