CN108192686B - Preparation method of steel slag oxygen carrier - Google Patents
Preparation method of steel slag oxygen carrier Download PDFInfo
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- CN108192686B CN108192686B CN201711381957.5A CN201711381957A CN108192686B CN 108192686 B CN108192686 B CN 108192686B CN 201711381957 A CN201711381957 A CN 201711381957A CN 108192686 B CN108192686 B CN 108192686B
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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Abstract
The invention relates to the technical field of preparation of oxygen carriers in chemical looping combustion systems, in particular to a preparation method of a steel slag oxygen carrier. The oxygen carrier takes steel slag as a main raw material, and the steel slag oxygen carrier with high oxygen carrying capacity, high reactivity and no agglomeration is obtained after drying, crushing and sulfation. The preparation method has the advantages of simplicity, low price of the prepared oxygen carrier, high oxygen carrying capacity, excellent reaction performance and the like. The invention provides a preparation method of a steel slag oxygen carrier with industrial potential, which overcomes the problems of low oxygen carrying capacity, high cost and the like of the current oxygen carrier, realizes the large-scale utilization of steel slag, and avoids the environmental pollution caused by occupying a large amount of land.
Description
Technical Field
The invention relates to the technical field of preparation of oxygen carriers in chemical looping combustion systems, in particular to a method for preparing a chemical looping combustion oxygen carrier by using steel slag.
Background
CO due to the heavy use of fossil fuels2The isothermal chamber gas emission increases dramatically. The chinese commitment will peak carbon dioxide emissions around 2030 years and strive to be implemented as early as possible. Thus, emission reduction of CO2Has important significance for China. CO in flue gas generated by traditional combustion mode2The concentration is only 10-14%, and the CO in the flue gas is restricted2Utilization and consumption of. The CO which is the main stream at present2Capture techniques include pre-combustion capture, in-combustion capture, and post-combustion capture, although CO can be achieved2But consumes a large amount of energy, resulting in high emission reduction cost. Chemical looping combustion is a novel combustion mode, and solid lattice oxygen replaces air for combustion in the combustion process, so that direct contact between fuel and air is avoided. In the fuel reaction chamber, the fuel reacts with the oxygen carrier to complete the oxidation of the fuel; the reduced oxygen carrier enters an air reaction chamber to carry out oxidation reaction with air, so that the regeneration of the oxygen carrier is realized. Wherein, the property of the oxygen carrier directly influences the stability of the operation of the whole chemical-looping combustion system.
At present, the oxygen carriers mainly studied are metal oxygen carriers including Fe, Ni, Co, Cu,Oxides of Mn, Cd and the like, and carriers mainly comprise: al (Al)2O3、TiO2、MgO、SiO2YSZ, etc. For example, patent CN104164273A discloses a method for preparing a calcium-based oxygen carrier using calcium sulfate as a main raw material and alumina, silica sol or glycerol as a carrier; patent CN104119983A discloses a preparation method of a copper-based composite oxygen carrier containing iron, wherein the mass fractions of CuO and FeO are respectively 95% and 5%; patent CN104152211A discloses a method for preparing a magnesium-copper based composite oxygen carrier composed of CuO (95%) and MgO (5%) by a sol-gel method. Among them, Fe-based oxygen carriers, especially natural iron ore, attract a wide range of attention because of its lowest cost relative to other oxygen carriers, its broadest source and good environmental benefits. However, the development and application of the Fe-based oxygen carrier are restricted by low oxygen loading and poor reactivity. In order to reduce the cost of the oxygen carrier and the problem that the oxygen carrying amount of the metal oxygen carrier is small, CaSO4The base oxygen carrier becomes an important choice. But also has the problems of easy decomposition in the reduction-oxidation process, unstable cycle performance and low-temperature CaSO4The reduction reaction performance of (2) is poor.
The steel slag is a solid waste generated in the steel making process, and the worldwide production amount of the steel slag is about 1.6 to 2.4 hundred million tons in 2016, wherein China accounts for half. The part of the steel slag can not be well utilized, which not only wastes resources, but also occupies a large amount of land and causes environmental pollution.
Disclosure of Invention
In order to solve the problems of low oxygen carrying capacity, high cost and the like of the oxygen carrier in the prior art, the invention provides the method for preparing the chemical-looping combustion oxygen carrier, which has the advantages of simple process, low cost, no environmental pollution and capability of realizing the large-scale utilization of steel slag waste.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the steel slag oxygen carrier with high oxygen carrying capacity and high reactivity is prepared by sulfating the steel slag as a main raw material.
A method for preparing a chemical-looping combustion oxygen carrier by using steel slag comprises the following steps:
s1, placing the steel slag in an oven, and drying to constant weight;
s2, adding the dried steel slag into a steam kinetic energy mill for crushing, and grading according to granularity by using a grader;
s3, selecting steel slag with the granularity of 3.15-15.78 μm to carry out sulfation treatment to obtain the chemical-looping combustion oxygen carrier.
The drying temperature of the steel slag is 100 ℃ and 120 ℃, and the water in the steel slag is removed.
The grinding pressure of the steam kinetic energy grinding is 0.7-0.9MPa, and the rotating speed of the classifier is 720 r/min.
The sulfation treatment is to place the steel slag in SO2Calcining for 0.5-1h in the atmosphere, wherein the calcining temperature is 800-1000 ℃.
The SO2The concentration is 1-5%.
Compared with the prior art, the invention has the beneficial effects that:
the chemical-looping combustion technology is combined with the steel slag recycling, so that the high-efficiency utilization of resources is realized, the steel slag can be consumed, and the technical support is provided for the carbon dioxide emission reduction; the oxygen carrier prepared by sulfating the steel slag has the advantages of low price, simple preparation method, environmental protection, high mechanical strength and high oxygen carrying capacity, and is a high-efficiency oxygen carrier. The components in the steel slag can effectively inhibit active components CaSO4The carrier obtained by the invention can be used for the oxygen carrier of chemical-looping combustion taking coal, biomass and municipal solid waste as fuels.
Drawings
FIG. 1 is an XRD spectrum of the steel slag oxygen carrier prepared by the invention.
FIG. 2 is a thermogravimetric graph of the steel slag oxygen carrier prepared by the invention in the oxidation reduction process.
FIG. 3 is a graph showing the change of oxygen loading of the steel slag oxygen carrier prepared by the present invention in the chemical looping combustion process.
FIG. 4 is a graph showing the change of sulfur loss in the chemical looping combustion process of the steel slag oxygen carrier prepared by the invention.
FIG. 5 shows the time for completing oxygen release of the steel slag oxygen carrier prepared by the present invention.
FIG. 6 is a scanning electron microscope image of the steel slag oxygen carrier prepared by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Placing 2g of steel slag in a drying oven, drying at 100 ℃ to constant weight to remove water, crushing the dried steel slag in a steam kinetic energy mill with the pressure of 0.7MPa, grading the crushed steel slag by a grader at the rotating speed of 720r/min, placing the steel slag with the granularity of 3.15-15.78 mu m in 5% SO with the flow of 200 ml/min2Calcining for 0.5h in the atmosphere at 800 ℃ to obtain the chemical-looping combustion oxygen carrier.
Example 2
Placing 2g of steel slag in a drying oven, drying at 110 ℃ to constant weight to remove water, crushing the dried steel slag in a steam kinetic energy mill with the pressure of 0.8MPa, grading the crushed steel slag by using a grader at the rotating speed of 720r/min, placing the steel slag with the granularity of 3.15-15.78 mu m in 1% SO with the flow of 200 ml/min2Calcining for 1h in the atmosphere at the calcining temperature of 1000 ℃ to obtain the chemical-looping combustion oxygen carrier.
Example 3
Placing 2g of steel slag in a drying oven, drying at 120 ℃ to constant weight to remove water, crushing the dried steel slag in a steam kinetic energy mill with the pressure of 0.9MPa, grading the crushed steel slag by using a grader at the rotating speed of 720r/min, placing the steel slag with the granularity of 3.15-15.78 mu m in 3% SO with the flow of 200 ml/min2Calcining for 0.8h in the atmosphere at 900 ℃ to obtain the chemical-looping combustion oxygen carrier.
As shown in FIG. 1, the steel slag of the present invention is mainlyCaO as the main active component of the steel slag oxygen carrier, and FeO, MgO and SiO in the steel slag2The specific surface area of the active component matrix can be effectively increased. The reactivity of the steel slag oxygen carrier is close to NiO and is obviously stronger than that of calcium sulfate, and the components in the steel slag can effectively inhibit the active component CaSO4Side reaction occurs, the carrier reaction activity is improved, the active ingredients can be completely converted in the oxidation-reduction process, and the reaction speed is high.
As shown in FIGS. 2-4, the maximum oxygen carrying capacity of the steel slag oxygen carrier prepared by the invention can reach 18% at the reaction temperature of 750-850 ℃, and the oxygen carrying capacity can be stabilized at about 12% after several cycles. At present, the oxygen carrying amount of the metal-based oxygen carrier which can stably operate is generally 3% -10%, and the oxygen carrying amount of the steel slag-based oxygen carrier prepared by the invention is obviously higher than that of the metal oxygen carrier.
As shown in FIG. 5, the steel slag oxygen carrier prepared by the invention can complete the release of oxygen within 10 minutes, and has excellent reaction performance. And CaSO4The oxygen carrier takes about 2 hours to complete the release of oxygen.
As shown in FIG. 6, the steel slag oxygen carrier prepared by the invention has the advantages of no obvious agglomeration, good dispersibility, fine oxygen carrier particles and stable performance.
Although only the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art, and all changes are encompassed in the scope of the present invention.
Claims (4)
1. A preparation method of a steel slag oxygen carrier is characterized by comprising the following steps:
s1, placing the steel slag in an oven, and drying to constant weight;
s2, adding the dried steel slag into a steam kinetic energy mill for crushing, and grading according to granularity by using a grader;
s3, selecting steel slag with the grain size of 3.15-15.78 μm to carry out sulfation treatment to obtain the chemical-looping combustion oxygen carrier, wherein the sulfation treatment is to place the steel slag in SO2Calcining for 0.5-1h in atmosphere at 800 deg.C-1000℃。
2. The preparation method of the steel slag oxygen carrier according to claim 1, wherein the preparation method comprises the following steps: the drying temperature of the steel slag is 100-120 ℃.
3. The preparation method of the steel slag oxygen carrier according to claim 1, wherein the preparation method comprises the following steps: the grinding pressure of the steam kinetic energy grinding is 0.7-0.9MPa, and the rotating speed of the classifier is 720 r/min.
4. The preparation method of the steel slag oxygen carrier according to claim 1, wherein the preparation method comprises the following steps: the SO2The concentration is 1-5%.
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| CN110054225B (en) * | 2019-05-09 | 2022-02-22 | 新奥科技发展有限公司 | Preparation method of oxygen carrier |
| CN113201377B (en) * | 2021-05-06 | 2022-08-09 | 内蒙古科技大学 | Preparation method of rare earth tailing based oxygen carrier |
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| CN101892110B (en) * | 2010-06-04 | 2013-04-24 | 青岛科技大学 | Preparation method of compound type oxygen carrier particles |
| CN102114383B (en) * | 2011-01-18 | 2013-01-09 | 上海交通大学 | Ammonia-chemical-chain-cycle-based carbon dioxide capture and conversion method |
| CN106145720B (en) * | 2015-03-27 | 2019-01-15 | 宝山钢铁股份有限公司 | A kind of processing method of steel-making slag powder |
| CN105327926B (en) * | 2015-10-27 | 2017-08-11 | 安徽工业大学 | A kind of method that calcium iron dioxygen carrier is prepared by raw material of converter slag |
| CN106753684B (en) * | 2016-12-25 | 2018-09-14 | 新昌县新诚工业产品设计有限公司 | A method of preparing the burning chemistry chains carrier of oxygen using blast furnace slag |
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