CN103980977A - Manganese-based compound oxygen carrier and preparation method thereof - Google Patents
Manganese-based compound oxygen carrier and preparation method thereof Download PDFInfo
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- CN103980977A CN103980977A CN201410209681.2A CN201410209681A CN103980977A CN 103980977 A CN103980977 A CN 103980977A CN 201410209681 A CN201410209681 A CN 201410209681A CN 103980977 A CN103980977 A CN 103980977A
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Abstract
The invention discloses a manganese-based compound oxygen carrier and a preparation method thereof. The oxygen carrier is composed of 95% by weight of MnO2 and 5% by weight of CuO. The preparation method comprises the following steps: adding MnO2 powder and CuO powder into a ball-milling tank in a mass ratio of 19:1 so as to ball-mill the mixed powder, and determining a ball-to-material ratio at 40:1; and separating ball-milling beads from materials by using a sieve, so that the compound metal oxide oxygen carrier can be obtained. According to the manganese-based compound oxygen carrier and the preparation method thereof disclosed by the invention, the MnO2 compound oxygen carrier is prepared by using a ball-milling method, the preparation process is simple and easy to operate, and the prepared compound oxygen carrier begins to release oxygen at extremely low temperatures, both the oxygen release rate and the release oxygen content are higher than those of common analytically pure MnO2 oxygen carriers, and therefore, the prepared compound oxygen carrier has good reaction performances.
Description
Technical field
The invention belongs to oxygen carrier granule preparing technical field in burning chemistry chains system, be specifically related to compound oxygen carrier of a kind of manganese base and preparation method thereof.
Background technology
The global warming issue being caused by Greenhouse effect just more and more causes people's concern.CO
2as topmost greenhouse gases, research CO
2emission-reduction technology extremely urgent.The CO of boiler combustion fossil oil discharge
2enormous amount, but CO in flue gas
2usually, by nitrogen dilution, make CO
2separation and cost recovery very high, simultaneously also can produce SO
2, NO
xdeng pollutent.Chemical chain burning technology, as cleaning of new generation, efficient burning technology, not only can be realized CO
2interior separation, avoid the generation of pollutent, and can realize the cascade utilization of chemical energy.This novel combustion technology has become the important directions of world energy sources and research on environmental issues.
The ultimate principle of burning chemistry chains is that traditional fuel and the direct catalytic burning of air are decomposed into two gas-solid reactions by means of the effect of oxygen carrier, and fuel, is delivered to airborne oxygen in fuel by oxygen carrier without contacting with air.Burning chemistry chains system is comprised of air reactor, fuel reactor and oxygen carrier.Solid oxygen carrier circulates between two reactors, realizes the transfer of oxygen.Oxygen carrier recycles between two reactors, and the reduction reaction that is fuel reactor by the oxidizing reaction at air reactor on the one hand provides oxygen, on the other hand the heat producing in the oxidizing reaction of air reactor is passed to fuel reactor.Recycle chemistry chain process, what follow is exactly oxidation and the reduction of oxygen carrier.Therefore, the physics and chemistry character of oxygen carrier is to realize the key point of different fuel 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.Wherein, at high temperature active and oxygen release amount decline of copper base load oxysome; Co is toxic, and price is relatively high; Metal oxide oxygen carrier MnO
2nontoxic owing to having, price is low, greater activity and be subject to widely paying close attention to compared with advantages such as low oxygen release temperature, but its oxygen carrier amount is less and Al
2o
3, SiO
2, TiO
2therefore react and be not suitable as the inert support of manganese base load oxysome with Yi Yuqi such as Sepiolite, also exist the deficiencies such as oxidation-reduction quality is poor, oxygen carrier rate is limited simultaneously.
Summary of the invention
The object of the invention is to overcome metal oxide oxygen carrier MnO in prior art
2the shortcomings such as oxidation-reduction quality is poor, oxygen carrier rate is limited, provide a kind of manganese base composite oxygen carrier particles and preparation method thereof.
To achieve these goals, the technical solution adopted in the present invention is: the compound oxygen carrier of a kind of manganese base, described oxygen carrier is by MnO
2form with CuO, wherein MnO
2content be 95wt.%, the content of CuO is 5wt.%.
A preparation method for the compound oxygen carrier of manganese base, comprises the following steps:
Step 1: MnO
2for 19:1 joins in ball grinder, carry out ball milling in mass ratio with CuO powder, determine that ratio of grinding media to material is 40:1;
Step 2: with sieve, ball milling pearl is separated with material, can obtain complex metal oxides oxygen carrier.
Ball milling speed described in step 1 is 3000rpm, and Ball-milling Time is 90min.
Compared with prior art, its advantage is in the present invention: the present invention adopts ball milled to prepare MnO
2compound oxygen carrier, preparation process is simple, easy to operate, and the compound oxygen carrier of preparing starts oxygen release at very low temperature, and oxygen release speed and oxygen release amount are all higher than the pure MnO of general analysis
2oxygen carrier, has good reactivity worth.
Accompanying drawing explanation
Fig. 1 is the oxygen release conversion rate curve figure of product of the present invention in fixture bed experiment
Embodiment
Below in conjunction with example, further illustrate the present invention:
Raw material in the present embodiment is analytical pure MnO
2with CuO product; Ball mill is planetary ball mill; Rotational speed of ball-mill is 3000rpm; Ball-milling Time is 90min; Ball grinder diameter 7.5cm; Ball grinder volume 250ml, ball milling pearl is diameter 6mm, 10mm and tri-kinds of mixing of 20mm.
Embodiment: get 4.75g MnO
2powder and 0.25g CuO powder are put into the ball grinder of 250ml, select diameter 6mm, and the nodule number of joining of the ball milling pearl of 10mm and 20mm is 60,25 and 2 (being that ratio of grinding media to material is 40:1), adds in ball grinder, covers sealing-ring and cover.The ball grinder that installs ball milling pearl and material is correctly placed on ball mill, first top handle is screwed clockwise, then below handle is locked clockwise, close upper cover.Connect ball mill power supply, on controller, setting operation scheme is speed 3000rpm, Ball-milling Time 90min, starter motor.After ball mill operation 90min, disable motor, cuts off the electricity supply, and opens cover cap, takes off ball grinder, pours out ball milling pearl and material wherein, with sieve, ball milling pearl is separated with material, can obtain complex metal oxides oxygen carrier.MnO wherein
2content be 95wt.%, the content of CuO is 5wt.%.Fixture bed experiment shows the MnO that this example makes
2compound oxygen carrier has good reactive behavior, and oxygen release speed obviously improves, as shown in Figure 1.
Claims (5)
1. the compound oxygen carrier of manganese base, is characterized in that, described oxygen carrier is by MnO
2form with CuO, wherein, MnO
2content be 95wt.%, the content of CuO is 5wt.%.
2. the compound oxygen carrier of manganese base according to claim 1, is characterized in that, described oxygen carrier is prepared by following steps:
Step 1: MnO
2for 19:1 joins in ball grinder, carry out ball milling in mass ratio with CuO powder, determine that ratio of grinding media to material is 40:1;
Step 2: with sieve, ball milling pearl is separated with material, can obtain complex metal oxides oxygen carrier.
3. the compound oxygen carrier of manganese base according to claim 2, is characterized in that, the ball milling speed described in step 1 is 3000rpm, and Ball-milling Time is 90min.
4. a preparation method for the compound oxygen carrier of manganese base, is characterized in that, comprises the following steps:
Step 1: MnO
2for 19:1 joins in ball grinder, carry out ball milling in mass ratio with CuO powder, determine that ratio of grinding media to material is 40:1;
Step 2: with sieve, ball milling pearl is separated with material, can obtain complex metal oxides oxygen carrier.
5. the preparation method of the compound oxygen carrier of manganese base according to claim 4, is characterized in that, the ball milling speed described in step 1 is 3000rpm, and Ball-milling Time is 90min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410209681.2A CN103980977A (en) | 2014-05-16 | 2014-05-16 | Manganese-based compound oxygen carrier and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410209681.2A CN103980977A (en) | 2014-05-16 | 2014-05-16 | Manganese-based compound oxygen carrier and preparation method thereof |
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|---|---|
| CN103980977A true CN103980977A (en) | 2014-08-13 |
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| CN201410209681.2A Pending CN103980977A (en) | 2014-05-16 | 2014-05-16 | Manganese-based compound oxygen carrier and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105462649A (en) * | 2014-09-05 | 2016-04-06 | 南京理工大学 | Calcium-containing cobalt-based composite oxygen carrier and preparation method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132501A (en) * | 1993-10-06 | 1996-10-02 | 尼古化学股份公司 | Gas developing agent |
| CN101880569A (en) * | 2010-06-24 | 2010-11-10 | 昆明理工大学 | Oxygen carrier for smokeless combustion technology and preparation method thereof |
| CN103496672A (en) * | 2013-09-30 | 2014-01-08 | 南京理工大学 | Device and process for preparing O2-CO2 mixed gas based on chemical-looping technology |
-
2014
- 2014-05-16 CN CN201410209681.2A patent/CN103980977A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132501A (en) * | 1993-10-06 | 1996-10-02 | 尼古化学股份公司 | Gas developing agent |
| CN101880569A (en) * | 2010-06-24 | 2010-11-10 | 昆明理工大学 | Oxygen carrier for smokeless combustion technology and preparation method thereof |
| CN103496672A (en) * | 2013-09-30 | 2014-01-08 | 南京理工大学 | Device and process for preparing O2-CO2 mixed gas based on chemical-looping technology |
Non-Patent Citations (2)
| Title |
|---|
| NASIM MOHAMMAD POUR 等: "Combined Cu/Mn Oxides as an Oxygen Carrier in Chemical Loopingwith Oxygen Uncoupling (CLOU)", 《ENERGY FUELS》 * |
| NASIM MOHAMMAD POUR 等: "Combined Cu/Mn Oxides as an Oxygen Carrier in Chemical Loopingwith Oxygen Uncoupling (CLOU)", 《ENERGY FUELS》, 23 September 2013 (2013-09-23) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105462649A (en) * | 2014-09-05 | 2016-04-06 | 南京理工大学 | Calcium-containing cobalt-based composite oxygen carrier and preparation method therefor |
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Application publication date: 20140813 |