CN114768816B - Metal supported catalyst and preparation method and application thereof - Google Patents
Metal supported catalyst and preparation method and application thereof Download PDFInfo
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
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- C07C249/10—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes from nitro compounds or salts thereof
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Abstract
The invention discloses a metal supported catalyst and a preparation method and application thereof, belonging to the technical field of catalysts, wherein the metal supported catalyst comprises a carrier, a first active component supported on the carrier, and a second active component covered on the surfaces of the first active component and the carrier; the first active component contains Ni and SnO 2 The SnO is a Ni-based catalyst of (2) 2 Coating the Ni surface; the second active ingredient is an alkali metal element. The catalyst can fully convert hydrogenation substrates in a reaction time of 4 hours, the conversion rate reaches 100%, and the selectivity of the corresponding oxime group compound can exceed 99%; the metal supported catalyst is prepared from Ni, snO 2 The catalyst is a first active component, and the alkali metal element is used as a second active component, so that the catalytic activity of the catalyst can be effectively improved, and the catalyst has long service life, extremely low cost and good commercial application prospect.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a metal supported catalyst, a preparation method and application thereof.
Background
Cyclohexanone oxime is a key intermediate for synthesizing caprolactam and further producing nylon 6, and the key intermediate has extremely important application in the fields of textile, machinery, electronic and electric appliances and transportation. Because the traditional process for synthesizing cyclohexanone oxime (cyclohexanone ammoximation process) has the defects of more intermediate steps, large pollution of raw materials and byproducts, large amount of low-value ammonium sulfate as byproducts and the like, a plurality of new synthesis processes and routes emerge in the last decades.
A process route for preparing nitrocyclohexane by cyclohexane nitration developed by DuPont in the last century, and preparing cyclohexanone oxime by subsequent hydrogenation of nitrocyclohexane. According to the process, N-hydroxyphthalimide (NHPI) is used as a catalyst, nitrocyclohexane can be effectively synthesized under mild conditions, and a supported PdPb catalyst is used for catalytic hydrogenation of nitrocyclohexane to prepare a target product cyclohexanone oxime. Since the popularization of the technology, the problem of the hydrogenation efficiency (70%) of nitrocyclohexane is a main reason that the technology is difficult to popularize, and the used Pb-containing catalyst is contrary to the current environmental protection concept.
In order to improve the hydrogenation efficiency of nitrocyclohexane, patent CN112604685A reports the use of Pt-In 2 O 3-x And Pt-SnO 2-x As a strategy for preparing the cyclohexanone oxime by hydrogenating the nitrocyclohexane, the selectivity of the catalyst for preparing the cyclohexanone oxime under mild conditions is more than 97%. However, the Pt-based catalyst used by the catalyst is expensive, the Pt loss is serious in the environment of using ethylenediamine as a solvent, and the cost for producing cyclohexanone oxime is far higher than that of the traditional cyclohexanone ammoximation process due to frequent replacement of the catalyst, so that the industrialization possibility is low.
Patent CN105777577a reports a metal-free hydrogenation catalyst for the hydrogenation of nitrocyclohexane. The preparation of the catalyst adopts melamine as a nitrogen source, and the melamine and the carbon nano tube are mixed and calcined at high temperature to prepare the final N-doped carbon nano tube catalyst. The catalyst does not contain metal, has low price, but the conversion rate of nitrocyclohexane is only 15 percent after the reaction for 8 hours at 0.3MPa and 80 ℃, the selectivity of cyclohexanone oxime is only 80 percent, the catalytic conversion efficiency is very low, and the possibility of industrial implementation is not great.
In summary, the research on the preparation of the cyclohexanone oxime by hydrogenation is that a catalyst with low cost, high performance, no toxicity and environmental protection is developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a metal supported catalyst, a preparation method and application thereof, wherein the metal supported catalyst can realize ultrahigh-selectivity hydrogenation of cyclohexanone oxime, and has low price and long service life.
In the prior art, ni-based catalysts (Raney Nickel, ni/C, ni/Al 2 O 3 Etc.) has a very broad industrial application base in the catalytic hydrogenation of nitro compounds, but highly active Ni is providing nitro (-NO) 2 ) The catalyst has high conversion activity and excellent hydrogenation performance on other unsaturated functional groups, so that the hydrogenation of the nitro compound is difficult to obtain a target product with high selectivity.
To this end, according to a first aspect of the present invention, there is provided a metal-supported catalyst comprising a support, a first active ingredient supported on the support, a second active ingredient coated on the first active ingredient and the surface of the support;
the first active component contains Ni and SnO 2 The SnO is a Ni-based catalyst of (2) 2 Coating the Ni surface;
the second active ingredient is an alkali metal element.
The inventors of the present invention found in a great deal of research that the metal supported catalyst was prepared from Ni and SnO 2 The catalyst is a first active component, and the alkali metal element is used as a second active component, so that the catalytic activity of the catalyst can be effectively improved, and the catalyst has long service life, extremely low cost and good commercial application prospect.
The hydrogenation of nitrocyclohexane is accompanied by the production of the cyclohexanone oxime as well as the deep hydrogenation product, cyclohexylamine, and the hydrodenitrogenation products, cyclohexanone and cyclohexanol, as shown in figure 1.
The hydrogenation schematic diagram of the metal supported catalyst is shown in figure 2, snO 2 Forms steric hindrance on the Ni surface, isolates the coupling of nitrocyclohexane and cyclohexanone oxime with the Ni center, but has very small molecule H 2 There is still an opportunity to cross SnO 2 The layer reaches the Ni surface to adsorb and dissociate, and overflows on SnO through H 2 Structurally stable formation of large amounts of Sn δ+ -OH + Structure is as follows. Sn (Sn) δ+ -OH + Sn with a large amount of unsaturated coordination in the structure δ+ Bit, electron-rich-NO 2 Is capable of promoting-NO 2 Activation, thereby inducing activated-NO 2 And surface H + Hydrogenation is carried out to generate nitrosocyclohexane, and finally, the nitrosocyclohexane is rearranged to generate a more stable cyclohexanone oxime structure, and after the cyclohexanone oxime is generated, sp 2 Activation of the hybridized-c=n-structure requires adsorption on the Ni surface (similar to hydrogenation of-c=c-bonds, commonly seen in the Horiuti-Polanyi mechanism), whereas SnO 2 The coating of the layer isolates this step from occurring, thus finally achieving ultra-high selectivity hydrogenation of cyclohexanone oxime.
The invention has surprisingly found in a great deal of research that the alkali metal element can effectively prevent agglomeration and dissolution loss of the first active ingredient Ni-based catalyst in the processes of reduction and reaction, can be well covered on the surfaces of the first active component and the carrier, forms steric hindrance, and has the functions of Ni and SnO 2 The motion agglomeration and dissolution loss on the surface of the carrier can play a physical limiting role, thereby playing a role in promoting the performance and service life of the catalyst.
As a preferred embodiment of the present invention, the Ni content is 0.1 to 10% by mass, the alkali metal element content is 0.1 to 10% by mass, and the SnO content is 0.1 to 10% by mass 2 The mass percentage of the (B) is 0.1-10%.
As a preferred embodiment of the present invention, the support is at least one of alumina, carbon nanotubes, carbon black, attapulgite clay, montmorillonite, halloysite, zeolite.
As a preferred embodiment of the present invention, the alkali metal element is at least one of Na, K, rb, cs.
In a second aspect of the present invention, there is provided a method for preparing a metal supported catalyst, comprising the steps of:
(1) Dispersing a carrier in water to form a suspension;
(2) Dropwise adding the Ni precursor solution into the suspension according to the load, and uniformly stirring to obtain a mixed solution;
(3) Dropwise adding an alkali solution into the mixed solution according to the addition amount, uniformly stirring, drying and calcining to obtain a first catalyst;
(4) And soaking the first catalyst in a tin salt solution for 1-4 h, centrifuging, filtering, drying and calcining to obtain the metal supported catalyst.
The preparation method can prepare the metal supported catalyst which can realize ultrahigh selectivity hydrogenation of cyclohexanone oxime, has low catalyst price and long service life.
As a preferred embodiment of the present invention, at least one of the following (a) to (c):
(a) The Ni precursor solution is at least one of nickel acetate solution, nickel nitrate solution, nickel chloride solution and nickel acetylacetonate solution, and the concentration of the Ni precursor solution is 0.05-2 mol/L;
(b) The alkali solution is at least one of potassium hydroxide solution, sodium hydroxide solution, rubidium hydroxide solution and cesium hydroxide solution, and the concentration of the alkali solution is 0.05-2 mol/L;
(c) The tin salt solution is at least one of tin tetrachloride solution, tin dichloride solution, tin nitrate solution and tin acetate solution, and the concentration of the tin salt solution is 0.05-2 mol/L.
As a preferred embodiment of the present invention, the calcination temperature in the step (3) is 520-600 ℃ and the calcination time is 2-6 hours; the calcination temperature in the step (4) is 500-600 ℃ and the calcination time is 1-4 h.
In a third aspect, the invention provides an application of a metal supported catalyst in preparing cyclohexanone oxime by catalytic hydrogenation, comprising the following steps:
fully reducing the metal supported catalyst, and transferring the metal supported catalyst into a reaction kettle;
adding a solvent and a hydrogenation substrate into a reaction kettle, and introducing H 2 Stirring uniformly to finish the reaction.
As a preferred embodiment of the present invention, the solvent is at least one of ethanol, methanol, ethylenediamine, n-butylamine, and ethanolamine.
As a preferred embodiment of the invention, the said passage of H 2 The pressure of (2) is 1-10 MPa.
As a preferred embodiment of the present invention, the hydrogenation substrate is at least one of nitrocyclohexane, 2-nitropropane, 1-nitrocyclobutane, 1-nitrocyclopentane, 1-nitrocyclooctane.
The invention has the beneficial effects that: (1) The catalyst can fully convert hydrogenation substrates in a reaction time of 4 hours, the conversion rate reaches 100%, and the selectivity of the corresponding oxime group compound can exceed 99%; (2) The metal supported catalyst is prepared from Ni, snO 2 The catalyst is a first active component, and the alkali metal element is used as a second active component, so that the catalytic activity of the catalyst can be effectively improved, and the catalyst has long service life, extremely low cost and good commercial application prospect; (3) The alkali metal element can effectively prevent agglomeration and dissolution loss of the first active ingredient Ni-based catalyst in the reduction and reaction processes, can well cover the surfaces of the first active ingredient and the carrier, forms steric hindrance, and has the advantages of high activity, low cost, and no pollution 2 The motion agglomeration and dissolution loss on the surface of the carrier can play a physical limiting role, thereby playing a role in promoting the performance and service life of the catalyst.
Drawings
FIG. 1 shows the composition of nitrocyclohexane hydrogenation products.
FIG. 2 is a schematic diagram of the hydrogenation of the metal supported catalyst according to the present invention
FIG. 3 is a diagram of Ni@SnO according to the present invention 2 /Al 2 O 3 STEM diagram of (c).
FIG. 4 is a diagram of Ni@SnO 2 /Al 2 O 3 And SnO 2 /Al 2 O 3 H of (2) 2 -TPR test result graph.
FIG. 5 is SnO 2 /Al 2 O 3 And Ni@SnO 2 /Al 2 O 3 The H/D isotope experiment result diagram of the catalyst for catalytic hydrogenation of nitrocyclohexane.
FIG. 6 is a diagram of Ni@SnO 2 /Al 2 O 3 Catalyst at D 2 In situ red under atmosphereAnd (5) an external spectrogram.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific dispersing and stirring treatment method in the present invention is not particularly limited.
Example 1
1. Metal supported catalyst (noted as Ni@SnO 2 /Al 2 O 3 Catalyst) comprising the steps of:
(1) By gamma-Al 2 O 3 As a carrier, fully stirring and vibrating with water to prepare suspension;
(2) Preparing a 1mol/L nickel acetate solution, dropwise adding the solution into the suspension according to the requirement that the Ni loading amount is 3wt%, and fully stirring and soaking for 1h;
(3) Dropwise adding 0.1mol/L NaOH solution, controlling Na content to be 0.5wt%, heating to 80 ℃ after dropwise adding, until evaporating suspension to dryness, grinding catalyst, transferring into a muffle furnace, calcining at 550 ℃ for 4h, and obtaining Ni/Al 2 O 3 A catalyst;
(4) Configuration of 1mol/LSnCl 4 Solution and used for stirring and impregnating Ni/Al 2 O 3 Centrifuging the catalyst for 3 hours, filtering the supernatant, vacuum drying the catalyst at 60 ℃, transferring the dried catalyst into a muffle furnace, and annealing the catalyst at 550 ℃ for 3 hours to prepare Ni@SnO 2 /Al 2 O 3 Catalysts, wherein Ni and SnO 2 The mass of the catalyst accounts for 3wt% and 1-5 wt% of the catalyst.
2. The prepared metal supported catalyst (Ni@SnO) 2 /Al 2 O 3 ) The application in preparing cyclohexanone oxime by catalyzing nitrocyclohexane hydrogenation is as follows: weighing according to the proportion of nitrocyclohexane to Ni=500The catalyst was placed in a tube furnace at 200℃and 5vol% H 2 /N 2 Fully reducing for 3H under the atmosphere, then transferring to a reaction kettle in situ, adding ethylenediamine and nitrocyclohexane into the reaction kettle immediately, starting stirring, and introducing 1MPa H 2 The reaction was stopped after the reaction was completed for 3 hours at 60 ℃. The reaction product was characterized for product composition by gas chromatography, and the test standard was normalized.
Example 2
1. Metal supported catalyst (noted as Ni@SnO 2 CNT catalyst) comprising the steps of:
(1) The CNT is taken as a carrier, and is fully stirred and oscillated with water to prepare suspension;
(2) Preparing a 1mol/L nickel nitrate solution, dropwise adding the solution into the suspension according to the requirement that the Ni loading amount is 1wt%, and fully stirring and soaking for 1h;
(3) Dropwise adding 0.1mol/L KOH solution, controlling the K content to be 1wt%, heating to 80 ℃ after the dropwise adding is completed, until the suspension is evaporated to be water, grinding the catalyst, and transferring the catalyst into a muffle furnace to be calcined for 4 hours at 550 ℃ to prepare the Ni/CNT catalyst;
(4) Configuration 1.5mol/LSnCl 2 Stirring and impregnating the solution with Ni/CNT catalyst for 3h, centrifuging, filtering to remove supernatant, vacuum drying the catalyst at 60deg.C, transferring into a muffle furnace, annealing at 550deg.C for 3h, and preparing Ni@SnO 2 CNT catalyst wherein Ni and SnO 2 The mass of the catalyst accounts for 1wt% and 5-10 wt% of the catalyst.
2. The prepared metal supported catalyst (Ni@SnO) 2 CNT) in the preparation of cyclohexanone oxime by catalytic hydrogenation of nitrocyclohexane: the catalyst was weighed according to the ratio of nitrocyclohexane to ni=200, placed in a tube furnace at 150 ℃,5vol% h 2 /N 2 Fully reducing for 3H under the atmosphere, then transferring to a reaction kettle in situ, adding ethylenediamine and nitrocyclohexane into the reaction kettle, starting stirring, and introducing 2MPa H 2 After the reaction was completed at 70℃for 3 hours, the reaction was stopped. The reaction product was characterized for product composition by gas chromatography, and the test standard was normalized.
Example 3
1. Metal supported catalyst (noted as Ni@SnO 2 ATP catalyst) comprising the steps of:
(1) Using attapulgite clay (ATP) as a carrier, and fully stirring and vibrating with water to prepare suspension;
(2) Preparing a 1mol/L nickel chloride solution, dropwise adding the nickel chloride solution into the suspension according to the requirement that the Ni loading amount is 1wt%, and fully stirring and soaking for 1h;
(3) Dropwise adding a RbOH solution with the concentration of 0.1mol/L, controlling the Rb content to be 1wt%, heating to 80 ℃ after the dropwise adding is completed until the suspension is evaporated to dryness, grinding the catalyst, and transferring the catalyst into a muffle furnace to be calcined for 4 hours at 550 ℃ to prepare the Ni/ATP catalyst;
(4) 1mol/L Sn (NO) 3 ) 2 The solution is used for stirring and impregnating the Ni/ATP catalyst for 3 hours, centrifuging, filtering the supernatant, vacuum drying the catalyst at 60 ℃, transferring the dried catalyst into a muffle furnace, and annealing at 550 ℃ for 3 hours to prepare Ni@SnO 2 ATP catalyst, wherein Ni and SnO 2 The mass of the catalyst accounts for 1 weight percent and 1 weight percent of the catalyst.
2. The prepared metal supported catalyst (Ni@SnO) 2 ATP) in catalyzing nitrocyclohexane hydrogenation to prepare cyclohexanone oxime: the catalyst was weighed according to the ratio of nitrocyclohexane to ni=300, placed in a tube furnace at 200 ℃,5vol% h 2 /N 2 Fully reducing for 3H under the atmosphere, then transferring to a reaction kettle in situ, adding ethylenediamine and nitrocyclohexane into the reaction kettle, starting stirring, and introducing 3MPa H 2 The reaction was stopped after the reaction was completed for 3 hours at 80 ℃. The reaction product was characterized for product composition by gas chromatography, and the test standard was normalized.
Example 4
1. Metal supported catalyst (noted as Ni@SnO 2 MMT catalyst) comprising the steps of:
(1) MMT is taken as a carrier, and is fully stirred and oscillated with water to prepare suspension;
(2) Preparing 1mol/L nickel acetylacetonate solution, dropwise adding the nickel acetylacetonate solution into the suspension according to the requirement of Ni loading of 3wt%, and fully stirring and soaking for 1h;
(3) Dropwise adding 0.1mol/L CsOH solution, controlling the Cs content to be 1wt%, heating to 80 ℃ after the dropwise adding is completed until the suspension is evaporated to dryness, grinding the catalyst, and transferring the catalyst into a muffle furnace to be calcined for 4 hours at 550 ℃ to prepare the Ni/MMT catalyst;
(4) Preparing a 1.5mol/L tin acetate solution, stirring and impregnating the Ni/MMT catalyst for 3h, centrifuging, filtering out supernatant, vacuum drying the catalyst at 60 ℃, transferring the dried catalyst into a muffle furnace, and annealing at 550 ℃ for 3h to obtain Ni@SnO 2 MMT catalyst wherein Ni and SnO 2 The mass of the catalyst accounts for 1 weight percent and 1.5 weight percent of the catalyst.
2. The prepared metal supported catalyst (Ni@SnO) 2 MMT) in catalyzing nitrocyclohexane hydrogenation to prepare cyclohexanone oxime: the catalyst was weighed according to the ratio of nitrocyclohexane to ni=400, placed in a tube furnace at 100 ℃,5vol% h 2 /N 2 Fully reducing for 3H under the atmosphere, then transferring to a reaction kettle in situ, adding ethylenediamine and nitrocyclohexane into the reaction kettle, starting stirring, and introducing 1.5MPa H 2 The reaction was stopped after the reaction was completed for 3 hours at 80 ℃. The reaction product was characterized for product composition by gas chromatography, and the test standard was normalized.
Example 5
1. Metal supported catalyst (noted as Ni@SnO 2 Halloysite catalyst), comprising the steps of:
(1) Taking halloysite as a carrier, and fully stirring and vibrating with water to prepare a suspension;
(2) Preparing a 1mol/L nickel acetate solution, dropwise adding the solution into the suspension according to the requirement that the Ni loading amount is 2wt%, and fully stirring and soaking for 1h;
(3) Dropwise adding 0.1mol/L NaOH solution, controlling the Na content to be 0.5wt%, heating to 80 ℃ after dropwise adding is completed, until the suspension is evaporated to be water, grinding the catalyst, and transferring the catalyst into a muffle furnace to be calcined for 4 hours at 550 ℃ to prepare the Ni/halloysite catalyst;
(4) Configuration of 1mol/L SnCl 4 Solution and used for stirring impregnation of Ni/erlotingThe stone catalyst is centrifuged for 3 hours, the supernatant is filtered, the catalyst is dried in vacuum at 60 ℃, and is transferred into a muffle furnace for annealing for 3 hours at 550 ℃ after being dried, and the Ni@SnO is prepared 2 Halloysite catalyst, wherein Ni and SnO 2 The mass of the catalyst accounts for 1 weight percent and 1 weight percent of the catalyst.
2. The prepared metal supported catalyst (Ni@SnO) 2 Halloysite) in catalyzing nitrocyclohexane hydrogenation to prepare cyclohexanone oxime: the catalyst was weighed according to the ratio of nitrocyclohexane to ni=400, placed in a tube furnace at 150 ℃,5vol% h 2 /N 2 Fully reducing for 3H under the atmosphere, then transferring to a reaction kettle in situ, adding ethylenediamine and nitrocyclohexane into the reaction kettle, starting stirring, and introducing 2.5MPa H 2 After the reaction was completed at 70℃for 3 hours, the reaction was stopped. The reaction product was characterized for product composition by gas chromatography, and the test standard was normalized.
Example 6
1. Metal supported catalyst (noted as Ni@SnO 2 ZSM-5 catalyst) comprising the steps of:
(1) ZSM-5 is taken as a carrier, and is fully stirred and oscillated with water to prepare suspension;
(2) Preparing a 2mol/L nickel acetate solution, dropwise adding the solution into the suspension according to the requirement that the Ni loading amount is 10wt%, and fully stirring and soaking for 1h;
(3) Dropwise adding 2mol/L NaOH solution, controlling the Na content to be 10wt%, heating to 80 ℃ after the dropwise adding is completed, until the suspension is evaporated to be water, grinding the catalyst, transferring the catalyst into a muffle furnace, and calcining for 4 hours at 550 ℃ to prepare the Ni/ZSM-5 catalyst;
(4) Preparing 2mol/L SnCl 4 The solution is used for stirring and impregnating the Ni/halloysite catalyst for 3 hours, centrifuging, filtering the supernatant, vacuum drying the catalyst at 60 ℃, transferring the dried catalyst into a muffle furnace, and annealing at 550 ℃ for 3 hours to prepare the Ni@SnO 2 ZSM-5 catalyst in which Ni and SnO 2 The mass of the catalyst accounts for 10 weight percent and 5 to 10 weight percent of the catalyst.
2. The prepared metal supported catalyst (Ni@SnO) 2 Preparation of/ZSM-5) by catalytic hydrogenation of nitrocyclohexaneUse in the preparation of cyclohexanone oxime: the catalyst was weighed according to the ratio of nitrocyclohexane to ni=400, placed in a tube furnace at 150 ℃,5vol% h 2 /N 2 Fully reducing for 3H under the atmosphere, then transferring to a reaction kettle in situ, adding ethylenediamine and nitrocyclohexane into the reaction kettle, starting stirring, and introducing 5MPa H 2 After the reaction was completed at 70℃for 3 hours, the reaction was stopped. The reaction product was characterized for product composition by gas chromatography, and the test standard was normalized.
Example 7
1. Metal supported catalyst (noted as Ni@SnO 2 XC-72 catalyst) comprising the steps of:
(1) XC-72 is taken as a carrier, and is fully stirred and oscillated with water to prepare suspension;
(2) Preparing a 2mol/L nickel acetate solution, dropwise adding the nickel acetate solution into the suspension according to the requirement that the Ni loading amount is 8wt%, and fully stirring and soaking for 1h;
(3) Dropwise adding 2mol/L NaOH solution, controlling the Na content to be 8wt%, heating to 80 ℃ after dropwise adding, until the suspension is evaporated to dryness, grinding the catalyst, transferring to a muffle furnace, and calcining at 550 ℃ for 4 hours to prepare the Ni/XC-72 catalyst;
(4) Preparing 2mol/L SnCl 4 The solution is used for stirring and impregnating the Ni/halloysite catalyst for 3 hours, centrifuging, filtering the supernatant, vacuum drying the catalyst at 60 ℃, transferring the dried catalyst into a muffle furnace, and annealing at 550 ℃ for 3 hours to prepare the Ni@SnO 2 XC-72 catalyst wherein Ni and SnO 2 The mass of the catalyst accounts for 8wt% and 5-8 wt% of the catalyst.
2. The prepared metal supported catalyst (Ni@SnO) 2 XC-72) in catalyzing nitrocyclohexane hydrogenation to prepare cyclohexanone oxime: the catalyst was weighed according to the ratio of nitrocyclohexane to ni=400, placed in a tube furnace at 150 ℃,5vol% h 2 /N 2 Fully reducing for 3H under the atmosphere, then transferring to a reaction kettle in situ, adding ethylenediamine and nitrocyclohexane into the reaction kettle, starting stirring, and introducing 5MPa H 2 After the reaction was completed at 70℃for 3 hours, the reaction was stopped. The reaction product was characterized by gas chromatography for product composition,the test standard adopts a normalization method.
Example 8
This example differs from example 1 in that Ni@SnO 2 /Al 2 O 3 The solvent used for the catalytic hydrogenation of nitrocyclohexane was ethanol and the other preparation and reaction conditions were the same as in example 1.
Example 9
This example differs from example 1 in that Ni@SnO 2 /Al 2 O 3 The solvent used for the catalytic hydrogenation of nitrocyclohexane was n-butylamine, and the other preparation and reaction conditions were the same as in example 1.
Example 10
This example differs from example 1 in that Ni@SnO 2 /Al 2 O 3 The solvent used for catalytic hydrogenation of nitrocyclohexane was ethanolamine, and the other preparation and reaction conditions were the same as in example 1.
Example 11
This example differs from example 1 in that Ni@SnO 2 /Al 2 O 3 The solvent used for catalytic hydrogenation of nitrocyclohexane was ethanol+ethylenediamine combination (volume ratio of ethanol to ethylenediamine=1:1), and the other preparation and reaction conditions were the same as in example 1.
Example 12
This example differs from example 1 in that Ni@SnO 2 /Al 2 O 3 The solvent used for catalytic hydrogenation of nitrocyclohexane was ethanol+ethylenediamine combination (volume ratio of ethanol to ethylenediamine=9:1), and the other preparation and reaction conditions were the same as in example 1.
Example 13
This example differs from example 1 in that the substrate for catalytic hydrogenation is 2-nitropropane and the other preparation and reaction conditions are the same as in example 1.
Example 14
This example differs from example 1 in that the substrate for catalytic hydrogenation is 1-nitrocyclobutane and other preparation and reaction conditions are the same as in example 1.
Example 15
This example differs from example 1 in that the substrate for catalytic hydrogenation is 1-nitrocyclopentane and the other preparation and reaction conditions are the same as in example 1.
Example 16
This example differs from example 1 in that the substrate for catalytic hydrogenation is 1-nitrocyclooctane and other preparation and reaction conditions are the same as in example 1.
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 is not impregnated with SnCl 4 Solution of Ni/Al 2 O 3 The catalyst is the same as the others.
Comparative example 2
Comparative example 2 is different from example 2 in that comparative example 2 is not impregnated with SnCl 2 The solution, which is a Ni/CNT catalyst, is the same as the others.
Comparative example 3
Comparative example 3 is different from example 3 in that comparative example 3 is not impregnated with Sn (NO 3 ) 2 The solution was Ni/ATP catalyst, all other things being equal.
Comparative example 4
Comparative example 4 differs from example 1 in that ni@sno 2 /Al 2 O 3 The catalyst was not impregnated with NaOH solution, and the other preparation conditions and nitrocyclohexane hydrogenation conditions were the same as in example 1.
Comparative example 5
Comparative example 5 differs from example 2 in that ni@sno 2 The CNT catalyst was not impregnated with KOH solution, and other preparation conditions and nitrocyclohexane hydrogenation conditions were the same as in example 2.
Comparative example 6
Comparative example 6 differs from example 3 in that ni@sno 2 The ATP catalyst was not impregnated with the RbOH solution and the other preparation conditions and nitrocyclohexane hydrogenation conditions were the same as in example 3.
Comparative example 7
Comparative example 7 differs from example 4 in that ni@sno 2 MMT catalyst is not impregnated with CsOH solution, other preparation conditions andthe nitrocyclohexane hydrogenation conditions were the same as in example 4.
Test examples
1. The Ni@SnO 2 /Al 2 O 3 The catalyst projection electron microscope photograph and the elemental energy spectrum analysis of the catalyst are shown in FIG. 3, and from FIG. 3, it can be seen that Al 2 O 3 Obvious Ni@SnO was observed on the surface of the support 2 Particles, and Ni and SnO 2 Uniformly dispersed on the surface of the catalyst.
2. To verify SnO 2 The component is H 2 Partial O reduction under atmosphere, respectively for Ni@SnO 2 /Al 2 O 3 And Ni/Al 2 O 3 Sample is H 2 TPR test, as shown in FIG. 4, it can be seen that H 2 SnO under atmosphere 2 /Al 2 O 3 At 215 ℃ obvious SnO 2 Surface layer Sn 4+ And the peak is at Ni@SnO 2 /Al 2 O 3 Also present, proved that Ni@SnO 2 /Al 2 O 3 Surface-coated SnO 2 The partial oxygen deficiency shown in fig. 2 occurs after the pre-reduction treatment.
3. To demonstrate the involvement of protons in-NO in FIG. 2 2 Reduction of Ni@SnO 2 /Al 2 O 3 And Ni/Al 2 O 3 Isotope experiments are carried out, the test chart is shown in figure 5, and the experimental results show that the Ni/Al 2 O 3 KIE of the catalytic hydrogenation nitrocyclohexane is only 1.1-1.5, and the test result accords with the normal H 2 、D 2 The rate deviation due to the difference in zero energy is generally considered to be the difference in bond breaking energy between Ni-H and Ni-D. While at Ni@SnO 2 /Al 2 O 3 KIE of the medium catalyst is as high as 3-4, which obviously involves H + /D + Is remote from (i) the O-H in the system of the invention + And O-D + The structure gives the bond energy difference required for protons.
4. Ni@SnO in the invention 2 /Al 2 O 3 Catalyst at D 2 In-situ infrared spectrum under atmosphere as shown in FIG. 6, it can be seen that D 2 In the atmosphere, the presence of a large number of-OD bonds in the catalyst demonstrates the junction of FIGS. 4 and 5And (5) fruits.
5. Table 1 shows the conversion of nitrocyclohexane and the selectivity towards cyclohexanone oxime in the examples according to the invention compared with the comparative examples.
TABLE 1
| Catalyst | Conversion/% | Selectivity/% | |
| Example 1 | Ni@SnO 2 /Al 2 O 3 (ethylenediamine solvent) | 100 | 98.7 |
| Example 2 | Ni@SnO 2 CNT (ethylenediamine solvent) | 100 | 97.7 |
| Example 3 | Ni@SnO 2 ATP (ethylenediamine solvent) | 100 | 98.8 |
| Example 4 | Ni@SnO 2 MMT (ethylenediamine solvent) | 96 | 98.1 |
| Example 5 | Ni@SnO 2 Halloysite (ethylenediamine solvent) | 100 | 97.9 |
| Example 6 | Ni@SnO 2 ZSM-5 (ethylenediamine solvent) | 100 | 98.8 |
| Example 7 | Ni@SnO 2 XC-72 (ethylenediamine solvent) | 100 | 99.1 |
| Example 8 | Ni@SnO 2 /Al 2 O 3 (ethanol solvent) | 50 | 11 |
| Example 9 | Ni@SnO 2 /Al 2 O 3 (n-butylamine solvent) | 90 | 87 |
| Example 10 | Ni@SnO 2 /Al 2 O 3 (Ethanolamine solvent) | 60 | 75 |
| Example 11 | Ni@SnO 2 /Al 2 O 3 (ethanol: ethylenediamine=1:1) | 100 | 96.8 |
| Example 12 | Ni@SnO 2 /Al 2 O 3 (ethanol: ethylenediamine=9:1) | 100 | 90.1 |
| Comparative example 1 | Ni/Al 2 O 3 | 100 | 8.7 |
| Comparative example 2 | Ni/CNT | 100 | 9.1 |
| Comparative example 3 | Ni/ATP | 100 | 7.6 |
| Comparative example 4 | Ni@SnO 2 /Al 2 O 3 (without Na + ) | 96.7 | 98.1 |
| Comparative example 5 | Ni@SnO 2 /CNT(without K + ) | 95.9 | 97.2 |
| Comparative example 6 | Ni@SnO 2 /ATP(without Rb + ) | 92.4 | 94.1 |
| Comparative example 7 | Ni@SnO 2 /MMT(without Cs + ) | 91.2 | 91.9 |
6. The lifetime comparison of the catalyst before and after alkali metal modification of the second active component is shown in table 2.
TABLE 2
| Catalyst | Number of cycles | |
| Example 1 | Ni@SnO 2 /Al 2 O 3 (with Na + ) | 12 |
| Example 2 | Ni@SnO 2 /CNT(with K + ) | 11 |
| Example 3 | Ni@SnO 2 /ATP(with Rb + ) | 11 |
| Example 4 | Ni@SnO 2 /MMT(with Cs + ) | 11 |
| Comparative example 4 | Ni@SnO 2 /Al 2 O 3 (without Na + ) | 3 |
| Comparative example 5 | Ni@SnO 2 /CNT(without K + ) | 3 |
| Comparative example 6 | Ni@SnO 2 /ATP(without Rb + ) | 3 |
| Comparative example 7 | Ni@SnO 2 /MMT(without Cs + ) | 3 |
7. Ni@SnO in the invention 2 /Al 2 O 3 (ethylenediamine solvent) conversion to other m-nitrocyclohexane and selectivity to the corresponding oxime compound, see Table 3
TABLE 3 Table 3
| Reaction substrate | Conversion/% | Selectivity/% | |
| Example 13 | 2-nitropropane | 100 | 99.3 |
| Example 14 | 1-nitrocyclobutane | 100 | 99.1 |
| Example 15 | 1-nitrocyclopentane | 100 | 98.8 |
| Example 16 | 1-nitrocyclooctane | 100 | 98.6 |
As can be seen from examples 1 to 7 in Table 1, the metal-supported catalyst of the present invention has excellent catalytic activity and cyclohexanone oxime selectivity for nitrocyclohexane hydrogenation, and after 3 hours of reaction, the nitrocyclohexane conversion rate reaches 100%, and the cyclohexanone oxime selectivity can be up to more than 99%.
Examples 8-12 examined the effect of solvents on the hydrogenation performance of the metal supported catalysts of the present invention. The result shows that the ethylenediamine is used as a solvent metal supported catalyst with optimal catalytic activity and selectivity, and is superior to other organic amine solvents such as butylamine and ethanolamine. Unlike basic organic amines, ethanol has very poor catalytic activity and selectivity as a solvent metal supported catalyst. From the experimental results we speculate that the overbasing of ethylenediamine is a key factor in promoting activity and selectivity, which is capable of etching a part of the high valence Sn (Sn 4+ ) Thereby making more Ni-Sn δ+ The interface is exposed. Since the alcohol solvent does not have corrosion to SnO 2 High coverage SnO during the reaction 2 Naturally also the catalytic properties of Ni are suppressed.
Examples 1 to 4 and comparative examples 4 to 7 compare the catalytic performance of the metal-supported catalysts before and after the alkali metal modification, and the alkali metal modification has an accelerating effect on the activity and selectivity of the catalysts in terms of hydrogenation activity and selectivity. Meanwhile, the results of the number of times of recycling of the catalyst in Table 2 show that Na + 、K + 、Rb + 、Cs + Modification can significantly improve catalyst life.
The results of examples 13-16 show that the metal-supported catalyst of the invention has excellent catalytic activity and selectivity to corresponding oxime products for secondary nitroalkane hydrogenation, the nitrocyclohexane conversion rate reaches 100% after 3 hours of reaction, and the selectivity to corresponding oxime products can be up to more than 99%.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The application of a metal supported catalyst in preparing cyclohexanone oxime by catalytic hydrogenation is characterized by comprising the following steps:
fully reducing the metal supported catalyst, and transferring the metal supported catalyst into a reaction kettle;
adding a solvent and a hydrogenation substrate into a reaction kettle, and introducing H 2 Stirring uniformly to finish the reaction;
the metal supported catalyst comprises a carrier, a first active ingredient supported on the carrier, and a second active ingredient covered on the surfaces of the first active ingredient and the carrier;
the first active component contains Ni and SnO 2 The SnO is a Ni-based catalyst of (2) 2 Coating the Ni surface;
the second active ingredient is an alkali metal element;
the mass percentage of Ni is 0.1-10%, the mass percentage of alkali metal element is 0.1-10%, and SnO is prepared from the following components in percentage by mass 2 The mass percentage content of the catalyst is 0.1-10%;
the carrier is at least one of alumina, carbon nano tube, carbon black, attapulgite clay, halloysite and zeolite;
the alkali metal element is at least one of Na, K, rb, cs.
2. The use according to claim 1, characterized in that the preparation method of the metal supported catalyst comprises the following steps:
(1) Dispersing a carrier in water to form a suspension;
(2) Dropwise adding the Ni precursor solution into the suspension according to the load, and uniformly stirring to obtain a mixed solution;
(3) Dropwise adding an alkali solution into the mixed solution according to the addition amount, uniformly stirring, drying and calcining to obtain a first catalyst;
(4) And soaking the first catalyst in a tin salt solution for 1-4 hours, centrifuging, filtering, drying and calcining to obtain the metal supported catalyst.
3. The use according to claim 2, wherein at least one of the following (a) - (c):
(a) The Ni precursor solution is at least one of nickel acetate solution, nickel nitrate solution, nickel chloride solution and nickel acetylacetonate solution, and the concentration of the Ni precursor solution is 0.05-2 mol/L;
(b) The alkali solution is at least one of potassium hydroxide solution, sodium hydroxide solution, rubidium hydroxide solution and cesium hydroxide solution, and the concentration of the alkali solution is 0.05-2 mol/L;
(c) The tin salt solution is at least one of a tin tetrachloride solution, a tin dichloride solution, a tin nitrate solution and a tin acetate solution, and the concentration of the tin salt solution is 0.05-2 mol/L.
4. The use according to claim 2, wherein the calcination temperature in step (3) is 520-600 ℃ and the calcination time is 2-6 hours; the calcination temperature in the step (4) is 500-600 ℃, and the calcination time is 1-4 h.
5. The use according to claim 1, wherein the solvent is at least one of ethanol, methanol, ethylenediamine, n-butylamine, ethanolamine.
6. The use according to claim 1, wherein the passage of H 2 The pressure of (2) is 1-10 MPa.
7. The use according to claim 1, wherein the hydrogenation substrate is at least one of nitrocyclohexane, 2-nitropropane, 1-nitrocyclobutane, 1-nitrocyclopentane, 1-nitrocyclooctane.
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