CN117643897B - Selective semi-hydrogenation catalyst for N-heterocycle and preparation method thereof - Google Patents
Selective semi-hydrogenation catalyst for N-heterocycle and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 238000005470 impregnation Methods 0.000 claims abstract description 34
- 238000012545 processing Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 28
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 19
- 241000219782 Sesbania Species 0.000 claims description 19
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 18
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 18
- 229960001545 hydrotalcite Drugs 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004898 kneading Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 238000011156 evaluation Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 25
- 239000000047 product Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 229910002845 Pt–Ni Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 230000003993 interaction Effects 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Abstract
The application discloses a selective semi-hydrogenation catalyst for N-heterocycle and a preparation method thereof, relates to the technical field of catalysts, and aims to solve the technical problem that the yield of the semi-hydrogenation product of the N-heterocycle is low in the existing catalyst. The preparation method comprises the following steps: preparing a first carrier; dissolving Ni salt by adopting pure water to obtain a first metal salt solvent; pouring the first metal salt solvent into the first carrier for impregnation, and after the impregnation is finished, putting the first carrier into a muffle furnace for heat treatment to obtain a Ni/first carrier; dissolving Pt salt by pure water to obtain a second metal salt solvent; pouring the second metal salt solvent into the Ni/first carrier for impregnation, and after the impregnation is finished, putting the Ni/first carrier into a muffle furnace for heat processing; and (3) after the heat processing treatment is finished, placing the catalyst into a tubular furnace for reduction reaction to obtain a catalyst finished product.
Description
Technical Field
The application relates to the technical field of catalysts, in particular to a selective half-hydrogenation catalyst for N-heterocycle and a preparation method thereof.
Background
Poor hydrogenation of the prior art catalysts may lead to a number of undesirable consequences. Such as due to incomplete or excessive hydrogenation of the reaction, byproducts or waste may be generated, increasing the processing cost and environmental burden. For example, the inefficient catalytic process may result in energy waste and increased production costs, reducing production efficiency and economic benefits. In addition, insufficient half-hydrogenation may also affect product quality and performance, reducing market competitiveness.
Therefore, a catalyst with better half-hydrogenation effect is needed.
Disclosure of Invention
The application provides a selective semi-hydrogenation catalyst for N-heterocycle and a preparation method thereof, and aims to solve the technical problem that the yield of the semi-hydrogenation product of the N-heterocycle is low by the existing catalyst.
In order to solve the technical problems, the embodiment of the application provides: a process for the preparation of a selective semi-hydrogenation catalyst for N-heterocycles comprising the steps of:
Preparing a first carrier; wherein the first carrier comprises any one of an Al 2O3 carrier and a hydrotalcite carrier;
dissolving Ni salt by adopting pure water to obtain a first metal salt solvent; pouring the first metal salt solvent into the first carrier for impregnation, and after the impregnation is finished, putting the first carrier into a muffle furnace for heat treatment to obtain a Ni/first carrier;
dissolving Pt salt by pure water to obtain a second metal salt solvent; pouring the second metal salt solvent into the Ni/first carrier for impregnation, and after the impregnation is finished, putting the Ni/first carrier into a muffle furnace for heat processing; and (3) after the heat processing treatment is finished, placing the catalyst into a tubular furnace for reduction reaction to obtain a catalyst finished product.
As some alternative embodiments of the application, the step of preparing the first carrier comprises:
Mixing pseudo-boehmite, sesbania powder, water and nitric acid according to a preset weight ratio, kneading and extruding, putting the extruded material into a muffle furnace for heat treatment, and crushing and screening after the treatment is finished to obtain an Al 2O3 carrier; the preset weight ratio of the pseudo-boehmite to the sesbania powder to the water to the nitric acid is 50:10:0.5:0.75.
As some alternative embodiments of the application, the step of preparing the first carrier comprises:
Mixing hydrotalcite, pseudo-boehmite, sesbania powder, water and nitric acid according to a preset weight ratio, kneading and extruding, putting the extruded material into a muffle furnace for heat processing, and crushing and screening after the processing is completed to obtain a hydrotalcite carrier; the preset weight ratio of hydrotalcite to pseudo-boehmite to sesbania powder to water to nitric acid is 50:50:3:50:2.
As some optional embodiments of the application, the treatment temperature of the thermal processing treatment is 400-600 ℃ and the treatment time is 2-6 hours.
As some optional embodiments of the present application, the dissolving Ni salt with pure water to obtain a first metal salt solvent; pouring the first metal salt solvent into the first carrier for impregnation, and after the impregnation is finished, putting the first carrier into a muffle furnace for heat treatment to obtain the Ni/first carrier, wherein the method comprises the following steps of:
weighing Ni salt; wherein the Ni salt comprises at least one of nickel nitrate and nickel chloride;
dissolving the Ni salt by pure water to obtain a first metal salt solvent;
Pouring the first metal salt solvent into the first carrier for soaking for 8-24 hours, and after soaking, putting the first carrier into a muffle furnace for heat treatment to obtain a Ni/first carrier; the heat treatment temperature is 400-600 ℃ and the treatment time is 4-6 hours.
As some optional embodiments of the present application, the step of dissolving the Pt salt with pure water to obtain the second metal salt solvent includes:
weighing Pt salt according to the theoretical loading amount of Pt; wherein the Pt salt includes at least one of chloroplatinic acid, platinum chloride, and potassium chloroplatinate;
dissolving Pt salt by pure water to obtain a second metal salt solvent;
pouring the second metal salt solvent into the Ni/first carrier for impregnation, and after the impregnation is finished, putting the Ni/first carrier into a muffle furnace for heat processing; after the heat processing treatment is finished, the catalyst is put into a tube furnace for reduction reaction, and the step of obtaining the catalyst finished product comprises the following steps:
Pouring the second metal salt solvent into the Ni/first carrier for soaking for 8-24 hours, and placing the second metal salt solvent into a muffle furnace for heat processing after soaking; and (3) after the heat processing treatment is finished, placing the catalyst into a tubular furnace for reduction reaction to obtain a catalyst finished product.
As some optional embodiments of the application, the treatment temperature of the thermal processing treatment is 400-600 ℃ and the treatment time is 4-6 hours.
As some optional embodiments of the present application, after the heat processing treatment is completed, the catalyst is put into a tube furnace to perform a reduction reaction, and the step of obtaining a catalyst finished product includes:
and after the heat processing treatment is finished, placing the catalyst into a tube furnace, and heating to 300-500 ℃ at a heating rate of 2-5 ℃/min for reduction reaction for 2-5 hours to obtain a catalyst finished product.
In order to solve the technical problems, the embodiment of the application further provides: a selective half-hydrogenation catalyst for N-heterocycles, obtainable by a process as described above.
As some optional embodiments of the application, the catalyst uses fixed bed reaction equipment, N-heterocycle is a hydrogen storage carrier, the flow rate of feed liquid is controlled to be 0.3mL/min, the reaction temperature is controlled to be 130 ℃, and the flow rate of hydrogen is set to be 90mL/min; the complete hydrogenation evaluation was cycled five times in total, and the products after each cycle were subjected to GC testing to evaluate the hydroconversion rate of the catalyst:
after the first cycle, the hydrogenation conversion rate is 61.885%; the five-turn later hydroconversion reached 77.472% with a conversion of 26.465% by half hydrogenation.
As described above, the existing catalyst research approaches mainly focus on promoting the conversion of organic liquids directly to perhydrogenation, resulting in lower interest in the conversion of organic liquids to hemihydrogenation and thus lower yields of the hemihydrogenation products. Therefore, in the preparation process of the catalyst, the catalyst with higher half-hydrogenation conversion rate is discovered, the hydrogenation effect of the catalyst is better, and the hydrogenation conversion rate of the catalyst is even higher than the conversion rate of palladium catalysts on the market along with the increase of the cycle times; the prepared catalyst has low preparation cost, and the hydrogenation conversion rate is even better than that of common palladium catalysts. The preparation method of the catalyst comprises the steps that if and only if Ni is firstly loaded on a first carrier and then Pt is loaded on the first carrier, the obtained catalyst has a better hydrogenation effect; the interaction exists between Pt and Ni, so that the reaction process is accelerated, and the hydrogenation performance of the catalyst is further improved; in the high-temperature hydrogenation reaction, ni or Pt of a single metal is easy to agglomerate and deactivate, and one or two modified metals are added, so that the activity and stability of the catalyst can be better improved due to the electron synergistic effect existing between the metals; on the other hand, impregnating the Ni metal on the carrier and then impregnating the Pt element can be regarded as loading Pt on the Ni-coated alumina carrier, and the active sites in the catalyst can comprise: ni is directly anchored to the alumina active site, pt is directly anchored to the alumina active site, and the active site where the unique interaction between Pt-Ni exists. Compared with the current commercial palladium catalyst, the catalyst has the advantages of low cost, easy preparation, easy industrial production and the like, and has higher half-hydrogenation yield when being used for the selective half-hydrogenation of N-heterocycle.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following description will make brief description of the drawings used in the description of the embodiments or the prior art.
FIG. 1 is a schematic flow chart of a process for preparing a selective semi-hydrogenation catalyst for N-heterocycles according to an embodiment of the present application;
FIG. 2 is a schematic representation of the active sites in a catalyst according to an embodiment of the application.
The achievement of the objects, functional features and advantages of the present application will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be noted that all directional indicators (such as up, down, left, right, front, and rear … …) in the embodiments of the present application are merely used to explain the relative positional relationship between the components, the movement condition, etc. in a specific posture, if the specific posture is changed, the directional indicators are correspondingly changed.
In the present application, unless specifically stated and limited otherwise, the terms "connected," "affixed," and the like are to be construed broadly, and for example, "affixed" may be a fixed connection, a removable connection, or an integral body; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.
In addition, if there is a description of "first", "second", etc. in the embodiments of the present application, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present application.
As mentioned above, poor hydrogenation of the prior art catalysts may have a number of undesirable consequences. First, by-products or waste may be generated due to incomplete or excessive hydrogenation of the reaction, increasing the processing cost and environmental burden. Second, inefficient catalytic processes may result in energy waste and increased production costs, reducing production efficiency and economic benefits. In addition, insufficient half-hydrogenation may also affect product quality and performance, reducing market competitiveness.
Accordingly, in order to solve these problems, the present application is directed to improving the performance and efficiency of the catalyst. This can be achieved by optimizing the structure, active site and surface properties of the catalyst. For example, new catalyst materials, such as nanoparticles, metal oxides, or composites, may be explored to improve catalytic activity and selectivity. In addition, the catalytic process can be optimized by changing the preparation method, conditions and reaction parameters of the catalyst.
In addition, a thorough understanding of the mechanism of interaction between the catalyst and the substrate is also critical for improving the catalyst. By studying the adsorption behavior of the catalyst surface, the formation of reaction intermediates, the dissociation process, etc., the mechanism of the catalytic reaction can be revealed and the design and optimization of the catalyst can be guided.
In summary, the poor results of the conventional catalyst include by-product formation, energy waste, increased production cost, reduced product quality, etc. In order to solve these problems, there is a need to improve the performance and efficiency of catalysts, including optimizing catalyst structure and preparation method, and to intensively study the mechanism of catalytic reaction. Thus, the efficiency and the selectivity of the semi-hydrogenation can be improved, the production cost can be reduced, the environmental pollution can be reduced, and the quality and the competitiveness of the product can be improved.
Based on this, as shown in fig. 1, the embodiment of the present application proposes: a process for the preparation of a selective semi-hydrogenation catalyst for N-heterocycles comprising the steps of:
Step S10, preparing and obtaining a first carrier.
Wherein the first carrier comprises any one of an Al 2O3 carrier and a hydrotalcite carrier.
For example, when the first carrier is an Al 2O3 carrier, the step of preparing the first carrier includes: mixing pseudo-boehmite, sesbania powder, water and nitric acid according to a preset weight ratio, kneading and extruding, putting the extruded material into a muffle furnace for heat treatment, and crushing and screening after the treatment is finished to obtain an Al 2O3 carrier; the preset weight ratio of the pseudo-boehmite to the sesbania powder to the water to the nitric acid is 50:10:0.5:0.75.
For another example, when the first carrier is a hydrotalcite carrier, the step of preparing the first carrier includes: mixing hydrotalcite, pseudo-boehmite, sesbania powder, water and nitric acid according to a preset weight ratio, kneading and extruding, putting the extruded material into a muffle furnace for heat processing, and crushing and screening after the processing is completed to obtain a hydrotalcite carrier; the preset weight ratio of hydrotalcite to pseudo-boehmite to sesbania powder to water to nitric acid is 50:50:3:50:2.
In the step of preparing the first carrier, the heat treatment is performed at 550 ℃ for 5 hours.
Step S20, dissolving Ni salt by pure water to obtain a first metal salt solvent; and pouring the first metal salt solvent into the first carrier for impregnation, and after the impregnation is finished, putting the first carrier into a muffle furnace for heat treatment to obtain the Ni/first carrier.
The method comprises the steps of dissolving Ni salt by pure water to obtain a first metal salt solvent; pouring the first metal salt solvent into the first carrier for impregnation, and after the impregnation is finished, putting the first carrier into a muffle furnace for heat treatment to obtain the Ni/first carrier, wherein the method comprises the following steps of: weighing Ni salt; wherein the Ni salt comprises at least one of nickel nitrate and nickel chloride. Dissolving the Ni salt by pure water to obtain a first metal salt solvent; pouring the first metal salt solvent into the first carrier for soaking for 8-24 hours, and after soaking, putting the first carrier into a muffle furnace for heat treatment to obtain a Ni/first carrier; the heat treatment temperature is 400-600 ℃ and the treatment time is 4-6 hours.
Step S30, dissolving Pt salt by pure water to obtain a second metal salt solvent; pouring the second metal salt solvent into the Ni/first carrier for impregnation, and after the impregnation is finished, putting the Ni/first carrier into a muffle furnace for heat processing; and (3) after the heat processing treatment is finished, placing the catalyst into a tubular furnace for reduction reaction to obtain a catalyst finished product.
The step of dissolving the Pt salt with pure water to obtain the second metal salt solvent includes: weighing Pt salt according to the theoretical loading amount of Pt; wherein the Pt salt includes at least one of chloroplatinic acid, platinum chloride, and potassium chloroplatinate. Dissolving Pt salt by pure water to obtain a second metal salt solvent; pouring the second metal salt solvent into the Ni/first carrier for soaking for 8-24 hours, and placing the second metal salt solvent into a muffle furnace for heat processing after soaking; and (3) after the heat processing treatment is finished, placing the catalyst into a tubular furnace for reduction reaction to obtain a catalyst finished product. The treatment temperature of the thermal processing treatment is 400-600 ℃, and the treatment time is 4-6 hours.
The Pt: the theoretical loading ratio of Ni is 1: 1-1: 5.
Specifically, after the thermal processing treatment is completed, the catalyst is put into a tube furnace for reduction reaction, and the step of obtaining a catalyst finished product comprises the following steps: and after the heat processing treatment is finished, placing the catalyst into a tube furnace, and heating to 300-500 ℃ at a heating rate of 2-5 ℃/min for reduction reaction for 2-5 hours to obtain a catalyst finished product. The atmosphere in the tube furnace is a hydrogen atmosphere or an argon-hydrogen mixed gas atmosphere.
The selective semi-hydrogenation catalyst for N-heterocycle, which is prepared by the method, is used for a fixed bed reaction device, the N-heterocycle is used as a hydrogen storage carrier, the flow rate of the feed liquid is controlled to be 0.3mL/min, the reaction temperature is controlled to be 130 ℃, and the flow rate of the hydrogen is set to be 90mL/min; the complete hydrogenation evaluation is carried out for five times in total, and the products after each cycle are subjected to GC test to evaluate the hydrogenation conversion rate of the catalyst, wherein the evaluation result is as follows: after the first cycle, the hydrogenation conversion rate is 61.885%; the five-turn later hydroconversion reached 77.472% with a conversion of 26.465% by half hydrogenation.
The following detailed description of the present application is provided in connection with specific embodiments, so as to facilitate understanding of the present application by those skilled in the art.
Example 1
Mixing 50g of pseudo-boehmite, 10g of sesbania powder, 0.5g of water and 0.75g of nitric acid, kneading for 2-3 times on a kneader, extruding strips on a strip extruder, burning the extruded materials in a muffle furnace at 550 ℃ for 5 hours, obtaining an alumina carrier before crushing, crushing on a crusher, and sieving to obtain small particles with 20-40 meshes for later use;
Then 1.25g of nickel nitrate hexahydrate is taken and ultrasonically dissolved in 2g of water, then added into 5g of the prepared alumina carrier, stirred uniformly and stood for 24 hours for impregnation; placing the impregnated material in a muffle furnace for pyrolysis at 550 ℃ for 4 hours to obtain Ni/Al 2O3;
Then 0.135g of hexahydrated chloroplatinic acid is taken and dissolved in 2g of water, added to 5g of Ni/Al 2O3 carrier, stirred uniformly and then kept stand for 24 hours for impregnation; then pyrolyzing for 4 hours at 550 ℃ in a muffle furnace;
transferring the burnt material into a tube furnace, and under the hydrogen atmosphere, heating to 450 ℃ at the heating rate of 2-5 ℃ per minute, and reducing for 4 hours to obtain the final catalyst sample 1% Pt-Ni/Al 2O3.
Example 2
Mixing 50g of pseudo-boehmite, 10g of sesbania powder, 0.5g of water and 0.75g of nitric acid, kneading for 2-3 times on a kneader, extruding strips on a strip extruder, burning the extruded materials in a muffle furnace at 550 ℃ for 5 hours, obtaining an alumina carrier before crushing, crushing on a crusher, and sieving to obtain small particles with 20-40 meshes for later use;
Then 1.25g of nickel nitrate hexahydrate is taken and ultrasonically dissolved in 2g of water, then added into 5g of the prepared alumina carrier, stirred uniformly and stood for 24 hours for impregnation; placing the impregnated material in a muffle furnace for pyrolysis at 550 ℃ for 4 hours to obtain Ni/Al 2O3;
then 0.675g of hexahydrated chloroplatinic acid is taken and dissolved in 2g of water, added to 5g of Ni/Al 2O3 carrier, stirred evenly and then kept stand for 24 hours for dipping; then pyrolyzing for 4 hours at 550 ℃ in a muffle furnace;
Transferring the burnt material into a tube furnace, and under the hydrogen atmosphere, heating to 450 ℃ at the heating rate of 2-5 ℃ per minute, and reducing for 4 hours to obtain the final catalyst sample of 5% Pt-Ni/Al 2O3.
Example 3
Mixing 50g of water talc, 50g of pseudo-boehmite, 3g of sesbania powder, 50g of water and 2g of nitric acid, kneading for 2-3 times on a kneader, extruding strips on a strip extruder, burning the extruded materials in a muffle furnace at 550 ℃ for 5 hours, obtaining an alumina carrier before crushing, crushing on a crusher, and sieving to obtain small particles with 20-40 meshes for later use;
Then 1.25g of nickel nitrate hexahydrate is taken and ultrasonically dissolved in 2g of water, then added into 5g of the prepared hydrotalcite carrier, stirred uniformly and stood for 24 hours for impregnation; placing the impregnated material in a muffle furnace for pyrolysis at 550 ℃ for 4 hours to obtain Ni/hydrotalcite;
Then 0.135g of hexahydrated chloroplatinic acid is taken and dissolved in 2g of water, added to 5g of Ni/hydrotalcite carrier, stirred uniformly and then kept stand for 24 hours for impregnation; then pyrolyzing for 4 hours at 550 ℃ in a muffle furnace;
transferring the burnt material into a tube furnace, and under the hydrogen atmosphere, heating to 450 ℃ at the heating rate of 2-5 ℃/min, and reducing for 4 hours to obtain the final catalyst sample 1% Pt-Ni/hydrotalcite.
Comparative example 1
Mixing 50g of pseudo-boehmite, 10g of sesbania powder, 0.5g of water and 0.75g of nitric acid, kneading for 2-3 times on a kneader, extruding strips on a strip extruder, burning the extruded materials in a muffle furnace at 550 ℃ for 5 hours, obtaining an alumina carrier before crushing, crushing on a crusher, and sieving to obtain small particles with 20-40 meshes for later use;
Then 0.135g of hexahydrated chloroplatinic acid is taken and dissolved in 2.2g of water by ultrasonic, then added into 5g of the prepared alumina carrier, stirred uniformly and stood for 24 hours for impregnation; placing the impregnated material in a muffle furnace for pyrolysis at 550 ℃ for 4 hours to obtain Pt/Al 2O3;
Transferring the burnt material into a tube furnace, and under the hydrogen atmosphere, raising the temperature to 350 ℃ at the heating rate of 2-5 ℃ per minute, and reducing for 4 hours to obtain the final catalyst sample 1% Pt/Al 2O3.
Comparative example 2
Mixing 50g of pseudo-boehmite, 10g of sesbania powder, 0.5g of water and 0.75g of nitric acid, kneading for 2-3 times on a kneader, extruding strips on a strip extruder, burning the extruded materials in a muffle furnace at 550 ℃ for 5 hours, obtaining an alumina carrier before crushing, crushing on a crusher, and sieving to obtain small particles with 20-40 meshes for later use;
Then 1.25g of nickel nitrate hexahydrate and 0.135g of chloroplatinic acid hexahydrate are taken to be dissolved in 2g of water together by ultrasonic, and then added into 5g of the prepared alumina carrier, stirred evenly and stood for 24 hours for impregnation; placing the impregnated material in a muffle furnace for pyrolysis at 550 ℃ for 4 hours to obtain 1% Pt-Ni/Al 2O3 -co-impregnation;
Transferring the burnt material into a tube furnace, and under the hydrogen atmosphere, heating to 450 ℃ at the heating rate of 2-5 ℃/min, and reducing for 4 hours to obtain the final catalyst sample 1% Pt-Ni/Al 2O3 -co-impregnation.
Comparative example 3
Mixing 50g of pseudo-boehmite, 10g of sesbania powder, 0.5g of water and 0.75g of nitric acid, kneading for 2-3 times on a kneader, extruding strips on a strip extruder, burning the extruded materials in a muffle furnace at 550 ℃ for 5 hours, obtaining an alumina carrier before crushing, crushing on a crusher, and sieving to obtain small particles with 20-40 meshes for later use;
Then 1.25g of nickel nitrate hexahydrate is taken and ultrasonically dissolved in 2g of water, then added into 5g of the prepared alumina carrier, stirred uniformly and stood for 24 hours for impregnation; placing the impregnated material in a muffle furnace for pyrolysis at 550 ℃ for 4 hours to obtain Ni/Al 2O3;
Transferring the burnt material into a tube furnace, and under the hydrogen atmosphere, heating to 450 ℃ at the heating rate of 2-5 ℃ per minute, and reducing for 4 hours to obtain a final catalyst sample Ni/Al 2O3.
Comparative example 4
Mixing 50g of pseudo-boehmite, 10g of sesbania powder, 0.5g of water and 0.75g of nitric acid, kneading for 2-3 times on a kneader, extruding strips on a strip extruder, burning the extruded materials in a muffle furnace at 550 ℃ for 5 hours, obtaining an alumina carrier before crushing, crushing on a crusher, and sieving to obtain small particles with 20-40 meshes for later use;
then 0.088g of palladium chloride is taken, ultrasonically dissolved in hydrochloric acid, diluted as required, added into 5g of the prepared alumina carrier, stirred uniformly and stood for 24 hours for impregnation; placing the impregnated material in a muffle furnace for pyrolysis at 500 ℃ for 4 hours to obtain Pd/Al 2O3;
Transferring the burnt material into a tube furnace, and under the hydrogen atmosphere, raising the temperature to 450 ℃ at a temperature raising rate of 5 DEG/min, and reducing for 4 hours to obtain the final catalyst sample of 1% Pd/Al 2O3.
Experimental example 1
To simulate commercial use, the catalysts of this experimental example were subjected to hydrogenation tests on a fixed bed test instrument.
The specific test instrument is an evaluation device of Beijing European flourishing S3; the evaluation conditions were 130℃and 5MPa, the liquid flow rate was 0.3ml/min and the hydrogen flow rate was 90ml/min. The organic solution used was N-heterocycle, and after 5 cycles, a small amount of liquid was taken to test GC after each cycle, thereby testing the hydroconversion of the N-heterocycle and evaluating the catalyst performance.
The evaluation results are shown in table 1:
Table 1:
As can be seen from table 1:
1) The Pt-Ni is loaded on an alumina or hydrotalcite carrier, and has a relatively good selective semi-hydrogenation conversion effect;
2) The performance of the pure Pt/Al 2O3 catalyst is poor, the performance of the pure Ni/Al 2O3 catalyst is poor, and the performance of the catalyst is also poor due to the fact that Pt-Ni is impregnated with an alumina carrier;
3) The catalyst obtained has better hydrogenation effect if and only after Ni is firstly loaded and then Pt is loaded on the alumina carrier; this is probably because there is interaction between Pt and Ni, so that the reaction process is accelerated, and the hydrogenation performance of the catalyst is further improved; in the high-temperature hydrogenation reaction, ni or Pt of a single metal is easy to agglomerate and deactivate, and one or two modified metals are added, so that the activity and stability of the catalyst can be better improved due to the electron synergistic effect existing between the metals; in another aspect, the first impregnation of Ni metal on the support followed by the impregnation of Pt element can be regarded as loading Pt on the Ni-coated alumina support (since Ni is first loaded, the number of Ni loaded on the alumina surface is large, which can be regarded as Ni-coated alumina, and then the second impregnation of Pt loaded, which can be regarded as Pt loaded on the Ni-coated alumina support, as shown in fig. 2), and the active sites in the catalyst are as shown in fig. 2, comprising: ni is directly anchored to the alumina active site (position 1), pt is directly anchored to the alumina active site (position 2), the active site where the unique interaction between Pt-Ni exists (plays a major role) (position 3).
4) Meanwhile, in example 1, compared with comparative example 4, comparing the performances of 1% Pt-Ni/Al 2O3 and 1% Pd/Al 2O3, it is not difficult to find that the half hydrogenation yield of the 1% Pt-Ni/Al 2O3 catalyst after hydrogenation is almost 2 times of that of 1% Pd/Al 2O3 on the premise of similar conversion rate.
In summary, the technical scheme of the application has the following advantages:
The preparation process is simple and convenient for industrialization; the catalyst cost is low, and the noble metal dosage is small; selective hydrogenation, high half hydrogenation conversion rate; under the action of the catalyst, the hydrogenation temperature of the hydrogen storage carrier is low, and the energy consumption is relatively smaller; the Ni element and the Pt element have mutual synergistic effect, so that the selective hydrogenation effect of the catalyst is good; pt catalysts have significant half-hydrogenation conversion compared to the most widely used Pd catalysts currently commercially available.
The foregoing description is only of the preferred embodiments of the present application, and is not intended to limit the scope of the application, but rather is intended to cover any equivalents of the structures or equivalent processes disclosed herein or in the alternative, which may be employed directly or indirectly in other related arts.
Claims (4)
1. Use of a selective half-hydrogenation catalyst for an N-heterocycle, characterized in that the catalyst is used for catalyzing a selective half-hydrogenation catalytic reaction of an N-heterocycle; when the catalyst is used for catalyzing the selective semi-hydrogenation catalytic reaction of N-heterocycle, the catalyst uses fixed bed reaction equipment, N-heterocycle is a hydrogen storage carrier, the flow rate of a feed liquid is controlled to be 0.3mL/min, the reaction temperature is controlled to be 130 ℃, and the flow rate of hydrogen is set to be 90mL/min; the complete hydrogenation evaluation was cycled five times in total, and the products after each cycle were subjected to GC testing to evaluate the hydroconversion rate of the catalyst: after the first cycle, the hydrogenation conversion rate is 61.885%; the hydroconversion after five turns reaches 77.472%, wherein the half-hydrogenation conversion is 26.465%;
the catalyst is prepared by the following steps:
Preparing a first carrier; wherein the first carrier comprises any one of an Al 2O3 carrier and a hydrotalcite carrier;
Weighing Ni salt; dissolving the Ni salt by pure water to obtain a first metal salt solvent; pouring the first metal salt solvent into the first carrier for soaking for 8-24 hours, and after soaking, putting the first carrier into a muffle furnace for heat treatment to obtain a Ni/first carrier; wherein the treatment temperature of the thermal processing treatment is 400-600 ℃ and the treatment time is 4-6 hours;
Weighing Pt salt according to the theoretical loading amount of Pt; dissolving Pt salt by pure water to obtain a second metal salt solvent; pouring the second metal salt solvent into the Ni/first carrier for impregnation, and after the impregnation is finished, putting the Ni/first carrier into a muffle furnace for heat processing; pouring the second metal salt solvent into the Ni/first carrier for soaking for 8-24 hours, and placing the second metal salt solvent into a muffle furnace for heat processing after soaking; after the heat processing treatment is finished, placing the catalyst into a tube furnace, and heating to 300-500 ℃ at a heating rate of 2-5 ℃/min for reduction reaction for 2-5 hours to obtain a catalyst finished product; the treatment temperature of the thermal processing treatment is 400-600 ℃, and the treatment time is 4-6 hours.
2. Use of a selective half-hydrogenation catalyst for N-heterocycles according to claim 1, characterized in that said step of preparing the first support comprises:
Mixing pseudo-boehmite, sesbania powder, water and nitric acid according to a preset weight ratio, kneading and extruding, putting the extruded material into a muffle furnace for heat treatment, and crushing and screening after the treatment is finished to obtain an Al 2O3 carrier; the preset weight ratio of the pseudo-boehmite to the sesbania powder to the water to the nitric acid is 50:10:0.5:0.75.
3. Use of a selective half-hydrogenation catalyst for N-heterocycles according to claim 1, characterized in that said step of preparing the first support comprises:
Mixing hydrotalcite, pseudo-boehmite, sesbania powder, water and nitric acid according to a preset weight ratio, kneading and extruding, putting the extruded material into a muffle furnace for heat processing, and crushing and screening after the processing is completed to obtain a hydrotalcite carrier; the preset weight ratio of hydrotalcite to pseudo-boehmite to sesbania powder to water to nitric acid is 50:50:3:50:2.
4. Use of a selective semi-hydrogenation catalyst for N-heterocycles according to claim 1, characterized in that the Ni salts comprise at least one of nickel nitrate and nickel chloride; the Pt salt includes at least one of chloroplatinic acid, platinum chloride, and potassium chloroplatinate.
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