CN103387865B - High-performance double-core iron-based oxygen carrier particle and preparation method thereof - Google Patents
High-performance double-core iron-based oxygen carrier particle and preparation method thereof Download PDFInfo
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- CN103387865B CN103387865B CN201210144139.4A CN201210144139A CN103387865B CN 103387865 B CN103387865 B CN 103387865B CN 201210144139 A CN201210144139 A CN 201210144139A CN 103387865 B CN103387865 B CN 103387865B
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Abstract
The invention provides a high-performance double-core iron-based oxygen carrier particle and a preparation method thereof. An oxygen carrier is an inert-component loaded active metal oxide, and the metal oxide comprises two active metal oxides as active components, wherein one of the active metal oxides is iron oxide. The high-performance double-core iron-based oxygen carrier particle has the advantages of simple preparation technology, the prepared double-core iron-based oxygen carrier particle has greatly improved performances compared with a mono-core iron-based oxygen carrier, and high conversion rates of raw materials in chemical chain combustion technology can be realized.
Description
Technical field
The invention belongs to the preparing technical field of oxygen carrier granule in burning chemistry chains system, particularly one is applicable to chemical chain burning technology, by the preparation method of metal oxide as the oxygen carrier granule of oxygen carrier.
Background technology
Chemical chain burning technology is a kind of novel flameless combustion technology, the advantage of this technology be fuel in its process of burning, Sauerstoffatom realizes the transmission from oxygen to fuel by oxygen carrier, and when using carbonaceous fuel, product only has CO
2and H
2o, just lower energy consumption can realize CO by simple condensation
2reduction of discharging, meanwhile also thoroughly eradicated all kinds of NO
xgeneration.In addition, because oxygen carrier circulates between reactor, achieve the transmission of heat, effectively improve the efficiency of burning chemistry chains system.Chemical chain burning technology has efficiently, clean and economic feature, and the preparation of oxygen carrier and to choose be the key realizing chemical chain burning technology.Oxygen carrier plays the effect of transmitting oxygen and heat in chemical chain burning technology, and therefore the performance of oxygen carrier directly affects the operation of whole burning chemistry chains system, requires that oxygen carrier possesses the feature of high reaction activity, high circulation activity.Oxygen carrier conventional mostly at present is metal oxide, and mainly contain Ni, Fe, CO, Cu, Mn, Ce, inert support mainly contains Al
2o
3, SiO
2, MgAl
2o
4, wilkinite, different active ingredients and inert component and preparation method, sintering temperature can have an impact to the performance of oxygen carrier.Other oxygen carrier relatively, it is high, cheap that iron-based oxygen carrier has oxygen carrier rate, environmental friendliness, can be used for the features such as chemical chain reforming hydrogen producing technology simultaneously.But for iron-based oxygen carrier, the speed of itself and fuel reaction is lower than the oxygen carrier such as nickel, copper.
Summary of the invention
The object of the invention is to solve the deficiencies in the prior art, provide one to carry high performance iron-based oxygen carrier and preparation method thereof, this oxygen carrier can realize the high conversion of chemical chain burning technology Raw.
For achieving the above object, technical scheme of the present invention is:
A kind of high-performance double-core iron-based oxygen carrier granule, oxygen carrier is the active metal oxide of inert component load, and described metal oxide comprises two kinds of active metal oxide as active ingredient, and wherein a kind of active metal oxide is ferric oxide.
Preferably, the weight ratio of described ferric oxide and other active metal oxide is: 65 ~ 99:1 ~ 35.
Preferably, other active metal oxide described is nickel oxide, cupric oxide, manganese oxide, cobalt oxide, cerium oxide or zinc oxide.
Preferably, two kinds of active metal oxide content of described inert component load account for the 40-80% of oxygen carrier gross weight.
Wherein, described inert component is preferably adopted as Al
2o
3, MgAl
2o
4, wilkinite or ZrO
2.
In order to prepare above-mentioned high-performance double-core iron-based oxygen carrier granule, invention further provides its preparation method, essential core is: prepare in oxygen carrier process, adds other metallic salt a kind of, obtain oxygen carrier granule through sintering in molysite.
Preferably, above-mentioned preparation method specifically comprises the steps:
(1) aluminum isopropylate is added in appropriate deionized water, be fully hydrolyzed, the Virahol generated by hydrolysis volatilization hydrolysis;
(2) get molysite and other active metal salt a kind of in proportion, dissolve, be mixed in deionized water; Then be added in the solution in step (1);
(3) abundant mix and blend, sintering obtains oxygen carrier.
The present invention adopts and add other activating oxide in iron-based oxygen carrier, can increase substantially the active speed of oxygen carrier and fuel.Except preparation method provided by the invention, double-core iron-based oxygen carrier can also apply other preparation method of the prior art and the different inert support of available selective gist, has suitability widely.The invention provides oxygen carrier granule and preparation method thereof, not affect original uniform and stable, high temperature resistant, the reproducibility of iron-based oxygen carrier strong, and its preparation technology is simple, improves a lot to the reactivity worth of iron-based oxygen carrier.
Accompanying drawing explanation
Fig. 1-5 is oxygen carrier transformation efficiency variation diagrams in time on TGA prepared in embodiment of the present invention 1-5;
Wherein, X=(m
ox-m)/(m
ox-m
red)
In formula:
M: sample quality
M
red: reduction-state sample quality
M
ox: oxidation state sample quality
In Fig. 1, Fe-Al represents with Al
2o
3for inert support, with Fe
2o
3for the oxygen carrier of active ingredient.Under Fe-Ni-Al represents similarity condition, with Al
2o
3for inert support, with Fe
2o
3be the oxygen carrier of active ingredient with NiO.The rest may be inferred, and Fe-Cu-Al, Fe-Co-Al, Fe-Mn-Al, Fe-Ce-Al in other figure represent respectively with Al
2o
3for inert support, with Fe
2o
3active metal corresponding to other is as the oxygen carrier of active ingredient.
Embodiment
The present invention is further illustrated below by embodiment, but not as limit.
It should be noted that, double-core iron-based oxygen carrier provided by the present invention, its core is that active ingredient contains ferric oxide and other active metal ferric oxide, and it can adopt any feasible inert component and any feasible preparation method in prior art.
Preparation method of the present invention mainly comprises: prepare in iron-based oxygen carrier process, need to use molysite, in molysite, add other active metal salt of corresponding proportion, mix, after evaporation drying, sintering obtains the oxygen carrier granule that active ingredient comprises ferric oxide and other activating oxide.Active metal oxide preferential oxidation nickel wherein, cupric oxide, manganese oxide, cobalt oxide, cerium oxide, zinc oxide, be more preferably nickel oxide, cupric oxide, cobalt oxide.Particularly, mixed processes, drying process and dried sintering circuit, as it will be appreciated by those skilled in the art that be, can adopt any feasible equipment and process process in prior art.
As preferably, the invention provides a kind of with Al
2o
3as the oxygen carrier preparation method of inert support, during preparation, using aluminum isopropylate as reaction raw materials, after carrying out for some time at a certain temperature, pass through poly-condensation and hydrolysis, stable, uniform sol system can be formed, add molysite and other active metal salt solution, still can keep its stable, uniform state.The colloidal sol of above-mentioned acquisition, through ageing, drying, calcining, can obtain required oxygen carrier granule.The reaction that wherein above-mentioned preparation method relates to comprises:
Hydrolysis reaction:
Al(OR)
3+xH
2O→Al(OR)
3-x(OH)
x+xROH
Polycondensation:
2Al(OR)
3-x(OH)
x→[Al(OR)
3-x(OH)
x-1]
2O+H
2O
(OR)
3-x(OH)
x-1AlOH+ROAl(OR)
2-x(OH)
x→(OR)
3-x(OH)
x-1Al-O-Al(OR)
2-x(OH)
x+ROH
In above-mentioned reaction formula, R represents sec.-propyl (-CH (CH
3)
2).
Embodiment 1:
Get 56.7g aluminum isopropylate, aluminum isopropylate is added in 500ml water, under 90 DEG C of conditions, start hydrolysis.After hydrolysis for some time, the Virahol of the generation of uncovered volatilization hydrolysis.Then salpeter solution is added, after being fully hydrolyzed, the Virahol that uncovered volatilization hydrolysis generates.Get 162gFe (NO
3)
3* 9H
2o, 3.86gNi (NO
3)
2* 6H
2o is dissolved in appropriate deionized water.After aluminum isopropylate is fully hydrolyzed, by Fe (NO
3)
3with Ni (NO
3)
2mixing solutions slowly add, after mixing, under 90 DEG C of conditions, keep 30min.Sample is placed in baking oven dry, temperature programming is calcined.Final calcining temperature is 1000 DEG C, can obtain required oxygen carrier.This oxygen carrier is with Al
2o
3for inert support, with Fe
2o
3be active ingredient with NiO, wherein NiO accounts for 3% of active ingredient, accounts for 2.1% of oxygen carrier gross weight.
Embodiment 2:
Get 56.7g aluminum isopropylate, aluminum isopropylate is added in 500ml water, under 90 DEG C of conditions, start hydrolysis.After hydrolysis for some time, the Virahol of the generation of uncovered volatilization hydrolysis.Then salpeter solution is added, after being fully hydrolyzed, the Virahol that uncovered volatilization hydrolysis generates.Get 162gFe (NO
3)
3* 9H
2o, 3.01gCu (NO
3)
2* 3H
2o is dissolved in appropriate deionized water.After aluminum isopropylate is fully hydrolyzed, by Fe (NO
3)
3with Cu (NO
3)
2mixing solutions slowly add, after mixing, under 90 DEG C of conditions, keep 30min.Sample is placed in baking oven dry, temperature programming is calcined.Final calcining temperature is 1000 DEG C, can obtain required oxygen carrier.This oxygen carrier is with Al
2o
3for inert support, with Fe
2o
3be active ingredient with CuO, wherein CuO accounts for 3% of active ingredient, accounts for 2.1% of oxygen carrier gross weight.
Embodiment 3:
Get 56.7g aluminum isopropylate, aluminum isopropylate is added in 500ml water, under 90 DEG C of conditions, start hydrolysis.After hydrolysis for some time, the Virahol of the generation of uncovered volatilization hydrolysis.Then salpeter solution is added, after being fully hydrolyzed, the Virahol that uncovered volatilization hydrolysis generates.Get 162gFe (NO
3)
3* 9H
2o, 3.85gCo (NO
3)
2* 6H
2o is dissolved in appropriate deionized water.After aluminum isopropylate is fully hydrolyzed, by Fe (NO
3)
3with Co (NO
3)
2mixing solutions slowly add, after mixing, under 90 DEG C of conditions, keep 30min.Sample is placed in baking oven dry, temperature programming is calcined.Final calcining temperature is 1000 DEG C, can obtain required oxygen carrier.This oxygen carrier is with Al
2o
3for inert support, with Fe
2o
3be active ingredient with CoO, wherein CoO accounts for 3% of active ingredient, accounts for 2.1% of oxygen carrier gross weight.
Embodiment 4:
Get 56.7g aluminum isopropylate, aluminum isopropylate is added in 500ml water, under 90 DEG C of conditions, start hydrolysis.After hydrolysis for some time, the Virahol of the generation of uncovered volatilization hydrolysis.Then salpeter solution is added, after being fully hydrolyzed, the Virahol that uncovered volatilization hydrolysis generates.Get 162gFe (NO
3)
3* 9H
2o, 3.50gMn (NO
3)
2* 6H
2o is dissolved in appropriate deionized water.After aluminum isopropylate is fully hydrolyzed, by Fe (NO
3)
3with Mn (NO
3)
2mixing solutions slowly add, after mixing, under 90 DEG C of conditions, keep 30min.Sample is placed in baking oven dry, temperature programming is calcined.Final calcining temperature is 1000 DEG C, can obtain required oxygen carrier.This oxygen carrier is with Al
2o
3for inert support, with Fe
2o
3be active ingredient with MnO, wherein MnO accounts for 3% of active ingredient, accounts for 2.1% of oxygen carrier gross weight.
Embodiment 5:
Get 56.7g aluminum isopropylate, aluminum isopropylate is added in 500ml water, under 90 DEG C of conditions, start hydrolysis.After hydrolysis for some time, the Virahol that uncovered volatilization hydrolysis generates.Then salpeter solution is added, after being fully hydrolyzed, the Virahol of the generation of uncovered volatilization hydrolysis.Get 162gFe (NO
3)
3* 9H
2o, 2.63gCe (NO
3)
3* 6H
2o is dissolved in appropriate deionized water.After aluminum isopropylate is fully hydrolyzed, by Fe (NO
3)
3with Ce (NO
3)
3mixing solutions slowly add, after mixing, under 90 DEG C of conditions, keep 30min.Sample is placed in baking oven dry, temperature programming is calcined.Final calcining temperature is 1000 DEG C, can obtain required oxygen carrier.This oxygen carrier is with Al
2o
3for inert support, with Fe
2o
3and CeO
2for active ingredient, wherein CeO
2account for 3% of active ingredient, account for 2.1% of oxygen carrier gross weight.
Embodiment 6:
Get 56.7g aluminum isopropylate, aluminum isopropylate is added in 500ml water, under 90 DEG C of conditions, start hydrolysis.After hydrolysis for some time, the Virahol of the generation of uncovered volatilization hydrolysis.Then salpeter solution is added, after being fully hydrolyzed, the Virahol of the generation of uncovered volatilization hydrolysis.Get 77.74gFeCl
3* 6H
2o, 49.03gCuCl
2* 2H
2o is dissolved in appropriate deionized water.After aluminum isopropylate is fully hydrolyzed, by FeCl
3* 6H
2o and CuCl
2* 6H
2the mixing solutions of O is slowly added, and after mixing, under 90 DEG C of conditions, keeps 30min.Sample is placed in baking oven dry, temperature programming is calcined.Final calcining temperature is 1000 DEG C, can obtain required oxygen carrier.This oxygen carrier is with Al
2o
3for inert support, with Fe
2o
3be active ingredient with CuO, wherein CuO accounts for 50% of active ingredient, accounts for 35% of oxygen carrier gross weight.
Above-described embodiment prepares the double-core iron-based oxygen carrier of gained, compare with monokaryon iron-based oxygen carrier, from Fig. 1-5, can find out significantly, double-core iron-based oxygen carrier is higher than the transformation efficiency of monokaryon iron-based oxygen carrier, the active speed of oxygen carrier and fuel can be increased substantially thus, improve reactivity worth.
It should be noted that and the foregoing is only preferred embodiment of the present invention, not thereby limit scope of patent protection of the present invention, the present invention can also replace the concrete operation step in aforesaid method and various reactant.Therefore the equivalence change that all utilizations specification sheets of the present invention and diagramatic content are done, or directly or indirectly apply to other correlative technology field and be all in like manner all contained in the scope that the present invention contains.
Claims (7)
1. a high-performance double-core iron-based oxygen carrier granule, oxygen carrier is the active metal oxide of inert component load, it is characterized in that, described metal oxide comprises two kinds of active metal oxide as active ingredient, and wherein a kind of active metal oxide is ferric oxide; The weight ratio of described ferric oxide and other active metal oxide is: 65 ~ 99:1 ~ 35; Two kinds of active metal oxide content of described inert component load account for the 40-80% of oxygen carrier gross weight.
2. oxygen carrier granule as claimed in claim 1, it is characterized in that, other active metal oxide described is nickel oxide, cupric oxide, manganese oxide, cobalt oxide, cerium oxide or zinc oxide.
3. oxygen carrier granule as claimed in claim 2, it is characterized in that, described inert component is Al
2o
3, MgAl
2o
4, wilkinite or ZrO
2.
4. the preparation method of a high-performance double-core iron-based oxygen carrier granule, this oxygen carrier is the active metal oxide of inert component load, described metal oxide comprises two kinds of active metal oxide as active ingredient, and wherein a kind of active metal oxide is ferric oxide; It is characterized in that,
Prepare in oxygen carrier process, in molysite, add other metallic salt a kind of, obtain oxygen carrier granule through sintering; The weight ratio of described ferric oxide and other active metal oxide is: 65 ~ 99:1 ~ 35, and two kinds of active metal oxide content of described inert component load account for the 40-80% of oxygen carrier gross weight.
5. preparation method according to claim 4, it is characterized in that, described active metal oxide is nickel oxide, cupric oxide, manganese oxide, cobalt oxide, cerium oxide or zinc oxide.
6. preparation method as claimed in claim 5, it is characterized in that, the inert component of described iron-based oxygen carrier is Al
2o
3, MgAl
2o
4, wilkinite or ZrO
2.
7. preparation method as claimed in claim 6, is characterized in that, specifically comprise the steps:
(1) aluminum isopropylate is added in appropriate deionized water, be fully hydrolyzed, the Virahol generated by hydrolysis volatilization hydrolysis;
(2) get molysite and other active metal salt a kind of in proportion, dissolve, be mixed in deionized water; Then be added in the solution in step (1);
(3) abundant mix and blend, sintering obtains oxygen carrier.
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| CN103849444A (en) * | 2014-03-17 | 2014-06-11 | 南京理工大学 | Copper-based compound oxygen carrier and preparation method thereof |
| CN108410498B (en) * | 2018-04-19 | 2020-10-27 | 大连理工大学 | Chemical chain circulation partial oxidation heavy oil processing method |
| CN110055120A (en) * | 2019-06-06 | 2019-07-26 | 河南城建学院 | A kind of preparation method and system of burning chemistry chains composite oxygen carrier |
| CN112408320A (en) * | 2020-11-27 | 2021-02-26 | 华中科技大学 | Load type double-active metal composite oxygen carrier and preparation method and application thereof |
| CN114735648B (en) * | 2021-01-07 | 2023-07-28 | 中国石油化工股份有限公司 | Oxygen carrier for chemical looping hydrogen production and preparation method and application thereof |
| CN114853076B (en) * | 2022-04-29 | 2024-04-09 | 东南大学 | Manganese modified iron-based oxygen carrier particle and preparation method thereof |
| CN115716660A (en) * | 2022-10-14 | 2023-02-28 | 东南大学 | Composite ternary metal oxide oxygen carrier material and preparation method and application thereof |
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| CN101906344A (en) * | 2010-08-12 | 2010-12-08 | 青岛科技大学 | Preparation method of multifunctional composite type oxygen carrier granules |
| CN102443454A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Oxygen carrier of chemical-looping combustion and preparation method and application thereof |
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| CN101906344A (en) * | 2010-08-12 | 2010-12-08 | 青岛科技大学 | Preparation method of multifunctional composite type oxygen carrier granules |
| CN102443454A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Oxygen carrier of chemical-looping combustion and preparation method and application thereof |
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