CN107413353B - Method for preparing decahydronaphthalene based on catalytic hydrogenation of tetralin - Google Patents
Method for preparing decahydronaphthalene based on catalytic hydrogenation of tetralin Download PDFInfo
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Abstract
The invention belongs to the technical field of industrial catalysis of petrochemical industry, and discloses a method for preparing decahydronaphthalene based on tetralin room-temperature catalytic hydrogenation and an organic solvent, wherein carbon nano tube-CNTs (activated carbon-AC or carbon black-C) is used as a carrier, and 0.4-6% Rh (Ir, Pt, Pd, Au or Ru) is used as a nano island load M1M2Ternary metal supported catalyst (denoted as M) of bimetallic nanoparticles1/M2M3/CNTs, wherein M1Rh, Ir, Pt, Pd, Au or Ru; m2Ni, Fe, Co or Cu; m3Ni, Fe, Co or Cu). M of the invention1/M2M3the/CNTs ternary metal supported catalyst has huge industrialization prospect, can obtain 100 percent of decalin selectivity and yield, and has the advantages of low loading capacity, simple preparation, low cost, good stability and repeated use.
Description
Technical Field
The invention belongs to the technical field of industrial catalysis in petrochemical industry, and particularly relates to a method for preparing decahydronaphthalene based on tetrahydronaphthalene room-temperature catalytic hydrogenation and an organic solvent.
Background
Aromatic hydrocarbons or naphthalene, for example, are important chemical raw materials and platform compounds, and an important product extension thereof is aromatic ring hydrogenation products. Such as tetralin (or naphthalene) catalytic hydrogenation, and the main products are tetralin, octahydronaphthalene, decahydronaphthalene and the like. Tetrahydronaphthalene and decahydronaphthalene are widely used high boiling point organic solvents, are mainly used as solvents of grease, resin, rubber and the like, and can also be used as paint removers, lubricants, dyes, pesticides, pharmacy, fuel cell hydrogen storage media and the like. At present, decahydronaphthalene is widely applied to the production of high-performance polyethylene fibers in dry spinning as a high-volatility polyethylene fiber solvent. In addition, the diesel oil with wide application is mainly obtained by processing petroleum, but the content of aromatic hydrocarbon is higher, so that the quality and the octane number of the diesel oil are reduced, and the aromatic hydrocarbon is a strong carcinogen, is harmful to human health and environment and does not meet the requirement of green chemistry. Then all over the worldVarious legislative policies are issued successively by China to reduce the content of aromatic hydrocarbons in oil products. Therefore, the removal of various aromatic hydrocarbons has great practical significance. The most dominant method for removing aromatics is catalytic hydrogenation (such as naphthalene catalytic hydrogenation). Thus, naphthalene hydrogenation is an extremely important reaction in chemical industry. The prior tetrahydronaphthalene (or naphthalene) catalytic hydrogenation catalyst mainly comprises a non-noble metal hydrogenation catalyst, a noble metal hydrogenation catalyst and novel transition metal carbide, nitride, phosphide and silicide hydrogenation catalysts according to different active components loaded on a carrier of the catalyst. However, these catalysts have some problems, such as low catalyst activity and selectivity, severe reaction conditions, complex catalyst preparation process, high catalyst price or poor catalyst stability. In addition, hydrogenation of tetralin (or naphthalene) is also a typical catalytic hydrogenation reaction of aromatic hydrocarbon, and this is used as a probe reaction in many researches to study the basic theory of catalysis. Therefore, the study of hydrogenation of tetralin (or naphthalene) is also of great theoretical significance. At present, Chinese invention patents about the preparation of decalin by catalytic hydrogenation of tetralin are not found. Some patents for preparing decalin by naphthalene hydrogenation report, for example, chinese patent publication No. CN104193578A, "a method for producing decalin and tetralin by naphthalene hydrogenation", which uses raney nickel as a catalyst and can catalyze naphthalene hydrogenation to prepare tetralin and decalin at a reaction temperature of 180-240 ℃ and a reaction pressure of 2.0-9.0 MPa. Chinese patent publication No. CN 104744203A, "a method for preparing decahydronaphthalene by industrial naphthalene hydrogenation", said method uses sulfide catalyst as hydrogenation refined catalyst-NiMo or NiW as active component; al (Al)2O3、SiO2-Al2O3Or Al2O3-TiO2The carrier or the noble metal catalyst is a deep hydrogenation catalyst-Pd or PtPd is an active component; al (Al)2O3、SiO2Or Al2O3-TiO2Is a carrier. In the method, the hydrofining reaction conditions are as follows: the reaction temperature is-160-340 ℃, and the hydrogen partial pressure is-2-8 MPa; the deep hydrogenation reaction conditions are as follows: the reaction temperature is-120-340 ℃, and the hydrogen partial pressure is 2-8 MPa. However, the above method has high reaction temperature and high energy consumption, which is not in accordance with the requirementsMeets the requirements of green chemical engineering process. Nanotechnology has important applications in catalysis, such as Huang et al (Yangqi Huang, Yao Ma, Youwei Cheng, Lijun Wang, Xi Li. supported nanometric platinum-nickel catalysts for solvent-free hydrogenation of organic catalysts, 69(2015)55-58) synthesized PtNi/AC binary metal supported catalyst under the reaction conditions: the reaction temperature is-100 ℃, the reaction pressure is-6 MPa, the reaction time is-0.5 h, and tetralin-3 mL. Can catalyze the selective hydrogenation of 98.6 percent of tetralin to synthesize the decalin. But because of high Pt loading (2.8 wt.%), the metal Pt is expensive, the catalyst cost is high, the reaction temperature and pressure are high (100 ℃ and 6MPa), the energy consumption is high, the method is unsafe, and the industrial application is difficult to realize.
In summary, the problems of the prior art are as follows: at present, in the method for preparing the decahydronaphthalene by catalytic hydrogenation of the tetrahydronaphthalene, because the controllable design and the preparation difficulty of the nano structure of the multi-metal (especially three-way) catalyst are higher, and when the multi-metal (such as two-way and three-way) catalysts are combined together to form nano particles, the size and the composition (large adjustable modification) of the multi-metal catalysts and the complexity of the structure (such as alloy, core shell, multi-layer load and the like) of the multi-metal catalysts are higher, the multi-metal catalysts are not reported and applied in the reaction so far. In addition, the existing catalyst for preparing the decalin by catalytic hydrogenation of the tetralin has the advantages of low performance, high reaction temperature, high energy consumption, high catalyst cost, unsafety and difficulty in realizing industrial application.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing decahydronaphthalene based on tetralin room-temperature catalytic hydrogenation and an organic solvent.
The invention is realized by the method for preparing the decahydronaphthalene based on the catalytic hydrogenation of the tetrahydronaphthalene at room temperature, wherein the polycyclic aromatic hydrocarbon compound, the hydrogen and the catalyst are respectively added into a reaction kettle of the method for preparing the decahydronaphthalene based on the catalytic hydrogenation of the tetrahydronaphthalene at room temperature; heating a high-pressure reaction kettle to 25-100 ℃, reacting at a constant temperature, discharging residual gas, performing centrifugal separation to obtain a product, and analyzing the composition of the product by using a gas chromatograph;
the catalyst adopts Rh, Ir, Pt, Pd, Au or Ru asA nano island; m1M2The ternary metal supported catalyst with bimetallic nano-particles as carriers is M1/M2/M3/CNTs, wherein M2Ni, Fe, Co or Cu; m3Ni, Fe, Co or Cu.
Further, the method for preparing decahydronaphthalene based on tetralin room-temperature catalytic hydrogenation comprises the following steps:
step one, taking carbon nano tubes, activated carbon or carbon black as a carrier, preparing a nano island load M which takes 0.4-6% of Rh, Ir, Pt, Pd, Au or Ru as a nano island1M2A ternary metal supported catalyst of bimetallic nanoparticles;
step two, adding a reaction polycyclic aromatic hydrocarbon compound, hydrogen and a catalyst into the high-pressure reaction kettle respectively;
and step three, heating the high-pressure reaction kettle to 25-100 ℃, reacting at a constant temperature, discharging residual gas, performing centrifugal separation to obtain a product, and analyzing the composition of the product by using a gas chromatograph.
Further, the catalyst is M1/M2M3the/CNTs ternary metal supported catalyst.
Further, preparing NiCo/CNTs, NiFe/CNTs, NiCu/CNTs, CoCu/CNTs and CoFe/CNTs by adopting a room-temperature liquid-phase reduction method; preparing low-load 0.4-6% Rh M by adopting in-situ reduction method1/M2M3the/CNTs ternary metal supported catalyst.
Further, M added into the high-pressure reaction kettle1/M2M3The mass ratio of the/CNTs ternary metal supported catalyst to the pure tetralin is 1: 200-400.
Further, the reaction conditions are that the high-pressure reaction kettle is heated to 25-100 ℃, the reaction pressure is 1.0-4.5 MPa, and the reaction is carried out at constant temperature.
Another object of the present invention is to provide decahydronaphthalene prepared by the method for preparing decahydronaphthalene based on tetralin room temperature catalytic hydrogenation.
It is another object of the present invention to provide an organic solvent prepared from the decalin.
Another object of the present invention is to provide a polyethylene fiber solvent prepared from the decalin.
Another object of the present invention is to provide a polyethylene fiber prepared from the polyethylene fiber solvent.
The invention has the advantages and positive effects that: in order to solve the defects of the prior industrial tetralin (or naphthalene) hydrogenation catalyst and realize better economic and social benefits and a green and environment-friendly production process, the carbon nano tube (active carbon or carbon black) is taken as a carrier, the catalyst is active and 100 percent selective, cheap and easy to prepare, and 0.4 to 6 percent Rh (Ir, Pt, Pd, Au or Ru) is taken as a nano island to be loaded on M1M2Ternary metal supported catalyst (denoted as M) of bimetallic nanoparticles1/M2M3/CNTs, wherein M1Rh, Ir, Pt, Pd, Au or Ru; m2Ni, Fe, Co or Cu; m3Ni, Fe, Co or Cu); the catalyst has good stability, high activity and mild reaction conditions (catalytic hydrogenation reaction can be carried out at room temperature, and the reported technology is not realized at present); m1/M2M3the/CNTs ternary metal supported catalyst has huge industrialization prospect, can obtain 100 percent of decalin selectivity and yield, and has the advantages of low loading capacity, simple preparation, low cost, good stability and repeated use.
The following table shows the comparison of the present invention with the prior art:
comparison with commercial-matured tetralin hydrogenation catalyst
Drawings
FIG. 1 is a flow chart of a method for preparing decahydronaphthalene based on tetralin room-temperature catalytic hydrogenation provided by the embodiment of the invention.
FIG. 2 is a diagram of M provided by an embodiment of the present invention1/M2M3A nano-structure schematic diagram of a/carbon nano-tube (active carbon or carbon black) ternary metal supported catalyst.
FIG. 3 is a transmission electron micrograph (TEM image) of the RhNiCo/CNTs catalyst provided by the example of the present invention.
FIG. 4 is a qualitative analysis spectrum (GC-MS spectrum) of a reaction product dissolved in cyclohexane (with the addition of an internal standard n-hexane) provided by the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following detailed description of the principles of the invention is provided in connection with the accompanying drawings.
As shown in fig. 1, the method for preparing decahydronaphthalene based on tetralin room temperature catalytic hydrogenation provided by the embodiment of the present invention comprises the following steps:
s101: carbon nano tube (active carbon or carbon black) is used as a carrier to prepare 0.4-6% Rh (Ir, Pt, Pd, Au or Ru) serving as a nano island load M1M2Ternary metal supported catalyst (denoted as M) of bimetallic nanoparticles1/M2M3/CNTs, wherein M1Rh, Ir, Pt, Pd, Au or Ru; m2Ni, Fe, Co or Cu; m3Ni, Fe, Co or Cu);
s102: respectively adding reaction raw materials (such as polycyclic aromatic hydrocarbon compounds such as naphthalene and the like) and a catalyst into a high-pressure reaction kettle, heating the high-pressure reaction kettle to 25-100 ℃, reacting at a constant temperature of 1.0-4.5 MPa for a period of time, discharging residual gas, performing centrifugal separation to obtain a product, and analyzing the composition of the product by using a gas chromatograph.
The catalyst is M1/M2M3the/CNTs ternary metal supported catalyst.
M added into a high-pressure reaction kettle1/M2M3The mass ratio of the/CNTs ternary metal supported catalyst to tetralin (or naphthalene) is 1: 200-400.
The catalyst is 0.4-6% Rh (Ir, Pt, Pd, Au or Ru) loaded on M as a nano island1M2Ternary metal supported catalyst (denoted as M) of bimetallic nanoparticles1/M2M3/CNTs, wherein M1Rh, Ir, Pt, Pd, Au or Ru; m2Ni, Fe, Co or Cu; m3Ni, Fe, Co or Cu).
The reaction conditions are that the high-pressure reaction kettle is heated to 25-100 ℃, the reaction pressure is 1.0-4.5 MPa, and the reaction is carried out for a certain time at constant temperature.
The application of the principles of the present invention will now be described in further detail with reference to specific embodiments.
Example 1
Synthesis of Rh/NiCo/CNTs catalyst:
1. weighing (0.45-3.6 g) NiCl2·6H2O and (0.45-3.6 g) CoCl2·6H2And dissolving O in deionized water (45-90 mL), and stirring at room temperature to obtain a clear solution.
2. Adding (5-15 mL) of ethanol to the NiCl2·6H2O and CoCl2·6H2In O solution.
3. Adding 5-25 mL of reducing agent solution (sodium borohydride, sodium hypophosphite, hydrazine hydrate, ascorbic acid, or glycol and other polyhydric alcohols).
4. Adding (0.45-2.5 g) carbon nano tubes (activated carbon or carbon black).
5. The reaction solution is heated to (100-200 ℃ C.).
6. Filtered and washed several times with ethanol and water, respectively.
7. Vacuum drying, and keeping at 60 deg.C for 6 h.
8. Weighing to obtain NiCo/CNTs nano material, adding into RhCl3In-situ reduction, filtration, washing, vacuum drying and keeping at 60 ℃ for 6 h.
9. The catalyst is 99.999 percent N at the temperature of 600-900 DEG C2And (5) roasting, and naturally cooling to room temperature to obtain the required catalyst.
Preparing 0.4-6% Rh (Ir, Pt, Pd, Au or Ru) serving as a nano island supported on M by using a similar method1M2Ternary metal supported catalyst (denoted as M) of bimetallic nanoparticles1/M2M3/CNTs, wherein M1Rh, Ir, Pt, Pd, Au or Ru; m2Ni, Fe, Co or Cu; m3Ni, Fe, Co or Cu).
Rh/CNTs were synthesized by a common impregnation method.
Example 2
Sequentially adding 0.0500g of Ru/NiCo/CNTs catalyst and 10.0mL of tetralin into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at the constant temperature of 25 ℃ for 11h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 15 percent.
Example 3
Sequentially adding 0.1500g of Ru/NiCo/CNTs catalyst and 10.0mL of tetrahydronaphthalene into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at the constant temperature of 25 ℃ for 13h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 65 percent. In addition, the catalyst is repeatedly recycled for 10 times, and the selectivity and the activity of the catalyst are not reduced.
Example 4
Sequentially adding 0.0500g of Ru/NiCo/CNTs catalyst and 10.0mL of tetralin into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at the constant temperature of 40 ℃ for 11h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 76 percent. In addition, the catalyst is repeatedly recycled for 10 times, and the selectivity and the activity of the catalyst are not reduced.
Example 5
Sequentially adding 0.0500g of Ru/NiCo/CNTs catalyst and 10.0mL of tetralin into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen to remove nitrogen in the kettle (the purity is more than or equal to 99.999%), closing an outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at a constant temperature of 100 ℃ for 0.5h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 82 percent.
Example 6
Sequentially adding 0.0750g of Ru/NiCo/CNTs catalyst and 10.0mL of tetralin into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at a constant temperature of 100 ℃ for 0.5h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 100 percent.
Example 7
Sequentially adding 0.1000g of Ru/NiCo/CNTs catalyst and 10.0mL of tetrahydronaphthalene into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at a constant temperature of 100 ℃ for 0.5h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 100 percent.
Example 8
Sequentially adding 0.0500g of Rh/NiCo/CNTs catalyst and 10.0mL of tetrahydronaphthalene into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at the constant temperature of 25 ℃ for 11h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 25 percent.
Example 9
Sequentially adding 0.0500g of Rh/NiCo/CNTs catalyst and 10.0mL of tetrahydronaphthalene into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at the constant temperature of 25 ℃ for 24h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 65 percent.
Example 10
Sequentially adding 0.1500g of Rh/NiCo/CNTs catalyst and 10.0mL of tetrahydronaphthalene into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at the constant temperature of 25 ℃ for 13h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 100 percent. In addition, the catalyst is repeatedly recycled for 10 times, and the selectivity and the activity of the catalyst are not reduced.
Example 11
Sequentially adding 0.0500g of Rh/NiCo/CNTs catalyst and 10.0mL of tetrahydronaphthalene into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at the constant temperature of 40 ℃ for 11h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 100 percent. In addition, the catalyst is repeatedly recycled for 10 times, and the selectivity and the activity of the catalyst are not reduced.
Example 12
Sequentially adding 0.0500g of Rh/NiCo/CNTs catalyst and 10.0mL of tetrahydronaphthalene into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting at a constant temperature of 100 ℃ for 0.5h, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 100 percent.
The following will describe the effects of the present invention in detail.
Comparative example 1
Sequentially adding 0.0500g of NiCo/CNTs catalyst and 10.0mL of tetrahydronaphthalene into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting for 3h at a constant temperature of 100 ℃, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 0 percent, and the yield of decalin is 0 percent.
Comparative example 2
Sequentially adding 0.0500g of Ru/CNTs catalyst and 10.0mL of tetrahydronaphthalene into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting for 3h at a constant temperature of 100 ℃, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 16 percent.
Comparative example 3
Sequentially adding 0.0500g of Rh/CNTs catalyst and 10.0mL of tetrahydronaphthalene into a high-pressure stirred tank reactor (MS-50-316L type, 50 mL); introducing nitrogen (the purity is more than or equal to 99.999%) to remove air in the kettle; introducing hydrogen (the purity is more than or equal to 99.999 percent) to remove the nitrogen in the kettle, closing the outlet valve, and continuously introducing the hydrogen when the reaction pressure is 4.5 MPa. Starting stirring, wherein the stirring speed is 500r/min, reacting for 3h at a constant temperature of 100 ℃, discharging residual gas after the reaction is stopped, performing centrifugal separation to obtain a product, analyzing the composition of the product by using a gas chromatograph, and obtaining a reaction result: the selectivity of decalin is 100 percent, and the yield of decalin is 20 percent.
TABLE 1 reaction conditions and catalytic activities of Ru/NiCo/CNTs, Rh/NiCo/CNTs, Ni/NiO/CNTs, Ru/CNTs and Rh/CNTs catalysts
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A method for preparing decahydronaphthalene based on tetralin catalytic hydrogenation is characterized by comprising the following steps:
step one, taking a carbon nano tube as a carrier, preparing a nano island load M taking 0.4-6% of Rh, Ir, Pt, Pd, Au or Ru as a nano island2M3A ternary metal supported catalyst of bimetallic nanoparticles;
step two, adding a polycyclic aromatic hydrocarbon compound, hydrogen and a catalyst into the high-pressure reaction kettle respectively;
heating the high-pressure reaction kettle to 25-100 ℃, reacting at a constant temperature, discharging residual gas, performing centrifugal separation to obtain a product, and analyzing the composition of the product by using a gas chromatograph;
the catalyst adopts Rh, Ir, Pt, Pd, Au or Ru as a nano island; ternary metal supported catalyst with M2M3The bimetallic nano-particles are used as carriers, and the ternary metal supported catalyst is M1/M2M3/CNTs, wherein M1Is a nano island, M2Ni, Fe, Co or Cu; m3Ni, Fe, Co or Cu.
2. The process for the preparation of decalin based on the catalytic hydrogenation of tetralin of claim 1, wherein the catalyst is M1/M2M3the/CNTs ternary metal supported catalyst.
3. The method for preparing decahydronaphthalene based on catalytic hydrogenation of tetralin according to claim 1, characterized in that NiCo/CNTs, NiFe/CNTs, NiCu/CNTs, CoCu/CNTs, CoFe/CNTs are prepared by a liquid phase reduction method; in-situ reduction method is adopted to prepare low-load M with 0.4-6% of Rh1/M2M3the/CNTs ternary metal supported catalyst.
4. The process for preparing decalin based on the catalytic hydrogenation of tetralin of claim 1, wherein M is added to the autoclave1/M2M3The mass ratio of the/CNTs ternary metal supported catalyst to the pure tetralin is 1: 200-400.
5. The method for preparing decahydronaphthalene based on tetralin catalytic hydrogenation according to claim 1, wherein the reaction conditions are that the high-pressure reaction kettle is heated to 25-100 ℃, the reaction pressure is 1.0-4.5 MPa, and the reaction is carried out at constant temperature.
6. Decahydronaphthalene prepared by the method for preparing decahydronaphthalene based on tetralin catalytic hydrogenation according to any one of claims 1 to 5.
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