CN106629596B - A kind of hydrogen production of chemical chain oxygen carrier with high load amount, preparation method and application - Google Patents
A kind of hydrogen production of chemical chain oxygen carrier with high load amount, preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of hydrogen production of chemical chain oxygen carrier and its preparation method and application with high load amount, and the oxygen carrier includes 5%~65% Fe2O3, 5%~65% hydroxyapatite, 30% ~ 90% LaNiO3.The oxygen carrier is with HAp/LaNiO3For carrier, using the precipitation method, using lanthanum nitrate, nickel nitrate as precursor preparation LaNiO3, then using calcium nitrate and diammonium hydrogen phosphate as the presoma of hydroxyapatite, it is added dropwise to LaNiO3It is co-precipitated in liquid, then in supported on carriers Fe2O3As active component, Fe is obtained2O3/HAp/LaNiO3Oxygen carrier.Oxygen carrier of the invention can be used for hydrogen production of chemical chain, have the characteristics that large specific surface area, active component dispersion degree are high；Its low temperature active is high, can reduce the temperature of burning chemistry chains reaction, save a large amount of energy consumptions, improves reactivity.
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 carriers, belong to hydrogen production of chemical chain field
Oxygen carrier body technique.
Background technique
Currently with the rapid growth of population, the increasingly increase of industrialization degree deepened constantly with energy demand, to change
Electric power based on stone fuel generates while meeting energy demand, also brings very big environmental hazard, and wherein fossil fires
The discharged CO of material burning2Lead to CO in atmosphere2Concentration is continuously increased, and greenhouse effects are constantly reinforced, therefore from fossil fuel
CO in combustion process2Control and emission reduction receive the close attention of international community.
Nineteen eighty-three, Germany scientist Richter and Knoche are put forward for the first time burning chemistry chains (chemical looping
Combustion, CLC) concept.The combustion technology and the maximum difference of common combustion technology are not directly using in air
Oxygen molecule, but the combustion process of fuel is completed using the oxygen atom in oxygen carrier, combustion product (mainly CO2And water
Steam) it will not be diluted and very high concentrations by the nitrogen in air, pure CO can be obtained by simple condensation dehydration2, simple and low
Realize CO to energy consumption2Separation and trapping.In addition, relatively due to fuel reactor and the running temperature of air reactor
It is low, generated in air reactor almost without thermal NO x and Quick-type NOx, and in fuel reactor, due to not with oxygen
Contact is generated without fuel type NOx.
Hydrogen is high, pollution-free with calorific value, does not generate the particular advantages such as greenhouse gases causes people more and more to pay close attention to,
It is possible that replacing fossil fuel, the clean energy resource as 21 century.In view of the CO of burning chemistry chains method2Interior separation characteristic, application
Chemical chain method hydrogen manufacturing also becomes a current research hotspot.It is identical as CLC Principle of Process, with vapor instead of air as
Oxidant is introduced into vapour reactor to aoxidize oxygen carrier, while the hydrogen in vapor is also reduced into hydrogen.Currently, the world
Upper many study groups include the Hatano of Japan to using solid waste such as polyethylene as fuel NiO and Fe2O3Deng for oxygen carrier,
South Korea Son et al. is to CH4For fuel NiO and Fe2O3For oxygen carrier, the U.S. Fan L-S teach study group to synthesis gas or
Coal is fuel Fe2O3It is studied for the hydrogen production of chemical chain process of oxygen carrier etc..
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.Oxygen carrier is as medium, alternate cycles between two reactors, ceaselessly in vapour reactor
Oxygen and reaction generate heat transfer to fuel reactor progress reduction reaction, therefore the property of oxygen carrier directly affect it is whole
The efficiency of a hydrogen production of chemical chain.High-performance oxygen carrier is to realize to have CO2The key of the hydrogen production of chemical chain technology of enriched character.Mesh
Before, the oxygen carrier 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 to this there are also a small amount of nonmetal oxide such as CaSO4Deng.Pass through thermodynamics meter
It calculates, the metal oxygen carrier of hydrogen production of chemical chain technology is suitble to there was only Fe2O3.Fe reported in the literature2O3It is usually to be supported on inert carrier
On, such as aluminium oxide, silica, it is provided solely for supporting and dispersing Fe2O3Effect.(patent Shen in the patent applied before us
Please numbers 201110188397.8,201110188403.X), Fe2O3It is to be supported on perofskite type oxide, Ca-Ti ore type oxidation
Object is in addition to supporting and dispersing Fe2O3, reaction is also participated in, there is certain activity, and the oxygen atom ratio on perofskite type oxide
It is relatively active, it is easy to obtain oxygen and oxygen loss, is suitble 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 dispersion degree of particle is very low, affects activity.
Summary of the invention
Small, the active component Fe for the carrier specific surface area that solves hydrogen production of chemical chain oxygen carrier in the prior art2O3Load capacity is low
And the problem of dispersion degree difference, the present invention provide one kind with LaNiO3Load the Fe that hydroxyapatite (HAp) is carrier2O3/HAp/
LaNiO3Oxygen carrier, this loaded catalyst have carrier large specific surface area, and activity component load quantity is big, dispersion degree is high, active
Good advantage.
Technical purpose of the invention is achieved through the following technical solutions:
A kind of hydrogen production of chemical chain oxygen carrier with high load amount, the component including following mass fraction:
Fe2O35%~65%
Hydroxyapatite 5%~65%
LaNiO3 30%~90%。
Further, the oxygen carrier preferably includes the component of following mass fraction:
Fe2O310%~40%
Hydroxyapatite 20%~50%
LaNiO3 40%~ 70%。
In the oxygen carrier, Fe2O3As active component, with LaNiO3Support hydroxyapatite (HAp/ LaNiO3) conduct
Carrier.The theoretical group of hydroxyapatite becomes Ca10(PO4)6(OH)2, Ca/P 5/3, HAp crystal is hexagonal crystal system, and structure is
Hexagonal cylinder.Hydroxyapatite has strong ion exchangeable, enhances the interaction between Metal-Support, the load of preparation
Type catalyst has the characteristics that large specific surface area, active component dispersion degree are high.
Another technical object of the present invention is to provide the preparation method of above-mentioned oxygen carrier, comprising the following steps:
1. carrier hydroxyapatite/LaNiO3Preparation: lanthanum nitrate hexahydrate and nickel nitrate solution are mixed, appearance is added dropwise to
In device, using sodium hydroxide as precipitating reagent, pH is adjusted, precipitating is complete；Calcium nitrate is dissolved in dehydrated alcohol, diammonium hydrogen phosphate is dissolved in
Calcium nitrate solution and ammonium dibasic phosphate solution are mixed, are added dropwise in the complete liquid of above-mentioned precipitating, with sodium hydroxide by ionized water
PH is adjusted, after precipitating completely, aging, suction filtration, washing, drying and roasting is carried out, obtains hydroxyapatite/LaNiO3；
2. loading Fe2O3: use infusion process by Fe3+It loads on carrier, dry, roasting obtains the oxygen carrier.
Further, step 1. in the temperature that precipitates twice be 30~90 DEG C, preferably 30~60 DEG C, use sodium hydroxide
Adjusting pH value is 8~12, and 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；Drying temperature is 60~200 DEG C, preferably
60~120 DEG C, drying time is 1~48 hour, preferably 12~24 hours；The temperature of roasting is 400~1000 DEG C, when roasting
Between be 2 ~ 15 hours, preferably roasting roast 6 ~ 12 hours at 700~1000 DEG C, and the sample after roasting is with hexagonal cylinder
The hydroxyapatite composite oxides of 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 is 8~24 hours, preferably 8~12 hours；Drying temperature be 60~200 DEG C, preferably 60~120
℃；Drying time is 1~48 hour, preferably 12~24 hours；Maturing temperature is 400~1000 DEG C, and the time is 2 ~ 15 hours,
It is roasted 6 ~ 12 hours preferably at 700~1000 DEG C.
Further, step 1. described in mixing calcium nitrate solution and ammonium dibasic phosphate solution, the mixing of two kinds of solution
Ratio is preferably according to hydroxyapatite (Ca10(PO4)6(OH)2) theoretical composition in Ca/P be 5/3 mixing.
The oxygen carrier of preparation can be the applicable shape in any this field such as spherical shape, bar shaped, and particle size is generally 40 ~
100 mesh, preferably 60 ~ 80 mesh.
Oxygen carrier of the invention can be used for hydrogen production of chemical chain, and reaction temperature of the oxygen carrier in fuel reactor be 600 ~
1200 DEG C, the reaction temperature in oxidation reactor is 600 ~ 1200 DEG C.The fuel used 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 be joined as carrier, hydroxyl
Apatite has strong ion exchangeable, enhances the interaction between Metal-Support, the loaded catalyst of preparation have than
Surface area is big, the dispersed high feature of active component.Particularly, oxygen carrier of the invention has the advantages that low temperature active is high, can
To reduce the temperature of burning chemistry chains reaction, save a large amount of energy consumptions, raising reactivity.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Embodiment 1
Weigh 23gNi (NO3)2˙6H2O is dissolved in 100mL distilled water, weighs 34.3g La (NO3)3˙6H2O is dissolved in
In 100mL distilled water, two solution are uniformly mixed, are then added drop-wise in beaker, stirred when being added dropwise, suitable hydrogen-oxygen is added
Change sodium solution and adjusts pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2˙4H2O is dissolved in 125mL dehydrated alcohol, is weighed
4.95g dihydrogen phosphate is dissolved in 75mL deionized water, and two solution are mixed and are slowly dropped in above-mentioned precipitation solution, hydrogen-oxygen is used
Change sodium solution adjust pH value be 9, then 30 DEG C of stirred in water bath 1h, 30 DEG C of agings for 24 hours, then filtered, and with distill
It water washing 3 times, is then dried for 24 hours at 110 DEG C, in 900 DEG C of 6 hours of roasting, obtains carrier HAp/LaNiO3。
The ferric nitrate for weighing metering is dissolved into suitable deionized water, weighs the carrier of metering, and the two mixes in equal volume
Steeped overnight afterwards, then dry 12h, 900 DEG C of Muffle kiln roasting 6h obtain Fe in 120 DEG C of drying boxes2O3/HAp/LaNiO3
Oxygen carrier, wherein Fe2O3Mass content is that 10%, HAp mass content is 20%, LaNiO3Mass content is 70%.
Embodiment 2
Weigh 23gNi (NO3)2˙6H2O is dissolved in 100mL distilled water, weighs 34.3g La (NO3)3˙6H2O is dissolved in
In 100mL distilled water, two solution are uniformly mixed, are then added drop-wise in beaker, stirred when being added dropwise, suitable hydrogen-oxygen is added
Change sodium solution and adjusts pH value.It is to be precipitated completely after, weigh 10.36g Ca (NO3)2˙4H2O is dissolved in 125mL dehydrated alcohol, is weighed
4.95g dihydrogen phosphate is dissolved in 75mL deionized water, and two solution are mixed and are slowly dropped in above-mentioned precipitation solution, hydrogen-oxygen is used
Change sodium solution adjust pH value be 9, then 30 DEG C of stirred in water bath 1h, 30 DEG C of agings for 24 hours, then filtered, and with distill
It water washing 3 times, is then dried for 24 hours at 110 DEG C, in 900 DEG C of 6 hours of roasting, obtains carrier HAp/LaNiO3。
The ferric nitrate for weighing metering is dissolved into suitable deionized water, weighs the carrier of metering, and the two mixes in equal volume
Steeped overnight afterwards, then dry 12h, 900 DEG C of Muffle kiln roasting 6h obtain Fe in 120 DEG C of drying boxes2O3/HAp/LaNiO3
Oxygen carrier, wherein Fe2O3Mass content is that 40%, HAp mass content is 10%, LaNiO3Mass content is 50%.
Embodiment 3
Weigh 11gNi (NO3)2˙6H2O is dissolved in 100mL distilled water, weighs 17g La (NO3)3˙6H2O is dissolved in 100mL
In distilled water, two solution are uniformly mixed, are then added drop-wise in beaker, stirred when being added dropwise, suitable sodium hydroxide is added
Solution adjusts pH value.It is to be precipitated completely after, weigh 30g Ca (NO3)2˙4H2O is dissolved in 250mL dehydrated alcohol, weighs 10g phosphoric acid
Hydrogen diamino is dissolved in 75mL deionized water, and two solution are mixed and are slowly dropped in above-mentioned precipitation solution, sodium hydroxide solution is used
Adjust pH value be 9, then 30 DEG C of stirred in water bath 1h, 30 DEG C of agings for 24 hours, then filtered, and be washed with distilled water 3
It is secondary, it is then dried for 24 hours at 110 DEG C, in 900 DEG C of 6 hours of roasting, obtains carrier HAp/LaNiO3。
The ferric nitrate for weighing metering is dissolved into suitable deionized water, weighs the carrier of metering, and the two mixes in equal volume
Steeped overnight afterwards, then dry 12h, 900 DEG C of Muffle kiln roasting 6h obtain Fe in 120 DEG C of drying boxes2O3/HAp/LaNiO3
Oxygen carrier, wherein Fe2O3Mass content is that 10%, HAp mass content is 50%, LaNiO3Mass content is 40%.
Embodiment 4
Weigh 23gNi (NO3)2˙6H2O is dissolved in 100mL distilled water, weighs 34.3g La (NO3)3˙6H2O is dissolved in
In 100mL distilled water, two solution are uniformly mixed, are then added drop-wise in beaker, stirred when being added dropwise, suitable hydrogen-oxygen is added
Change sodium solution and adjusts pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2˙4H2O is dissolved in 125mL dehydrated alcohol, is weighed
4.95g dihydrogen phosphate is dissolved in 75mL deionized water, and two solution are mixed and are slowly dropped in above-mentioned precipitation solution, hydrogen-oxygen is used
Change sodium solution adjust pH value be 11, then 30 DEG C of stirred in water bath 1h, 30 DEG C of agings for 24 hours, then filtered, and with distill
It water washing 3 times, is then dried for 24 hours at 110 DEG C, in 900 DEG C of 6 hours of roasting, obtains carrier HAp/LaNiO3。
The ferric nitrate for weighing metering is dissolved into suitable deionized water, weighs the carrier of metering, and the two mixes in equal volume
Steeped overnight afterwards, then dry 12h, 900 DEG C of Muffle kiln roasting 6h obtain Fe in 120 DEG C of drying boxes2O3/HAp/LaNiO3
Oxygen carrier, wherein Fe2O3Mass content is that 10%, HAp mass content is 20%, LaNiO3Mass content is 70%.
Embodiment 5
Weigh 23gNi (NO3)2˙6H2O is dissolved in 100mL distilled water, weighs 34.3g La (NO3)3˙6H2O is dissolved in
In 100mL distilled water, two solution are uniformly mixed, are then added drop-wise in beaker, stirred when being added dropwise, suitable hydrogen-oxygen is added
Change sodium solution and adjusts pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2˙4H2O is dissolved in 125mL dehydrated alcohol, is weighed
4.95g dihydrogen phosphate is dissolved in 75mL deionized water, and two solution are mixed and are slowly dropped in above-mentioned precipitation solution, hydrogen-oxygen is used
Change sodium solution adjust pH value be 9, then 30 DEG C of stirred in water bath 1h, 30 DEG C of agings for 24 hours, then filtered, and with distill
It water washing 3 times, is then dried for 24 hours at 110 DEG C, in 700 DEG C of 6 hours of roasting, obtains carrier HAp/LaNiO3。
The ferric nitrate for weighing metering is dissolved into suitable deionized water, weighs the carrier of metering, and the two mixes in equal volume
Steeped overnight afterwards, then dry 12h, 900 DEG C of Muffle kiln roasting 6h obtain Fe in 120 DEG C of drying boxes2O3/HAp/LaNiO3
Oxygen carrier, wherein Fe2O3Mass content is that 10%, HAp mass content is 20%, LaNiO3Mass content is 70%.
Embodiment 6
Weigh 23gNi (NO3)2˙6H2O is dissolved in 100mL distilled water, weighs 34.3g La (NO3)3˙6H2O is dissolved in
In 100mL distilled water, two solution are uniformly mixed, are then added drop-wise in beaker, stirred when being added dropwise, suitable hydrogen-oxygen is added
Change sodium solution and adjusts pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2˙4H2O is dissolved in 125mL dehydrated alcohol, is weighed
4.95g dihydrogen phosphate is dissolved in 75mL deionized water, and two solution are mixed and are slowly dropped in above-mentioned precipitation solution, hydrogen-oxygen is used
Change sodium solution adjust pH value be 9, then 30 DEG C of stirred in water bath 1h, 30 DEG C of agings for 24 hours, then filtered, and with distill
It water washing 3 times, is then dried for 24 hours at 110 DEG C, in 1000 DEG C of 12 hours of roasting, obtains carrier HAp/LaNiO3。
The ferric nitrate for weighing metering is dissolved into suitable deionized water, weighs the carrier of metering, and the two mixes in equal volume
Steeped overnight afterwards, then dry 12h, 900 DEG C of Muffle kiln roasting 6h obtain Fe in 120 DEG C of drying boxes2O3/HAp/LaNiO3
Oxygen carrier, wherein Fe2O3Mass content is that 10%, HAp mass content is 20%, LaNiO3Mass content is 70%.
Embodiment 7
Weigh 23gNi (NO3)2˙6H2O is dissolved in 100mL distilled water, weighs 34.3g La (NO3)3˙6H2O is dissolved in
In 100mL distilled water, two solution are uniformly mixed, are then added drop-wise in beaker, stirred when being added dropwise, suitable hydrogen-oxygen is added
Change sodium solution and adjusts pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2˙4H2O is dissolved in 125mL dehydrated alcohol, is weighed
4.95g dihydrogen phosphate is dissolved in 75mL deionized water, and two solution are mixed and are slowly dropped in above-mentioned precipitation solution, hydrogen-oxygen is used
Change sodium solution adjust pH value be 9, then 30 DEG C of stirred in water bath 1h, 30 DEG C of agings for 24 hours, then filtered, and with distill
It water washing 3 times, is then dried for 24 hours at 110 DEG C, in 700 DEG C of 6 hours of roasting, obtains carrier HAp/LaNiO3。
The ferric nitrate for weighing metering is dissolved into suitable deionized water, weighs the carrier of metering, and the two mixes in equal volume
Steeped overnight afterwards, then dry 12h, 700 DEG C of Muffle kiln roasting 6h obtain Fe in 120 DEG C of drying boxes2O3/HAp/LaNiO3
Oxygen carrier, wherein Fe2O3Mass content is that 10%, HAp mass content is 20%, LaNiO3Mass content is 70%.
Embodiment 8
Weigh 23gNi (NO3)2˙6H2O is dissolved in 100mL distilled water, weighs 34.3g La (NO3)3˙6H2O is dissolved in
In 100mL distilled water, two solution are uniformly mixed, are then added drop-wise in beaker, stirred when being added dropwise, suitable hydrogen-oxygen is added
Change sodium solution and adjusts pH value.It is to be precipitated completely after, weigh 14.8g Ca (NO3)2˙4H2O is dissolved in 125mL dehydrated alcohol, is weighed
4.95g dihydrogen phosphate is dissolved in 75mL deionized water, and two solution are mixed and are slowly dropped in above-mentioned precipitation solution, hydrogen-oxygen is used
Change sodium solution adjust pH value be 9, then 30 DEG C of stirred in water bath 1h, 30 DEG C of agings for 24 hours, then filtered, and with distill
It water washing 3 times, is then dried for 24 hours at 110 DEG C, in 700 DEG C of 6 hours of roasting, obtains carrier HAp/LaNiO3。
The ferric nitrate for weighing metering is dissolved into suitable deionized water, weighs the carrier of metering, and the two mixes in equal volume
Steeped overnight afterwards, then dry 12h, 1000 DEG C of Muffle kiln roasting 12h obtain Fe in 120 DEG C of drying boxes2O3/HAp/
LaNiO3Oxygen carrier, wherein Fe2O3Mass content is that 10%, HAp mass content is 20%, LaNiO3Mass content is 70%.
Comparative example 1
Using volume impregnation method prepare Fe2O3/ LaNiO3Oxygen carrier.
Weigh 5.5gNi (NO3)2˙6H2O is dissolved in 50mL distilled water, weighs 8.5g La (NO3)3˙6H2O is dissolved in 50mL
In distilled water, two solution are uniformly mixed, are then added drop-wise in beaker, stirred when being added dropwise, suitable sodium hydroxide is added
Solution adjusts pH value.It is to be precipitated completely after, then 30 DEG C of stirred in water bath 1h, 30 DEG C of agings for 24 hours, then filtered, and
It is washed with distilled water 3 times, is then dried for 24 hours at 110 DEG C, in 900 DEG C of 6 hours of roasting, obtain carrier LaNiO3。
The ferric nitrate for weighing metering is dissolved into suitable deionized water, weighs the carrier of metering, and the two mixes in equal volume
Steeped overnight afterwards, then dry 12h, 1000 DEG C of Muffle kiln roasting 12h obtain Fe in 120 DEG C of drying boxes2O3/LaNiO3It carries
Oxysome, wherein Fe2O3Mass content is 10%, LaNiO3Mass content is 90%.
Embodiment 9
Prepared catalyst performance evaluation carries out as follows in above-described embodiment and comparative example.Evaluating catalyst examination
It tests and is carried out in continuous fixed bed reactor, take catalyst 5ml, 1:1 is mixed by volume with same mesh number quartz sand.Fuel
Gas is methane (10vol%CH4, 90vol%N2), flow 100ml/min, reaction temperature is 750 DEG C, and reaction pressure is normal pressure.
After reduction, nitrogen is switched to, temperature remains unchanged, and is kept for 20 minutes.Then water, flow 0.1ml/ are injected with syringe pump
Min, water are first gasified, and subsequently into preheater, the temperature of preheater is maintained at 500 DEG C, enters back into reactor, and reaction temperature is
After 800 DEG C, reaction 3 minutes, then switch to nitrogen.It is passed through fuel gas again, reaction condition is consistent with above-mentioned reduction reaction conditions.It adopts
With SP-3820 type gas-chromatography on-line analysis, 5A molecular sieve column and Porapak Q column, TCD detection.Evaluation results are shown in Table
1。
The reactivity worth of 1. catalyst of table
*Hydrogen output is (water is excessive) calculated based on Fe, i.e., every gram of iron restores vapor
The volume of hydrogen can be generated.
Methane conversion and hydrogen output are the average value for recycling 100 times.
Claims (8)
1. a kind of hydrogen production of chemical chain oxygen carrier with high load amount, it is characterised in that: the oxygen carrier includes following quality point
Several components:
Fe2O35%~65%
Hydroxyapatite 5%~65%
LaNiO3 30%~90%；
The oxygen carrier is prepared by the following method:
1. carrier hydroxyapatite/LaNiO3Preparation: lanthanum nitrate hexahydrate and nickel nitrate solution are mixed, are added dropwise in container,
Using sodium hydroxide as precipitating reagent, pH is adjusted, precipitating is complete；Calcium nitrate is dissolved in dehydrated alcohol, diammonium hydrogen phosphate is dissolved in deionization
Calcium nitrate solution and ammonium dibasic phosphate solution are mixed, are added dropwise in the complete liquid of above-mentioned precipitating, are adjusted with sodium hydroxide by water
PH carries out aging, suction filtration, washing, drying and roasting, obtains hydroxyapatite/LaNiO after precipitating completely3；
2. loading Fe2O3: use infusion process by Fe3+It loads on carrier, dry, roasting obtains the oxygen carrier.
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 oxygen carrier of any of claims 1 or 2, comprising the following steps:
1. carrier hydroxyapatite/LaNiO3Preparation: lanthanum nitrate hexahydrate and nickel nitrate solution are mixed, are added dropwise in container,
Using sodium hydroxide as precipitating reagent, pH is adjusted, precipitating is complete；Calcium nitrate is dissolved in dehydrated alcohol, diammonium hydrogen phosphate is dissolved in deionization
Calcium nitrate solution and ammonium dibasic phosphate solution are mixed, are added dropwise in the complete liquid of above-mentioned precipitating, are adjusted with sodium hydroxide by water
PH carries out aging, suction filtration, washing, drying and roasting, obtains hydroxyapatite/LaNiO after precipitating completely3；
2. loading Fe2O3: use infusion process by Fe3+It loads on carrier, dry, 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, adjusting pH value with sodium hydroxide is 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 roasting
Temperature is 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 roasting
Time is 2 ~ 15 hours.
7. application of the oxygen carrier of any of claims 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 be 600 ~
1200 DEG C, the reaction temperature in oxidation reactor is 600 ~ 1200 DEG C.
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| CN106629596A (en) | 2017-05-10 |
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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. |