CN104707617A - Double-perovskite metal oxide catalyst and preparation method thereof - Google Patents
Double-perovskite metal oxide catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a double-perovskite metal oxide catalyst. The formula of the double-perovskite metal oxide catalyst is LaSrFeMo1-xCoxO6, wherein x is greater than or equal to 0.1 and less than or equal to 1. The invention discloses four methods, that is, a coprecipitation method, a gel-sol method, a reversed-phase microemulsion method and a hard template method in all to prepare a series of double-perovskite metal oxide catalysts. As nitrate, ammonium carbonate, citric acid, glucose and the like are taken as raw materials, the double-perovskite metal oxide catalyst is wide in raw material source, easy to prepare and low in cost; under conditions of specific reaction steps and process parameters, a complete double-perovskite crystal form is formed through specific high-temperature roasting, the whole preparation method is simple, and the yield is relatively high.
Description
Technical field
The present invention relates to catalyst technical field, particularly relate to a kind of double-perovskite metal oxide catalyst and preparation method thereof.
Background technology
Natural gas due to its rich reserves, cheap, pollute the feature such as little and be called as a new generation's " clean energy resource ", China's natural gas rich reserves, main component methane volumetric content often reaches 80-90% or higher.Methane Stability Analysis of Structures, other hydro carbons of its ratio of combustion need higher flame temperature, and high-temp combustion easily causes the generation of nitrogen oxide.The catalytic combustion of natural gas is a kind of controllable reaction, and initiation temperature is low, can burn more complete in excess air, not only the thermal efficiency is high, and effectively can eliminate NOx and CO discharge, there is energy saving standard advantage, numerous industry such as using energy source and exhaust-gas treatment can be applied to.Exploitation is applicable to CH
4the catalyst of catalytic combustion becomes the emphasis of people's research gradually.
The catalyst being applied to methane catalytic combustion at present has noble metal and composite oxide catalysts.Noble metal catalyst activity is high, but it is expensive, and at high temperature easy carbon distribution, be not widely used.Due to the cation in double-perovskite skeleton structure have certain can substituted, oxygen vacancies or transition metal oxide variation of valence can be produced and form defect, the adsorption desorption character of oxygen can be changed thus, improve catalytic performance.Perovskite catalyst is owing to having high activity and stability has attracted the concern of numerous scholars.As far back as early 1970s, first libby etc. open the work of application perofskite type oxide catalytic hydrocarbon, wherein perofskite type oxide LaCoO
3very high catalytic activity is shown, at La to methane
1-xsr
xmO
3(0<x<0.4) on catalyst, when M is Mn, Co and Fe, have higher methyl hydride combustion active, but for the research in this regard of Double Perovskite type oxide and report little.2004, researcher's Late Cambrian utilized citric acid decomposition method to have synthesized Sr
2feMoO
6and as the catalyst of methane high-temp combustion, demonstrate good application background.But up to the present, other Double Perovskite type composite oxides are applied to catalytic methane burning and have not been reported, and rare earth Double Perovskite type is then more rare as methyl hydride combustion catalyst.In Double Perovskite type composite oxides preparation method, adopt solid phase method, hydrothermal synthesis method, sol-gal process etc., product prepared by these methods has the features such as purity is high, epigranular is tiny more, is also generally subject to people all the time and pays close attention to.
Summary of the invention
Based on the technical problem that background technology exists, the present invention proposes a kind of double-perovskite metal oxide catalyst and preparation method thereof.Described catalyst is a kind of thermally-stabilised good, active high, double-perovskite type metal oxide catalyst of being applicable to industrial applications, and can at a lower temperature by complete for methane catalytic combustion.
A kind of double-perovskite metal oxide catalyst that the present invention proposes, described double-perovskite metal oxide catalyst general formula is LaSrFeMo
1-xco
xo
6, wherein, 0.1≤x≤1.Wherein, x=0.3 or x=0.5 or x=0.7 or x=0.9.
The invention allows for a kind of preparation method of described double-perovskite metal oxide catalyst, comprise the steps:
S1, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution;
S2, the first solution that S1 is obtained, the second solution and (NH
4)
2cO
3solution adds in reactor to stir and stir and obtains reactant liquor;
After S3, the reactant liquor obtained by S2 leave standstill, suction filtration, washing, drying obtains material A;
S4, the material A grinding obtained by S3 are placed on roasting in muffle furnace, then carry out compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
Preferably, the preparation method of described double-perovskite metal oxide catalyst, comprises the steps:
S1, by molar part by 1 part of La (NO
3)
36H
2o, 1 part of Sr (NO
3)
2, 1 part of Fe (NO
3)
39H
2o and 1-x part Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution, and solution concentration is 0.25-0.6mol/L, by x part MoO
3add in ammoniacal liquor, after dissolving completely, obtain the second solution, wherein 0.1≤x≤1;
S2, the first solution obtained by S1, the second solution and concentration are the (NH of 0.4-0.6mol/L
4)
2cO
3solution adds in reactor to heat and stir and obtains reactant liquor, and heating-up temperature is 50-70 DEG C, and mixing time is 1-2h, and in whipping process, the pH value of reactant liquor is 6.5-9;
After S3, the reactant liquor obtained by S2 leave standstill 2-4h, vacuum filtration, washing, drying obtains material A, and wherein baking temperature is 100-140 DEG C, drying time 10-14h;
S4, the material A grinding obtained by S3 are placed on roasting in muffle furnace, and sintering temperature is 700-900 DEG C, and roasting time is 3-5h, then carries out compressing tablet, and tableting pressure is 20 ~ 30MPa, then crosses 40-60 mesh sieve and obtains double-perovskite metal oxide catalyst.
Preferably, in S1, the concentration of the first solution can be 0.3mol/L, 0.33mol/L, 0.35mol/L, 0.39mol/L, 0.43mol/L, 0.47mol/L, 0.50mol/L, 0.52mol/L, 0.55mol/L, 0.57mol/L.
Preferably, in S1, the concentration of ammoniacal liquor is 25-28wt%;
Preferably, in S2, heating-up temperature is 52 DEG C, 54 DEG C, 55 DEG C, 57 DEG C, 62 DEG C, 63 DEG C, 65 DEG C, 66 DEG C, 67 DEG C, 68 DEG C; Mixing time is 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h; In whipping process, the pH value of reactant liquor is 6.8,7.0,7.2,7.5,8.0,8.2,8.5,8.7,8.9.
Preferably, in S3, baking temperature is 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C; Drying time is 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h.
Preferably, in S4, sintering temperature is 720 DEG C, 740 DEG C, 760 DEG C, 800 DEG C, 820 DEG C, 830 DEG C, 860 DEG C, 880 DEG C; Roasting time is 3.2h, 3.4h, 3.6h, 3.8h, 4.0h, 4.3h, 4.6h, 4.8h.
The invention allows for a kind of preparation method of double-perovskite metal oxide catalyst, comprise the steps:
S1, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution; Citric acid or cellulose are dissolved in deionized water and obtain the 3rd solution;
S2, the first solution obtained by S1, the second solution, the 3rd solution add in reactor to heat and stir and obtain Gel Precursor;
S3, the Gel Precursor obtained by S2 are first dry, grinding, then are placed in muffle furnace roasting, then compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
Preferably, the preparation method of described double-perovskite metal oxide catalyst, comprises the steps:
S1, by molar part by 1 part of La (NO
3)
36H
2o, 1 part of Sr (NO
3)
2, 1 part of Fe (NO
3)
39H
2o and 1-x part Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution, and solution concentration is 0.25-0.6mol/L; By x part MoO
3add in ammoniacal liquor, after dissolving completely, obtain the second solution; Citric acid or cellulose are dissolved in deionized water and obtain the 3rd solution, wherein citric acid or cellulosic amount of substance are 1.2-1.5 times of total metal ion, and the 3rd solution concentration is 0.6-1.0mol/L;
S2, the first solution obtained by S1, the second solution, the 3rd solution add in reactor and carry out heating stirring reaction and obtain Gel Precursor, and heating-up temperature is 50-70 DEG C, and in whipping process, the pH value of reactant liquor is 6.5-9, and mixing time is 1-2h;
S3, the Gel Precursor obtained by S2 are first dry, and baking temperature is 110-130 DEG C, and drying time is 10-14h, then grinds, then is placed in muffle furnace roasting, and sintering temperature is 700-900 DEG C, and roasting time is 3-5h; Then compressing tablet, tableting pressure is 20 ~ 30MPa, and the person of connecing crosses 40-60 mesh sieve and obtains double-perovskite metal oxide catalyst.
Preferably, in S1, the concentration of the first solution can be 0.3mol/L, 0.33mol/L, 0.35mol/L, 0.39mol/L, 0.43mol/L, 0.47mol/L, 0.50mol/L, 0.52mol/L, 0.55mol/L, 0.57mol/L.
Preferably, in S2, heating-up temperature is 52 DEG C, 54 DEG C, 55 DEG C, 57 DEG C, 62 DEG C, 63 DEG C, 65 DEG C, 66 DEG C, 67 DEG C, 68 DEG C; Mixing time is 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h; In whipping process, the pH value of reactant liquor is 6.8,7.0,7.2,7.5,8.0,8.2,8.5,8.7,8.9.
Preferably, in S3, baking temperature is 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C; Drying time is 10.5,11h, 11.5h, 12h, 12.5h, 13h, 13.5h.
Preferably, in S3, sintering temperature is 720 DEG C, 740 DEG C, 760 DEG C, 800 DEG C, 820 DEG C, 830 DEG C, 860 DEG C, 880 DEG C; Roasting time is 3.2h, 3.4h, 3.6h, 3.8h, 4.0h, 4.3h, 4.6h, 4.8h.
The invention allows for a kind of preparation method of described double-perovskite metal oxide catalyst, comprise the steps:
S1, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution; Mixing salt solution is obtained by after described first solution and the mixing of the second solution;
In the emulsion that Trition X-100, n-hexyl alcohol and cyclohexane that it is 0.8-1.2: 1.0-1.4: 1.8-2.2 that S2, the mixing salt solution obtained by S1 join by volume ratio form, obtain reverse micro emulsion A;
S3, by (NH
4)
2cO
3be dissolved in deionized water and obtain the 3rd solution, in the emulsion that Trition X-100, n-hexyl alcohol and cyclohexane that to be joined by the 3rd solution by volume ratio be 0.8-1.2: 1.0-1.4: 1.8-2.2 form, obtain reverse micro emulsion B;
S4, the reverse micro emulsion A obtained by S2 join in the reverse micro emulsion B that S3 obtains, and stir and obtain reactant liquor;
S5, the reactant liquor obtained by S4 leave standstill to after there is flocculent deposit, and centrifugation obtains solid fines;
S6, the solid fines that obtained by S5 are dry, then are placed in muffle furnace and carry out first time roasting, then grind, then are placed in muffle furnace and carry out second time roasting, then compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
Preferably, the preparation method of described double-perovskite metal oxide catalyst, comprises the steps:
S1, by molar part by 1 part of La (NO
3)
36H
2o, 1 part of Sr (NO
3)
2, 1 part of Fe (NO
3)
39H
2o and 1-x part Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution, by x part MoO
3be dissolved in ammoniacal liquor and obtain the second solution; Obtain mixing salt solution by after the first solution and the mixing of the second solution, in described mixing salt solution, total ion concentration is 0.4-0.6mol/L;
In the emulsion that Trition X-100, n-hexyl alcohol and cyclohexane surfactant that it is 1: 1.2: 2 that S2, the mixing salt solution obtained by S1 join by volume ratio form, obtain reverse micro emulsion A, wherein the volume ratio of mixing salt solution and emulsion is 1:4-5;
S3, be (the NH of 2.0-4.0mol/L by concentration
4)
2cO
3in the emulsion that Trition X-100, n-hexyl alcohol and cyclohexane that it is 1: 1.2: 2 that solution joins by volume ratio form, obtain reverse micro emulsion B, wherein (NH
4)
2cO
3the volume ratio of solution and emulsion is 1:4-5; ;
S4, the reverse micro emulsion A obtained by S2 are added drop-wise in the reverse micro emulsion B that S3 obtains, and carry out magnetic agitation and obtain reactant liquor, in whipping process, reacting liquid temperature is 30-50 DEG C, and pH value is 7-8, and mixing time is 0.5-1.5h;
After S5, the reactant liquor obtained by S4 at room temperature leave standstill 20-28h, centrifugation obtains solid fines, and the speed of centrifugation is 45000-60000r/min, and the time is 8-12min;
S6, the solid fines obtained by S5 are dry, and baking temperature is 80-120 DEG C, and drying time is 10-14h, then grind, then be placed in muffle furnace and carry out first time roasting, first time sintering temperature be 400-600 DEG C, roasting time 3-5h, then grind, then be placed in muffle furnace and carry out second time roasting, second time sintering temperature is 700-900 DEG C, roasting time 3-5h, then compressing tablet, tableting pressure is 20 ~ 30Mp, crosses 40-60 mesh sieve and obtains double-perovskite metal oxide catalyst.
Preferably, in S1, in mixing salt solution, total concentration of metal ions can be 0.3mol/L, 0.33mol/L, 0.35mol/L, 0.39mol/L, 0.43mol/L, 0.47mol/L, 0.50mol/L, 0.52mol/L, 0.55mol/L, 0.57mol/L.
Preferably, in S2, the volume ratio of mixing salt solution and emulsion is 1:4.2,1:4.3,1:4.4,1:4.5,1:4.6,1:4.7,1:4.8,1:4.9.
Preferably, in S3, (NH
4)
2cO
3the volume ratio of solution and emulsion is 1:4.2,1:4.3,1:4.4,1:4.5,1:4.6,1:4.7,1:4.8,1:4.9.
Preferably, in S4, in whipping process, reacting liquid temperature is 32 DEG C, 34 DEG C, 35 DEG C, 37 DEG C, 42 DEG C, 43 DEG C, 45 DEG C, 46 DEG C, 47 DEG C, 48 DEG C; PH value is 7.1,7.2,7.3,7.4,7.5,7.6,7.7,7.8,7.9; Mixing time is 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.2h, 1.3h, 1.4h.
Preferably, in S5, the speed of centrifugation is 46000r/min, 47000r/min, 48000r/min, 49000r/min, 50000r/min, 53000r/min, 55000r/min, 57000r/min, 59000r/min; Time is 8.2min, 8.5min, 9.1min, 9.5min, 9.9min, 10.2in, 10.5min, 11min, 11.3min, 11.8min.
Preferably, in S6, baking temperature is 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C; Drying time is 10.5,11h, 11.5h, 12h, 12.5h, 13h, 13.5h.
Preferably, in S6, sintering temperature is 420 DEG C, 440 DEG C, 460 DEG C, 500 DEG C, 520 DEG C, 530 DEG C, 560 DEG C, 580 DEG C for the first time; Roasting time 3.2h, 3.4h, 3.6h, 3.8h, 4.0h, 4.3h, 4.6h, 4.8h.
Preferably, in S6, second time sintering temperature is 720 DEG C, 740 DEG C, 760 DEG C, 800 DEG C, 820 DEG C, 830 DEG C, 860 DEG C, 880 DEG C; Roasting time is 3.2h, 3.4h, 3.6h, 3.8h, 4.0h, 4.3h, 4.6h, 4.8h.
The invention allows for a kind of preparation method of double-perovskite metal oxide catalyst, comprise the steps:
S1, glucose added in deionized water obtain D/W, D/W is placed in reactor and heats, stir and obtain reactant liquor, after described reactant liquor is cooled to room temperature, centrifugation is precipitated thing, and washed by sediment, drying obtains carbosphere hard template;
S2, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution, by MoO
3be dissolved in ammoniacal liquor and obtain the second solution;
Obtain mixed solution after S3, the first solution obtained by S2 and the second mixing, carry out ultrasonic add the carbosphere template that S1 obtains in described mixed solution after, then be placed in reactor and heat, after stirring, obtain reactant liquor;
Be precipitated thing after S4, the reactant liquor centrifugation that obtained by S3, described sediment, through washing, obtains presoma after oven dry;
S5, the presoma grinding obtained by S4 are placed on roasting in muffle furnace, then carry out compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
Preferably, the preparation method of described double-perovskite metal oxide catalyst, comprises the steps:
S1, glucose is added in the deionized water of 40-60ml, the D/W that concentration is 0.4-0.5mol/L is obtained after magnetic agitation 0.5-2h, polytetrafluoroethylene (PTFE) reactor D/W being placed in 100mL heats and stirs and obtains reactant liquor, heating-up temperature is 160-200 DEG C, and mixing time is 5-7h; After described reactant liquor is cooled to room temperature, be that under the condition of 40000-60000r/min, centrifugation 10-20min is precipitated thing at rotating speed, described sediment water and ethanol are washed to substantially colourless, after putting into 100 DEG C of dry 2-6h of baking oven, obtains carbosphere hard template;
S2, by molar part by 1 part of La (NO
3)
36H
2o, 1 part of Sr (NO
3)
2, 1 part of Fe (NO
3)
39H
2o and 1-x part Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By x part MoO
3be dissolved in ammoniacal liquor and obtain the second solution;
Obtain mixed solution after S3, the first solution obtained by S2 and the second mixing, wherein in mixed solution, total concentration of metal ions is 0.4-0.6mol/L, and volume is 40-50mL; In described mixed solution, add ultrasonic 0.5-1.5h after the carbosphere template that S1 obtains, then the polytetrafluoroethylene (PTFE) reactor being placed in 100mL heats, and obtains reactant liquor after stirring, heating-up temperature is 160-200 DEG C, and mixing time is 4-8h;
Be precipitated thing, described sediment after S4, the reactant liquor centrifugation that obtained by S3 through washing 2-3 time, oven dry obtains presoma;
S5, the presoma obtained by S4 are placed in muffle furnace roasting after grinding again, and sintering temperature is 600-1000 DEG C, and roasting time is 3-5h, then compressing tablet, and tableting pressure is 20 ~ 30Mp, cross 40-60 mesh sieve and obtain double-perovskite metal oxide catalyst.
Preferably, in S3, the amount of substance of the carbosphere template that S1 obtains is 1.2-1.5 times of total metal ion.
Preferably, in S3, in mixed solution, total concentration of metal ions can be 0.43mol/L, 0.45mol/L, 0.46mol/L, 0.47mol/L, 0.50mol/L, 0.52mol/L, 0.55mol/L, 0.57mol/L; Heating-up temperature is 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C; Mixing time is 4.2h, 4.5h, 4.9h, 5.2h, 5.5h, 6.1h, 6.7h, 7.2h, 7.7h.
Preferably, in S5, sintering temperature is 720 DEG C, 740 DEG C, 760 DEG C, 800 DEG C, 820 DEG C, 830 DEG C, 860 DEG C, 880 DEG C; Roasting time is 3.2h, 3.4h, 3.6h, 3.8h, 4.0h, 4.3h, 4.6h, 4.8h.
Described in the present invention, catalyst application burns in catalytic methane, also may be used in power plant and the various fields such as using energy source and exhaust-gas treatment simultaneously.
Compared with prior art, tool of the present invention has the following advantages:
(1) propose coprecipitation in the present invention, sol-gal process, reverse microemulsion process, hard template method four kinds of methods have prepared a series of double-perovskite metal oxide catalyst, by adopting some nitrate, ammonium carbonate, citric acid and glucose etc. as raw material, raw material sources are wide, easy acquisition, cost is low; Under specific reactions steps and technological parameter condition, define complete double-perovskite crystal formation through specific high-temperature roasting, whole preparation method is simple, and productive rate is higher.
(2) the double-perovskite metal oxide catalyst character described in is by the Fe of the specified quantitative that adulterates in double-perovskite crystalline structure
3+, Mo
2+, Co
2+, its high temperature active when catalytic methane burns is strengthened significantly, simultaneously this catalyst stabilization, wear-resisting, can keep certain activity in a long time, catalyst operating temperature window is wide, within the scope of 350-800 DEG C, all have activity.
Detailed description of the invention
A kind of double-perovskite metal oxide catalyst that the present invention proposes, described double-perovskite metal oxide catalyst general formula is LaSrFeMo
1-xco
xo
6, wherein, 0.1≤x≤1.
Based on above-mentioned double-perovskite metal oxide catalyst, the invention allows for four kinds of preparation methods, be described in detail below by specific embodiment.
The preparation method of a kind of double-perovskite metal oxide catalyst that method one, the present invention propose, comprises the steps:
S1, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution;
S2, the first solution that S1 is obtained, the second solution and (NH
4)
2cO
3solution adds in reactor to heat and stir and obtains reactant liquor;
After S3, the reactant liquor obtained by S2 leave standstill, suction filtration, washing, drying obtains material A;
S4, the material A grinding obtained by S3 are placed on roasting in muffle furnace, then carry out compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
The preparation method of a kind of double-perovskite metal oxide catalyst that method two, the present invention propose, comprises the steps:
S1, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution; Citric acid or cellulose are dissolved in deionized water and obtain the 3rd solution;
S2, the first solution obtained by S1, the second solution, the 3rd solution add in reactor to heat and stir and obtain Gel Precursor;
S3, the Gel Precursor obtained by S2 are first dry, grinding, then are placed in muffle furnace roasting, then compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
The preparation method of a kind of double-perovskite metal oxide catalyst that method three, the present invention propose, is characterized in that, comprise the steps:
S1, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution; Mixing salt solution is obtained by after described first solution and the mixing of the second solution;
In the emulsion that Trition X-100, n-hexyl alcohol and cyclohexane that it is 0.8-1.2: 1.0-1.4: 1.8-2.2 that S2, the mixing salt solution obtained by S1 join by volume ratio form, obtain reverse micro emulsion A;
S3, by (NH
4)
2cO
3be dissolved in deionized water and obtain the 3rd solution, in the emulsion that Trition X-100, n-hexyl alcohol and cyclohexane that to be joined by the 3rd solution by volume ratio be 0.8-1.2: 1.0-1.4: 1.8-2.2 form, obtain reverse micro emulsion B;
S4, the reverse micro emulsion A obtained by S2 join in the reverse micro emulsion B that S3 obtains, and stir and obtain reactant liquor;
S5, the reactant liquor obtained by S4 leave standstill to after there is flocculent deposit, and centrifugation obtains solid fines;
S6, the solid fines that obtained by S5 are dry, then are placed in muffle furnace and carry out first time roasting, then grind, then are placed in muffle furnace and carry out second time roasting, then compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
The preparation method of a kind of double-perovskite metal oxide catalyst that method four, the present invention propose, comprises the steps:
S1, glucose added in deionized water obtain D/W, D/W is placed in reactor and heats, stir and obtain reactant liquor, after described reactant liquor is cooled to room temperature, centrifugation is precipitated thing, and washed by sediment, drying obtains carbosphere hard template;
S2, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution;
Obtain mixed solution after the mixing of S3, the first solution obtained by S2 and the second solution, carry out ultrasonic add the carbosphere template that S1 obtains in described mixed solution after, then be placed in reactor and heat, after stirring, obtain reactant liquor;
Be precipitated thing after S4, the reactant liquor centrifugation that obtained by S3, described sediment, through washing, obtains presoma after oven dry;
S5, the presoma grinding obtained by S4 are placed on roasting in muffle furnace, then carry out compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
Embodiment 1
A kind of double-perovskite metal oxide catalyst, described double-perovskite metal oxide catalyst general formula is LaSrFeMo
0.9co
0.1o
6.
The preparation method of described double-perovskite metal oxide catalyst, comprises the steps:
S1, by 5.4mmol La (NO
3)
36H
2o, 5.4mmol Sr (NO
3)
2, 5.4mmol Fe (NO
3)
39H
2o and 0.54mmol Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution that concentration is 0.5mol/L, by 4.86mmol MoO
3add in ammoniacal liquor, after dissolving completely, obtain the second solution;
S2, the first solution obtained by S1, the second solution and concentration are the (NH of 0.5mol/L
4)
2cO
3solution adds in reactor, stirs 1.5h and obtain reactant liquor under 60 DEG C of waters bath with thermostatic control, keeps the pH value of reactant liquor in whipping process between 6.5-9;
After S3, the reactant liquor obtained by S2 leave standstill 3h, vacuum filtration, wash three times, under 120 DEG C of conditions, dry 12h obtains material A;
S4, the material A grinding obtained by S3 are placed on roasting in muffle furnace, and roasting 4h under 800 DEG C of conditions, carries out compressing tablet under 20 ~ 30MPa condition, then crosses 40-60 mesh sieve and obtains described double-perovskite metal oxide catalyst.
Catalyst activity test is carried out in normal pressure micro-reaction equipment, and crystal reaction tube diameter is 8mm, catalyst amount 0.3g, catalyst bed layer height 8-12mm, reaction gas composition (percent by volume): the CH4 of 1% and the mixing air of 99%.First with 50000h
-1air speed pass into after reaction gas certain hour reaches balance, then carry out temperature programming with the speed of 5 DEG C/min, investigate catalyst LaSrFeMo
0.9co
0.1o
6methyl hydride combustion between 300 ~ 800 DEG C at differential responses temperature is active.Record LaSrFeMo
0.9co
0.1o
6catalyst catalytic performance is as follows:
| CH 4Conversion ratio (%) | 10 | 90 |
| Temperature (DEG C) | 432 | 632 |
Embodiment 2
A kind of double-perovskite metal oxide catalyst, described double-perovskite metal oxide catalyst general formula is LaSrFeMo
0.9co
0.1o
6.
The preparation method of described double-perovskite metal oxide catalyst, comprises the steps:
S1, by 5.4mmol La (NO
3)
36H
2o, 5.4mmol Sr (NO
3)
2, 5.4mmol Fe (NO
3)
39H
2o and 0.54mmol Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution that concentration is 0.45mol/L, by 4.86mmol MoO
3be dissolved in ammoniacal liquor, after dissolving completely, obtain the second solution; The citric acid of 29.16mmol or cellulose are dissolved in deionized water and obtain the 3rd solution that concentration is 0.8mol/L;
S2, the first solution obtained by S1, the second solution, the 3rd solution add in reactor, stir the Gel Precursor that 1.5h is obtained by reacting under 60 DEG C of conditions, control the pH value of reactant liquor in heating whipping process between 6.5-9;
S3, the Gel Precursor first dry 12h under 120 DEG C of conditions obtained by S2, then grind, then be placed in muffle furnace, roasting 4h under 800 DEG C of conditions, then compressing tablet, tableting pressure is 20 ~ 30MPa, then crosses 40-60 mesh sieve and obtains double-perovskite metal oxide catalyst.
Catalyst activity test is carried out in normal pressure micro-reaction equipment, and crystal reaction tube diameter is 8mm, catalyst amount 0.3g, catalyst bed layer height 8-12mm, reaction gas composition (percent by volume): the CH4 of 1% and the mixing air of 99%.First with 50000h
-1air speed pass into after reaction gas certain hour reaches balance, then carry out temperature programming with the speed of 5 DEG C/min, investigate catalyst LaSrFeMo
0.9co
0.1o
6methyl hydride combustion between 300 ~ 800 DEG C at differential responses temperature is active.Record LaSrFeMo
0.9co
0.1o
6catalyst catalytic performance is as follows:
| CH 4Conversion ratio (%) | 10 | 90 |
| Temperature (DEG C) | 400 | 621 |
Embodiment 3
A kind of double-perovskite metal oxide catalyst, described double-perovskite metal oxide catalyst general formula is LaSrFeMo
0.9co
0.1o
6.
The preparation method of described double-perovskite metal oxide catalyst, comprises the steps:
S1, by 5.4mmol La (NO
3)
36H
2o, 5.4mmol Sr (NO
3)
2, 5.4mmol Fe (NO
3)
39H
2o and 0.54mmol Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution, by 4.86mmol MoO
3be dissolved in ammoniacal liquor and obtain the second solution; Obtain mixing salt solution by after the first solution and the mixing of the second solution, in described mixing salt solution, total concentration of metal ions is 0.491mol/L, and volume is 44ml;
S2, the mixing salt solution obtained by S1 join in the emulsion be made up of 44ml Trition X-100,52ml n-hexyl alcohol and 88ml cyclohexane surfactant, obtain reverse micro emulsion A after stirring;
S3, be 3.0mol/L by concentration, volume is the (NH of 45ml
4)
2cO
3solution joins in the emulsion be made up of 44ml Trition X-100,52ml n-hexyl alcohol and 88ml cyclohexane surfactant, obtains reverse micro emulsion B;
S4, the reverse micro emulsion A obtained by S2 are added drop-wise in the reverse micro emulsion B that S3 obtains, 40 DEG C, condition lower magnetic force stirs 1h and obtain reactant liquor, to keep in whipping process reacting liquid pH value between 7-8;
After S5, the reactant liquor obtained by S4 at room temperature leave standstill 24h, under 50000r/min condition, centrifugation 10min obtains solid fines;
S6, the solid fines first dry 12h under 100 DEG C of conditions that S5 is obtained, then be placed in muffle furnace roasting, roasting 4h under 500 DEG C of conditions; Then grind, then continue to be placed in muffle furnace roasting, roasting 4h under 800 DEG C of conditions; Then compressing tablet, pressure is 20 ~ 30Mp, crosses 40-60 mesh sieve and obtains double-perovskite metal oxide catalyst.
Catalyst activity test is carried out in normal pressure micro-reaction equipment, and crystal reaction tube diameter is 8mm, catalyst amount 0.3g, catalyst bed layer height 8-12mm, reaction gas composition (percent by volume): the CH4 of 1% and the mixing air of 99%.First with 50000h
-1air speed pass into after reaction gas certain hour reaches balance, then carry out temperature programming with the speed of 5 DEG C/min, investigate catalyst LaSrFeMo
0.9co
0.1o
6methyl hydride combustion between 300 ~ 800 DEG C at differential responses temperature is active.Record LaSrFeMo
0.9co
0.1o
6catalyst catalytic performance is as follows:
| CH 4Conversion ratio (%) | 10 | 90 |
| Temperature (DEG C) | 421 | 618 |
Embodiment 4
A kind of double-perovskite metal oxide catalyst, described double-perovskite metal oxide catalyst general formula is LaSrFeMo
0.9co
0.1o
6.
The preparation method of described double-perovskite metal oxide catalyst, comprises the steps:
S1,4.5g glucose is added in the deionized water of 50ml, after magnetic agitation 1h D/W, D/W is placed in the polytetrafluoroethylene (PTFE) reactor of 100mL, stirs 6h under 180 DEG C of conditions and obtain reactant liquor; After described reactant liquor is cooled to room temperature, be that under the condition of 5000r/min, centrifugation 15min is precipitated thing at rotating speed, described sediment water and ethanol washed to substantially colourless, after putting into 100 DEG C of dry 4h of baking oven, obtains carbosphere hard template;
S2, by 5.4mmol La (NO
3)
36H
2o, 5.4mmol Sr (NO
3)
2, 5.4mmol Fe (NO
3)
39H
2o and 0.054mmol Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution, by 4.86mol MoO
3be dissolved in ammoniacal liquor and obtain the second solution;
The mixed solution of 44mL is obtained after S3, the first solution obtained by S2 and the second mixing, to add after the carbosphere template that 0.25g S1 obtains after ultrasonic 1h in described mixed solution, be placed in the polytetrafluoroethylene (PTFE) reactor of 100mL again, stir 6h under 180 DEG C of conditions and obtain reactant liquor;
Be precipitated thing after S4, the reactant liquor centrifugation that obtained by S3, described sediment after ethanol washs 3 times, then is dried and is obtained presoma;
S5, the presoma obtained by S4 are placed in muffle furnace roasting after grinding again, and under 800 DEG C of conditions, sintering temperature is 4h, then carries out compressing tablet, and tableting pressure is 20 ~ 30Mp, cross 40-60 mesh sieve and obtain double-perovskite metal oxide catalyst.
Catalyst activity test is carried out in normal pressure micro-reaction equipment, and crystal reaction tube diameter is 8mm, catalyst amount 0.3g, catalyst bed layer height 8-12mm, reaction gas composition (percent by volume): the CH4 of 1% and the mixing air of 99%.First with 50000h
-1air speed pass into after reaction gas certain hour reaches balance, then carry out temperature programming with the speed of 5 DEG C/min, investigate catalyst LaSrFeMo
0.9co
0.1o
6methyl hydride combustion between 300 ~ 800 DEG C at differential responses temperature is active.Record LaSrFeMo
0.9co
0.1o
6catalyst catalytic performance is as follows:
| CH 4Conversion ratio (%) | 10 | 90 |
| Temperature (DEG C) | 441 | 636 |
The above; be only the present invention's preferably detailed description of the invention; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. a double-perovskite metal oxide catalyst, is characterized in that, described double-perovskite metal oxide catalyst general formula is LaSrFeMo
1-xco
xo
6, wherein, 0.1≤x≤1.
2. double-perovskite metal oxide catalyst as claimed in claim 1, is characterized in that, x=0.3 or x=0.5 or x=0.7 or x=0.9.
3. a preparation method for double-perovskite metal oxide catalyst as claimed in claim 1 or 2, is characterized in that, comprise the steps:
S1, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution;
S2, the first solution that S1 is obtained, the second solution and (NH
4)
2cO
3solution adds in reactor to heat and stir and obtains reactant liquor;
After S3, the reactant liquor obtained by S2 leave standstill, suction filtration, washing, drying obtains material A;
S4, the material A grinding obtained by S3 are placed on roasting in muffle furnace, then carry out compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
4. the preparation method of double-perovskite metal oxide catalyst as claimed in claim 3, is characterized in that, comprise the steps:
S1, by molar part by 1 part of La (NO
3)
36H
2o, 1 part of Sr (NO
3)
2, 1 part of Fe (NO
3)
39H
2o and 1-x part Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution, and solution concentration is 0.25-0.6mol/L, by x part MoO
3add in ammoniacal liquor, after dissolving completely, obtain the second solution, wherein 0.1≤x≤1;
S2, the first solution obtained by S1, the second solution and concentration are the (NH of 0.4-0.6mol/L
4)
2cO
3solution adds in reactor to heat and stir and obtains reactant liquor, and heating-up temperature is 50-70 DEG C, and mixing time is 1-2h, and in whipping process, the pH value of reactant liquor is 6.5-9;
After S3, the reactant liquor obtained by S2 leave standstill 2-4h, vacuum filtration, washing, drying obtains material A, and wherein baking temperature is 100-140 DEG C, and drying time is 10-14h;
S4, the material A grinding obtained by S3 are placed on roasting in muffle furnace, and sintering temperature is 700-900 DEG C, and roasting time is 3-5h, then carries out compressing tablet, and tableting pressure is 20 ~ 30MPa, then crosses 40-60 mesh sieve and obtains double-perovskite metal oxide catalyst.
5. a preparation method for double-perovskite metal oxide catalyst as claimed in claim 1 or 2, is characterized in that, comprise the steps:
S1, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution; Citric acid or cellulose are dissolved in deionized water and obtain the 3rd solution;
S2, the first solution obtained by S1, the second solution, the 3rd solution add in reactor to heat and stir and obtain Gel Precursor;
S3, the Gel Precursor obtained by S2 are first dry, grinding, then are placed in muffle furnace roasting, then compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
6. the preparation method of double-perovskite metal oxide catalyst as claimed in claim 5, is characterized in that, comprise the steps:
S1, by molar part by 1 part of La (NO
3)
36H
2o, 1 part of Sr (NO
3)
2, 1 part of Fe (NO
3)
39H
2o and 1-x part Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution, and solution concentration is 0.25-0.6mol/L; By x part MoO
3add in ammoniacal liquor, after dissolving completely, obtain the second solution; Citric acid or cellulose are dissolved in deionized water and obtain the 3rd solution, wherein citric acid or cellulosic amount of substance are 1.2-1.5 times of total metal ion, and the 3rd solution concentration is 0.6-1.0mol/L;
S2, the first solution obtained by S1, the second solution, the 3rd solution add in reactor and carry out heating stirring reaction and obtain Gel Precursor, and heating-up temperature is 50-70 DEG C, and in whipping process, the pH value of reactant liquor is 6.5-9, and mixing time is 1-2h;
S3, the Gel Precursor obtained by S2 are first dry, and baking temperature is 100-140 DEG C, and drying time is 10-14h, then grinds, then is placed in muffle furnace roasting, and sintering temperature is 700-900 DEG C, and roasting time is 3-5h; Then compressing tablet, tableting pressure is 20 ~ 30MPa, then crosses 40-60 mesh sieve and obtains double-perovskite metal oxide catalyst.
7. a preparation method for double-perovskite metal oxide catalyst as claimed in claim 1 or 2, is characterized in that, comprise the steps:
S1, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution; Mixing salt solution is obtained by after described first solution and the mixing of the second solution;
In the emulsion that Trition X-100, n-hexyl alcohol and cyclohexane that it is 0.8-1.2: 1.0-1.4: 1.8-2.2 that S2, the mixing salt solution obtained by S1 join by volume ratio form, obtain reverse micro emulsion A;
S3, by (NH
4)
2cO
3be dissolved in deionized water and obtain the 3rd solution, in the emulsion that Trition X-100, n-hexyl alcohol and cyclohexane that to be joined by the 3rd solution by volume ratio be 0.8-1.2: 1.0-1.4: 1.8-2.2 form, obtain reverse micro emulsion B;
S4, the reverse micro emulsion A obtained by S2 join in the reverse micro emulsion B that S3 obtains, and stir and obtain reactant liquor;
S5, the reactant liquor obtained by S4 leave standstill to after there is flocculent deposit, and centrifugation obtains solid fines;
S6, the solid fines that obtained by S5 are dry, then are placed in muffle furnace and carry out first time roasting, then grind, then are placed in muffle furnace and carry out second time roasting, then compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
8. the preparation method of double-perovskite metal oxide catalyst as claimed in claim 7, is characterized in that, comprise the steps:
S1, by molar part by 1 part of La (NO
3)
36H
2o, 1 part of Sr (NO
3)
2, 1 part of Fe (NO
3)
39H
2o and 1-x part Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution, by x part MoO
3be dissolved in ammoniacal liquor and obtain the second solution; Obtain mixing salt solution by after the first solution and the mixing of the second solution, wherein in mixing salt solution, total concentration of metal ions is 0.25-0.6mol/L;
In the emulsion that Trition X-100, n-hexyl alcohol and cyclohexane surfactant that it is 1: 1.2: 2 that S2, the mixing salt solution obtained by S1 join by volume ratio form, obtain reverse micro emulsion A, wherein the volume ratio of mixing salt solution and emulsion is 1:4-5;
S3, be (the NH of 2.0-4.0mol/L by concentration
4)
2cO
3in the emulsion that Trition X-100, n-hexyl alcohol and cyclohexane that it is 1: 1.2: 2 that solution joins by volume ratio form, obtain reverse micro emulsion B, wherein (NH
4)
2cO
3the volume ratio of solution and emulsion is 1:4-5;
S4, the reverse micro emulsion A obtained by S2 are added drop-wise in the reverse micro emulsion B that S3 obtains, and carry out magnetic agitation and obtain reactant liquor, in whipping process, reacting liquid temperature is 30-50 DEG C, and pH value is 7-8, and mixing time is 0.5-1.5h;
After S5, the reactant liquor obtained by S4 at room temperature leave standstill 20-28h, centrifugation obtains solid fines, and the speed of centrifugation is 45000-60000r/min, and the time is 8-12min;
S6, the solid fines obtained by S5 are dry, and baking temperature is 80-120 DEG C, and drying time is 10-14h, be placed in muffle furnace again and carry out first time roasting, sintering temperature is 400-600 DEG C, roasting time 3-5h for the first time, then grinds, be placed in muffle furnace again and carry out second time roasting, second time sintering temperature is 700-900 DEG C, roasting time 3-5h, then compressing tablet, tableting pressure is 20 ~ 30Mp, crosses 40-60 mesh sieve and obtains double-perovskite metal oxide catalyst.
9. a preparation method for double-perovskite metal oxide catalyst as claimed in claim 1 or 2, is characterized in that, comprise the steps:
S1, glucose added in deionized water obtain D/W, D/W is placed in reactor and heats, stir and obtain reactant liquor, after described reactant liquor is cooled to room temperature, centrifugation is precipitated thing, and washed by sediment, drying obtains carbosphere hard template;
S2, by La (NO
3)
36H
2o, Sr (NO
3)
2, Fe (NO
3)
39H
2o and Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution; By MoO
3be dissolved in ammoniacal liquor and obtain the second solution;
Obtain mixed solution after the mixing of S3, the first solution obtained by S2 and the second solution, carry out ultrasonic add the carbosphere template that S1 obtains in described mixed solution after, then be placed in reactor and heat, after stirring, obtain reactant liquor;
Be precipitated thing after S4, the reactant liquor centrifugation that obtained by S3, described sediment, through washing, obtains presoma after oven dry;
S5, the presoma grinding obtained by S4 are placed on roasting in muffle furnace, then carry out compressing tablet, sieve and obtain double-perovskite metal oxide catalyst.
10. the preparation method of double-perovskite metal oxide catalyst as claimed in claim 9, is characterized in that, comprise the steps:
S1, glucose is added in the deionized water of 40-60ml, the D/W that concentration is 0.4-0.5mol/L is obtained after magnetic agitation 0.5-2h, polytetrafluoroethylene (PTFE) reactor D/W being placed in 100mL heats and stirs and obtains reactant liquor, heating-up temperature is 160-200 DEG C, and mixing time is 5-7h; After described reactant liquor is cooled to room temperature, be that under the condition of 40000-60000r/min, centrifugation 10-20min is precipitated thing at rotating speed, described sediment water and ethanol are washed to substantially colourless, after putting into 100 DEG C of dry 2-6h of baking oven, obtains carbosphere hard template;
S2, by molar part by 1 part of La (NO
3)
36H
2o, 1 part of Sr (NO
3)
2, 1 part of Fe (NO
3)
39H
2o and 1-x part Co (NO
3)
26H
2o is dissolved in deionized water and obtains the first solution, by x part MoO
3be dissolved in ammoniacal liquor and obtain the second solution;
Obtain mixed solution after S3, the first solution obtained by S2 and the second mixing, wherein in mixed solution, total concentration of metal ions is 0.4-0.6mol/L, and volume is 40-50mL; In described mixed solution, add ultrasonic 0.5-1.5h after the carbosphere template that S1 obtains, then the polytetrafluoroethylene (PTFE) reactor being placed in 100mL heats and stirs and obtains reactant liquor, heating-up temperature is 160-200 DEG C, and mixing time is 4-8h;
Be precipitated thing after S4, the reactant liquor centrifugation that obtained by S3, described sediment is through ethanol washing 2-3 time, and oven dry obtains presoma;
S5, the presoma obtained by S4 are placed in muffle furnace roasting after grinding again, and sintering temperature is 700-900 DEG C, and roasting time is 3-5h, then compressing tablet, and tableting pressure is 20 ~ 30Mp, cross 40-60 mesh sieve and obtain double-perovskite metal oxide catalyst.
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| CN115805069A (en) * | 2022-11-14 | 2023-03-17 | 天津大学 | Catalyst for diesel engine based on highly dispersed perovskite catalytic component and preparation method |
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Application publication date: 20150617 |