CN112853381A - Preparation method of carbon-based catalyst for hydrogen peroxide preparation and carbon-based catalyst - Google Patents
Preparation method of carbon-based catalyst for hydrogen peroxide preparation and carbon-based catalyst Download PDFInfo
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Abstract
The invention provides a preparation method of a carbon-based catalyst for preparing hydrogen peroxide and the carbon-based catalyst, wherein the method comprises the following steps: carrying out ultrasonic treatment on the mixed solution of the vacuum residue, the toluene and the salt substances; removing toluene in the mixed solution after ultrasonic treatment; heating the mixture of the vacuum residue and the salt substances after the toluene removal, controlling the carbonization temperature to be 500-1000 ℃, and carbonizing the vacuum residue in a nitrogen atmosphere, wherein the carbonization temperature is lower than the melting point of the salt substances; after the carbonization treatment is finished, cooling the mixture after the carbonization treatment, and in the process of cooling, converting the nitrogen atmosphere into an atmosphere containing nitrogen and oxygen until the temperature is reduced to room temperature to obtain a mixture of a carbon product and a salt substance; and washing the mixture containing the carbon product and the salt substance with water to remove the salt substance to obtain the carbon-based catalyst. The preparation method is simple and low in cost, and the carbon-based catalyst has high catalytic activity and selectivity.
Description
Technical Field
The invention relates to the technical field of catalyst production, in particular to a preparation method of a carbon-based catalyst for preparing hydrogen peroxide and the carbon-based catalyst.
Background
Hydrogen peroxide (H)2O2) Is an important chemical product and is widely used for papermaking, spinning, chemical synthesis, environmental management, medical disinfection and the like. At present, the anthraquinone method is mainly adopted for producing H in industry2O2H with different concentrations is obtained by the processes of hydrogenation, oxidation, extraction, purification, concentration and the like2O2However, the method is complex in process, discontinuous in production process, high in energy consumption and high in danger because toxic raw materials, toxic solvents, noble metal catalysts, explosive H2 and the like are used.
Another prior art process for preparing hydrogen peroxide utilizes oxygen (O) in two electron paths2) The reduction reaction can convert O into2And water are converted into H through one-step electrochemical reaction2O2Is a simple and clean H2O2The production method is expected to replace the current multistep anthraquinone method. However, the method has the disadvantages of immature preparation technology, high preparation cost, complex preparation method and the like, and low preparation efficiency, and cannot meet the requirement of industrial mass production of hydrogen peroxide.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a carbon-based catalyst for preparing hydrogen oxide and the carbon-based catalyst, the preparation method of the carbon-based catalyst is simple, and the carbon-based catalyst is applied to the preparation of hydrogen peroxide, so that the preparation efficiency of the hydrogen peroxide can be effectively improved, and the requirement of industrial large-scale production can be met.
The first aspect of the present invention provides a method for preparing a carbon-based catalyst for hydrogen peroxide production, comprising:
providing a vacuum residuum;
carrying out ultrasonic treatment on the mixed solution of the vacuum residue, the toluene and the salt substances;
removing toluene in the mixed solution after ultrasonic treatment;
heating a mixture of the vacuum residue and salt substances after toluene removal, controlling the carbonization temperature to be 500-1000 ℃, and carbonizing the vacuum residue in a nitrogen atmosphere, wherein the carbonization temperature is lower than the melting point of the salt substances;
after the carbonization treatment is finished, cooling the mixture subjected to the carbonization treatment, and in the process of cooling, converting the nitrogen atmosphere into an atmosphere containing nitrogen and oxygen until the carbonization temperature is reduced to room temperature to obtain a mixture of a carbon product and a salt substance;
and washing the mixture containing the carbon product and the salt substance with water to remove the salt substance to obtain the carbon-based catalyst.
According to one embodiment of the present invention, in the mixed solution of the vacuum residue, the toluene and the salt-like substance, the mass ratio of the vacuum residue to the salt-like substance is 1: (10-80).
According to one embodiment of the invention, the volume of the toluene solution is 20-40 mL.
According to one embodiment of the present invention, the removing toluene from the sonicated mixed solution comprises: and removing the toluene in the mixed solution by adopting a reduced pressure distillation method.
According to an embodiment of the present invention, a mixture of the vacuum residue after removing toluene and salt is heated, and the vacuum residue is carbonized at 500-: and heating the mixture of the vacuum residue and the salt substances after the toluene removal, and carbonizing the vacuum residue for 2 hours at the heating temperature of 700-800 ℃ in a nitrogen atmosphere with the flow rate of 0.05L/min.
According to an embodiment of the present invention, after the carbonization treatment, the mixture after the carbonization treatment is cooled, and during the cooling, the nitrogen atmosphere is switched to an atmosphere containing nitrogen and oxygen until the carbonization temperature is reduced to room temperature, so as to obtain a mixture of a carbon product and a salt substance, further comprising: and after the carbonization treatment is finished, cooling the mixture after the carbonization treatment, and when the temperature is reduced to the range of 500-550 ℃, converting the nitrogen atmosphere into the atmosphere of nitrogen with the flow rate of 0.05L/min and oxygen with the flow rate of 0.01L/min until the temperature is reduced to the room temperature to obtain the mixture of the carbon product and the salt substance.
According to an embodiment of the present invention, the melting point of the salt substance is greater than or equal to 500 ℃ and less than or equal to 1000 ℃.
According to an embodiment of the present invention, the salt is sodium chloride.
A second aspect of the present invention provides a carbon-based catalyst prepared by the method for preparing a carbon-based catalyst for hydrogen peroxide production according to the embodiment of the first aspect, the carbon-based catalyst having a pore structure, and an oxygen-containing group being formed on an outer surface of the carbon-based catalyst. When the carbon product is used as a carbon-based catalyst, the carbon-based catalyst adsorbs O in the electrocatalysis process2After the molecule, an intermediate of-OOH is formed, and the O-O bond is not easy to break, so that O2The reduction proceeds to H according to two electron paths2O2Promoting the electrocatalysis O2Reduction of H2O2Selectivity of (2).
A third aspect of the present invention provides a method for producing hydrogen peroxide, comprising: the hydrogen peroxide is prepared by taking a carbon-based catalyst as a catalyst and adopting an electrocatalytic oxidation reduction method, wherein the carbon-based catalyst is the carbon-based catalyst in the embodiment of the second aspect. The method can improve the production efficiency of hydrogen peroxide.
The preparation method of the carbon-based catalyst for preparing hydrogen peroxide, which is provided by the invention, adopts the vacuum residue as the raw material, has low preparation cost and simple method, and can prepare the carbon-based catalyst with high catalytic activity, selectivity and stability. The carbon-based catalyst is applied to the preparation process of the hydrogen peroxide generated by electricity, can perform reduction reaction on two electrons O2, and improves the production efficiency of the hydrogen peroxide.
Drawings
FIG. 1 is a flow diagram illustrating a method of preparing a carbon-based catalyst for hydrogen peroxide production according to an exemplary embodiment of the present invention;
FIG. 2 is a graph of rotating ring disk electrode disk current density as a function of potential for three catalysts;
FIG. 3 is H for three catalysts2O2Graph of selectivity versus potential.
Detailed Description
First, the discovery of the technical problem to be solved by the method for producing a carbon-based catalyst for hydrogen peroxide production of the present invention will be described.
Oxygen (O) in two electron paths2) Reduction reaction of O2Further electrochemically reacted with water to convert to H2O2In the method, the catalyst is electricity generation H2O2Is critical. The inventor analyzes the existing catalyst, and concretely comprises the following steps:
noble metal catalysts, such as Au-Ni-Pt [ Adv. Mater.28(2016)9949-]、Au-Pd[J.Am.Chem.Soc.133(2011)19432-19441]、Pt-Hg[Nat.Mater.12(2013)1137-1143]、Pd-Hg[Nano Lett.14(2014)1603-1608]、Pd-Sn[ACS Catal.8(2018)3418-3423]、Ag-Pt[ACS Catal.8(2018)2880-2889]These catalysts are expensive and difficult to be applied on a large scale, and some of the catalysts contain heavy metal Hg and are easy to run off when used as electrode materials, thereby causing product pollution or environmental pollution. The synthesis requirement is high, taking Au catalyst as an example, 111 and 110 crystal faces have high selectivity to 2 electron ORR, but the batch synthesis of the catalyst with the preferred orientation of a specific crystal face is very difficult. The current research only evaluates the intrinsic catalytic activity and selectivity of the catalyst, and whether the catalyst can show higher electricity generation H in a gas diffusion electrode2O2The activity and selectivity are not described.
Metal complexes, metal oxide catalysts, such as Co (N2O2) [ J.Am.chem.Soc.139(2017)16458-16461]、CoII(Ch)[J.Am.Chem.Soc.135(2013)2800-2808]The catalyst, Fe3O4/C [ electrochim. acta 162(2015) 263-270-]Mn-Ru oxide [ J.Mater.chem.A4(2016)9266-9274]The catalyst has metal loss risk. The complex metal ion itself can catalyze H2O2Decomposition of electricity and H production2O2. Gas diffusion electrode made of catalystIt is not described whether the high activity and selectivity of the electric H2O2 can be expressed.
Monatomic catalysts such as Pt/TiC, Pt/TiN [ ACS Cat.7 (2017) 1301-. Monatomic catalysis is a high-utilization heterogeneous catalysis method which disperses the metal atoms of a catalyst on the surface of a carrier. The main challenge of the current methods for synthesizing monatomic catalysts, such as impregnation, ion exchange, hydrothermal treatment, coprecipitation, etc., is how to prepare them on a large scale. When the catalyst is prepared under laboratory conditions, the synthesis conditions can be controlled to give a metal catalyst with atomic dispersion properties. But when the scale amplification production is carried out according to the synthesis proportion, uneven mass transfer and heat transfer effects always exist, and local concentration unevenness is easily caused, so that the agglomeration of metal is caused. In addition, the stability of the monatomic catalyst is poor, and the long-term application requirement in industry cannot be met.
The carbon-based catalyst and the carbon material have the advantages of rich raw materials, acid and alkali resistance, no toxicity, easy regulation and control of structure and the like, and are electrocatalysis O2Reduction synthesis of H2O2The ideal catalyst of (1). However, the mass preparation technology of the carbon material is still not mature, the preparation cost is high, and the functionalization method is complicated.
Therefore, after the inventors have found the above-mentioned technical problems, they have studied to obtain a technical means of the method for producing a carbon-based catalyst for hydrogen peroxide production of the present invention. Hereinafter, the technical solution of the present invention will be described in detail.
A method for preparing a carbon-based catalyst for hydrogen peroxide production according to a first aspect of an embodiment of the present invention will be described in detail with reference to fig. 1. As can be seen from fig. 1, the preparation method of the carbon-based catalyst for hydrogen peroxide preparation comprises the following steps:
step 1, providing vacuum residue.
And 2, carrying out ultrasonic treatment on the mixed solution of the vacuum residue, the toluene and the salt substance.
And 3, removing the toluene in the mixed solution subjected to ultrasonic treatment.
And 4, heating the mixture of the vacuum residue and the salt substances after the toluene removal, and carbonizing the vacuum residue in a nitrogen atmosphere at the heating temperature of 500-1000 ℃.
And 5, after the carbonization treatment is finished, cooling the mixture subjected to the carbonization treatment, and in the process of cooling, converting the nitrogen atmosphere into an atmosphere containing nitrogen and oxygen until the temperature is reduced to room temperature to obtain a mixture of the carbon product and the salt substance.
And 6, washing the mixture containing the carbon product and the salt substance with water, and removing the salt substance to obtain the carbon-based catalyst.
In the method of the embodiment of the invention, the carbon-based catalyst is prepared by taking the vacuum residue as the carbon source, the preparation efficiency is high, the cost is low, the preparation method is simple, and the mass production can be realized. In the method, the salt substance is used as a hard template, so that the carbonized vacuum residue has rich large and medium pore structures, the specific surface area of the carbon product is improved, and the apparent activity of the carbonized vacuum residue is obviously improved when the carbonized vacuum residue is used as a catalyst. And oxygen is introduced in the process of cooling, so that a proper amount of oxygen-containing groups (such as carboxyl, ether oxygen and the like) are introduced to the surface of the carbon product, and when the carbon product is used as a carbon-based catalyst due to the introduction of the oxygen-containing groups, the carbon-based catalyst adsorbs O in the electrocatalysis process2After the molecule, an intermediate of-OOH is formed, and the O-O bond is not easy to break, so that O2The reduction proceeds to H according to two electron paths2O2Promoting the electrocatalysis O2Reduction of H2O2Selectivity of (2).
The above steps are explained in detail below with reference to fig. 1.
As shown in fig. 1, step 1, provides a vacuum residuum.
In the examples of the present invention, vacuum residue was used as a raw material for producing a carbon-based catalyst. The vacuum residue is a low-value product generated in the petroleum refining process, is cheap and easily available, is rich in polycyclic aromatic hydrocarbon, has high carbon content, and is a high-quality carbon source for preparing the carbon catalyst. Therefore, the method has rich carbon sources, and compared with the catalyst used in the prior art, the carbon source has the advantages of low cost, acid and alkali resistance, no toxicity, easy structure regulation and control and the like.
And 2, carrying out ultrasonic treatment on the mixed solution of the vacuum residue, the toluene and the salt substance.
In the embodiment of the invention, after the carbon source and the salt substance are blended, the carbon-based catalyst can be prepared by carbonizing the carbon source at high temperature, no additional energy is needed to be input, and the process is simple.
In the embodiment of the present invention, the ultrasonic treatment time in this step may be between 10min and 60min, and in the preferred embodiment of the present invention, 30min may be adopted, so that the mixture can be sufficiently and uniformly mixed.
In the embodiment of the invention, the mass ratio of the vacuum residue to the salt substances is 1: (10-80). For example, the mass ratio of the vacuum residue to the salt-like substance may be 1: 10. 1: 20. 1: 30. 1: 40. 1: 50. 1: 60. 1: 70. 1: 80.
in embodiments of the present invention, the volume of toluene may be selected based on the amount of vacuum residue and salts, for example, the weight of vacuum residue ranges from 0.5g to 1g, the weight of salts ranges from 5g to 20g, and the volume of toluene may range from 20mL to 40 mL.
In one embodiment of the present invention, the salt species has a melting point greater than 500 ℃ and a boiling point less than 1000 ℃. Generally, the carbonization temperature of the vacuum residue is between 500 ℃ and 1000 ℃. Therefore, in order to ensure that the salt can play the role of a hard template, the carbonization temperature is prevented from exceeding the melting point of the salt in the carbonization process, so that the salt can play the role of a hard template. For example, sodium chloride (NaCl) can be selected, the cost of the sodium chloride is low, the melting point meets the requirement of carbonization temperature, and after the carbonization is finished and the sodium chloride is removed, the carbon product with a large-hole and medium-hole structure can be obtained, and the specific surface area of the carbon product is increased. In addition, salts having an activating pore-forming action on the carbon material, such as ZnCl, should be avoided2Such salts lead to the formation of numerous micropores and a decrease in the electrical conductivity of the carbon material, which is disadvantageousThe electrocatalytic activity of the catalyst is improved.
And 3, removing the toluene in the mixed solution subjected to ultrasonic treatment.
In the embodiment of the invention, a conventional method for removing toluene can be adopted, and the invention preferably uses a reduced pressure distillation method for removing toluene, so that the toluene can be effectively separated from the mixed solution, and other substances are not introduced. The separated toluene can be recycled, and the cost is effectively saved.
And 4, heating the mixture of the vacuum residue and the salt substances after the toluene removal, controlling the carbonization temperature to be 500-1000 ℃, and carbonizing the vacuum residue in a nitrogen atmosphere, wherein the carbonization temperature is lower than the melting point of the salt substances.
In the embodiment of the invention, the carbonization temperature can be selected to be 500-1000 ℃, and the temperature is lower than the melting point of the salt substance. For example, if the salt is sodium chloride, the melting point of sodium chloride is 801 ℃, and the carbonization temperature may be 800 ℃ or lower. Preferably, the temperature can be selected to be between 700 and 800 ℃, and the carbonization treatment time can be controlled to be about 2 hours, so as to better perform carbonization treatment on the vacuum residue.
In one embodiment of the present invention, the nitrogen atmosphere may be a nitrogen gas introduced into a reaction furnace for carbonization. Wherein, the flow of the introduced nitrogen can be adjusted according to the requirement. Preferably, the flow rate of the introduced nitrogen is selected to be 0.05L/min, so as to ensure that a clean carbon product can be obtained in the vacuum residue carbonization process.
And 5, after the carbonization treatment is finished, cooling the mixture subjected to the carbonization treatment, and in the process of cooling, converting the nitrogen atmosphere into an atmosphere containing nitrogen and oxygen until the temperature is reduced to room temperature to obtain a mixture of the carbon product and the salt substance.
In one embodiment of the present invention, the atmosphere containing nitrogen and oxygen may be an atmosphere in which only nitrogen is originally introduced while oxygen is introduced when the temperature is lowered to a predetermined temperature. For example, in step 4, the carbonization temperature is controlled to 7And when the temperature is reduced to 500-550 ℃ between 00-800 ℃, introducing nitrogen with the flow rate of 0.05L/min and oxygen with the flow rate of 0.01L/min into the reaction furnace so as to convert the nitrogen and oxygen into the atmosphere. In the method, a proper amount of oxygen-containing groups (such as carboxyl, ether oxygen and the like) can be introduced to the surface of the carbon product by introducing a small amount of oxygen into the reaction furnace in the process of cooling, and the introduction of the oxygen-containing groups ensures that the catalyst adsorbs O in the electrocatalysis process2Only intermediates containing-OOH are formed after the molecule. And makes the O-O bond less prone to break. Thus, when the carbon product is produced as electricity H2O2When a catalyst of (2) is used, O2The reduction proceeds to H according to two electron paths2O2Promoting the electrocatalysis O2Reduction of H2O2Selectivity of (2).
And 6, washing the mixture containing the carbon product and the salt substance with water, and removing the salt substance to obtain the carbon-based catalyst. Salt substances are dissolved in water and kneaded through water washing, and the salt substances can be effectively separated from carbon products, so that a pure carbon-based catalyst is obtained. In addition, the salt substance can be recycled, and the cost is further reduced.
According to the preparation method of the carbon-based catalyst for preparing hydrogen peroxide, vacuum residue is used as a raw material, the preparation cost is low, the method is simple, and the carbon-based catalyst with high catalytic activity, selectivity and stability can be prepared. The carbon-based catalyst is applied to the preparation process of the hydrogen peroxide by electric production and can be used for two electrons O2The reduction reaction improves the production efficiency of the hydrogen peroxide.
The second aspect of the embodiments of the present invention also provides a carbon-based catalyst, which is prepared by the preparation method provided in the embodiment of the first aspect. The carbon-based catalyst has a pore structure, and oxygen-containing groups are formed on the outer surface of the carbon-based catalyst. The carbon-based catalyst is loaded on a rotating ring disk electrode for testing, and the disk current density and the electricity yield H2O2The selectivity is higher than that of a commercial carbon-based catalyst, namely cabot XC-72R conductive carbon black, and the carbonization yield is about 25-35 percent. Meanwhile, the stability is good, and the apparent activity is high.
The third aspect of the embodiments of the present invention further provides a method for preparing hydrogen peroxide, in which a carbon-based catalyst is used as a catalyst, and an electrocatalytic oxidation-reduction method is adopted to prepare hydrogen peroxide, and the carbon-based catalyst is prepared by the preparation method of the first aspect. Because the carbon-based catalyst is adopted as the catalyst and has oxygen-containing groups, the introduction of the oxygen-containing groups ensures that the catalyst adsorbs O in the electrocatalysis process2Only intermediates containing-OOH are formed after the molecule. And makes the O-O bond less prone to break. Thus, O2The reduction proceeds to H according to two electron paths2O2Promoting the electrocatalysis O2Reduction of H2O2Selectivity of (2). And because of the macroporous and mesoporous structure of the carbon-based catalyst, the apparent activity is high, and the yield of the hydrogen peroxide is improved.
The preparation of the carbon-based catalyst for hydrogen peroxide production is further described below by way of specific examples.
Conventional methods and apparatuses are used for methods, apparatuses, and the like which are not described in detail in the following examples.
Example 1
1) After 0.5g of vacuum residue was mixed with 20mL of toluene and 5g of NaCl, the mixture was sonicated for 30 min.
2) The toluene is removed by distillation under reduced pressure, and the toluene is recovered and reused.
3) And (3) putting the blend of the vacuum residue after toluene removal and sodium chloride into a carbonization reaction furnace, heating the reaction furnace, and introducing 0.05L/min nitrogen into the reaction furnace for carbonization for 2 hours under the condition that the carbonization temperature reaches 700 ℃.
4) After the carbonization process is finished, when the temperature is reduced to 500 ℃, 0.05L/min N is introduced into the reaction furnace2And 0.01L/min O2And (4) until the temperature in the furnace is reduced to 25 ℃, and obtaining a mixture of the carbon product and NaCl.
5) Washing the mixture obtained in the step 4) with water to remove sodium chloride, thereby obtaining the carbon-based catalyst. The aqueous solution of sodium chloride can be recovered and used.
Example 2
1) 1g of vacuum residue, 40mL of toluene and 20g of NaCl were mixed and then subjected to ultrasonic treatment for 30 min.
2) The toluene is removed by distillation under reduced pressure, and the toluene is recovered and reused.
3) And (3) putting the blend of the vacuum residue after toluene removal and sodium chloride into a carbonization reaction furnace, heating the reaction furnace, and introducing 0.05L/min nitrogen into the reaction furnace for carbonization for 2 hours under the condition that the carbonization temperature reaches 800 ℃.
4) After the carbonization process is finished, when the temperature is reduced to 550 ℃, 0.05L/min N is introduced into the reaction furnace2And 0.01L/min O2And (4) until the temperature in the furnace is reduced to 25 ℃, and obtaining a mixture of the carbon product and NaCl.
5) Washing the mixture obtained in the step 4) with water to remove sodium chloride, thereby obtaining the carbon-based catalyst. The aqueous solution of sodium chloride can be recovered and used.
Example 3
1) After 0.8g of vacuum residue was mixed with 30mL of toluene and 10g of NaCl, the mixture was subjected to ultrasonic treatment for 30 min.
2) The toluene is removed by distillation under reduced pressure, and the toluene is recovered and reused.
3) And (3) putting the blend of the vacuum residue after toluene removal and sodium chloride into a carbonization reaction furnace, heating the reaction furnace, and introducing 0.05L/min nitrogen into the reaction furnace for carbonization for 2 hours under the condition that the carbonization temperature reaches 750 ℃.
4) After the carbonization process is finished, when the temperature is reduced to 520 ℃, 0.05L/min N is introduced into the reaction furnace2And 0.01L/min O2And (4) until the temperature in the furnace is reduced to 25 ℃, and obtaining a mixture of the carbon product and NaCl.
5) Washing the mixture obtained in the step 4) with water to remove sodium chloride, thereby obtaining the carbon-based catalyst. The aqueous solution of sodium chloride can be recovered and used.
The current density and H of any of the carbon-based catalyst disks prepared in the above examples were tested2O2And (4) selectivity. Two samples of the comparative example were tested. The comparative examples are: carbon-based compounds prepared without addition of salts, and CBZXC-72R conductive carbon black is produced. With particular reference to fig. 2 and 3.
FIG. 2 is a graph of current density versus potential for a rotating disk electrode disk for three catalysts. As shown in fig. 2, line 1 represents the change curve of the disc current density with the potential of the carbon-based compound prepared without adding a salt substance, i.e., the carbon-based catalyst directly carbonized without adding a salt substance; line 2 represents the disk current density versus potential curve for XC-72R conductive carbon black; line 3 shows the disk current density versus potential for the carbon-based catalyst produced in the example of the invention. As can be seen from FIG. 2, the disk current density of the carbon-based catalyst produced by the method of the present invention is significantly higher than that of the carbon-based catalyst produced without the addition of the salt species and XC-72R conductive carbon black.
FIG. 3 is H for three catalysts2O2Graph of selectivity versus potential. As shown in FIG. 3, line 1 represents H of a carbon-based catalyst obtained by directly carbonizing a carbon-based compound obtained without adding a salt-based substance2O2A curve of selectivity versus potential; line 2 represents H for XC-72R conductive carbon black2O2A curve of selectivity versus potential; line 3 represents H for the carbon-based catalyst produced in the example of the invention2O2Selectivity versus potential. As can be seen in FIG. 3, the process of the present invention produces H for a carbon-based catalyst2O2The selectivity is obviously higher than that of a carbon-based catalyst and XC-72R conductive carbon black which are produced without adding salt substances.
The foregoing is directed to embodiments of the present invention, and it is understood by those skilled in the art that various changes, modifications and improvements may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a carbon-based catalyst for preparing hydrogen peroxide is characterized by comprising the following steps:
providing a vacuum residuum;
carrying out ultrasonic treatment on the mixed solution of the vacuum residue, the toluene and the salt substances;
removing toluene in the mixed solution after ultrasonic treatment;
heating a mixture of the vacuum residue and salt substances after toluene removal, controlling the carbonization temperature to be 500-1000 ℃, and carbonizing the vacuum residue in a nitrogen atmosphere, wherein the carbonization temperature is lower than the melting point of the salt substances;
after the carbonization treatment is finished, cooling the mixture subjected to the carbonization treatment, and in the process of cooling, converting the nitrogen atmosphere into an atmosphere containing nitrogen and oxygen until the carbonization temperature is reduced to room temperature to obtain a mixture of a carbon product and a salt substance;
and washing the mixture containing the carbon product and the salt substance with water to remove the salt substance to obtain the carbon-based catalyst.
2. The preparation method according to claim 1, wherein in the mixed solution of the vacuum residue, the toluene and the salt-like substance, the weight ratio of the vacuum residue to the salt-like substance is 1:
(10～80)。
3. the method according to claim 2, wherein the volume of toluene is 20 to 40 mL.
4. The method according to claim 1, wherein the removing toluene from the sonicated mixed solution comprises:
and removing the toluene in the mixed solution by adopting a reduced pressure distillation method.
5. The method as claimed in claim 1, wherein the mixture of the vacuum residue and the salt-like substance after removing toluene is heated, and the vacuum residue is carbonized at 500-1000 ℃ in a nitrogen atmosphere, further comprising:
and heating the mixture of the vacuum residue and the salt substances after the toluene removal, and carbonizing the vacuum residue for 2 hours at the heating temperature of 700-800 ℃ in a nitrogen atmosphere with the flow rate of 0.05L/min.
6. The method according to claim 5, wherein after the carbonization treatment, the mixture is cooled, and during the cooling, the nitrogen atmosphere is switched to an atmosphere containing nitrogen and oxygen until the carbonization temperature is cooled to room temperature, so as to obtain a mixture of the carbon product and the salt substance, further comprising:
and after the carbonization treatment is finished, cooling the mixture after the carbonization treatment, and when the temperature is reduced to the range of 500-550 ℃, converting the nitrogen atmosphere into the atmosphere of nitrogen with the flow rate of 0.05L/min and oxygen with the flow rate of 0.01L/min until the temperature is reduced to the room temperature to obtain the mixture of the carbon product and the salt substance.
7. The method according to claim 1, wherein the salt has a melting point of more than 500 ℃ and a boiling point of less than 1000 ℃.
8. The method according to claim 1, wherein the salt is sodium chloride.
9. A carbon-based catalyst, which is prepared by the method for preparing a carbon-based catalyst for hydrogen peroxide production according to any one of claims 1 to 8, and which has a pore structure, wherein oxygen-containing groups are formed on the outer surface of the carbon-based catalyst.
10. A method for producing hydrogen peroxide, comprising:
preparing the hydrogen peroxide by an electrocatalytic oxidation-reduction method by using a carbon-based catalyst as a catalyst, wherein the carbon-based catalyst is the carbon-based catalyst according to claim 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010215744A (en) * | 2009-03-16 | 2010-09-30 | Tokyo Institute Of Technology | Electron-ion mixture conductive film and method for producing hydrogen peroxide using the same |
| CN102049252A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for preparing residual oil hydrogenation catalyst, and catalyst |
| CN109666949A (en) * | 2019-01-03 | 2019-04-23 | 深圳清华大学研究院 | The preparation method of the activated carbon electrodes of multi-element doping, the characterization of activated-carbon catalyst and hydrogen reduction electro-catalysis test method |
| US20200173045A1 (en) * | 2017-08-23 | 2020-06-04 | The Board Of Trustees Of The Leland Stanford Junior University | N- and O-Doped Carbon with High Selectivity for Electrochemical H2O2 Production in Neutral Condition |
| CN112029076A (en) * | 2020-07-23 | 2020-12-04 | 南京航空航天大学 | Catalyst for preparing hydrogen peroxide by electrocatalysis and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010215744A (en) * | 2009-03-16 | 2010-09-30 | Tokyo Institute Of Technology | Electron-ion mixture conductive film and method for producing hydrogen peroxide using the same |
| CN102049252A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for preparing residual oil hydrogenation catalyst, and catalyst |
| US20200173045A1 (en) * | 2017-08-23 | 2020-06-04 | The Board Of Trustees Of The Leland Stanford Junior University | N- and O-Doped Carbon with High Selectivity for Electrochemical H2O2 Production in Neutral Condition |
| CN109666949A (en) * | 2019-01-03 | 2019-04-23 | 深圳清华大学研究院 | The preparation method of the activated carbon electrodes of multi-element doping, the characterization of activated-carbon catalyst and hydrogen reduction electro-catalysis test method |
| CN112029076A (en) * | 2020-07-23 | 2020-12-04 | 南京航空航天大学 | Catalyst for preparing hydrogen peroxide by electrocatalysis and preparation method thereof |
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