CN105462649A - Calcium-containing cobalt-based composite oxygen carrier and preparation method therefor - Google Patents
Calcium-containing cobalt-based composite oxygen carrier and preparation method therefor Download PDFInfo
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- CN105462649A CN105462649A CN201410454239.6A CN201410454239A CN105462649A CN 105462649 A CN105462649 A CN 105462649A CN 201410454239 A CN201410454239 A CN 201410454239A CN 105462649 A CN105462649 A CN 105462649A
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- oxygen carrier
- based composite
- calcic
- cobalt
- composite oxygen
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Abstract
The invention discloses a calcium-containing cobalt-based composite oxygen carrier and a preparation method therefor. The oxygen carrier is composed of Co3O4 and CaO, wherein the mass percentage of Co3O4 is 95% and the mass percentage of CaO is 5%. According to the preparation method disclosed by the invention, the calcium-containing cobalt-based composite oxygen carrier which is uniform in grain size and good in dispersity is prepared by controlling appropriate reaction conditions by virtue of a sol-gel method. The calcium-containing cobalt-based composite oxygen carrier is simple in preparation method, and the prepared composite oxygen carrier has a relatively great reaction rate, and the oxygen release rate is obviously increased.
Description
Technical field
The invention belongs to the preparing technical field of oxygen carrier oxygen carrier granule in chemical chain oxygen decoupled system, be specifically related to a kind of calcic cobalt-based composite oxygen carrier and preparation method thereof.
Background technology
The global warming issue that greenhouse gas emission brings is causing the attention of people.CO
2as topmost greenhouse gases, research CO
2emission-reduction technology is extremely urgent.CO in flue gas
2usually by a large amount of nitrogen dilution, CO
2separation and cost recovery very high.Generate the CO of high density in combustion
2or be convenient to CO
2the gas phase mixture be separated, eliminates the generation of other pollutents simultaneously, discharge is an effective way.Burning chemistry chains (Chemical-LoopingCombustion is called for short CLC) has a kind of new combustion mode of above-mentioned characteristic just, has received more concern.
The ultimate principle of burning chemistry chains (chemicalloopingcombustion) is the direct reaction of fuel by traditional and air, be two step gas-solid reactions by the action breaks of oxygen carrier, fuel does not directly contact with air, but between the reactor of two series connection, the transfer of oxygen has been carried out by oxygen carrier, two reactors are respectively air reactor and fuel reactor, and burning chemistry chains achieves the cascade utilization of fuel chemical energy.
Oxygen carrier is the medium of burning chemistry chains, circulate between two reactors, ceaselessly the heat that the oxygen generated in air reactor and reaction generate is delivered in fuel reactor and carries out reduction reaction, therefore, the performance of oxygen carrier directly affects the operation of whole burning chemistry chains.
At present, the main research of oxygen carrier concentrates on the oxide compound of the transition metal such as Ni, Fe, Co, Co, Mn and vitriol oxygen carrier and perovskite typed oxygen carrier etc.Metal oxide oxygen carrier is paid close attention to widely owing to having higher reactivity and resistant to elevated temperatures advantage and receiving, but also there is the shortcomings such as speed of reaction is fast not.
Wang Jie, Wang Wenju etc. the progress [J] of oxygen carrier in chemical chain burning technology. modern chemical industry, 2012, in 32 (11): 13-17., Co is proposed
3o
4oxygen carrier at high temperature active and cyclical stability reduces, and easily occurs sintering, the shortcomings such as speed of reaction is fast not.
Summary of the invention
The object of the invention is to the shortcoming overcoming prior art existence, a kind of calcic Co is provided
3o
4composite oxygen carrier particles and its preparation method and application.Co
3o
4oxygen carrier has higher activity and larger oxygen carrying capability, Co
3o
4react for thermopositive reaction with carbon, the energy requirement in fuel reactor can be reduced.But Co
3o
4lower fusing point makes its at high temperature active and cyclical stability reduction, easily occurs sintering, at Co
3o
4add CaO in oxygen carrier oxygen carrier granule and obtain uniform particle sizes by sol-gel method, speed of reaction is calcic Co faster
3o
4composite oxygen carrier.
In order to realize foregoing invention the technical solution adopted in the present invention be: a kind of calcic Co
3o
4composite oxygen carrier, described oxygen carrier is by Co
3o
4with CaO composition, wherein Co
3o
4mass percent be the mass percent of 95%, CaO be 5%, this ratio fully can promote the reactivity worth of composite oxygen carrier.
A kind of calcic Co
3o
4the preparation method of composite oxygen carrier, comprises the following steps:
Step 1: by Ca (NO
3)
2solution is added drop-wise to Co (NO
3)
2in solution, be stirred to and mix;
Step 2: add citric acid solution again, 70-80 DEG C evaporates limit below and is stirred to mixed solution formation wet gel;
Step 3: become xerogel after wet gel drying;
Step 4: be fired to organism Thorough combustion at xerogel being placed in 500 DEG C and nitrate decomposes completely, then be warming up to 800 DEG C, activation oxygen carrier;
Step 5: oxygen carrier granule grinding step 4 obtained, screening can obtain calcic cobalt-based composite oxygen carrier.
Wherein, the Co (NO described in step 1
3)
2with Ca (NO
3)
2mass ratio be 18.12:1.
The mol ratio of the citric acid described in step 2 and Co atom is 2:1.
In step 3, drying conditions is at 105 DEG C dry 24 hours.
In step 4, calcination condition is calcine 5 hours at 500 DEG C, after being warming up to 800 DEG C, activates 5 hours.
The present invention's advantage is compared with prior art: (one) the present invention adopts sol-gel method, controls suitable reaction conditions, prepares uniform particle sizes, the calcic cobalt-based composite oxygen carrier of good dispersion degree.(2) preparation method of calcic cobalt-based composite oxygen carrier of the present invention is simple, and the composite oxygen carrier prepared has speed of reaction and higher oxygen release quality faster, and oxygen release speed and oxygen release quality are obviously promoted.
Accompanying drawing explanation
Fig. 1 is the oxygen carrier oxygen release conversion rate curve that composite oxygen carrier of the present invention is drawn by tube furnace.
Embodiment
The present invention is further illustrated below in conjunction with example:
Composition graphs 1, the raw material in the present embodiment is analytical pure Co (NO
3)
2product; Complexing agent is analytical pure citric acid; The metal nitrate of doping is analytical pure Ca (NO
3)
2.
Embodiment 1:
Get 38.62gCo (NO
3)
26H
2o puts into the beaker of 500ml, adds the distilled water of 100ml, then beaker is placed on the magnetic stirring apparatus with water bath with thermostatic control, and stirring velocity is 400rpm.Get 4.86gCa (NO
3)
24H
2o puts into the beaker of 100ml, adds the distilled water of 50ml, is stirred to and dissolves completely.Then ca nitrate soln is added drop-wise in copper nitrate solution, dropping limit, limit is stirred.Get 49.87g citric acid, be placed with in the beaker of 100ml distilled water and be stirred to whole dissolving, after above-mentioned solution stirring is even, add citric acid solution slowly, dropping limit, limit is stirred.Stir after 6 hours, solution has dewatered and has become thick wet gel.Wet gel is placed in the air dry oven of 105 DEG C, after dry 24 hours, in beaker, wet gel becomes xerogel.Taken out by xerogel, the retort furnace calcining 5 being placed in 500 DEG C is littlely decomposed completely up to citric acid and nitrate, then retort furnace is warming up to 800 DEG C, constant temperature calcining 5 hours, for activating oxygen carrier, then the grinding of oxygen carrier oxygen carrier granule, screening are obtained complex metal oxides oxygen carrier, wherein Co
3o
4mass content be the content of 95wt.%, CaO be 5wt.%.As shown in Figure 1, calcic cobalt-based composite oxygen carrier of the present invention with do not mix compared with CaO, oxygen release speed and oxygen release quality significantly improve.
Claims (10)
1. a calcic cobalt-based composite oxygen carrier, is characterized in that: described oxygen carrier is by Co
3o
4with CaO composition, wherein Co
3o
4mass percent be the mass percent of 95%, CaO be 5%.
2. calcic cobalt-based composite oxygen carrier according to claim 1, it is characterized in that, described oxygen carrier is prepared by following steps:
Step 1: by Ca (NO
3)
2solution is added drop-wise to Co (NO
3)
2in solution, be stirred to and mix;
Step 2: add citric acid solution again, 70-80 DEG C evaporates limit below and is stirred to mixed solution formation wet gel;
Step 3: become xerogel after wet gel drying;
Step 4: be fired to organism Thorough combustion at xerogel being placed in 500 DEG C and nitrate decomposes completely, then be warming up to 800 DEG C, activation oxygen carrier;
Step 5: oxygen carrier granule grinding step 4 obtained, screening can obtain calcic cobalt-based composite oxygen carrier.
3. calcic cobalt-based composite oxygen carrier according to claim 2, is characterized in that: the Co (NO described in step 1
3)
2with Ca (NO
3)
2mass ratio be 18.12:1.
4. calcic cobalt-based composite oxygen carrier according to claim 2, is characterized in that: the mol ratio of the citric acid described in step 2 and Co atom is 2:1.
5. calcic cobalt-based composite oxygen carrier according to claim 2, is characterized in that: in step 3, drying conditions is at 105 DEG C dry 24 hours.
6. calcic cobalt-based composite oxygen carrier according to claim 2, is characterized in that: in step 4, calcination condition is calcine 5 hours at 500 DEG C, after being warming up to 800 DEG C, activates 5 hours.
7. a preparation method for calcic cobalt-based composite oxygen carrier, is characterized in that, comprises the following steps:
Step 1: by Ca (NO
3)
2solution is added drop-wise to Co (NO
3)
2in solution, be stirred to and mix;
Step 2: add citric acid solution again, 70-80 DEG C evaporates limit below and is stirred to mixed solution formation wet gel;
Step 3: become xerogel after wet gel drying;
Step 4: be fired to organism Thorough combustion at xerogel being placed in 500 DEG C and nitrate decomposes completely, then be warming up to 800 DEG C, activation oxygen carrier;
Step 5: oxygen carrier granule grinding step 4 obtained, screening can obtain calcic cobalt-based composite oxygen carrier.
8. the preparation method of calcic cobalt-based composite oxygen carrier according to claim 7, is characterized in that: the Co (NO described in step 1
3)
2with Ca (NO
3)
2mass ratio be 18.12:1, the mol ratio of the citric acid described in step 2 and Co atom is 2:1.
9. the preparation method of calcic cobalt-based composite oxygen carrier according to claim 7, is characterized in that: in step 3, drying conditions is at 105 DEG C dry 24 hours.
10. the preparation method of calcic cobalt-based composite oxygen carrier according to claim 7, is characterized in that: in step 4, calcination condition is calcine 5 hours at 500 DEG C, after being warming up to 800 DEG C, activates 5 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107090323A (en) * | 2017-03-03 | 2017-08-25 | 中国科学院青岛生物能源与过程研究所 | It is a kind of that there is composite oxygen carrier of control oxidative function and preparation method thereof |
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|---|---|---|---|---|
| CN103113955A (en) * | 2013-02-01 | 2013-05-22 | 东南大学 | Preparation method of nano porous iron-base oxygen carrier for biological oil chemical-looping hydrogen production |
| CN103789061A (en) * | 2014-01-17 | 2014-05-14 | 南京理工大学 | Cobalt-based composite oxygen carrier and preparation method thereof |
| CN103785389A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | High-activity oxygen carrier and preparation method and application thereof |
| CN103980977A (en) * | 2014-05-16 | 2014-08-13 | 南京理工大学 | Manganese-based compound oxygen carrier and preparation method thereof |
-
2014
- 2014-09-05 CN CN201410454239.6A patent/CN105462649A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785389A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | High-activity oxygen carrier and preparation method and application thereof |
| CN103113955A (en) * | 2013-02-01 | 2013-05-22 | 东南大学 | Preparation method of nano porous iron-base oxygen carrier for biological oil chemical-looping hydrogen production |
| CN103789061A (en) * | 2014-01-17 | 2014-05-14 | 南京理工大学 | Cobalt-based composite oxygen carrier and preparation method thereof |
| CN103980977A (en) * | 2014-05-16 | 2014-08-13 | 南京理工大学 | Manganese-based compound oxygen carrier and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107090323A (en) * | 2017-03-03 | 2017-08-25 | 中国科学院青岛生物能源与过程研究所 | It is a kind of that there is composite oxygen carrier of control oxidative function and preparation method thereof |
| CN107090323B (en) * | 2017-03-03 | 2019-09-17 | 中国科学院青岛生物能源与过程研究所 | A kind of composite oxygen carrier and preparation method thereof with control oxidative function |
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Application publication date: 20160406 |