CN104119984A - Calcium-containing copper-based composite oxygen carrier and preparation method thereof - Google Patents
Calcium-containing copper-based composite oxygen carrier and preparation method thereof Download PDFInfo
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- CN104119984A CN104119984A CN201410385734.6A CN201410385734A CN104119984A CN 104119984 A CN104119984 A CN 104119984A CN 201410385734 A CN201410385734 A CN 201410385734A CN 104119984 A CN104119984 A CN 104119984A
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- oxygen carrier
- calcic
- copper base
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Abstract
The invention discloses a calcium-containing copper-based composite oxygen carrier and a preparation method thereof. The oxygen carrier comprises the following components in percentage by mass: 95% of CuO and 5% of CaO. By adopting a sol-gel method, the calcium-containing copper-based composite oxygen carrier which is uniform in particle size and good in dispersity can be prepared by controlling proper reaction conditions; the preparation method of the calcium-containing copper-based composite oxygen carrier is simple, the prepared composite oxygen carrier has higher reaction rate, and the oxygen release rate can be obviously promoted.
Description
Technical field
The invention belongs to the preparing technical field of 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 people's attention.CO
2as topmost greenhouse gases, research CO
2emission-reduction technology is extremely urgent.CO in flue gas
2usually by a large amount of nitrogen dilutions, CO
2separation and cost recovery very high.In combustion processes, generate the CO of high density
2or be convenient to CO
2the gas phase mixture separating, generation, the discharge of eliminating other pollutents are effective ways simultaneously.Burning chemistry chains (Chemical-Looping Combustion is called for short CLC) has the novel combustion system of one of above-mentioned characteristic just, has been subjected to more concern.
The ultimate principle of burning chemistry chains (chemical looping combustion) is by the direct reaction of traditional fuel and air, be decomposed into two step gas-solid reactions by the effect of oxygen carrier, fuel does not directly contact with air, but between the reactor of two series connection, complete the transfer of oxygen by oxygen carrier, two reactors are respectively air reactor and fuel reactor, and burning chemistry chains has been realized the cascade utilization of fuel chemical energy.
Oxygen carrier is the medium of burning chemistry chains, between two reactors, circulate, ceaselessly the heat of the oxygen generating in air reactor and reaction generation is delivered in fuel reactor and carries out reduction reaction, therefore, the performance of oxygen carrier has directly affected 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 perovskite typed oxygen carrier etc.Metal oxide oxygen carrier has been subject to paying close attention to widely owing to having compared with high reactivity and resistant to elevated temperatures advantage, but also exists the shortcomings such as speed of reaction is fast not.
Wang Jie, Wang Wenju etc. the progress of oxygen carrier [J] in chemical chain burning technology. modern chemical industry, 2012,32 (11): in 13-17., propose the at high temperature active and cyclical stability reduction of CuO oxygen carrier, easily occur sintering, the shortcoming such as speed of reaction is fast not.
Summary of the invention
The object of the invention is to overcome the shortcoming that prior art exists, a kind of calcic CuO composite oxygen carrier particles and its preparation method and application is provided.CuO oxygen carrier has higher active and larger oxygen carrying capability, and CuO and carbon reaction, for 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, in CuO oxygen carrier granule, adding CaO, to obtain particle diameter by sol-gel method even, and speed of reaction is the compound oxygen carrier of calcic CuO faster.
In order to realize foregoing invention the technical solution adopted in the present invention be: the compound oxygen carrier of a kind of calcic CuO, described oxygen carrier is made up of CuO and CaO, the mass percent that wherein mass percent of CuO is 95%, CaO is 5%, and this ratio can fully promote the reactivity worth of compound oxygen carrier.
A preparation method for the compound oxygen carrier of calcic CuO, comprises the following steps:
Step 1: by Ca (NO
3)
2solution is added drop-wise to Cu (NO
3)
2in solution, be stirred to and mix;
Step 2: add citric acid solution, 70-80 DEG C evaporates below limit and be stirred to mixed solution formation wet gel again;
Step 3: become xerogel after wet gel is dry;
Step 4: xerogel is placed in and is fired at 500 DEG C that organism fully burns and nitrate decomposes completely, then be warming up to 800 DEG C, activation oxygen carrier;
Step 5: the particle that step 4 is obtained grinds, screening can obtain the compound oxygen carrier of calcic copper base.
Wherein, the Cu (NO described in step 1
3)
2and Ca (NO
3)
2mass ratio be 21.38:1.
The mol ratio of the citric acid described in step 2 and Cu atom is 2:1.
In step 3, drying conditions is to be dried 24 hours at 105 DEG C.
In step 4, calcination condition is at 500 DEG C, to calcine 5 hours, is warming up to after 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 particle diameter even, good dispersion degree containing the compound oxygen carrier of magnesium copper base.(2) preparation method of the compound oxygen carrier of calcic copper base of the present invention is simple, and the compound oxygen carrier of preparing has speed of reaction and higher oxygen release quality faster, and oxygen release speed and oxygen release quality are obviously promoted.
Brief description of the drawings
Fig. 1 is the unit mass oxygen carrier oxygen release conversion rate curve that the compound oxygen carrier of the present invention draws by tube furnace.
Embodiment
Further illustrate the present invention below in conjunction with example:
The compound oxygen carrier of a kind of calcic copper base, described oxygen carrier is made up of CuO and CaO, and the mass percent that wherein mass percent of CuO is 95%, CaO is 5%.
Above-mentioned oxygen carrier is prepared by following steps:
Step 1: by Ca (NO
3)
2solution is added drop-wise to Cu (NO
3)
2in solution, be stirred to and mix;
Step 2: add again citric acid solution, 70-80 DEG C, evaporation limit, limit is stirred to mixed solution and forms wet gel;
Step 3: become xerogel after wet gel is dry;
Step 4: xerogel is placed in to 500 DEG C, is fired to that organism fully burns and nitrate decomposes completely, then be warming up to 800 DEG C, activation oxygen carrier;
Step 5: the oxygen carrier granule that step 4 is obtained grinds, screening can obtain the compound oxygen carrier of calcic copper base.
Cu (NO described in step 1
3)
2and Ca (NO
3)
2mass ratio be 21.38:1.
The mol ratio of the citric acid described in step 2 and Cu atom is 2:1.
In step 3, drying conditions is to be dried 24 hours at 105 DEG C.
In step 4, calcination condition is at 500 DEG C, to calcine 5 hours, is warming up to after 800 DEG C, activates 5 hours.
A preparation method for the compound oxygen carrier of calcic copper base, comprises the following steps:
Step 1: by Ca (NO
3)
2solution is added drop-wise to Cu (NO
3)
2in solution, be stirred to and mix;
Step 2: add citric acid solution, 70-80 DEG C evaporates below limit and be stirred to mixed solution formation wet gel again;
Step 3: become xerogel after wet gel is dry;
Step 4: xerogel is placed in and is fired at 500 DEG C that organism fully burns and nitrate decomposes completely, then be warming up to 800 DEG C, activation oxygen carrier;
Step 5: the oxygen carrier granule that step 4 is obtained grinds, screening can obtain the compound oxygen carrier of calcic copper base.
Cu (NO described in step 1
3)
2and Ca (NO
3)
2mass ratio be 21.38:1, the mol ratio of the citric acid described in step 2 and Cu atom is 2:1.
In step 3, drying conditions is to be dried 24 hours at 105 DEG C.
In step 4, calcination condition is at 500 DEG C, to calcine 5 hours, is warming up to after 800 DEG C, activates 5 hours.
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 Ca (NO
3)
2.
Embodiment 1:
Get 28.62 g Cu (NO
3)
23H
2o puts into the beaker of 500 ml, adds the distilled water of 100 ml, then beaker is placed on the magnetic stirring apparatus with water bath with thermostatic control, and stirring velocity is 400 rpm.Get 2.13g Ca (NO
3)
24H
2o puts into the beaker of 100 ml, adds the distilled water of 50 ml, is stirred to completely and dissolves.Then ca nitrate soln is added drop-wise in copper nitrate solution, stir on dropping limit, limit.Get 49.87 g citric acids, the beaker of putting into 100 ml distilled water is stirred to whole dissolvings, after above-mentioned solution stirring is even, adds slowly citric acid solution, and stir on dropping limit, limit.Stir after 6 hours, solution has dewatered and has become thick wet gel.Wet gel is placed in to the air dry oven of 105 DEG C, dry after 24 hours, in beaker, wet gel becomes xerogel.Xerogel is taken out, being placed in the retort furnace of 500 DEG C calcines and decomposes completely to citric acid and nitrate for 5 hours, retort furnace is warming up to 800 DEG C again, constant temperature calcining 5 hours, be used for activating oxygen carrier, again oxygen carrier granule grinding, screening are obtained to complex metal oxides oxygen carrier, wherein the mass content of CuO is 95wt.%, and the content of CaO is 5wt.%.As shown in Figure 1, the compound oxygen carrier of calcic copper base of the present invention is not compared with mixing CaO, and oxygen release speed and oxygen release quality obviously improve.
Claims (10)
1. the compound oxygen carrier of calcic copper base, is characterized in that: described oxygen carrier is made up of CuO and CaO, the mass percent that wherein mass percent of CuO is 95%, CaO is 5%.
2. the compound oxygen carrier of calcic copper base according to claim 1, is characterized in that described oxygen carrier prepared by following steps:
Step 1: by Ca (NO
3)
2solution is added drop-wise to Cu (NO
3)
2in solution, be stirred to and mix;
Step 2: add again citric acid solution, 70-80 DEG C, evaporation limit, limit is stirred to mixed solution and forms wet gel;
Step 3: become xerogel after wet gel is dry;
Step 4: xerogel is placed in to 500 DEG C, is fired to that organism fully burns and nitrate decomposes completely, then be warming up to 800 DEG C, activation oxygen carrier;
Step 5: the oxygen carrier granule that step 4 is obtained grinds, screening can obtain the compound oxygen carrier of calcic copper base.
3. the compound oxygen carrier of calcic copper base according to claim 2, is characterized in that: the Cu (NO described in step 1
3)
2and Ca (NO
3)
2mass ratio be 21.38:1.
4. the compound oxygen carrier of calcic copper base according to claim 2, is characterized in that: the mol ratio of the citric acid described in step 2 and Cu atom is 2:1.
5. the compound oxygen carrier of calcic copper base according to claim 2, is characterized in that: in step 3, drying conditions is to be dried 24 hours at 105 DEG C.
6. the compound oxygen carrier of calcic copper base according to claim 2, is characterized in that: in step 4, calcination condition is at 500 DEG C, to calcine 5 hours, is warming up to after 800 DEG C, activates 5 hours.
7. a preparation method for the compound oxygen carrier of calcic copper base, is characterized in that comprising the following steps:
Step 1: by Ca (NO
3)
2solution is added drop-wise to Cu (NO
3)
2in solution, be stirred to and mix;
Step 2: add citric acid solution, 70-80 DEG C evaporates below limit and be stirred to mixed solution formation wet gel again;
Step 3: become xerogel after wet gel is dry;
Step 4: xerogel is placed in and is fired at 500 DEG C that organism fully burns and nitrate decomposes completely, then be warming up to 800 DEG C, activation oxygen carrier;
Step 5: the oxygen carrier granule that step 4 is obtained grinds, screening can obtain the compound oxygen carrier of calcic copper base.
8. the preparation method of the compound oxygen carrier of calcic copper base according to claim 7, is characterized in that: the Cu (NO described in step 1
3)
2and Ca (NO
3)
2mass ratio be 21.38:1, the mol ratio of the citric acid described in step 2 and Cu atom is 2:1.
9. the preparation method of the compound oxygen carrier of calcic copper base according to claim 7, is characterized in that: in step 3, drying conditions is to be dried 24 hours at 105 DEG C.
10. the preparation method of the compound oxygen carrier of copper calcic base according to claim 7, is characterized in that: in step 4, calcination condition is at 500 DEG C, to calcine 5 hours, is warming up to after 800 DEG C, activates 5 hours.
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Cited By (3)
| 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 |
| CN107674727A (en) * | 2017-09-27 | 2018-02-09 | 昆明理工大学 | A kind of preparation method of calcium oxygen carrier |
| CN107674728A (en) * | 2017-09-27 | 2018-02-09 | 昆明理工大学 | A kind of preparation method of composite calcium-base oxygen carrier |
-
2014
- 2014-08-07 CN CN201410385734.6A patent/CN104119984A/en active Pending
Cited By (4)
| 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 |
| CN107674727A (en) * | 2017-09-27 | 2018-02-09 | 昆明理工大学 | A kind of preparation method of calcium oxygen carrier |
| CN107674728A (en) * | 2017-09-27 | 2018-02-09 | 昆明理工大学 | A kind of preparation method of composite calcium-base oxygen carrier |
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Application publication date: 20141029 |