CN113648997B - δ-MnO 2 Method for loading graphene oxide Bi-Pd composite catalyst and application - Google Patents
δ-MnO 2 Method for loading graphene oxide Bi-Pd composite catalyst and application Download PDFInfo
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
Abstract
The invention provides delta-MnO 2 A method for loading graphene oxide Bi-Pd composite catalyst and application thereof. Preparation of delta-MnO by sol-gel method 2 Then loading the graphene oxide and Bi-Pd to delta-MnO by adopting an ion exchange method 2 Finally obtaining Bi-Pd/GO/delta-MnO 2 A catalyst. Wherein the loading of GO is less than or equal to 1.5wt%, the loading of Bi is less than or equal to 0.1wt%, and the loading of Pd is less than or equal to 0.5wt%. The catalyst prepared by the invention has the temperature of 100-300 ℃ and the airspeed of 60,000-240,000 h ‑1 Under the condition of (1), the catalyst has good catalytic elimination effect on high-concentration toluene of 1000-3000 ppm, toluene conversion rate of 95-99% and stability (the activity is unchanged in the reaction for 70 h). The catalyst has higher stability, can obviously enhance the electron migration efficiency between Bi-Pd-Mn after being doped with graphene, thereby enhancing the catalytic efficiency, reducing the conversion temperature, and has the advantages of simple preparation process, low cost, good stability and the like.
Description
Technical Field
The invention relates to a delta-MnO for catalyzing and eliminating toluene 2 Preparation method of supported graphene oxide Bi-Pd composite catalyst and application of supported graphene oxide Bi-Pd composite catalyst in selective catalytic elimination of toluene.
Background
Benzene series have great harm to the environment, and threaten the daily life and physical health of people. For example, the international cancer research institution recognizes benzene as a class of carcinogens; ethylbenzene, toluene and xylene are all possible carcinogens, and the reduction of the white blood cell, lymphocyte, B cell and platelet count of the human body is obvious when the benzene concentration in the air is only 1 ppm. Benzene toxicity is generated by substitution ofThe metabolic products, that is, benzene must be metabolized before it is harmful to the living body, and benzene can be metabolized in the liver and bone marrow, which are the formation sites of red blood cells, white blood cells and platelets, so that benzene enters the body to form metabolic products with blood toxicity in hematopoietic tissues themselves. Long-term benzene exposure can cause bone marrow and genetic damage, and hemogram examination can find leucopenia, thrombocytopenia, whole blood cytopenia and aplastic anemia, even leukemia. The health condition of workers who are exposed to low-concentration benzene has been investigated, and the results show that: the number of peripheral blood leucocytes is within the normal range, but is obviously lower than that of the control group; the distribution of the micronucleus rate of the lymphocytes of the frequent benzene contact workers is higher than that of the non-benzene contact group, and the difference between the micronucleus rate of the lymphocytes of the observation population in the benzene production workshop and the comparison of the micronucleus rate of the lymphocytes in the comparison group is remarkable; along with the increase of the benzene concentration in the working environment, the white blood cell number tends to be reduced, and the micronucleus rate of the lymphocyte tends to be increased, which proves that the low-concentration benzene has damage to the health of working population, especially the damage to genetic material of human body needs to be paid attention to, and 12.8mg is inhaled 3 The above short period of time has not only mucosa and lung irritation, but also central nerve inhibiting effect, and can be accompanied with headache, emesis, gait instability, coma, spasmolysis and arrhythmia, and inhaled 44.7mg 3 The above benzene dies immediately. About 48% of toluene enters the body and finally is discharged out of the body through the liver, brain, lung and kidney, and the toluene can harm the nervous system in the process, when the toluene concentration in the blood reaches 1250mg/m 3 At this time, the short-term memory, attention persistence, and sensory motor speed of the contactor are significantly reduced.
In view of the toxicity of toluene and its harm to human body, common treatment methods mainly include physical adsorption and catalysis. Wherein, the catalysis technology can completely oxidize toluene into carbon dioxide and water, which is a truly harmless treatment. At present, the noble metal catalyst has better performance on low-temperature catalytic oxidation of toluene, but has limited practical application to a certain extent due to the factors of high price, easier sintering at high temperature and the like. Therefore, the search for new catalytic materials to replace noble metal catalysts either partially or completely has become a trend in the catalytic field.
δ-MnO 2 The manganese oxide mineral material is a two-dimensional layered structure water-containing mineral material, and is a manganese oxide mineral commonly existing in soil, sediment and ocean manganese nodules. The microporous nature of birnessite and its rich content in sea make it as a high-efficiency adsorbent or heterogeneous catalyst, including heavy metal adsorption, oxidation of alcohol and carbon monoxide, reduction of nitrogen monoxide, hydrogenation of olefine, and decomposition of organic sulfide. Graphene oxide is a powerful two-dimensional 2D carbon sheet hybridized by sp2, and has attracted extensive attention in the field of catalysis due to its unique 2D structure, high surface area and good electron transport capability 2 Noble metal-loaded catalytic oxidation of toluene, but graphene oxide-loaded and Bi-Pd-catalyzed toluene are not studied much. Thus, the patent adopts sol-gel method to prepare delta-MnO 2 The Bi-Pd/GO/delta-MnO is prepared by an ion exchange method 2 The catalyst can catalyze the toluene at a lower temperature to show better activity and stability.
The implementation of the project is as follows: national natural science foundation project (number: 21277008; 20777005); the grant of the national emphasis development program (No. 2017YFC0209905) is also the content of the study of these projects.
Disclosure of Invention
The invention relates to a delta-MnO for catalyzing and eliminating toluene 2 Preparation method of supported graphene oxide Bi-Pd composite catalyst and application of supported graphene oxide Bi-Pd composite catalyst in selective catalytic elimination of toluene. The catalyst can eliminate high concentration toluene in 1000-3000 ppm at 100-300 deg.c and has excellent catalytic eliminating effect and toluene converting rate of 95-99%. The catalyst can obviously enhance the electron migration efficiency between Bi-Pd-Mn after being doped with graphene, thereby enhancing the catalytic efficiency, reducing the conversion temperature, and has the advantages of simple preparation process, low cost, good stability and the like.
The invention provides a delta-MnO for catalyzing and eliminating toluene 2 Loaded graphene oxide Bi-Pd complexThe preparation method of the catalyst comprises the following steps:
1. sol-gel delta-MnO process 2 Carrier preparation
50mL 0.38mol/L KMnO 4 Adding the solution into 20ml of 1.4mol/L glucose solution, stirring for 30s to form brown gel, discharging water generated every 20 min during gel synthesis, drying at 110deg.C for 24h to obtain brown xerogel, and calcining at 400deg.C for 2h to obtain delta-MnO 2 Gray black gray. Washing with water and drying at 110deg.C to obtain pure delta-MnO 2 。
2、Bi-Pd/GO/δ-MnO 2 Catalyst preparation
Dispersing 0.005-0.045g of single-layer graphene oxide powder in 50-100mL of deionized water, and then carrying out ultrasonic treatment for 6h to obtain a single-layer graphene oxide suspension solution. Pd (NO) 3 ) 2 ·2H 2 O was configured as Pd (NO) at 0.0037mol/L 3 ) 2 ·2H 2 O solution, biCl 3 BiCl configured to 0.0158mol/L 3 The solution was prepared by taking 1.32-3.96ml of Pd (NO) 3 ) 2 ·2H 2 O solution and 0.09-0.9ml BiCl 3 The solution was added to 50-100mL deionized water to form a homogeneous Pd and Bi mixed solution. Adding 5-22.5mg of polyvinyl alcohol and 50-100mL of graphene oxide suspension prepared above into the Pd and Bi mixed solution, stirring for 30 minutes, and injecting 2.0g/L of NaBH 4 The solution was stirred for a further 1 hour, forming a dark brown Bi-Pd/GO suspension. Then 1.0-3.0g delta-MnO is added 2 Added to the 50-200mL Bi-Pd/GO suspension described above and stirred for an additional 6 hours. The samples were washed twice with deionized water and absolute ethanol and then dried in an oven at 80-120 ℃ for 12-24 hours. Finally, calcining the obtained sample in a muffle furnace at 350-450 ℃ for 2-4h at a heating rate of 3-5 ℃/min to obtain a Bi-Pd/GO/delta-MnO sample 2 。
3. The catalyst of the invention has a reaction pressure of 1atm at normal pressure and a space velocity of 60,000h -1 ～240,000h -1 、20vol.％O 2 Toluene concentration of 1000-3000 ppm and balance gas of N 2 Under the condition that the temperature is 100-300 ℃, the p-toluene has high catalysisThe activity and the conversion rate are 95-99 percent. The method comprises the steps of carrying out a first treatment on the surface of the At a reaction pressure of 1atm at normal pressure and a space velocity of 60,000h -1 ～240,000h -1 、20vol.％O 2 Toluene concentration of 1000-3000 ppm and balance gas of N 2 Under the condition, the supported Bi-Pd/delta-MnO is examined 2 And Bi-Pd/GO/delta-MnO 2 The catalyst is kept at a temperature point within the range of 180-250 ℃ and is tested to react for 70 hours. The catalytic activity still shows high stability at the temperature range studied.
Drawings
FIG. 1 shows Bi-Pd/delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention 2 、Bi-Pd/GO/δ-MnO 2 -I、Bi-Pd/GO/δ-MnO 2 -II and Bi-Pd/GO/delta-MnO 2 XRD pattern of the III catalyst.
FIG. 2 shows Bi-Pd/delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention 2 、Bi-Pd/GO/δ-MnO 2 -I、Bi-Pd/GO/δ-MnO 2 -II and Bi-Pd/GO/delta-MnO 2 N of the-III catalyst 2 Adsorption/desorption of the drawing.
FIG. 3 shows Bi-Pd/delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention 2 、Bi-Pd/GO/δ-MnO 2 -I、Bi-Pd/GO/δ-MnO 2 -II and Bi-Pd/GO/delta-MnO 2 -III catalytic oxidation toluene activity profile.
FIG. 4 shows Bi-Pd/delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention 2 、Bi-Pd/GO/δ-MnO 2 -I、Bi-Pd/GO/δ-MnO 2 -II and Bi-Pd/GO/delta-MnO 2 The stability of the III catalyst at 210℃for 70 hours.
Detailed Description
Example 1
1. Sol-gel delta-MnO process 2 Carrier preparation
50mL 0.38mol/L KMnO 4 Adding the solution into 20ml of 1.4mol/L glucose solution, stirring for 30s to form brown gel, discharging water generated every 20 min during gel synthesis, drying at 110deg.C for 24h to obtain brown xerogel, and calcining at 400deg.C for 2h to obtain delta-MnO 2 Gray black gray. Washing with water and drying at 110deg.C to obtain pure delta-MnO 2 。
2、Bi-Pd/δ-MnO 2 Catalyst preparation
Preparation of Bi-Pd/delta-MnO by ion exchange method 2 And (3) a sample. Pd (NO) 3 ) 2 ·2H 2 O was configured as Pd (NO) at 0.0037mol/L 3 ) 2 ·2H 2 O solution, biCl 3 Configured to be 0.0158mol/L BiCl 3 1.32ml of Pd (NO) 3 ) 2 ·2H 2 O solution and 0.09ml of BiCl 3 Adding the solution into 50mL of deionized water to form a uniform Pd and Bi mixed solution, adding 5mg of polyvinyl alcohol into the Pd and Bi mixed solution under the ice water bath condition, stirring for 30 minutes, and injecting 2.0g/L of NaBH 4 The solution was stirred for a further 1 hour, forming a dark brown Bi-Pd/GO suspension. Then 1.0g of delta-MnO 2 Added to the 50ml Bi-Pd suspension described above and stirred for a further 6 hours. The samples were washed twice with deionized water and absolute ethanol and then dried in an oven at 80 ℃ for 12 hours. Finally, the obtained sample is calcined in a muffle furnace for 2h at a heating rate of 3 ℃/min, and the obtained sample is Bi-Pd/delta-MnO 2 。
3. The catalyst of the invention has a reaction pressure of 1atm at normal pressure and a space velocity of 60,000h -1 、20vol.％O 2 Toluene concentration 1000ppm and balance gas N 2 Under the condition that the catalyst has high catalytic activity in the temperature range of 100-300 ℃, the toluene conversion rate is 95%; at a reaction pressure of 1atm at normal pressure and a space velocity of 60,000h -1 、20vol.％O 2 Toluene concentration 1000ppm and balance gas N 2 Under the condition of 210 ℃ to examine Pd/delta-MnO 2 Bi-Pd/δ-MnO 2 Toluene conversion in 70 hours for the sample. The catalytic activity still shows high stability at the temperatures studied.
Example 2
1. Sol-gel delta-MnO process 2 Carrier preparation
50mL 0.38mol/L KMnO 4 Adding the solution into 20ml of 1.4mol/L glucose solution, stirring for 30s to form brown gel, discharging water generated every 20 min during gel synthesis, drying at 110deg.C for 24 hr to obtain brown xerogel, and drying the xerogel in a containerCalcining at 400 ℃ for 2 hours to obtain delta-MnO 2 Gray black gray. Washing with water and drying at 110deg.C to obtain pure delta-MnO 2 。
2、Bi-Pd/GO/δ-MnO 2 -I catalyst preparation
0.005g of single-layer graphene oxide powder was dispersed in 50ml of deionized water, and then sonicated for 6 hours to obtain a single-layer graphene oxide suspension solution. Pd (NO) 3 ) 2 ·2H 2 O was configured as Pd (NO) at 0.0037mol/L 3 ) 2 ·2H 2 O solution, biCl 3 Configured to be 0.0158mol/L BiCl 3 1.32ml of Pd (NO) 3 ) 2 ·2H 2 O solution and 0.09ml of BiCl 3 The solution was added to 50mL deionized water to form a homogeneous Pd and Bi mixed solution. Under the ice water bath condition, 6mg of polyvinyl alcohol and 50ml of graphene oxide suspension solution prepared above are added into the Pd and Bi mixed solution and stirred for 30 minutes, and then 2.0g/L of NaBH is injected 4 The solution was stirred for a further 1 hour, forming a dark brown Bi-Pd/GO suspension. Then 1.0g of delta-MnO 2 To 100ml of the Bi-Pd/GO suspension described above, and stirring was continued for 6 hours. The samples were washed twice with deionized water and absolute ethanol and then dried in an oven at 100 ℃ for 12 hours. Finally, calcining the obtained sample in a muffle furnace at 400 ℃ for 2 hours at a heating rate of 3 ℃/min to obtain a Bi-Pd/GO/delta-MnO sample 2 -I。
3. The catalyst of the invention has a reaction pressure of 1atm at normal pressure and a space velocity of 120,000h -1 、20vol.％O 2 Toluene concentration 1500ppm and balance gas N 2 Under the condition that the catalyst has high catalytic activity in the temperature range of 100-270 ℃, the toluene conversion rate is 97%; at a reaction pressure of 1atm at normal pressure, a space velocity of 120,000h -1 、20vol.％O 2 Toluene concentration 1500ppm and balance gas N 2 Under the condition of 210 ℃, the Bi-Pd/GO/delta-MnO is inspected 2 I conversion of toluene in 70 hours for the sample. The catalytic activity still shows high stability at the temperatures studied.
Example 3
1. Sol-gel delta-MnO process 2 Carrier preparation
50mL 0.38mol/L KMnO 4 Adding the solution into 20ml of 1.4mol/L glucose solution, stirring for 30s to form brown gel, discharging water generated every 20 min during gel synthesis, drying at 110deg.C for 24h to obtain brown xerogel, and calcining at 400deg.C for 2h to obtain delta-MnO 2 Gray black gray. Washing with water and drying at 110deg.C to obtain pure delta-MnO 2 。
2、Bi-Pd/GO/δ-MnO 2 -II catalyst preparation
0.02g of single-layer graphene oxide powder was dispersed in 50ml of deionized water, and then sonicated for 6 hours to obtain a single-layer graphene oxide suspension solution. Pd (NO) 3 ) 2 ·2H 2 O was configured as Pd (NO) at 0.0037mol/L 3 ) 2 ·2H 2 O solution, biCl 3 Configured to be 0.0158mol/L BiCl 3 2.64ml of Pd (NO) was taken as a solution 3 ) 2 ·2H 2 O solution and 0.3ml of BiCl 3 The solution was added to 50mL deionized water to form a homogeneous Pd and Bi mixed solution. Under the ice water bath condition, 13mg of polyvinyl alcohol and 50ml of graphene oxide suspension solution prepared above are added into the Pd and Bi mixed solution and stirred for 30 minutes, and then 2.0g/L of NaBH is injected 4 The solution was stirred for a further 1 hour, forming a dark brown Bi-Pd/GO suspension. Then 2.0g of delta-MnO 2 To 100ml of the Bi-Pd/GO suspension described above, and stirring was continued for 6 hours. The samples were washed twice with deionized water and absolute ethanol and then dried in an oven at 110 ℃ for 24 hours. Finally, calcining the obtained sample in a muffle furnace at 400 ℃ for 3 hours at a heating rate of 4 ℃/min to obtain a Bi-Pd/GO/delta-MnO sample 2 -II。
3. The catalyst of the invention has a reaction pressure of 1atm at normal pressure and a space velocity of 180,000 h -1 、20vol.％O 2 Toluene concentration 2000ppm and balance gas N 2 Under the condition that the catalyst has high catalytic activity in the temperature range of 100-230 ℃, the toluene conversion rate is 98%; at a reaction pressure of 1atm at normal pressure, a space velocity of 120,000h -1 、20vol.％O 2 Toluene concentration 2000ppm and balance gas N 2 Under the condition of 210 ℃ to examine Bi-Pd/GO/δ-MnO 2 -II conversion of toluene in 70 hours for sample. The catalytic activity still shows high stability at the temperatures studied.
Example 4
1. Sol-gel delta-MnO process 2 Carrier preparation
50mL 0.38mol/L KMnO 4 Adding the solution into 20ml of 1.4mol/L glucose solution, stirring for 30s to form brown gel, discharging water generated every 20 min during gel synthesis, drying at 110deg.C for 24h to obtain brown xerogel, and calcining at 400deg.C for 2h to obtain delta-MnO 2 Gray black gray. Washing with water and drying at 110deg.C to obtain pure delta-MnO 2 。
2、Bi-Pd/GO/δ-MnO 2 -III catalyst preparation
0.045g of single-layer graphene oxide powder was dispersed in 100ml of deionized water, and then sonicated for 6 hours to obtain a single-layer graphene oxide suspension solution. Pd (NO) 3 ) 2 ·2H 2 O was configured as Pd (NO) at 0.0037mol/L 3 ) 2 ·2H 2 O solution, biCl 3 Configured to be 0.0158mol/L BiCl 3 3.96ml of Pd (NO) was taken as a solution 3 ) 2 ·2H 2 O solution and 0.9ml of BiCl 3 The solution was added to 100mL deionized water to form a homogeneous Pd and Bi mixed solution. Under the ice water bath condition, 22.5mg of polyvinyl alcohol and 100mL of graphene oxide suspension solution prepared above are added into the Pd and Bi mixed solution and stirred for 30 minutes, and then 2.0g/L of NaBH is injected 4 The solution was stirred for a further 1 hour, forming a dark brown Bi-Pd/GO suspension. Then 3.0g of delta-MnO 2 To 200mL of the Bi-Pd/GO suspension above was added and stirring was continued for 6 hours. The samples were washed twice with deionized water and absolute ethanol and then dried in an oven at 120 ℃ for 12 hours. Finally, calcining the obtained sample in a muffle furnace at 450 ℃ for 4 hours at a heating rate of 5 ℃/min to obtain a Bi-Pd/GO/delta-MnO sample 2 -III。
3. The catalyst of the invention has a reaction pressure of 1atm at normal pressure and a space velocity of 240,000h -1 、20vol.％O 2 Toluene concentration 3000ppm and balance gasIs N 2 Under the condition that the catalyst has high catalytic activity in the temperature range of 100-250 ℃, the toluene conversion rate is 99%; at a reaction pressure of 1atm at normal pressure, a space velocity of 240,000h -1 、20vol.％O 2 Toluene concentration 3000ppm and balance gas N 2 Under the condition of 210 ℃, the Bi-Pd/GO/delta-MnO is inspected 2 -III conversion of toluene in 70 hours for the sample. The catalytic activity still shows high stability at the temperatures studied.
Claims (2)
1.δ-MnO 2 The method for loading the graphene oxide Bi-Pd composite catalyst is characterized by comprising the following steps of:
1) delta-MnO by sol-gel method 2 Carrier preparation
50mL 0.38mol/L KMnO 4 Adding the solution into 20mL of 1.4mol/L glucose solution, stirring for 30s to form brown gel, discharging water every 20 min during gel synthesis, drying at 110deg.C for 24h to obtain brown xerogel, and calcining at 400deg.C for 2h to obtain delta-MnO 2 A gray black gray; washing with water and drying at 110deg.C to obtain pure delta-MnO 2 ；
2)、Bi-Pd/GO/δ-MnO 2 Catalyst preparation
Dispersing 0.005-0.045g of single-layer graphene oxide powder in 50-100mL of deionized water, and then carrying out ultrasonic treatment for 6 hours to obtain a single-layer graphene oxide suspension solution; 1.32-3.96mL of Pd (NO) with a concentration of 0.0037mol/L 3 ) 2 ·2H 2 O solution and 0.09-0.9mL of BiCl with concentration of 0.0158mol/L 3 Adding the solution into 50-100mL deionized water to form uniform Pd and Bi mixed solution; adding 5-22.5mg of polyvinyl alcohol and 50-100mL of graphene oxide GO suspension prepared above into the Pd and Bi mixed solution, stirring for 30 minutes, and injecting 2.0g/L NaBH 4 Stirring the solution for 1h to form dark brown Bi-Pd/GO suspension; then 1.0-3.0g delta-MnO is added 2 Adding the mixture into 50-200mL of the Bi-Pd/GO suspension, and continuously stirring for 6h; washing the sample twice with deionized water and absolute ethyl alcohol, and then drying the sample in an oven at 80-120 ℃ for 12-24 hours; finally, the obtained sampleCalcining the product in a muffle furnace at 350-450deg.C for 2-4 hr at heating rate of 3-5deg.C/min to obtain Bi-Pd/GO/delta-MnO as sample 2 。
2. The use of the catalyst prepared by the process of claim 1 for the removal of toluene, characterized in that: the catalyst was placed in a continuous flow fixed bed unit and charged with a catalyst containing 20vol.% O 2 1000-3000 ppm toluene and N 2 The reaction is carried out in the mixed gas used as balance gas; the reaction pressure is normal pressure 1atm, and the reaction space velocity is 60,000-240,000 h -1 The reaction temperature is 100-300 ℃.
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