CN102862960A - Application and preparation of high-activity composite oxide oxygen carrier in chemical link circulation hydrogen production - Google Patents
Application and preparation of high-activity composite oxide oxygen carrier in chemical link circulation hydrogen production Download PDFInfo
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Abstract
The invention discloses application and preparation of a composite oxide with perovskite structure in chemical link circulation hydrogen production. The composite metal oxide with perovskite structure is AxA'1-xByB'1-yO3, wherein A is rare earth metal lanthanum, A' is metal metallic potassium, B is transition metal cobalt, and B' is precious metal palladium, 0.7<x<1, and 0.8<y<1. The reaction temperature of an oxygen carrier in fuel is 500-1250 DEG C, and the reaction temperature of the oxygen carrier in steam is 500-1250 DEG C. A preparation method of the oxygen carrier includes utilizing cobalt nitrate, lanthanum nitrate, potassium nitrate and palladium chloride acid as precursors, utilizing citric acid or ethylene glycol as complexing agents, preparing solution, evenly mixing the solution, then conducting water evaporation till the solution is converted into thick gel from transparent sol and finally conducting drying and burning. A burnt sample is a composite metal oxide with the perovskite structure. The oxygen carrier is high in oxygen carrying rate, high in catalytic activity, strong in carbon deposit resistance, strong in high temperature sintering resistance and good in stability.
Description
Technical field
The present invention relates to application and the preparation method of a kind of perovskite structure composite oxide in the recycle chemistry chain hydrogen production technology, belong to the hydrogen production of chemical chain field.
Background technology
Nineteen eighty-three, Germany scientist Richter and Knoche propose the concept of burning chemistry chains (chemical looping combustion, CLC) first.The difference of this combustion technology and common combustion technology maximum is directly not use airborne oxygen molecule, but finishes the combustion processes of fuel with the Sauerstoffatom in the oxygen carrier, and products of combustion (mainly is CO
2And water vapour) can be by airborne nitrogen dilution and very high concentrations can obtain almost pure CO by simple condensation
2, realized to simple and less energy-consumption CO
2Separation and capture; In addition, because the operating temperature of fuel reactor and air reactor is relatively low, in air reactor, almost generates without thermal NO x and Quick-type NOx, and in fuel reactor, owing to not contacting with oxygen, do not have fuel type NOx to generate.
Hydrogen has received close concern as pollution-free, the eco-friendly economy energy, and widely purposes is arranged.CO in view of the burning chemistry chains method
2Interior separation characteristic, the hydrogen manufacturing of applied chemistry chain combustion method also becomes a current study hotspot.Similar with the CLC process, replace air to finish the regeneration of oxygen carrier as oxygenant introducing air reactor with water vapour, water vapour also is reduced generation hydrogen simultaneously.Current, the Hatano that comprises Japan of a lot of study group is to take solid waste such as polyethylene as fuel NiO and Fe in the world
2O
3Deng being the people such as oxygen carrier, Korea S Son to CH
4Be fuel NiO and Fe
2O
3For the Fan L-S of oxygen carrier, U.S. professor study group to the Fe take coal as fuel
2O
3For the CLC hydrogen production process of oxygen carrier etc. is studied.
Oxygen carrier is as medium, between two reactors, circulate, ceaselessly the heat of the oxygen in air (water vapour) reactor and reaction generation is delivered to fuel reactor and carries out reduction reaction, so the character of oxygen carrier has directly affected the operation of whole burning chemistry chains/hydrogen manufacturing.Therefore, the high-performance oxygen carrier is to realize having CO
2The key of the burning chemistry chains/hydrogen producing technology of enriched character.At present, the oxygen carrier of main research is the metal oxygen carrier, comprises Fe, Ni, Co, Cu, Mn, Cd etc., and carrier mainly contains: Al
2O
3, TiO
2, MgO, SiO
2, YSZ etc., also have a small amount of nonmetal oxide such as CaSO
4Deng.In burning chemistry chains/hydrogen production process, oxygen carrier is in continuous oxygen loss-De oxygen condition, so the activity of oxygen is very important in the oxygen carrier.Comparatively speaking, oxygen carrier NiO/NiAl
2O
4(CHO P etc. Fuel, 2004,83 (9)), Fe
2O
3/ Al
2O
3(MATTISSON T etc. Fuel, 2001,80 (13)) and CoO-NiO/YSZ(JIN H G etc. Energy Fuels, 1998,12 (6)) etc. over-all properties is better, and the oxygen carrier rate is limited, circulating reaction is lower, can't bear the not high deficiency of higher temperature of reaction, metal oxide dispersity in oxygen carrier but exist.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of complex metal oxides with perovskite structure and be used for oxygen carrier of recycle chemistry chain hydrogen production and preparation method thereof, the oxygen carrier rate of this oxygen carrier is high, the oxygen cycle ability strong, good stability.
The complex metal oxides oxygen carrier of recycle chemistry chain hydrogen production of the present invention is the complex metal oxides with perovskite structure, and general formula is A
xA '
1-xB
yB '
1-yO
3, wherein A is rare earth lanthanum, and A ' is potassium metal, and B is transition metals cobalt, and B ' is precious metal palladium, 0.7＜x＜1,0.8＜y＜1.
During the present invention uses, with uhligite A
xA '
1-xB
yB '
1-yO
3The complex metal oxides of structure is oxygen carrier, and the temperature of reaction of oxygen carrier in fuel is 500 ~ 1250 ℃, and the temperature of reaction of oxygen carrier in water vapour is 500 ~ 1250 ℃, and the fuel of use can be that solid fuel also can be gaseous fuel, the preferred latter.
Above-mentioned complex metal oxides oxygen carrier can be the suitable shape such as sphere, bar shaped, microballoon or abnormity, and particle size is generally 10 μ m ~ 500 μ m, and preferred particle size is 50 μ m ~ 200 μ m.Can add other suitable inorganic refractory component during use, as aluminum oxide, titanium oxide, magnesium oxide, silicon oxide etc. one or more.
The complex metal oxides oxygen carrier of perovskite structure adopts the citric acid complex method preparation.Detailed process is as follows: take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, lanthanum nitrate, saltpetre, the acid of chlorine palladium as presoma, take citric acid or ethylene glycol as complexing agent, wiring solution-forming and mixing and stirring, then carry out the moisture evaporation, solution is transformed into the gel of thickness by red-purple colloidal sol, then dry, roasting, the sample that obtains is for having the perovskite structure complex metal oxides.
In the method for preparing catalyst of the present invention, complexing agent can be citric acid or ethylene glycol, and complexing agent and metal ion mol ratio are 1:1～6:1, are preferably 1:1～3:1.Preparation and stirred solution are preferably under 50～80 ℃ and carry out at 20～90 ℃.Stir speed (S.S.) is 200～500rpm, is preferably 300～400rpm.Churning time is 3～8 hours, is preferably 4～6 hours.Drying temperature is 60～200 ℃, is preferably 80～150 ℃.Be 1～36 hour time of drying, is preferably 8～24 hours.Maturing temperature is 400～1000 ℃, and roasting time is roasting 2 ~ 15 hours, is preferably 700～900 ℃ of lower roastings 3～8 hours.
Compared with prior art, hydrogen production of chemical chain composite metal oxide oxygen carrier of the present invention and its preparation method and application has following advantage:
1, the present invention prepares a kind of complex metal oxides oxygen carrier with perovskite structure, and general formula is A
xA '
1-xB
yB '
1-yO
3, wherein A is rare earth lanthanum, and A ' is potassium metal, and B is transition metals cobalt, and B ' is precious metal palladium, 0.7＜x＜1,0.8＜y＜1;
2, the preparation method of the complex metal oxides of perovskite structure of the present invention is simple, and cost is low, is conducive to industrial application;
3, the present invention has the complex metal oxides A of perovskite structure
xA '
1-xB
yB '
1-yO
3(0.7＜x＜1,0.8＜y＜1) not only can improve stability and the anti-carbon deposition ability of uhligite behind the containing transition metal potassium of A position, prolong cycle index, can also adjust the valence state of B position metal, increase the quantity of lattice oxygen, improve oxygen carrier rate and activity, the transition metal Co that has catalytic activity on the B position can provide sufficient lattice oxygen for burning chemistry chains, behind the doped precious metal palladium of B position, can make Co metal ion electric charge, radius changes, and lattice parameter changes, form more oxygen room and provide enough lattice oxygen for hydrogen production of chemical chain, improve oxygen carrier rate and the activity of oxygen carrier;
4, perovskite structure oxide has advantages of Heat stability is good, can form the oxygen room of some amount in roasting process, and the adsorb oxygen on the oxygen room is more active, can oxygenated fuel, and lattice oxygen can be replenished the adsorb oxygen of continuous consumption simultaneously; After entering hydrogen-manufacturing reactor, water vapour can provide oxygen to uhligite again, and the while releasing hydrogen gas is so uhligite is a suitable oxygen carrier.
Description of drawings
Fig. 1 is the X-ray diffractogram of the embodiment of the invention 1,2,4,5 prepared complex metal oxides oxygen carriers with perovskite structure.
Embodiment
Further specify process and the effect of the inventive method below in conjunction with embodiment.
Embodiment 1
Get 21.85gCo (NO
3)
26H
2O puts into the beaker of 500mL, adds the distilled water of 100mL, slowly drips the chlorine palladium acid solution that contains Pd4%, the distilled water that adds again 100mL, the mol ratio that makes its Co and Pd is 0.95/0.05, then beaker is placed 80 ℃ water-bath, stirring velocity is 400rpm, is stirred to whole dissolvings.Get 30.87g La (NO
3)
36H
2O and 0.8gKNO
3Put into the beaker of 100mL distilled water, be stirred to whole dissolvings, the mol ratio that makes its La and K is 0.9/0.1.Then lanthanum nitrate and potassium nitrate solution are added drop-wise in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the chlorine palladium acid solution, stir while dripping.Get the 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, and add slowly citric acid solution this moment after above-mentioned mixing solutions stirs 30 minutes, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the loft drier of putting into 110 ℃ dried overnight.Then take out dried uhligite precursor, place retort furnace, rise to 400 ℃ with the temperature rise rate of 3 ℃/min from room temperature, constant temperature calcining 3 hours, temperature rise rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 4 hours obtains the complex metal oxides oxygen carrier.
Embodiment 2
Get 20.7gCo (NO
3)
26H
2O puts into the beaker of 500mL, slowly drips the chlorine palladium acid solution that contains Pd4%, adds the distilled water of 100mL again, and the mol ratio that makes its Co and Pd is 0.9/0.1, then beaker is placed 80 ℃ water-bath, and stirring velocity is 400rpm, is stirred to whole dissolvings.Get 29.15g La (NO
3)
36H
2O and 1.2gKNO
3Put into the beaker of 100mL distilled water, be stirred to whole dissolvings, the mol ratio that makes its La and K is 0.85/0.15.Then lanthanum nitrate and potassium nitrate solution are added drop-wise in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the chlorine palladium acid solution, stir while dripping.Get the 67g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixing solutions stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the loft drier of putting into 110 ℃ dried overnight.Then take out dried uhligite precursor, place retort furnace, rise to 400 ℃ with the temperature rise rate of 3 ℃/min from room temperature, constant temperature calcining 3 hours, temperature rise rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 4 hours obtains the complex metal oxides oxygen carrier.
Embodiment 3
Get 21.85gCo (NO
3)
26H
2O puts into the beaker of 500mL, adds the distilled water of 100mL, slowly drips the chlorine palladium acid solution that contains Pd4%, the distilled water that adds again 100mL, the mol ratio that makes its Co and Pd is 0.95/0.05, then beaker is placed 80 ℃ water-bath, stirring velocity is 400rpm, is stirred to whole dissolvings.Get 27.44g La (NO
3)
36H
2O and 1.6gKNO
3Put into the beaker of 100mL distilled water, be stirred to whole dissolvings, the mol ratio that makes its La and K is 0.8/0.2.Then lanthanum nitrate and potassium nitrate solution are added drop-wise in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the chlorine palladium acid solution, stir while dripping.Get the 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixing solutions stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the loft drier of putting into 110 ℃ dried overnight.Then take out dried uhligite precursor, place retort furnace, rise to 400 ℃ with the temperature rise rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, temperature rise rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains the complex metal oxides oxygen carrier.
Embodiment 4
Get 19.55gCo (NO
3)
26H
2O puts into the beaker of 500mL, slowly drips the chlorine palladium acid solution that contains Pd4%, adds the distilled water of 100mL again, and the mol ratio that makes its Co and Pd is 0.85/0.15, then beaker is placed 80 ℃ water-bath, and stirring velocity is 400rpm, is stirred to whole dissolvings.Get 25.73g La (NO
3)
36H
2O and 2gKNO
3Put into the beaker of 100mL distilled water, be stirred to whole dissolvings, the mol ratio that makes its La and K is 0.75/0.25.Then lanthanum nitrate and potassium nitrate solution are added drop-wise in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the chlorine palladium acid solution, stir while dripping.Get the 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixing solutions stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the loft drier of putting into 110 ℃ dried overnight.Then take out dried uhligite precursor, place retort furnace, rise to 400 ℃ with the temperature rise rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, temperature rise rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains the complex metal oxides oxygen carrier.。
Embodiment 5
Get 20.7gCo (NO
3)
26H
2O puts into the beaker of 500mL, slowly drips the chlorine palladium acid solution that contains Pd4%, adds the distilled water of 100mL again, and the mol ratio that makes its Co and Pd is 0.9/0.1, then beaker is placed 80 ℃ water-bath, and stirring velocity is 400rpm, is stirred to whole dissolvings.Get 24.01g La (NO
3)
36H
2O and 2.4gKNO
3Put into the beaker of 100mL distilled water, be stirred to whole dissolvings, the mol ratio that makes its La and K is 0.7/0.3.Then lanthanum nitrate and potassium nitrate solution are added drop-wise in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the chlorine palladium acid solution, stir while dripping.Get the 67g citric acid, citric acid and metal ion total amount mol ratio are 2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixing solutions stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the loft drier of putting into 110 ℃ dried overnight.Then take out dried uhligite precursor, place retort furnace, rise to 400 ℃ with the temperature rise rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, temperature rise rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains the complex metal oxides oxygen carrier.
Embodiment 6
Get 21.85gCo (NO
3)
26H
2O puts into the beaker of 500mL, slowly drips the chlorine palladium acid solution that contains Pd4%, adds the distilled water of 100mL again, and the mol ratio that makes its Co and Pd is 0.95/0.05, then beaker is placed 80 ℃ water-bath, and stirring velocity is 400rpm, is stirred to whole dissolvings.Get 32.59g La (NO
3)
36H
2O and 0.4gKNO
3Put into the beaker of 100mL distilled water, be stirred to whole dissolvings, the mol ratio that makes its La and K is 0.95/0.05.Then lanthanum nitrate and potassium nitrate solution are added drop-wise in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the chlorine palladium acid solution, stir while dripping.Get the 100g citric acid, citric acid and metal ion total amount mol ratio are 3:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixing solutions stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the loft drier of putting into 110 ℃ dried overnight.Then take out dried uhligite precursor, place retort furnace, rise to 400 ℃ with the temperature rise rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, temperature rise rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains the complex metal oxides oxygen carrier.
Comparative example 1
Adopt conventional sol-gel method to prepare cobalt oxide particle (loading on the silicon oxide), maturing temperature is with embodiment 1.
Comparative example 2
The A position potassium metal that undopes, the B position palladium that undopes adopts the same method preparation to have the LaCoO of perovskite structure
3Complex metal oxides.
Catalyst performance evaluation prepared in above-described embodiment and the comparative example is carried out as follows.Evaluating catalyst test is carried out in continuous fixed bed reactor, gets catalyzer 5ml, with count with order quartz sand by volume 1:1 mix.Fuel gas is synthetic gas (30vol%H
2, 60vol%CO, 10 vol%N
2), flow is 120ml/min, and temperature of reaction is 700 ℃, and reaction pressure is normal pressure.After reduction in 3 minutes finishes, switch to nitrogen, simultaneous temperature is down to 650 ℃, keeps 30 minutes.Then pass into water vapour, flow is 30ml/min, and temperature remains on 650 ℃.React after 10 minutes, switch to nitrogen again, simultaneous temperature rises to 700 ℃.Pass into fuel gas, reaction conditions is consistent with above-mentioned reduction reaction conditions again.Adopt the on-line analysis of SP-3820 type gas-chromatography, 5A molecular sieve column and Porapak Q post, TCD detects.Evaluation results sees Table 1.
The reactivity worth of table 1 catalyzer.
| Catalyzer | Circulate CO transformation efficiency % 50 times | Circulate CO transformation efficiency % 100 times | H 2Output *，（ml/g Co） | Coke content, wt% |
| Embodiment 1 | 99 | 99 | 381 | 0.06 |
| Embodiment 2 | 99 | 98 | 385 | 0.17 |
| Embodiment 3 | 99 | 98 | 397 | 0.09 |
| Embodiment 4 | 99 | 98 | 339 | 0.10 |
| Embodiment 5 | 99 | 98 | 338 | 0.13 |
| Embodiment 6 | 98 | 98 | 354 | 0.21 |
| Comparative example 1 | 87 | 85 | 220 | 5.35 |
| Comparative example 2 | 97 | 95 | 259 | 1.42 |
*The productive rate of hydrogen calculates (water is excessive) take Co as the basis, i.e. every gram Co reductive water steam
Can generate the volume of hydrogen.
Claims (6)
1. the application of oxygen carrier in recycle chemistry chain hydrogen production, this oxygen carrier is the complex metal oxides with perovskite structure, general formula is A
xA '
1-xB
yB '
1-yO
3, wherein A is rare earth lanthanum, and A ' is potassium metal, and B is transition metals cobalt, and B ' is precious metal palladium, 0.7＜x＜1,0.8＜y＜1.
2. according to application claimed in claim 1, it is characterized in that: the complex metal oxides oxygen carrier is sphere, bar shaped, microballoon or abnormity, and particle size is 10 μ m ~ 500 μ m.
3. according to application claimed in claim 1, wherein the temperature of combustion of complex metal oxides oxygen carrier in the water vapour reactor is 500～1250 ℃, and the reduction temperature in fuel reactor is 500～1250 ℃.
4. the preparation method of the described oxygen carrier of claim 1, it is characterized in that: the oxygen carrier preparation method is take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, lanthanum nitrate, saltpetre, the acid of chlorine palladium as presoma, take citric acid or ethylene glycol as complexing agent, wiring solution-forming and mixing and stirring, then carry out the moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, final drying, roasting, and the sample after the roasting is the perovskite structure complex metal oxides.
5. method according to claim 4, it is characterized in that: described complexing agent and metal ion mol ratio are 1:1～3:1, preparation and stirred solution are at 50～70 ℃, stir speed (S.S.) is 300～400rpm, churning time is 4～6 hours, drying temperature is 80～150 ℃, and be 8～24 hours time of drying, 600～900 ℃ of lower roastings 3～8 hours.
6. according to claim 4 or 5 described methods, it is characterized in that: described complexing agent and metal ion mol ratio are 1:1～3:1, preparation and stirred solution are at 50～70 ℃, stir speed (S.S.) is 300～400rpm, churning time is 4～6 hours, drying temperature is 80～150 ℃, and be 8～24 hours time of drying, 600～900 ℃ of lower roastings 3～8 hours.
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Cited By (5)
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| CN109250763A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | A kind of method of hydrogen sulfide methane reforming hydrogen manufacturing |
| CN111389411A (en) * | 2019-01-03 | 2020-07-10 | 天津大学 | Perovskite electrocatalyst and preparation method and application thereof |
| CN112892541A (en) * | 2021-01-26 | 2021-06-04 | 华中科技大学 | Modified nickel-iron composite oxygen carrier and preparation method and application thereof |
| CN115069267A (en) * | 2022-06-02 | 2022-09-20 | 厦门固洛璞科技有限公司 | Perovskite-based catalyst for hydrogen production from formic acid and preparation method and application thereof |
| GB2623602A (en) * | 2022-10-18 | 2024-04-24 | Guangzhou Ganyuan Intelligent Tech Co Ltd | Smart magic cube with ball shaft |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109250763A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | A kind of method of hydrogen sulfide methane reforming hydrogen manufacturing |
| CN109250763B (en) * | 2017-07-14 | 2020-11-10 | 中国石油化工股份有限公司 | Method for preparing hydrogen by reforming hydrogen sulfide and methane |
| CN111389411A (en) * | 2019-01-03 | 2020-07-10 | 天津大学 | Perovskite electrocatalyst and preparation method and application thereof |
| CN112892541A (en) * | 2021-01-26 | 2021-06-04 | 华中科技大学 | Modified nickel-iron composite oxygen carrier and preparation method and application thereof |
| CN115069267A (en) * | 2022-06-02 | 2022-09-20 | 厦门固洛璞科技有限公司 | Perovskite-based catalyst for hydrogen production from formic acid and preparation method and application thereof |
| GB2623602A (en) * | 2022-10-18 | 2024-04-24 | Guangzhou Ganyuan Intelligent Tech Co Ltd | Smart magic cube with ball shaft |
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