CN115650167A - Oxygen carrier for preparing synthesis gas by methane chemical-looping reforming and preparation method and application thereof - Google Patents
Oxygen carrier for preparing synthesis gas by methane chemical-looping reforming and preparation method and application thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000001301 oxygen Substances 0.000 title claims abstract description 154
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- 239000002243 precursor Substances 0.000 claims abstract description 38
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- 238000000034 method Methods 0.000 claims abstract description 25
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an oxygen carrier for preparing synthesis gas by methane chemical chain reforming, a preparation method and application thereof, wherein the oxygen carrier is prepared by the following processes: according to Y x La 1‑x FeO 3 Dissolving precursors of La, Y and Fe in deionized water to form a precursor solution; wherein x is more than 0 and less than 1; adding citric acid into the precursor solution, stirring until the citric acid is dissolved, adjusting the pH to 7-8, stirring to be viscous under the heating condition, drying, grinding and calcining to obtain the oxygen carrier for preparing the synthesis gas by methane chemical chain reforming. The oxygen carrier is used in the methane chemical-looping reforming process, the reaction activity of the oxygen carrier and methane can be effectively improved, the methane conversion rate is up to more than 92%, the selectivity of synthesis gas is more than 90%, and the oxygen carrier has excellent carbon deposition resistance and excellent methane reaction activity and circulation stability in the multiple oxidation-reduction processes.
Description
Technical Field
The invention relates to the field of synthesis gas preparation by methane chemical-looping reforming, in particular to an oxygen carrier for preparing synthesis gas by methane chemical-looping reforming and a preparation method and application thereof.
Background
Since the industrial revolution, the dependence of human activities on fossil energy has led to the atmospheric CO 2 The content of the greenhouse gases represented by the general formula is increased year by year, the global warming, ocean acidification, sea level rise and the formation of severe climate are increased, and the living environment of human beings is threatened greatly. Methane is the main component of coal bed gas, shale gas, combustible ice and biological methane, and is the second largest greenhouse gas emitted by human activities at present, and is only second to carbon dioxide, but the unit greenhouse effect of the methane is more than 20 times of that of the carbon dioxide.
Methane dry gas reforming (CH) 4 +CO 2 →2CO+2H 2 ，ΔH 0 298K =247 kJ/mol) can convert methane and carbon dioxide into industrially important synthesis gas, but the reaction is strongly endothermic, energy consumption is large, carbon deposition is easily formed to cover active sites and cause catalyst deactivation; furthermore, the synthesis gas produced has a hydrogen to carbon ratio of about 1 if a subsequent methanol synthesis or Fischer-Tropsch synthesis is to be carried out (desired H) 2 the/CO ratio is 2) a gas regulating process needs to be added, and the energy consumption is increased. The methane chemical looping reforming technique decouples the gas-gas reaction into two gas-solid half-reactions (CH) by means of the circulation of an oxygen carrier (generally a metal oxide, MO) between the fuel reactor and the regeneration reactor 4 + MO＝2H 2 +CO，CO 2 + M = MO + CO), not only is capable of producing H 2 The synthesis gas with the ratio of 2/CO can be directly used as the raw material gas for the subsequent methanol synthesis or Fischer-Tropsch synthesis, and can also convert greenhouse gases into CO if the CO is converted into the CO 2 Is replaced by H 2 O(H 2 O +M＝MO+H 2 ) And high-purity hydrogen free from carbon pollution can be obtained. The key to the successful operation of the methane chemical-looping reforming technology is the development of an oxygen carrier that is resistant to high temperatures and has excellent performance.
The current research on chemical chain oxygen carriers is mainly transition metal oxide oxygen carriers and composite metal oxide oxygen carriers. The iron-based oxygen carrier is cheap and easy to obtain, is environment-friendly and carries oxygenHigh amount of CO 2 Or good water vapor reactivity, and the like, and is considered to be one of ideal oxygen carrier materials.
Dai et al [ J.Phys.chem.B,2006,110,45,22525-22531]Three iron-based perovskite oxides AFeO were studied 3 (A = La, nd, eu) for partial oxidation of methane chemical chain to produce synthesis gas, and LaFeO was found 3 The best syngas yield is shown due to the high oxygen mobility. But pure LaFeO 3 The reactivity of the oxygen carrier with methane is not high (methane conversion is about 60-70%), and the cycle stability is poor.
At present, the problems of low methane conversion rate, poor circulation stability and the like still exist when the methane chemical-looping reforming technology is suitable for Fe-based perovskite oxygen carriers.
Disclosure of Invention
In order to overcome the problems of low reactivity and poor circulation stability of Fe-based perovskite oxygen carriers and methane in the prior art, the invention aims to provide an oxygen carrier for preparing synthesis gas by methane chemical-looping reforming, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
an oxygen carrier for preparing synthetic gas by chemical chain reforming of methane has perovskite structure and structure formula of Y x La 1-x FeO 3 Wherein x is more than 0 and less than 1.
Furthermore, x is more than or equal to 0.05 and less than or equal to 0.2.
Further, x is 0.05,0.1,0.2,0.4,0.6, or 0.8.
A preparation method of an oxygen carrier for preparing synthesis gas by methane chemical chain reforming comprises the following steps:
according to Y x La 1-x FeO 3 Dissolving precursors of La, Y and Fe in deionized water to form a precursor solution; wherein x is more than 0 and less than 1;
adding citric acid into the precursor solution, stirring until the citric acid is dissolved, adjusting the pH to 7-8, stirring to be viscous under the heating condition, drying, grinding and calcining to obtain the oxygen carrier for preparing the synthesis gas by methane chemical chain reforming.
Further, the precursor of La is La (NO) 3 ) 3 ·6H 2 O and H 14 ClLaO 7 At least one of; the precursor of Y is Y (NO) 3 ) 3 ·6H 2 O and YCl 3 At least one of; precursor of Fe is FeCl 3 、Fe(NO 3 ) 3 ·9H 2 O and FeSO 4 At least one of (1).
Furthermore, the total concentration of the precursors of La, Y and Fe in the precursor solution is 1-1.2 mol/L.
Further, the amount of citric acid is 1.5 to 2.5 times the total molar amount of La, Y and Fe.
Further, the calcining process comprises the following steps: calcining at 300-500 deg.c for 2-5 hr and then at 800-1000 deg.c for 2-5 hr.
Use of an oxygen carrier as described above in the production of synthesis gas by chemical looping reforming of methane, characterized in that the oxygen carrier is circulated between two communicating fuel reactors and a regeneration reactor; wherein, in the fuel reactor, the oxygen carrier oxidizes methane at 800-1000 ℃ to generate synthesis gas; in the regeneration reactor, the oxygen carrier is oxidized and regenerated at 800-1000 ℃ under an oxidizing atmosphere and then enters the fuel reactor.
Furthermore, the fuel reactor is a mixed gas of methane and inert gas, and the oxidizing atmosphere is a mixed gas of carbon dioxide and inert gas, a mixed gas of water vapor and inert gas, a mixed gas of oxygen and inert gas or a mixed gas of water vapor and carbon dioxide.
Furthermore, the volume fraction of methane in the mixed gas of methane and inert gas is 2-100%, the volume fraction of carbon dioxide in the mixed gas of carbon dioxide and inert gas is 2-100%, the volume fraction of water vapor in the mixed gas of water vapor and inert gas is 2-100%, and the volume fraction of oxygen in the mixed gas of oxygen and inert gas is 2-100%.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the composite metal oxide Y with the perovskite structure x La 1-x FeO 3 (x =0,0.05,0.1,0.2,0.4,0.6 and 0.8) series oxygen carriers, doping of Y does not form a hetero-phase, Y with smaller radius 3+ Ion successfully replaces part of La 3+ The crystal grain size of the oxygen carrier is effectively reduced by ions, the dispersibility and the transmission and diffusion capacity of lattice oxygen are improved, and the perovskite structure is maintained in the multiple circulation processes, so that the prepared oxygen carrier is high-temperature resistant, strong in sintering resistance and stable in mechanical property in the circulation process.
The composite metal oxide Y with the perovskite structure prepared by the invention x La 1-x FeO 3 (x =0.05,0.1,0.2,0.4,0.6 and 0.8) series oxygen carriers, which have excellent methane activation capacity and cycle stability. In the methane reduction process, the Fe species in the Y-doped oxygen carrier is deeply reduced, zero-valent iron is generated on the surface, and the effects of efficiently adsorbing and activating methane are achieved. The reaction activity of the oxygen carrier and methane after Y doping is greatly improved, but carbon deposition is not found, which indicates that the oxygen supply of the oxygen carrier is sufficient in the reaction process, and the doping of Y greatly improves the transmission and diffusion capacity of lattice oxygen in a bulk phase, so that a lattice oxygen source is continuously conveyed from the bulk phase to the surface for oxidizing the activated methane and partially oxidizing the methane into synthesis gas with high selectivity. In addition, the Y doping also obviously improves the dispersibility of the active components, inhibits the agglomeration and sintering of oxygen carrier particles in the reaction process and further improves the cycle stability. When x =0.1, Y 0.1 La 0.9 FeO 3 The oxygen carrier has the best methane reaction activity, the methane conversion rate and the synthetic gas selectivity can still reach more than 90 percent by 30 times of circulation, and H 2 The mol ratio of the carbon dioxide to CO is maintained between 1.9 and 2.1, which is close to an ideal value of 2, and the quality of the synthesis gas is higher. The oxygen carrier is shown to have outstanding methane reaction activity, synthesis gas selectivity, carbon deposition resistance and circulation stability.
Y having perovskite structure in the present invention x La 1-x FeO 3 Composite metal oxide atmosphere toolHas universality, can realize oxidative regeneration in air, water, carbon dioxide or a water/carbon dioxide mixture, and shows excellent cycle stability. The preparation method of the oxygen carrier is simple, environment-friendly and easy for industrial production.
Drawings
Fig. 1 is an X-ray powder diffraction pattern of the oxygen carrier prepared in comparative example 1 and examples 1, 2, and 3 in a fresh state.
Fig. 2 is a kinetic profile of the oxygen carrier prepared in comparative example 1 during the reaction.
FIG. 3 is a kinetic profile of the oxygen carrier prepared in example 1 during the course of the reaction.
FIG. 4 is a kinetic profile of the oxygen carrier prepared in example 5 during the course of the reaction.
FIG. 5 is a graph showing CH of oxygen carriers prepared in comparative example 1, example 2 and example 4 during 10 cycles of reaction 4 Conversion and H 2 Comparative plot of/CO.
FIG. 6 is a graph comparing the synthesis gas yield and the oxygen output of the oxygen carriers prepared in comparative example 1, example 2 and example 4 during 10 cycles of reaction.
Fig. 7 is an X-ray powder diffraction pattern of the oxygen carrier prepared in comparative example 1 in a fresh state and after 2 reductions, 2 cycles, 10 reductions, and 10 cycles, respectively.
Fig. 8 is an X-ray powder diffraction pattern of the oxygen carrier prepared in example 2 in a fresh state and after 2 times of reduction, 2 times of cycles, 10 times of reduction, and 10 times of cycles, respectively.
FIG. 9 is a graph of the conversion, selectivity and H for the oxygen carrier prepared in example 2 over a 30 cycle reaction process 2 the/CO diagram.
Detailed Description
The present invention will be described in detail below with reference to the drawings and specific examples, but the present invention is not limited to the following examples.
The oxygen carrier for preparing the synthesis gas by methane chemical chain reforming is a composite metal oxide with a perovskite structure, and the structural general formula of the oxygen carrier is Y x La 1-x FeO 3 Wherein 0 < x < 1, preferably, x is0.05,0.1,0.2,0.4,0.6 or 0.8.
The preparation method of the oxygen carrier comprises the following steps:
specifically, the oxygen carrier is prepared by a sol-gel method, firstly, precursors of La, Y and Fe are added according to the required stoichiometric ratio and completely dissolved in deionized water to form a precursor solution, citric acid solid is weighed and added into the precursor solution to be stirred until the citric acid solid is fully dissolved, and ammonia water is used for adjusting the pH value of the solution to be 7-8. Then the solution is stirred under the condition of constant temperature water bath until the solution is sticky colloid, and then the sticky colloid is dried, ground and calcined to obtain the required oxygen carrier.
Wherein the precursor of La is La (NO) 3 ) 3 ·6H 2 O and H 14 ClLaO 7 At least one of; the precursor of Y is Y (NO) 3 ) 3 ·6H 2 O and YCl 3 At least one of; precursor of Fe is FeCl 3 、Fe(NO 3 ) 3 ·9H 2 O and FeSO 4 At least one of (a); the total concentration of the precursors of La, Y and Fe in the precursor solution is 1-1.2 mol/L; the amount of citric acid required is 1.5 to 2.5 times the molar amount of the total metal cations in the solution; the drying process is drying for 8-12 hours at 50-80 ℃; the calcination process is to calcine for 2 to 5 hours at 300 to 500 ℃ and then calcine for 2 to 5 hours at 800 to 1000 ℃.
The oxygen carrier as described above is applied to a methane chemical looping reforming process, in particular the oxygen carrier is circulated between two communicating reactors (a fuel reactor and a regeneration reactor); wherein, in the fuel reactor, the oxygen carrier oxidizes methane to produce syngas; in the regeneration reactor, the oxygen carrier is oxidized and regenerated in the oxidizing atmosphere and enters the next circulation process; the reaction is carried out under normal pressure, and the reaction temperature is 800-1000 ℃; the fuel reactor is a mixed gas of methane and inert gas, and the oxidation atmosphere in the regeneration reactor is a mixed gas of carbon dioxide and inert gas, or a mixed gas of water vapor and inert gas, or a mixed gas of oxygen and inert gas, or a mixed gas of water vapor and carbon dioxide.
Wherein the volume fraction of methane in the mixed gas of methane and inert gas is 2-100%, the volume fraction of carbon dioxide in the mixed gas of carbon dioxide and inert gas is 2-100%, the volume fraction of water vapor in the mixed gas of water vapor and inert gas is 2-100%, and the volume fraction of oxygen in the mixed gas of oxygen and inert gas is 2-100%.
The oxygen carrier can effectively improve the reaction activity of the oxygen carrier and methane, the conversion rate of the methane is up to more than 92%, if carbon dioxide is adopted as an oxidizing atmosphere, the selectivity of synthesis gas is more than 90%, and the oxygen carrier has excellent carbon deposition resistance, wherein H is 2 the/CO is 2 and can be directly used for Fischer-Tropsch synthesis. The oxygen carrier has excellent methane reactivity and stability in multiple redox cycles. Wherein, if water vapor and water/carbon dioxide are used as oxidizing atmosphere, high-added-value products such as high-purity hydrogen, carbon monoxide or synthesis gas can be generated.
Comparative example 1
LaFeO 3 Preparation of oxygen carriers
Weighing a certain amount of La (NO) according to the stoichiometric ratio 3 ) 3 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is dissolved in deionized water, and after complete dissolution, the citric acid solid (citric acid: metal cation = 2.5). And after the citric acid is fully dissolved, adjusting the pH of the solution to be 7-8 by using ammonia water. And then stirring the solution in a constant-temperature water bath at 80 ℃ until the water in the solution is evaporated into viscous colloid, then drying the viscous colloid in a forced air drying oven at 150 ℃ for 12 hours to obtain a black precursor, fully grinding the black precursor, then calcining the sample in a muffle furnace, and calcining the sample at constant temperature at 400 ℃ for 4 hours to remove organic impurities in the sample. After the temperature is reduced to the room temperature, the sample is ground again, and then the ground sample is placed at the constant temperature of 900 ℃ for calcination for 4 hours. The obtained oxygen carrier powder is pressed into 20-40 mesh granules under the pressure of 10MPa, and the granules are marked and bagged for later use.
Example 1
Y 0.05 La 0.95 FeO 3 Preparation of oxygen carriers
Weighing a certain amount of Y (NO) according to the stoichiometric ratio 3 ·6H 2 O、La(NO 3 ) 3 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is dissolved in deionized water and after complete dissolution, the citric acid solid (citric acid: cation = 2.5). And after the citric acid is fully dissolved, adjusting the pH of the solution to be 7-8 by using ammonia water. And then placing the solution in a constant-temperature water bath at 80 ℃ for stirring until the water content of the solution is evaporated into a viscous colloid, then placing the viscous colloid in a forced air drying oven at 150 ℃ for drying for 12 hours to obtain a black precursor, fully grinding, placing the sample in a muffle furnace for calcining, and calcining at the constant temperature of 400 ℃ for 4 hours to remove organic impurities in the sample. After the temperature is reduced to the room temperature, the sample is ground again, and then the ground sample is placed at the constant temperature of 900 ℃ for calcination for 4 hours. The obtained oxygen carrier powder is pressed into 20-40 mesh granules under the pressure of 10MPa, and the granules are marked and bagged for standby.
Example 2
Y 0.1 La 0.9 FeO 3 Preparation of oxygen carriers
The procedure is as in example 1, except that Y (NO) is present in the precursor solution 3 ·6H 2 O and La (NO) 3 ) 3 In a molar ratio of 1.
Example 3
Y 0.2 La 0.8 FeO 3 Preparation of oxygen carriers
The procedure is as in example 1, except that Y (NO) is present in the precursor solution 3 ·6H 2 O and La (NO) 3 ) 3 The molar ratio of (a) to (b) is 2.
Example 4
Y 0.4 La 0.8 FeO 3 Preparation of oxygen carriers
The procedure is as in example 1, except that Y (NO) is present in the precursor solution 3 ·6H 2 O and La (NO) 3 ) 3 4.
Example 5
Y 0.6 La 0.4 FeO 3 Preparation of oxygen carriers
The procedure is as in example 1, except that Y (NO) is present in the precursor solution 3 ·6H 2 O and La (NO) 3 ) 3 The molar ratio of (a) to (b) is 6.
Example 6
Y 0.8 La 0.2 FeO 3 Preparation of oxygen carriers
The procedure is as in example 1, except that Y (NO) is present in the precursor solution 3 ·6H 2 O and La (NO) 3 ) 3 In a molar ratio of 8
Example 7
XRD testing of the oxygen carrier prepared in comparative example 1 and examples 1, 2 and 3 was performed on an X' pert Pro Super type radiation diffractometer manufactured by PAN Analytical, inc. of the Netherlands. The copper target K α line was the light source (λ =0.15432 nm), the graphite monochromator, the tube voltage and the tube current were 40kV and 40mA, respectively. The X-ray diffraction test results are shown in fig. 1.
As can be seen from FIG. 1, only perovskite LaFeO was observed in all oxygen carriers 3 And phase diffraction peaks show that the oxygen carriers after roasting are all pure-phase perovskite structures, and no impurity phase is generated. Meanwhile, as the amount of Y substitution increases, laFeO 3 The diffraction peak is gradually shifted toward high angles due to Y 3+ Radius of ion
Less than La 3+ Radius of ion
Description of Y 3+ Successful ion substitution of La 3+ Ions enter LaFeO 3 In the crystal lattice, Y is formed x La 1-x FeO 3 And (5) structure.
Example 8
And (3) evaluating the activity of the oxygen carrier prepared in the comparative example 1 on the methane chemical chain reforming reaction of the oxygen carrier by adopting a fixed bed reactor. The dosage of the oxygen carrier is 200mg, and the granularity is 20-40 meshes. Fuel gas composition of 5% 4 Ar, the flow rate is 15ml/min, the reaction temperature is 900 ℃, the reaction time is 15min, and the reaction pressure is normal pressure. The gas at the outlet of the reactor was analyzed on-line using a GAM-200 mass spectrometer. The reaction results are shown in FIG. 2.
As can be seen from fig. 2, the x =0 oxygen carrier had a small amount of CO at the beginning of the reaction 2 Production in the presence of large amounts of unreacted methane, H 2 And the generation of CO both show a tendency to decrease first and then increase slowly, indicating that methane has a lower reactivity and that the rate of release of lattice oxygen in the oxygen carrier is slower.
Example 9
For the oxygen carriers prepared in examples 1 and 5, the activity evaluation of the oxygen carrier methane chemical-looping reforming reaction was performed using a fixed-bed reactor. The dosage of the oxygen carrier is 200mg, and the granularity is 20-40 meshes. The fuel gas composition is 5% CH 4 Ar, the flow rate is 15ml/min, the reaction temperature is 900 ℃, the reaction time is 15min, and the reaction pressure is normal pressure. The gas at the outlet of the reactor was analyzed on-line using a GAM-200 mass spectrometer. The reaction results are shown in FIGS. 3 and 4.
As can be seen from FIGS. 3 and 4, pure LaFeO was obtained in comparison with that in comparative example 1 3 Compared with the prior art, the content of unreacted methane of the Y-doped oxygen carrier is greatly reduced, the synthesis gas is rapidly generated in the initial reaction stage (within 2.5 min), and the yield of the synthesis gas is obviously improved, which indicates that the converted methane is mainly selectively oxidized into the synthesis gas. It can be seen that the doping of Y can significantly improve the activity of the oxygen carrier reacting with methane and the rate of oxygen release from the crystal lattice.
Example 10
The cycle stability of the oxygen carrier methane chemical-looping reforming was evaluated using a fixed bed reactor on the oxygen carriers prepared in comparative example 1, example 2 and example 4. The dosage of the oxygen carrier is 200mg, and the granularity is 20-40 meshes. The fuel gas composition is 5% CH 4 Ar, the flow rate is 15ml/min, the reaction temperature is 900 ℃, and the reaction pressure is normal pressure. After the reduction was completed for 8 minutes, the reaction was switched to Ar purge for 5 minutes at a flow rate of 15ml/min and then switched to an oxidizing atmosphere, the composition was 5% CO 2 Ar, the flow rate is 15ml/min, the reaction temperature is 900 ℃, and the reaction time is 10min. The above procedure was repeated 10 times to test the oxygen carrier stability. The reactor outlet gas was analyzed on-line using a GAM-200 mass spectrometer, and the stability evaluation results are shown in FIGS. 5 and 6.
From FIG. 5, it can be seen that pure LaFeO 3 The methane conversion rate is only about 60 percent, and when the doping amount of Y is respectively 0.1 and 0.4, the methane conversion rate of the oxygen carrier is greatly improved from 60 percent to more than 92 percent and 90 percent, and the oxygen carrier is always stable in the oxidation-reduction process for 10 times, and simultaneously has proper H 2 /CO(～2)。
From FIG. 6, it can be seen that pure LaFeO 3 The yield and the oxygen output of the synthesis gas are only about 1.3mmol/g and 0.6mmol/g, and when a small amount of Y is doped (x = 0.1), the yield and the oxygen output of the synthesis gas are greatly improved to 2.25mmol/g and 1.05mmol/g, which are respectively improved by 73 percent and 75 percent, and the performance is obviously improved. Moreover, various performances of the oxygen carrier after Y doping are kept stable in the oxidation-reduction process for 10 times, and the oxygen carrier has no descending trend. Therefore, the doping of Y not only obviously improves the reactivity of the oxygen carrier and methane, but also improves the cycling stability.
The oxygen carriers prepared in example 1 (x = 0.05) and example 3 (x = 0.2) have similar performance to those of example 2 (x = 0.1) and example 4 (x = 0.4) described above.
Example 11
For the oxygen carriers prepared in comparative example 1 and example 2, XRD testing during recycling of the oxygen carriers was performed on an X' pert Pro Super type radiation diffractometer manufactured by PAN Analytical, inc. of the Netherlands. The copper target K α line was the light source (λ =0.15432 nm), the graphite monochromator, the tube voltage and the tube current were 40kV and 40mA, respectively. The X-ray diffraction test results are shown in fig. 7 and 8.
LaFeO is found from FIGS. 7 and 8 3 And Y 0.1 La 0.9 FeO 3 The perovskite structure of the oxygen carrier is maintained in the process of 10 cycles, which indicates that the structure is stable. In the methane reduction process, the Y-doped oxygen carrier is deeply reduced, zero-valent iron is generated on the surface, and the Y-doped oxygen carrier can be used as an active center for absorbing methane. Although the reaction activity of the oxygen carrier and methane after Y doping is greatly improved, no carbon deposition is found, which indicates that the oxygen supply of the oxygen carrier is sufficient in the reaction process, and the activated methane can be quickly oxidized to generate synthesis gas. The results show that the doping of Y not only promotes the deep reduction of Fe, is beneficial to the activation of methane and the great improvement of oxygen output, but also obviously improves the bulk phase lattice oxygenThe migration capability enables the lattice oxygen source to be continuously transported from a bulk phase to the surface in a migration mode and used for oxidizing methane after being adsorbed and activated, and the migration capability is probably an important reason that the Y-doped modified oxygen carrier has excellent methane reaction activity, high cycle stability and carbon deposition resistance.
Example 12
The oxygen carrier prepared in example 2 was evaluated for cycle stability of methane chemical looping reforming using a fixed bed reactor. The dosage of the oxygen carrier is 200mg, and the granularity is 20-40 meshes. The fuel gas composition is 5% CH 4 Ar, the flow rate is 15ml/min, the reaction temperature is 900 ℃, and the reaction pressure is normal pressure. After the reduction was completed for 8 minutes, switching to Ar purge for 5 minutes at a flow rate of 15ml/min and then switching to oxidizing atmosphere at a composition of 5% CO 2 Ar, the flow rate is 15ml/min, the reaction temperature is 900 ℃, and the reaction time is 10min. The above procedure was repeated 30 times to test the oxygen carrier stability. The reactor outlet gas was analyzed on-line using a GAM-200 mass spectrometer. The stability evaluation results are shown in fig. 9.
From FIG. 9, Y doping Y can be seen 0.1 La 0.9 FeO 3 The oxygen carrier can still reach over 90 percent of methane conversion rate and synthesis gas selectivity even when the oxygen carrier reaches the 30 th cycle, and H 2 The mol ratio of the carbon dioxide to CO is always maintained between 1.9 and 2.1, which is close to an ideal value of 2, and the quality of the synthesis gas is high. The above results show that the Y-doped oxygen carrier still shows excellent methane reactivity and cycle stability in 30 consecutive high-temperature redox reaction processes.
Example 13
Using the oxygen carrier prepared in example 2, the evaluation procedure was identical to that of example 10 except that the regeneration atmosphere was changed to 5% CO 2 Ar or 5% of H 2 O/Ar。
Example 14
For the oxygen carrier prepared in example 1, the activity of the oxygen carrier methane chemical-looping reforming reaction was evaluated by using a fixed-bed reactor. The dosage of the oxygen carrier is 200mg, and the granularity is 20-40 meshes. The fuel gas composition is 5% CH 4 Ar, flow rate of 15ml/min, reaction temperature of 800 ℃, reaction time of 15min, reaction pressure ofAnd (4) normal pressure.
Example 15
For the oxygen carrier prepared in example 5, the activity of the oxygen carrier methane chemical-looping reforming reaction was evaluated by using a fixed-bed reactor. The dosage of the oxygen carrier is 200mg, and the granularity is 20-40 meshes. The fuel gas composition is 5% CH 4 Ar, the flow rate is 15ml/min, the reaction temperature is 950 ℃, the reaction time is 15min, and the reaction pressure is normal pressure.
Example 16
Y 0.1 La 0.9 FeO 3 Preparation of oxygen carriers
Weighing a certain amount of Y (NO) according to the stoichiometric ratio 3 ·6H 2 O、La(NO 3 ) 3 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is dissolved in deionized water and after complete dissolution, the citric acid solid (citric acid: cation = 2.5). And after the citric acid is fully dissolved, adjusting the pH of the solution to be 7-8 by using ammonia water. And then placing the solution in a constant-temperature water bath at 70 ℃ for stirring until the water content of the solution is evaporated into a viscous colloid, then placing the viscous colloid in a forced air drying oven at 150 ℃ for drying for 10 hours to obtain a black precursor, fully grinding, placing the sample in a muffle furnace for calcining, and calcining at the constant temperature of 400 ℃ for 3 hours to remove organic impurities in the sample. After the temperature is reduced to the room temperature, the sample is ground again, and then the ground sample is placed at the constant temperature of 800 ℃ for calcination for 5 hours. The obtained oxygen carrier powder is pressed into 20-40 mesh granules under the pressure of 10MPa, and the granules are marked and bagged for later use.
Example 17
Y 0.2 La 0.8 FeO 3 Preparation of oxygen carriers
Weighing a certain amount of Y (NO) according to the stoichiometric ratio 3 ·6H 2 O、La(NO 3 ) 3 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is dissolved in deionized water and after complete dissolution, the citric acid solid (citric acid: cation = 2.5). And after the citric acid is fully dissolved, adjusting the pH of the solution to be 7-8 by using ammonia water. Then the solution is stirred in a constant temperature water bath condition of 70 ℃ until the water content of the solution is evaporated into sticky colloidAnd then putting the sample into a 150 ℃ forced air drying oven for drying for 10h to obtain a black precursor, fully grinding the black precursor, putting the sample into a muffle furnace for calcining, and calcining the sample at the constant temperature of 400 ℃ for 5h to remove organic impurities in the sample. After the temperature is reduced to the room temperature, the sample is ground again, and then the ground sample is placed at the constant temperature of 1000 ℃ for calcination for 2.5h. The obtained oxygen carrier powder is pressed into 20-40 mesh granules under the pressure of 10MPa, and the granules are marked and bagged for later use.
Example 18
For the oxygen carriers prepared in example 16 and example 17, the activity evaluation of the methane chemical-looping reforming reaction of the oxygen carrier was performed using a fixed-bed reactor. The dosage of the oxygen carrier is 200mg, and the granularity is 20-40 meshes. Fuel gas composition of 5% 4 Ar, the flow rate is 15ml/min, the reaction temperature is 900 ℃, the reaction time is 15min, and the reaction pressure is normal pressure.
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 protection scope of the technical solution of the present invention.
Claims (10)
1. An oxygen carrier for preparing synthetic gas by reforming methane chemical chain is characterized in that the oxygen carrier has a perovskite structure and the structural formula is Y x La 1-x FeO 3 Wherein x is more than 0 and less than 1.
2. The oxygen carrier for methane chemical looping reforming to syngas according to claim 1, wherein x is 0.05,0.1,0.2,0.4,0.6, or 0.8.
3. A preparation method of an oxygen carrier for preparing synthesis gas by methane chemical chain reforming is characterized by comprising the following steps:
according to Y x La 1-x FeO 3 Dissolving precursors of La, Y and Fe in deionized water to form a precursor solution; wherein x is more than 0 and less than 1;
adding citric acid into the precursor solution, stirring until the citric acid is dissolved, adjusting the pH to 7-8, stirring to be viscous under the heating condition, drying, grinding and calcining to obtain the oxygen carrier for preparing the synthesis gas by methane chemical chain reforming.
4. The method for preparing an oxygen carrier for methane chemical looping reforming synthesis gas according to claim 3, wherein the precursor of La is La (NO) 3 ) 3 ·6H 2 O and H 14 ClLaO 7 At least one of (a); the precursor of Y is Y (NO) 3 ) 3 ·6H 2 O and YCl 3 At least one of; precursor of Fe is FeCl 3 、Fe(NO 3 ) 3 ·9H 2 O and FeSO 4 At least one of (1).
5. The method for preparing the oxygen carrier for the synthesis gas through the chemical looping reforming of methane according to claim 3, wherein the total concentration of the precursors of La, Y and Fe in the precursor solution is 1-1.2 mol/L.
6. The method for preparing the oxygen carrier for the chemical chain reforming of methane to prepare the synthesis gas according to claim 3, wherein the amount of the citric acid is 1.5 to 2.5 times of the total molar amount of La, Y and Fe.
7. The method for preparing the oxygen carrier for the synthesis gas by the chemical looping reforming of methane according to claim 3, wherein the calcination process comprises: calcining at 300-500 deg.c for 2-5 hr and then at 800-1000 deg.c for 2-5 hr.
8. Use of an oxygen carrier according to any of claims 1 or 2 in the chemical looping reforming of methane to synthesis gas, wherein the oxygen carrier is circulated between two communicating fuel reactors and a regeneration reactor; wherein, in the fuel reactor, the oxygen carrier oxidizes methane at 800-1000 ℃ to generate synthesis gas; in the regeneration reactor, the oxygen carrier is oxidized and regenerated at 800-1000 ℃ under an oxidizing atmosphere and then enters the fuel reactor.
9. The use according to claim 8, wherein the fuel reactor is a mixture of methane and an inert gas and the oxidizing atmosphere is a mixture of carbon dioxide and an inert gas, a mixture of water vapor and an inert gas, a mixture of oxygen and an inert gas or a mixture of water vapor and carbon dioxide.
10. The use according to claim 8, wherein the volume fraction of methane in the mixture of methane and inert gas is between 2% and 100%, the volume fraction of carbon dioxide in the mixture of carbon dioxide and inert gas is between 2% and 100%, the volume fraction of water vapor in the mixture of water vapor and inert gas is between 2% and 100%, and the volume fraction of oxygen in the mixture of oxygen and inert gas is between 2% and 100%.
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| CN108855109A (en) * | 2018-07-02 | 2018-11-23 | 西北大学 | A kind of chemical chain partial oxidation methane preparing synthetic gas carrier of oxygen and its preparation method and application |
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