3D printing catalyst for preparing 1, 4-butanediol through hydrogenation of 1, 4-butynediol as well as preparation method and application of 3D printing catalyst
By constructing Ni-based stirred paddle catalysts using 3D printing technology, the structural controllability and stability issues of Ni-based catalysts in the hydrogenation process of 1,4-butynediol were solved, achieving efficient catalytic conversion and integrated design, and improving the selectivity and catalytic lifetime of 1,4-butanediol.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-31
- Publication Date
- 2026-04-10
AI Technical Summary
Existing Ni-based catalysts for the hydrogenation of 1,4-butynediol to 1,4-butanediol suffer from problems such as uneven distribution of active sites, easy coverage by side reaction sites, poor structural controllability, easy agglomeration of catalyst particles, and limited mass transfer, resulting in insufficient selectivity and stability.
Ni-based stirred paddle catalysts were prepared using 3D printing technology. Through selective laser melting, molten salt treatment, ultrasonic cleaning, and high-temperature reduction, an integrated structure of catalyst and reactor was constructed, achieving controllable design and high mechanical stability of the catalyst.
It improves the selectivity and catalytic lifetime of 1,4-butanediol, breaks through the limitations of traditional catalyst and reactor separation design, provides a new path for integrated and modular catalytic reaction systems, and has good prospects for industrial application.
Smart Images
Figure FT_1 
Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalyst preparation technology, and particularly relates to a 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol, its preparation method and application. Background Technology
[0002] 1,4-Butanediol (BAD) is an important basic chemical raw material and organic intermediate, widely used in the synthesis of polyesters, engineering plastics, and pharmaceutical chemical products. Therefore, the highly selective preparation of this compound is of great significance to the chemical industry.
[0003] In its preparation route, the catalytic hydrogenation conversion of 1,4-butynediol (BYD) is the key pathway to achieve industrial-scale production of BAD. However, since the hydrogenation of BYD to prepare BAD is a typical tandem reaction, this process is prone to hydrogenolysis and isomerization reactions, generating byproducts such as n-butanol, 4-hydroxybutyraldehyde, or 2-hydroxytetrahydrofuran, leading to a decrease in the selectivity of BAD.
[0004] In the existing BYD hydrogenation catalytic system, Ni-based catalysts have become an important research object due to their high hydrogenation activity and cost advantages. However, traditional Ni-based catalysts generally have the following problems: (1) the active sites are unevenly distributed and easily covered by side reaction sites, resulting in poor structural controllability; (2) catalyst particles are prone to agglomeration, loss or mechanical breakage, leading to activity decay; (3) the catalyst and the reaction device are structurally independent, making it difficult to achieve efficient mass transfer and structural synergy.
[0005] In traditional reaction systems, catalysts are typically dispersed in the reaction medium as powder or particles, while the reactor serves only as a physical container. This separation of structure and function makes it difficult to achieve efficient energy and mass transfer, resulting in limited mass transfer, high energy consumption, and insufficient stability under multiphase reaction conditions. Summary of the Invention
[0006] The purpose of this invention is to provide a 3D-printed catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol, its preparation method, and its application. The catalyst of this invention integrates catalysis and structural function, possessing high mechanical stability, structural controllability, and excellent catalytic activity. It can achieve efficient and stable catalytic conversion in the hydrogenation of BYD to BAD, significantly improving the selectivity and catalytic lifetime of the target product, and providing a novel integrated catalytic device and method for complex hydrogenation reaction systems.
[0007] This invention provides a method for preparing a 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol, comprising the following steps:
[0008] A) Ni-based alloy powder was 3D printed using selective laser melting to obtain a Ni-based impeller precursor;
[0009] B) The Ni-based impeller precursor is subjected to molten salt treatment in a mixed molten salt to obtain a molten salt-treated Ni-based impeller precursor;
[0010] The molten salt comprises a mixed molten salt of potassium chloride and sodium chloride;
[0011] C) The Ni-based impeller precursor after molten salt treatment is cleaned and dried to obtain a dried Ni-based impeller precursor.
[0012] D) The dried Ni-based impeller precursor was subjected to reduction treatment in a reducing atmosphere to obtain a reduced sample;
[0013] E) The reduced sample is passivated in an oxidizing atmosphere to obtain a Ni-based 3D printed impeller catalyst.
[0014] Preferably, the Ni-based alloy powder in step A) contains iron and / or chromium.
[0015] Preferably, the molten salt is a binary molten salt system composed of sodium chloride and potassium chloride, and the molar ratio of sodium chloride to potassium chloride is 3:7 to 7:3.
[0016] Preferably, the temperature of the molten salt treatment in step B) is 500~900℃, and the time of the molten salt treatment is 2~12 hours.
[0017] Preferably, in step C), the cleaning is ultrasonic cleaning, the drying is vacuum drying, the drying temperature is 80~120℃, and the drying time is 8~12 hours.
[0018] Preferably, steps B) and C) are repeated multiple times to obtain the dried Ni-based impeller precursor.
[0019] Preferably, the reduction treatment temperature in step D) is 300~900℃, and the reduction treatment time is 3~12 hours.
[0020] Preferably, in step E), the volume fraction of the oxidizing gas in the oxidizing atmosphere is 0.1~3 vol%; the passivation temperature is 20~40℃; and the passivation time is 1~6h.
[0021] This invention provides a 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol, which is prepared according to the preparation method described above. The 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol includes a bushing and a blade, and the bushing has an assembly through hole in its wall.
[0022] This invention provides the application of the 3D-printed catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol as described above in the hydrogenation of 1,4-butynediol to 1,4-butanediol.
[0023] This invention provides a method for preparing a 3D-printed catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol, comprising the following steps: A) 3D printing Ni-based alloy powder using selective laser melting to obtain a Ni-based impeller precursor; B) etching and selectively dissolving the Ni-based impeller precursor in a mixed molten salt to obtain an etched Ni-based impeller precursor; the molten salt includes a mixed molten salt of potassium chloride and sodium chloride; C) cleaning and drying the etched Ni-based impeller precursor to obtain a dried Ni-based impeller precursor; D) reducing the dried Ni-based impeller precursor in a reducing atmosphere to obtain a reduced sample; E) passivating the reduced sample in an oxidizing atmosphere to obtain a Ni-based 3D-printed impeller catalyst.
[0024] Compared with the prior art, the beneficial effects achieved by the present invention are:
[0025] 1. This invention utilizes 3D printing technology to construct BYD-based BAD stirred impeller catalysts. Compared to traditional catalyst preparation methods, this approach enables controllable design of the catalyst structure, giving the catalyst a high degree of structural tunability and functional customization.
[0026] 2. The obtained impeller catalyst has high mechanical strength, wear resistance and pressure resistance, and can operate stably for a long time under high temperature and high pressure conditions.
[0027] 3. This invention integrates the functions of the catalyst and the reactor into one, forming an integrated device, which breaks through the limitations of the traditional separate design of "catalyst-reactor components" and provides a new technical path for the integration and modularization of future catalytic reaction systems.
[0028] 4. This invention uses Ni-based alloy powder as the main raw material and combines molten salt treatment, ultrasonic washing and high-temperature reduction methods. It has the advantages of strong process controllability and good repeatability, and has good prospects for industrial application. Attached Figure Description
[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0030] Figure 1The diagram shows the structure and physical image of the 3D-printed stirring paddle catalyst described in Embodiment 1 of this invention.
[0031] Figure A shows a schematic diagram of the overall structure of the 3D-printed impeller catalyst; Figure B shows a top view of the 3D-printed impeller catalyst; and Figure C shows a photograph of the actual 3D-printed impeller catalyst. Detailed Implementation
[0032] This invention provides a method for preparing a 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol, comprising the following steps:
[0033] A) Ni-based alloy powder was 3D printed using selective laser melting to obtain a Ni-based impeller precursor;
[0034] B) The Ni-based impeller precursor is subjected to molten salt treatment in a mixed molten salt to obtain an etched Ni-based impeller precursor;
[0035] The molten salt comprises a mixed molten salt of potassium chloride and sodium chloride;
[0036] C) The etched Ni-based impeller precursor is cleaned and dried to obtain a dried Ni-based impeller precursor.
[0037] D) The dried Ni-based impeller precursor was subjected to reduction treatment in a reducing atmosphere to obtain a reduced sample;
[0038] E) The reduced sample is passivated in an oxidizing atmosphere to obtain a Ni-based 3D printed impeller catalyst.
[0039] In this invention, the Ni-based alloy powder contains iron and / or chromium. The particle size of the Ni-based alloy powder is preferably 10-60 μm, with a sphericity of not less than 0.9 and a Hall flow rate not exceeding 20 s / 50 g. Commonly used Ni-based alloys for 3D printing in the art can be used. Specifically, in some embodiments of this invention, GH4169 Ni-based alloy powder is used as the printing base material. A three-dimensional geometric model of the impeller is established using 3D modeling software. Selective laser melting (SLM) technology is used to melt and print layer by layer in an inert atmosphere to obtain the Ni-based impeller precursor. After printing, the impeller is sequentially cut, desupported, surface-planed, and annealed to obtain the initial Ni-based 3D printed impeller.
[0040] In this invention, the three-dimensional modeling software is selected from any one of SolidWorks, 3Ds MAX, AutoCAD or Materialise Magics. The selective laser melting layer-by-layer melting printing, cutting, support removal and surface flattening can all be carried out using the selective laser melting layer-by-layer melting printing, cutting, support removal and surface flattening methods commonly used in the art, which will not be described in detail in this invention.
[0041] In this invention, the annealing temperature is preferably 600~1000℃, more preferably 700~900℃, such as 600℃, 650℃, 700℃, 750℃, 800℃, 850℃, 900℃, 950℃, 1000℃, preferably a range of values with any of the above values as the upper or lower limit; the annealing time is preferably 3~8 hours, more preferably 5~8 hours.
[0042] After obtaining the Ni-based impeller precursor, the present invention mixes it with a mixed molten salt and performs molten salt treatment to obtain the molten salt treated Ni-based impeller precursor.
[0043] During the molten salt treatment process, the reaction between halide ions in the molten salt and the chemically active metal components in the alloy generates soluble metal halides. Specifically, in this application, Fe and / or Cr in the Ni-based alloy are etched, selectively dissolved, and precipitated by chloride molten salt, and removed during the subsequent cleaning process. This can regulate the surface microstructure, promote the exposure of Ni species on the surface, and form an active surface with defective structures.
[0044] In this invention, the mixed molten salt comprises sodium chloride and potassium chloride, wherein the molar ratio of sodium chloride to potassium chloride is preferably 3:7 to 7:3, more preferably 4:6 to 6:4, such as 3:7, 3.5:6.5, 4:6, 4.5:5.5, 5:5, 5.5:4.5, 6:4, 6.5:3.5, 7:3, and preferably a range of values with any of the above values as the upper or lower limit; the temperature of the molten salt treatment is preferably 500 to 900 °C. The temperature is preferably 500~800℃, such as 500℃, 550℃, 600℃, 650℃, 660℃, 670℃, 680℃, 690℃, 700℃, 710℃, 720℃, 730℃, 740℃, 750℃, 800℃, 850℃, 900℃, preferably within the range of any of the above values as the upper or lower limit; the molten salt treatment time is preferably 2~12 hours, more preferably 5~10 hours.
[0045] After the molten salt treatment is completed, the catalyst treated with molten salt is subjected to multiple ultrasonic washes to remove residual salt and etch soluble metal halides, and then vacuum dried to obtain the dried Ni-based stirring impeller precursor.
[0046] In this invention, the ultrasonic washing time for each cycle is preferably 5-15 minutes, more preferably 10-15 minutes, the number of cycles is preferably 30-50, the vacuum drying temperature is preferably 80-120°C, more preferably 90-110°C, such as 80°C, 90°C, 100°C, 110°C, 120°C, preferably within the range of any of the above values as the upper or lower limit; the vacuum drying time is preferably 8-12 hours, more preferably 9-10 hours.
[0047] The present invention preferably repeats the above-described steps of molten salt treatment, ultrasonic washing, and vacuum drying to ensure uniform distribution of surface-active species. There is no particular limitation on the number of repetitions; specifically, in some embodiments of the present invention, the steps may be repeated 1 to 20 times.
[0048] After obtaining the dried Ni-based impeller precursor, the present invention performs a reduction treatment on it in a reducing atmosphere to further regulate its surface structure and obtain a reduced sample.
[0049] In this invention, the reducing atmosphere is preferably hydrogen, the temperature of the reduction treatment is preferably 300~900℃, more preferably 400~800℃, such as 300℃, 350℃, 400℃, 450℃, 500℃, 550℃, 600℃, 650℃, 700℃, 750℃, 800℃, 850℃, 900℃, preferably a range of values with any of the above values as the upper or lower limit; the time of the reduction treatment is preferably 3~12 hours, more preferably 5~10 hours, and the heating rate of the reduction treatment is preferably 1~8℃ / min, more preferably 3~5℃ / min.
[0050] After the reduction treatment is completed, the reduced sample is cooled and then passivated in an oxidizing atmosphere. The passivation can form an ultrathin stable oxide layer on the catalyst surface, protecting the active components, and thus obtaining a Ni-based 3D printed stirring paddle catalyst.
[0051] In this invention, the oxidizing atmosphere is preferably a diluted oxygen atmosphere, and the volume fraction of oxygen is preferably 0.1~3 vol%, more preferably 0.5~2.5 vol%, such as 0.1 vol%, 0.5 vol%, 1 vol%, 1.5 vol%, 2 vol%, 2.5 vol%, 3 vol%, preferably within the range of any of the above values as the upper or lower limit. The passivation temperature is preferably 20~40℃, more preferably 30~35℃, and the passivation time is preferably 1~6 hours.
[0052] The present invention also provides a 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol, which is prepared according to the preparation method described above. The 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol includes a bushing and a blade, and the bushing has an assembly through hole in its wall.
[0053] Specifically, in some embodiments of the present invention, the 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol has... Figure 1 The structure shown is a hollow impeller structure with a central through hole along the axial direction of the bushing. The diameter of the hole is 6-8 mm, the wall thickness is 2-5 mm, and the overall height is 10-20 mm. Impeller blades with specific tilt angles are provided on both sides, and the impeller blades are flush with the height of the impeller body. A fixing hole with a diameter of 3 mm is provided in the center of the bushing wall, which can be stably assembled with the reaction device by means of a metal pin.
[0054] This invention also provides the application of the 3D-printed catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol described above in the hydrogenation of 1,4-butynediol to 1,4-butanediol. The 3D-printed catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol can be used as a stirring paddle assembly of a reaction vessel.
[0055] This invention provides a method for preparing a 3D-printed catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol, comprising the following steps: A) 3D printing Ni-based alloy powder using selective laser melting to obtain a Ni-based impeller precursor; B) etching and selectively dissolving the Ni-based impeller precursor in a mixed molten salt to obtain an etched Ni-based impeller precursor; the molten salt includes a mixed molten salt of potassium chloride and sodium chloride; C) cleaning and drying the etched Ni-based impeller precursor to obtain a dried Ni-based impeller precursor; D) reducing the dried Ni-based impeller precursor in a reducing atmosphere to obtain a reduced sample; E) passivating the reduced sample in an oxidizing atmosphere to obtain a Ni-based 3D-printed impeller catalyst.
[0056] Compared with the prior art, the beneficial effects achieved by the present invention are:
[0057] 1. This invention utilizes 3D printing technology to construct BYD-based BAD stirred impeller catalysts. Compared to traditional catalyst preparation methods, this approach enables controllable design of the catalyst structure, giving the catalyst a high degree of structural tunability and functional customization.
[0058] 2. The obtained impeller catalyst has high mechanical strength, wear resistance and pressure resistance, and can operate stably for a long time under high temperature and high pressure conditions.
[0059] 3. This invention integrates the functions of the catalyst and the reactor into one, forming an integrated device, which breaks through the limitations of the traditional separate design of "catalyst-reactor components" and provides a new technical path for the integration and modularization of future catalytic reaction systems.
[0060] 4. This invention uses Ni-based alloy powder as the main raw material and combines molten salt treatment, ultrasonic washing and high-temperature reduction methods. It has the advantages of strong process controllability and good repeatability, and has good prospects for industrial application.
[0061] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, describes a 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol provided by the present invention, its preparation method, and its application, but this should not be construed as limiting the scope of protection of the present invention.
[0062] Example 1
[0063] 1) 3Ds MAX software was used for assisted modeling and design to create structural modules and generate a stirring impeller skeleton structure model. The Ni-based stirring impeller catalyst has a hollow impeller structure with a central through-hole along the axial direction. The hole diameter is 6 mm, the wall thickness is 3 mm, and the overall height is 20 mm. The two sides are inclined at an angle of 45 degrees. o The stirring blades are flush with the main body of the stirring blade. A 3 mm diameter fixing hole is located in the center of the stirring blade, allowing for a secure connection to the reaction device via a metal pin.
[0064] 2) 3D printing was performed using GH4169 Ni-based alloy powder as raw material and SLM technology. The particle size range of the alloy powder was 20~60 μm, the sphericity was 0.9, and the Hall flow rate was 20 s / 50 g. The printing parameters were set as follows: laser power 300W, scanning rate 1 m / s, printing layer thickness 70 μm, and printing was carried out in an N2 atmosphere with a flow rate of 3 L / min.
[0065] 3) Cut and peel the Ni-based stirring paddle printed in step 2) from the substrate, and then perform support removal, surface polishing and annealing treatment in sequence. The annealing process has a heating rate of 5℃ / min, a holding temperature of 850℃ and a holding time of 8 h, and then is cooled in the furnace to 200℃ at a cooling rate of 15℃ / min before being removed from the furnace and air-cooled.
[0066] 4) The Ni-based stirred paddle catalyst precursor annealed in step 3) was thoroughly mixed with 20.8 g of a mixed molten salt system (sodium chloride and potassium chloride molar ratio of 1:1). The mixture was placed in a muffle furnace and heated to 700°C at a heating rate of 5°C / min, and maintained at this temperature for 12 h for etching and selective dissolution treatment.
[0067] 5) Wash the sample after step 4) thoroughly with deionized water and dry it in a vacuum drying oven at 100℃ for 12 hours.
[0068] 6) Repeat steps 4) and 5) above 10 times to obtain a sample with a stable surface structure and sufficient exposure of active sites.
[0069] 7) The sample obtained in step 6) was placed in a tube furnace under a hydrogen atmosphere and reduced at 700°C for 3 h. After cooling, it was passivated at 30°C for 6 h under a diluted oxygen atmosphere (oxygen content 1 vol%) to finally obtain the Ni-based stirred paddle catalyst, named Ni-10KN-AB-700. Here, KN represents KCl and NaCl, 10 represents the number of times steps 4) and 5) are repeated, AB refers to the stirred paddle, and 700 represents the temperature of molten salt etching and selective dissolution.
[0070] Example 2
[0071] The Ni-based stirred paddle catalyst was prepared according to the method in Example 1, except that the molten salt system used in step 4) was KCl, and the molar amount of KCl was the sum of the molar amounts of KCl and NaCl in Example 1. The remaining steps were the same as in Example 1. Finally, a Ni-based stirred paddle sample was obtained and named Ni-10K-AB-700.
[0072] Example 3
[0073] The difference between this embodiment and embodiment 1 is that the molten salt system used in step 4) is only NaCl, and the molar amount of NaCl is the sum of the molar amounts of KCl and NaCl in embodiment 1. The remaining steps are the same as in embodiment 1. Finally, a Ni-based stirring impeller sample is obtained and named Ni-10N-AB-700.
[0074] Example 4
[0075] The difference between this embodiment and Embodiment 1 is that in step 4), the temperature is increased to 500℃, 600℃, 700℃, 800℃ and 900℃ at a heating rate of 5℃ / min, and maintained at the target temperature for 12 h. The other preparation steps are the same as in Embodiment 1. The Ni-based stirring impeller sample was finally obtained and named Ni-10KN-AB-X (X represents the etching and selective dissolution temperature, and the value of X is 500, 600, 800 and 900).
[0076] Example 5
[0077] The difference between Example 5 and Example 1 is that the number of repetitions M in step 6) is variable, set to 1, 5, 15, and 20 times respectively. The other preparation steps are the same as in Example 1. The final Ni-based stirring impeller sample was obtained and named Ni-MKN-AB-700 (M represents the number of calcinations 1, 5, 15, and 20).
[0078] Comparative Example 1
[0079] The difference between this comparative example and Comparative Example 1 is that the initial Ni-based impeller sample precursor was not subjected to any surface treatment, and the Ni-based impeller after printing and annealing was used directly as the catalyst. The catalyst sample was named Fresh-Ni-AB.
[0080] Comparative Example 2
[0081] The difference between this comparative example and Comparative Example 1 is that the initial Ni-based impeller sample precursor was only calcined in an air atmosphere for surface treatment, without molten salt etching. The catalyst was named Air-Ni-AB-700.
[0082] Application examples
[0083] The Ni-based stirred-paddle catalysts from the above embodiments and comparative examples were connected to a semi-batch reactor system. The stirred paddle was fixed by a pin and connected to the center of the reactor liquid level for performance testing of the BYD hydrogenation to BAD reaction. Before the reaction, N2 was introduced to 4 MPa to check the airtightness of the device. After confirming no leakage, H2 was introduced to adjust the reaction pressure to 4.0 MPa. The catalyst performance was evaluated by increasing the temperature to 120℃ at a programmed rate of 5℃ / min. The product after 4 hours of reaction was used for detection and analysis.
[0084] Table 1 lists the catalytic performance of the Ni-based stirred paddle catalysts obtained in the above examples and comparative examples in the BYD hydrogenation to BAD reaction. The performance results show that the 3D-printed Ni-based stirred paddle catalysts exhibit significant differences in performance under different activation conditions.
[0085] The untreated Ni-based stirred paddle catalyst (Fresh-Ni-AB) exhibits certain catalytic activity, with the main detected products being the semi-hydrogenation product 1,4-butenediol (BED) and the byproduct 2-hydroxytetrahydrofuran (HTHF). The sample with surface activation treatment by air calcination (Air-Ni-AB) shows higher catalytic activity, with a BYD conversion rate of 85%, but the selectivity for the semi-hydrogenation products BED and 2-hydroxytetrahydrofuran (HTHF) still reaches 45.2% and 18.5%, respectively, while the formation of the byproduct BOL is also detected.
[0086] After treatment with a single molten salt (Ni-10K-AB-700, Ni-10N-AB-700), the BYD conversion rate can be increased to about 95%, but the total selectivity of the byproducts n-butanol (BOL) and 2-hydroxytetrahydrofuran (HTHF) can reach 25.9% and 21.1%, respectively. After treatment with a mixed molten salt system at 700℃, the BYD conversion rate of the Ni-10KN-AB-700 catalyst can reach 100%, the BAD yield can be significantly increased to 96%, and the selectivity of the byproduct BOL is only 3.9%, with no detection of the semi-hydrogenation product BED and the byproduct HTHF.
[0087] Table 1 Catalytic performance of Ni-based stirred paddle catalysts in the examples and comparative examples.
[0088]
[0089] Further research on the effect of different molten salt treatment temperatures on catalytic performance showed that as the molten salt treatment temperature gradually increased from 500℃ to 900℃, the BYD conversion rate first increased from 93.7% to 100% and then decreased to 98.8%. The selectivity of the target product BAD also showed a trend of first increasing and then decreasing, indicating that excessively high or low molten salt etching and selective dissolution temperatures are not conducive to the formation of the target product BAD. In summary, 700℃ is the optimal temperature for etching and selective dissolution.
[0090] Furthermore, as the number of molten salt treatments increased from 1 to 10, the BYD conversion rate and BAD selectivity gradually increased. When the number of molten salt treatments gradually increased to 20, the BYD conversion rate remained at 100%, but the selectivity of the target product BAD showed a significant decreasing trend, while the selectivity of the main byproduct BOL relatively increased. At the same time, the total selectivity of the semi-hydrogenation product BED and the byproduct HTHF also increased significantly. In summary, the Ni-10KN-AB-700 catalyst exhibited the best catalytic performance.
[0091] This invention provides a 3D-printed Ni-based stirred paddle catalyst for the preparation of BAD via BYD hydrogenation. Based on computer-aided modeling software and combined with metal 3D printing technology, GH4169 Ni-based alloy powder is used as the printing base material. The stirred paddle catalyst is printed using selective laser melting (SLM) 3D printing technology. The printed stirred paddle precursor is subjected to annealing, molten salt etching and surface treatment, and post-treatment operations such as drying and reduction to obtain the catalyst sample, which has good activity for the preparation of BAD via BYD hydrogenation.
[0092] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing a 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol, comprising the following steps: A) Ni-based alloy powder was 3D printed using selective laser melting to obtain a Ni-based impeller precursor; B) The Ni-based impeller precursor is subjected to molten salt treatment in a mixed molten salt to obtain a molten salt-treated Ni-based impeller precursor; The molten salt comprises a mixed molten salt of potassium chloride and sodium chloride; C) The Ni-based impeller precursor after molten salt treatment is cleaned and dried to obtain a dried Ni-based impeller precursor. D) The dried Ni-based impeller precursor was subjected to reduction treatment in a reducing atmosphere to obtain a reduced sample; E) The reduced sample is passivated in an oxidizing atmosphere to obtain a Ni-based 3D printed impeller catalyst.
2. The method for preparing the 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol according to claim 1, characterized in that, The Ni-based alloy powder in step A) contains iron and / or chromium.
3. The method for preparing the 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol according to claim 1, characterized in that, The molten salt is a binary molten salt system composed of sodium chloride and potassium chloride, with a molar ratio of sodium chloride to potassium chloride of 3:7 to 7:
3.
4. The method for preparing the 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol according to claim 1, characterized in that, In step B), the temperature of the molten salt treatment is 500~900℃, and the time of the molten salt treatment is 2~12 hours.
5. The method for preparing the 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol according to claim 1, characterized in that, In step C), the cleaning is ultrasonic cleaning, the drying is vacuum drying, the drying temperature is 80~120℃, and the drying time is 8~12 hours.
6. The method for preparing the 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol according to claim 1, characterized in that, Repeat steps B) and C) multiple times to obtain the dried Ni-based impeller precursor.
7. The method for preparing the 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol according to claim 1, characterized in that, The reduction treatment temperature in step D) is 300~900℃, and the reduction treatment time is 3~12 hours.
8. The method for preparing the 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol according to claim 1, characterized in that, In step E), the volume fraction of the oxidizing gas in the oxidizing atmosphere is 0.1~3 vol%; the passivation temperature is 20~40℃; and the passivation time is 1~6h.
9. A 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol, prepared according to the preparation method of any one of claims 1 to 8, wherein the 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol comprises a bushing and a blade, and the wall of the bushing is provided with an assembly through hole.
10. The application of the 3D printing catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol as described in claim 9 in the hydrogenation of 1,4-butynediol to 1,4-butanediol.