CN116020506A - Carbon or nitrogen modified catalyst and preparation method and application thereof - Google Patents

Carbon or nitrogen modified catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN116020506A
CN116020506A CN202111259042.3A CN202111259042A CN116020506A CN 116020506 A CN116020506 A CN 116020506A CN 202111259042 A CN202111259042 A CN 202111259042A CN 116020506 A CN116020506 A CN 116020506A
Authority
CN
China
Prior art keywords
catalyst
carbon
nitrogen
metal
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111259042.3A
Other languages
Chinese (zh)
Inventor
郑南峰
阮朋朋
刘圣杰
陈洁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen University
Original Assignee
Xiamen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen University filed Critical Xiamen University
Priority to CN202111259042.3A priority Critical patent/CN116020506A/en
Priority to PCT/CN2021/130354 priority patent/WO2023070752A1/en
Publication of CN116020506A publication Critical patent/CN116020506A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/03—Monoamines
    • C07C211/07—Monoamines containing one, two or three alkyl groups, each having the same number of carbon atoms in excess of three
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/03—Monoamines
    • C07C211/08—Monoamines containing alkyl groups having a different number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/29—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C211/34—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton
    • C07C211/35—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton containing only non-condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
    • C07C217/58—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a carbon or nitrogen modified catalyst, a preparation method and application thereof, wherein the metal-based active center and a reducing carbon-containing gas or a reducing nitrogen-containing gas are subjected to chemical reaction, so that carbon atoms or nitrogen atoms are embedded into crystal lattices of the metal-based active center to form M 3 C x Or M 3 N x Wherein M is a metal-based active center including a metal element selected from group VIII. The catalyst provided by the invention can greatly improve the activity and selectivity of the catalyst to organic amine products in aldehyde/ketone-based reductive amination reaction, has good batch stability and can be repeatedly used.

Description

Carbon or nitrogen modified catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to a carbon or nitrogen modified catalyst, a preparation method thereof and application thereof in aldehyde/ketone reductive amination reaction.
Background
Primary amine ligands are widely used as chemical products with high added value in the fields of chemistry, biology, energy, materials and environment, in particular in the fields of medicine and the like. For example, 80% of the drugs in the first 200 world sales in 2018 are amine-containing, and studies have shown that these amine groups play a crucial role in the activity of drug molecules. For preparing and functionalizing these amine compounds, aldehyde/ketone reductive amination has been widely focused as a green and inexpensive strategy in recent years: the corresponding target primary amine product is obtained through the catalytic hydrogenation of aldehyde or ketone in ammonia water by a catalyst. Among such reaction catalysts, the unique reductive amination catalytic performance and sustainable development of the inexpensive transition metal nickel or cobalt-based catalytic gene are of great interest.
In 2017, beller, m. et al reported on science that a metal Co-MOF catalyst can catalyze the reductive amination of aldehyde groups with organic amine ligands, which catalyst can be applied to different substrates, but the catalyst catalysis conditions are severe (120 degrees, 4 MPa). Subsequently, 2019 Kempe, R.et Al reported Ni/Al on Nature Catalysis 2 O 3 Can effectively realize the reductive amination reaction of aldehyde groups and ammonia water to prepare a series of primary amine ligands. 2017, zhang Zehui et al reported on CN106552661a that a nitrogen-doped carbon-supported cobalt catalyst can effectively catalyze aldehyde group reductive amination reactions. However, the above catalysts are susceptible to oxidation when exposed to air, resulting in loss of catalyst activity.
And researches show that the catalytic activity and selectivity of the catalyst are not high at present, mainly because various side reactions are easy to occur in aldehyde/ketone reductive amination reaction, such as direct hydrogenation of aldehyde/ketone compounds into alcohol byproducts, or condensation of generated amine and raw materials to obtain another byproduct imine, which is easy to further hydrogenate to obtain multistage amine byproducts. Therefore, the preparation of an inexpensive metal catalyst having both high activity and high selectivity and high oxidation resistance is critical for the development of a green and inexpensive reductive amination catalyst.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a carbon or nitrogen-modified catalyst comprising a metal-based active site that chemically reacts with a reducing carbon-containing gas or a reducing nitrogen-containing gas to intercalate carbon atoms or nitrogen atoms into the lattice of the metal-based active site and form M 3 C x Or M 3 N x Wherein M is a metal-based active center including a metal element selected from group VIII.
Further, the M comprises nickel or cobalt.
Further, the value of X is 0 to 1. Preferably, the value of X is 0.15 to 1.
Further, the carbon-modified catalyst comprises 2-25% of carbon element by mole, and the nitrogen-modified catalyst comprises 2-25% of nitrogen element by mole.
Further, the reducing carbon-containing gas comprises carbon monoxide, acetylene or methane, preferably carbon monoxide.
Further, the reducing nitrogen-containing gas includes ammonia.
In a second aspect, the present invention provides a method for preparing a carbon or nitrogen modified catalyst, comprising the steps of: placing a catalyst containing a metal-based active center in a reducing carbon-containing gas to carry out carbonization reaction, thus obtaining a carbon-modified catalyst; or placing the catalyst containing the metal-based active center in a reducing nitrogen-containing gas to perform nitridation reaction, thus obtaining the nitrogen modified catalyst.
Further, the catalyst containing metal-based active sites includes a nickel-based catalyst or a cobalt-based catalyst.
Further, the carbonization reaction temperature is 100-1000 ℃, and the nitridation reaction temperature is 100-1000 ℃. .
Further, the carbonization reaction time is 1-12 h, and the nitridation reaction time is 1-12 h.
The invention also provides an application of the carbon-modified catalyst, which comprises the following steps: adding the catalyst provided by the invention or the catalyst prepared by the preparation method provided by the invention, an aldehyde compound or ketone compound, an amine source and a solvent into a reaction kettle to form a mixture, introducing nitrogen to replace air in the reaction kettle, sealing the reaction kettle, then introducing reducing gas, pressurizing and stirring the mixture until the reaction is completed.
Further, the reaction temperature is 50-100 ℃, the reaction time is 0.5-3 h, and the reaction pressure is 0.5-3 MPa.
Further, the amine source is ammonia water, liquid ammonia or ammonia gas; the reducing gas is hydrogen.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The invention improves the selectivity of the nickel-based/cobalt-based catalyst for catalyzing aldehyde reductive amination reaction by modifying the nickel-based/cobalt-based catalyst by the reductive carbon-containing or nitrogen-containing gas, can realize the selectivity of primary amine close to 100% under the relatively mild condition, and can be applied to the field of biological pharmacy.
(2) The invention improves the oxidation resistance of the catalyst by modifying the nickel-based/cobalt-based catalyst by the reductive carbon-containing or nitrogen gas, breaks the limitation that the traditional nickel-based catalyst is easy to be oxidized and deactivated, has extremely high oxidation resistance in air, can be stably stored in the air, and does not reduce the catalytic activity.
(3) The invention can reduce under extremely mild condition, the reduced catalyst is stable in contact with air, combustion can not occur, and the experimental performance and safety of the nickel-based/cobalt-based catalyst are greatly improved.
(4) The method provided by the invention is simple to operate, low in cost, high in repeatability and wide in substrate universality, can be popularized and applied to catalysts such as commercial nickel black, raney nickel and Raney cobalt, and provides convenience for the industrialization of catalyst preparation.
(5) The catalyst prepared by the invention can be suitable for high-activity high-selectivity reductive amination of aldehyde/ketone substrates with various functional groups, has good batch stability when being used, can be repeatedly used, further improves the quality of products and reduces the process cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate and together with the embodiments of the invention serve to explain the invention and do not limit the invention.
FIG. 1 is an XRD pattern of nickel nanoparticles of the present invention under different temperature carbon modification treatment conditions;
FIG. 2 (a) is a temperature programmed reduced TPR chart of a nickel-based catalyst of the invention without carbon or nitrogen modification treatment;
FIG. 2 (b) is a temperature programmed desorption-mass spectrometry TPD-MS diagram of a nickel-based catalyst without carbon or nitrogen modification treatment according to the present invention;
FIG. 3 (a) is a temperature programmed reduction TPR chart of the catalyst prepared in example 1 of the present invention;
FIG. 3 (b) is a temperature programmed desorption-mass spectrometry TPD-MS diagram of the catalyst prepared in example 1 of the present invention;
FIG. 4 (a) is a temperature programmed reduction TPR chart of the catalyst prepared in example 3 of the present invention;
fig. 4 (b) is a temperature programmed desorption-mass spectrometry TPD-MS diagram of the catalyst prepared in example 3 of the present invention.
FIG. 5 is an XPS chart of nickel element of the catalyst prepared in example 1 of the present invention;
FIG. 6 is a graph showing the catalytic stability of the catalyst prepared in example 1 of the present invention.
Detailed Description
Other advantages and features of the present invention will become readily apparent to those skilled in the art from the following detailed description, wherein it is shown and described only certain embodiments and the accompanying drawings.
It should be understood that the structures, proportions, sizes, etc. shown in the drawings are shown only in connection with the present disclosure for the understanding and reading by those skilled in the art, and are not intended to limit the scope of the invention, which is defined by the claims, so that any structural modifications, proportional changes, or dimensional adjustments should not be made in the technical spirit of the invention, and are not required to affect the efficacy or achievement of the present invention.
The following examples illustrate the detailed process and conditions of the preparation method of the present invention.
Example 1
Carbon modification treatment: a commercial nickel black catalyst was placed in an alumina crucible and placed in a tube furnace. Introducing CO gas at 25 ℃ for 30 minutes to remove oxygen in the pipeline, then heating to 250 ℃ at the rate of 5 ℃ per minute, carbonizing at 250 ℃ for 1 hour under CO atmosphere to prepare Ni 3 C 0.15 A catalyst.
FIG. 1 is an XRD pattern of a commercial nickel black catalyst under carbon modification treatment conditions at various temperatures, it can be seen that M increases with increasing carbon modification treatment temperature 3 C x Is more and more pronounced, indicating that M is generated 3 C x There are more and more crystalline phases.
Fig. 3 (a) is a temperature programmed reduction TPR diagram of the catalyst prepared in example 1 of the present invention, and fig. 3 (b) is a temperature programmed desorption-mass spectrometry TPD-MS diagram of the catalyst prepared in example 1 of the present invention. Compared with the commercial nickel black catalyst without carbon or nitrogen modification treatment, the commercial nickel black catalyst with carbon monoxide carbon modification treatment at 250 ℃ for one hour in the embodiment 1 of the invention can observe two reduction peaks, and the reduction peak at the low temperature of 75 ℃ is very weak and is the reduction of nickel carbide with oxidized surface, and the reduction peak at the high temperature of 240 ℃ is the reduction of lattice carbon, so that the carbon under the condition can be calculated according to the hydrogen consumptionThe modification treatment results in Ni 3 C 0.15 A catalyst. Meanwhile, as can be seen from experimental data results, the carbonized catalyst can be reduced under a relatively mild condition (75 ℃), which shows that the carbonized catalyst can effectively improve the oxidation resistance of the catalyst, and the surface oxidized species can be easily reduced, thereby further providing stable preparation of the nickel-based catalyst.
FIG. 5 is an XPS (XPS) chart of nickel element of the catalyst prepared in example 1 of the invention, and the catalyst after carbon modification treatment shows a mainly zero-valent nickel signal, thereby further confirming that the nickel carbide catalyst can be stably stored in air.
Catalytic efficiency
Performance evaluation was performed on the catalyst prepared in this example 1: 1mmol of benzaldehyde, 6mg of Ni prepared in this example 1 3 C 0.15 Adding a catalyst, 1mL of ammonia water and 2mL of absolute ethyl alcohol into a reaction kettle to form a mixture, introducing nitrogen into the reaction kettle for continuously displacing air in the reaction kettle for 3 times, sealing the reaction kettle, introducing hydrogen into the reaction kettle, starting stirring when the pressure in the reaction kettle is 2MPa, maintaining the reaction temperature at not higher than 80 ℃, observing the hydrogen consumption condition every minute until no pressure drop change is generated, stopping the reaction, reacting for 120 minutes, and analyzing by using gas chromatography after the reaction is finished, wherein the conversion rate is 99.9% and the selectivity is 98.3% according to the analysis result of the gas chromatography.
The catalyst is reused for a plurality of times
Under the same conditions of the catalytic efficiency test, the reaction time is 1 hour, and Ni prepared in the embodiment 1 of the invention is continuously applied 3 C 0.15 The catalysts were sampled separately and the selectivity data and the change in reactivity after application are shown in figure 6.
FIG. 6 is a graph showing the catalytic stability of the catalyst prepared in example 1 of the present invention, as can be seen from FIG. 6, ni of the present invention 3 C 0.15 After the catalyst is continuously and repeatedly used, the high conversion rate and the high selectivity are still maintained, which indicates that the catalyst has good catalytic stability.
Example 2
This practice isExample 2 preparation procedure and selection of materials the same as in example 1, except that in the carbon modification treatment, in example 2, the carbonization treatment was carried out at 225℃for 1 hour under CO atmosphere, and the catalyst obtained was Ni 3 C 0.09 The remaining preparation steps and materials were the same as in example 1.
Catalytic efficiency
The catalyst prepared in this example 2 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and as a result of gas chromatography analysis, the conversion was 99.9% and the selectivity was 91%.
Example 3
The procedure and materials used in this example 3 were the same as those used in example 1, except that in the carbon modification treatment, in this example 3, the carbonization treatment was carried out at 275℃for 1 hour under CO atmosphere, and the catalyst obtained was Ni 3 C 0.3 The remaining preparation steps and materials were the same as in example 1.
Fig. 4 (a) is a temperature programmed reduction TPR diagram of nickel carbide of the catalyst prepared in example 3 of the present invention, and fig. 4 (b) is a temperature programmed desorption-mass spectrometry TPD-MS diagram of the catalyst prepared in example 3 of the present invention. It can be deduced that the carbon monoxide modification treatment at 275℃for one hour of example 3 of the present invention resulted in Ni 3 C 0.3 A catalyst. The increase of the carbon content accords with the XRD characterization data result, the generation of nickel carbide is further verified, and the reduction peak signal of the oxide on the surface of the nickel-based catalyst after the carbon modification treatment is weak, which indicates that the nickel carbide is very stable in the air, and can be reduced even if weak oxidation occurs at 75 ℃, so that the practicability and the safety of the nickel-based catalyst are improved.
Catalytic efficiency
The catalyst prepared in this example 3 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and as a result of gas chromatography analysis, the conversion was 99.6% and the selectivity was 98.5%.
Example 4
The procedure and materials used in this example 4 were the same as those used in example 1, except that in the carbon modification treatment, in this example 4, the carbonization treatment was carried out at 300℃for 1 hour under a CO atmosphere, and the catalyst obtained wasNi 3 C 0.38 The remaining preparation steps and materials were the same as in example 1.
Catalytic efficiency
The catalyst prepared in this example 4 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and as a result of gas chromatography analysis, the conversion was 99.9% and the selectivity was 98.2%.
Example 5
The procedure and materials used in this example 5 were the same as those used in example 1, except that in the carbon modification treatment, in this example 5, the catalyst obtained was Ni by carbonizing at 250℃for 3 hours under CO atmosphere 3 C 0.45 The remaining preparation steps and materials were the same as in example 1.
Catalytic efficiency
The catalyst prepared in example 5 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and the conversion was 99.9% and the selectivity was 98% as a result of gas chromatography analysis.
Example 6
The procedure and materials used in this example 6 were the same as those used in example 1, except that in the carbon modification treatment, in this example 6, the catalyst obtained was Ni by carbonizing at 250℃for 5 hours under CO atmosphere 3 C 0.58 The remaining preparation steps and materials were the same as in example 1.
Catalytic efficiency
The catalyst prepared in example 6 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and the conversion was 99.9% and the selectivity was 98.5% as a result of gas chromatography analysis.
Example 7
The procedure and materials used in this example 7 were the same as those used in example 1, except that in the carbon modification treatment, in this example 5, the catalyst obtained was Ni by carbonizing at 250℃for 12 hours under CO atmosphere 3 C 0.75 The remaining preparation steps and materials were the same as in example 1.
Catalytic efficiency
The catalyst prepared in example 7 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and the conversion was 99.9% and the selectivity was 97.5% as a result of gas chromatography analysis.
Example 8
The procedure and materials used in this example 8 were the same as those used in example 1, except that in the carbon modification treatment, in this example 8, the catalyst obtained was Ni by carbonizing at 250℃for 24 hours under CO atmosphere 3 C 0.8 The remaining preparation steps and materials were the same as in example 1.
Catalytic efficiency
The catalyst prepared in example 8 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and the conversion was 99.9% and the selectivity was 96.8% as a result of gas chromatography analysis.
Example 9
The procedure and materials used in this example 9 were the same as those used in example 1, except that in the carbon-modified treatment, in this example 9, the commercial nickel-black catalyst obtained was placed in a high-pressure reactor, CO gas at 3 atm was introduced, and after 3 times of aeration and deflation, the high-pressure reactor was placed in an oil bath at 200℃for 1 hour, and the catalyst obtained was Ni 3 C 0.17 The remaining preparation steps and materials were the same as in example 1.
Catalytic efficiency
The catalyst prepared in example 9 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and the conversion was 99.8% and the selectivity was 98.7% as a result of gas chromatography analysis.
Example 10
Carbon modification treatment: a commercial nickel black catalyst was placed in an alumina crucible and placed in a tube furnace. Introducing acetylene gas at 25 ℃ for 30 minutes to remove oxygen in the pipeline, then heating to 250 ℃ at the rate of 5 ℃ per minute, and carbonizing at 250 ℃ for 1 hour in acetylene atmosphere to prepare Ni 3 C 0.34 A catalyst.
Catalytic efficiency
The catalyst prepared in example 10 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and the conversion was 99.9% and the selectivity was 97.5% as a result of gas chromatography analysis.
Example 11
Carbon modification treatment: a commercial nickel black catalyst was placed in an alumina crucible and placed in a tube furnace. Introducing methane gas at 25deg.C for 30 min to remove oxygen in the pipeline, heating to 350deg.C at a rate of 5deg.C per min, and carbonizing at 350deg.C under methane atmosphere for 1 hr to obtain Ni 3 C 0.22 A catalyst.
Catalytic efficiency
The catalyst prepared in this example 11 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and as a result of gas chromatography analysis, the conversion was 99.9% and the selectivity was 98.4%.
Example 12
Nitrogen modification treatment: a commercial nickel black catalyst was placed in an alumina crucible and placed in a tube furnace. Introducing ammonia gas at 25 ℃ for 30 minutes to remove oxygen in the pipeline, then heating to 350 ℃ at the rate of 5 ℃ per minute, and nitriding for 2 hours at 350 ℃ in ammonia atmosphere to prepare Ni 3 N 0.38 A catalyst.
Catalytic efficiency
The catalyst prepared in this example 10 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and as a result of gas chromatography analysis, the conversion was 99.9% and the selectivity was 98.5%.
Example 13
(1) 2.30g of nickel nitrate is weighed and dissolved in 10mL of ethanol to obtain nickel nitrate solution; simultaneously weighing 1g of active carbon carrier, and dispersing in 50mL of ethanol to obtain an active carbon dispersion liquid; dropwise adding nickel nitrate solution into the active carbon dispersion liquid, fully stirring for 5min, heating to 80 ℃, and evaporating ethanol to obtain a Ni/C catalyst precursor; catalyst precursor at 5%H 2 Reducing for 2 hours at 500 ℃ in Ar atmosphere to obtain the Ni/C catalyst with 30 percent of load.
(2) Carbon modification treatment: the Ni/C catalyst obtained above was placed in an alumina crucible and placed in a tube furnace. CO gas is firstly introduced for 30 minutes at 25 ℃ to remove the pipelineThe oxygen in the alloy is heated to 250 ℃ at the rate of 5 ℃ per minute, and carbonized for 1h at 250 ℃ in CO atmosphere to prepare Ni 3 C 0.15 catalyst/C.
Catalytic efficiency
The catalyst prepared in this example 11 was evaluated for its performance, except that 6mg of 30wt% Ni was used 3 C 0.15 The reaction conditions were the same as in example 1 except that the catalyst/C was used, and the conversion was 99.9% and the selectivity was 92% as a result of gas chromatography analysis.
Example 14
Raney nickel was placed as a nickel-based catalyst in an alumina crucible and placed in a tube furnace. Introducing CO gas at 25deg.C for 30 min to remove oxygen in the pipeline, heating to 250deg.C at a rate of 5deg.C per minute, and carbonizing at 250deg.C under CO atmosphere for 1 hr to obtain Raney Ni 3 C 0.15 A catalyst.
Catalytic efficiency
The catalyst prepared in example 12 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and the conversion was 99.9% and the selectivity was 98.6% as a result of gas chromatography analysis.
Example 15
Raney cobalt was placed as a cobalt-based catalyst in an alumina crucible and placed in a tube furnace. Introducing CO gas at 25deg.C for 30 min to remove oxygen in the pipeline, heating to 250deg.C at a rate of 5deg.C per minute, and carbonizing at 250deg.C under CO atmosphere for 1 hr to obtain Raney Co 3 C 0.15 A catalyst.
Catalytic efficiency
The catalyst prepared in example 13 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and as a result of gas chromatography analysis, the conversion was 99.9% and the selectivity was 98.1%.
Example 16
Raney cobalt was placed as a cobalt-based catalyst in an alumina crucible and placed in a tube furnace. Introducing ammonia gas at 25deg.C for 30 min to remove oxygen in the pipeline, and heating at 5deg.C per minAmination is carried out for 1h at 350 ℃ under ammonia gas at 350 ℃ to prepare Raney Co 3 N 0.33 A catalyst.
Catalytic efficiency
The catalyst prepared in example 16 was evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and the conversion was 99.9% and the selectivity was 98.3% as a result of gas chromatography analysis.
Table 1, examples 1 to 15 reaction data for the reductive amination of benzaldehyde
Figure BDA0003323760810000091
As can be seen from Table 1, the catalysts under the modified treatment conditions of carbon or nitrogen containing gases with different reducibility are used for the reductive amination of benzaldehyde, the conversion rate can be up to 99.9 percent, and the selectivity can be up to 98.7 percent, so that the surface of the catalyst subjected to the carbon or nitrogen modification treatment is carbonized or nitrided to form stable M 3 C x Crystalline phase or M 3 N x The crystalline phase can effectively improve the amine selectivity of the reductive amination reaction of the catalyst.
Examples 17 to 32
The preparation steps and materials of the catalysts of examples 17 to 32 are the same as those of example 1, and the catalysts are different from example 1 only in that the substrates used in performance evaluation of the catalysts are different, and the examples 17 to 32 are respectively prepared by using furfural, 4-chlorobenzaldehyde, 4-fluorobenzaldehyde, 4-bromobenzaldehyde, 4-methylbenzaldehyde, 4-methoxybenzaldehyde, 3-fluorobenzaldehyde, 3-methylbenzaldehyde, 2-fluorobenzaldehyde, 2-methylbenzaldehyde, 3, 5-dimethylbenzaldehyde, phenylacetaldehyde, phenylpropionaldehyde, n-octanal, 2-octanone and cyclohexanone instead of the benzaldehyde in example 1, and the other preparation steps and materials are the same as those of example 1. The catalysts prepared in examples 14 to 29 were also evaluated for their performance, and the catalytic reaction conditions were the same as in example 1, and the results of the gas chromatographic analysis were shown in Table 2.
TABLE 2 reaction data for the different substrates for examples 17 to 32
Figure BDA0003323760810000101
Figure BDA0003323760810000111
As can be seen from Table 2, the carbon or nitrogen modified catalyst provided by the invention has excellent catalytic effects on catalyzing aldehyde ketone reductive amination reaction aiming at different aldehyde compounds or ketone compounds as substrates.
Comparative example 1
Comparative example 1 the same commercial nickel black catalyst as in example 1 was used, except that no carbonization treatment or nitridation treatment was performed.
Fig. 2 (a) is a temperature programmed reduction TPR diagram of a commercial nickel black catalyst not subjected to carbon or nitrogen modification treatment, and fig. 2 (b) is a temperature programmed desorption-mass spectrometry TPD-MS diagram of a commercial nickel black catalyst not subjected to carbon or nitrogen modification treatment, it can be seen that the commercial nickel black catalyst not subjected to carbon or nitrogen modification treatment has only one reduction peak at 175 ℃, and the signal generated by the peak corresponding to the mass spectrometry is water, indicating that the nickel oxide on the surface of the commercial nickel black catalyst not subjected to carbon or nitrogen modification treatment is reduced to generate water, and that the nickel base material not subjected to carbon or nitrogen modification treatment consumes a large amount of hydrogen compared with the nickel base material not subjected to carbon or nitrogen modification treatment, which indicates that oxidation occurring on the surface of the nickel base material not subjected to carbon or nitrogen modification treatment is more serious and that the nickel base material is less likely to be reduced after oxidation compared with the nickel base catalyst subjected to carbon or nitrogen modification treatment.
Comparative example 2
Comparative example 2 a Ni/C supported catalyst of 30wt% mass fraction was prepared using the same preparation conditions as in example 11, except that no carbonization treatment or nitridation treatment was performed.
Comparative example 3
Comparative example 2 the same commercial raney nickel catalyst as in example 12 was used except that no carbonization or nitridation treatment was performed.
Comparative example 4
Comparative example 2 the same commercial Raney cobalt catalyst as in example 13 was used, except that no carbonization or nitridation treatment was performed.
The catalysts of comparative examples 1 to 4 were each evaluated for performance, and the catalytic reaction conditions were the same as in example 1, and the results were shown in Table 3.
Table 3, comparative examples 1 to 4 reaction data for the reductive amination of benzaldehyde
Figure BDA0003323760810000121
As can be seen from comparing tables 1 to 3, the nickel-based/cobalt-based catalyst which is not modified by carbon or nitrogen has a significant difference in catalytic selectivity for the reductive amination reaction of benzaldehyde compared with the nickel-based/cobalt-based catalyst which is modified by carbon or nitrogen and provided by the invention. The modified material is improved from 29 to 55 percent to 92 to 99 percent before modification.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications to the above would be obvious to those of ordinary skill in the art, without departing from the spirit and scope of the present invention. The scope of the invention is therefore intended to be indicated by the appended claims.

Claims (10)

1. A carbon or nitrogen modified catalyst comprising a metal-based active site which chemically reacts with a reducing carbon-containing gas or a reducing nitrogen-containing gas to intercalate carbon or nitrogen atoms into the lattice of the metal-based active site and form M 3 C x Or M 3 N x Wherein M is a metal-based active center including a metal element selected from group VIII.
2. The catalyst of claim 1, wherein M comprises nickel or cobalt.
3. The catalyst according to claim 2, wherein x has a value of 0 to 1.
4. The catalyst according to claim 1, wherein the molar percentage of carbon or nitrogen in the catalyst is 2-25%.
5. The catalyst of claim 1, wherein the reducing carbon-containing gas comprises carbon monoxide, acetylene or methane and the reducing nitrogen-containing gas comprises ammonia.
6. A method for preparing the carbon or nitrogen modified catalyst according to any one of claims 1 to 5, comprising the steps of: placing a catalyst containing a metal-based active center in a reducing carbon-containing gas to carry out carbonization reaction, thus obtaining a carbon-modified catalyst; or placing the catalyst containing the metal-based active center in a reducing nitrogen-containing gas to perform nitridation reaction, thus obtaining the nitrogen modified catalyst.
7. The method according to claim 6, wherein the carbonization reaction temperature is 100 to 1000 ℃ and the nitridation reaction temperature is 100 to 1000 ℃.
8. The method according to claim 6, wherein the carbonization reaction time is 1 to 12 hours and the nitridation reaction time is 1 to 12 hours.
9. Use of a carbon or nitrogen modified catalyst according to any one of claims 1 to 5 for the preparation of primary amines by reductive amination of aldehydes/ketones.
10. Use of a catalyst according to claim 9, comprising the steps of:
adding the catalyst, the aldehyde compound or ketone compound, an amine source and a solvent into a reaction kettle to form a mixture, introducing nitrogen to replace air in the reaction kettle, sealing the reaction kettle, then introducing reducing gas, pressurizing and stirring the mixture until the reaction is completed.
CN202111259042.3A 2021-10-27 2021-10-27 Carbon or nitrogen modified catalyst and preparation method and application thereof Pending CN116020506A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202111259042.3A CN116020506A (en) 2021-10-27 2021-10-27 Carbon or nitrogen modified catalyst and preparation method and application thereof
PCT/CN2021/130354 WO2023070752A1 (en) 2021-10-27 2021-11-12 Carbon or nitrogen-modified catalyst, preparation method therefor and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111259042.3A CN116020506A (en) 2021-10-27 2021-10-27 Carbon or nitrogen modified catalyst and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116020506A true CN116020506A (en) 2023-04-28

Family

ID=86071122

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111259042.3A Pending CN116020506A (en) 2021-10-27 2021-10-27 Carbon or nitrogen modified catalyst and preparation method and application thereof

Country Status (2)

Country Link
CN (1) CN116020506A (en)
WO (1) WO2023070752A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4287095A (en) * 1980-06-24 1981-09-01 The United States Of America As Represented By The Secretary Of The Interior High surface area transition metal catalysts and method of preparing same
CN104357841A (en) * 2014-10-29 2015-02-18 北京工业大学 Iron-group carbide nano crystal-graphene nanoribbon composite material as well as preparation and application thereof
CN104812490A (en) * 2012-10-24 2015-07-29 沙索技术有限公司 Process for preparing a Fischer-tropsch catalyst
CN105944746A (en) * 2016-05-18 2016-09-21 中国科学院理化技术研究所 Carbon supported nickel nitride catalyst and preparation method and application thereof
CN112206803A (en) * 2020-09-30 2021-01-12 润泰化学（泰兴）有限公司 Catalyst for generating isobutyraldehyde through selective hydrogenation of methacrolein and preparation method thereof
CN113522294A (en) * 2021-08-11 2021-10-22 中国科学院青岛生物能源与过程研究所 Ni-based catalyst, preparation method thereof and application thereof in reductive amination

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4287095A (en) * 1980-06-24 1981-09-01 The United States Of America As Represented By The Secretary Of The Interior High surface area transition metal catalysts and method of preparing same
CN104812490A (en) * 2012-10-24 2015-07-29 沙索技术有限公司 Process for preparing a Fischer-tropsch catalyst
CN104357841A (en) * 2014-10-29 2015-02-18 北京工业大学 Iron-group carbide nano crystal-graphene nanoribbon composite material as well as preparation and application thereof
CN105944746A (en) * 2016-05-18 2016-09-21 中国科学院理化技术研究所 Carbon supported nickel nitride catalyst and preparation method and application thereof
CN112206803A (en) * 2020-09-30 2021-01-12 润泰化学（泰兴）有限公司 Catalyst for generating isobutyraldehyde through selective hydrogenation of methacrolein and preparation method thereof
CN113522294A (en) * 2021-08-11 2021-10-22 中国科学院青岛生物能源与过程研究所 Ni-based catalyst, preparation method thereof and application thereof in reductive amination

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GAO JIAN FEI等: "Solid-phase synthesis and electrochemical pseudo-capacitance of nitrogen-atom interstitial compound Co3N", SUSTAINABLE ENERGY FUELS, vol. 2, 27 March 2018 (2018-03-27), pages 1178 - 1188, XP093061007, DOI: 10.1039/C8SE00009C *

Also Published As

Publication number Publication date
WO2023070752A1 (en) 2023-05-04

Similar Documents

Publication Publication Date Title
CN105032424B (en) A kind of catalyst and preparation method thereof for aromatic nitro compound selective hydrogenation
Alexander et al. The reduction of various nitrides under hydrogen: Ni 3 N, Cu 3 N, Zn 3 N 2 and Ta 3 N 5
WO2020048019A1 (en) Supported transition metal carbide catalyst and one-step synthesis method therefor
CN110652991A (en) Molybdenum carbide/cerium oxide catalyst for ammonia synthesis and preparation method thereof
US20060100462A1 (en) Metallic hydrogenation catalysts, production and use thereof
Xu et al. Stable Ni catalyst encapsulated in N-doped carbon nanotubes for one-pot reductive amination of nitroarenes with aldehydes
CN111185214A (en) Alumina biomass charcoal composite material, preparation method and application thereof
Gao et al. Oxidation of benzene to phenol by dioxygen over vanadium oxide nano-plate
CN108686660B (en) Catalyst for synthesizing isophorone diamine by reducing and aminating isophorone nitrile and preparation method and application thereof
CN116020506A (en) Carbon or nitrogen modified catalyst and preparation method and application thereof
WO2024027109A1 (en) Catalyst, preparation method therefor and use thereof
CN114618545A (en) Monoatomic Ru catalyst, preparation thereof and application thereof in aldehyde ketone reductive amination
CN112827501A (en) Controllable synthesis of alpha-MoC supported indium and modified catalyst thereof and application of alpha-MoC supported indium in reaction for preparing methanol by carbon dioxide hydrogenation
EP3577073B1 (en) Production of acetonitrile and/or hydrogen cyanide from ammonia and methanol
CN114588940B (en) Nickel-based catalyst for hydrogenation of phenolic compounds, and preparation method and application thereof
CN114805259A (en) Method for preparing furfuryl amine through selective amination of furfuryl alcohol on deactivation-resistant nickel-based catalyst
Li et al. Chirality inversion in enantioselective hydrogenation of isophorone over Pd/MgO catalysts in the presence of (S)-proline: Effect of Pd particle size
CN113731443B (en) Pt/CoFe-LDH supported nano solid catalyst and preparation method and application thereof
JP2023519667A (en) Method for preparing hexamethylenediamine by hydrogenating adiponitrile with suppressed formation of diaminocyclohexane
CN113351214A (en) Carbon-doped silicon dioxide-loaded nickel-copper alloy and preparation method and application thereof
SU677658A3 (en) Method of producing hexamethylenimine
CN115155631B (en) Carbon-modified metal-based reduction catalyst and preparation method and application thereof
CN1706808B (en) Direct one-step aminating synthesis of toluidine from toluene
CN116902958A (en) Preparation method and application of carbon-based hollow sphere material
CN114849700B (en) High-selectivity Pt-based hydrogenation catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination