CN106629596A - Oxygen carrier with high loading capacity and used for chemical-looping hydrogen production, and preparation method and application thereof - Google Patents
Oxygen carrier with high loading capacity and used for chemical-looping hydrogen production, and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
- C01B3/063—Cyclic methods
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses an oxygen carrier with high loading capacity and used for chemical-looping hydrogen production, and a preparation method and an application thereof. The oxygen carrier comprises 5% to 65% of Fe2O3, 5% to 65% of hydroxyapatite and 30% to 90% of LaNiO3. The oxygen carrier is prepared by using HAp/LaNiO3 as a carrier through the following steps: by adopting a precipitation method, preparing LaNiO3 by using lanthanum nitrate and nickel nitrate as precursors, then with calcium nitrate and diammonium hydrogen phosphate as precursors of the hydroxyapatite, dropwise adding the precursors into a LaNiO3 coprecipitation solution, and loading Fe2O3 used as an active component onto the carrier so as to obtain a Fe2O3/HAp/LaNiO3 oxygen carrier. The oxygen carrier provided by the invention can be used for chemical-looping hydrogen production, has the characteristics of large specific surface area and high active component dispersibility, has high low-temperature activity, can reduce the temperature of a chemical-looping combustion reaction, saves a large amount of energy consumption and improves reaction activity.
Description
Technical field
The present invention relates to a kind of oxygen carrier, more particularly to a kind of hydrogen production of chemical chain oxygen carrier, belong to the oxygen carrier body technique in hydrogen production of chemical chain field.
Background technology
Current rapid growth, the increasingly increase deepened constantly with energy demand of industrialization degree with population, electric power based on fossil fuel is generated while energy demand is met, also very big environmental hazard, the CO that wherein combustion of fossil fuel is discharged are brought2Cause CO in air2Concentration is continuously increased, and greenhouse effects are constantly strengthened, therefore from the CO in fossil fuel combustion process2Control and reduction of discharging receive the close attention of international community.
Nineteen eighty-three, Germany scientist Richter and Knoche propose first burning chemistry chains（chemical looping combustion, CLC）Concept.The combustion technology difference maximum with common combustion technology is directly not use the oxygen molecule in air, but the combustion process of fuel, combustion product are completed using the oxygen atom in oxygen carrier（Mainly CO2And vapor）Will not be diluted and very high concentrations by the nitrogen in air, pure CO is obtained by simple condensation dehydration2, realize CO to simple and low energy consumption2Separation and trapping.Further, since the running temperature of fuel reactor and air reactor is relatively low, generate almost without thermal NO x and Quick-type NOx in air reactor, and in fuel reactor, due to contact with oxygen, without fuel type NOx generations.
Hydrogen has that calorific value is high, pollution-free, do not produce the particular advantages such as greenhouse gases causes people more and more to pay close attention to, it is possible to replaces fossil fuel, become the clean energy resource of 21 century.In view of the CO of burning chemistry chains method2Interior separation characteristic, applied chemistry chain method hydrogen manufacturing also becomes a current study hotspot.It is identical with CLC Principles of Process, it is incorporated into vapour reactor to aoxidize oxygen carrier instead of air as oxidant with vapor, while the hydrogen in vapor is also reduced into hydrogen.Currently, in the world many seminar include the Hatano of Japan to solid waste such as polyethylene as fuel NiO and Fe2O3Deng being oxygen carrier, Korea Son et al. to CH4For fuel NiO and Fe2O3Fan L-S for oxygen carrier, the U.S. teach seminar to synthesis gas or coal as fuel Fe2O3Hydrogen production of chemical chain process for oxygen carrier etc. is studied.
Hydrogen production of chemical chain process mainly includes three aspects, i.e. oxygen carrier, reactor and system design, and wherein oxygen carrier is research emphasis at this stage.Used as medium, between two reactors alternate cycles, ceaselessly carry out reduction reaction to oxygen carrier the heat transfer that the oxygen in vapour reactor and reaction are generated to fuel reactor, therefore the property of oxygen carrier directly affects the efficiency of whole hydrogen production of chemical chain.High-performance oxygen carrier is to realize thering is CO2The key of the hydrogen production of chemical chain technology of enriched character.The oxygen carrier for being presently used for burning chemistry chains is mainly metal oxygen carrier, and including Fe, Ni, Co, Cu, Mn, Cd etc., carrier mainly has：Al2O3、TiO2、MgO、SiO2, YSZ etc., in addition also a small amount of nonmetal oxide such as CaSO4Deng.By calculation of thermodynamics, the metal oxygen carrier for being adapted to hydrogen production of chemical chain technology only has Fe2O3.The Fe of document report2O3Typically load on a inert carrier, such as aluminum oxide, silica, be provided solely for supporting and disperseing Fe2O3Effect.In the patent applied before us (number of patent application 201110188397.8,201110188403.X), Fe2O3It is to be supported on perofskite type oxide, perofskite type oxide is except supporting and disperseing Fe2O3, reaction is also participated in, with certain activity, and the oxygen atom on perofskite type oxide is more active, easy to obtain oxygen and oxygen loss, is adapted to oxidation-reduction reaction.But perofskite type oxide specific surface area very little, only 5m2/ g or so, loads Fe2O3When limit its load capacity, and Fe2O3The decentralization of particle is very low, have impact on activity.
The content of the invention
The carrier specific surface area of hydrogen production of chemical chain oxygen carrier is little in solve prior art, active component Fe2O3The problem that load capacity is low and decentralization is poor, the present invention provides one kind with LaNiO3Load hydroxyapatite (HAp) is the Fe of carrier2O3/HAp/
LaNiO3Oxygen carrier, this loaded catalyst has carrier specific surface area big, and activity component load quantity is big, decentralization is high, the advantage that activity is good.
The technical purpose of the present invention is achieved through the following technical solutions：
A kind of hydrogen production of chemical chain oxygen carrier with high capacity amount, including the component of following mass fraction：
Fe2O3
5%～65%
Hydroxyapatite
5%～65%
LaNiO3
30%~90%。
Further, the oxygen carrier preferably includes the component of following mass fraction：
Fe2O3
10%～40%
Hydroxyapatite
20%～50%
LaNiO3
40%~
70%。
In the oxygen carrier, Fe2O3As active component, with LaNiO3Support hydroxyapatite（HAp/ LaNiO3）As carrier.The theory of hydroxyapatite consists of Ca10(PO4)6(OH)2, Ca/P is that 5/3, HAp crystal is hexagonal crystal system, and its structure is hexagonal cylinder.Hydroxyapatite possesses strong ion exchangeable, enhances the interaction between Metal-Support, and the loaded catalyst of preparation has the characteristics of specific surface area is big, active component decentralization is high.
Another technical purpose of the present invention is the preparation method for providing above-mentioned oxygen carrier, is comprised the following steps：
1. carrier hydroxyapatite/LaNiO3Preparation：Lanthanum nitrate hexahydrate and nickel nitrate solution are mixed, in dropping to container, with NaOH as precipitating reagent, pH is adjusted, precipitation is complete；Calcium nitrate is dissolved in into absolute ethyl alcohol, diammonium hydrogen phosphate is dissolved in deionized water, calcium nitrate solution and ammonium dibasic phosphate solution are mixed, above-mentioned precipitation is added dropwise to completely in liquid, pH is adjusted with NaOH, after precipitating completely, aging, suction filtration, washing, drying and roasting are carried out, obtain hydroxyapatite/LaNiO3；
2. Fe is loaded2O3：Using infusion process by Fe3+Load on carrier, be dried, roasting obtains the oxygen carrier.
Further, step 1. in the temperature that precipitates twice be 30～90 DEG C, preferably 30～60 DEG C, adjust pH value with NaOH and be 8～12, preferably 9～11；Aging temperature be 30～90 DEG C, preferably 30～80 DEG C, ageing time be 2～72, preferably 24～48 hours；Washing times are 1～5 time, preferably 3～5 times；Baking temperature is 60～200 DEG C, and preferably 60～120 DEG C, drying time is 1～48 hour, preferably 12～24 hours；The temperature of roasting is 400～1000 DEG C, and roasting time is 2 ~ 15 hours, preferably roasting roasting 6 ~ 12 hours at 700～1000 DEG C, and the sample after roasting is the hydroxyapatite composite oxides with hexagonal column structure.
Further, step 2. described in dipping be preferably incipient impregnation, dipping temperature be 30～90 DEG C, preferably 20～40 DEG C, dip time be 8～24 hours, preferably 8～12 hours；Baking temperature is 60～200 DEG C, preferably 60～120 DEG C；Drying time is 1～48 hour, preferably 12～24 hours；Sintering temperature is 400～1000 DEG C, and the time is 2 ~ 15 hours, roasting 6 ~ 12 hours preferably at 700～1000 DEG C.
Further, step 1. described in mix calcium nitrate solution and ammonium dibasic phosphate solution, the mixed proportion of two kinds of solution is preferably according to hydroxyapatite（Ca10(PO4)6(OH)2）Theoretical composition in Ca/P be 5/3 to mix.
The oxygen carrier of preparation can be the applicable shape in any this area such as spherical, bar shaped, and particle size is generally 40 ~ 100 mesh, preferably 60 ~ 80 mesh.
The oxygen carrier of the present invention can be used for hydrogen production of chemical chain, and reaction temperature of the oxygen carrier in fuel reactor is 600 ~ 1200 DEG C, and the reaction temperature in oxidation reactor is 600 ~ 1200 DEG C.The fuel for using can be liquid fuel, solid fuel or fuel gas, preferably fuel gas.
Beneficial effects of the present invention：
Compared with prior art, Fe of the invention2O3/HAp/
LaNiO3Hydroxyapatite is added as carrier, hydroxyapatite possesses strong ion exchangeable, enhance the interaction between Metal-Support, the loaded catalyst of preparation has the characteristics of specific surface area is big, active component is dispersed high.Particularly, oxygen carrier of the invention has the advantages that low temperature active is high, can reduce the temperature of burning chemistry chains reaction, save a large amount of energy consumptions, improves reactivity.
Specific embodiment
Following non-limiting examples can make one of ordinary skill in the art that the present invention is more fully understood, but limit the present invention never in any form.
Embodiment 1
Weigh 23gNi (NO3)2 ˙6H2O, in being dissolved in 100mL distilled water, weighs 34.3g La (NO3)3 ˙6H2O, in being dissolved in 100mL distilled water, two solution is well mixed, and is then added drop-wise in beaker, is stirred when being added dropwise, and adds appropriate sodium hydroxide solution to adjust pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2 ˙4H2O is dissolved in 125mL absolute ethyl alcohols, weigh 4.95g DAPs to be dissolved in 75mL deionized waters, the mixing of two solution is slowly dropped in above-mentioned precipitation solution, it is 9 to adjust pH value with sodium hydroxide solution, then in 30 DEG C of stirred in water bath 1h, 30 DEG C of aging 24h, then carries out suction filtration, and with distillation water washing 3 times, then 24h is dried at 110 DEG C, in 900 DEG C of roastings, 6 hours, obtains carrier HAp/LaNiO3。
The ferric nitrate of metering is weighed, in being dissolved into appropriate deionized water, the carrier of metering is weighed, then steeped overnight after both equal-volume mixing is dried 12h, 900 DEG C of Muffle kiln roasting 6h in 120 DEG C of drying boxes, obtains Fe2O3/HAp/LaNiO3Oxygen carrier, wherein Fe2O3It is 20%, LaNiO that mass content is 10%, HAp mass contents3Mass content is 70%.
Embodiment 2
Weigh 23gNi (NO3)2 ˙6H2O, in being dissolved in 100mL distilled water, weighs 34.3g La (NO3)3 ˙6H2O, in being dissolved in 100mL distilled water, two solution is well mixed, and is then added drop-wise in beaker, is stirred when being added dropwise, and adds appropriate sodium hydroxide solution to adjust pH value.It is to be precipitated completely after, weigh 10.36g Ca (NO3)2 ˙4H2O is dissolved in 125mL absolute ethyl alcohols, weigh 4.95g DAPs to be dissolved in 75mL deionized waters, the mixing of two solution is slowly dropped in above-mentioned precipitation solution, it is 9 to adjust pH value with sodium hydroxide solution, then in 30 DEG C of stirred in water bath 1h, 30 DEG C of aging 24h, then carries out suction filtration, and with distillation water washing 3 times, then 24h is dried at 110 DEG C, in 900 DEG C of roastings, 6 hours, obtains carrier HAp/LaNiO3。
The ferric nitrate of metering is weighed, in being dissolved into appropriate deionized water, the carrier of metering is weighed, then steeped overnight after both equal-volume mixing is dried 12h, 900 DEG C of Muffle kiln roasting 6h in 120 DEG C of drying boxes, obtains Fe2O3/HAp/LaNiO3Oxygen carrier, wherein Fe2O3It is 10%, LaNiO that mass content is 40%, HAp mass contents3Mass content is 50%.
Embodiment 3
Weigh 11gNi (NO3)2 ˙6H2O, in being dissolved in 100mL distilled water, weighs 17g La (NO3)3 ˙6H2O, in being dissolved in 100mL distilled water, two solution is well mixed, and is then added drop-wise in beaker, is stirred when being added dropwise, and adds appropriate sodium hydroxide solution to adjust pH value.It is to be precipitated completely after, weigh 30g Ca (NO3)2 ˙4H2O is dissolved in 250mL absolute ethyl alcohols, weigh 10g DAPs to be dissolved in 75mL deionized waters, the mixing of two solution is slowly dropped in above-mentioned precipitation solution, it is 9 to adjust pH value with sodium hydroxide solution, then in 30 DEG C of stirred in water bath 1h, 30 DEG C of aging 24h, then carries out suction filtration, and with distillation water washing 3 times, then 24h is dried at 110 DEG C, in 900 DEG C of roastings, 6 hours, obtains carrier HAp/LaNiO3。
The ferric nitrate of metering is weighed, in being dissolved into appropriate deionized water, the carrier of metering is weighed, then steeped overnight after both equal-volume mixing is dried 12h, 900 DEG C of Muffle kiln roasting 6h in 120 DEG C of drying boxes, obtains Fe2O3/HAp/LaNiO3Oxygen carrier, wherein Fe2O3It is 50%, LaNiO that mass content is 10%, HAp mass contents3Mass content is 40%.
Embodiment 4
Weigh 23gNi (NO3)2 ˙6H2O, in being dissolved in 100mL distilled water, weighs 34.3g La (NO3)3 ˙6H2O, in being dissolved in 100mL distilled water, two solution is well mixed, and is then added drop-wise in beaker, is stirred when being added dropwise, and adds appropriate sodium hydroxide solution to adjust pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2 ˙4H2O is dissolved in 125mL absolute ethyl alcohols, weigh 4.95g DAPs to be dissolved in 75mL deionized waters, the mixing of two solution is slowly dropped in above-mentioned precipitation solution, it is 11 to adjust pH value with sodium hydroxide solution, then in 30 DEG C of stirred in water bath 1h, 30 DEG C of aging 24h, then carries out suction filtration, and with distillation water washing 3 times, then 24h is dried at 110 DEG C, in 900 DEG C of roastings, 6 hours, obtains carrier HAp/LaNiO3。
The ferric nitrate of metering is weighed, in being dissolved into appropriate deionized water, the carrier of metering is weighed, then steeped overnight after both equal-volume mixing is dried 12h, 900 DEG C of Muffle kiln roasting 6h in 120 DEG C of drying boxes, obtains Fe2O3/HAp/LaNiO3Oxygen carrier, wherein Fe2O3It is 20%, LaNiO that mass content is 10%, HAp mass contents3Mass content is 70%.
Embodiment 5
Weigh 23gNi (NO3)2 ˙6H2O, in being dissolved in 100mL distilled water, weighs 34.3g La (NO3)3 ˙6H2O, in being dissolved in 100mL distilled water, two solution is well mixed, and is then added drop-wise in beaker, is stirred when being added dropwise, and adds appropriate sodium hydroxide solution to adjust pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2 ˙4H2O is dissolved in 125mL absolute ethyl alcohols, weigh 4.95g DAPs to be dissolved in 75mL deionized waters, the mixing of two solution is slowly dropped in above-mentioned precipitation solution, it is 9 to adjust pH value with sodium hydroxide solution, then in 30 DEG C of stirred in water bath 1h, 30 DEG C of aging 24h, then carries out suction filtration, and with distillation water washing 3 times, then 24h is dried at 110 DEG C, in 700 DEG C of roastings, 6 hours, obtains carrier HAp/LaNiO3。
The ferric nitrate of metering is weighed, in being dissolved into appropriate deionized water, the carrier of metering is weighed, then steeped overnight after both equal-volume mixing is dried 12h, 900 DEG C of Muffle kiln roasting 6h in 120 DEG C of drying boxes, obtains Fe2O3/HAp/LaNiO3Oxygen carrier, wherein Fe2O3It is 20%, LaNiO that mass content is 10%, HAp mass contents3Mass content is 70%.
Embodiment 6
Weigh 23gNi (NO3)2 ˙6H2O, in being dissolved in 100mL distilled water, weighs 34.3g La (NO3)3 ˙6H2O, in being dissolved in 100mL distilled water, two solution is well mixed, and is then added drop-wise in beaker, is stirred when being added dropwise, and adds appropriate sodium hydroxide solution to adjust pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2 ˙4H2O is dissolved in 125mL absolute ethyl alcohols, weigh 4.95g DAPs to be dissolved in 75mL deionized waters, the mixing of two solution is slowly dropped in above-mentioned precipitation solution, it is 9 to adjust pH value with sodium hydroxide solution, then in 30 DEG C of stirred in water bath 1h, 30 DEG C of aging 24h, then carries out suction filtration, and with distillation water washing 3 times, then 24h is dried at 110 DEG C, in 1000 DEG C of roastings, 12 hours, obtains carrier HAp/LaNiO3。
The ferric nitrate of metering is weighed, in being dissolved into appropriate deionized water, the carrier of metering is weighed, then steeped overnight after both equal-volume mixing is dried 12h, 900 DEG C of Muffle kiln roasting 6h in 120 DEG C of drying boxes, obtains Fe2O3/HAp/LaNiO3Oxygen carrier, wherein Fe2O3It is 20%, LaNiO that mass content is 10%, HAp mass contents3Mass content is 70%.
Embodiment 7
Weigh 23gNi (NO3)2 ˙6H2O, in being dissolved in 100mL distilled water, weighs 34.3g La (NO3)3 ˙6H2O, in being dissolved in 100mL distilled water, two solution is well mixed, and is then added drop-wise in beaker, is stirred when being added dropwise, and adds appropriate sodium hydroxide solution to adjust pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2 ˙4H2O is dissolved in 125mL absolute ethyl alcohols, weigh 4.95g DAPs to be dissolved in 75mL deionized waters, the mixing of two solution is slowly dropped in above-mentioned precipitation solution, it is 9 to adjust pH value with sodium hydroxide solution, then in 30 DEG C of stirred in water bath 1h, 30 DEG C of aging 24h, then carries out suction filtration, and with distillation water washing 3 times, then 24h is dried at 110 DEG C, in 700 DEG C of roastings, 6 hours, obtains carrier HAp/LaNiO3。
The ferric nitrate of metering is weighed, in being dissolved into appropriate deionized water, the carrier of metering is weighed, then steeped overnight after both equal-volume mixing is dried 12h, 700 DEG C of Muffle kiln roasting 6h in 120 DEG C of drying boxes, obtains Fe2O3/HAp/LaNiO3Oxygen carrier, wherein Fe2O3It is 20%, LaNiO that mass content is 10%, HAp mass contents3Mass content is 70%.
Embodiment 8
Weigh 23gNi (NO3)2 ˙6H2O, in being dissolved in 100mL distilled water, weighs 34.3g La (NO3)3 ˙6H2O, in being dissolved in 100mL distilled water, two solution is well mixed, and is then added drop-wise in beaker, is stirred when being added dropwise, and adds appropriate sodium hydroxide solution to adjust pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2 ˙4H2O is dissolved in 125mL absolute ethyl alcohols, weigh 4.95g DAPs to be dissolved in 75mL deionized waters, the mixing of two solution is slowly dropped in above-mentioned precipitation solution, it is 9 to adjust pH value with sodium hydroxide solution, then in 30 DEG C of stirred in water bath 1h, 30 DEG C of aging 24h, then carries out suction filtration, and with distillation water washing 3 times, then 24h is dried at 110 DEG C, in 700 DEG C of roastings, 6 hours, obtains carrier HAp/LaNiO3。
The ferric nitrate of metering is weighed, in being dissolved into appropriate deionized water, the carrier of metering is weighed, then steeped overnight after both equal-volume mixing is dried 12h, 1000 DEG C of Muffle kiln roasting 12h in 120 DEG C of drying boxes, obtains Fe2O3/HAp/LaNiO3Oxygen carrier, wherein Fe2O3It is 20%, LaNiO that mass content is 10%, HAp mass contents3Mass content is 70%.
Comparative example 1
Using volume impregnation method prepare Fe2O3/ LaNiO3Oxygen carrier.
Weigh 5.5gNi (NO3)2 ˙6H2O, in being dissolved in 50mL distilled water, weighs 8.5g La (NO3)3 ˙6H2O, in being dissolved in 50mL distilled water, two solution is well mixed, and is then added drop-wise in beaker, is stirred when being added dropwise, and adds appropriate sodium hydroxide solution to adjust pH value.It is to be precipitated completely after, then in 30 DEG C of stirred in water bath 1h, 30 DEG C of aging 24h, then carry out suction filtration, and with water washing 3 times is distilled, be then dried 24h at 110 DEG C, in 900 DEG C of roastings, 6 hours, obtain carrier LaNiO3。
The ferric nitrate of metering is weighed, in being dissolved into appropriate deionized water, the carrier of metering is weighed, then steeped overnight after both equal-volume mixing is dried 12h, 1000 DEG C of Muffle kiln roasting 12h in 120 DEG C of drying boxes, obtains Fe2O3/LaNiO3Oxygen carrier, wherein Fe2O3Mass content is 10%, LaNiO3Mass content is 90%.
Embodiment 9
Prepared catalyst performance evaluation is carried out as follows in above-described embodiment and comparative example.Catalyst Evaluation Test is carried out in continuous fixed bed reactor, takes catalyst 5ml, with same mesh number quartz sand by volume 1:1 mixing.Fuel gas is methane（10vol%CH4, 90vol%N2）, flow is 100ml/min, and reaction temperature is 750 DEG C, and reaction pressure is normal pressure.After reduction terminates, nitrogen is switched to, temperature keeps constant, kept for 20 minutes.Then water is injected with syringe pump, flow is 0.1ml/min, and water is first gasified, and subsequently into preheater, the temperature of preheater is maintained at 500 DEG C, enters back into reactor, reaction temperature is 800 DEG C, after reacting 3 minutes, then switches to nitrogen.Fuel gas is passed through again, and reaction condition is consistent with above-mentioned reduction reaction conditionses.Using SP-3820 type gas-chromatography on-line analyses, 5A molecular sieve columns and Porapak Q posts, TCD detections.Evaluation results are shown in Table 1.
The reactivity worth of the catalyst of table 1.
*Hydrogen output is calculated based on Fe（Water is excessive）, i.e., every gram iron reduces vapor can generate the volume of hydrogen.
Methane conversion and hydrogen output are to circulate the mean value of 100 times.
Claims (8)
1. a kind of hydrogen production of chemical chain oxygen carrier with high capacity amount, it is characterised in that：The oxygen carrier includes the component of following mass fraction：
Fe2O35%～65%
Hydroxyapatite 5%～65%
LaNiO3 30%~90%。
2. oxygen carrier according to claim 1, it is characterised in that：The oxygen carrier includes the component of following mass fraction：
Fe2O310%～40%
Hydroxyapatite 20%～50%
LaNiO3 40%~ 70%。
3. the preparation method of the oxygen carrier described in claim 1 or 2, comprises the following steps：
1. carrier hydroxyapatite/LaNiO3Preparation：Lanthanum nitrate hexahydrate and nickel nitrate solution are mixed, in dropping to container, with NaOH as precipitating reagent, pH is adjusted, precipitation is complete；Calcium nitrate is dissolved in into absolute ethyl alcohol, diammonium hydrogen phosphate is dissolved in deionized water, calcium nitrate solution and ammonium dibasic phosphate solution are mixed, above-mentioned precipitation is added dropwise to completely in liquid, pH is adjusted with NaOH, after precipitating completely, aging, suction filtration, washing, drying and roasting are carried out, obtain hydroxyapatite/LaNiO3；
2. Fe is loaded2O3：Using infusion process by Fe3+Load on carrier, be dried, roasting obtains the oxygen carrier.
4. the preparation method of oxygen carrier according to claim 3, it is characterised in that：Step 1. in the temperature that precipitates twice be 30～90 DEG C, adjust pH value with NaOH and be 8～12.
5. the preparation method of oxygen carrier according to claim 3, it is characterised in that：Step 1. with step 2. described in the temperature of roasting be 400～1000 DEG C.
6. the preparation method of oxygen carrier according to claim 3, it is characterised in that：Step 1. with step 2. described in time of roasting be 2 ~ 15 hours.
7. application of the oxygen carrier described in claim 1 or 2 in hydrogen production of chemical chain.
8. application according to claim 7, it is characterised in that：Reaction temperature of the oxygen carrier in fuel reactor is 600 ~ 1200 DEG C, and the reaction temperature in oxidation reactor is 600 ~ 1200 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111229266A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Supported hydroxyapatite catalyst and preparation and application thereof |
| CN111229266B (en) * | 2018-11-28 | 2023-03-24 | 中国科学院大连化学物理研究所 | Supported hydroxyapatite catalyst and preparation and application thereof |
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Effective date of registration: 20230815 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |