CN111087026A - Chemical chain methane partial oxidation oxygen carrier and preparation method and application thereof - Google Patents
Chemical chain methane partial oxidation oxygen carrier and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of oxygen carriers, and discloses a chemical chain methane partial oxidation oxygen carrier, a preparation method and application thereof3Is doped at B site and has the general formula of LaMn1‑x‑yFexCoyO3X is more than 0 and less than 1, and y is more than 0 and less than 1; the preparation method comprises the following steps: firstly, lanthanum nitrate, cobalt nitrate, ferric nitrate and manganese nitrate are used as precursors to be prepared into solution with citric acid; the clear sol is then converted to a viscous gel by evaporation; and aging and roasting to obtain the target product. The oxygen carrier provided by the invention has the advantages of higher conductivity of ions and electrons, better thermal stability, sintering resistance, good oxygen supply capacity, high activity, less carbon deposition and strong oxygen storage-release capacity, so that the reaction rate of preparing the synthesis gas by partial oxidation of methane is accelerated, the synthesis gas can be prepared under the condition of higher airspeed, and high methane conversion rate can be obtainedThe conversion rate.
Description
Technical Field
The invention belongs to the technical field of oxygen carriers, and particularly relates to a manganese-based perovskite type composite metal oxide oxygen carrier, a preparation method thereof, and application of the oxygen carrier in preparation of synthesis gas by chemical chain methane reforming.
Technical Field
With the rapid rise of global energy demand and the continuous aggravation of greenhouse gas emission problems, fossil energy such as petroleum, coal, natural gas and the like still is the biggest promotion of world economic developmentThe power accounts for more than 80% of the total energy, wherein natural gas is the fastest energy. At present, the proven resource reserves of shale gas, coal bed gas and dense gas in China are about 31 multiplied by 1012m3And the natural gas is ranked second worldwide, accounting for 13.9% of the total amount of the non-conventional natural gas resources in the world. Therefore, methane is widely concerned due to the cleanness, high efficiency and low pollution of the combustion process, natural gas resources can possibly replace traditional fossil energy in foreseeable future energy structures, and development and utilization of non-conventional natural gas have profound significance for economic development of China.
At present, two main types of industrial utilization of natural gas exist, the first type is a direct conversion method, which is used as a production raw material to be directly converted into chemical products, such as aromatic hydrocarbon preparation through methane anaerobic aromatization, olefin preparation through methane oxidative coupling, ethane preparation through methane anaerobic low temperature and the like; the second method adopts an indirect methane conversion method, which mainly converts methane into synthesis gas, and then uses the synthesis gas as a raw material to prepare downstream products, such as synthetic ammonia, dimethyl ether, F-T synthetic oil and the like. However, the reaction needs to be carried out under high temperature and high pressure, the conversion rate is low, and the catalyst is easy to be poisoned and deactivated, so the research and development of the direct conversion method are restricted to a certain extent.
In the indirect conversion of methane, the technology of preparing synthesis gas by partial oxidation of chemical chain methane is an important step in the indirect conversion, the technology can realize near-zero energy consumption in-situ separation of products while preparing the synthesis gas, utilizes a chemical chain concept, redesigns a reaction path, decomposes a total reaction into two or more sub-reactions which are carried out in different spaces or time, and transmits substances and energy in a system by recycling the oxidation-reduction process of a solid oxygen carrier (usually metal oxide), realizes the respective conversion of raw materials and the in-situ separation of the products, and integrally solves the problems of heat supply and separation. The technology for preparing synthetic gas by partial oxidation of chemical chain methane is characterized by that it essentially adopts two reactors, one fuel or reforming reactor, and the lattice oxygen in oxide or compound can be substituted for molecular oxygen in air to partially oxidize methane, and the oxide without lattice oxygen can be used for oxidizing methane by utilizing air and oxygenAnd (4) carrying out lattice oxygen recovery on oxidants such as carbon and the like to form cyclic uninterrupted synthesis gas preparation. Specifically, the method comprises the following steps: the active oxygen carrier is firstly exposed in reducing gas, oxygen carrier particles absorb heat energy and generate active oxygen at high temperature, oxygen anions diffuse and migrate from bulk phase to surface due to the chemical potential gradient of the oxygen, and the chemical potential gradient of the oxygen is balanced by electron countercurrent so as to keep the overall charge balance; at the same time, the oxygen carrier is reduced to the lower oxide MeOx－1Or elemental Me and generating H2O and CO, reduced oxygen carrier in air reactor, with O2And in addition, carbon deposition generated by methane cracking reacts with air, so that the purpose of removing the carbon deposition is achieved, and the perovskite phase crystal lattice oxygen is recovered while the performance of the oxygen carrier is recovered. The chemical chain methane partial oxidation reaction (CL-POM) can directly convert natural gas into synthesis gas, so that not only can natural gas resources be efficiently utilized, but also the greenhouse effect can be effectively relieved; in addition, the methane is oxidized by utilizing the air instead of pure oxygen, so that the capital cost is reduced, the chemical energy is utilized in a gradient manner, and the utilization efficiency of energy is improved, therefore, the method has great research value.
The research of the oxygen carrier in the chemical chain methane partial oxidation reaction is the key point of the whole process, the oxygen carrier circulates between two reactors to transfer oxygen and also transfer heat generated by the reaction, and the oxygen carrier is the most important factor in preparing synthesis gas by the whole methane chemical chain partial oxidation. The oxygen carrier is used as a main active component, has good valence change characteristic and strong oxygen migration capacity, and simultaneously needs to consider that methane cannot be completely oxidized and has high synthesis gas selectivity; in addition, when the oxygen carrier is in contact reaction with reducing gas, the oxygen carrier needs to have rich pore channel structures and high specific surface area in particles, so that the oxygen carrier has low mass transfer resistance and reacts at specific active sites on the surfaces of the particles to form a required product; the catalyst also has high methane cracking activity and proper oxidation characteristic, and can ensure that the cracked methane reacts with lattice oxygen in the oxygen carrier to generate carbon monoxide; the oxygen carrier should have high mechanical stability and not be crushed or sintered during the reaction. Oxygen carrier capable of being used for methane chemical chain steam reformingMainly comprises transition metal oxides of Ni, Cu, Fe, Mn and the like and rare earth metal oxides. From a thermodynamic point of view, MeOx/MeOx-yEquilibrium oxygen partial pressure PO of redox couple2Or the chemical potential of oxygen determines the upper limit of the fuel oxidation degree, and the perovskite type composite oxide has good ion and electron conduction capability, is an oxygen carrier material with potential application value, and can be suitable for wide substitution of various A site cations and B site cations. Since in CL-POM the choice of oxygen carrier is of crucial importance, the oxygen carrier must have a high oxygen storage capacity, a sufficient oxygen transport capacity and a high reaction rate. Under the condition of alternate oxidation and reduction, the perovskite has continuous cyclic thermal stability and excellent mechanical property and oxygen/cation defects, so that the supplement and supply of oxygen are changed, the oxygen storage and release capacity is improved, the oxygen transfer capacity of the oxygen carrier is further improved, and the oxygen carrier keeps good reactivity and stability. Perovskite LaMnO with cubic crystal form3The CO selectivity is not high due to its low methane conversion. Therefore, researchers modify the perovskite composite oxide structure by doping different elements and the like, dope the B site cations with Fe element, and form the perovskite composite oxide structure La by using a citric acid complexation method2MnFeO6And activity evaluation was performed using a fixed bed reactor. Due to the doping of active elements, lattice distortion and oxygen coordination change are caused, so that vacancy formation energy is reduced, the oxygen supply performance of the oxygen carrier is enhanced, and the oxygen absorption/release performance and stability of the perovskite-based oxygen carrier are obviously improved. But this structure has a lower syngas selectivity due to its surface abundance of oxygen species, resulting in methane peroxidation.
Disclosure of Invention
The invention aims to provide a chemical chain methane partial oxidation oxygen carrier, a preparation method thereof and application thereof in preparing synthesis gas by reforming chemical chain methane, wherein Co is adopted3+And Fe3+For LaMnO3Doping to form a specific simple cubic crystal structure, and adding multiple elements into LaMnO3The lattice distortion and the increase in the oxygen vacancy concentration in the lattice of (1), and the increase in the rate of migration of oxygen ions from the bulk phase to the surface, contribute toEliminating carbon deposition, counteracting the negative effect of serious sintering and changing the surface chemical composition, and thus obtaining high synthesis gas selectivity and stability.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a chemical chain methane partial oxidation oxygen carrier is of a perovskite structure and has a general formula of LaMn1-x- yFexCoyO3，0＜x＜1，0＜y＜1。
Further, the crystal structures of the oxygen carriers are all cubic crystal structures.
A preparation method of the chemical chain methane partial oxidation oxygen carrier comprises the following steps:
Further, the complexing agent is at least one of citric acid, ethylene glycol, glycine and urea.
The application of the chemical chain methane partial oxidation oxygen carrier in preparing synthesis gas by oxidizing methane through a chemical chain part has the reaction temperature of 500-1000 ℃. Introducing a mixed gas of methane and nitrogen in the reduction stage, wherein the volume percentage of the methane is 5-50%, the volume space velocity of the reaction is controlled to be 150-3000 h by taking the methane as a reference-1. Oxygen vacancies are present in the oxygen carrier in the fuel reactor to enable the transport of oxygen at high temperatures. Oxygen carrier lattice oxygen willThe alkane is partially oxidized into synthesis gas, and the oxygen carrier can improve oxygen transfer on the surface, so that carbon deposit on the surface is fully contacted with oxygen, the carbon deposit on the metal surface is easier to eliminate, the reaction can be carried out at high space velocity, and high methane conversion rate and selectivity of the synthesis gas are obtained; h in syngas2The molar ratio of/CO is close to 2, and the catalyst is suitable for being used as a raw material for synthesizing methanol and F-T. The reduced oxygen carrier is oxidized by air, and the oxygen carrier supplements lattice oxygen in an air reactor through air calcination.
The invention has the beneficial effects that:
the invention (I) prepares a composite oxide oxygen carrier with a perovskite structure, and the general formula of the composite oxide oxygen carrier is LaMn1-x- yFexCoyO3X is more than 0 and less than 1, y is more than 0 and less than 1, the composite perovskite structure belongs to a cubic crystal structure, and has higher lattice oxygen activity, synthesis gas yield and good carbon deposition resistance when being used as an oxygen carrier in the reaction of preparing synthesis gas by oxidizing methane at a chemical chain part; aiming at the process for preparing synthesis gas by chemical chain methane partial oxidation (CL-POM), provides LaMnO3The oxygen carrier with excellent oxidation-reduction performance and oxygen transmission capacity is prepared by doping and modifying an oxide with cheap metals of Co and Fe for a perovskite substrate, the movement capacity of lattice oxygen is enhanced, sintering and carbon deposition to a certain degree are relieved, the activation energy of high-temperature lattice oxygen is reduced, and partial oxidation of methane is facilitated to generate synthesis gas CO and H2And the defect that the oxygen carrier with higher energy is not fully utilized in the air oxidation process is avoided.
(II) the perovskite type composite oxide oxygen carrier LaMn prepared by the invention1-x-yFexCoyO3X is more than 0 and less than or equal to 1, and y is more than 0 and less than or equal to 1; the oxygen carrier has good structural stability, is still a pure perovskite crystalline phase after being subjected to a plurality of oxidation reduction regeneration cycle tests, has a lower wear rate and high carbon deposition resistance, is used as a reactive material, and has the characteristics of low production cost, environmental protection and the like.
Drawings
FIG. 1 shows LaMn obtained in examples 1, 2, 3 and 41/3Fe1/3Co1/3O3、LaFeO3、LaCoO3、LaMnO3XRD pattern of oxygen carrier;
FIG. 2 shows LaMn obtained in examples 5, 6, 7 and 81/3Fe1/3Co1/3O3XRD pattern of oxygen carrier;
FIG. 3 shows LaMn obtained in examples 1, 8, 9 and 101/3Fe1/3Co1/3O3XRD pattern of oxygen carrier;
FIG. 4 shows LaMn obtained in examples 1 and 151-x-yFexCoyO3XRD pattern of oxygen carrier;
FIG. 5 shows LaMn obtained in examples 1, 2, 3 and 41/3Fe1/3Co1/3O3、LaFeO3、LaCoO3、LaMnO3Reaction performance result graphs of 10 circulation methane reduction stages of the oxygen carrier; wherein (A) CH4Conversion, (B) H2/(CO+CO2) Molar ratio, (C) H2Selectivity, (D) CO selectivity, (E) CO2Selectivity, (F) carbon deposition selectivity, (G) syngas yield;
FIG. 6 shows LaMn obtained in examples 1, 15 and 161-x-yFexCoyO3A reaction performance result diagram of the methane reduction stage of the oxygen carrier;
FIG. 7 shows LaMn obtained in example 11/3Fe1/3Co1/3O350 cycle stability test results of the oxygen carrier are shown.
FIG. 8 shows fresh LaMn obtained in example 11-x-yFexCoyO3Oxygen carrier and 50-cycle LaMn thereof1-x- yFexCoyO3XRD pattern of oxygen carrier.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1:
step (1), weighing 9.7470g of hexahydrateLanthanum nitrate La (NO)3)3·nH2O, 2.9103g cobalt nitrate hexahydrate Co (NO)3)3·6H2O, 4.04g iron nitrate nonahydrate Fe (NO)3)3·9H2O, 3.5790g (50 wt%) of an aqueous solution of manganese nitrate, 15.1301g of citric acid, 4.4689g of ethylene glycol were dissolved in 40mL of deionized water. Wherein the molar ratio of the citric acid to the ethylene glycol to the total amount of metal ions in the precursor solution is 1.2: 1;
step (2), evaporating the solution to dryness at 85 ℃ under the stirring condition to form gel, stirring at the speed of 500rpm, then putting the gel into a 130 ℃ constant-temperature drying oven for fully drying for 12h, and roasting the obtained precursor powder for 4h at 900 ℃ in a muffle furnace to obtain a composite perovskite structure with the molecular formula of LaMn1/3Fe1/3Co1/3O3。
Respectively weighing an oxygen carrier, crushing the oxygen carrier, taking 0.6mL of 20-40-mesh particles, uniformly mixing the oxygen carrier with 0.4mL of quartz sand with the same mesh number, adding the mixture into a fixed bed tubular reactor, and carrying out an experiment at the temperature of 900 ℃ under normal pressure. In N2After the temperature is raised to 900 ℃ under the atmosphere, (1) introducing (6 ml/minCH)4，54ml/minN2) The volume of the methane accounts for 10 percent of the total volume of the mixed gas, the gas composition of the methane within 5min is continuously collected by utilizing gas chromatography on-line analysis, and (2) nitrogen with the volume of 60ml/min is used for purging for 15 min; (3) introducing air flow (80ml/min), and purging with air for 15 min; (4) continuously purging with nitrogen for 15 min; and (4) completing a complete cycle in the steps (1) to (4).
Comparative example 2:
the preparation was carried out as described in example 1, with the only difference that in step (1) 9.7476g of lanthanum nitrate hexahydrate La (NO) were weighed out3)3·nH2O, 4.04g iron nitrate nonahydrate Fe (NO)3)3·9H2O, 15.1301g citric acid, 4.4689g ethylene glycol, was dissolved in 40mL deionized water. Wherein the molar ratio of the citric acid to the ethylene glycol to the total amount of metal ions in the precursor solution is 1.2: 1; the molecular formula of the oxygen carrier obtained after roasting is LaFeO3。
Comparative example 3:
prepared by the method of example 1, whichExcept that 9.7476g of lanthanum nitrate hexahydrate La (NO) was weighed in step (1)3)3·nH2O, 10.7370g (50 wt%) of an aqueous solution of manganese nitrate, 15.1301g of citric acid, 4.4689g of ethylene glycol were dissolved in 40mL of deionized water. Wherein the molar ratio of the citric acid to the ethylene glycol to the total amount of metal ions in the precursor solution is 1.2: 1; roasting to obtain the oxygen carrier with the molecular formula of LaMnO3。
Comparative example 4:
the preparation was carried out as described in example 1, with the only difference that 9.7470g of lanthanum nitrate hexahydrate La (NO) were weighed out in step (1)3)3·nH2O, 8.7315g cobalt nitrate hexahydrate Co (NO)3)3·6H2O, 15.1301g citric acid, 4.4689g ethylene glycol, was dissolved in 40mL deionized water. Wherein the molar ratio of the citric acid to the ethylene glycol to the total amount of metal ions in the precursor solution is 1.2: 1; the molecular formula of the oxygen carrier obtained after roasting is LaCoO3。
Example 5:
the preparation was carried out as described in example 1, with the only difference that 4.4689g of ethylene glycol were used as complexing agent in step (1), the molar ratio of ethylene glycol to the total amount of metal ions in the precursor solution being 1.2:1.
Example 6:
the preparation was carried out as described in example 1, with the only difference that 5.4051g glycine was used as complexing agent in step (1), the molar ratio of glycine to the total amount of metal ions in the precursor solution being 1.2:1.
Example 7:
the preparation was carried out as described in example 1, with the only difference that 4.3242g of urea were used as complexing agent in step (1), the molar ratio of urea to the total amount of metal ions in the precursor solution being 1.2:1.
Example 8:
the preparation was carried out as described in example 1, with the only difference that 15.1301g of citric acid was used as complexing agent in step (1), the molar ratio of citric acid to the total amount of metal ions in the precursor solution being 1.2:1.
Example 9:
the preparation was carried out as described in example 1, with the only difference that 15.1301g of citric acid and 5.4051g of glycine were used as complexing agent in step (1), the molar ratio of citric acid and glycine to the total amount of metal ions in the precursor solution being 1.2:1.2: 1.
Example 10:
the preparation was carried out as described in example 1, with the only difference that 15.1301g of citric acid and 4.3242g of urea were used as complexing agent in step (1), the molar ratio of citric acid and urea to the total amount of metal ions in the precursor solution being 1.2:1.2: 1.
Example 11:
the preparation was carried out by the method of example 1, except that the drying temperature of the oven was 100 ℃ and the drying time was 24 hours in step (2).
Example 12:
the preparation was carried out by the method of example 1, except that the drying temperature of the oven was 180 ℃ and the drying time was 6 hours in step (2).
Example 13:
the preparation was carried out by the method of example 1, except that the calcination temperature in step (2) was 1000 ℃ and the calcination time was 2 hours.
Example 14:
the preparation was carried out by the method of example 1, except that the calcination temperature in step (2) was 800 ℃ and the calcination time was 6 hours.
Example 15:
Example 16:
the Lamn prepared in example 15 was measured separately1-x-yFexCoyO30.6mL of oxygen carrier is diluted and mixed evenly with 0.4mL of quartz sand with the same mesh number, and the mixture is added into a fixed bed tubular reactor, and the experiment is carried out under the condition of 900 ℃ and normal pressure. In N2After the temperature is raised to 900 ℃ under the atmosphere, (1) introducing (6 ml/minCH)4，54ml/minN2) The volume of the methane accounts for 10 percent of the total volume of the mixed gas, the gas composition of the methane within 5min is continuously collected by utilizing gas chromatography on-line analysis, and (2) nitrogen with the volume of 60ml/min is used for purging for 15 min; (3) introducing air flow (80ml/min), and purging with air for 15 min; (4) continuously purging with nitrogen for 15 min; and (4) completing a complete cycle in the steps (1) to (4). The volume space velocity of the reaction is calculated to be 600h by taking the reactant methane as the reference-1。
Example 17:
the experiment was carried out as described in example 1, with the only difference that the LaMn prepared in example 1 was metered in1/3Fe1/3Co1/ 3O30.2mL of oxygen carrier and 0.4mL of diluent quartz sand with the same mesh number are uniformly mixed (the volume ratio of the oxygen carrier to the diluent is 1: 2). The volume space velocity of the reaction is calculated to be 1800h by taking the reactant methane as the reference-1。
Example 18:
an experiment was carried out in the same manner as in example 1, sectionIn addition to the amount of LaMn prepared in example 11/3Fe1/3Co1/ 3O3Oxygen carrier 1ml, and the volume space velocity of the reaction is calculated to be 360h based on reactant methane-1。
Example 19:
the experiment was carried out in the same manner as in example 1, except that the evaluation experiment was carried out under atmospheric conditions at 1000 ℃.
Example 20:
the experiment was carried out by the method of example 1, except that the evaluation experiment was carried out under atmospheric conditions at 500 ℃.
Example 21:
LaMn prepared in example 1 was metered in1/3Fe1/3Co1/3O30.6mL of oxygen carrier and quartz sand with the same mesh number as 0.4mL are diluted and mixed uniformly, added into a fixed bed tubular reactor, and added into the fixed bed tubular reactor, and the experiment is carried out at the temperature of 900 ℃ under normal pressure. In N2After the temperature is raised to 900 ℃ in the atmosphere, (1) introducing 5min of mixed gas of methane and nitrogen with the total flow of 300ml/min, wherein the volume of the methane accounts for 10% of the total volume of the mixed gas, collecting tail gas within 5min, and analyzing the composition by using gas chromatography; (2) purging with 180ml/min nitrogen for 15 min; (3) introducing air flow of 400ml/min), and blowing air for 15 min; (4) continuously purging with nitrogen for 15 min; and (4) completing a complete cycle in the steps (1) to (4). The volume space velocity of the reaction is calculated to be 3000h by taking the reactant methane as the reference-1。
Example 22:
LaMn prepared in example 1 was metered in1/3Fe1/3Co1/3O30.6mL of oxygen carrier and quartz sand with the same mesh number as 0.4mL are diluted and mixed uniformly, added into a fixed bed tubular reactor, and added into the fixed bed tubular reactor, and the experiment is carried out at the temperature of 900 ℃ under normal pressure. In N2After the temperature is raised to 900 ℃ in the atmosphere, (1) introducing 5min of mixed gas of methane and nitrogen with the total flow of 30ml/min, wherein the volume of the methane accounts for 10% of the total volume of the mixed gas, collecting tail gas within 5min, and analyzing the composition by using gas chromatography; (2) purging with 180ml/min nitrogen for 15 min; (3) introducing air flow (400ml/min), and purging with air for 15 min; (4) by usingContinuously purging with nitrogen for 15 min; and (4) completing a complete cycle in the steps (1) to (4). The volume space velocity of the reaction is calculated to be 300h based on the reactant methane-1。
Example 23:
LaMn prepared in example 1 was metered in1/3Fe1/3Co1/3O30.6mL of oxygen carrier is diluted and mixed evenly with 0.4mL of quartz sand with the same mesh number, and the mixture is added into a fixed bed tubular reactor, and the experiment is carried out under the condition of 900 ℃ and normal pressure. In N2After the temperature is raised to 900 ℃ in the atmosphere, (1) introducing 5min of mixed gas of methane and nitrogen with the total flow of 15ml/min, wherein the volume of the methane accounts for 10% of the total volume of the mixed gas, collecting tail gas within 5min, and analyzing the composition by using gas chromatography; (2) purging with 60ml/min nitrogen for 15 min; (3) introducing air flow (20ml/min), and purging with air for 15 min; (4) continuously purging with nitrogen for 15 min; and (4) completing a complete cycle in the steps (1) to (4). The volume space velocity of the reaction is calculated to be 150h based on the reactant methane-1。
Example 24:
LaMn prepared in example 1 was metered in1/3Fe1/3Co1/3O30.6mL of oxygen carrier is diluted and mixed evenly with 0.4mL of quartz sand with the same mesh number, and the mixture is added into a fixed bed tubular reactor, and the experiment is carried out under the condition of 900 ℃ and normal pressure. In N2After the temperature is raised to 900 ℃ in the atmosphere, (1) introducing 5min of mixed gas of methane and nitrogen with the total flow of 60ml/min, wherein the volume of the methane accounts for 5% of the total volume of the mixed gas, collecting tail gas within 5min, and analyzing the composition of the tail gas by using gas chromatography; (2) purging with 60ml/min nitrogen for 15 min; (3) introducing air flow (20ml/min), and purging with air for 15 min; (4) continuously purging with nitrogen for 15 min; and (4) completing a complete cycle in the steps (1) to (4). The volume space velocity of the reaction is calculated to be 300h based on the reactant methane-1。
Example 25:
LaMn prepared in example 1 was metered in1/3Fe1/3Co1/3O30.6mL of oxygen carrier is diluted and mixed evenly with 0.4mL of quartz sand with the same mesh number, and the mixture is added into a fixed bed tubular reactor, and the experiment is carried out under the condition of 900 ℃ and normal pressure. In N2Heating to the temperature under the atmosphereAfter the temperature is 900 ℃ (1) introducing 5min of mixed gas of methane and nitrogen with the total flow of 60ml/min, wherein the volume of the methane accounts for 50% of the total volume of the mixed gas, collecting tail gas within 5min, and analyzing the composition by using gas chromatography; (2) purging with 60ml/min nitrogen for 15 min; (3) introducing air flow (20ml/min), and purging with air for 15 min; (4) continuously purging with nitrogen for 15 min; and (4) completing a complete cycle in the steps (1) to (4). The volume space velocity of the reaction is calculated to be 3000h by taking the reactant methane as the reference-1。
Example 26:
experiment with the method of example 1, LaMn1/3Fe1/3Co1/3O30.6mL of oxygen carrier is diluted and uniformly mixed with 0.4mL of quartz sand with the same mesh number, and then the mixture is continuously tested for 50 cycles.
For the results of the above example, the following discussion is made:
(I) different Co and Fe addition amounts for preparing LaMn1-x-yFexCoyO3(0 < x < 1, 0 < y < 1;) oxygen carrier: oxygen carriers prepared by the methods of examples 1, 2, 3 and 4 were subjected to X-ray powder diffraction (XRD) tests, and the XRD test results are shown in fig. 1. As can be seen from FIG. 1, LaMnO3Is a characteristic diffraction peak corresponding to a cubic system, LaCoO3Characteristic diffraction peaks attributable to orthorhombic system, LaFeO3Is a characteristic diffraction peak, LaMn, corresponding to an orthorhombic system1/3Fe1/3Co1/3O3Spectrum of (1), peak type and LaMnO3Close, the whole is shifted towards high angles.
(II) preparing LaCo by changing the kind of complexing agent1/3Mn1/3Fe1/3O3Influence of oxygen carrier: oxygen carriers prepared by the methods of examples 5, 6, 7 and 8, respectively, were subjected to X-ray powder diffraction (XRD) tests, the XRD test results of which are shown in fig. 2. As can be seen from FIG. 2, the respective citric acid, ethylene glycol, glycine and urea can be used to prepare the LaCo with cubic lattice structure1/ 3Mn1/3Fe1/3O3A perovskite oxygen carrier.
(III) preparation by using only one or two complexing agents simultaneouslyPreparation of LaCo1/3Mn1/3Fe1/3O3Influence of oxygen carrier: oxygen carriers prepared by the methods of examples 8, 9, 10, and 1, respectively, were subjected to X-ray powder diffraction (XRD) tests, the XRD test results of which are shown in fig. 3. As can be seen from FIG. 3, the addition of one or both complexing agents can produce a cubic lattice LaCo1/3Mn1/3Fe1/3O3A perovskite oxygen carrier.
(IV) different Co and Fe addition amounts for preparing LaMn1-x-yFexCoyO3(0 < x < 1, 0 < y < 1;) oxygen carrier: an X-ray powder diffraction (XRD) test was carried out on the oxygen carrier prepared by the method of example 15, and the XRD test results are shown in fig. 4. As can be seen from FIG. 4, LaMn was prepared with different Co and Fe addition levels1-x-yFexCoyO3In which LaCo1/6Mn1/3Fe1/ 2O3、LaCo1/2Mn1/3Fe1/6O3、LaCo1/5Mn7/15Fe1/3O3、LaCo1/2Mn1/6Fe1/3O3Oxygen carrier and LaCo1/3Mn1/3Fe1/3O3The lattice structures of the crystal are consistent and are all cubic crystal structures.
(V) to study Co, Fe Co-substituted LaMnO3Influence of oxygen carrier on partial oxidation reaction performance of chemical chain methane: the tests were carried out by the methods of examples 1, 2, 3 and 4, and the results of the reaction performance test in the methane reduction stage are shown in FIG. 5. When the molar ratio of La to Co to Mn to Fe is 3:1:1:1 (LaCo)1/3Mn1/3Fe1/3O3) The oxygen carrier has the highest methane conversion rate and CO selectivity, and has good chemical chain methane partial oxidation reaction performance.
(VI) preparing LaMn by adopting different Co and Fe addition amounts1-x-yFexCoyO3Influence of partial oxidation reaction performance of oxygen carrier chemical chain methane: the tests were carried out by the methods of example 16 and example 1, and the results of the reaction performance test in the methane reduction stage are shown in FIG. 6. From FIG. 6, it can be seen thatThe bar chart shows methane conversion rate, hydrogen selectivity, carbon monoxide selectivity or carbon dioxide selectivity, and the star in the dot line chart corresponds to H in the product2The ratio of/CO. LaMn prepared by different Co and Fe doping amounts1-x-yFexCoyO3Oxygen carriers, LaMn1/3Fe1/3Co1/3O3Has the highest methane conversion and synthesis gas selectivity. Comparative Lamn1/6Fe1/3Co1/ 2O3，LaMn7/15Fe1/3Co1/5O3，LaMn1/3Fe1/3Co1/3O3It can be seen that as the Mn content increases, the methane conversion of the oxygen carrier shows a tendency to increase first and then decrease. Fixed Mn content of 1/3, comparative LaMn1/6Fe1/3Co1/2O3，LaMn7/15Fe1/3Co1/ 5O3，LaMn1/3Fe1/3Co1/3O3With the increase of the Fe content, the methane conversion rate of the oxygen carrier and the yield of the synthesis gas both show a trend of increasing and then decreasing. Complete oxidation product (CO) for all samples2) The selectivity of carbon deposition is lower than 5 percent, wherein, LaMn1/ 3Fe1/3Co1/3O3And the lowest. This indicates that the B site Fe and Co Co-doped LaMn1/3Fe1/3Co1/3O3The oxygen carrier has the best reactivity in the methane reduction stage.
(seventhly) influence of different oxygen carriers and diluent volume ratios on partial oxidation of methane to prepare synthesis gas: the tests were carried out by the methods of examples 1, 17 and 18, in which LaCo1/3Mn1/3Fe1/3O3The results of the methane conversion of the oxygen carrier are shown in table 1. As can be seen from the table, when the volume ratio of the oxygen carrier to the diluent is 1: 0-3: 2, the methane conversion rate does not change obviously along with the volume ratio of the oxygen carrier to the diluent.
TABLE 1 LaCo volume ratio of different oxygen carriers and diluents1/3Mn1/3Fe1/3O3Effect of oxygen carrier methane conversion
(eighthly) effect of different reaction temperatures on methane conversion: example 1 was used (where the oxygen carrier was LaCo)1/3Mn1/ 3Fe1/3O3) The methods 19 and 20 were tested and the results for methane conversion are shown in table 2. As can be seen from the table, the methane conversion rate gradually increased with the increase in the reaction temperature.
TABLE 2 LaCo1/3Mn1/3Fe1/3O3Conversion of methane at different reaction temperatures of the oxygen carrier
| Reaction temperature (. degree.C.) | 500 | 900 | 1000 |
| Methane conversion (%) | 35 | 96 | 100 |
(nine) Effect of different reaction space velocities (volume space velocity) on methane conversion: example 21 was used (where the oxygen carrier was LaCo)1/3Mn1/3Fe1/3O3) The methods of 22 and 23 were tested and the results for methane conversion are shown in table 3. It can be seen from the table that the methane conversion gradually decreases with increasing space velocity of the reaction.
TABLE 3 LaCo1/3Mn1/3Fe1/3O3Oxygen carrierMethane conversion at different reaction space velocities
| Volumetric space velocity (h)-1) | 150 | 300 | 3000 |
| Methane conversion (%) | 98 | 95 | 73 |
(ten) effect of different reaction gas compositions on methane conversion: example 1 was used (where the oxygen carrier was LaCo)1/ 3Mn1/3Fe1/3O3C), 24 and 25, see table 4 for results of methane conversion. It can be seen from the table that the methane conversion gradually decreases as the volume percentage of methane in the reaction gas increases.
TABLE 4 LaCo1/3Mn1/3Fe1/3O3Methane conversion rate of oxygen carrier with different reaction gas composition
(eleven) effect on methane conversion with 50 cycles: using the method of example 26, the results of the performance test in the methane reduction stage are shown in FIG. 7. from FIG. 7, it can be seen that LaCo is measured in the 50 cycle stability test1/3Mn1/3Fe1/3O3Oxygen carrier performanceHigh methane reaction performance and good stability are obtained. The conversion rate of methane is stabilized between 88 percent and 95 percent, and the partial oxidation product H of methane2And CO selectivity higher than 87%, H2the/CO ratio is stable and close to the theoretical value of 2, which indicates that the LaCo is1/3Mn1/3Fe1/3O3The oxygen carrier has higher synthetic gas selectivity and excellent chemical chain methane partial oxidation reaction performance.
(twelfth) in order to investigate the stability of the oxygen carrier structure in the long cycle test process, the reacted oxygen carrier of example 26 was taken, the reaction performance remained stable, and the XRD characterization comparison was performed on the recycled oxygen carrier and the fresh oxygen carrier. As can be seen from FIG. 8, LaMn1/3Fe1/3Co1/3O3The application of the perovskite composite oxygen carrier in preparing synthesis gas by oxidizing methane at a chemical chain part. XRD spectrograms of the oxygen carrier after 50 times of cyclic reaction are perovskite characteristic diffraction peaks, and no impurity phase is detected, indicating that the oxygen carrier is still a pure perovskite crystalline phase, indicating that the oxygen carrier has no obvious structural change and grain aggregation growth in repeated cyclic regeneration test under high temperature condition, and shows relatively superior methane activity and relatively low carbon deposition selectivity, and the oxygen movement and release rate of the oxygen carrier after metal is improved, so that the oxygen [ O ] in the oxygen carrier]Can be cracked with methane at a higher speed]And the reaction is carried out, so that the carbon deposition amount is reduced, and therefore, the oxygen carrier has better sintering resistance and cycling stability.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.
Claims (7)
1. A chemical chain methane partial oxidation oxygen carrier is characterized in that the oxygen carrier is of a perovskite structure and has a general formula ofFormula is LaMn1-x-yFexCoyO3，0＜x＜1，0＜y＜1。
2. A chemical chain methane partial oxidation oxygen carrier according to claim 1, wherein the crystal structure of the oxygen carrier is cubic.
3. A process for the preparation of a chemical chain methane partial oxidation oxygen carrier according to any one of claims 1-2, wherein the process is carried out according to the following steps:
step 1, according to LaMn1-x-yFexCoyO3Weighing lanthanum nitrate, manganese nitrate, ferric nitrate, cobalt nitrate and a complexing agent according to a stoichiometric ratio, dissolving the lanthanum nitrate, the manganese nitrate, the ferric nitrate, the cobalt nitrate and the complexing agent in deionized water to prepare a precursor solution, wherein the molar ratio of the complexing agent to the total amount of metal ions in the precursor solution is 1.2: 1-2.4: 1;
step 2, evaporating the solution obtained in the step 1 to dryness to be gelatinous under the condition of continuous stirring; then the mixture is put into a constant-temperature drying oven with the temperature of 100-180 ℃ for full drying for 6-24 h, and the obtained precursor powder is fully roasted for 2-6 h at the temperature of 800-1000 ℃ to obtain LaMn with the molecular formula1-x-yFexCoyO3X is more than 0 and less than 1, and y is more than 0 and less than 1.
4. The method according to claim 3, wherein the complexing agent is at least one of citric acid, ethylene glycol, glycine and urea.
5. Use of an oxygen carrier according to any one of claims 1-2 in the partial oxidation of methane to synthesis gas by chemical looping, wherein in the reduction stage the oxygen carrier reacts with methane in the absence of oxygen, and the lattice oxygen in the oxygen carrier partially oxidizes methane to form synthesis gas, while the oxygen carrier is reduced; in the oxidation stage, the reduced oxygen carrier reacts with air to realize the cyclic regeneration of the catalyst, and the catalyst is restored to the perovskite structure before reacting with methane.
6. The use of the oxygen carrier according to claim 5 in the production of synthesis gas by partial oxidation of methane with a chemical chain, wherein a mixture of methane and nitrogen is introduced into the reduction stage, wherein the volume percentage of methane is 5-50%, and the volume space velocity of the reaction is controlled to be 150-3000 h based on methane-1(ii) a The reaction temperature is 500-1000 ℃.
7. The use of the oxygen carrier according to claim 5 in the preparation of synthesis gas by partial oxidation of methane with chemical chains, wherein air is introduced in the oxidation stage to supplement lattice oxygen by calcination at a reaction temperature of 500-1000 ℃.
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