CN112473662A - Ruthenium-carbon catalyst and preparation method thereof - Google Patents
Ruthenium-carbon catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a ruthenium-carbon catalyst and a preparation method thereof, and the ruthenium-carbon catalyst comprises the following steps: adjusting the pH value of the solution of the ruthenium organic complex to be neutral, and carrying out cation exchange to obtain a ruthenium-containing solution with the conductivity of 20-40 mu S/cm; the ligand of the ruthenium organic complex contains phosphorus element; adding phosphine-tolerant algae into the ruthenium-containing solution for fermentation until the ruthenium content in the solution system is below 10 ppm; taking out the phosphine-resistant algae, crushing, and performing anaerobic fermentation to obtain anaerobic fermentation biogas residues; and carrying out carbonization-reduction reaction on the anaerobic fermentation biogas residue to obtain the ruthenium-carbon catalyst. Adjusting the ruthenium organic complex solution containing the phosphorus element to be neutral, carrying out cation exchange to remove most of metal cations, and controlling the specific conductivity of the ruthenium-containing solution after the cation exchange; and then adding the ruthenium-containing solution into the phosphine-resistant algae, fermenting until the ruthenium content is reduced to be below 10ppm, and carrying out carbonization reduction reaction on the phosphine-resistant algae after anaerobic fermentation to obtain the high-dispersion ruthenium-carbon catalyst, thereby greatly improving the effective utilization rate of ruthenium.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a ruthenium-carbon catalyst and a preparation method thereof.
Background
The ruthenium-carbon catalyst is a catalyst which loads metal ruthenium on the surface of active carbon, and has a very wide application scene. Generally, the synthesis of ruthenium carbon can be classified into chemical methods and physical methods. The physical method is generally used for depositing metal atoms on the surface of the activated carbon by using a physical method, and is not widely applied. Chemical methods are commonly used in industrial production for preparation, and are generally divided into impregnation and reduction. However, the current solutions produce ruthenium-carbon catalysts having a low degree of dispersion of ruthenium, where the degree of dispersion is the proportion of the number of atoms of the active component exposed on the surface of the catalyst to the total number of atoms of the component in the catalyst, and generally the degree of dispersion of ruthenium does not exceed 40%, i.e., more than 60% of ruthenium is not effectively used. Therefore, how to improve the dispersity of the ruthenium-carbon catalyst is a technical problem to be solved urgently.
Disclosure of Invention
In view of this, there is a need for a ruthenium carbon catalyst capable of improving the degree of dispersion and a method for preparing the same.
A preparation method of a ruthenium-carbon catalyst comprises the following steps:
adjusting the pH value of the solution of the ruthenium organic complex to be neutral, and carrying out cation exchange to remove metal cation impurities to obtain a ruthenium-containing solution with the conductivity of 20-40 mu S/cm; the ligand of the ruthenium organic complex contains phosphorus;
adding phosphine-tolerant algae into the ruthenium-containing solution for fermentation until the ruthenium content in the solution system is below 10 ppm;
taking out the phosphine-resistant algae, crushing, and performing anaerobic fermentation to obtain anaerobic fermentation biogas residues;
and carrying out a carbonization reduction reaction on the anaerobic fermentation biogas residue to obtain the ruthenium-carbon catalyst.
Research shows that the inorganic ruthenium solution without phosphorus is added into the phosphine-resistant algae for fermentation, and ruthenium can not enter the algae; further, the subsequent step of taking out and crushing the phosphine-tolerant algae for anaerobic fermentation cannot be performed, and the subsequent carbonization-reduction reaction cannot be performed, so that the ruthenium-carbon catalyst cannot be prepared by the preparation method of the present application. And the method is very critical for removing metal cation impurities by adjusting the pH value of the solution of the ruthenium organic complex to be neutral and carrying out cation exchange, and further controlling the conductivity of the obtained ruthenium-containing solution to be 20-40 mu S/cm. If the conductivity of the ruthenium-containing solution is not within the above range, ruthenium does not enter the algae well; further, the subsequent step of taking out and crushing the phosphine-tolerant algae for anaerobic fermentation cannot be performed, and the subsequent carbonization-reduction reaction cannot be performed, so that the ruthenium-carbon catalyst cannot be prepared by the preparation method of the present application.
According to the preparation method of the ruthenium-carbon catalyst, the ruthenium organic complex containing the phosphorus element is used, the ruthenium organic complex solution is adjusted to be neutral, cation exchange is carried out to remove most of metal cations, the influence of metal cation impurities is avoided, and the specific conductivity of the ruthenium-containing solution after cation exchange is controlled; and then adding the ruthenium-containing solution into the phosphine-resistant algae, fermenting until the ruthenium content is reduced to be below 10ppm, and carrying out carbonization reduction reaction on the phosphine-resistant algae after anaerobic fermentation to obtain the high-dispersion ruthenium-carbon catalyst, thereby greatly improving the effective utilization rate of ruthenium.
Further, controlling the conductivity of the ruthenium-containing solution to be 25 to 35 mu S/cm; in some specific examples, the conductivity of the ruthenium-containing solution is controlled to be 30. mu.S/cm. Thus, the dispersion degree of the prepared ruthenium-carbon catalyst can be favorably improved by controlling the conductivity of the ruthenium-containing solution.
In some embodiments, the ligand of the ruthenium organic complex is at least one of triphenylphosphine and a derivative of triphenylphosphine.
In some embodiments, the ruthenium-containing solution has a mass concentration of 0.01% to 1%. By controlling the mass concentration of the ruthenium-containing solution within a suitable range, the fermentation step of the phosphine-tolerant algae in the ruthenium-containing solution of step S200 can be facilitated to be better performed. In some specific examples thereof, the ruthenium-containing solution may have a mass concentration of 0.05%, 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%.
In some of these embodiments, the phosphine-tolerant algae is selected from at least one of chlorella and cyanobacteria. It is understood that the species of the phosphine-tolerant algae include, but are not limited to, these.
In some of these embodiments, the fermentation time with the addition of the phosphine-tolerant algae is 3 days to 5 days. By controlling the time for adding the phosphine-tolerant algae to the ruthenium-containing solution for fermentation within the above-mentioned suitable range, the fermentation step of the phosphine-tolerant algae in the ruthenium-containing solution can be better performed.
In some of these embodiments, the anaerobic fermentation is for a period of 2 to 4 days. By controlling the time of anaerobic fermentation within the proper range, the prepared ruthenium-carbon catalyst has better dispersity. In some of these embodiments, the cation exchange is performed using a cation exchange resin. Further, the cation exchange resin may be a hydrogen type cation exchange resin, such as cation exchange resin 201, to exchange impurities such as sodium ions therein.
In some of these embodiments, the temperature of the carbomorphism reduction reaction is from 240 ℃ to 350 ℃. A large number of researches show that the dispersity of the prepared ruthenium-carbon catalyst is further improved by controlling the hydrogen reduction temperature of the fluidized bed.
In some of these embodiments, the carbomorphism reduction reaction is carried out in a fluidized bed of hydrogen; the temperature of the hydrogen fluidized bed is 240-300 ℃, and the residence time of the fluid is 1-3 seconds.
A ruthenium carbon catalyst is prepared by adopting the preparation method of the ruthenium carbon catalyst.
The mass fraction of ruthenium atoms in the ruthenium-carbon catalyst prepared by the preparation method of the ruthenium-carbon catalyst is 0.01-1%. The dispersity of the prepared ruthenium-carbon catalyst is 70-90%.
The ruthenium-carbon catalyst prepared by the preparation method of the ruthenium-carbon catalyst has high dispersity and high effective utilization rate of the ruthenium noble metal, and can fully exert and utilize the function of the expensive ruthenium noble metal. The prepared ruthenium-carbon catalyst has wide application range and can be widely applied to the following application fields: 1) reduction of aliphatic carbonyl groups to alcohols; 2) reducing aromatic hydrocarbon compounds; 3) the glucose is hydrogenated to sorbitol.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The ruthenium carbon catalyst is a carrier catalyst which loads ruthenium on active carbon, and belongs to one of noble metal catalysts. The application fields of the ruthenium-carbon catalyst mainly comprise: 1) reduction of aliphatic carbonyl groups to alcohols; 2) reducing aromatic hydrocarbon compounds; 3) the glucose is hydrogenated to sorbitol.
One embodiment of the present invention provides a method for preparing a ruthenium carbon catalyst, including the following steps S100 to S400.
Step S100: adjusting the pH value of the solution of the ruthenium organic complex to be neutral, and carrying out cation exchange to remove metal cation impurities to obtain a ruthenium-containing solution with the conductivity of 20-40 mu S/cm; the ligand of the ruthenium organic complex contains phosphorus element.
A large number of researches show that under the condition of no change of other conditions, the phosphorus-free inorganic ruthenium solution is adopted and the phosphine-resistant algae is added for fermentation, so that ruthenium cannot enter the algae; further, the subsequent step of taking out and crushing the phosphine-tolerant algae for anaerobic fermentation cannot be performed, and the subsequent carbonization-reduction reaction cannot be performed, so that the ruthenium-carbon catalyst cannot be prepared by the preparation method of the present application. Reference may be made specifically to example 1 and comparative example 1 of the specific examples section of the present invention.
A large number of researches show that the method is very critical to remove metal cation impurities by adjusting the pH value of the solution of the ruthenium organic complex to be neutral and performing cation exchange in step S100, and further to control the conductivity of the obtained ruthenium-containing solution to be 20-40 mu S/cm. Specifically, referring to example 1 and comparative example 2 of the present invention, if the conductivity of the ruthenium-containing solution is controlled to be outside the above range, ruthenium does not enter algae well; further, the subsequent step of taking out and crushing the phosphine-tolerant algae for anaerobic fermentation cannot be performed, and the subsequent carbonization-reduction reaction cannot be performed, so that the ruthenium-carbon catalyst cannot be prepared by the preparation method of the present application.
In some embodiments, the ligand of the ruthenium organic complex is at least one of triphenylphosphine and a derivative of triphenylphosphine. Derivatives of triphenylphosphine include, but are not limited to, sulfonated triphenylphosphine, triarylphosphine oxides, fluorine-containing phosphine ligands. Further, in some examples, the ruthenium organic complex can be triphenylphosphine ruthenium chloride.
Further, controlling the conductivity of the ruthenium-containing solution to be 25 to 35 mu S/cm; in some specific examples, the conductivity of the ruthenium-containing solution is controlled to be 30. mu.S/cm. Thus, the dispersion degree of the prepared ruthenium-carbon catalyst can be favorably improved by controlling the conductivity of the ruthenium-containing solution.
It is understood that in other embodiments, the conductivity of the ruthenium-containing solution can be controlled to be 20. mu.S/cm, 22. mu.S/cm, 24. mu.S/cm, 25. mu.S/cm, 26. mu.S/cm, 28. mu.S/cm, 31. mu.S/cm, 33. mu.S/cm, 36. mu.S/cm, 38. mu.S/cm, 40. mu.S/cm, and the like.
In some of these embodiments, the reagent used to adjust the ph to neutrality is liquid caustic (i.e., sodium hydroxide in liquid form). It is understood that in other embodiments, the agent used to adjust the ph to neutrality may be a sodium hydroxide solution, including but not limited to.
In some of these embodiments, the cation exchange is performed using a cation exchange resin; further, the cation exchange resin may be a hydrogen type cation exchange resin, such as cation exchange resin 201, to exchange impurities such as sodium ions therein.
Step S200: adding phosphine-tolerant algae into the ruthenium-containing solution for fermentation until the ruthenium content in the solution system is below 10 ppm.
The fermentation step of step S200 can reduce the ruthenium content in the solution system to below 10ppm, which indicates that the phosphine-tolerant algae has high utilization rate of ruthenium metal materials, and greatly reduces the environmental problem caused by ruthenium metal discharge.
In some embodiments, the ruthenium-containing solution has a mass concentration of 0.01% to 1%. By controlling the mass concentration of the ruthenium-containing solution within a suitable range, the fermentation step of the phosphine-tolerant algae in the ruthenium-containing solution of step S200 can be facilitated to be better performed. In some specific examples thereof, the ruthenium-containing solution may have a mass concentration of 0.05%, 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%.
It is understood that the phosphine-tolerant algae can be adapted to grow in an environment containing phosphorus, and the solution of ruthenium organic complex containing phosphorus element in the ligand in step S100 is matched, so that the fermentation step in step S200 can promote the normal growth of the phosphine-tolerant algae in the ruthenium-containing solution.
In some of these embodiments, the phosphine-tolerant algae is selected from at least one of chlorella and cyanobacteria. It is understood that the species of the phosphine-tolerant algae include, but are not limited to, these. Further, step S200 is performed in an algae pond containing phosphine-tolerant algae. In other words, in step S200, the ruthenium-containing solution prepared in step S100 is fermented in an algae pond containing phosphine-tolerant algae.
The fermentation in step S200 is performed at normal temperature to promote the normal growth of the phosphine-tolerant algae in the ruthenium-containing solution. It is worth noting that the "normal temperature" in the present invention is 25 ℃. + -. 5 ℃. In other words, the "normal temperature" in the present invention is 20 to 30 ℃.
In some embodiments, the fermentation time with the addition of the phosphine-tolerant algae is 3 days to 5 days, e.g., 3 days, 4 days, or 5 days. By controlling the time for adding the phosphine-tolerant algae to the ruthenium-containing solution for fermentation within the above-mentioned suitable range, the fermentation step of the phosphine-tolerant algae in the ruthenium-containing solution can be better performed.
In some embodiments, the ruthenium content in the solution system is 1ppm to 10ppm by fermentation in step S200; further fermenting until the ruthenium content in the solution system is 3 ppm-10 ppm, and further fermenting until the ruthenium content in the solution system is 3 ppm-7 ppm.
Wherein, the anaerobic fermentation is carried out under anaerobic condition, such as air-free environment.
Step S300: and taking out the phosphine-resistant algae, crushing, and performing anaerobic fermentation to obtain anaerobic fermentation biogas residues.
In some of these embodiments, the period of anaerobic fermentation is from 2 days to 4 days, such as 2 days, 3 days, or 4 days. By controlling the time of the anaerobic fermentation in the step S300 within the appropriate range, the prepared ruthenium carbon catalyst can be further realized to have a better dispersion degree.
Step S400: and carrying out carbonization-reduction reaction on the anaerobic fermentation biogas residue to obtain the ruthenium-carbon catalyst.
Step S400, carrying out carbonization-reduction reaction on the anaerobic fermentation biogas residues to carbonize and reduce organic matters in the anaerobic fermentation biogas residues to form carbon; and further obtaining the ruthenium metal catalyst which is highly dispersed and loaded on the carbon, namely the ruthenium carbon catalyst.
In some of these embodiments, the temperature of the carbomorphism reduction reaction is from 240 ℃ to 350 ℃. In some embodiments, the temperature of the carbonization-reduction reaction can be 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃. Further, the temperature of the carbonization-reduction reaction is 240 ℃ to 310 ℃. Furthermore, the temperature of the carbonization-reduction reaction is 240 ℃ to 300 ℃. A large number of researches show that the dispersity of the prepared ruthenium-carbon catalyst is further improved by controlling the hydrogen reduction temperature of the fluidized bed. Reference may be made in particular to a comparison of example 1 and example 3 of the specific examples section of the present invention. In some of these embodiments, the carbomorphism reduction reaction is carried out in a fluidized bed of hydrogen; the temperature of the hydrogen fluidized bed is 240-300 ℃, and the residence time of the fluid is 1-3 seconds.
In some embodiments, the method further comprises the step of drying the anaerobic fermentation biogas residues and crushing the anaerobic fermentation biogas residues into powder before the anaerobic fermentation biogas residues are subjected to the carbonization reduction reaction. Further, the drying step can adopt vacuum drying, and the temperature of the vacuum drying can be 70-100 ℃.
According to the preparation method of the ruthenium-carbon catalyst, the ruthenium organic complex containing the phosphorus element is used, the ruthenium organic complex solution is adjusted to be neutral, cation exchange is carried out to remove most of metal cations, the influence of metal cation impurities is avoided, and the specific conductivity of the ruthenium-containing solution after cation exchange is controlled; and then adding the ruthenium-containing solution into the phosphine-resistant algae, fermenting until the ruthenium content is reduced to be below 10ppm, and carrying out carbonization reduction reaction on the phosphine-resistant algae after anaerobic fermentation to obtain the high-dispersion ruthenium-carbon catalyst, thereby greatly improving the effective utilization rate of ruthenium.
The mass fraction of ruthenium atoms in the ruthenium-carbon catalyst prepared by the preparation method of the ruthenium-carbon catalyst is 0.01-1%. The dispersity of the prepared ruthenium-carbon catalyst is 70-90%.
Another embodiment of the present invention provides a ruthenium carbon catalyst prepared by the method for preparing a ruthenium carbon catalyst according to any one of the above.
The dispersion degree of the ruthenium-carbon catalyst is high, and the detection shows that the dispersion degree of the ruthenium-carbon catalyst is 70-90%.
The ruthenium-carbon catalyst prepared by the preparation method of the ruthenium-carbon catalyst has high dispersity and high effective utilization rate of the ruthenium noble metal, and can fully exert and utilize the function of the expensive ruthenium noble metal. The prepared ruthenium-carbon catalyst has wide application range and can be widely applied to the following application fields: 1) reduction of aliphatic carbonyl groups to alcohols; 2) reducing aromatic hydrocarbon compounds; 3) the glucose is hydrogenated to sorbitol.
In order to make the objects, technical solutions and advantages of the present invention more concise and clear, the present invention is described with the following specific embodiments, but the present invention is by no means limited to these embodiments. The following described examples are only preferred embodiments of the present invention, which can be used to describe the present invention and should not be construed as limiting the scope of the present invention. It should be understood that any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
In order to better illustrate the invention, the following examples are given to further illustrate the invention. The following are specific examples.
Example 1
The ruthenium-carbon catalyst and the preparation method thereof comprise the following specific steps:
1) preparing triphenylphosphine ruthenium chloride solution containing 100 g of ruthenium atoms; adjusting the triphenylphosphine ruthenium chloride solution to be neutral by using liquid alkali, and removing most of cations by using cation exchange resin 201 to obtain a ruthenium-containing solution with the conductivity of 30 mu S/cm and the mass concentration of 0.18%;
2) adding 15kg of phosphine-tolerant algae (chlorella) into the ruthenium-containing solution, and fermenting for 3 days to reduce the ruthenium content in the solution system to 7 ppm;
3) taking out and crushing the phosphine-tolerant algae, and performing anaerobic fermentation for 4 days to obtain anaerobic fermentation biogas residues; then drying in vacuum at 70 ℃ and crushing into anaerobic fermentation powder;
4) and (3) reducing the anaerobic fermentation powder in a fluidized bed at 250 ℃ by hydrogen, and staying for 2 seconds to obtain 10kg of the high-dispersion ruthenium-carbon catalyst.
It was confirmed that the ruthenium carbon catalyst prepared in this example had a ruthenium atom content of 0.5 wt% and a degree of dispersion of the ruthenium carbon catalyst, as measured by a chemisorption meter, of 75%.
Example 2
The ruthenium-carbon catalyst and the preparation method thereof comprise the following specific steps:
1) preparing triphenylphosphine ruthenium chloride solution containing 10 g of ruthenium atoms; adjusting the triphenylphosphine ruthenium chloride solution to be neutral by using liquid alkali, and removing most of cations by using cation exchange resin 201 to obtain a ruthenium-containing solution with the conductivity of 30 mu S/cm and the mass concentration of 0.18%;
2) adding 15kg of phosphine-tolerant algae (chlorella) into the ruthenium-containing solution, and fermenting for 3 days to reduce the ruthenium content in the solution system to 3 ppm;
3) taking out and crushing the phosphine-tolerant algae, and performing anaerobic fermentation for 4 days to obtain anaerobic fermentation biogas residues; then drying in vacuum at 70 ℃ and crushing into anaerobic fermentation powder;
4) and (3) reducing the anaerobic fermentation powder in a fluidized bed at 300 ℃ by hydrogen, and staying for 3 seconds to obtain 10kg of the high-dispersion ruthenium-carbon catalyst.
It was confirmed that the ruthenium carbon catalyst prepared in this example had a ruthenium atom content of 0.05 wt% and a dispersity of 87% as measured by a chemisorption meter.
Example 3
Example 3 is essentially the same as example 1, except that: step 4) the temperature of the fluidized bed hydrogen reduction was 310 ℃. Specifically, the ruthenium carbon catalyst of example 3 and the preparation method thereof specifically include the following steps:
1) preparing triphenylphosphine ruthenium chloride solution containing 100 g of ruthenium atoms; adjusting the triphenylphosphine ruthenium chloride solution to be neutral by using liquid alkali, and removing most of cations by using cation exchange resin 201 to obtain a ruthenium-containing solution with the conductivity of 30 mu S/cm and the mass concentration of 0.18%;
2) adding 15kg of phosphine-tolerant algae (chlorella) into the ruthenium-containing solution, and fermenting for 3 days to reduce the ruthenium content in the solution system to 7 ppm;
3) taking out and crushing the phosphine-tolerant algae, and performing anaerobic fermentation for 4 days to obtain anaerobic fermentation biogas residues; then drying in vacuum at 70 ℃ and crushing into anaerobic fermentation powder;
4) and (3) reducing the anaerobic fermentation powder in a fluidized bed at 310 ℃ by hydrogen, and staying for 2 seconds to obtain 10kg of the high-dispersion ruthenium-carbon catalyst.
It was confirmed that the ruthenium carbon catalyst prepared in this example had a ruthenium atom content of 0.5 wt% and a dispersion degree of 45% as measured by a chemical adsorption apparatus.
Comparative example 1
Comparative example 1 is essentially the same as example 1 except that: replacing the triphenylphosphine ruthenium chloride solution prepared in the step 1) with a ruthenium nitrate solution with the same molar concentration of ruthenium atoms. Specifically, the ruthenium carbon catalyst of comparative example 1 and the preparation method thereof were as follows:
1) preparing a ruthenium nitrate solution containing 100 g of ruthenium atoms; regulating the ruthenium nitrate solution to be neutral by using liquid alkali, and removing most of cations by using cation exchange resin 201 to obtain a ruthenium-containing solution with the conductivity of 30 mu S/cm;
2) 15kg of phosphine-tolerant algae (chlorella) is added into the ruthenium-containing solution to be fermented for 3 days, and the ruthenium content in the solution system does not change greatly, which indicates that ruthenium can not enter the algae under the condition.
Comparative example 2
Comparative example 2 is essentially the same as example 1, except that: the conductivity of the ruthenium-containing solution controlled in step 1) was 46. mu.S/cm. Specifically, the ruthenium carbon catalyst of comparative example 2 and the preparation method thereof were as follows:
1) preparing triphenylphosphine ruthenium chloride solution containing 100 g of ruthenium atoms; regulating the triphenylphosphine ruthenium chloride solution to be neutral by using liquid alkali, and removing cations by using cation exchange resin 201 to obtain a ruthenium-containing solution with the conductivity of 46S/cm;
2) when 15kg of phosphine-tolerant algae (chlorella) was added to the ruthenium-containing solution and fermented for 3 days, the ruthenium content decreased by only 11.5%, indicating that ruthenium did not enter the algae well.
As can be seen from comparison between example 1 and comparative example 1, under the condition of no change of other conditions, the phosphorus-free inorganic ruthenium solution is adopted and the phosphine-resistant algae is added for fermentation, and ruthenium can not enter the algae; further, the subsequent step of taking out and crushing the phosphine-tolerant algae for anaerobic fermentation cannot be performed, and the subsequent carbonization-reduction reaction cannot be performed, so that the ruthenium-carbon catalyst cannot be prepared by the preparation method of the present application.
As can be seen from comparison between example 1 and comparative example 2, under the condition of keeping other conditions unchanged, the conductivity of the controlled ruthenium-containing solution is 46 muS/cm, and the ruthenium content is only reduced by 11.5% after 3 days of fermentation in step 2), which indicates that ruthenium cannot enter algae well; further, the subsequent step of taking out and crushing the phosphine-tolerant algae for anaerobic fermentation cannot be performed, and the subsequent carbonization-reduction reaction cannot be performed, so that the ruthenium-carbon catalyst cannot be prepared by the preparation method of the present application.
Examples 1 and 2 show that the content of ruthenium atoms is 0.5 wt% or 0.05 wt%, and the high dispersity can be achieved, specifically, the dispersity of the ruthenium carbon catalyst prepared in example 1 can reach 75-87%.
As can be seen from comparison between example 1 and example 3, in example 1, the dispersion degree of the ruthenium carbon catalyst prepared in example 1 was much greater than that of the ruthenium carbon catalyst prepared in example 3 by controlling the temperature of the fluidized bed hydrogen reduction in step 4). Specifically, the dispersion degree of the ruthenium carbon catalyst prepared in example 1 was 75%, and the dispersion degree of the ruthenium carbon catalyst prepared in example 3 was 45%.
Therefore, the steps of the preparation method of the ruthenium-carbon catalyst provided by the invention act synergistically to form an organic integral technical scheme. Specifically, the preparation method of the ruthenium-carbon catalyst uses the ruthenium organic complex containing the phosphorus element, adjusts the ruthenium organic complex solution to be neutral, carries out cation exchange to remove most of metal cations, avoids the influence of metal cation impurities, and controls the specific conductivity of the ruthenium-containing solution after cation exchange; and then adding the ruthenium-containing solution into the phosphine-resistant algae, fermenting until the ruthenium content is reduced to be below 10ppm, and carrying out carbonization reduction reaction on the phosphine-resistant algae after anaerobic fermentation to obtain the high-dispersion ruthenium-carbon catalyst, thereby greatly improving the effective utilization rate of ruthenium.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the ruthenium-carbon catalyst is characterized by comprising the following steps:
adjusting the pH value of the solution of the ruthenium organic complex to be neutral, and carrying out cation exchange to remove metal cation impurities to obtain a ruthenium-containing solution with the conductivity of 20-40 mu S/cm; the ligand of the ruthenium organic complex contains phosphorus;
adding phosphine-tolerant algae into the ruthenium-containing solution for fermentation until the ruthenium content in the solution system is below 10 ppm;
taking out the phosphine-resistant algae, crushing, and performing anaerobic fermentation to obtain anaerobic fermentation biogas residues; and
and carrying out a carbonization reduction reaction on the anaerobic fermentation biogas residue to obtain the ruthenium-carbon catalyst.
2. The method of preparing a ruthenium on carbon catalyst as claimed in claim 1, wherein the ligand of the ruthenium organic complex is at least one of triphenylphosphine and a derivative of triphenylphosphine.
3. The method for preparing a ruthenium on carbon catalyst according to claim 1, wherein the ruthenium-containing solution has a mass concentration of 0.01 to 1%.
4. The method for preparing a ruthenium on carbon catalyst according to claim 1, wherein the phosphine-tolerant algae is at least one selected from chlorella and cyanobacteria.
5. The method of preparing ruthenium on carbon catalyst according to claim 1, wherein the time for fermentation by adding the phosphine-tolerant algae is 3 to 5 days.
6. The method of preparing the ruthenium carbon catalyst according to claim 1, wherein the anaerobic fermentation is performed for 2 to 4 days.
7. The method of preparing a ruthenium on carbon catalyst according to claim 1, wherein the cation exchange is carried out using a cation exchange resin.
8. The method of preparing a ruthenium on carbon catalyst according to any one of claims 1 to 7, wherein the temperature of the carbonization-reduction reaction is 240 ℃ to 350 ℃.
9. The method of preparing a ruthenium on carbon catalyst according to claim 8, wherein the carbonization-reduction reaction is carried out in a fluidized bed of hydrogen; the temperature of the hydrogen fluidized bed is 240-300 ℃, and the residence time of the fluid is 1-3 seconds.
10. A ruthenium carbon catalyst produced by the method for producing a ruthenium carbon catalyst according to any one of claims 1 to 9.
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