CN103289777A - Composite oxide oxygen carrier as well as preparation method and application thereof in chemical chain oxygen decoupling - Google Patents
Composite oxide oxygen carrier as well as preparation method and application thereof in chemical chain oxygen decoupling Download PDFInfo
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- CN103289777A CN103289777A CN2013102578204A CN201310257820A CN103289777A CN 103289777 A CN103289777 A CN 103289777A CN 2013102578204 A CN2013102578204 A CN 2013102578204A CN 201310257820 A CN201310257820 A CN 201310257820A CN 103289777 A CN103289777 A CN 103289777A
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- oxygen
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Abstract
The invention discloses a composite oxide oxygen carrier as well as a preparation method and an application thereof. The preparation method comprises the following steps of: utilizing nitrate as active ingredient, selecting Cu(NO3)2 and Zr(NO3)4 with a mass ratio of (3.4-84.4):1 to prepare a solution, adding citric acid or ethylene glycol to serve as a complexing agent, selecting a mol ratio of 1:(1-3) for the complexing agent and metal ions, and drying and calcining to obtain the composite oxide oxygen carrier, wherein the mass fraction of CuO is 80%-99% and the mass fraction of ZrO2 is 1%-20%. The composite oxide oxygen carrier is applied in the chemical chain oxygen decoupling technology, and the oxygen release temperature of the oxygen carrier in an oxygen release reactor is 800-1000 DEG C. The preparation method provided by the invention is simple, and the prepared composite oxide oxygen carrier is of a porous structure and has the advantages of small particle diameter, good dispersibility of active ingredient, high oxygen suction and oxygen release speeds, low oxygen release and oxygen suction temperatures and good reactivity and circulation stability.
Description
Technical field
The invention belongs to the preparing technical field of oxygen carrier material in the chemical chain oxygen decoupling technology, be specifically related to a kind of preparation method and application of composite oxides oxygen carrier.
Background technology
Chemical chain burning technology can be realized CO as a kind of cleaning, efficient burning technology of novelty
2In separate and avoid NO
xPollutent produces, and can realize the cascade utilization of energy, studies this novel combustion system and has great importance.Traditional burning chemistry chains is applicable to H
2, CO, CH
4Deng geseous fuel, in China, geseous fuel poornesss such as Sweet natural gas, and solid fuel reserves such as coal and biomass are abundant, study solid-fuelled chemical chain burning technology to China can source clean, efficiently utilize and reduce greenhouse gas emission and have active effect.Solid fuel can gasify earlier and produce synthetic gas, feeds the fuel reaction device again, but gasification need be from the air separation pure oxygen, and system's power consumption increases.Second method is that solid fuel is directly introduced the fuel reaction device, and with the direct contact reacts of oxygen carrier, but solid-solid undercompounding in the reactor has limited the combustion processes of fuel.
In order to address the above problem, the concept of chemical chain oxygen decoupling technology is suggested, and utilizes oxygen carrier to discharge molecule O
2Characteristic, the reaction in the fuel reaction device was divided into for two steps: at first oxygen carrier decompose to produce O
2, solid fuel and O then
2The reaction of generation ordinary combustion.The major advantage of chemistry chain oxygen decoupling technology is to have improved solid-fuelled speed of reaction in the combustion reactor, has accelerated solid-fuelled conversion.
The oxygen carrier that is fit to the decoupling zero of chemical chain oxygen is the emphasis of chemical chain oxygen decoupling zero research always, requires the oxygen carrier can be in 800 ~ 1200 ℃ of scopes of temperature of combustion and O
2Reversible reaction takes place, and namely oxygen carrier can carry out oxygen uptake in air reactor, discharges molecular oxygen in the fuel reaction device.Existing report has proved that the oxygen carrier that can be applied to the decoupling zero of chemical chain oxygen has CuO/Cu
2O, Mn
2O
3/ Mn
3O
4And Co
3O
4/ CoO.Compare with the cobalt-based oxygen carrier with the manganese base, copper base load oxysome oxygen carrier amount is big, has oxygen uptake faster and oxygen release performance, is not easy to carrier and reacts, and carbon laydown is also less; Copper base load oxysome and carbon reaction are thermopositive reaction, can reduce the energy requirement of fuel reaction device, be the suitable oxygen carrier of oxygen decoupling zero process, but also exist oxygen uptake before the order copper base load oxysome and shortcomings such as the oxygen release temperature is too high, oxygen uptake and oxygen release speed slow, cyclical stability difference and easy-sintering.
Summary of the invention
At the deficiency that prior art exists, the invention provides a kind of oxygen uptake and the oxygen release temperature is lower, reactivity worth good, the composite oxides oxygen carrier that is used for chemical chain oxygen decoupling technology of stable cycle performance and preparation method thereof.
The present invention also provides the application of a kind of composite oxides oxygen carrier in the decoupling zero of chemical chain oxygen.
The technical solution that realizes the object of the invention is: a kind of composite oxides oxygen carrier, and by active ingredient CuO and ZrO
2Form, by the weight percentage of oxygen carrier, the content of CuO is 80% ~ 99%, ZrO in the described oxygen carrier granule
2Content be 1% ~ 20%.
The preparation method of above-mentioned composite oxides oxygen carrier may further comprise the steps:
Step 1: cupric nitrate and zirconium nitrate are made remix behind the solution respectively;
Step 2: in mixed solution, add citric acid solution or ethylene glycol, be evaporated to the wet gel shape in the time of below 100 ℃ while stirring;
In the time of below step 3:150 ℃ above-mentioned wet gel is dried to the xerogel shape;
Step 4: xerogel is calcined under 500-700 ℃ of condition;
Step 5: be warming up to 800-900 ℃ and continue to obtain target product after the calcining.
Cu (NO described in the step 1
3)
2And Zr (NO
3)
4Mass ratio be (3.4-84.4): 1.
The preferred 80-100 of vaporization temperature described in the step 2 ℃, the mol ratio of described citric acid or ethylene glycol and metal ion (Cu and Zr) is 1:(1-3).
Drying described in the step 3 adopts air dry oven, the preferred 100-120 of described drying temperature ℃.
Retort furnace is adopted in calcining described in the step 4, and described calcination time is 3-5 hour.
Calcination time described in the step 5 is 1-5 hour.
The application of composite oxides oxygen carrier of the present invention in chemical chain oxygen decoupling technology, under high pure nitrogen atmosphere, its oxygen release temperature in the oxygen release reactor is 800-1000 ℃.
Compared with prior art, the preparation method of composite oxides oxygen carrier of the present invention is simple, the compound oxygen carrier granule particle diameter of preparing is little, the good dispersity of active ingredient, composite type oxygen carrier granule is vesicular structure, and oxygen uptake and oxygen release speed are fast, and oxygen release and oxygen uptake temperature are lower, and have good cyclical stability and reactivity worth, can be used for solid-fuelled chemical chain oxygen decoupling burnings such as coal and biomass.
Description of drawings
Fig. 1 is the scanning electronic microscope shape appearance figure of product of the present invention.
Fig. 2 is product of the present invention oxygen release curve under 800 ℃, 900 ℃ and 1000 ℃ of conditions on the fixed bed respectively.
Embodiment
Further specify process of the present invention below in conjunction with embodiment:
Raw material in the present embodiment is analytical pure Cu (NO
3)
23H
2O and analytical pure Zr (NO
3)
45H
2O; Complexing agent is analytical pure citric acid or analytical pure ethylene glycol; Vaporization temperature is below 100 ℃; Drying temperature is below 150 ℃; Calcining temperature is 500-700 ℃; Activation temperature is 800-900 ℃.
The product of gained of the present invention can pass through scanning electronic microscope (SEM) and characterize pattern, fixed bed test oxygen release and speed of oxygen intake.
Concrete preparation technology's flow process of present embodiment is as follows:
Step 1: cupric nitrate and zirconium nitrate are joined respectively in the beaker that fills water, be stirred to solid and dissolve fully, wherein Cu (NO
3)
2With Zr (NO
3)
4Mass ratio be (3.4-84.4): 1;
Step 2: will fill Cu (NO
3)
2The beaker of solution places on the magnetic stirring apparatus that has water bath with thermostatic control, with Zr (NO
3)
4Drips of solution is added to Cu (NO
3)
2In the solution, stir while dripping;
Step 3: complexing agent is put into the beaker that fills distilled water be stirred to whole dissolvings, after treating that above-mentioned solution stirring evenly, in beaker, add enveloping agent solution slowly, stir while dripping, wherein the mol ratio of complexing agent citric acid or ethylene glycol and metal ion (Cu and Zr) is 1:(1-3);
Step 4: when not being higher than 100 ℃, gained solution being stirred to solution dehydrates forming thick wet gel while evaporating;
Step 5: when not being higher than 150 ℃, wet gel is dried to the formation xerogel;
Step 6: xerogel is taken out from beaker, place be fired under retort furnace 500-700 ℃ organism fully burn and nitrate decompose fully;
Step 7: retort furnace is warming up to 800-900 ℃ of calcining and activating oxygen carrier, can collects and obtain the composite oxides oxygen carrier.
Embodiment 1:
Get 24.16g Cu (NO
3)
23H
2O(18.8g Cu (NO
3)
2) put into the beaker of 500 ml, add the distilled water of 100 ml, beaker is placed on the magnetic stirring apparatus that has water bath with thermostatic control stir then.Get 6.99g Zr (NO
3)
45H
2O(5.52g Zr (NO
3)
4) put into the beaker of 100 ml, add the distilled water of 50 ml, be stirred to dissolving fully.Then zirconium nitrate solution is added drop-wise in the copper nitrate solution, stirs while dripping.Get 48.83 g citric acids, the beaker of putting into 100 ml distilled water is stirred to whole dissolvings, treat that above-mentioned solution stirring evenly after, add citric acid solution slowly, the stirring while dripping.80 ℃ are stirred after 6 hours down, and solution has dewatered and become thick wet gel.Wet gel is placed 100 ℃ air dry oven, and after dry 24 hours, wet gel becomes xerogel in the beaker.Xerogel is taken out, place 500 ℃ retort furnace calcining 5 hours to citric acid and nitrate to decompose fully, retort furnace is warming up to 800 ℃ again, constant temperature calcining 5 hours obtains 10 g CuO/ZrO after the cooling
2The composite oxides oxygen carrier, wherein the mass content of CuO is 80%, ZrO
2Content be 20%.
Embodiment 2:
Get 27.23g Cu (NO
3)
23H
2O(21.15 g Cu (NO
3)
2) put into the beaker of 500 ml, add the distilled water of 100 ml, beaker is placed on the magnetic stirring apparatus that has water bath with thermostatic control stir then.Get 3.49g Zr (NO
3)
45H
2O(2.76 g Zr (NO
3)
4) put into the beaker of 100 ml, add the distilled water of 50 ml, be stirred to dissolving fully.Then zirconium nitrate solution is added drop-wise in the copper nitrate solution, stirs while dripping.Get 50.66 g citric acids, the beaker of putting into 100 ml distilled water is stirred to whole dissolvings, treat that above-mentioned solution stirring evenly after, add citric acid solution, the stirring while dripping.90 ℃ are stirred after 5 hours down, and solution has dewatered and become thick wet gel.Wet gel is placed 110 ℃ air dry oven, and after dry 18 hours, wet gel becomes xerogel in the beaker.Xerogel is taken out, place 600 ℃ retort furnace calcining 4 hours to citric acid and nitrate to decompose fully, retort furnace is warming up to 850 ℃ again, constant temperature calcining 3 hours obtains 10 g CuO/ZrO after the cooling
2The composite oxides oxygen carrier, wherein the mass content of CuO is 90%, ZrO
2Content be 10%.
SEM shows that composite oxides oxygen carrier that example 2 makes has that particle diameter is little, good dispersion degree, porosity height, form uniform advantage, as shown in Figure 1.Get the composite oxides oxygen carrier that example 2 makes and carry out the oxygen release experimental study at fixed bed, carrier gas is high-purity N
2, flow is 50 ml/min, and temperature is respectively 800 ℃, 900 ℃ and 1000 ℃, chooses the research that experimentizes of 1g composite oxides oxygen carrier at every turn, and the oxygen concentration of release adopts gas analyzer to detect.Fig. 2 shows that the compound oxygen carrier that this example makes has good oxygen release characteristic.
Embodiment 3:
Get 59.89g Cu (NO
3)
23H
2O(46.53 g Cu (NO
3)
2) put into the beaker of 500 ml, add the distilled water of 100 ml, beaker is placed on the magnetic stirring apparatus that has water bath with thermostatic control stir then.Get 0.7g Zr (NO
3)
45H
2O(0.55 g Zr (NO
3)
4) put into the beaker of 100 ml, add the distilled water of 50 ml, be stirred to dissolving fully.Then zirconium nitrate solution is added drop-wise in the copper nitrate solution, stirs while dripping.After treating that above-mentioned solution stirring evenly, get 30.89 g ethylene glycol and slowly add in the mixing solutions of zirconium nitrate and cupric nitrate, stir while dripping.100 ℃ are stirred after 4 hours down, and solution has dewatered and become thick wet gel.Wet gel is placed 120 ℃ air dry oven, and after dry 12 hours, wet gel becomes xerogel in the beaker.Xerogel is taken out, place 700 ℃ retort furnace calcining 3 hours to ethylene glycol and nitrate to decompose fully, retort furnace is warming up to 900 ℃ again, constant temperature calcining 1 hour can obtain 20 g CuO/ZrO after the cooling
2The composite oxides oxygen carrier, wherein the mass content of CuO is 99 %, ZrO
2Content be 1%.
Claims (5)
1. a composite oxides oxygen carrier is characterized in that described oxygen carrier is by active ingredient CuO and ZrO
2Form, by the weight percentage of oxygen carrier, the content of CuO is 80% ~ 99%, ZrO
2Content be 1% ~ 20%.
2. the preparation method of a composite oxides oxygen carrier is characterized in that described oxygen carrier granule prepares according to the following steps:
Step 1: stirring and dissolving cupric nitrate and zirconium nitrate are made remix behind the solution respectively;
Step 2: add complexing agent, be evaporated to the wet gel shape in the time of below 100 ℃ while stirring;
In the time of below step 3:150 ℃ above-mentioned wet gel is dried to the xerogel shape;
Step 4: xerogel is calcined under 500-700 ℃ of condition;
Step 5: be warming up to 800-900 ℃ of continuation calcining and activating oxygen carrier and obtain target product.
3. the preparation method of composite oxides oxygen carrier according to claim 2 is characterized in that the Cu (NO described in the step 1
3)
2And Zr (NO
3)
4Mass ratio be (3.4-84.4): 1; Complexing agent described in the step 2 is citric acid or ethylene glycol; The mol ratio of described complexing agent and metal ion is 1:(1-3); The preferred 80-100 of described vaporization temperature ℃.
4. the preparation method of composite oxides oxygen carrier according to claim 2 is characterized in that the drying described in the step 3 adopts air dry oven, the preferred 100-120 of described drying temperature ℃; Retort furnace is adopted in calcining described in the step 4, and described calcination time is 3-5 hour; Calcination time described in the step 5 is 1-5 hour.
5. the application of composite oxides oxygen carrier in chemical chain oxygen decoupling technology, it is characterized in that the described oxygen carrier of claim 1 is applied in the chemical chain oxygen decoupling technology, its oxygen release temperature in the oxygen release reactor is 800-1000 ℃, and described carrier gas is nitrogen.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849444A (en) * | 2014-03-17 | 2014-06-11 | 南京理工大学 | Copper-based compound oxygen carrier and preparation method thereof |
| CN106140161A (en) * | 2016-07-06 | 2016-11-23 | 江苏大学 | A kind of preparation method and application of copper/zirconium oxide bar-shaped xerogel catalyst |
| CN108680017A (en) * | 2018-05-28 | 2018-10-19 | 中石化（洛阳）科技有限公司 | Reheat furnace system and furnace apparatus |
| CN114768818A (en) * | 2022-03-10 | 2022-07-22 | 天津大学 | Water-heat oxygen decoupling catalyst, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811054A (en) * | 2009-02-24 | 2010-08-25 | 华东理工大学 | Copper-cerium solid solution catalyst for methane catalytic combustion, and preparation method thereof |
-
2013
- 2013-06-25 CN CN2013102578204A patent/CN103289777A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811054A (en) * | 2009-02-24 | 2010-08-25 | 华东理工大学 | Copper-cerium solid solution catalyst for methane catalytic combustion, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| TOBIAS MATTISSON: "chemical-looping with oxygen uncoupling using CuO/ZrO2 with petroleum coke", 《FUEL》, vol. 88, 14 October 2008 (2008-10-14), pages 2 - 1 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849444A (en) * | 2014-03-17 | 2014-06-11 | 南京理工大学 | Copper-based compound oxygen carrier and preparation method thereof |
| CN106140161A (en) * | 2016-07-06 | 2016-11-23 | 江苏大学 | A kind of preparation method and application of copper/zirconium oxide bar-shaped xerogel catalyst |
| CN106140161B (en) * | 2016-07-06 | 2018-08-21 | 江苏大学 | A kind of preparation method and application of the rodlike xerogel catalyst of copper/zirconium oxide |
| CN108680017A (en) * | 2018-05-28 | 2018-10-19 | 中石化（洛阳）科技有限公司 | Reheat furnace system and furnace apparatus |
| CN114768818A (en) * | 2022-03-10 | 2022-07-22 | 天津大学 | Water-heat oxygen decoupling catalyst, preparation method and application |
| CN114768818B (en) * | 2022-03-10 | 2023-08-15 | 天津大学 | Hydrothermal oxygen decoupling catalyst, preparation method and application |
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Application publication date: 20130911 |