CN114085154B - Method for synthesizing p-fluoroaniline based on high-activity framework nickel - Google Patents

Method for synthesizing p-fluoroaniline based on high-activity framework nickel Download PDF

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CN114085154B
CN114085154B CN202111447364.0A CN202111447364A CN114085154B CN 114085154 B CN114085154 B CN 114085154B CN 202111447364 A CN202111447364 A CN 202111447364A CN 114085154 B CN114085154 B CN 114085154B
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fluoroaniline
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CN114085154A (en
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刘亮
刘杰
解卫宇
聂祥平
陈少君
顾林江
徐巧巧
宋小艳
解海翔
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Zhejiang Xieshi New Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J35/61—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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
    • 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

Abstract

The invention discloses a method for synthesizing p-fluoroaniline based on high-activity framework nickel, which comprises the following steps: preparing a Zr-MOF material, namely modifying a polydopamine layer on the surface of the Zr-MOF material in situ to obtain a polydopamine modified Zr-MOF material, dissolving nickel nitrate hexahydrate in deionized water, adding the prepared polydopamine modified Zr-MOF material, adding urea, sodium citrate and hexamethylenetetramine, stirring, heating for reaction, cooling to room temperature after the reaction is finished, filtering the reaction solution, drying the obtained solid, and calcining in a muffle furnace to obtain the porous catalyst; adding the prepared porous catalyst into a reactor, adding p-fluoronitrobenzene, adopting nitrogen to replace air in the reactor, introducing hydrogen, heating for reaction, filtering the reaction liquid after the reaction is finished, evaporating the solvent from the filtrate, and performing reduced pressure distillation to obtain the p-fluoroaniline. The method provided by the invention is simple to operate, and the prepared product has higher yield and purity.

Description

Method for synthesizing p-fluoroaniline based on high-activity framework nickel
Technical Field
The invention relates to the technical field of preparation of para-fluoroaniline, in particular to a method for synthesizing para-fluoroaniline based on high-activity framework nickel.
Background
Para-fluoroaniline is an important fine chemical product and has important application in the fields of medicine, dye, agriculture and the like. At present, two main methods for synthesizing p-fluoroaniline are mainly available, one method is to directly join p-fluoroaniline by taking azidobenzene, N-phenylammonium hydroxide, p-chloronitrobenzene and the like as raw materials through one-step reaction. And in the other step, fluorobenzene or p-chloronitrobenzene is used as a raw material course, and p-fluoroaniline is prepared by reduction.
The patent with the application number of CN201810921419.9 provides a preparation method of p-fluoroaniline, which comprises the following steps: under the catalysis of modified Raney nickel, the p-fluoronitrobenzene is subjected to hydrogenation reduction reaction in a hydrogen atmosphere, and after the reaction is finished, the p-fluoroaniline is obtained through post-treatment; the modified Raney nickel is modified by Mo and Cr. In the above technology, modified Raney nickel is used as a catalyst to prepare p-fluoroaniline, and although the reaction yield can be well improved, the recycling performance and catalytic activity of the catalyst need to be further improved.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the defects existing in the prior art, the invention provides a method for synthesizing p-fluoroaniline based on high-activity framework nickel, which adopts the prepared Zr-MOF material as a framework, adopts a polydopamine layer as an adhesive layer on the surface of the Zr-MOF material, then adds the Zr-MOF material into nickel salt solution, adopts hexamethylenetetramine as a structure guiding agent to adhere on the framework to generate nickel hydroxide nano-sheets, and adopts a composite catalyst formed by calcination treatment to form stacked zirconia microsphere frameworks, wherein the surface of the composite catalyst is modified with a nitrogen-doped carbon layer material, and the nickel oxide nano-sheet layer is deposited on the outer layer of the composite catalyst.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for synthesizing p-fluoroaniline based on high-activity framework nickel comprises the following steps:
(1) Dissolving zirconium chloride and 2-amino terephthalic acid in N, N-dimethylformamide, adding deionized water, stirring for reaction treatment, filtering the reaction solution after the reaction is finished, drying the solid to obtain a Zr-MOF material, adding the Zr-MOF material into a Tris-HCl buffer solution of dopamine for stirring for treatment, filtering, and drying the filtered solid to obtain a polydopamine modified Zr-MOF material;
(2) Dissolving nickel nitrate hexahydrate in deionized water, adding the prepared polydopamine modified Zr-MOF material, adding urea, sodium citrate and hexamethylenetetramine, stirring, heating for reaction, cooling to room temperature after the reaction is finished, filtering the reaction solution, drying the obtained solid, and calcining in a muffle furnace to obtain the porous catalyst;
(3) Adding the prepared porous catalyst into a reactor, adding p-fluoronitrobenzene, adopting nitrogen to replace air in the reactor, introducing hydrogen, heating for reaction, filtering the reaction liquid after the reaction is finished, and carrying out reduced pressure distillation on the filtrate to obtain the p-fluoroaniline.
As a preferable mode of the technical scheme, in the step (1), the molar ratio of zirconium chloride to 2-amino terephthalic acid is 1:1, the stirring reaction temperature is room temperature, and the stirring reaction time is 20-25h.
As a preference of the above technical scheme, in the step (1), the concentration of the Tris-HCl buffer solution is 10mmol/L, the pH is 8.5, the concentration of dopamine is 1-1.5mg/ml, and the mass ratio of dopamine to Zr-MOF material is 1: (2-3).
As a preferable mode of the above technical scheme, in the step (2), the mass ratio of the nickel nitrate hexahydrate, the polydopamine modified Zr-MOF material, urea, sodium citrate and hexamethylenetetramine is 1: (1-2): 1:0.005: (0.01-0.02).
As the preferable choice of the technical scheme, in the step (2), the temperature of the heating reaction is 85-95 ℃ and the time is 5-6h.
As a preferable mode of the technical scheme, in the step (2), the calcining atmosphere is nitrogen, the temperature rising rate during the calcining is 1-2 ℃/min, the calcining temperature is 600 ℃, and the calcining time is 2-3h.
As a preferable mode of the above technical scheme, in the step (3), the mass ratio of the para-fluoroaniline to the porous catalyst is 1: (0.001-0.002).
As a preferable mode of the technical scheme, in the step (3), the temperature during the heating reaction is 75-85 ℃, the pressure of the reactor is 0.6MPa, and the reaction time is 5-6h.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the method takes the p-fluoronitrobenzene as the raw material, and the p-fluoroaniline as the target product is prepared by the reduction reaction of the p-fluoronitrobenzene and hydrogen under the action of the catalyst.
The preparation method comprises the steps of firstly preparing a Zr-MOF material, then in-situ modifying a polydopamine layer on the surface of the Zr-MOF material, penetrating a porous skeleton structure of the Zr-MOF material by the polydopamine layer to form a continuous layer, adhering a nickel hydroxide nano sheet layer on the surface of the polydopamine layer, calcining the polydopamine layer in a nitrogen atmosphere to generate zirconia microspheres, converting the original Zr-MOF material into a continuous nitrogen doped carbon layer serving as a connecting skeleton to realize effective lap joint between the zirconia microspheres, forming a stable skeleton, and positioning the nickel oxide nano sheet formed by calcination on the surface of the skeleton.
Detailed Description
The invention is further illustrated below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
Dissolving 2mol of zirconium chloride and 2mol of 2-amino terephthalic acid in 100ml of N, N-dimethylformamide, adding 2ml of deionized water, stirring at room temperature for reaction treatment for 20 hours, filtering the reaction liquid after the reaction is finished, drying the solid to obtain a Zr-MOF material, adding 1g of Zr-MOF material into 333ml of dopamine Tris-HCl buffer solution with the concentration of 1.5mg/ml, stirring for treatment for 3 hours, filtering, and drying the filtered solid to obtain the polydopamine modified Zr-MOF material;
dissolving 1g of nickel nitrate hexahydrate in deionized water, adding 1g of the prepared polydopamine modified Zr-MOF material, adding 1g of urea, 0.005g of sodium citrate and 0.01g of hexamethylenetetramine, heating to 90 ℃ for reaction for 5 hours after stirring treatment, cooling to room temperature after the reaction is finished, filtering the reaction solution, drying the obtained solid, placing the solid in a muffle furnace, heating to 600 ℃ at a heating rate of 1 ℃/min in nitrogen atmosphere, and calcining for 2 hours to obtain the porous catalyst;
adding 1g of the prepared porous catalyst into a reactor, adding 1000g of p-fluoronitrobenzene, replacing air in the reactor with nitrogen, introducing hydrogen, reacting for 6 hours at 80 ℃ under the pressure of 0.6MPa, filtering the reaction solution after the reaction is finished, and distilling the filtrate under reduced pressure to obtain the p-fluoroaniline.
Example 2
Dissolving 2mol of zirconium chloride and 2mol of 2-amino terephthalic acid in 100ml of N, N-dimethylformamide, adding 2ml of deionized water, stirring at room temperature for reaction for 25 hours, filtering the reaction liquid after the reaction is finished, drying the solid to obtain a Zr-MOF material, adding 1g of Zr-MOF material into 333ml of dopamine Tris-HCl buffer solution with the concentration of 1.5mg/ml for stirring for 3 hours, filtering, and drying the filtered solid to obtain the polydopamine modified Zr-MOF material;
dissolving 1g of nickel nitrate hexahydrate in deionized water, adding 1g of the prepared polydopamine modified Zr-MOF material, adding 1g of urea, 0.005g of sodium citrate and 0.02g of hexamethylenetetramine, heating to 90 ℃ for reaction for 6 hours after stirring treatment, cooling to room temperature after the reaction is finished, filtering the reaction solution, drying the obtained solid, placing the solid in a muffle furnace, heating to 600 ℃ at a heating rate of 1.5 ℃/min in nitrogen atmosphere, and calcining for 2 hours to obtain the porous catalyst;
adding 1g of the prepared porous catalyst into a reactor, adding 1000g of p-fluoronitrobenzene, replacing air in the reactor with nitrogen, introducing hydrogen, reacting for 6 hours at 80 ℃ under the pressure of 0.6MPa, filtering the reaction solution after the reaction is finished, and distilling the filtrate under reduced pressure to obtain the p-fluoroaniline.
Example 3
Dissolving 2mol of zirconium chloride and 2mol of 2-amino terephthalic acid in 100ml of N, N-dimethylformamide, adding 2ml of deionized water, stirring at room temperature for reaction for 22 hours, filtering the reaction liquid after the reaction is finished, drying the solid to obtain a Zr-MOF material, adding 1g of Zr-MOF material into 333ml of dopamine Tris-HCl buffer solution with the concentration of 1.5mg/ml, stirring for 3 hours, filtering, and drying the filtered solid to obtain the polydopamine modified Zr-MOF material;
dissolving 1g of nickel nitrate hexahydrate in deionized water, adding 1g of the prepared polydopamine modified Zr-MOF material, adding 1g of urea, 0.005g of sodium citrate and 0.015g of hexamethylenetetramine, heating to 90 ℃ for reaction for 5 hours after stirring treatment, cooling to room temperature after the reaction is finished, filtering the reaction solution, drying the obtained solid, placing the solid in a muffle furnace, heating to 600 ℃ at a heating rate of 1 ℃/min in nitrogen atmosphere, and calcining for 3 hours to obtain the porous catalyst;
adding 1.2g of the prepared porous catalyst into a reactor, adding 1000g of p-fluoronitrobenzene, replacing air in the reactor with nitrogen, introducing hydrogen, reacting for 6 hours at 80 ℃ under the pressure of 0.6MPa, filtering the reaction solution after the reaction is finished, and distilling the filtrate under reduced pressure to obtain the p-fluoroaniline.
Example 4
Dissolving 2mol of zirconium chloride and 2mol of 2-amino terephthalic acid in 100ml of N, N-dimethylformamide, adding 2ml of deionized water, stirring at room temperature for reaction for 23 hours, filtering the reaction liquid after the reaction is finished, drying the solid to obtain a Zr-MOF material, adding 1g of Zr-MOF material into 333ml of dopamine Tris-HCl buffer solution with the concentration of 1.5mg/ml for stirring for 3 hours, filtering, and drying the filtered solid to obtain the polydopamine modified Zr-MOF material;
dissolving 1g of nickel nitrate hexahydrate in deionized water, adding 1g of the prepared polydopamine modified Zr-MOF material, adding 1g of urea, 0.005g of sodium citrate and 0.015g of hexamethylenetetramine, heating to 90 ℃ for reaction for 5 hours after stirring treatment, cooling to room temperature after the reaction is finished, filtering the reaction solution, drying the obtained solid, placing the solid in a muffle furnace, heating to 600 ℃ at a heating rate of 1.5 ℃/min in nitrogen atmosphere, and calcining for 2 hours to obtain the porous catalyst;
adding 1g of the prepared porous catalyst into a reactor, adding 1000g of p-fluoronitrobenzene, replacing air in the reactor with nitrogen, introducing hydrogen, reacting for 6 hours at 80 ℃ under the pressure of 0.6MPa, filtering the reaction solution after the reaction is finished, and performing reduced pressure distillation on the filtrate to obtain the p-fluoroaniline.
Example 5
Dissolving 2mol of zirconium chloride and 2mol of 2-amino terephthalic acid in 100ml of N, N-dimethylformamide, adding 2ml of deionized water, stirring at room temperature for reaction for 24 hours, filtering the reaction liquid after the reaction is finished, drying the solid to obtain a Zr-MOF material, adding 1g of Zr-MOF material into 333ml of dopamine Tris-HCl buffer solution with the concentration of 1.5mg/ml for stirring for 3 hours, filtering, and drying the filtered solid to obtain the polydopamine modified Zr-MOF material;
dissolving 1g of nickel nitrate hexahydrate in deionized water, adding 1g of the prepared polydopamine modified Zr-MOF material, adding 1g of urea, 0.005g of sodium citrate and 0.015g of hexamethylenetetramine, heating to 90 ℃ for reaction for 5 hours after stirring treatment, cooling to room temperature after the reaction is finished, filtering the reaction solution, drying the obtained solid, placing the solid in a muffle furnace, heating to 600 ℃ at a heating rate of 1.5 ℃/min in nitrogen atmosphere, and calcining for 2 hours to obtain the porous catalyst;
adding 1g of the prepared porous catalyst into a reactor, adding 1000g of p-fluoronitrobenzene, replacing air in the reactor with nitrogen, introducing hydrogen, reacting for 6 hours at 80 ℃ under the pressure of 0.6MPa, filtering the reaction solution after the reaction is finished, and distilling the filtrate under reduced pressure to obtain the p-fluoroaniline.
Comparative example
The porous catalyst prepared in example 5 was subjected to catalytic reaction-washing cycle 5 times and then subjected to catalytic reaction again, and the conditions for specific catalytic reaction were the same as those in example 5.
The following is carried out to track the yield and purity of the product, and the calculation method of the yield of the target product is as follows: (actual yield of target product/theoretical yield of target product). Times.100%, the test results are shown in Table 1.
TABLE 1
Yield% Purity of%
Example 1 98.9 99.2
Example 2 98.9 99.2
Example 3 98.8 99.2
Example 4 98.9 99.2
Example 5 98.9 99.2
Comparative example 97.5 99.0
The test results show that the product prepared by the method provided by the invention has high purity and obviously improved yield. The catalyst provided by the invention has no obvious reduction in catalytic performance after 5 times of catalytic reaction-washing cycle.
Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.

Claims (7)

1. The method for synthesizing the p-fluoroaniline based on the high-activity framework nickel is characterized by comprising the following steps of:
(1) Dissolving zirconium chloride and 2-amino terephthalic acid in N, N-dimethylformamide, adding deionized water, stirring for reaction treatment, filtering the reaction solution after the reaction is finished, drying the solid to obtain a Zr-MOF material, adding the Zr-MOF material into a Tris-HCl buffer solution of dopamine for stirring for treatment, filtering, and drying the filtered solid to obtain a polydopamine modified Zr-MOF material;
(2) Dissolving nickel nitrate hexahydrate in deionized water, adding the prepared polydopamine modified Zr-MOF material, adding urea, sodium citrate and hexamethylenetetramine, stirring, heating for reaction, cooling to room temperature after the reaction is finished, filtering the reaction solution, drying the obtained solid, and calcining in a muffle furnace to obtain the porous catalyst;
(3) Adding the prepared porous catalyst into a reactor, adding p-fluoronitrobenzene, adopting nitrogen to replace air in the reactor, introducing hydrogen, heating for reaction, filtering the reaction liquid after the reaction is finished, and carrying out reduced pressure distillation on the filtrate to obtain p-fluoroaniline; the mass ratio of the p-fluoroaniline to the porous catalyst is 1: (0.001-0.002).
2. The method for synthesizing p-fluoroaniline from high-activity skeletal nickel according to claim 1, wherein in the step (1), the molar ratio of zirconium chloride to 2-amino terephthalic acid is 1:1, the stirring reaction temperature is room temperature, and the stirring reaction time is 20-25h.
3. The method for synthesizing p-fluoroaniline based on high activity skeletal nickel according to claim 1, wherein in the step (1), the concentration of the Tris-HCl buffer solution is 10mmol/L, the pH is 8.5, the concentration of dopamine is 1-1.5mg/ml, and the mass ratio of dopamine to Zr-MOF material is 1: (2-3).
4. The method for synthesizing p-fluoroaniline based on high activity skeletal nickel according to claim 1, wherein in the step (2), the mass ratio of nickel nitrate hexahydrate, polydopamine modified Zr-MOF material, urea, sodium citrate and hexamethylenetetramine is 1: (1-2): 1:0.005: (0.01-0.02).
5. The method for synthesizing p-fluoroaniline from high-activity skeletal nickel according to claim 1, wherein in the step (2), the temperature of the heating reaction is 85-95 ℃ for 5-6h.
6. The method for synthesizing p-fluoroaniline from high-activity skeletal nickel according to claim 1, wherein in the step (2), the calcining atmosphere is nitrogen, the temperature rising rate during the calcining is 1-2 ℃/min, the calcining temperature is 600 ℃, and the calcining time is 2-3h.
7. The method for synthesizing p-fluoroaniline from high-activity skeletal nickel according to claim 1, wherein in the step (3), the heating reaction is carried out at a temperature of 75-85 ℃, the reactor pressure is 0.6MPa, and the reaction time is 5-6h.
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