CN102862956A - Application of oxygen carrier with perovskite structure in chemical looping hydrogen production and preparation thereof - Google Patents
Application of oxygen carrier with perovskite structure in chemical looping hydrogen production and preparation thereof Download PDFInfo
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Abstract
The invention discloses an application of a composite oxide with a perovskite structure in chemical looping hydrogen production and a preparation thereof. the composite metal oxide with the perovskite structure is AB'xB1-xO3, wherein A is rare earth meal lanthanum, B and B' are respectively transition metals cobalt and copper, and x is less than 1 and greater than 0. The application of an oxygen carrier in chemical looping hydrogen production is as follows: the combustion temperature in a steam reactor is 500-800 DEG C and the reduction temperature in a fuel reactor is 500-800 DEG C. The preparation method of the oxygen carrier comprises the following steps of: preparing a solution from a precursor composed of cobalt nitrate, copper nitrate and lanthanum nitrate and citric acid or ethylene glycol which is used as a complexing agent, mixing and uniformly stirring, vaporizing moisture until the solution becomes a viscous gel from a transparent sol, and finally drying and roasting. The roasted sample is the composite metal oxide with the perovskite structure. The oxygen carrier provided by the invention has high oxygen carrying rate, high activity, good stability and the like.
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 do not contact 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 is 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 AB '
xB
1-xO
3, wherein A is rare earth lanthanum, and B ' is transition metal copper, and B is transition metals cobalt, 0＜x＜1.
During the present invention uses, with uhligite AB '
xB
1-xO
3The complex metal oxides of structure is oxygen carrier, and the temperature of reaction of oxygen carrier in fuel is 500 ~ 800 ℃, and the temperature of reaction of oxygen carrier in water vapour is 500 ~ 800 ℃, 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 of perovskite structure of the present invention adopts the citric acid complex method preparation.Detailed process is as follows: take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, lanthanum nitrate, cupric nitrate as presoma, citric acid or ethylene glycol are complexing agent, wiring solution-forming and mixing and stirring; Then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, final drying, roasting, and 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 1:1～8:1, are preferably 1:1～4:1.Preparation and stirred solution are preferably under 50～70 ℃ 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, recycle chemistry chain hydrogen production composite metal oxide oxygen carrier of the present invention and its preparation method and application has following advantage:
1, to prepare a kind of complex metal oxides general formula with perovskite structure be AB ' in the present invention
xB
1-xO
3, wherein A is rare earth lanthanum, and B ' is transition metal copper, and B is transition metals cobalt, 0＜x＜1.
2, the present invention has the application of complex metal oxides in the hydrogen production of chemical chain technology of perovskite structure, rare earth lanthanum on the A position can improve structural stability and the thermostability of uhligite, improve oxygen carrier and continue circulation ability and work-ing life, the upper two kinds of different transition metal in B position mix mutually, make its metal ion electric charge, radius changes, lattice parameter changes, form more oxygen room and provide enough lattice oxygen for hydrogen production of chemical chain, improve the oxygen carrier rate of oxygen carrier, promote that oxygen carrier carries out efficient oxidation-reduction process, accelerate the cycle efficiency of oxygen carrier in air reactor and combustion reactor.
3, the present invention has that the complex metal oxides oxygen carrier preparation method of perovskite structure is simple, cost is low, is suitable for industrial application.
Description of drawings
Fig. 1 is the X-ray diffractogram of the prepared complex metal oxides oxygen carrier with perovskite structure of the embodiment of the invention 1.
Embodiment
Further specify process and the effect of the inventive method below in conjunction with embodiment.
Embodiment 1
Get 20.7gCo (NO
3)
26H
2O and 1.9gCu (NO
3)
23H
2O puts into the beaker of 500mL, and the mol ratio that makes its Co and Cu is 0.9/0.1, adds the distilled water of 100mL, then beaker is placed 80 ℃ water-bath, and stirring velocity is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate, stirs 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 16.1gCo (NO
3)
26H
2O and 5.7gCu (NO
3)
23H
2O puts into the beaker of 500mL, and making the mol ratio of Co and Cu is 0.7/0.3, is stirred to whole dissolvings.Then the distilled water that adds 100mL place beaker 80 ℃ water-bath, and stirring velocity is 400rpm.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the copper nitrate solution, stirs 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 11.5g Co (NO
3)
26H
2O, 9.5gCu (NO
3)
23H
2O puts into the beaker of 500mL, and the mol ratio that makes Co and Cu is 0.5/0.5, adds the distilled water of 100mL, then beaker is placed 80 ℃ water-bath, and stirring velocity is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate, stirs 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 4.6g Co (NO
3)
26H
2O and 15.2gCu (NO
3)
23H
2O puts into the beaker of 500mL, and the mol ratio that makes Co and Cu is to put into the beaker of 500mL, and the mol ratio that makes Co and Cu is 0.2/0.8, the distilled water that adds 100mL, then beaker is placed 80 ℃ water-bath, stirring velocity is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate, stirs 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 and 1.9gCu (NO
3)
23H
2O puts into the beaker of 500mL, and the mol ratio that makes its Co and Cu is 0.9/0.1, adds the distilled water of 100mL, then beaker is placed 80 ℃ water-bath, and stirring velocity is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate, stirs 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 20.7gCo (NO
3)
26H
2O and 1.9gCu (NO
3)
23H
2O puts into the beaker of 500mL, and the mol ratio that makes its Co and Cu is 0.9/0.1, adds the distilled water of 100mL, then beaker is placed 80 ℃ water-bath, and stirring velocity is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate, stirs 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 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 600 ℃, keeps 30 minutes.Then pass into water vapour, flow is 30ml/min, and temperature remains on 600 ℃.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 | 98 | 98 | 347 | 0.54 |
| Embodiment 2 | 98 | 98 | 355 | 0.37 |
| Embodiment 3 | 98 | 98 | 351 | 0.48 |
| Embodiment 4 | 99 | 97 | 329 | 0.29 |
| Embodiment 5 | 98 | 98 | 335 | 0.43 |
| Embodiment 6 | 98 | 98 | 324 | 0.46 |
| 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 hydrogen production of chemical chain, it is characterized in that: this oxygen carrier is the complex metal oxides with perovskite structure, general formula is AB '
xB
1-xO
3, wherein A is rare earth lanthanum, and B ' is transition metal copper, and B is transition metals cobalt, 0＜x＜1.
2. according to application claimed in claim 1, it is characterized in that: described 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 oxygen carrier in the water vapour reactor is 500～800 ℃, and the reduction temperature in fuel reactor is 500～800 ℃.
4. the preparation method of oxygen carrier claimed in claim 1, it is characterized in that: take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, lanthanum nitrate, cupric nitrate as presoma, citric acid or ethylene glycol are complexing agent, wiring solution-forming and mixing and stirring; Then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, final drying, roasting, and the sample that obtains is for having the perovskite structure complex metal oxides.
5. in accordance with the method for claim 4, it is characterized in that: complexing agent and metal ion mol ratio are 1:1～8:1, preparation and stirred solution carry out under 20～90 ℃, churning time is 3～8 hours, stirring velocity is 200～500rpm, drying temperature is 60～200 ℃, and be 1～36 hour time of drying, and roasting was at 400～1000 ℃ of lower roasting 2-15 hours.
6. according to claim 4 or 5 described methods, it is characterized in that: complexing agent and metal ion mol ratio are 1:1～4:1, preparation and stirred solution carry out under 50～70 ℃, churning time is 4～6 hours, stir speed (S.S.) is 300～400rpm, drying temperature is 80～150 ℃, and be 8～24 hours time of drying, and roasting was 700～900 ℃ of lower roastings 3～8 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110217756A (en) * | 2019-06-28 | 2019-09-10 | 桂林电子科技大学 | A kind of preparation method and application of the aluminum-based composite hydrogen manufacturing material of carbon load bismuth |
| CN110980644A (en) * | 2019-12-31 | 2020-04-10 | 中国科学院工程热物理研究所 | Water-based chemical chain circulation hydrogen production system and method |
| CN112275291A (en) * | 2020-09-15 | 2021-01-29 | 上海理工大学 | Iron-doped perovskite intercalated montmorillonite composite catalyst and preparation method and application thereof |
| CN117902552A (en) * | 2024-03-15 | 2024-04-19 | 临涣焦化股份有限公司 | Method for preparing high-purity hydrogen through PSA (pressure sensitive adhesive) purification |
-
2011
- 2011-07-07 CN CN201110188426.0A patent/CN102862956B/en active Active
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| Title |
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| N. TIEN-THAO ET AL: "Conversion of syngas to higher alcohols over nanosized LaCo0.7Cu0.3O3 perovskite precursors", 《APPLIED CATALYSIS A: GENERAL》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110217756A (en) * | 2019-06-28 | 2019-09-10 | 桂林电子科技大学 | A kind of preparation method and application of the aluminum-based composite hydrogen manufacturing material of carbon load bismuth |
| CN110980644A (en) * | 2019-12-31 | 2020-04-10 | 中国科学院工程热物理研究所 | Water-based chemical chain circulation hydrogen production system and method |
| CN110980644B (en) * | 2019-12-31 | 2021-10-22 | 中国科学院工程热物理研究所 | Water-based chemical chain circulation hydrogen production system and method |
| CN112275291A (en) * | 2020-09-15 | 2021-01-29 | 上海理工大学 | Iron-doped perovskite intercalated montmorillonite composite catalyst and preparation method and application thereof |
| CN112275291B (en) * | 2020-09-15 | 2023-02-10 | 上海理工大学 | Iron-doped perovskite intercalated montmorillonite composite catalyst and preparation method and application thereof |
| CN117902552A (en) * | 2024-03-15 | 2024-04-19 | 临涣焦化股份有限公司 | Method for preparing high-purity hydrogen through PSA (pressure sensitive adhesive) purification |
| CN117902552B (en) * | 2024-03-15 | 2024-06-04 | 临涣焦化股份有限公司 | Method for preparing high-purity hydrogen through PSA (pressure sensitive adhesive) purification |
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