CN103215102A - Composite-type oxygen carrier particles, preparation, and application in chemical chain oxygen decoupling technology - Google Patents
Composite-type oxygen carrier particles, preparation, and application in chemical chain oxygen decoupling technology Download PDFInfo
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- CN103215102A CN103215102A CN 201310146909 CN201310146909A CN103215102A CN 103215102 A CN103215102 A CN 103215102A CN 201310146909 CN201310146909 CN 201310146909 CN 201310146909 A CN201310146909 A CN 201310146909A CN 103215102 A CN103215102 A CN 103215102A
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- oxygen carrier
- oxygen
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- preparation
- carrier granule
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Abstract
The invention discloses a composite-type oxygen carrier as well as a preparation method and an application for the same. The preparation method comprises the following steps of: taking nitrate as an active component, selecting the mass ratio of Cu(NO3)2 to Y(NO3) to be (3.85-95.6): 1 and preparing a solution, taking citric acid or ethylene glycol as a complexing agent, selecting the molar ratio of the complexing agent to metal ions to be 1: (1-3), and obtaining composite-type oxygen carrier particles containing CuO in a mass fraction of 80-99% and Y2O3 in a mass fraction of 1-20% via drying and calcining. In an application for the obtained composite-type oxygen carrier particles in a chemical chain oxygen decoupling technology, the oxygen absorption temperature of the oxygen carrier in air is 400-1000 DEG C, and the oxygen release temperature of the oxygen carrier in a fuel reactor after being oxidized is 800-1000 DEG C. The preparation method disclosed by the invention is simple; the obtained composite metal oxide oxygen carrier particles are of a porous structure and small in particle size; the active component is good in dispersibility, fast in oxygen absorption and oxygen release speeds, and low in oxygen release and oxygen absorption temperatures; and moreover, the composite metal oxide oxygen carrier particles are good in cycling stability and reaction performance.
Description
Technical field
The invention belongs to the preparing technical field of oxygen carrier granule in the chemical chain oxygen decoupling technology, be specifically related to a kind of composite type oxygen carrier granule and its production and application.
Background technology
Because discharging CO such as fossil energy utilization
2The Greenhouse effect that cause have become the focus of people's growing interest, reduce discharging CO
2Become the important directions of world energy sources, research on environmental issues.CO
2Capture and the technology of sealing up for safekeeping be considered to large coal-fired power plant and reduce CO
2A kind of effective means of discharging.But because the CO in traditional flue gas
2Content is lower, and separating needs to consume lot of energy, causes the cost of power plant to increase decrease in efficiency.Chemical chain burning technology can be realized CO as a kind of cleaning, efficient burning technology of novelty
2In separate and avoid NO
x Pollutent 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 notion of chemical chain oxygen decoupling technology is suggested, and utilizes the characteristic of oxygen carrier, and the reaction in the fuel reaction device was divided into for two steps: at first oxygen carrier decomposes generation O
2, solid fuel and O then
2The reaction of generation ordinary combustion.The major advantage of oxygen decoupling zero chemistry chain technology is to have improved solid-fuelled speed of reaction in the combustion reactor, has accelerated solid-fuelled conversion.
Oxygen carrier is the key that realizes chemical chain burning technology, at present the more oxygen carrier of research has metal oxide oxygen carrier, vitriol oxygen carrier and perovskite typed oxygen carrier etc., must be in 800 ~ 1200 ℃ of scopes of temperature of combustion and O and be fit to the oxygen carrier of chemical chain oxygen decoupling zero
2Reversible reaction takes place, and promptly oxygen carrier can carry out the oxygen uptake reaction 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 type oxygen carrier granule that is used for chemical chain oxygen decoupling technology of stable cycle performance and preparation method thereof and application.
A kind of composite type oxygen carrier granule is by active ingredient CuO and Y
2O
3Form, by the weight percentage of oxygen carrier, the content of CuO is 80% ~ 99% in the described oxygen carrier granule, Y
2O
3Content be 1% ~ 20%.
The preparation method of above-mentioned composite type oxygen carrier granule may further comprise the steps:
Step 1: stirring and dissolving Cu (NO
3)
2And Y (NO
3)
3Make solution respectively;
Step 2: 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 3:120 ℃ 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.
Cu (NO described in the step 1
3)
2And Y (NO
3)
3Mass ratio be (3.85-95.6): 1.
The preferred 80-90 of vaporization temperature described in the step 2 ℃, the mol ratio of described citric acid or ethylene glycol and metal ion (Cu and Y) is 1:(1-3).
Drying described in the step 3 adopts air dry oven, the preferred 90-110 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 type oxygen carrier granule of the present invention in chemical chain oxygen decoupling technology, wherein, the aerial oxygen uptake temperature of oxygen carrier is 400-1000 ℃, the oxygen release temperature after the oxidation in the fuel reaction device is 800-1000 ℃.
Compared with prior art, the preparation method of composite type oxygen carrier granule 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 a 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 before circulating reaction.
Fig. 2 is the scanning electronic microscope shape appearance figure of product of the present invention behind circulating reaction.
Fig. 3 is the conversion rate curve of product oxygen release of the present invention and oxygen uptake.
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)
2Product; Complexing agent is analytical pure citric acid or analytical pure ethylene glycol; Adulterated metal nitrate is analytical pure Y (NO
3)
3Cu (NO
3)
2Y (NO
3)
3Mass ratio be (3.85-95.6): 1; The mol ratio of complexing agent and metal ion (Cu and Y) is 1:(1-3); Vaporization temperature is below 100 ℃; Drying temperature is below 120 ℃; 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, thermogravimetric analyzer (TGA) test oxygen release and speed of oxygen intake.
Concrete preparation technology's flow process of present embodiment is as follows:
Step 1: Cu (NO
3)
2And Y (NO
3)
3Join respectively in the beaker that fills water, be stirred to the solution uniform mixing, solid dissolves fully;
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 Y (NO
3)
3Drips 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 is stirred to whole dissolvings, treat that above-mentioned solution stirring evenly after, in beaker, add enveloping agent solution slowly, stirring while dripping.
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 120 ℃, 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 composite metal oxygen oxygen carrier granule.
Embodiment 1:
Get 24.16 g Cu (NO
3)
33H
2O puts into the beaker of 500 ml, adds the distilled water of 100 ml, then beaker is placed on the magnetic stirring apparatus that has water bath with thermostatic control, and stirring velocity is 400 rpm.Get 3.27 g Y (NO
3)
36H
2O puts into the beaker of 100 ml, adds the distilled water of 50 ml, is stirred to dissolving fully.Then yttrium nitrate solution is added drop-wise in the copper nitrate solution, stirs while dripping.Get 42 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, stirring while dripping.Stir after 2 hours under 100 ℃ of conditions, solution dehydrates becomes 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 500 ℃ retort furnace calcining 5 hours to citric acid and nitrate to decompose fully, retort furnace is warming up to 900 ℃ again, constant temperature calcining 1 hour is used to activate oxygen carrier, obtains the complex metal oxides oxygen carrier, wherein the mass content of CuO is 80%, Y
2O
3Content be 20%.
Embodiment 2:
Get 54.36 g Cu (NO
3)
33H
2O puts into the beaker of 500 ml, adds the distilled water of 100 ml, then beaker is placed on the magnetic stirring apparatus that has water bath with thermostatic control, and stirring velocity is 400 rpm.Get 3.27 g Y (NO
3)
36H
2O puts into the beaker of 100 ml, adds the distilled water of 50 ml, is stirred to dissolving fully.Then yttrium nitrate solution is added drop-wise in the copper nitrate solution, stirs while dripping.Get 84 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, stirring while dripping.Stir after 5 hours under 90 ℃ of conditions, solution has dewatered and has 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 is used to activate oxygen carrier, obtains the complex metal oxides oxygen carrier, wherein the mass content of CuO is 90%, Y
2O
3Content be 10%.SEM shows that the compound oxygen carrier of CuO that this example makes has that particle diameter is little, good dispersion degree, porosity height, form advantage of uniform, as shown in Figure 1.The CuO composite type oxygen carrier granule that this example made after Fig. 2 demonstration repeatedly circulated has good stability.Fig. 3 shows that present embodiment makes composite type oxygen carrier granule and have good oxygen release performance under 950 ℃ of conditions, under 600 ℃ of conditions, has good oxygen uptake performance, can satisfy the demand of chemical chain oxygen decoupling technology, can be used for solid-fuelled burning chemistry chains such as coal and biomass.
Embodiment 3:
Get 59.79 g Cu (NO
3)
33H
2O puts into the beaker of 500 ml, adds the distilled water of 100 ml, then beaker is placed on the magnetic stirring apparatus that has water bath with thermostatic control, and stirring velocity is 400 rpm.Get 0.33 g Y (NO
3)
36H
2O puts into the beaker of 100 ml, adds the distilled water of 50 ml, is stirred to dissolving fully.Then yttrium nitrate solution is added drop-wise in the copper nitrate solution, stirs while dripping.After treating that above-mentioned solution stirring evenly, get 24.8 g ethylene glycol and add slowly in the mixing solutions of Yttrium trinitrate and cupric nitrate, stir while dripping.Stir after 6 hours under 80 ℃ of conditions, solution dehydrates becomes 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 700 ℃ retort furnace calcining 3 hours to ethylene glycol and nitrate to decompose fully, retort furnace is warming up to 800 ℃ again, constant temperature calcining 5 hours is used to activate oxygen carrier, obtains the complex metal oxides oxygen carrier, wherein the mass content of CuO is 99%, Y
2O
3Content be 1%.
Claims (9)
1. a composite type oxygen carrier granule is characterized in that described oxygen carrier granule is by active ingredient CuO and Y
2O
3Form, by the weight percentage of oxygen carrier, the content of CuO is 80% ~ 99%, Y
2O
3Content be 1% ~ 20%.
2. composite type oxygen carrier granule according to claim 1 is characterized in that described oxygen carrier granule prepares according to the following steps:
Step 1: stirring and dissolving Cu (NO
3)
2And Y (NO
3)
3Make solution respectively;
Step 2: 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 3:120 ℃ 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. composite type oxygen carrier granule according to claim 1 is characterized in that the Cu (NO described in the step 1
3)
2And Y (NO
3)
3Mass ratio be (3.85-95.6): 1; The preferred 80-90 of vaporization temperature described in the step 2 ℃, the mol ratio of described citric acid or ethylene glycol and metal ion is 1:(1-3).
4. composite type oxygen carrier granule according to claim 1 is characterized in that the drying described in the step 3 adopts air dry oven, the preferred 90-110 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 preparation method of a composite type oxygen carrier granule is characterized in that said method comprising the steps of:
Step 1: stirring and dissolving Cu (NO
3)
2And Y (NO
3)
3Make solution respectively;
Step 2: 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 3:120 ℃ 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.
6. the preparation method of composite type oxygen carrier granule according to claim 5 is characterized in that the Cu (NO described in the step 1
3)
2And Y (NO
3)
3Mass ratio be (3.85-95.6): 1; The preferred 80-90 of vaporization temperature described in the step 2 ℃, the mol ratio of described citric acid or ethylene glycol and metal ion is 1:(1-3).
7. the preparation method of composite type oxygen carrier granule according to claim 5 is characterized in that the drying described in the step 3 adopts air dry oven, the preferred 90-110 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.
8. the application of composite type oxygen carrier granule in chemical chain oxygen decoupling technology is characterized in that the aerial oxygen uptake temperature of described oxygen carrier is 400-1000 ℃, and the oxygen release temperature after the oxidation in the fuel reaction device is 800-1000 ℃.
9. the application of composite type oxygen carrier granule according to claim 1 in chemical chain oxygen decoupling technology is characterized in that described oxygen carrier is by active ingredient CuO and Y
2O
3Form, by the weight percentage of oxygen carrier, the content of CuO is 80% ~ 99%, Y
2O
3Content be 1% ~ 20%.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (2)
| 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 |
| CN110982580A (en) * | 2019-12-12 | 2020-04-10 | 华中科技大学 | Preparation method and product of composite material oxygen carrier with compact structure |
-
2013
- 2013-04-24 CN CN 201310146909 patent/CN103215102A/en active Pending
Cited By (2)
| 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 |
| CN110982580A (en) * | 2019-12-12 | 2020-04-10 | 华中科技大学 | Preparation method and product of composite material oxygen carrier with compact structure |
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Application publication date: 20130724 |