CN105462650A - Aluminum-containing copper-based composite oxygen carrier and preparation method therefor - Google Patents
Aluminum-containing copper-based composite oxygen carrier and preparation method therefor Download PDFInfo
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- CN105462650A CN105462650A CN201410454323.8A CN201410454323A CN105462650A CN 105462650 A CN105462650 A CN 105462650A CN 201410454323 A CN201410454323 A CN 201410454323A CN 105462650 A CN105462650 A CN 105462650A
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- oxygen carrier
- base composite
- composite oxygen
- aluminum bronze
- bronze base
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Abstract
The invention discloses an aluminum-containing copper-based composite oxygen carrier and a preparation method therefor. The oxygen carrier is composed of CuO and Al2O3, wherein the mass percentage of CuO is 95% and the mass percentage of Al2O3 is 5%. According to the preparation method disclosed by the invention, the aluminum-containing copper-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 aluminum-containing copper-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 composite metal oxide oxygen carrier and its preparation method and application.
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, Cu, Co, Mn, and vitriol oxygen carrier and aluminium titanium ore type 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, propose the at high temperature active and cyclical stability reduction of CuO oxygen carrier in 32 (11): 13-17., easily occur 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, provide a kind of containing aluminium CuO composite oxygen carrier oxygen carrier granule and its preparation method and application.CuO oxygen carrier has higher activity and larger oxygen carrying capability, and CuO and carbon reaction are thermopositive reaction, can reduce the energy requirement in fuel reactor.But the fusing point that CuO is lower makes its at high temperature active and cyclical stability reduction, easily occurs sintering, at C
ual is added in O oxygen carrier oxygen carrier granule
2o
3obtain uniform particle sizes by sol-gel method, speed of reaction is faster containing aluminium CuO composite oxygen carrier.
In order to realize foregoing invention the technical solution adopted in the present invention be: a kind of containing aluminium CuO composite oxygen carrier, described oxygen carrier is by CuO and Al
2o
3composition, wherein the mass percent of CuO is 95%, Al
2o
3mass percent be 5%, this ratio fully can promote the reactivity worth of composite oxygen carrier.
Containing a preparation method for aluminium CuO composite oxygen carrier, comprise the following steps:
Step 1: by Al (NO
3)
3solution is added drop-wise to Cu (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 containing aluminum bronze base composite oxygen carrier.
Wherein, the Cu (NO described in step 1
3)
2with Al (NO
3)
3mass ratio be 12.02:1.
The mol ratio of the citric acid described in step 2 and Cu 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, good dispersion degree containing aluminum bronze base composite oxygen carrier.(2) the present invention is simple containing the preparation method of aluminum bronze base composite oxygen carrier, 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 unit mass 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 Cu (NO
3)
2product; Complexing agent is analytical pure citric acid; The metal nitrate of doping is analytical pure Al (NO
3)
3.
Embodiment 1:
Get 28.62gCu (NO
3)
23H
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 5.03gAl (NO
3)
39H
2o puts into the beaker of 100ml, adds the distilled water of 50ml, is stirred to and dissolves completely.Then aluminum nitrate solution 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.Xerogel is taken out, the retort furnace calcining 5 being placed in 500 DEG C is littlely decomposed completely up to citric acid and nitrate, again retort furnace is warming up to 800, DEG C constant temperature calcining 5 hours, for activating oxygen carrier, again the grinding of oxygen carrier oxygen carrier granule, screening are obtained complex metal oxides oxygen carrier, wherein the mass content of CuO is 95wt.%, Al
2o
3content be 5wt.%.As shown in Figure 1, the present invention contains aluminum bronze base composite oxygen carrier and does not mix Al
2o
3compare, oxygen release speed and oxygen release quality significantly improve.
Claims (10)
1., containing an aluminum bronze base composite oxygen carrier, it is characterized in that: described oxygen carrier is by CuO and Al
2o
3composition, wherein the mass percent of CuO is 95%, Al
2o
3mass percent be 5%.
2. according to claim 1 containing aluminum bronze base composite oxygen carrier, it is characterized in that described oxygen carrier is prepared by following steps:
Step 1: by Al (NO
3)
3solution is added drop-wise to Cu (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 containing aluminum bronze base composite oxygen carrier.
3. according to claim 2 containing aluminum bronze base composite oxygen carrier, it is characterized in that: the Cu (NO described in step 1
3)
2with Al (NO
3)
3mass ratio be 12.02:1.
4. according to claim 2 containing aluminum bronze base composite oxygen carrier, it is characterized in that: the mol ratio of the citric acid described in step 2 and Cu atom is 2:1.
5. according to claim 2 containing aluminum bronze base composite oxygen carrier, it is characterized in that: in step 3, drying conditions is at 105 DEG C dry 24 hours.
6. according to claim 2 containing aluminum bronze base composite oxygen carrier, it 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., containing a preparation method for aluminum bronze base composite oxygen carrier, it is characterized in that comprising the following steps:
Step 1: by Al (NO
3)
3solution is added drop-wise to Cu (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 containing aluminum bronze base composite oxygen carrier.
8. the preparation method containing aluminum bronze base composite oxygen carrier according to claim 7, is characterized in that: the Cu (NO described in step 1
3)
2with Al (NO
3)
3mass ratio be 12.02:1, the mol ratio of the citric acid described in step 2 and Cu atom is 2:1.
9. the preparation method containing aluminum bronze base 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. copper according to claim 7 is containing the preparation method of aluminum-base composite oxygen carrier, it 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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|---|---|---|---|
| CN201410454323.8A CN105462650A (en) | 2014-09-05 | 2014-09-05 | Aluminum-containing copper-based composite oxygen carrier and preparation method therefor |
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|---|---|---|---|
| CN201410454323.8A CN105462650A (en) | 2014-09-05 | 2014-09-05 | Aluminum-containing copper-based composite oxygen carrier and preparation method therefor |
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|---|---|
| CN105462650A true CN105462650A (en) | 2016-04-06 |
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ID=55600818
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116179171A (en) * | 2023-03-02 | 2023-05-30 | 昆明理工大学 | Preparation method of core-shell structure Al-Cu@CuO composite phase change heat storage material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952603A (en) * | 2012-11-07 | 2013-03-06 | 华中科技大学 | Method and device for batch preparation of chemical chain combustion oxygen carriers |
| CN103215104A (en) * | 2013-04-24 | 2013-07-24 | 南京理工大学 | Mixed metal oxide oxygen carrier and preparation method thereof |
| CN103361146A (en) * | 2012-04-01 | 2013-10-23 | 清华大学 | Preparation method of high performance oxygen-carrying particles |
-
2014
- 2014-09-05 CN CN201410454323.8A patent/CN105462650A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361146A (en) * | 2012-04-01 | 2013-10-23 | 清华大学 | Preparation method of high performance oxygen-carrying particles |
| CN102952603A (en) * | 2012-11-07 | 2013-03-06 | 华中科技大学 | Method and device for batch preparation of chemical chain combustion oxygen carriers |
| CN103215104A (en) * | 2013-04-24 | 2013-07-24 | 南京理工大学 | Mixed metal oxide oxygen carrier and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116179171A (en) * | 2023-03-02 | 2023-05-30 | 昆明理工大学 | Preparation method of core-shell structure Al-Cu@CuO composite phase change heat storage material |
| CN116179171B (en) * | 2023-03-02 | 2024-01-26 | 昆明理工大学 | Preparation method of core-shell structure Al-Cu@CuO composite phase change heat storage material |
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Application publication date: 20160406 |