CN110548391A - Catalytic oxidation system for treating benzene organic matters by manganese-based catalyst prepared based on waste ternary electrode material - Google Patents

Abstract

The invention discloses a catalytic oxidation system for treating benzene series organic matter based on a manganese-based catalyst prepared from waste ternary electrode materials. The system includes the first and second air pumps, gas distribution system, benzene-based organic compound generator, buffer device, preheating device and catalytic reaction device; the system uses the first air pump to carry the organic matter in the benzene-based organic compound generator into the buffer device, adjust the second air pump to dilute the organic matter carried out, and enter the preheating device after stabilization, and then pass through the catalytic reaction device with the honeycomb cordierite as the carrier and the manganese-based catalyst prepared based on the waste ternary electrode material. Organic matter is catalytically degraded. The catalytic oxidation system of the present invention reduces the reaction activation energy of the oxidation reaction of organic matter through the manganese-based catalyst prepared based on waste ternary electrode materials, thereby reducing the reaction temperature, increasing the reaction rate, degrading the organic matter into H ₂ O and CO ₂ , and reducing the oxidation system Improve the degradation rate while treating the energy consumed by organic waste gas.

Description

A manganese-based catalyst based on waste ternary electrode materials for the treatment of benzene-based organic Catalytic Oxidation System

technical field

The invention belongs to the technical field of waste gas treatment, and in particular relates to a catalytic oxidation system for treating benzene series organic matter with a manganese-based catalyst prepared from waste ternary electrode materials.

Background technique

In recent years, the frequent occurrence of smog has seriously affected the surrounding environment and human health, and has aroused widespread concern. One of the major causes of frequent smog is the release of toxic and harmful gases, of which the generation of VOCs occupies an important proportion. The Ministry of Ecology and Environment Various regulations and standards are issued to limit the emission of polluting gases. In the emission of VOCs, the waste gas produced by the chemical industry accounts for the largest proportion, and the waste gas produced by the chemical industry has the characteristics of complex composition, high concentration, and instability. The most effective and widely used technology for the waste gas produced by the chemical industry is direct Thermal combustion and thermal catalytic oxidation, direct thermal combustion requires additional fuel, because the combustion temperature is relatively high, and the requirements for equipment materials are also relatively high, resulting in a significant increase in operating costs. In addition, direct combustion at high temperatures will produce thermal nitrogen Oxides cause secondary pollution, and incomplete combustion also exists. In contrast, the catalytic oxidation temperature of thermodynamic catalytic oxidation is relatively low, no additional fuel is required, there is no secondary pollution problem, and the operating cost is relatively low, and the organic waste gas generated in the chemical industry does not need to be concentrated and can be used directly For catalytic combustion, the selection of noble metals for thermodynamic catalysis will increase its operating costs. Compared with noble metals, general transition metal oxides also have good catalytic degradation effects, and the performance of catalysts obtained by compounding transition metals can be comparable to that of noble metals. Catalyst selection is critical to the overall technology. At present, waste lithium batteries are widely used and are facing the problem of a large number of scrapping, and the positive electrode materials contain a large amount of valuable metal elements. The application of waste ternary electrode materials in the preparation of catalytic oxidation catalysts not only simplifies the preparation of battery positive electrode materials The recovery procedure also reduces the cost of catalytic oxidation degradation and achieves the purpose of treating waste with waste, which can make catalytic oxidation technology play a more important role and have more advantages in industrial waste gas treatment.

Contents of the invention

In view of this, the object of the present invention is to provide a catalytic oxidation system for treating benzene-based organics based on a manganese-based catalyst prepared from waste ternary electrode materials. The system can reduce the reaction activation energy of the oxidation reaction of organic matter through high-efficiency catalysts, thereby reducing the reaction temperature, increasing the reaction rate, degrading organic matter into H ₂ O and CO ₂ , reducing the energy consumed by the oxidation system to treat organic waste gas and improving the degradation rate.

The technical solution of the present invention is specifically introduced as follows.

A catalytic oxidation system for treating benzene-series organics with a manganese-based catalyst prepared from waste ternary electrode materials, which includes a first air pump, a second air pump, a gas distribution system, a benzene-series organics generating device, a first buffer device, and a preheating device , a catalytic reaction device and a second buffer device; the first air pump is sequentially connected with the benzene-based organic matter generating device and the first buffer device through the gas distribution system, and is used to carry out the benzene-based organic matter into the first buffer device, and the second air pump passes through the distribution system The gas system is connected to the first buffer device, which is used to dilute the benzene-series organic matter carried out; the first buffer device is connected to the preheating device and the catalytic reaction device in turn through pipelines, and is used to heat the benzene-series organic matter through the preheating device Then enter the catalytic reaction device to carry out catalytic oxidation reaction, and degrade the benzene series organic matter; the ceramic regenerator is set in the preheating device, and the ceramic regenerator is heated by the first thermocouple, and the first thermocouple and the first temperature control The catalytic reaction device uses a tubular reactor, and the second thermocouple is used to heat the tubular reactor. The second thermocouple is connected to the second temperature controller. The tubular reactor is equipped with a waste ternary The supported manganese-based catalyst prepared by the electrode material; the degraded benzene series organic matter is discharged from the discharge port after passing through the second buffer device.

In the present invention, the concentration of the benzene-series organics entering the preheating device is 300-2500 mg/m ³ ; further, the concentration of the benzene-series organics is 1200-2500 mg/m ³ .

In the present invention, the benzene series organic substances include benzene and toluene.

In the present invention, the supported manganese-based catalyst prepared based on the waste ternary electrode material takes honeycomb cordierite as a carrier, and its preparation method is as follows:

(1) Place the honeycomb cordierite in a drying oven at a temperature of 100-110°C for 10-12 hours;

(2) Dissolve 0.5~1g LiNi _{1− x − y} Co _x Mn _y O ₂ ternary cathode material of waste lithium battery with 30~50ml aqua regia to prepare the required impregnation solution;

(3) Immerse the dried carrier in step (1) in the impregnation solution prepared in step (2) for 3-4 hours;

(4) Treat the impregnated sample in an oven at a temperature of 100-110°C for 10-12 hours;

(5) Treat and activate in a muffle furnace at 1150~1250°C to make a catalytic oxidation catalyst.

In the present invention, the temperature in the preheating device is 100-200°C; the temperature in the catalytic reaction device is 175-375°C.

In the present invention, the air distribution volume of the first air pump is between 0-10 L/min, the air distribution volume of the second air pump is between 0-50 L/min; the space velocity in the catalytic reaction device is 5000-12000h ^-1 .

Compared with prior art, the beneficial effect of the present invention is:

The invention can reduce the degradation temperature of benzene series organic matter, and compared with the traditional combustion process, the reaction system is more energy-saving.

The active component of the catalyst used in the present invention is a composite metal oxide prepared based on NCM, the ternary positive electrode material of waste lithium batteries, which is lower in price than traditional noble metal catalysts, has the characteristics of regeneration, and has higher degradation of benzene-based organics Rate.

The invention selects the honeycomb cordierite as the carrier for the activity test, and compared with the traditional carrier, it has the characteristics of high mechanical strength, small pressure drop, good heat resistance and the like.

Description of drawings

Figure 1 is a schematic structural diagram of a catalytic oxidation system for organic waste gas treatment.

Fig. 2 is a cross-sectional view of a honeycomb cordierite carrier.

Labels in the figure: 1-first air pump, 2-second air pump, 3-gas distribution system, 4-benzene-based organic matter generator, 5-first buffer device, 6-ceramic heat storage body, 7-first temperature control instrument, 8-second temperature controller, 9-tubular reactor, 10-second buffer device, 11-tube furnace, 12-outlet, 13-sampling port, 14-honeycomb cordierite carrier, 15- 1st thermocouple, 16 - 2nd thermocouple.

Detailed ways

The technical solutions of the present invention will be described in detail below in conjunction with the drawings and embodiments.

The present invention provides a catalytic oxidation system capable of efficiently treating benzene series organics (Figure 1), which includes:

The first air pump 1, the second air pump 2, the gas distribution system 3, the benzene series organic matter generating device 4 and the first buffer device 5; the benzene series organic matter generating device 4 includes a temperature control system, which keeps a low temperature through the temperature control system, such as 1 ℃, to ensure that the benzene-series organics in the benzene-series organics generator 4 remain in a liquid state. At the same time, only the flow of air (first air pump 1) to carry out the benzene-series organics cannot meet the experimental requirements. Another air flow (second air pump 2) is specially used to dilute the carried-out benzene-series organics to adjust its concentration. It intelligently controls the flow rate of the air pump through the computer to adjust the concentration of benzene series organic matter in the first buffer device 5 .

In the embodiment, the first air pump 1 (0-10 L/min) for blowing liquid toluene 3 and the second air pump 2 (0-50 L/min) for blowing air are used to control the gas concentration. By adjusting the first air pump 1, the temperature The toluene in the benzene series organic matter generating device 4 in the control system is carried out into the first buffer device, and the second air pump 2 is adjusted to dilute the carried out toluene to control the concentration of the target degradation product toluene. The total flow rate of the gas is 12 L/ min, the toluene gas concentration was maintained at 1500 mg/m ³ .

After the gas is stabilized, the toluene passing through the gas distribution system 3 enters the ceramic regenerator 6 in the preheating device, and the first thermocouple 15 connected to the first temperature controller 7 heats up the temperature of the target pollutant toluene. The ceramic regenerator 6 is a cylinder with a cross-sectional diameter of 20 cm, and the diameter of the honeycomb holes in the regenerator is 0.5 cm; the ceramic regenerator 6 selected in the system has high strength, high temperature resistance, corrosion resistance, wear resistance, etc. characteristic. The temperature in the preheating device is between 100-200°C.

The preheated gas enters the catalytic reaction device, and the device selects a tubular reactor 9 as the catalytic reaction device. The tubular reactor 9 is a quartz tube with a length of 450 mm, an inner diameter of 22 mm, and an outer diameter of 25 mm. mm, the volume is 168 mL, the catalyst is placed inside the quartz tube, heated by a tube furnace, and the bed temperature is tested by the second thermocouple 16, which is connected to the second temperature controller 8 to control the tube furnace to the bed. Layer heating temperature;

In the embodiment, the catalyst placed in the tubular reactor 9 is a manganese-based catalyst prepared from waste ternary electrode materials. The specific preparation method is as follows:

Place cordierite in a drying oven at 110°C and dry for 10 hours, then dissolve 1 g of waste lithium battery ternary cathode material LiNi _{1− x − y} Co _x Mn _y O ₂ with 50 ml of aqua regia to prepare the required impregnation solution. The dried carrier is immersed in the prepared impregnation solution for 3 hours, then the impregnated catalyst is treated in an oven at 100°C for 10 hours, and finally activated in a muffle furnace at 1200°C to obtain Catalytic oxidation catalyst, which can effectively reduce the degradation temperature of organic pollutants, reduce energy waste, and improve reaction activity.

In the example, 1 g of waste lithium battery ternary positive electrode material LiNi _{1− x − y} Co _x Mn _y O ₂ was taken in an electric furnace, calcined, placed in 50 ml of aqua regia, and then digested by microwave The content of metal elements measured by ICP-AES shows that manganese accounts for 66.49%, nickel accounts for 16.11%, cobalt accounts for 7.94%, lithium accounts for 7.69%, and contains a small amount of 1.78% aluminum.

The toluene gas after the degradation is carried out to the residual organic gas in the tail gas by the second buffer device 10 that is placed with gac.

Remove by adsorption.

After the system is stabilized, the inlet and outlet gases are sampled respectively, the inlet concentration is sampled through the sampling port 13, and the outlet concentration is sampled through the outlet 12; after sampling with a sampling needle, the gas concentration is measured by a gas chromatograph to The performance of the organic waste gas catalytic oxidation system was evaluated.

Environmental working condition influencing factor test

The temperature in the preheating device of the present invention is set at 150° C., and the measurement is performed after the catalytic degradation reaction device has run stably for 10 minutes. Change the regulating valves of the two air pumps to control the gas concentration to maintain stability.

The present invention controls the temperature in the catalytic reaction device to be 375°C and the concentration of the intake air to be 1500mg/m ³ under constant conditions, respectively set the space velocity with a certain interval, and after the reaction system runs stably for 10 minutes, the reaction system is respectively at the front end and the rear of the reactor. Sampling analysis was carried out at the end, and the conversion efficiency of toluene was measured under the conditions of space velocity of 5372.5, ^5732.5 , 7643.3, 9554.1, and 12420.4 h ^-1 respectively. It can reach more than 85%, and with the increase of space velocity, the degradation rate of toluene of the prepared catalyst will decrease to a certain extent.

In the present invention, the required intake air concentration is obtained by adjusting the flow rate of the air pump. The temperature of the catalytic reaction device is controlled at 375°C, and the air velocity is controlled at 5732.5h ^-1 . When the concentration gradient of the intake air is 319.9, 982.4, 1622.7, 2311.2 mg/m ³ , the analysis by gas chromatography after sampling shows that the difference between the conversion rate of toluene at the highest concentration and the lowest concentration is less than 4%, which is not much different. , the degradation rate of toluene can reach 80%.

In an example of the present invention, the gas distribution volume is controlled to 12 L/min, the space velocity is 5732.5 h ^-1 , the toluene gas concentration is 1500 mg/m ³ , the honeycomb cordierite is used as the carrier, and the load is from waste ternary electrodes The manganese-based catalyst prepared in the material was used for the degradation experiment of organic matter. The temperature in the catalytic reaction device was set between 175-375 °C, and the temperature gradient was set at 25 °C. During the temperature rise from 250-375 °C, the toluene The conversion rate starts to increase from 30%, and tends to be stable at 350 ℃, and the highest degradation efficiency can reach more than 85%.

In an example of the present invention, the gas distribution volume is controlled at 12 L/min, the space velocity is 5732.5 h ^-1 , and the toluene gas concentration is 1500 mg/m ³ . The degradation experiment of organic matter with cordierite was carried out. As the temperature continued to rise in the range of 200-350 ℃, the removal of toluene was almost unchanged, and the highest removal rate of toluene on the unloaded cordierite carrier was no more than 5%.

To sum up, the organic pollutant catalytic oxidation system provided by the present invention takes benzene-based organic matter toluene as the degradation object, uses honeycomb ceramic regenerator to preheat organic pollutants, and controls the temperature at 100-200 ° C. Honeycomb cordierite is used as the carrier, and the load is manganese-based catalyst prepared from waste ternary electrode materials to reduce the degradation temperature of organic pollutants, improve the reactivity, and achieve the purpose of degrading organic matter at a lower temperature, avoiding waste of excess At the same time, the prepared manganese-based composite metal oxide catalyst can be obtained from waste ternary batteries. The selected composite metal oxide catalyst has similar performance to the noble metal catalyst, which can effectively reduce the cost of the catalyst, save costs, and achieve The purpose of treating waste with waste. Therefore, the present invention has the advantages of environmental protection, economy and high efficiency.

Although the present invention has provided specific implementation methods and cases, the above-mentioned embodiments are illustrative, and the scope of the present invention is not limited thereto. Those skilled in the technical field of the present invention can modify the above cases within the scope of the present invention.

Claims (7)

1. Catalytic oxidation system for treating benzene organic matters by using manganese-based catalyst prepared based on waste ternary electrode material

characterized in that the device comprises a first air pump, a second air pump, an air distribution system, a benzene series organic matter generating device, a first buffer device, a preheating device, a catalytic reaction device and a second buffer device; the first air pump is sequentially connected with the benzene system organic matter generating device and the first buffer device through the air distribution system and used for loading the benzene system organic matters into the first buffer device, and the second air pump is connected with the first buffer device through the air distribution system and used for diluting the loaded benzene system organic matters; the first buffer device is connected with the preheating device and the catalytic reaction device sequentially through a pipeline and is used for heating benzene organic matters through the preheating device and then enabling the benzene organic matters to enter the catalytic reaction device for catalytic oxidation reaction, and degrading the benzene organic matters; the catalytic reaction device adopts a tubular reactor, the tubular reactor is heated by a second thermocouple, the second thermocouple is connected with the second temperature controller, and a supported manganese-based catalyst prepared based on waste ternary electrode materials is arranged in the tubular reactor; and the degraded benzene organic matters are discharged from the discharge port after passing through the second buffer device.

2. The catalytic oxidation system according to claim 1, wherein the concentration of the benzene-based organic compound entering the preheating device is 300-2500mg/m ³.

3. The catalytic oxidation system according to claim 1, wherein the concentration of the benzene-based organic compound entering the preheating device is 1200-2500mg/m ³.

4. The catalytic oxidation system of claim 1, wherein the benzene-based organic comprises benzene and toluene.

5. The catalytic oxidation system of claim 1, wherein the supported manganese-based catalyst prepared based on the waste ternary electrode material is prepared by using honeycomb cordierite as a carrier; the preparation method comprises the following steps:

(1) Placing the honeycomb cordierite into a drying box to be dried for 10-12 hours at the temperature of 100-110 ℃;

(2) Dissolving 0.5 ~ 1g of waste lithium battery ternary positive electrode material LiNi _{1- x - y} Co _x Mn _y O ₂ by using 30 ~ 50ml of aqua regia to prepare required impregnation liquid;

(3) Placing the carrier dried in the step (1) into the impregnation liquid prepared in the step (2) for impregnation for 3-4 hours;

(4) Treating the impregnated sample in an oven at a temperature of 100-110 ℃ for 10-12 hours;

(5) The catalyst is treated and activated in a muffle furnace at 1150 ~ 1250 ℃ to prepare the catalytic oxidation catalyst.

6. The catalytic oxidation system of claim 1, wherein the temperature in the preheating device is 100-200 ℃; the temperature in the catalytic reaction device is 175-375 ℃.

^-17. The catalytic oxidation system of claim 1, wherein the air distribution amount of the first air pump is 0-10L/min, the air distribution amount of the second air pump is 0-50L/min, and the space velocity in the catalytic reaction device is 5000-.