CN109833877B - Catalyst for preparing synthesis gas by oxidizing methane through chemical chain part and preparation and application thereof - Google Patents
Catalyst for preparing synthesis gas by oxidizing methane through chemical chain part and preparation and application thereof Download PDFInfo
- Publication number
- CN109833877B CN109833877B CN201711228801.3A CN201711228801A CN109833877B CN 109833877 B CN109833877 B CN 109833877B CN 201711228801 A CN201711228801 A CN 201711228801A CN 109833877 B CN109833877 B CN 109833877B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- synthesis gas
- equal
- methane
- oxidizing
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a catalyst for preparing synthesis gas by oxidizing methane with a chemical chain part, in particular to a composite oxide containing lanthanum, strontium, iron and aluminum, and preparation and application thereof. Different metal precursors are mixed evenly according to a certain proportion and then are roasted for a certain time at a certain temperature to prepare the composite oxide catalyst. The catalyst has simple preparation method and good repeatability, can oxidize methane to generate synthesis gas by utilizing self-lattice oxygen with high selectivity (> 90%) in a wider temperature range, can be regenerated in various oxidizing atmospheres such as air, water vapor, carbon dioxide, water/carbon dioxide mixed gas and the like, and can generate high-added-value products such as high-purity hydrogen, carbon monoxide or synthesis gas and the like. After multiple cyclic reactions, the catalyst has no obvious changes in reaction activity and synthesis gas selectivity, and shows excellent cyclic stability. The invention provides a catalyst for preparing synthesis gas by partially oxidizing methane with a chemical chain, which has high efficiency and low cost.
Description
Technical Field
The invention relates to a catalyst for preparing synthesis gas (a mixture of hydrogen and carbon monoxide) by partially oxidizing methane with a chemical chain, in particular to a catalyst for preparing synthesis gas by partially oxidizing methane with a chemical chain, and preparation and application thereof.
Background
Methane is the main component of natural gas, and the conversion of methane into liquid fuel can not only improve the added value, but also facilitate the product transportation. At the present stage, the main means for industrially preparing the liquid fuel from methane is to convert the methane into synthesis gas firstly and then into liquid chemicals by methods such as Fischer-Tropsch synthesis and the like. Currently, there are three main methods for producing synthesis gas from methane, including steam reforming, carbon dioxide dry reforming, and partial oxidation. Since both steam reforming and carbon dioxide reforming are strongly endothermic processes, a large amount of energy is consumed. The partial oxidation process, by contrast, is a mild exothermic and, from an energy efficiency standpoint, is the most potential synthesis gas production process of the three processes above, and its productsH2The ratio of/CO is close to 2, and the catalyst can be directly used as raw material gas for downstream methanol production and Fischer-Tropsch reaction. However, to avoid NO in downstream reactionsxThe partial oxidation method needs pure oxygen combustion technology, and the use of an air separation system (for providing oxygen) greatly increases the production cost; on the other hand, direct mixing of methane and oxygen tends to result in over-oxidation of methane to CO2And H2O, reduces syngas yield and presents an explosion hazard. Therefore, the development of the process for preparing the synthesis gas from the methane with low energy consumption, economy and safety has important application and research values.
Chemical Looping Partial Oxidation (CLPO) is a new type of process for preparing synthesis gas from methane, which meets the above requirements, and its basic principle is to utilize metal oxide as oxygen carrier to decompose the direct contact reaction of methane and oxygen into 2 gas-solid reactions, and the reaction device includes fuel reactor and regeneration reactor, and the oxygen carrier circulates between the two connected reactors. In the fuel reactor, methane is oxidized by the lattice oxygen of the oxygen carrier to produce syngas. The reduced oxygen carrier is then transported to a regeneration reactor where it reacts with an oxidizing gas such as oxygen to complete the regeneration process. H in synthesis gas product prepared from methane by CLPO method2the/CO ratio was 2. However, the method can directly use air as raw material gas, does not need an air separation device, greatly reduces the production cost, simultaneously avoids the direct mixing of methane and oxygen, and reduces the safety risk. In addition, when H is used2O、CO2Or H2O-CO2High purity H can also be prepared when the atmosphere is regenerated by oxidation2CO or syngas.
In the CLPO process, oxygen carriers are the key to the chemical chain partial oxidation technology as a bridge connecting the fuel reactor and the air reactor. In recent years, the research on oxygen carriers has been mainly focused on transition metal oxides, composite and modified metal oxides. Among them, iron-based oxygen carriers are receiving more and more attention because of their advantages such as low price, environmental friendliness, and high mechanical strength. However, pure iron oxide is rapidly agglomerated and sintered due to phase change during redox, and has poor cycle stability. Although to some extent possible by selection of an appropriate carrierThe sintering of iron is inhibited but the deactivation of iron-based oxygen carriers cannot be avoided completely, mainly because the high temperature redox conditions cause the iron oxide to phase separate from the carrier or interact to form spinel, thereby reducing the performance of the oxygen carrier (appl. cat., B,2015,164, 371-379). In addition, pure or supported Fe2O3Too strong oxidizing property to make CH4Transitional oxidation to CO2And H2O (int.J. hydrogen Energy,2009,34, 1301-. Mihai et al (Ind. Eng. chem. Res.,2011,50,2613-2621) found LaFeO with perovskite structure3Can quickly oxidize methane with high selectivity to generate synthesis gas, but Fe in the synthesis gas3+Can only be rapidly reduced to Fe in methane atmosphere2+Further reducing to elemental Fe0The rate of (a) is very slow, resulting in a low storage capacity of the material. Li et al (ChemCatchem,2014,6,790-799) by reaction at Fe2O3The nano particles are coated with a layer of La1-xSrxFeO3(LSF) gel precursor to obtain Fe2O3@ LSF core-shell material, further improves oxygen carrying capacity. However, due to the limitations of the preparation method, Fe2O3Not being completely covered by LSF, resulting in a lower syngas selectivity than pure phase LSF. Therefore, improving the oxygen storage capacity, the cycle stability and the syngas selectivity of the iron-based oxygen carrier under high temperature conditions is an important basic problem faced by the methane CLPO process.
Disclosure of Invention
The invention aims to provide a catalyst for preparing synthesis gas by partially oxidizing methane through a chemical chain, and preparation and application thereof.
The invention is realized by the following technical scheme:
a catalyst for preparing synthetic gas by oxidizing methane with chemical chain part is prepared from La, Sr, Fe and Al through preparing composite oxide material (La) with perovskite structure1-xSrxFe1-yAlyO3-δ) Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, and delta is more than or equal to 0.5 and less than or equal to 1.
The catalyst can be prepared by two different methods:
adding a La, Sr, Fe and Al precursor into a citric acid solution by adopting a sol-gel method, wherein the molar ratio of citric acid to cations of La, Sr, Fe and Al is 1-3:1, the total concentration of the cations is more than or equal to 0.5mol/L and less than or equal to 5mol/L, ethylene glycol cannot be added or is added, and the molar ratio of the ethylene glycol to the citric acid is 0-2: 1, adjusting the pH to 4-9 by using ammonia water, wherein the concentration of the ammonia water is 25% -28%; evaporating the solution to a gel state in a water bath at the temperature of 60-100 ℃, drying for 2-24h at the temperature of 60-150 ℃, and roasting for 1-12h at the temperature of 700-1400 ℃ to obtain a composite oxide catalyst;
or dissolving a precursor of La, Sr, Fe and Al into deionized water at the temperature of 30-80 ℃ by adopting a coprecipitation method, wherein the total final concentration of cations of La, Sr, Fe and Al is 0.1-2 mol/L, adding an ammonium carbonate solution at the concentration of 0.5-5 mol/L into the solution, adjusting the pH to 8-10, rapidly stirring for 2-4h, standing and aging for 2-4h, filtering, washing, drying for 2-24h at the temperature of 60-150 ℃, and roasting for 1-12h at the temperature of 700-1400 ℃ to obtain the composite oxide catalyst.
The La, Sr, Fe and Al precursors are respectively lanthanum nitrate, ferric nitrate, strontium nitrate and aluminum nitrate; the concentration of the ammonia water in the sol-gel method is between 5 and 28 percent.
The preparation conditions of the catalyst in the sol-gel method are preferably that the molar ratio of citric acid to cations is 2, the total concentration of the cations is 0.2mol/L, the molar ratio of ethylene glycol to citric acid is 0, the pH value of ammonia water is adjusted to 6-8, the drying temperature and time are preferably 150 ℃ for drying 12h, and the roasting temperature and time are preferably 1200 ℃ for roasting 4 h.
The preparation conditions of the catalyst in the coprecipitation method are preferably that the total cation concentration is 0.2mol/L, the ammonium carbonate solution concentration is 1mol/L, the final pH is 8-9, the coprecipitation and aging temperature is 60 ℃, the drying temperature and time are preferably 80 ℃ for drying 12h, and the roasting temperature and time are preferably 1200 ℃ for roasting 4 h.
Two communicated reactors are adopted, and the catalyst circulates between the fuel reactor and the regeneration reactor; wherein the catalyst is used for oxidizing methane in a fuel reactor by self-lattice oxygen at high selectivity, and the reaction temperature is 800-950 ℃; and then oxidizing and regenerating the catalyst in a regeneration reactor, wherein the reaction temperature is 800-950 ℃.
The raw material reacted in the fuel reactor is volumeContent of CH 1% -100%4The volume content of the raw material in the oxidation regeneration reactor is 1-100 percent of O2/He or H2O/He or CO2/He or H2O-CO2/He。
Compared with the prior art, the invention has the substantial characteristics that:
1. the invention prepares a composite metal oxide with a perovskite structure, and the molecular formula of the composite metal oxide is
La1-xSrxFe1-yAlyO3-δWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, and delta is more than or equal to 0.5 and less than or equal to 1.
2. The catalyst shows higher reaction activity, synthesis gas selectivity and circulation stability in the reaction of preparing synthesis gas by partially oxidizing methane in a chemical chain.
3. The composite metal oxide with the perovskite structure has excellent universality on an oxidizing atmosphere, and can realize oxidation regeneration in air, water, carbon dioxide or a water/carbon dioxide mixture.
Drawings
FIG. 1 shows X-ray powder diffraction patterns of catalysts of examples 1 to 8. CP refers to the preparation by coprecipitation method, and the other samples which are not marked are all prepared by sol-gel method.
FIG. 2 CH of examples 1-3 and 5-7 catalysts in 20 reactions4And (4) conversion rate. The oxidizing atmosphere was 5% O2/He。
FIG. 3 CO Selectivity of the catalysts of examples 1-3 and 5-7 in 20 reactions. The oxidizing atmosphere was 5% O2/He。
FIG. 4H of catalysts of examples 1-3 and 5-7 in 20 reactions2The ratio of/CO. The oxidizing atmosphere was 5% O2/He。
FIG. 5 CH of examples 3 and 4 catalysts in 20 reactions4Conversion and CO selectivity were compared. The oxidizing atmosphere was 5% O2/He。
FIG. 6 shows an oxidizing atmosphere of 5% H2O-2.5％CO2Reaction performance for example 3 for/He.
Detailed Description
Examples
By usingIn the sol-gel method, nitrate precursors of La, Sr, Fe and Al (the total amount of cation is 20mmol) in a stoichiometric ratio are added into 100ml of citric acid solution with the concentration of 0.4mol/L, and the pH is adjusted to 7 by using ammonia water with the concentration of 28 percent. Evaporating the above solution to dryness in 80 deg.C water bath to gel state, drying at 150 deg.C for 12 hr, and roasting at 1200 deg.C for 4 hr to obtain La1-xSrxFe1- yAlyO3-δA composite oxide catalyst.
By adopting a coprecipitation method, adding a nitrate precursor (the total amount of cation substances is 20mmol) of La, Sr, Fe and Al in a stoichiometric ratio into 100ml of deionized water, heating the mixture to 60 ℃ in a water bath, fully stirring and dissolving the mixture, quickly adding an ammonium carbonate solution with the concentration of 1mol/L into the solution, rapidly stirring the solution, standing and aging the solution, filtering the solution, washing the solution, drying the solution at the temperature of 80 ℃ for 12 hours, and roasting the solution at the temperature of 1200 ℃ or 900 ℃ (embodiment 1) for 4 hours to obtain the composite oxide catalyst.
The details of the prepared composite oxide are shown in examples 1 to 17.
TABLE 1 La of different chemical compositions1-xSrxFe1-yAlyO3-δComposite oxide
And evaluating the performance of the catalyst for preparing the synthesis gas by oxidizing methane at the chemical chain part by adopting a fixed bed reactor. The dosage of the catalyst is 100mg, and the granularity is 80-120 meshes. The fuel gas composition is 5% CH4He, flow rate of 30ml/min, reaction temperature of 900 deg.C, reaction pressure of normal pressure. After 5 minutes of reduction, the reaction was switched to He purge for 5 minutes at a flow rate of 30ml/min and then switched to an oxidizing atmosphere with a composition of 5% O2He, flow rate of 30ml/min, reaction temperature of 900 deg.C, and time of 5 min. When the oxidizing atmosphere is 5% H2O-2.5％CO2In the case of/He, the reduction time is shortened to 4min, oxygenThe regeneration time was adjusted so that the other conditions were not changed. The above procedure was repeated 20 times to test catalyst stability. A four-stage mass spectrometer is adopted to analyze the composition of the outlet of the reactor on line.
As can be seen from FIG. 1, the calcined catalyst has a pure phase perovskite structure. After the catalyst is applied to the reaction of preparing synthesis gas by oxidizing methane by a chemical chain part, Sr doping can be found to reduce the conversion rate (figure 2) and CO selectivity (figure 3) of the catalyst to a certain degree, and proper amount of Al doping can effectively improve CH4And improves CO selectivity and cycle stability. However, when the Al content is too high (y ═ 0.5), methane cracking is induced, resulting in H in the product2the/CO ratio is much greater than 2. The results in fig. 5 show that differences in the preparation process slightly significantly affect methane conversion, while having less impact on CO selectivity, indicating that the factors affecting catalyst performance are primarily their chemical composition. When the oxidizing gas is H2O-CO2In the case of mixed gas (FIG. 6), La0.7Sr0.3Fe0.8Al0.2O3-δThe catalyst still exhibits excellent cycle stability and the catalyst regeneration process also produces syngas.
The foregoing is only a preferred embodiment of the present invention and is not intended to limit the invention in any way; any person skilled in the art can make many possible modifications, equivalents or improvements to the solution of the invention using the methods described above without departing from the scope of the solution of the invention. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (3)
1. The application of the catalyst for preparing the synthesis gas by partially oxidizing methane with a chemical chain is characterized in that: the catalyst is composed of lanthanum, strontium, iron and aluminum and is a composite oxide material La with a perovskite structure1-xSrxFe1-yAlyO3-δWherein x is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0.2 and less than or equal to 0.5, and delta is more than or equal to 0.5 and less than or equal to 1;
the catalyst is used for preparing synthesis gas by oxidizing methane by a chemical chain part, two communicated reactors are adopted, and the catalyst circulates between a fuel reactor and a regeneration reactor; wherein the catalyst is used for oxidizing methane in a fuel reactor by self-lattice oxygen at high selectivity, and the reaction temperature is 800-950 ℃; then oxidizing and regenerating the catalyst in a regeneration reactor, wherein the reaction temperature is 800-950 ℃;
the raw material for reaction in the fuel reactor is CH with the volume content of 1-100 percent4The volume content of the raw material in the oxidation regeneration reactor is 1-100 percent of O2/He or H2O/He or CO2/He or H2O-CO2/He。
2. Use according to claim 1, characterized in that: the preparation method of the catalyst comprises the following steps:
adding a La, Sr, Fe and Al precursor into a citric acid solution by adopting a sol-gel method, wherein the molar ratio of citric acid to cations of La, Sr, Fe and Al is 1-3:1, the total concentration of the cations is more than or equal to 0.5mol/L and less than or equal to 5mol/L, adding or not adding ethylene glycol, and the molar ratio of the ethylene glycol to the citric acid is 0-2: 1, adjusting the pH value to 4-9 by ammonia water; mixing the above solutions at 60-100 deg.CoEvaporating to dryness in water bath to gel state, and passing through 60-150 deg.CoC drying for 2-24h, 700-oC, roasting for 1-12h to obtain a composite oxide catalyst;
or dissolving La, Sr, Fe and Al precursors to 30-80 by adopting a coprecipitation methodoC deionized water, the total final concentration of the positive ions of La, Sr, Fe and Al is 0.1-2 mol/L, ammonium carbonate solution with the concentration of 0.5-5 mol/L is added into the solution, the pH value is 8-10, the solution is rapidly stirred for 2-4h, the solution is kept stand and aged for 2-4h, filtered and washed, and the concentration is 60-150oC drying for 2-24h, 700-oAnd C, roasting for 1-12h to obtain the composite oxide catalyst.
3. Use according to claim 2, characterized in that: the La, Sr, Fe and Al precursors are respectively lanthanum nitrate, ferric nitrate, strontium nitrate and aluminum nitrate; the concentration of the ammonia water in the sol-gel method is between 5 and 28 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711228801.3A CN109833877B (en) | 2017-11-29 | 2017-11-29 | Catalyst for preparing synthesis gas by oxidizing methane through chemical chain part and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711228801.3A CN109833877B (en) | 2017-11-29 | 2017-11-29 | Catalyst for preparing synthesis gas by oxidizing methane through chemical chain part and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109833877A CN109833877A (en) | 2019-06-04 |
| CN109833877B true CN109833877B (en) | 2021-10-22 |
Family
ID=66882335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711228801.3A Active CN109833877B (en) | 2017-11-29 | 2017-11-29 | Catalyst for preparing synthesis gas by oxidizing methane through chemical chain part and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109833877B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087026B (en) * | 2019-12-31 | 2022-06-28 | 天津大学 | Chemical chain methane partial oxidation oxygen carrier and preparation method and application thereof |
| CN111285327B (en) * | 2020-02-18 | 2021-10-19 | 西北大学 | Method for preparing synthesis gas by partial oxidation of methane chemical chain |
| CN111266113A (en) * | 2020-02-27 | 2020-06-12 | 西北大学 | Oxygen carrier for chemical chain combustion and cracking and preparation method and application thereof |
| CN111232920B (en) * | 2020-03-17 | 2023-03-14 | 昆明理工大学 | Method for producing hydrogen by coke oven coal chemical looping |
| CN111569891B (en) * | 2020-05-25 | 2023-03-10 | 太原理工大学 | Medium-temperature methane partial oxidation catalyst and preparation method and application thereof |
| CN113289612A (en) * | 2021-04-30 | 2021-08-24 | 桂林理工大学 | Synthesis of perovskite catalyst and application technical field of perovskite catalyst in methane oxidation coupling reaction |
| CN114887638B (en) * | 2022-04-27 | 2023-10-20 | 昆明理工大学 | Molten salt oxidative coupling or dehydrogenation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101072627A (en) * | 2004-12-10 | 2007-11-14 | 乔治洛德方法研究和开发液化空气有限公司 | Catalytic membrane reactor |
| CN102008954A (en) * | 2010-10-14 | 2011-04-13 | 北京石油化工学院 | Hexaaluminate metal oxide catalyst, preparation methods and application thereof |
-
2017
- 2017-11-29 CN CN201711228801.3A patent/CN109833877B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101072627A (en) * | 2004-12-10 | 2007-11-14 | 乔治洛德方法研究和开发液化空气有限公司 | Catalytic membrane reactor |
| CN102008954A (en) * | 2010-10-14 | 2011-04-13 | 北京石油化工学院 | Hexaaluminate metal oxide catalyst, preparation methods and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Methane oxidation over perovskite-related ferrites:Effects of oxygen nonstoichiometry;V.V. Kharton等;《Solid State Sciences》;20051014;第7卷;第1344–1352页 * |
| V.V. Kharton等.Methane oxidation over perovskite-related ferrites:Effects of oxygen nonstoichiometry.《Solid State Sciences》.2005,第7卷第1344–1352. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109833877A (en) | 2019-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109833877B (en) | Catalyst for preparing synthesis gas by oxidizing methane through chemical chain part and preparation and application thereof | |
| CN108855109B (en) | Synthetic gas oxygen carrier prepared by oxidizing methane with chemical chain part and preparation method and application thereof | |
| Luhui et al. | Effect of precipitants on Ni-CeO2 catalysts prepared by a co-precipitation method for the reverse water-gas shift reaction | |
| Pojanavaraphan et al. | Effect of catalyst preparation on Au/Ce1− xZrxO2 and Au–Cu/Ce1− xZrxO2 for steam reforming of methanol | |
| KR20140067676A (en) | Iron modified ni-based perovskite type catalyst, preparing method thereof, and producing method of synthesis gas from combined steam co2 reforming of methane using the same | |
| CN110876941B (en) | Load type iron-tungsten bimetal composite oxide and preparation method and application thereof | |
| CN109731579A (en) | A kind of mesoporous lanthanum oxide catalyst of nickel load and preparation method thereof | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| CN107552056B (en) | Catalyst for preparing carbon monoxide by carbon dioxide hydrogenation, preparation method and application thereof | |
| Cheng et al. | Effect of calcination temperature on the performance of hexaaluminate supported CeO2 for chemical looping dry reforming | |
| Zeng et al. | Promotional effect of preparation methods on catalytic reduction of NO by CO over CoCeO x catalysts | |
| CN113292411A (en) | Application of perovskite catalyst in preparation of formic acid by catalyzing carbon dioxide hydrogenation and preparation method | |
| Zhao et al. | Interface engineering of Mn3O4/Co3O4 S-scheme heterojunctions to enhance the photothermal catalytic degradation of toluene | |
| Zhao et al. | High syngas selectivity and near pure hydrogen production in perovskite oxygen carriers for chemical looping steam methane reforming | |
| Yang et al. | Boosted carbon resistance of ceria-hexaaluminate by in-situ formed CeFexAl1− xO3 as oxygen pool for chemical looping dry reforming of methane | |
| Gao et al. | Plasma-assisted low temperature ammonia decomposition on 3d transition metal (Fe, Co and Ni) doped CeO2 catalysts: Synergetic effect of morphology and co-doping | |
| CN107335446A (en) | A kind of cobalt-base catalyst and its preparation and application that mixed alcohol is produced for one-step method from syngas | |
| Fu et al. | Mechanistic insights into CoO x–Ag/CeO 2 catalysts for the aerobic oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid | |
| CN109847747A (en) | A kind of low temperature steam transformation catalyst and preparation method | |
| CN102442640B (en) | Application of composite metal oxide oxygen carrier to recycle chemistry chain hydrogen production and preparation thereof | |
| CN116809070A (en) | Monoatomic catalyst for low-temperature reverse steam transformation and preparation method thereof | |
| CN115837275A (en) | Perovskite type high-entropy oxide and preparation method and application thereof | |
| Du et al. | Synthesis gas generation by chemical-looping selective oxidation of methane using Pr1− xZrxO2− δ oxygen carriers | |
| CN113145127B (en) | Cu catalyst for preparing hydrogen by reforming methanol and steam, and preparation method and application thereof | |
| CN115626666A (en) | Tricalcium titanium ore type composite metal oxide oxygen carrier and preparation method and application thereof |
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 |