CN102941099A - Lanthanum calcium iron cobalt calcium titanium ore type catalyst for oxidizing and reforming ethanol and method for preparing catalyst - Google Patents
Lanthanum calcium iron cobalt calcium titanium ore type catalyst for oxidizing and reforming ethanol and method for preparing catalyst Download PDFInfo
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- CN102941099A CN102941099A CN2012104773616A CN201210477361A CN102941099A CN 102941099 A CN102941099 A CN 102941099A CN 2012104773616 A CN2012104773616 A CN 2012104773616A CN 201210477361 A CN201210477361 A CN 201210477361A CN 102941099 A CN102941099 A CN 102941099A
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Abstract
The invention discloses a lanthanum calcium iron cobalt calcium titanium ore type catalyst for oxidizing and reforming ethanol and a method for preparing the catalyst. The chemical formula of the catalyst is La1-xCaxFe1-yCoyO3, wherein the x is in a range of 0.1 to 0.5, and the y is in a range of 0.1 to 0.5. The method for preparing the catalyst includes that corresponding metal salt is dissolved in deionized water according to a molar ratio of metal ions to be prepared into a salt solution, citric acids are added according to a molar ratio of the citric acids and the metal ions, citric acids and polyethylene glycol 400 are added in a salt solution according to a molar ratio of the citric acids and the polyethylene glycol, uniform complexes are obtained after stirring, and then the complexes are subjected to evaporation concentration, drying and calcining to obtain the lanthanum calcium iron cobalt calcium titanium ore type catalyst. The lanthanum calcium iron cobalt calcium titanium ore type catalyst for oxidizing and reforming ethanol and the method for preparing the catalyst have the advantages that the manufacture process is simple, and the obtained catalyst has good reactivity and high hydrogen selectivity, and excellent stability and anti-carbon deposition capabilities simultaneously.
Description
Technical field
The present invention relates to a kind ofly for oxidation of ethanol reformation lanthanum calcium iron cobalt perovskite type catalyst and preparation method, particularly relate to a kind of for oxidation of ethanol reforming reaction La
1-xCa
xFe
1-yCo
yO
3Catalyst and preparation method belong to the load type metal catalyst technology that hydrocarbon is reformed.
Background technology
Co is catalyst based owing to its high ethanol reformation catalytic activity and relatively cheap price are subject to people's favor.The catalytic activity of the interaction partners catalyst between metal Co and the carrier, product distribute and the stability of catalyst has great impact.In addition, cobalt-base catalyst faces sintering and the oxidation of metallic cobalt particle, and the deactivation phenomenom that causes of carbon distribution.By selecting suitable catalyst carrier, can effectively suppress the inactivation of catalyst.The catalyst based carrier of Co that is used for of having reported has Al
2O
3, ZnO, SiO
2, MgO, ZrO
2, CeO
2, CeO
2-ZrO
2, La
2O
3And Y
2O
3Deng.Haga etc. have studied different metal and have loaded on Al
2O
3On catalytic performance, under T=673K, carry out the ethanol reforming reaction, the result shows: the reaction selectivity that the Co catalyst is reformed to ethanol is far longer than Ni.Jordi Llorca etc. has studied carrier and has been used for the impact that low temperature (300～450 ℃) ethanol steam reforming reacts for cobalt series catalyst, and wherein the catalytic activity of Co/ZnO is best, and hydrogen selectively is 73.8% in the product, CO
2Selectively be 24.2%.By more different catalyst carriers, find that Co/ZnO shows best ethanol reformation performance, but the stability test result of this catalyst shows that its deactivation phenomenom is apparent in view, the sintering of carbon distribution and metal Co and oxidized be the reason that causes catalysqt deactivation.Many reports show that the charging the inside adds a certain amount of oxygen (O/C=0.5), can greatly reduce producing carbon distribution in the course of reaction, affect hardly hydrogen selective simultaneously.But the affiliation that adds of oxygen discharges extra heat, makes catalyst surface produce focus, and accelerator activator is active metal component such as Ni particularly, and the sintering of Co etc. causes inactivation, so see that from this angle it is disadvantageous that oxygen adds.
At present, be mainly about the used catalyst carrier of oxidation of ethanol reforming reaction: CeO
2, ZnO, MgO, ZrO etc., there is not yet to be and use La
1-xCa
xFe
1-yCo
yO
3Pertinent literature report as catalyst.This patent proposes a kind of perovskite type catalyst, and the Co that obtains high dispersive after the perovskite reduction loads on the perovskite oxide, and has relatively strong interaction.In addition, because Ca and mixing of Co have produced the oxygen room, active oxygen can freely be come in and gone out and be circulated, and has effectively reduced the production of carbon distribution, and has prevented the sintering of active component Co, keeps the catalyst high stability.Like this, oxygen exists and can greatly reduce carbon distribution, again can the accelerator activator sintering, thus become a kind of Catalyst for Hydrogen Manufacture from Ethanol Reforming of high stability.
Summary of the invention
The object of the invention is to provide that a kind of this catalyst has good reactivity and high-temperature stability for oxidation of ethanol reformation lanthanum calcium iron cobalt perovskite type catalyst and preparation method, possesses simultaneously good anti-carbon performance, and its preparation method process is simple.
The present invention realized by following technical proposals, and a kind of for oxidation of ethanol reformation lanthanum calcium iron cobalt perovskite type catalyst, this catalyst chemical formula is La
1-xCa
xFe
1-yCo
yO
3, x=0.1 ~ 0.5 wherein, y=0.1 ~ 0.5; When x=0.3, y=0.3, in the chemical formula XRD diffracting spectrum ◆ symbol is the characteristic diffraction peak of this catalyst.
The preparation method of above-mentioned catalyst is characterized in that comprising following process: the mol ratio according to lanthanum, calcium, iron, cobalt is 1-x:x:1-y:y, x=0.1 ~ 0.5 wherein, and y=0.1 ~ 0.5 takes by weighing La (NO
3)
36H
2O, Ca (NO
3)
24H
2O, Fe (NO
3)
39H
2O, Co (NO
3)
26H
2O is dissolved in the deionized water, salting liquid stirs to get, be 1:(1 ~ 1.5 by citric acid with total metal ion mol ratio), and be 1:(0.5 ~ 1 by PEG400 and Citric Acid Dosage mol ratio), add citric acid and PEG400 to nitrate solution, after stirring, obtain even La-Ca-Fe-Co citric acid complex, complex compound forms the foam-like solid in 80 ~ 90 ℃ of lower water-bath evaporation and concentration of temperature, obtain powder through 100 ~ 120 ℃ of drying 20 ~ 24h of temperature again, powder places Muffle furnace to be warming up to 400 ~ 500 ℃ of constant temperature calcining 2 ~ 3h with 5 ~ 10 ℃/min of heating rate, be warming up to 700 ~ 750 ℃ of constant temperature calcining 5 ~ 6h with 5 ~ 10 ℃/min of heating rate afterwards, cooling obtains lanthanum calcium iron cobalt perovskite type catalyst naturally.
Advantage of the present invention has: the preparation method that the present invention adopts is easier than infusion process, namely obtain lanthanum calcium iron cobalt perovskite type catalyst by one step of citric acid complexometry, Co in the course of reaction in the perovskite is reduced, and high dispersive is on perovskite oxide, catalyst has the oxygen room simultaneously, so that this catalyst has good catalytic activity, high stability and good anti-carbon performance in oxidation and reformation.Prepared catalyst is 1000 ~ 240,000 ml gcat
-1h
-1In the air speed scope, have good stability and high anti-carbon performance at 500 ~ 750 ℃.
Description of drawings:
Fig. 1 is the XRD diffracting spectrum of the embodiment of the invention 3 prepared lanthanum calcium iron cobalt perovskite type catalysts.
Fig. 2 is the XRD diffracting spectrums of the embodiment of the invention 3 prepared lanthanum calcium iron cobalt perovskite type catalyst reactions after 200 hours.
Fig. 3 is that the embodiment of the invention 3 prepared catalyst are used for the oxidation of ethanol reformation, and ethanol conversion and each selectivity of product vary with temperature curve.
Among the figure: curve (1) is the ethanol conversion rate curve, curve (2) is the hydrogen selective curve, curve (3) is the carbon monoxide selective curve, curve (4) is the carbon dioxide selectivity curve, curve (5) is the methane selectively curve, curve (6) is the acetone selectivity curve, and curve (7) is the acetaldehyde selectivity curve.
Fig. 4 is the embodiment of the invention 3 prepared catalyst, carries out oxidation of ethanol reformation stability experiment curve with this catalyst.
Among the figure: curve 1 is the ethanol conversion rate curve, and curve (2) is the hydrogen selective curve, and curve (3) is the carbon monoxide selective curve, and curve (4) is the carbon dioxide selectivity curve, and curve (5) is the methane selectively curve.
Fig. 5 is the thermogravimetric analysis DTA-TG spectrogram of the embodiment of the invention 3 prepared catalyst sample behind 650 ℃ of reaction 200h.
Among the figure: curve (1) is the thermogravimetric curve behind the embodiment 3 prepared catalyst reactions; Curve (2) is the differential thermal analysis curve behind the embodiment 3 prepared catalyst reactions.
The specific embodiment
Catalyst preparation process is as follows: weigh in the balance and get La (NO
3)
36H
2O 5.116g, Ca (NO
3)
24H
2O 0.307g, Fe (NO
3)
39H
2O 4.749g, Co (NO
3)
26H
2O 0.378g, citric acid 6.521g, PEG400 0.5g joins wiring solution-forming in the deionized water of 250ml, stirred in water bath at 85 ℃, stir speed (S.S.) is 120N/min, and evaporation and concentration obtains sticky solid, and is then lower dry 24 hours at 120 ℃, obtain the roasting in Muffle furnace of foamed solid, be warmed up to 450 ℃ of roastings 2 hours with 5 ℃/min of heating rate, and then be warmed up to 750 ℃ of roastings 6 hours take heating rate as 5 ℃/min, obtain La
0.9Ca
0.1Fe
0.9Co
0.1O
3Catalyst 2.783g, yield are 92%.
The above catalyst that makes is used for oxidation of ethanol preparing hydrogen rich gas through reforming body:
The performance test of catalyst is carried out at micro fixed-bed reactor, and catalyst amount is 75mg, 40 ~ 60 orders.Use first N before the reaction
2Purge 10 minutes, use again the H of 5vol.%
2-Ar gaseous mixture, flow velocity are 50ml/min, 650 ℃ of lower reduction 60min of temperature programming.After reduction finishes, change temperature to the reaction temperature that needs, mixed solution with micro pump input second alcohol and water, the mol ratio of ethanol and water is 1:3, the mol ratio of ethanol and oxygen is 2:1, enter reactor and begin reaction after 140 ℃ of vaporizer vaporizations, the active testing mass space velocity is 80,000mL/gcat*h.Be 240,000mL/gcat*h at mass space velocity, temperature is to carry out stability test under 650 ℃ the condition.Adopt SP2100 type gas-chromatography to carry out on-line analysis, separate H with the TDX-01 molecular sieve column
2, N
2, CO, CO
2And CH
4, carrier gas is high-purity He, flow velocity is 30 ml/min; Separate H with Porapak-Q
2The products such as O, ethanol, acetaldehyde and acetone.Carrier gas is high-purity H
2, flow velocity is 30 ml/min.TCD detects.
Test result is as follows: La
0.9Ca
0.1Fe
0.9Co
0.1O
3Catalyst ethanol in the time of 650 ℃ transforms fully, and the hydrogen selective average is more than 50% in the probe temperature interval.
Catalyst preparation process is as follows: weigh in the balance and get La (NO
3)
36H
2O 4.743g, Ca (NO
3)
24H
2O 0.640g, Fe (NO
3)
39H
2O 4.402g, Co (NO
3)
26H
2O 0.789g, citric acid 6.800g, PEG400 0.5g joins wiring solution-forming in the deionized water of 250ml, stirred in water bath at 85 ℃, stir speed (S.S.) is 120N/min, and evaporation and concentration obtains sticky solid, and is then lower dry 24 hours at 120 ℃, obtain the roasting in Muffle furnace of foamed solid, be warmed up to 450 ℃ of roastings 2 hours with 5 ℃/min of heating rate, and then be warmed up to 750 ℃ of roastings 6 hours take heating rate as 5 ℃/min, obtain La
0.8Ca
0.2Fe
0.8Co
0.2O
3Catalyst 2.835g, yield are 94%.
The above catalyst that makes is used for oxidation of ethanol preparing hydrogen rich gas through reforming body, and the condition of reorganization is with embodiment 1.Test result is as follows: La
0.8Ca
0.2Fe
0.8Co
0.2O
3Catalyst ethanol in the time of 650 ℃ transforms fully, and the hydrogen selective average is more than 60% in the probe temperature interval.
Catalyst preparation process is as follows: weigh in the balance and get La (NO
3)
36H
2O 4.335g, Ca (NO
3)
24H
2O 1.003g, Fe (NO
3)
39H
2O 4.024g, Co (NO
3)
26H
2O 1.236g, citric acid 7.105g, PEG400 0.5g joins wiring solution-forming in the deionized water of 250ml, stirred in water bath at 85 ℃, stir speed (S.S.) is 120N/min, and evaporation and concentration obtains sticky solid, and is then lower dry 24 hours at 120 ℃, obtain the roasting in Muffle furnace of foamed solid, be warmed up to 450 ℃ of roastings 2 hours with 5 ℃/min of heating rate, and then be warmed up to 750 ℃ of roastings 6 hours take heating rate as 5 ℃/min, obtain La
0.7Ca
0.3Fe
0.7Co
0.3O
3Catalyst 2.895g, yield are 96%, and its chemical formula XRD diffracting spectrum as shown in Figure 1.
Make catalyst more than inciting somebody to action and be used for oxidation of ethanol preparing hydrogen rich gas through reforming body, the condition of reorganization is with embodiment 1.Test result is as follows: La
0.7Ca
0.3Fe
0.7Co
0.3O
3Catalyst ethanol in the time of 550 ℃ transforms fully, and the hydrogen selective average is more than 68%, as shown in Figure 3 in the probe temperature interval.With this catalyst at 650 ℃, air speed 240,000 ml gcat
-1h
-1The reaction 200h carry out stability experiment, the XRD diffracting spectrum of post catalyst reaction as shown in Figure 2, the same embodiment 1 of stability test, ethanol conversion is always 100%, hydrogen selective is all the time more than 68%, as shown in Figure 4.Test result shows La
0.7Ca
0.3Fe
0.7Co
0.3O
3Have good stability and anti-carbon performance, reacting 200 hours rear catalyst weight-loss ratios only is 2%, as shown in Figure 5.
Catalyst preparation process is as follows: weigh in the balance and get La (NO
3)
36H
2O 3.891g, Ca (NO
3)
24H
2O 1.400g, Fe (NO
3)
39H
2O 3.611g, Co (NO
3)
26H
2O 1.725g, citric acid 7.437g, PEG400 0.5g joins wiring solution-forming in the deionized water of 250ml, stirred in water bath at 85 ℃, stir speed (S.S.) is 120N/min, and evaporation and concentration obtains sticky solid, and is then lower dry 24 hours at 120 ℃, obtain the roasting in Muffle furnace of foamed solid, be warmed up to 450 ℃ of roastings 2 hours with 5 ℃/min of heating rate, and then be warmed up to 750 ℃ of roastings 6 hours take heating rate as 5 ℃/min, obtain La
0.6Ca
0.4Fe
0.6Co
0.4O
3Catalyst 2.793g, yield are 93%.
The above catalyst that makes is used for oxidation of ethanol preparing hydrogen rich gas through reforming body, and the condition of reorganization is with embodiment 1.Test result is as follows: La
0.6Ca
0.4Fe
0.6Co
0.4O
3The complete conversion ratio of ethanol in the time of 550 ℃, the hydrogen selective average is more than 67% in the probe temperature interval.
Catalyst preparation process is as follows: weigh in the balance and get La (NO
3)
36H
2O 3.401g, Ca (NO
3)
24H
2O 1.836g, Fe (NO
3)
39H
2O 3.157g, Co (NO
3)
26H
2O 2.263g, citric acid 7.803g, PEG400 0.5g joins wiring solution-forming in the deionized water of 250ml, stirred in water bath at 85 ℃, stir speed (S.S.) is 120N/min, and evaporation and concentration obtains sticky solid, and is then lower dry 24 hours at 120 ℃, obtain the roasting in Muffle furnace of foamed solid, be warmed up to 450 ℃ of roastings 2 hours with 5 ℃/min of heating rate, and then be warmed up to 750 ℃ of roastings 6 hours take heating rate as 5 ℃/min, obtain La
0.5Ca
0.5Fe
0.5Co
0.5O
3Catalyst 2.855g, yield are 95%.
Make catalyst more than inciting somebody to action and be used for oxidation of ethanol preparing hydrogen rich gas through reforming body, the condition of reorganization is with embodiment 1.Test result is as follows: La
0.5Ca
0.5Fe
0.5Co
0.5O
3The complete conversion ratio of ethanol in the time of 500 ℃, the hydrogen selective average is more than 68% in the probe temperature interval.
Claims (2)
1. one kind is used for oxidation of ethanol reformation lanthanum calcium iron cobalt perovskite type catalyst, and this catalyst chemical formula is La
1-xCa
xFe
1-yCo
yO
3, x=0.1 ~ 0.5 wherein, y=0.1 ~ 0.5; When x=0.3, y=0.3, in the chemical formula XRD diffracting spectrum ◆ symbol is the characteristic diffraction peak of this catalyst.
2. press the preparation method for oxidation of ethanol reformation lanthanum calcium iron cobalt perovskite type catalyst claimed in claim 1 for one kind, it is characterized in that comprising following process:
Mol ratio according to lanthanum, calcium, iron, cobalt is 1-x:x:1-y:y, x=0.1 ~ 0.5 wherein, and y=0.1 ~ 0.5 takes by weighing La (NO
3)
36H
2O, Ca (NO
3)
24H
2O, Fe (NO
3)
39H
2O, Co (NO
3)
26H
2O is dissolved in the deionized water, salting liquid stirs to get, be 1:(1 ~ 1.5 by the citric acid mole with total metal ion mol ratio), and be 1:(0.5 ~ 1 by PEG400 and Citric Acid Dosage mol ratio), add citric acid and PEG400 to nitrate solution, after stirring, obtain even La-Ca-Fe-Co citric acid complex, complex compound forms the foam-like solid in 80 ~ 90 ℃ of lower water-bath evaporation and concentration of temperature, obtain powder through 100 ~ 120 ℃ of drying 20 ~ 24h of temperature again, powder places Muffle furnace to be warming up to 400 ~ 500 ℃ of constant temperature calcining 2 ~ 3h with 5 ~ 10 ℃/min of heating rate, be warming up to 700 ~ 750 ℃ of constant temperature calcining 5 ~ 6h with 5 ~ 10 ℃/min of heating rate afterwards, cooling obtains lanthanum calcium iron cobalt perovskite type catalyst naturally.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104071845A (en) * | 2014-07-15 | 2014-10-01 | 渤海大学 | Preparation method for SLTON perovskite NOx powder |
| CN104085927A (en) * | 2014-07-18 | 2014-10-08 | 渤海大学 | Preparation method of LSTON (La, Sc, Ta, O and N) perovskite-type nitrogen oxide solid solution powder |
| CN106563456A (en) * | 2016-10-21 | 2017-04-19 | 广东石油化工学院 | A preparing method and an application of a LaPrFeNi<x>Co<1-x>O6 double-perovskite catalyst for hydrogen production by bioethanol reforming |
| CN107042111A (en) * | 2017-01-11 | 2017-08-15 | 成都理工大学 | The laminated perovskite type catalyst and preparation method of a kind of acetic acid self-heating reforming hydrogen manufacturing |
| CN108671927A (en) * | 2018-04-28 | 2018-10-19 | 中国科学院工程热物理研究所 | Composite catalyst and preparation method, the hydrogen production process of hydrogen production from methanol-steam reforming |
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| CN104071845A (en) * | 2014-07-15 | 2014-10-01 | 渤海大学 | Preparation method for SLTON perovskite NOx powder |
| CN104071845B (en) * | 2014-07-15 | 2016-01-06 | 渤海大学 | A kind of SLTON perovskite typed oxynitride raw powder's production technology |
| CN104085927A (en) * | 2014-07-18 | 2014-10-08 | 渤海大学 | Preparation method of LSTON (La, Sc, Ta, O and N) perovskite-type nitrogen oxide solid solution powder |
| CN104085927B (en) * | 2014-07-18 | 2016-03-09 | 渤海大学 | The preparation method of LSTON perovskite typed oxynitride solid-solution powder |
| CN106563456A (en) * | 2016-10-21 | 2017-04-19 | 广东石油化工学院 | A preparing method and an application of a LaPrFeNi<x>Co<1-x>O6 double-perovskite catalyst for hydrogen production by bioethanol reforming |
| CN107042111A (en) * | 2017-01-11 | 2017-08-15 | 成都理工大学 | The laminated perovskite type catalyst and preparation method of a kind of acetic acid self-heating reforming hydrogen manufacturing |
| CN110479294A (en) * | 2017-07-06 | 2019-11-22 | 于清花 | A kind of photochemical catalyst preparation method and its processing method handling phenolic waste water |
| CN110479293A (en) * | 2017-07-06 | 2019-11-22 | 于清花 | A kind of photochemical catalyst preparation method |
| CN108671927A (en) * | 2018-04-28 | 2018-10-19 | 中国科学院工程热物理研究所 | Composite catalyst and preparation method, the hydrogen production process of hydrogen production from methanol-steam reforming |
| CN108671927B (en) * | 2018-04-28 | 2022-08-23 | 中国科学院工程热物理研究所 | Composite catalyst for hydrogen production by methanol steam reforming, preparation method and hydrogen production method |
| CN108722431A (en) * | 2018-05-15 | 2018-11-02 | 昆明理工大学 | A kind of A doping type double-perovskite catalyst and the preparation method and application thereof |
| CN108722431B (en) * | 2018-05-15 | 2021-06-18 | 昆明理工大学 | A-site doped double perovskite catalyst and preparation method and application thereof |
| CN113332992A (en) * | 2021-05-31 | 2021-09-03 | 华中科技大学 | Perovskite catalyst and preparation method thereof |
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Application publication date: 20130227 |