CN110801844B - Method for preparing demercuration catalyst by using waste anode material and application of demercuration catalyst - Google Patents

Method for preparing demercuration catalyst by using waste anode material and application of demercuration catalyst Download PDF

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CN110801844B
CN110801844B CN201911192023.6A CN201911192023A CN110801844B CN 110801844 B CN110801844 B CN 110801844B CN 201911192023 A CN201911192023 A CN 201911192023A CN 110801844 B CN110801844 B CN 110801844B
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demercuration
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waste
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CN110801844A (en
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刘志楼
李子良
徐志峰
严康
张溪
昝苗苗
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Jiangxi University of Science and Technology
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Abstract

The invention discloses a method for preparing a demercuration catalyst by using a waste anode material, which comprises the following steps: (1) carrying out dealuminization treatment on the waste positive electrode material to obtain a dealuminized positive electrode material; (2) carrying out heat treatment on the dealuminized cathode material obtained in the step (1) under the protection of inert gas to obtain a metal oxide composite carbon catalyst; (3) grinding the metal oxide composite carbon catalyst obtained in the step (2), placing the ground metal oxide composite carbon catalyst in reducing gas for heating and activating, and cooling to obtain the demercuration catalyst. The invention also provides an application of the demercuration catalyst. The method takes the waste ternary cathode material as the raw material to prepare the demercuration catalyst, thereby changing waste into valuable, realizing the cyclic utilization of resources, and having low raw material cost and high economic value of the demercuration catalyst. The catalyst has high demercuration efficiency, the catalytic oxidation efficiency can reach more than 90 percent, and the economic benefit can be obviously improved.

Description

Method for preparing demercuration catalyst by using waste anode material and application of demercuration catalyst
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method and application of a demercuration catalyst.
Background
In the traditional industrial production processes of coal burning, smelting, cement and the like, mercury in coal and minerals can volatilize into flue gas in a high-temperature process to form mercury-containing flue gas. China is a large country for producing electric power, metal and cement, and the atmospheric mercury discharge amount of China is huge. In order to reduce the harm of mercury to the environment and human beings, the reduction of mercury emission in the atmosphere in our country is urgently needed.
The mercury in the flue gas is mainly in the oxidized state mercury (Hg)2+) Granular mercury (Hg)p) And elemental mercury (Hg)0) Three forms exist, most of which is Hg2+And HgpCan be removed in the flue gas washing and dedusting processes respectively. Relative ratio of Hg to Hg2+And Hgp，Hg0Due to low solubility and high chemical stability, it is difficult to remove by existing flue gas treatment assemblies, and therefore specialized techniques are required to achieve Hg0The removal is efficient.
Currently directed to Hg0The removal technology mainly consists of two strategies of adsorption and catalytic oxidation. The adsorption technique mainly utilizes Hg0Affinity with active carbon, halogen, sulfide and other substances, and finally Hg0Conversion to Hgp. Although adsorption techniques can achieve Hg0The mercury-containing particles formed after the capture still have the risk of secondary mercury pollution, and the operation cost is relatively high. The catalytic oxidation technology is to convert Hg0Catalytic oxidation to Hg2+Has become a reduction in Hg due to low operating costs and high oxidation efficiency0An efficient way of discharging. At present Hg0The catalyst mainly focuses on the aspects of copper oxide, noble metal, rare earth metal oxide and the like, the production cost of the material is high, and the wide application of the material is limited, so that the development of an economical and efficient composite metal catalyst is urgent.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background art, and provide a method for preparing a demercuration catalyst by using waste cathode materials and application of the demercuration catalyst. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for preparing a demercuration catalyst by using a waste anode material comprises the following steps:
(1) carrying out dealuminization treatment on the waste positive electrode material to obtain a dealuminized positive electrode material;
(2) carrying out heat treatment on the dealuminized cathode material obtained in the step (1) under the protection of inert gas (such as high-purity nitrogen or argon) to obtain a metal oxide composite carbon catalyst;
(3) grinding the metal oxide composite carbon catalyst obtained in the step (2), placing the ground metal oxide composite carbon catalyst in reducing gas for heating and activating, and cooling to obtain the demercuration catalyst.
In the invention, metal oxide in the power battery is adhered to the aluminum foil through the adhesive to form the anode material, and part of the aluminum foil inevitably exists in the obtained waste anode material in the process of recycling the waste power battery. If aluminum is not removed, the aluminum foil may reduce the activity of the catalyst during subsequent catalyst preparation, such as reaction with metal oxides during calcination in an inert atmosphere to form a less active composite, thereby requiring a dealumination operation. In addition, the waste positive electrode material may contain a part of lithium, which is mainly present in the form of lithium cobaltate, lithium cobalt manganese oxide, and the like.
In the above method for preparing a demercuration catalyst, preferably, the inert gas is a flowing inert gas, and the flow rate of the inert gas is controlled to be 0.5 to 1.2L/min.
In the above method for preparing the demercuration catalyst, preferably, the heating rate of the heat treatment is controlled to be 2-6 ℃/min, the heat treatment temperature is 600-800 ℃, and the heat preservation time is 30-90 min. The heat treatment process parameters can ensure that all organic matters in the waste anode material are volatilized and carbonized. The temperature range, the heating rate and the heat preservation time of the heat treatment can ensure the high-efficiency carbonization of organic matters (such as a binder), and are beneficial to the formation of the porous composite catalyst.
In the above method for preparing a demercuration catalyst, preferably, the reducing gas is a hydrogen-nitrogen mixed gas or a carbon monoxide-nitrogen mixed gas, the volume of hydrogen in the hydrogen-nitrogen mixed gas is 2-5%, and the volume of carbon monoxide in the carbon monoxide-nitrogen mixed gas is 4-10%. The amount of reducing gas should not be too high, and the amount is related to the activation time and temperature, and the main purpose is to prevent excessive reduction and formation of a large amount of elemental metal.
In the above method for preparing the demercuration catalyst, preferably, the activation temperature is controlled to be 400-. The purpose of the heating activation in a reducing atmosphere is to stabilize LiCoO by partial reduction2Reduction of the surface of the oxide to form Co3+/Co2+、Mn4+/Mn3+And the electrons are equivalent to active sites to promote the catalytic oxidation of mercury. Too high heating temperature and too long activation time can lead to excessive reduction and reduced catalyst activity, too low heating temperature and too short activation time can lead to insufficient reduction degree and fewer surface catalytic active sites, which is not beneficial to mercury catalysis.
In the above method for preparing a demercuration catalyst, preferably, the dealumination treatment is to add the waste positive electrode material into an alkali liquor, stir and dissolve the waste positive electrode material, and control a solid-to-liquid ratio (mass ratio) of the waste positive electrode material to the alkali liquor to be 1: (3-7), wherein the pH value of the alkali liquor is 10-12.
In the above method for preparing the demercuration catalyst, preferably, the reaction temperature is controlled to be 40-60 ℃ during stirring and dissolving, the reaction time is 0.5-1.5h, and the stirring speed is 400-800 r/min.
In the above method for preparing a demercuration catalyst, preferably, the waste positive electrode material is a nickel-cobalt-manganese ternary positive electrode material.
As a general technical concept, the invention also provides an application of the demercuration catalyst prepared by the method, the demercuration catalyst is used for catalytic oxidation of elemental mercury in mercury-containing flue gas, and the temperature of the catalytic oxidation is 100-250 ℃. The demercuration catalyst is particularly suitable for treating industrial mercury-containing flue gas such as fire coal, colored flue gas, cement flue gas and the like, and researches show that the proper action temperature range of the specific catalyst is 100-250 ℃, and the catalytic oxidation efficiency of the catalyst is high in the temperature range.
The invention directly utilizes the waste anodeThe material is used for preparing a demercuration catalyst, the waste anode material contains carbon such as a binder and a conductive agent and metal cobalt/manganese/nickel metal oxide, the carbon containing the binder and the conductive agent in the waste anode material is subjected to heat treatment under an inert atmosphere to form a porous carbon material framework, a carrier is provided for metal oxide active substances in the anode material, and therefore the composite carbon material is formed with the metal oxide, and after the heat treatment, the anode material can form holes, so that the specific surface area of the material is favorably improved, and the catalytic performance is improved; the stable high-valence Co/Mn/Ni metal oxide in the anode material forms high-activity heterojunction active sites on the surface thereof through controlled reduction, such as Co2O3CoO and MnO2/Mn3O4A heterojunction formed on the surface of the catalyst and having high-activity Co3+/Co2+And the high-efficiency catalytic oxidation of the elemental mercury in the flue gas can be realized by waiting for the electron pair.
The waste positive electrode material contains a part of lithium, which is mainly in the form of lithium cobaltate, lithium cobalt manganese oxide, and the like.
Compared with the prior art, the invention has the advantages that:
1. the method takes the waste ternary cathode material as the raw material to prepare the demercuration catalyst, thereby changing waste into valuable, realizing the cyclic utilization of resources, and having low raw material cost and high economic value of the demercuration catalyst.
2. The preparation process of the catalyst is simple and environment-friendly, and meets the requirements of industrial production.
3. The catalyst has high demercuration efficiency, the catalytic oxidation efficiency can reach more than 90 percent, and the economic benefit can be obviously improved.
4. The adsorbent can be widely applied to the field of mercury removal of various industrial flue gases, has a wide application range, can be directly applied to the existing flue gas treatment equipment, and does not need to change the existing treatment process.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
in the method for preparing the demercuration catalyst by using the waste cathode material in this embodiment, the waste cathode material in this embodiment is a nickel-cobalt-manganese ternary cathode material, and the molar ratio of the nickel-cobalt-manganese ternary cathode material to the waste cathode material is 1: 1: 1, comprising the following steps:
(1) preparing 100mL of NaOH solution with pH of 11, adding 30g of waste anode material into the prepared solution, stirring at the rotating speed of 500r/min, reacting at 50 ℃ for 1h, filtering and washing slurry after reaction, and drying at 60 ℃ for more than 10h to obtain a dealuminized anode material;
(2) placing the dealuminized anode material in a tube furnace, and introducing high-purity N at the flow rate of 1L/min2As protective gas, heating to different temperatures (see table 1 below) at a heating rate of 5 ℃/min, and keeping the temperature for 30min to obtain different metal oxide composite carbon catalysts;
(3) grinding the prepared metal oxide composite carbon catalyst, placing the ground metal oxide composite carbon catalyst in an atmosphere furnace, and introducing 5% H reducing gas2+95％N2(volume ratio), heating to 500 ℃ for activation, wherein the activation time is 10min, stopping introducing reducing gas after reaction, and naturally cooling to room temperature to obtain the demercuration catalyst in the embodiment.
Taking the prepared demercuration catalyst, and placing the demercuration catalyst in a fixed bed for catalytic evaluation, wherein the specific method comprises the following steps: fixing 50mg of demercuration catalyst on a fixed bed, controlling the reaction temperature at 150 ℃, controlling the gas flow at 1L/min, and making the flue gas component be 10ppm HCl + 5% O2+180μg/m3 Hg0Final Hg of0Catalytic oxidation efficiency results are shown in table 1。
Table 1: different heating temperatures for Hg0Effect of Oxidation efficiency
Sample numbering Heating temperature (. degree.C.) Hg0Catalytic oxidation efficiency (%)
Comparison group - 34.5
1 500 83.3
2 600 91.3
3 700 92.5
4 800 91.6％
5 900 86.4％
As can be seen from Table 1, the Hg content can be significantly increased by high temperature calcination under inert atmosphere0The heating temperature is in the range of 600-800 ℃, Hg0The catalytic oxidation efficiency is over 90 percent. The comparative group was treated at room temperature and the rest of the procedure was the same.
Example 2:
in the method for preparing the demercuration catalyst by using the waste cathode material in this embodiment, the waste cathode material in this embodiment is a nickel-cobalt-manganese ternary cathode material, and the molar ratio of the nickel-cobalt-manganese ternary cathode material to the waste cathode material is 1: 1: 1, comprising the following steps:
(1) preparing 100mL of NaOH solution with pH of 11, adding 30g of waste anode material into the prepared solution, stirring at the rotating speed of 500r/min, reacting at 50 ℃ for 1h, filtering and washing slurry after reaction, and drying at 60 ℃ for more than 10h to obtain a dealuminized anode material;
(2) placing the obtained dealuminized anode material in a tube furnace, and introducing high-purity N at the flow rate of 1L/min2As protective gas, heating to 700 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 30min to obtain the metal oxide composite carbon catalyst;
(3) grinding the prepared metal oxide composite carbon catalyst, placing the ground metal oxide composite carbon catalyst in an atmosphere furnace, and introducing 5% H reducing gas2+95％N2(volume ratio), heating to different activation temperatures and activation times for activation (see table 2 below for details), stopping introducing reducing gas after reaction, and naturally cooling to room temperature to obtain the demercuration catalyst in the embodiment.
Taking the prepared demercuration catalyst, and placing the demercuration catalyst in a fixed bed for catalytic evaluation, wherein the specific method comprises the following steps: fixing 50mg of demercuration catalyst on a fixed bed, controlling the reaction temperature at 150 ℃, controlling the gas flow at 1L/min, and making the flue gas component be 10ppm HCl + 5% O2+180μg/m3 Hg0Final Hg of0The catalytic oxidation efficiency results are shown in table 2.
Table 2: different activating and roasting temperatures and heat preservation times for Hg0Effect of catalytic Oxidation efficiency
Sample numbering Activation temperature (. degree.C.) Incubation time (min) Hg0Oxidation efficiency (%)
Comparison group - - 62.8
1 300 10 80.1
2 400 10 90.4
3 500 2 75.2
4 500 10 92.5
5 500 30 84.8
6 600 10 90.7
7 700 10 82.9
As can be seen from Table 2, the reduction activation can significantly improve the mercury removal efficiency of the catalyst, and the activation temperature is 400-600 ℃ Hg0The catalytic oxidation efficiency of (2) is higher, and the formation of active oxygen vacancies on the surface of the catalyst is not favorable for too short and too long holding time, thereby causing Hg0The oxidation efficiency is decreased.
Example 3:
in the method for preparing the demercuration catalyst by using the waste cathode material in this embodiment, the waste cathode material in this embodiment is a nickel-cobalt-manganese ternary cathode material, and the molar ratio of the nickel-cobalt-manganese ternary cathode material to the waste cathode material is 1: 1: 1, comprising the following steps:
(1) preparing 100mL of NaOH solution with pH of 11, adding 30g of waste anode material into the prepared solution, stirring at the rotating speed of 500r/min, reacting at 50 ℃ for 1h, filtering and washing slurry after reaction, and drying at 60 ℃ for more than 10h to obtain a dealuminized anode material;
(2) placing the obtained dealuminized anode material in a tube furnace, and introducing high-purity N at the flow rate of 1L/min2As protective gas, heating to 700 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 30min to obtain the metal oxide composite carbon catalyst;
(3) grinding the prepared metal oxide composite carbon catalyst, placing the ground metal oxide composite carbon catalyst in an atmosphere furnace, and introducing reductionOriginal gas 5% H2+95％N2(volume ratio), heating to 500 ℃ for activation, wherein the activation time is 10min, stopping introducing reducing gas after reaction, and naturally cooling to room temperature to obtain the demercuration catalyst in the embodiment.
Taking the prepared demercuration catalyst, and placing the demercuration catalyst in a fixed bed for catalytic evaluation, wherein the specific method comprises the following steps: fixing 50mg of demercuration catalyst on a fixed bed, controlling Hg in flue gas at a gas flow of 1L/min0Is 180 mu g/m3Changing the temperature of the catalytic reaction and the HCl and O in the flue gas2The concentration determines the appropriate application conditions for the catalyst, its final Hg0The catalytic oxidation efficiency results are shown in table 3.
Table 3: different catalytic reaction temperatures and flue gas composition pairs Hg0Effect of Oxidation efficiency
Figure BDA0002293808280000051
Figure BDA0002293808280000061
As can be seen from Table 3, the optimum temperature range for the catalyst is 100-250 ℃. HCl and O2All can increase the catalyst to Hg0Wherein Hg is present in the absence of HCl0The oxidation efficiency of the catalyst can still reach 80 percent, which shows that the catalyst can realize the oxidation of mercury under the condition of no chlorine.
Example 4:
the method for preparing the demercuration catalyst by using the waste lithium cobaltate cathode material in the embodiment comprises the following steps of:
(1) preparing 100mL of NaOH solution with the pH value of 11, adding 30g of waste lithium cobaltate positive electrode material into the prepared solution, stirring at the rotating speed of 500r/min, reacting at 50 ℃ for 1h, filtering and washing slurry after reaction, and drying at 60 ℃ for more than 10h to obtain a dealuminized lithium cobaltate positive electrode material;
(2) placing the obtained dealuminized lithium cobalt oxide in a tube furnaceIn the method, high-purity N is introduced at a flow rate of 1L/min2As protective gas, heating to 700 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 30min to obtain the metal oxide composite carbon catalyst;
(3) grinding the prepared metal oxide composite carbon catalyst, placing the ground metal oxide composite carbon catalyst in an atmosphere furnace, and introducing 5% H reducing gas2+95％N2(volume ratio), heating to 500 ℃ for activation, wherein the activation time is 10min, stopping introducing reducing gas after reaction, and naturally cooling to room temperature to obtain the demercuration catalyst in the embodiment.
Taking the prepared demercuration catalyst, and placing the demercuration catalyst in a fixed bed for catalytic evaluation, wherein the specific method comprises the following steps: fixing 50mg of demercuration catalyst on a fixed bed, controlling the reaction temperature at 150 ℃, controlling the gas flow at 1L/min, and making the flue gas component be 10ppm HCl + 5% O2+180μg/m3 Hg0The mercury catalytic oxidation efficiency of the final lithium cobaltate catalyst was 83.4%.

Claims (9)

1. A method for preparing a demercuration catalyst by using a waste anode material is characterized by comprising the following steps:
(1) carrying out dealuminization treatment on the waste positive electrode material to obtain a dealuminized positive electrode material;
(2) carrying out heat treatment on the dealuminized cathode material obtained in the step (1) under the protection of inert gas to obtain a metal oxide composite carbon catalyst;
(3) grinding the metal oxide composite carbon catalyst obtained in the step (2), placing the ground metal oxide composite carbon catalyst in reducing gas for heating and activating, and cooling to obtain the demercuration catalyst.
2. The method for preparing a demercuration catalyst according to claim 1, wherein the inert gas is a flowing inert gas, and the flow rate of the inert gas is controlled to be 0.5 to 1.2L/min.
3. The method for preparing a demercuration catalyst as claimed in claim 1, wherein the temperature rise rate of the heat treatment is controlled to be 2-6 ℃/min, the heat treatment temperature is 600-800 ℃, and the heat preservation time is 30-90 min.
4. The method for preparing a demercuration catalyst according to claim 1, wherein the reducing gas is a hydrogen-nitrogen mixed gas or a carbon monoxide-nitrogen mixed gas, the hydrogen volume ratio in the hydrogen-nitrogen mixed gas is 2-5%, and the carbon monoxide volume ratio in the carbon monoxide-nitrogen mixed gas is 4-10%.
5. The method for preparing a demercuration catalyst as claimed in claim 1, wherein the heating activation is performed at a temperature of 400 ℃ and 600 ℃ for 5-15 min.
6. The method for preparing the demercuration catalyst according to any one of claims 1 to 5, wherein the dealumination treatment is to add the waste cathode material into the alkali liquor to be stirred and dissolved, and the solid-liquid ratio of the waste cathode material to the alkali liquor is controlled to be 1: (3-7), wherein the pH value of the alkali liquor is 10-12.
7. The method for preparing a demercuration catalyst as claimed in claim 6, wherein the reaction temperature is controlled to be 40-60 ℃, the reaction time is controlled to be 0.5-1.5h, and the stirring speed is 400-800 r/min.
8. The method for preparing a demercuration catalyst according to any one of claims 1 to 5, wherein the waste cathode material is a nickel-cobalt-manganese ternary cathode material.
9. Use of a demercuration catalyst prepared by the method as set forth in any one of claims 1-8, wherein the demercuration catalyst is used for catalytic oxidation of elemental mercury in mercury-containing flue gas, and the temperature of the catalytic oxidation is 100-250 ℃.
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