CN110302778B - Carbon-loaded ruthenium-based ammonia synthesis catalyst and preparation method thereof - Google Patents
Carbon-loaded ruthenium-based ammonia synthesis catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of catalysts, and particularly discloses a carbon-loaded ruthenium-based ammonia synthesis catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: 1) soaking the carbon material in a metal nitrate aqueous solution, drying the soaked carbon material, placing the dried carbon material in a tubular furnace, and roasting the carbon material for 5-30 min at the temperature of 600-1000 ℃ under an inert atmosphere to obtain a metal nitrate modified carbon material; 2) soaking the modified carbon material in a ruthenium trichloride aqueous solution, adding a precipitator, washing and drying the soaked modified carbon material to obtain the carbon-loaded ruthenium-based ammonia synthesis catalyst. The method of the invention has simple operation, avoids the use of acid solution, has the ammonia synthesis rate higher than that of the traditional ruthenium catalyst by more than 50 percent, and greatly improves the ammonia synthesis activity and the heat-resistant stability of the catalyst.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a carbon-loaded ruthenium-based ammonia synthesis catalyst and a preparation method thereof.
Background
Ammonia synthesis is a backbone of the chemical industry, and as one of the raw materials for fertilizers and various nitrogen-containing chemicals, it has a crucial impact on agricultural production. Besides, ammonia has the properties of no carbon, high hydrogen content, and easy storage and transportation, and can also be used as an energy carrier for hydrogen storage and conversion, so that ammonia is considered to play an important role in future economy.
The ruthenium catalyst is known as the second generation ammonia synthesis catalyst because of excellent performance, and the ruthenium catalyst with application prospect at present consists of a carbon carrier, active metal ruthenium and an auxiliary agent. Patent application documents with publication numbers CN101053834A, CN101579627A, CN105413683A, CN108435166A, CN104084197A, etc. describe the preparation method of the ruthenium catalyst in detail, and it can be seen that the active component in the ruthenium catalyst mainly uses ruthenium trichloride as a precursor, and the patent application document with publication number CN101053834A also describes the effective removal method of chloride ions in detail, and the used auxiliary agents mainly use alkali metals, alkaline earth metals and rare earth metals.
Generally, when preparing a carbon-supported ruthenium-based ammonia synthesis catalyst, firstly, the carbon carrier is placed in a hydrogen atmosphere and treated at the temperature of 800-1000 ℃ for 10-20h to remove elements such as chlorine, sulfur, nitrogen, oxygen and the like on the surface of the carbon carrier, and then an acid solution is usually selected to oxidize the carbon material in a liquid phase to introduce oxygen-containing functional groups to promote the dispersion of active component ruthenium so as to improve the ammonia synthesis performance of the ruthenium catalyst. However, this method not only generates waste acid solution to cause serious environmental pollution, but also has reported that carbon carrier surface oxygen groups are gasified with carbon carriers under ammonia synthesis reaction conditions to destroy the carbon carrier structure, thereby reducing the stability of the catalyst.
Therefore, for the preparation of ruthenium catalysts with higher ammonia synthesis performance, the influence of the active components cannot be simply considered, and the dispersion of the auxiliary agent on the carbon support and the interaction between the auxiliary agent and the carbon support also influence the ammonia synthesis performance of the ruthenium catalyst.
Disclosure of Invention
The invention aims to provide a carbon-loaded ruthenium-based ammonia synthesis catalyst and a preparation method thereof, wherein the preparation method is simple to operate, not only avoids the use of an acid solution, but also improves the ammonia synthesis activity and the heat-resistant stability of the prepared catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a carbon-loaded ruthenium-based ammonia synthesis catalyst comprises the following steps:
(1) soaking the carbon material in a metal nitrate aqueous solution, drying the soaked carbon material, placing the dried carbon material in a tubular furnace, and roasting the carbon material for 5-30 min at the temperature of 600-1000 ℃ under an inert atmosphere to obtain a metal nitrate modified carbon material;
(2) and (2) dipping the modified carbon material obtained in the step (1) into a ruthenium trichloride aqueous solution, adding a precipitator, washing and drying the dipped modified carbon material to obtain the carbon-loaded ruthenium-based ammonia synthesis catalyst.
According to the method, the auxiliary agent nitrate compound and the carbon carrier are compounded and then subjected to heat treatment, and decomposition of the metal nitrate is utilized, so that the defect content on the surface of the carbon carrier is increased, the ruthenium nano particles are further stabilized, the dispersion of the auxiliary agent on the carbon carrier can be improved, the interaction force between the auxiliary agent and the carbon carrier is enhanced, and the ammonia synthesis activity and the heat resistance stability of the ruthenium catalyst are improved.
In the step (1), the carbon material is pretreated, and the pretreatment specifically comprises the following steps: and washing the carbon material with deionized water, heating to 80-140 ℃, drying, and then placing in a hydrogen atmosphere for high-temperature treatment. In the pretreatment process, firstly, dust on the surface of the carbon material is washed and removed, and then, chlorine, sulfur, nitrogen, oxygen and other species on the surface of the carbon material are removed by utilizing high-temperature treatment of hydrogen.
The carbon material is coconut shell activated carbon, carbon nano tubes or graphite with high specific surface area. The carbon material is preferably coconut shell activated carbon, and the ammonia synthesis activity and the heat-resistant stability of the catalyst prepared by using the coconut shell activated carbon are higher.
The metal nitrate is a group IA or IIA metal nitrate, preferably barium nitrate (Ba (NO) 3 ) 2 ) Potassium nitrate (KNO) 3 ) Or cesium nitrate (CsNO) 3 )。
Preferably, the temperature is raised to 600-850 ℃ in an inert atmosphere for roasting for 10-15 min, and the dispersion degree of the auxiliary agent on the surface of the carbon material can be fully improved after roasting under the roasting condition, so that the defect amount of the surface of the carbon material is further improved.
The inert gas is one or more of nitrogen, helium or argon, and the flow rate of the gas is 30-100 mL/min.
In the step (2), the precipitator is a dilute ammonia solution with the volume concentration of 5-20%. The volume usage of the precipitator is 10-20 mL/g based on the mass of the carbon material; the precipitation time is 6-14 h. Adding a precipitant to react Ru 3+ And precipitating, washing with deionized water to remove the precipitate, and drying to obtain the ruthenium-based catalyst.
In the step (1) and the step (2), the dipping temperature is 20-50 ℃, and the dipping time is 8-14 h.
In the step (1) and the step (2), the drying temperature is 80-140 ℃, and the drying is carried out until the weight is constant.
The mass ratio of the metal nitrate to the ruthenium trichloride to the carbon material is 4-30: 5-10: 100.
the invention also discloses the carbon-loaded ruthenium-based ammonia synthesis catalyst prepared by the preparation method, and the catalyst has excellent ammonia synthesis activity and heat-resistant stability and has good application prospect in the ammonia synthesis industry.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method disclosed by the invention is simple to operate, avoids the use of an acid solution, reduces the environmental protection pressure caused by a waste acid solution, and is convenient for large-scale application of the ruthenium catalyst.
(2) The method greatly improves the ammonia synthesis activity and the heat-resistant stability of the catalyst, and the ammonia synthesis rate of the prepared ruthenium catalyst is higher than that of the traditional ruthenium catalyst without heat treatment by more than 50 percent; and at 5MPa, 500 ℃ and 30000h -1 After the catalyst is subjected to heat resistance for 14 hours under the condition, the ammonia synthesis rate of the catalyst can be further improved, and good heat resistance stability is shown.
Drawings
FIG. 1 is a TEM representation of the ammonia synthesis catalyst prepared in example 1, wherein (a) is barium nitrate supported on coconut shell activated carbon and (b) is barium nitrate supported on coconut shell carbon calcined at 850 ℃.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1:
(1) dissolving 15.2g of barium nitrate in 180mL of deionized water to obtain an impregnation solution A; weighing 100g of pretreated coconut shell activated carbon dried to constant weight, adding the coconut shell activated carbon into the impregnation liquid A, impregnating for 12 hours at 25 ℃, and drying to constant weight in an air blast drying oven at 120 ℃;
(2) placing the sample dried in the step (1) in a tube furnace, heating to 850 ℃ in an argon atmosphere, and roasting for 10min to obtain barium nitrate modified coconut shell activated carbon;
(3) dissolving 10g of ruthenium trichloride in 180mL of deionized water to obtain a soaking solution B; and (3) adding the barium nitrate modified coconut shell activated carbon prepared in the step (2) into the impregnation liquid B, impregnating for 12 hours at 25 ℃, directly adding 1000mL of dilute ammonia water solution with volume concentration of 10% to soak for 12 hours, finally fully washing by using deionized water until no white precipitate is detected in the filtrate by using silver nitrate solution, and drying in a blast drying oven at 120 ℃ until the weight is constant to obtain the carbon-supported ruthenium-based ammonia synthesis catalyst.
Example 2:
(1) dissolving 15.2g of barium nitrate in 180mL of deionized water to obtain an impregnation solution A; weighing 100g of pretreated coconut shell activated carbon dried to constant weight, adding the coconut shell activated carbon into the impregnation liquid A, impregnating for 12 hours at 25 ℃, and drying to constant weight in an air blast drying oven at 120 ℃;
(2) placing the sample dried in the step (1) in a tube furnace, heating to 600 ℃ in an argon atmosphere, and roasting for 10min to obtain barium nitrate modified coconut shell activated carbon;
(3) dissolving 10g of ruthenium trichloride in 180mL of deionized water to obtain a soaking solution B; and (3) adding the barium nitrate modified coconut shell activated carbon obtained in the step (2) into the impregnation liquid B, impregnating for 12 hours at 25 ℃, directly adding 1000mL of dilute ammonia water solution with volume concentration of 10% to soak for 12 hours, finally fully washing by using deionized water until no white precipitate is detected in the filtrate by using silver nitrate solution, and drying in a blast drying oven at 120 ℃ until the weight is constant to obtain the carbon-supported ruthenium-based ammonia synthesis catalyst.
Example 3:
(1) dissolving 15.2g of barium nitrate in 180mL of deionized water to obtain an impregnation solution A; weighing 100g of pretreated coconut shell activated carbon dried to constant weight, adding the coconut shell activated carbon into the impregnation liquid A, impregnating for 12 hours at 25 ℃, and drying to constant weight in an air blast drying oven at 120 ℃;
(2) placing the sample dried in the step (1) in a tube furnace, heating to 1000 ℃ in an argon atmosphere, and roasting for 10min to obtain barium nitrate modified coconut shell activated carbon;
(3) dissolving 10g of ruthenium trichloride in 180mL of deionized water to obtain a soaking solution B; and (3) adding the barium nitrate modified coconut shell activated carbon obtained in the step (2) into the impregnation liquid B, impregnating for 12 hours at 25 ℃, directly adding 1000mL of dilute ammonia water solution with volume concentration of 10% to soak for 12 hours, finally fully washing by using deionized water until no white precipitate is detected in the filtrate by using silver nitrate solution, and drying in a blast drying oven at 120 ℃ until the weight is constant to obtain the carbon-supported ruthenium-based ammonia synthesis catalyst.
Example 4:
(1) dissolving 20.6g of potassium nitrate in 180mL of deionized water to obtain an immersion liquid A; weighing 100g of pretreated coconut shell activated carbon dried to constant weight, adding the coconut shell activated carbon into the impregnation liquid A, impregnating for 12 hours at 25 ℃, and drying to constant weight in an air blast drying oven at 120 ℃;
(2) placing the dried sample in the step (1) in a tubular furnace, heating to 600 ℃ in an argon atmosphere, and roasting for 10min to obtain potassium nitrate modified coconut shell activated carbon;
(3) dissolving 10g of ruthenium trichloride in 180mL of deionized water to obtain a soaking solution B; and (3) adding the barium nitrate modified coconut shell activated carbon obtained in the step (2) into the impregnation liquid B, impregnating for 12 hours at 25 ℃, directly adding 1000mL of dilute ammonia water solution with volume concentration of 10% to soak for 12 hours, finally fully washing by using deionized water until no white precipitate is detected in the filtrate by using silver nitrate solution, and drying in a blast drying oven at 120 ℃ until the weight is constant to obtain the carbon-supported ruthenium-based ammonia synthesis catalyst.
Comparative example 1:
(1) dissolving 15.2g of barium nitrate in 180mL of deionized water to obtain an impregnation solution A; weighing 100g of pretreated coconut shell activated carbon dried to constant weight, adding the coconut shell activated carbon into the impregnation liquid A, impregnating for 12 hours at 25 ℃, and drying to constant weight in an air blast drying oven at 120 ℃;
(2) dissolving 10g of ruthenium trichloride in 180mL of deionized water to obtain a soaking solution B; and (2) adding the sample obtained in the step (1) into the impregnation liquid B, impregnating for 12 hours at 25 ℃, directly adding 1000mL of dilute ammonia water solution with volume concentration of 10% to soak for 12 hours, finally fully washing with deionized water until no white precipitate is detected in the filtrate by using a silver nitrate solution, and drying in a blast drying oven at 120 ℃ to constant weight.
Example 5:
(1) dissolving 15.2g of barium nitrate in 560mL of deionized water to obtain an impregnation solution A; weighing 100g of pretreated carbon nanotubes dried to constant weight, adding the pretreated carbon nanotubes into the impregnation liquid A, impregnating for 12 hours at 25 ℃, and drying to constant weight in a blast drying oven at 120 ℃;
(2) placing the sample dried in the step (1) in a tube furnace, heating to 600 ℃ in an argon atmosphere, and roasting for 10min to obtain a barium nitrate modified carbon nanotube;
(3) dissolving 10g of ruthenium trichloride in 560mL of deionized water to obtain a soaking solution B; and (3) adding the barium nitrate modified carbon nano tube prepared in the step (2) into the impregnation liquid B, impregnating for 12 hours at 25 ℃, directly adding 1000mL of dilute ammonia water solution with volume concentration of 10% to soak for 12 hours, fully washing by using deionized water till no white precipitate is detected in the filtrate by using silver nitrate solution, and drying in a blast drying oven at 120 ℃ to constant weight to obtain the carbon-supported ruthenium-based ammonia synthesis catalyst.
Comparative example 2:
(1) dissolving 15.2g of barium nitrate in 560mL of deionized water to obtain an impregnation solution A; weighing 100g of pretreated carbon nanotubes dried to constant weight, adding the pretreated carbon nanotubes into the impregnation liquid A, impregnating for 12 hours at 25 ℃, and drying to constant weight in a blast drying oven at 120 ℃;
(2) dissolving 10g of ruthenium trichloride in 560mL of deionized water to obtain a soaking solution B; and (2) adding the sample prepared in the step (1) into the impregnation liquid B, impregnating for 12 hours at 25 ℃, directly adding 1000mL of dilute ammonia water solution with volume concentration of 10% to soak for 12 hours, finally fully washing with deionized water until no white precipitate is detected in the filtrate by using a silver nitrate solution, and drying in a blast drying oven at 120 ℃ until the weight is constant to obtain the carbon-supported ruthenium-based ammonia synthesis catalyst.
And (3) performance testing:
the evaluation of the activity of the catalyst was carried out in a high-pressure activity test apparatus, the reactor being a fixed bed with an internal diameter of 14 mm. The catalyst particles are 1.0-1.4 mm, the stacking volume is 2mL, and the catalyst is filled in an isothermal zone of the reactor; the reaction gas is a mixed gas of nitrogen and hydrogen, and the ratio of hydrogen to nitrogen is 3: 1.
Table 1 below shows the catalysts obtained in the above examples and comparative examples at 400 deg.C, 10MPa, 10000h -1 And (4) ammonia synthesis performance test results under the conditions.
TABLE 1 Ammonia Synthesis reaction rates for ruthenium catalysts
As can be seen from Table 1, under the same carbon carrier conditions, the ammonia synthesis rate of the ruthenium catalyst prepared by the invention can be more than 50% higher than that of the ruthenium catalyst without heat treatment; at 5MPa, 500 ℃ and 30000h -1 After the catalyst is subjected to heat resistance for 14 hours under the condition, the ammonia synthesis rate of the catalyst is not reduced, good heat-resistant stability is shown, and the catalyst has a good industrial prospect.
Claims (8)
1. A preparation method of a carbon-loaded ruthenium-based ammonia synthesis catalyst comprises the following steps:
(1) soaking the carbon material in a metal nitrate aqueous solution, drying the soaked carbon material, placing the dried carbon material in a tubular furnace, and roasting the carbon material for 5-30 min at the temperature of 600-1000 ℃ under an inert atmosphere to obtain a metal nitrate modified carbon material; the metal nitrate is І A or І І A group metal nitrate; the carbon material is coconut shell activated carbon, carbon nano tubes or graphite with high specific surface area;
(2) and (2) dipping the modified carbon material obtained in the step (1) into a ruthenium trichloride aqueous solution, adding a precipitator, washing and drying the dipped modified carbon material to obtain the carbon-loaded ruthenium-based ammonia synthesis catalyst.
2. The method for preparing the carbon-supported ruthenium-based ammonia synthesis catalyst according to claim 1, wherein in the step (1), the carbon material is pretreated firstly, and the specific pretreatment conditions are as follows: and washing the carbon material with deionized water, heating to 80-140 ℃, drying, and then placing in a hydrogen atmosphere for high-temperature treatment.
3. The preparation method of the carbon-supported ruthenium-based ammonia synthesis catalyst according to claim 1, wherein in the step (1), the catalyst is calcined at 600-850 ℃ for 10-15 min under inert atmosphere.
4. The method for preparing the carbon-supported ruthenium-based ammonia synthesis catalyst according to claim 1, wherein in the step (2), the precipitator is a dilute ammonia solution with a volume concentration of 5-20%.
5. The preparation method of the carbon-supported ruthenium-based ammonia synthesis catalyst according to claim 4, wherein the volume of the precipitant is 10-20 mL/g based on the mass of the carbon material, and the precipitation time is 6-14 h.
6. The preparation method of the carbon-supported ruthenium-based ammonia synthesis catalyst according to claim 1, wherein in the step (1) and the step (2), the impregnation temperature is 20-50 ℃, and the impregnation time is 8-14 h.
7. The preparation method of the carbon-supported ruthenium-based ammonia synthesis catalyst according to claim 1, wherein the mass ratio of the metal nitrate, the ruthenium trichloride and the carbon material is 4-30: 5-10: 100.
8. a carbon-supported ruthenium-based ammonia synthesis catalyst, which is characterized by being prepared by the preparation method of any one of claims 1 to 7.
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