CN114426506A - Method for preparing thioarylamine by catalytic hydrogenation - Google Patents
Method for preparing thioarylamine by catalytic hydrogenation Download PDFInfo
- Publication number
- CN114426506A CN114426506A CN202011083355.3A CN202011083355A CN114426506A CN 114426506 A CN114426506 A CN 114426506A CN 202011083355 A CN202011083355 A CN 202011083355A CN 114426506 A CN114426506 A CN 114426506A
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- CN
- China
- Prior art keywords
- transition metal
- acid
- catalyst
- catalytic hydrogenation
- carbon
- Prior art date
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- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 69
- 239000002114 nanocomposite Substances 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 43
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 36
- 150000003624 transition metals Chemical class 0.000 claims abstract description 32
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 15
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 claims abstract description 14
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 41
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- -1 amino, mercapto Chemical class 0.000 claims description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
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- 239000001301 oxygen Substances 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 15
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- 125000003118 aryl group Chemical group 0.000 claims description 12
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- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 claims description 7
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- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
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- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
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- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
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- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 3
- 125000004149 thio group Chemical group *S* 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- BVHNGWRPAFKGFP-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenyl)sulfonylbenzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 BVHNGWRPAFKGFP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 231100000572 poisoning Toxicity 0.000 abstract description 5
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- 150000001412 amines Chemical class 0.000 abstract description 2
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- DGBISJKLNVVJGD-UHFFFAOYSA-N 2-phenylsulfanylaniline Chemical compound NC1=CC=CC=C1SC1=CC=CC=C1 DGBISJKLNVVJGD-UHFFFAOYSA-N 0.000 description 4
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- 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
- B01J23/72—Copper
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- 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
- B01J23/745—Iron
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- 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
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/082—Decomposition and pyrolysis
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
Abstract
The invention provides a method for preparing thioarylamine by catalytic hydrogenation, which comprises the following steps: the method comprises the step of carrying out catalytic hydrogenation reaction on a thio-aromatic nitro compound by taking a carbon-coated transition metal nano composite material as a catalyst, wherein the nano composite material comprises a core-shell structure with a shell layer and an inner core, the shell layer is an oxygen-doped graphitized carbon layer, and the inner core is transition metal nano particles. The method can directly catalyze and hydrogenate the thioaromatic nitro compound to obtain the thioaromatic amine by adopting the specific catalyst, the catalyst has excellent capability of resisting sulfur compound poisoning, the catalytic performance is excellent, the product selectivity is more than 99 percent, the industrial cost is effectively reduced, and the method has a large industrial value.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a method for preparing thioarylamine by catalytic hydrogenation.
Background
The thioarylamine compounds are important organic chemicals and have wide application in the fields of pesticides, dyes, medicines, rubber and the like. For example, 2-aminodiphenyl sulfide is a raw material for synthesizing the antipsychotic drug quetiapine hemifumarate, and 3,3 '-diaminodiphenyl sulfone and 4, 4' -diaminodiphenyl sulfone are important epoxy resin curing agents.
The thioarylamine compound is usually prepared by reducing a thioaromatic nitro compound, and the conventional industrial production methods comprise a metal powder reduction method, a sodium sulfide reduction method and a catalytic hydrogenation reduction method. The metal powder reduction method and the sodium sulfide reduction method have mature processes, but a large amount of waste water and waste residues are generated as byproducts. The catalytic hydrogenation reduction method has the advantages of less three-waste discharge, low energy consumption, high product quality and the like, and is a green process.
Nickel-containing catalysts and noble metal catalysts such as platinum, palladium, rhodium and the like are widely applied to various catalytic hydrogenation reactions due to high catalytic hydrogenation activity. However, both nickel-containing catalysts and noble metal catalysts are very sensitive to sulfur-containing compounds. For example, in the literature (Indian Journal of Chemistry,2011,50B (9): 1195-1201), a method for producing 2-aminodiphenyl sulfide by catalytic hydrogenation of 2-nitrodiphenyl sulfide using Raney's nickel as a catalyst is reported, but the catalyst is deactivated rapidly and is difficult to recycle. Chinese patent CN106883157B discloses a Ni-based catalyst2P/SiO2A method for synthesizing thioarylamine by catalytic hydrogenation of a catalyst. Compared with a metal catalyst, the metal phosphide catalyst has higher sulfur resistance, but the hydrogenation activity is reduced, and the defects that the catalyst is complicated to prepare, needs high-temperature activation before use and the like exist.
In addition, researchers have considered that poisoning of the catalyst to sulfur-containing compounds can be avoided by performing a simple shell coating treatment on the transition metal catalyst. However, the literature (Jinlei Li, et al, "differential active sites in a biofunctional Co @ N-doped graphene shell based catalyst for the oxidative dehydrogenation and hydrogenation reactions," Journal of Catalysis 355(2017):53-62.) discloses the use of a nitrogen-doped graphene-coated cobalt material as a catalyst for oxidative dehydrogenation or hydrogenation reactions, wherein the nitrogen-doped graphene-coated cobalt material is prepared by cyanamide assisted pyrolysis, and a material coated with a graphene shell layer on the surface of transition metal cobalt is obtained by adding a large amount of cyanamide compound to a precursor and performing pyrolysis. However, when potassium thiocyanate (KSCN) is present in the reaction system, the catalyst is still poisoned.
Therefore, the method for synthesizing the thioarylamine by catalyzing and hydrogenating the thioaromatic nitro compound by using the metal catalyst with high sulfur resistance, high catalytic selectivity and low cost is developed, and has important significance for synthesizing the thioarylamine and the derivatives thereof in an industrial environment-friendly manner at low cost.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention mainly aims to overcome at least one defect in the prior art and provide a method for preparing thioarylamine by catalytic hydrogenation, so as to solve the problems that thioarylamine prepared by hydrogenation of thioaromatic nitro compounds catalyzed by the existing metal catalyst is easy to deactivate and difficult to recycle.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing thioarylamine by catalytic hydrogenation, which comprises the following steps: the method comprises the step of carrying out catalytic hydrogenation reaction on a thio-aromatic nitro compound by taking a carbon-coated transition metal nano composite material as a catalyst, wherein the nano composite material comprises a core-shell structure with a shell layer and a core, the shell layer is a graphitized carbon layer doped with oxygen, and the core is transition metal nano particles.
According to one embodiment of the present invention, the thioaromatic nitro compound is represented by the following formula (I):
wherein X is selected from one or more of sulfur and sulfuryl, R1Selected from hydrogen, C1-C6Hydrocarbyl radical, C1-C3Halogenated hydrocarbon group, C1-C3One or more of a hydroxyalkyl, a mercapto, an aryl and an aromatic thio group, R2Selected from hydrogen, C1-C6One or more of hydrocarbyl, hydroxyl, carboxyl, halogen, amino, mercapto, aryl, aromatic thio and nitro, the aryl being unsubstituted or substituted with one or more of the following groups: nitro radical, C1-C6Hydrocarbyl, hydroxy, carboxy, halogen, amino, or amino.
According to one embodiment of the invention, the compound of formula (I) is selected from one or more of 4-nitroanisole, 2-nitrodiphenyl sulfide, 4-nitrothiophenol, 3 '-dinitrodiphenyl sulfone and 4, 4' -dinitrodiphenyl sulfone.
According to one embodiment of the invention, the catalyst has a pickling loss of 50% or less, preferably 30% or less, more preferably 10% or less.
According to one embodiment of the invention, the temperature of the catalytic hydrogenation reaction is between 20 ℃ and 250 ℃, preferably between 40 ℃ and 200 ℃.
According to one embodiment of the present invention, the pressure of the catalytic hydrogenation reaction is 0.5MPa to 4 MPa.
According to one embodiment of the present invention, the catalyst and the thioaromatic nitro compound are subjected to a catalytic hydrogenation reaction in a solvent selected from one or more of alcohols, ethers, alkanes and water.
According to one embodiment of the invention, the transition metal nanoparticles are selected from one or more of iron, cobalt, nickel and copper, preferably nickel.
According to one embodiment of the present invention, the nanocomposite is a mesoporous material having at least one mesopore distribution peak, preferably a mesoporous material having two or more mesopore distribution peaks.
According to one embodiment of the present invention, the content of metal in the catalyst is 5% to 85%, the content of carbon is 14% to 93%, the content of oxygen is 0.3% to 10%, the content of nitrogen is 0% to 6%, and the content of hydrogen is 0.1% to 2.5%, based on the total mass of the catalyst.
According to one embodiment of the present invention, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
According to one embodiment of the present invention, a method for preparing a catalyst comprises: putting a transition metal compound and polybasic organic carboxylic acid into a solvent to be mixed to form a homogeneous solution; removing the solvent in the homogeneous solution to obtain a precursor; and pyrolyzing the precursor at high temperature in an inert atmosphere or a reducing atmosphere; wherein the transition metal compound is selected from one or more of transition metal hydroxide, transition metal oxide and transition metal salt, and the polybasic organic carboxylic acid is selected from one or more of ethylenediamine tetraacetic acid, iminodiacetic acid, diethylenetriamine pentaacetic acid, 1, 3-propane diamine tetraacetic acid, citric acid, maleic acid, trimesic acid, terephthalic acid and malic acid.
According to the technical scheme, the invention has the beneficial effects that:
the invention provides a method for preparing thioarylamine by catalytic hydrogenation, which can directly perform catalytic hydrogenation on thioaromatic nitro compound to obtain the thioarylamine by adopting a carbon-coated transition metal nano composite material as a specific catalyst. The catalyst in the method has excellent capability of resisting sulfur-containing compound poisoning, excellent catalytic performance and product selectivity of more than 99 percent, effectively reduces the cost of industrially relevant reactions, and has great industrial value.
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 embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is an X-ray diffraction (XRD) spectrum of a carbon-coated nickel nanocomposite material of preparation example 1;
FIG. 2A is nitrogen (N) of carbon-coated nickel nanocomposite of preparation example 12) Adsorption and desorption isotherm graphs;
FIG. 2B is a graph of pore size distribution of the carbon-coated nickel nanocomposite of preparation example 1;
FIGS. 3A and 3B are Transmission Electron Microscope (TEM) images of the carbon-coated nickel nanocomposite of preparation example 2 at different magnifications, respectively;
FIG. 4A is N of carbon-coated nickel nanocomposite of preparation example 22Adsorption and desorption isotherm graphs;
FIG. 4B is a graph of pore size distribution for the carbon-coated nickel nanocomposite of preparation example 2;
fig. 5 is a TEM image of the carbon-coated nickel nanocomposite of preparation example 3.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The term "core-shell structure" in the invention means that the inner core is metal nano-particles, and the shell layer is an oxygen-doped or nitrogen-oxygen-doped graphitized carbon layer. The term "graphitized carbon layer" means a carbon structure in which a layered structure is clearly observed under a high-resolution transmission electron microscope, not an amorphous structure, and the interlayer distance is about 0.34 nm. The composite material formed after the graphitized carbon layer is coated with the transition metal nano particles is spherical or quasi-spherical.
The term "acid wash loss ratio" refers to the loss ratio of transition metal after acid washing of the carbon-coated transition metal nanocomposite, which is used to reflect the tightness of coating of the transition metal nanoparticles by the graphitized carbon layer. If the graphitized carbon layer does not tightly coat the transition metal nanoparticles, the transition metal in the inner core is dissolved by acid and lost after acid washing. The greater the acid washing loss rate is, the lower the tightness of the coating of the transition metal nano-particles by the graphitized carbon layer is; conversely, the smaller the acid washing loss rate, the more rigorous the coating of the transition metal nanoparticles by the graphitized carbon layer is indicated.
The "pickling loss ratio" was measured and calculated in the following manner:
adding 1g of sample into 20mL of sulfuric acid aqueous solution (1mol/L), treating the sample at 90 ℃ for 8h, then washing the sample to be neutral by using deionized water, weighing and analyzing the sample after drying, and calculating the pickling loss rate according to the following formula.
The acid pickling loss rate is [1- (mass fraction of transition metal in the composite material after acid pickling × mass of the composite material after acid pickling) ÷ (mass fraction of transition metal in the composite material to be pickled × mass of the composite material to be pickled) ] × 100%.
The term "mesoporous" is defined as a pore having a pore diameter in the range of 2 to 50 nm. Pores with a pore size of less than 2nm are defined as micropores and pores with a pore size of more than 50nm are defined as macropores.
The term "mesopore distribution peak" refers to a mesopore distribution peak on a pore distribution curve calculated from a desorption curve according to the Barrett-Joyner-Halenda (BJH) method.
The term "unsaturated compound" means an organic compound having an unsaturated group, the number of hydrogen atoms being not the largest in the same number of carbon atoms, for example, an organic compound having a double bond, a triple bond or a ring.
The invention provides a method for preparing thioarylamine by catalytic hydrogenation, which comprises the following steps: the method comprises the step of carrying out catalytic hydrogenation reaction on a thio-aromatic nitro compound by taking a carbon-coated transition metal nano composite material as a catalyst, wherein the nano composite material comprises a core-shell structure with a shell layer and a core, the shell layer is a graphitized carbon layer doped with oxygen, and the core is transition metal nano particles.
According to the invention, the thioarylamine compound is usually prepared by reducing the thioaromatic nitro compound, wherein the catalytic hydrogenation method has the advantages of less three-waste emission, low energy consumption, high product quality and the like, and is a green preferred process. However, the prior metal catalyst for catalyzing hydrogenation of the thioaromatic nitro compound to prepare the thioarylamine is easy to deactivate and difficult to recycle. The inventor of the invention finds that the catalyst can not be poisoned and can further improve the whole catalytic hydrogenation effect by adopting the specific catalyst to carry out catalytic hydrogenation on the thio-aromatic nitro compound, thereby having important industrial application value.
Specifically, the carbon-coated transition metal nanocomposite of the present invention is a composite material composed of "transition metal nanoparticles tightly coated with a graphitized carbon layer (not in contact with the outside)", "transition metal nanoparticles in contact with the outside and confined", and a carbon material having a mesoporous structure. The carbon material has catalytic activity and can act with the transition metal nanoparticles in a synergistic manner, so that the nano composite material has better catalytic performance. Meanwhile, the transition metal is coated or limited by the graphitized carbon layer, so that the transition metal can not directly contact with the sulfide, the catalyst poisoning is avoided, the hydrogenation raw material does not need to be pretreated, and the production cost is greatly reduced.
In some embodiments, the aforementioned nanocomposite material has an acid wash loss of 50% or less, preferably 30% or less, and more preferably 10% or less. The lower the pickling loss, the higher the degree of carbon coating. Compared with the non-tightly-coated composite material, the tightly-coated composite material can better ensure that the loss rate of the transition metal of the inner core is reduced in the preparation and application processes, thereby better playing the role of the composite material. Furthermore, it is generally recognized in the art that the active site for catalyzing the hydrogenation reaction is a transition metal and that regardless of the specific structure of the catalyst, it is necessary to be able to contact the reactants with the metal site. The nano composite material of the invention, which is tightly coated with the transition metal by the graphitized carbon layer, still has excellent capability of catalyzing hydrogenation reduction of organic compounds.
In addition, as known to those skilled in the art, mesoporous materials generally have large specific surface areas and relatively regular channel structures, so that the mesoporous materials can play a better role in separation, adsorption and catalytic reactions of macromolecules and can be used as microreactors for limited-domain catalysis. The nano composite material has rich mesoporous structure, so that the nano composite material has higher mass transfer efficiency and more excellent catalytic performance.
In some embodiments, the nanocomposite is a mesoporous material having at least one mesopore distribution peak. That is, the nano composite material has at least one mesoporous distribution peak on a pore distribution curve obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method. In some embodiments, a single batch fabricated composite has two peaks in the mesopore range; if a plurality of batches of the composite material are mixed, more distribution peaks can be obtained in the mesoporous range. When the nano composite material has the multilevel mesoporous structure with different aperture ranges, the nano composite material can show more unique performance, and the applicable application range of the multilevel mesoporous structure is wider.
According to the present invention, in some embodiments, the mesoporous structure has one mesopore distribution peak in a pore size range of 2nm to 7nm and a pore size range of 8nm to 20nm, respectively.
According to the present invention, in some embodiments, the proportion of mesopore volume to the total pore volume in the composite material is greater than 50%, preferably greater than 80%. In some embodiments, the proportion of mesopore volume to the total pore volume is greater than 90%, and even 100%.
According to the present invention, in some embodiments, the mesopore volume can be 0.05cm3/g~1.25cm3Per g, also may be 0.30cm3/g~0.50cm3/g。
According to the present invention, in some embodiments, the specific surface area is generally greater than 140m2/g, may be greater than 200m2/g。
According to the invention, the fuel does not spontaneously ignite in air and can be stored in air.
According to the present invention, in some embodiments, the carbon layer of the nanocomposite is doped with an oxygen element and not doped with a nitrogen element.
According to the present invention, in some embodiments, the carbon layer of the nanocomposite is doped with an oxygen element and a nitrogen element.
According to the invention, in some embodiments, the carbon layer of the nanocomposite is doped with only oxygen and not with elements other than hydrogen and oxygen.
According to the present invention, in some embodiments, the nanocomposite has a metal content of 5% to 85%, e.g., 5%, 15%, 20%, 35%, 40%, 50%, 55%, 60%, 70%, 75%, 80%, 85%, etc., a carbon content of 14% to 93%, e.g., 14%, 20%, 24%, 29%, 31%, 36%, 40%, 50%, 60%, 70%, 80%, 90%, etc., and an oxygen content of 0.3% to 10%, e.g., 0.3%, 1%, 1.5%, 5%, 8%, 10%, etc., based on the total mass of the catalyst. The catalytic performance of the graphitized carbon layer can be adjusted by adjusting the oxygen content in the nano composite material, so that the graphitized carbon layer is suitable for catalyzing different reactions. In some embodiments, the oxygen content is preferably 0.2% to 5.0%. The nitrogen content is 0% to 6%, for example, 0% (i.e., no nitrogen), 1%, 2%, 3%, 4%, 5%, 6%, etc., and the hydrogen content is 0.1% to 2.5%, for example, 0.1%, 0.5%, 1%, 1.4%, 2%, 2.5%, etc.
According to the invention, the sum of the contents of the components in the nanocomposite is 100%.
In some embodiments, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
In some embodiments, the core-shell structure has a particle size of 1nm to 200nm, preferably 3nm to 100nm, more preferably 4nm to 50 nm.
In some embodiments, the transition metal is selected from one or more of iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu), preferably nickel.
Specifically, the preparation method of the nanocomposite material is as follows:
putting a transition metal compound and polybasic organic carboxylic acid into a solvent to be mixed to form a homogeneous solution;
removing the solvent in the homogeneous solution to obtain a precursor;
and pyrolyzing the precursor at high temperature in an inert atmosphere or a reducing atmosphere.
Specifically, the precursor is a water-soluble mixture, which refers to a transition metal compound-containing water-soluble mixture obtained by dissolving a transition metal compound and a polybasic organic carboxylic acid in a solvent such as water, ethanol and the like to form a homogeneous solution, and then directly evaporating and removing the solvent. The foregoing temperature and process of evaporating the solvent may be by any available prior art, for example, spray drying at 80 ℃ to 120 ℃ or drying in an oven.
Other organic compounds than the two mentioned above, which can be any organic compound that can supplement the carbon source required in the product without containing other doping atoms, can also be added to form a homogeneous solution. Organic compounds having no volatility such as organic polyols, lactic acid and the like are preferable. In addition, nitrogen-containing compounds including but not limited to hexamethylenetetramine can be added to adjust the nitrogen content of the nanocomposite according to the actual application requirements.
The transition metal compound may be a transition metal hydroxide, a transition metal oxide, or a transition metal salt, and nickel may be nickel hydroxide, nickel oxide, or a nickel salt, for example. The transition metal salt includes, but is not limited to, one or more of organic acid salt, carbonate and basic carbonate, and the organic acid salt of the transition metal is preferably organic carboxylate of the transition metal without heteroatom, more preferably acetate of the transition metal without heteroatom, wherein the heteroatom refers to a metal atom other than the transition metal.
The polyvalent organic carboxylic acid may be a nitrogen-containing polyvalent organic carboxylic acid, for example, ethylenediaminetetraacetic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, 1, 3-propylenediaminetetraacetic acid, etc.; it may also be a nitrogen-free polyvalent organic carboxylic acid such as citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, etc. When the polybasic organic carboxylic acid is a nitrogen-free polybasic organic carboxylic acid and the other organic compounds do not contain nitrogen, the graphitized carbon layer of the obtained composite material does not contain nitrogen and is only doped with oxygen. In this case, the mass ratio of the transition metal compound, the polyvalent organic carboxylic acid and the other organic compound is 1:0.1 to 10:0 to 10, preferably 1:0.5 to 5:0 to 5, more preferably 1:0.8 to 3:0 to 3, that is, the other organic compound may not be added at all.
When the polybasic organic carboxylic acid is a polybasic organic carboxylic acid containing no nitrogen, but a nitrogen-containing compound is added; or the polybasic organic carboxylic acid is nitrogenous polybasic organic carboxylic acid, the graphitized carbon layer of the obtained composite material contains nitrogen and oxygen. Note that, when the polyvalent organic carboxylic acid is a nitrogen-containing polyvalent organic carboxylic acid, the nitrogen-containing compound may not be added, and it is only necessary to make the mass ratio of the nitrogen element to the mass ratio of the transition metal compound and the polyvalent organic carboxylic acid within a certain range. In some embodiments, the mass ratio of the transition metal compound, the organic polycarboxylic acid and the nitrogen-containing compound is 1: 0.1-100: 0-100, preferably 1: 0.5-5, and more preferably 1: 0.8-2: 1-2.
In some embodiments, the high temperature pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-30 ℃/min, preferably 1-10 ℃/min; the temperature of the constant temperature section is 400-800 ℃, and preferably 500-800 ℃; the constant temperature time is 20min to 600min, preferably 60min to 480 min; the inert atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of an inert gas and hydrogen, for example, a small amount of hydrogen is doped in the inert atmosphere.
According to another embodiment of the present invention, the present invention further comprises subjecting the product of the high-temperature pyrolysis described above to an acid treatment.
Specifically, the acid treatment is preferably with a strong non-oxidizing acid including, but not limited to, one or any combination of hydrofluoric acid, hydrochloric acid, nitric acid, and sulfuric acid, preferably hydrochloric acid and/or sulfuric acid.
In some embodiments, the acid treatment conditions are: the treatment is carried out at 30 to 100 ℃ for 1 hour or more, preferably at 60 to 100 ℃ for 1 to 20 hours, and more preferably at 70 to 90 ℃ for 1 to 10 hours.
The present invention prepares a carbon-coated transition metal nanocomposite through the above method without using a method of pyrolysis using metal-organic framework compounds (MOFs) as precursors, which requires preparing a carbon-coated transition metal nanocomposite having a good thermal conductivity in a solvent at high temperature and high pressureCrystalline solid materials (i.e., MOFs) with a desired structure are generally prepared under strict conditions, and the required ligands are expensive and difficult to produce in large quantities; the precursor of the high-temperature pyrolysis of the invention is directly generated by the reaction of a transition metal compound and water-soluble fatty acid, and the atom utilization rate of the transition metal of the precursor can reach 100 percent. In the preparation process, dicyanodiamine, melamine and the like which are commonly used in the traditional method are not needed to be easily sublimated or decomposed, and the ligand of the carbon nanotube is easily generated; and overcomes the defects that the preparation of the metal organic framework structure precursor in the prior art needs the self-assembly of a high-temperature high-pressure reaction kettle, a large amount of organic solvent is wasted, the purification steps are complicated, and the like. In addition, when the water-soluble fatty acid containing amino groups is used as a carbon source and a nitrogen source of the nano material, the water-soluble fatty acid simultaneously carbonizes at high temperature to play a role of a carbon reducing agent, so that a combustible reducing gas such as hydrogen or methane (CH) does not need to be introduced in the preparation process4) Ethane (C)2H4) And the like.
According to the invention, the aforementioned thioaromatic nitro compounds are also referred to as compounds of the formula (I),
wherein X is selected from one or more of sulfur and sulfuryl, R1Selected from hydrogen, C1-C6Hydrocarbyl radical, C1-C3Halogenated hydrocarbon group, C1-C3One or more of a hydroxyalkyl, a mercapto, an aryl and an aromatic thio group, R2Selected from hydrogen, C1-C6One or more of hydrocarbyl, hydroxyl, carboxyl, halogen, amino, mercapto, aryl, aromatic thio and nitro, the aryl being unsubstituted or substituted with one or more of the following groups: nitro radical, C1-C6Hydrocarbyl, hydroxy, carboxy, halogen, amino, or amino.
In one embodiment, X is sulfur, and the conversion of the thioaromatic nitro compound to a thioaromatic amine is shown below in formula A:
in one embodiment, X is a sulfone group, where the thioaromatic nitro compound is converted to a thioarylamine as shown in formula B below:
wherein when R is above1、R2In the case of no nitro group, R1’、R2' with corresponding R1、R2The same; when R is1、R2When at least one of them contains a nitro group, the nitro group is at the corresponding R1’、R2' into amino group.
Preferably, the thioaromatic nitro compound is selected from 4-nitroanisole2-Nitro diphenyl sulfide4-nitrothiophenol3, 3' -dinitrodiphenyl sulfoneAnd 4, 4' -dinitrodiphenyl sulfoneOne or more of (a). Correspondingly, the thioarylamine is 4-aminoanisole sulfide2-aminodiphenyl sulfide4-aminothiophenols3, 3' -diaminodiphenyl sulfoneAnd 4, 4' -diaminodiphenyl sulfoneOne or more of (a).
In some embodiments, the temperature of the catalytic hydrogenation reaction is 20 ℃ to 250 ℃, for example, 20 ℃,50 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 170 ℃, 180 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, etc., preferably 40 ℃ to 200 ℃; the reaction pressure is 0.5MPa to 4MPa, for example, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, etc.
In some embodiments, the catalyst and the thio-aromatic nitro compound are subjected to catalytic hydrogenation reaction in a solvent, wherein the solvent is selected from one or more of alcohols, ethers, alkanes and water, and the choice of the solvent can be made according to actual needs, but the invention is not limited thereto.
In conclusion, the carbon-coated transition metal nano composite material is used as a specific catalyst and is applied to the reaction for catalyzing the hydrogenation of the thioaromatic nitro compound to prepare the thioarylamine. The transition metal in the catalyst has a tightly coated graphitized carbon layer with a specific structure, so that excellent catalytic hydrogenation capability is ensured, meanwhile, the catalyst can be effectively prevented from poisoning sulfur-containing compounds, the production cost is effectively reduced, and the catalyst has important industrial application value.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, reagents, materials and the like used in the present invention are commercially available.
Instrumentation and testing
The invention detects elements on the surface of the material by an X-ray photoelectron spectrum analyzer (XPS). The X-ray photoelectron analyzer was produced by VG scientific Inc. and Escalab220i equipped with Avantage V5.926 softwareThe XL type ray electron spectrometer has the following analysis and test conditions of X-ray photoelectron spectroscopy: the excitation source is monochromatized A1K alpha X-ray, the power is 330W, and the basic vacuum is 3X 10 during analysis and test-9mbar。
The pore structure property of the material is detected by a BET test method. Specifically, a Quantachrome AS-6B type analyzer is adopted for determination, the specific surface area of the catalyst is obtained by a Brunauer-Emmett-Taller (BET) method, and a pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
The four elements of carbon (C), hydrogen (H), oxygen (O) and nitrogen (N) of the present invention were analyzed on an Elementar Micro Cube element analyzer. The specific operation method and conditions are as follows: weighing 1-2mg of sample in a tin cup, placing the sample in an automatic sample feeding disc, feeding the sample into a combustion tube through a ball valve for combustion, wherein the combustion temperature is 1000 ℃ (for removing atmospheric interference during sample feeding, helium gas is adopted for blowing), and then reducing the combusted gas by using reduced copper to form nitrogen, carbon dioxide and water. The mixed gas is separated by three desorption columns and sequentially enters a TCD detector for detection. The oxygen element is analyzed by converting oxygen in a sample into CO under the action of a carbon catalyst by utilizing pyrolysis, and then detecting the CO by adopting TCD.
The content of the metal elements is the normalized result of the material after the content of carbon, hydrogen, oxygen and nitrogen is removed.
Preparation example 1
This preparation example illustrates the preparation of a carbon-coated nickel nanocomposite material according to one embodiment
1) Weighing 4.38g (15mmol) of ethylenediamine tetraacetic acid and 1.85g (20mmol) of nickel hydroxide, adding into 150mL of deionized water, stirring at 75 ℃ to obtain a homogeneous solution, continuously heating and evaporating to dryness, and grinding the solid to obtain a precursor.
2) Placing the precursor obtained in the step 1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen at a flow rate of 80mL/min, heating to 600 ℃ at a speed of 3 ℃/min, keeping the temperature for 3h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the composite material.
3) Adding 60mL of 0.5mol/L H into the composite material obtained in the step 2)2SO4And stirring and refluxing the solution at 80 ℃ for 6h, then carrying out suction filtration on the solution, washing the solution to be neutral by using deionized water, and then placing the powder in an oven at 100 ℃ for drying for 2h to obtain the carbon-coated nickel nano composite material.
As shown in fig. 1, which is an XRD pattern of the carbon-coated nickel nanocomposite. FIG. 1 shows that only diffraction peaks of the carbon material and diffraction peaks of hcp-Ni and fcc-Ni exist. FIG. 2A is N of carbon-coated nickel nanocomposite of preparation example 12Adsorption and desorption isotherm graphs; fig. 2B is a graph of pore size distribution of the carbon-coated nickel nanocomposite of preparation example 1. The pore size distribution of this material is shown to show two peaks at diameters of 3.7nm and 10.0 nm. The specific surface area of the nanocomposite material is 224m2Per g, pore volume 0.457cm3(ii)/g, wherein the mesopore volume accounts for 99.7% of the total pore volume. The elemental analyzer determined that the nano-material has a C content of 37.42%, an H content of 0.54%, an N content of 1.45%, an O content of 1.86%, and a normalized Ni content of 58.73%. The loss rate of pickling of the composite material before purification obtained in this example, measured and calculated by the method described in the section of the term, was 12%. The pickling loss rate remains substantially unchanged by continuing to increase the pickling time on the basis of the process described in the nomenclature section.
Preparation example 2
This preparation example is intended to illustrate the preparation of a carbon-coated nickel nanocomposite material according to another embodiment
1) Weighing 10mmol of nickel hydroxide and 10mmol of citric acid, adding into 150mL of deionized water, stirring at 80 ℃ to obtain a homogeneous solution, continuously heating and evaporating to dryness, and grinding the solid to obtain a precursor.
2) Placing the precursor obtained in the step 1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen at a flow rate of 150mL/min, heating to 575 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the composite material.
3) Adding 50mL of 1mol/L H into the composite material obtained in the step 2)2SO4Stirring and refluxing the solution at 90 deg.C for 4 hr, vacuum filtering, washing with deionized water to neutrality, and placing the powder into a container of 10And drying in an oven at 0 ℃ for 2h to obtain the carbon-coated nickel nanocomposite.
Fig. 3A and 3B are TEM images of carbon-coated nickel nanocomposites prepared in preparation example 2 at different magnifications, respectively. It can be seen from fig. 3A that the nanoparticles are uniform in size and well dispersed. It can be seen from fig. 3B that the outer layer of the nickel nanoparticle is wrapped with a carbon layer having a certain graphitization degree to form a complete core-shell structure. Further, the average particle diameter of the Ni nanoparticles was 8.4nm as calculated according to the scherrer equation.
FIG. 4A is N of carbon-coated nickel nanocomposite prepared in preparation example 22Adsorption and desorption isotherm graphs. Fig. 4B is a pore size distribution diagram of the carbon-coated nickel nanocomposite prepared in preparation example 2. It can be seen from FIG. 4A that this material is in p/p0Obvious hysteresis loops appear between 0.4 and 1.0. As can be seen from FIG. 4B, the pore size distribution of this material shows two distribution peaks at the diameters of 3.3nm and 6.3 nm. The nanocomposite material had a specific surface area of 168m2Per g, pore volume 0.246cm3(ii)/g, wherein the mesopore volume accounts for 100% of the total pore volume. The content of C in the nano material measured by an element analyzer is 28.60%, the content of H is 0.40%, the content of O is 1.94%, and the content of Ni after normalization is 69.06%. The acid loss of the composite material produced in this example before purification was 16% and the acid loss of the purified material was less than 1%, as measured and calculated by the methods described in the nomenclature section. The pickling loss rate remains substantially unchanged by continuing to increase the pickling time on the basis of the process described in the nomenclature section.
Preparation example 3
This preparation example is intended to illustrate the preparation of a carbon-coated nickel nanocomposite material according to another embodiment
1) Weighing 10g of nickel acetate and 10g of citric acid, adding the nickel acetate and the citric acid into a beaker containing 30mL of deionized water, stirring the mixture at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating the homogeneous solution to dryness to obtain a solid precursor.
2) And (2) placing the solid obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 100mL/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature under the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite. The TEM image of the material is shown in FIG. 5, and the particle size of the carbon-coated metallic nickel nanoparticles is 5 nm-20 nm. It can be seen that the material is a carbon-coated nickel nanocomposite, and a graphitized carbon layer is coated on the outer layer of the nickel nanoparticles to form a complete core-shell structure. Through an acid washing experiment, the acid washing loss rate of the material is 36.2%. On the basis of the method, the pickling time is continuously increased, and the pickling loss rate is basically kept unchanged.
Example 1
This example illustrates the synthesis of 2-aminodiphenyl sulfide by catalytic hydrogenation of 2-nitrodiphenyl sulfide using the nanocomposite of preparation example 1 as a catalyst.
80mg of the nanocomposite, 427mg of 2-nitrodiphenyl sulfide, 27mL of isopropanol and 3mL of water were added to a reaction kettle, and H was introduced2Replacing the reaction kettle for 4 times, stirring and heating up under low pressure to the preset reaction temperature of 80 ℃, and then H2And (3) keeping the pressure in the reaction kettle at 1.0MPa, continuously reacting for 2 hours, stopping heating, reducing the temperature to room temperature, discharging pressure, opening the reaction kettle, and taking out a product for chromatographic analysis. The reactant conversion and the target product selectivity were calculated by the following formulas:
conversion rate-reacted mass of reaction substance/addition of reaction substance. times.100%
The selectivity is the mass of the target product/mass of the reaction product x 100%
After analysis, the conversion rate of the obtained 2-nitro diphenyl sulfide is 100%, and the selectivity of the 2-amino diphenyl sulfide is more than 99.9%.
Example 2
This example illustrates the catalytic hydrogenation of 4-nitrothiophenol to 4-aminothiophenol using the nanocomposite of preparation 1 as a catalyst.
Adding 100mg of nano composite material, 310mg of 4-nitrothiophenol and 30mL of ethanol into a reaction kettle, and introducing H2Replacing the reaction kettle for 4 times, stirring and heating up under low pressure to the preset reaction temperature of 85 ℃, and then H2The pressure in the reaction kettle is 1.0MPa, the heating is stopped after the reaction is continued for 1 hour, the pressure is discharged after the temperature is reduced to the room temperature, and the reaction is startedThe kettle was taken out of the product for chromatographic analysis.
After analysis, the conversion rate of the obtained 4-nitrothiophenol is 100 percent, and the selectivity of the 4-aminothiophenol is more than 99.9 percent.
Example 3
This example illustrates the synthesis of 4-aminothioanisole by catalytic hydrogenation of 4-nitroanisole using the nanocomposite of preparation 2 as catalyst.
80mg of the nanocomposite, 338mg of 4-nitroanisole, 27mL of ethanol and 3mL of H2Adding O into a reaction kettle, and introducing H2Replacing the reaction kettle for 4 times, stirring and heating up under low pressure to the preset reaction temperature of 90 ℃, and then H2And (3) keeping the pressure in the reaction kettle at 1.0MPa, continuously reacting for 40min, stopping heating, reducing the temperature to room temperature, discharging pressure, opening the reaction kettle, and taking out a product for chromatographic analysis.
After analysis, the conversion rate of the obtained 4-nitroanisole thioether is 100 percent, and the selectivity of the 4-aminothioanisole thioether is more than 99.9 percent.
Example 4
This example illustrates the synthesis of 4-aminothioanisole by catalytic hydrogenation of 4-nitroanisole using the nanocomposite of preparation 3 as catalyst.
80mg of nanocomposite, 338mg of 4-nitroanisole, 27mL of isopropanol and 3mL of H2Adding O into a reaction kettle, and introducing H2After replacing the reaction kettle for 4 times, introducing H again2And (3) keeping the pressure in the reaction kettle at 1.0MPa, stirring, heating to the preset reaction temperature of 80 ℃, continuously reacting for 40min, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, taking out a product, and performing chromatographic analysis.
After analysis, the conversion rate of the obtained 4-nitroanisole thioether is 100 percent, and the selectivity of the 4-aminothioanisole thioether is more than 99.9 percent.
Example 5
This example illustrates the synthesis of 3,3 '-diaminodiphenyl sulfone by catalytic hydrogenation of 3, 3' -dinitrodiphenyl sulfone using the nanocomposite of preparation 3 as a catalyst.
Mixing 100mg of the nanocomposite, 308mg of p-nitrophenylacetonitrile, 27mL of ethanol and 3mL of the mixtureH2Adding O into a reaction kettle, and introducing H2Replacing the reaction kettle for 4 times, heating to the predetermined reaction temperature of 80 ℃, and then H2And (3) keeping the pressure in the reaction kettle at 1.0MPa, continuously reacting for 50min, stopping heating, reducing the temperature to room temperature, discharging pressure, opening the reaction kettle, and taking out a product for chromatographic analysis.
After analysis, the conversion rate of the obtained 3,3 '-dinitrodiphenyl sulfone is 100 percent, and the selectivity of the 3, 3' -diamino diphenyl sulfone is more than 99.9 percent.
The carbon-coated transition metal nano composite material is used as a catalyst, can be directly used for catalyzing and hydrogenating a thio-aromatic nitro compound to synthesize the thio-aromatic amine, and has the product selectivity of more than 99 percent, thereby effectively reducing the cost of industrial related reactions. In addition, the nano composite material has stable catalytic performance, and shows good repeatability, high activity and high selectivity.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (11)
1. A method for preparing thioarylamine by catalytic hydrogenation is characterized by comprising the following steps: the method comprises the step of carrying out catalytic hydrogenation reaction on a thio-aromatic nitro compound by taking a carbon-coated transition metal nano composite material as a catalyst, wherein the nano composite material comprises a core-shell structure with a shell layer and an inner core, the shell layer is an oxygen-doped graphitized carbon layer, and the inner core is transition metal nano particles.
2. The method according to claim 1, wherein the thioaromatic nitro compound is represented by the following formula (I):
wherein X is selected from one or more of sulfur and sulfone group,R1Selected from hydrogen, C1-C6Hydrocarbyl radical, C1-C3Halogenated hydrocarbon group, C1-C3One or more of a hydroxyalkyl, a mercapto, an aryl and an aromatic thio group, R2Selected from hydrogen, C1-C6One or more of hydrocarbyl, hydroxyl, carboxyl, halogen, amino, mercapto, aryl, aromatic thio and nitro, the aryl being unsubstituted or substituted with one or more of the following groups: nitro radical, C1-C6Hydrocarbyl, hydroxy, carboxy, halogen, amino, or amino.
3. The method according to claim 2, wherein the thio-aromatic nitro compound is selected from one or more of 4-nitroanisole, 2-nitrodiphenyl sulfide, 4-nitrothiophenol, 3 '-dinitrodiphenyl sulfone and 4, 4' -dinitrodiphenyl sulfone.
4. The method of claim 1, wherein the catalyst has a wash loss of 50% or less.
5. The method of claim 1, wherein the temperature of the catalytic hydrogenation reaction is 20 ℃ to 250 ℃ and the reaction pressure is 0.5MPa to 4 MPa.
6. The process according to claim 1, wherein the catalytic hydrogenation reaction is carried out between the catalyst and the compound of formula (I) in a solvent selected from one or more of alcohols, ethers, alkanes and water.
7. The method of claim 1, wherein the transition metal nanoparticles are selected from one or more of iron, cobalt, nickel, and copper.
8. The method of claim 1, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak.
9. The method of claim 1, wherein the catalyst comprises from 5% to 85% metal, from 14% to 93% carbon, from 0.3% to 10% oxygen, from 0% to 6% nitrogen, and from 0.1% to 2.5% hydrogen, based on the total mass of the catalyst.
10. The method according to claim 1, wherein the graphitized carbon layer has a thickness of 0.3nm to 6.0 nm.
11. The method of claim 1, wherein the catalyst is prepared by a method comprising:
putting a transition metal compound and polybasic organic carboxylic acid into a solvent to be mixed to form a homogeneous solution;
removing the solvent in the homogeneous solution to obtain a precursor; and
pyrolyzing the precursor at high temperature in an inert atmosphere or a reducing atmosphere;
wherein the transition metal compound is selected from one or more of transition metal hydroxide, transition metal oxide and transition metal salt, and the polybasic organic carboxylic acid is selected from one or more of ethylenediamine tetraacetic acid, iminodiacetic acid, diethylenetriamine pentaacetic acid, 1, 3-propane diamine tetraacetic acid, citric acid, maleic acid, trimesic acid, terephthalic acid and malic acid.
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