CN113181923A - Method for preparing NiZnTi catalyst by coprecipitation and application of NiZnTi catalyst in hydrogenation reaction of nitroaromatic or halogenated nitroaromatic - Google Patents

Method for preparing NiZnTi catalyst by coprecipitation and application of NiZnTi catalyst in hydrogenation reaction of nitroaromatic or halogenated nitroaromatic Download PDF

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CN113181923A
CN113181923A CN202110518702.9A CN202110518702A CN113181923A CN 113181923 A CN113181923 A CN 113181923A CN 202110518702 A CN202110518702 A CN 202110518702A CN 113181923 A CN113181923 A CN 113181923A
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catalyst
kettle
niznti
nitroaromatic
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刘平乐
刘煜
熊伟
郝芳
吕扬
罗和安
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Xiangtan University
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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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
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    • 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

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Abstract

The invention discloses a method for preparing a NiZnTi catalyst by coprecipitation and application of the NiZnTi catalyst in hydrogenation reaction of nitroaromatic or halogenated nitroaromatic. The NiZnTi catalyst is obtained by coprecipitation reaction of nickel salt, zinc salt and titanium salt. The catalyst obtained by the invention can improve the yield of aromatic amine under mild reaction conditions, is low in cost, economical, effective, strong in universality, environment-friendly and free of corrosion to equipment, effectively improves production conditions, reduces production cost and improves product quality. The invention adopts a very simple and effective coprecipitation method for preparation, is simple and controllable, not only can obviously reduce the cost, but also can have higher catalytic activity in the reaction of preparing aromatic amine or halogenated aromatic amine by hydrogenation of nitroaromatic or halogenated nitroaromatic.

Description

Method for preparing NiZnTi catalyst by coprecipitation and application of NiZnTi catalyst in hydrogenation reaction of nitroaromatic or halogenated nitroaromatic
Technical Field
The invention relates to preparation of a catalyst, in particular to a method for preparing a NiZnTi catalyst by coprecipitation and application of the NiZnTi catalyst in hydrogenation reaction of nitroaromatic or halogenated nitroaromatic.
Background
The aromatic amine is an intermediate of various dye products such as direct dye, acid dye, ice dye, disperse dye and the like, is also a main raw material of pesticide, herbicide and various rubber anti-aging agents, and is an important intermediate of a plurality of special chemicals. The traditional process for producing aromatic amine is to reduce corresponding nitroaromatic hydrocarbon by using Fe/HCl (Bechamp method) or sulfide reduction method, but the process has many defects, such as complex route, low yield, and serious environmental pollution caused by formation of a large amount of waste water. Therefore, a great deal of researchers focus on liquid-phase catalytic hydrogenation reaction, and the aromatic amine is prepared by catalytic hydrogenation with a supported noble metal catalyst, and the noble metal catalyst such as Pt, Pd, Au, Ru and the like is applied to the preparation of the aromatic amine by hydrogenation of nitroarene, and shows excellent catalytic performance. However, the high cost and scarce resources of such catalysts have greatly limited their widespread use in industry.
The invention CN102989476A relates to a nickel-based saturated hydrogenation catalyst, which is a catalyst containing Ni, Zn and other components simultaneously and obtained by an impregnation method without using noble metals, and can show good catalytic performance in the hydrogenation reaction of unsaturated hydrocarbons such as olefin. However, in order to obtain higher strength, the catalyst adopts an impregnation method to load a main active ingredient and a plurality of auxiliary active ingredients on a carrier, which finally still causes higher cost and increases the uncontrollable property of the process due to excessive components.
In view of the above, there is a need to find a catalyst with low cost, high activity, high selectivity and high stability for preparing aromatic amine by catalytic hydrogenation of nitroarene.
Disclosure of Invention
Aiming at the problem that the prior industrial application of preparing aromatic amine or halogenated aromatic amine by hydrogenating nitro-aromatic hydrocarbon or halogenated nitro-aromatic hydrocarbon adopts iron powder reduction or sodium sulfide reduction to seriously pollute the environment and has low yield; the noble metal catalyst is adopted, so that the cost is high; the invention provides a method for preparing a NiZnTi catalyst by coprecipitation and application thereof in hydrogenation reaction of nitroaromatic, which adopts a very simple and effective coprecipitation method for preparation, is simple and controllable, not only can obviously reduce the cost, but also has higher catalytic activity in the reaction of preparing aromatic amine or halogenated aromatic amine by hydrogenation of nitroaromatic or halogenated nitroaromatic.
The technical scheme of the invention is as follows:
the method for preparing the NiZnTi catalyst by coprecipitation is characterized in that the NiZnTi catalyst is obtained by coprecipitation reaction of nickel salt, zinc salt and titanium salt.
Further, the method comprises the steps of:
(1) dissolving nickel salt, zinc salt and titanium salt in water to obtain a mixed solution of metal salt;
(2) slowly adding (preferably at an adding speed of 5-15 mL/min) the alkaline solution into the mixed solution obtained in the step (1) under the stirring condition until the pH value is 9-11, then continuously stirring at 70-100 ℃ for 12-36 hours, centrifuging the obtained turbid solution, washing to be neutral, and drying;
(3) roasting the dried solid obtained in the step (2);
(4) and (4) reducing the solid roasted in the step (3) to obtain a final product, namely the NiZnTi catalyst.
Further, in the step (1), the nickel salt is one or more than two of nickel acid, nickel chloride, nickel bromide, nickel sulfate and nickel acetate; the zinc salt is one or more than two of zinc nitrate, zinc sulfate, zinc chloride and zinc sulfate; the titanium salt is one or more than two of titanium sulfate, tetrabutyl titanate, titanyl sulfate and titanium tetrachloride.
Further, in the step (1), the amount ratio of the nickel salt, the zinc salt and the titanium salt is 0.5-6: 0.8-1.2, wherein the amount ratio of the zinc to the nickel is 0-4: 0-4, and the amount ratio of the zinc to the nickel is 0, preferably 0.05-4: 0.05-4.
In step (2), the alkaline solution is a sodium carbonate solution or/and a sodium hydroxide solution, preferably a mixed solution of sodium carbonate and sodium hydroxide, and more preferably the mass ratio of sodium carbonate to sodium hydroxide is 2-3: 3-5.
Further, in the step (3), the roasting temperature is 350-550 ℃, more preferably 400-500 ℃, and the roasting time is 1-4 hours, preferably 2-3 hours; roasting is carried out in a muffle furnace; and (3) heating the roasting by adopting a programmed heating method, wherein the heating rate is preferably 3-6 ℃/min.
Further, in the step (4), the reduction temperature is 400-550 ℃, more preferably 450-500 ℃, and the reduction time is 1-4 hours, preferably 2-3 hours; the reduction is carried out in a tube furnace; and (3) heating the reduction by adopting a programmed heating method, wherein the heating rate is preferably 3-6 ℃/min.
The NiZnTi catalyst obtained by the method can also be applied to the reaction of preparing aromatic amine or halogenated aromatic amine by hydrogenation of nitroaromatic or halogenated nitroaromatic.
Further, the application comprises the following steps: adding a NiZnTi catalyst with the mass of 5-20% of that of the nitroaromatic or the halogenated nitroaromatic and the nitroaromatic or the halogenated nitroaromatic into a high-pressure reaction kettle, adding an organic solvent, then adding magnetons, sealing the high-pressure kettle, replacing the air in the kettle with nitrogen for 2-5 times, heating to 50-80 ℃, introducing hydrogen, pressurizing to 0.5-0.8MPa, and reacting for 4-8 hours.
Further, the organic solvent is one or more than two of N, N-dimethylformamide, methanol or ethanol, and the dosage ratio of the organic solvent to the nitro aromatic hydrocarbon or the halogenated nitro aromatic hydrocarbon is 10-30 ml: 0.5 to 2 g.
The invention has the beneficial effects that:
(1) obtained by coprecipitationThe catalyst is generally considered to have insufficient strength, however, the catalyst obtained by the present invention, Ti, Zn and Ni can exert better interaction, so that higher strength is obtained, and the reaction-deactivated catalyst can be regenerated by means of hydrogen reduction. And can effectively adjust TiO by changing the proportion of Ni and Zn2The interaction among the three species of Zn and Ni can effectively improve the content of active metal on the surface of the catalyst and the content of oxygen vacancy, reduce the size of Ni and further improve the activity.
(2) The catalyst obtained by the invention can improve the yield of aromatic amine under relatively mild reaction conditions, is low in cost, economical, effective, strong in universality, environment-friendly and free of corrosion to equipment, effectively improves production conditions, reduces production cost and improves product quality.
Drawings
FIG. 1 shows Ni at different Ni/Zn ratiosxZnyTi1XRD pattern of catalyst: (a) ni1Ti1,(b)Ni0.8Zn0.2Ti1,(c)Ni0.67Zn0.33Ti1,(d)Ni0.5Zn0.5Ti1,(e)Ni0.33Zn0.67Ti1,(f)Ni0.2Zn0.8Ti1,(g)Zn1Ti1. As shown in FIG. 1, no TiO interaction was found in the XRD spectra of all samples2Peak of correlation, which may be due to TiO2In the form of an amorphous phase. In Ni1Ti1Has peaks associated with metal Ni at 2 θ 44.5, 51.8 and 76.4 °. With the introduction of zinc, the diffraction peak of the NiZn alloy phase shifts to a low angle, and the lower the Ni/Zn ratio, the more pronounced the shift.
FIG. 2 shows four typical samples (Ni)0.5Zn0.5Ti1,Ni0.67Zn0.33Ti1,Ni0.33Zn0.67Ti1And Ni1Ti1) An EPR map of (1). Four samples showed significant signals at g 2.004 and g 1.989, the former due to oxygen vacancies in the samples and the latter assignable to Ti3+. As can be seen from FIG. 2, Ni0.5Zn0.5Ti1Has the highestOxygen vacancy concentration.
FIG. 3 shows Ni1Ti1(a) And Ni0.5Zn0.5Ti1(b) High resolution transmission electron microscope images of two samples, and finding Ni by measuring lattice spacing0.5Zn0.5Ti1The lattice spacing of the Ni (111) crystal plane in the sample was 0.205nm (FIG. 3b), Ni1Ti1The lattice spacing of the Ni (111) crystal planes in the sample was 0.203nm (fig. 3a), indicating that the introduction of Zn results in the formation of a nickel zinc alloy. In addition, in Ni0.5Zn0.5Ti1Lattice spacing of d ═ 0.254nm was found in the samples, corresponding to ZnTiO3The (110) crystal plane of (a). Furthermore, no lattice spacing matching with titania was observed by high resolution transmission electron microscopy characterization, indicating that titania is indeed present in an amorphous form.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto.
Example 1
Ni0.2Zn0.8Ti1Preparation of
(1) Two solutions were prepared, solution a: weighing a certain amount of Zn (NO)3)2,Ni(NO3)2,Ti(SO4)2Dissolved in 60mL of distilled water, wherein Ti (SO)4)2Has a concentration of 0.1mol/L, Ni (NO)3)2In a concentration of 0.02mol/L, Zn (NO)3)2The concentration of (A) is 0.08 mol/L; solution B: weighing a certain amount of NaCO3And NaOH in 60mL of distilled water, wherein NaCO3The concentration is 0.3mol/L, and the concentration of NaOH is 0.4 mol/L.
(2) During stirring, solution B was added to solution A at a rate of 10mL/min until the pH was 10. Then stirring for 24h at 90 ℃, centrifugally washing the obtained turbid solution to be neutral, and drying at 70 ℃ overnight;
(3) the dried solid was ground to a powder in a mortar and then placed in a muffle furnace for calcination: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increase rate of 5 ℃/min; the second section is roasted for 2h at 500 ℃ and 500 ℃; cooling to room temperature in the third section;
(4) placing the baked powder into a tubular furnace for programmed temperature rise reduction: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increasing rate of 5 ℃/min under the protection of nitrogen; the second section is reduced for 2h under the hydrogen condition of 500 ℃ and 500 ℃; cooling to room temperature under the protection of nitrogen in the third section to obtain Ni0.2Zn0.8Ti1。
Example 2
Ni0.33Zn0.67Ti1Preparation of
(1) Two solutions were prepared, solution a: weighing a certain amount of Zn (NO)3)2,Ni(NO3)2,Ti(SO4)2Dissolved in 60mL of distilled water, wherein Ti (SO)4)2Has a concentration of 0.1mol/L, Ni (NO)3)2Has a concentration of 0.033mol/L, Zn (NO)3)2The concentration of (A) is 0.067 mol/L; solution B: weighing a certain amount of NaCO3And NaOH in 60mL of distilled water, wherein NaCO3The concentration is 0.3mol/L, and the concentration of NaOH is 0.4 mol/L.
(2) During stirring, solution B was added to solution A at a rate of 10mL/min until the pH was 10. Then stirring for 24h at 90 ℃, centrifugally washing the obtained turbid solution to be neutral, and drying at 70 ℃ overnight;
(3) the dried solid was ground to a powder in a mortar and then placed in a muffle furnace for calcination: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increase rate of 5 ℃/min; the second section is roasted for 2h at 500 ℃ and 500 ℃; cooling to room temperature in the third section;
(4) placing the baked powder into a tubular furnace for programmed temperature rise reduction: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increasing rate of 5 ℃/min under the protection of nitrogen; the second section is reduced for 2h under the hydrogen condition of 500 ℃ and 500 ℃; cooling to room temperature under the protection of nitrogen in the third section to obtain Ni0.33Zn0.67Ti1。
Example 3
Ni0.5Zn0.5Ti1Preparation of
(1) Two solutions were prepared, solution a: weighing a certain amount of Zn (NO)3)2,Ni(NO3)2,Ti(SO4)2Dissolved in 60mL of distilled water, wherein Ti (SO)4)2Has a concentration of 0.1mol/L, Ni (NO)3)2Has a concentration of 0.05mol/L, Zn (NO)3)2The concentration of (A) is 0.05 mol/L; solution B: weighing a certain amount of NaCO3And NaOH in 60mL of distilled water, wherein NaCO3The concentration is 0.3mol/L, and the concentration of NaOH is 0.4 mol/L.
(2) During stirring, solution B was added to solution A at a rate of 10mL/min until the pH was 10. Then stirring for 24h at 90 ℃, centrifugally washing the obtained turbid solution to be neutral, and drying at 70 ℃ overnight;
(3) the dried solid was ground to a powder in a mortar and then placed in a muffle furnace for calcination: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increase rate of 5 ℃/min; the second section is roasted for 2h at 500 ℃ and 500 ℃; cooling to room temperature in the third section;
(4) placing the baked powder into a tubular furnace for programmed temperature rise reduction: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increasing rate of 5 ℃/min under the protection of nitrogen; the second section is reduced for 2h under the hydrogen condition of 500 ℃ and 500 ℃; cooling to room temperature under the protection of nitrogen in the third section to obtain Ni0.5Zn0.5Ti1。
Example 4
Ni0.67Zn0.33Ti1Preparation of
(1) Two solutions were prepared, solution a: weighing a certain amount of Zn (NO)3)2,Ni(NO3)2,Ti(SO4)2Dissolved in 60mL of distilled water, wherein Ti (SO)4)2Has a concentration of 0.1mol/L, Ni (NO)3)2Has a concentration of 0.067mol/L, Zn (NO)3)2The concentration of (A) is 0.033 mol/L; solution B: weighing a certain amount of NaCO3And NaOH in 60mL of distilled water, wherein NaCO3The concentration is 0.3mol/L, and the concentration of NaOH is 0.4 mol/L.
(2) During stirring, solution B was added to solution A at a rate of 10mL/min until the pH was 10. Then stirring for 24h at 90 ℃, centrifugally washing the obtained turbid solution to be neutral, and drying at 70 ℃ overnight;
(3) the dried solid was ground to a powder in a mortar and then placed in a muffle furnace for calcination: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increase rate of 5 ℃/min; the second section is roasted for 2h at 500 ℃ and 500 ℃; cooling to room temperature in the third section;
(4) placing the baked powder into a tubular furnace for programmed temperature rise reduction: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increasing rate of 5 ℃/min under the protection of nitrogen; the second section is reduced for 2h under the hydrogen condition of 500 ℃ and 500 ℃; cooling to room temperature under the protection of nitrogen in the third section to obtain Ni0.67Zn0.33Ti1。
Example 5
Ni0.8Zn0.2Ti1Preparation of
(1) Two solutions were prepared, solution a: weighing a certain amount of Zn (NO)3)2,Ni(NO3)2,Ti(SO4)2Dissolved in 60mL of distilled water, wherein Ti (SO)4)2Has a concentration of 0.1mol/L, Ni (NO)3)2Has a concentration of 0.08mol/L, Zn (NO)3)2The concentration of (A) is 0.02 mol/L; solution B: weighing a certain amount of NaCO3And NaOH in 60mL of distilled water, wherein NaCO3The concentration is 0.3mol/L, and the concentration of NaOH is 0.4 mol/L.
(2) During stirring, solution B was added to solution A at a rate of 10mL/min until the pH was 10. Then stirring for 24h at 90 ℃, centrifugally washing the obtained turbid solution to be neutral, and drying at 70 ℃ overnight;
(3) the dried solid was ground to a powder in a mortar and then placed in a muffle furnace for calcination: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increase rate of 5 ℃/min; the second section is roasted for 2h at 500 ℃ and 500 ℃; cooling to room temperature in the third section;
(4) placing the baked powder into a tubular furnace for programmed temperature rise reduction: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increasing rate of 5 ℃/min under the protection of nitrogen; the second section is reduced for 2h under the hydrogen condition of 500 ℃ and 500 ℃; cooling to room temperature under the protection of nitrogen in the third section to obtain Ni0.8Zn0.2Ti1。
Example 6
Ni2Zn1Ti1Preparation of
(1) Two solutions were prepared, solution a: weighing a certain amount of Zn (NO)3)2，Ni(NO3)2，Ti(SO4)2Dissolved in 60mL of distilled water, wherein Ti (SO)4)2Has a concentration of 0.1mol/L, Ni (NO)3)2Has a concentration of 0.2mol/L, Zn (NO)3)2The concentration of (A) is 0.1 mol/L; solution B: weighing a certain amount of NaCO3And NaOH in 60mL of distilled water, wherein NaCO3The concentration is 0.3mol/L, and the concentration of NaOH is 0.6 mol/L;
(2) during stirring, solution B was added to solution A at a rate of 10mL/min until the pH was 10. Then stirring for 24h at 90 ℃, centrifugally washing the obtained turbid solution to be neutral, and drying at 70 ℃ overnight;
(3) the dried solid was ground to a powder in a mortar and then placed in a muffle furnace for calcination: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increase rate of 5 ℃/min; the second section is roasted for 2h at 500 ℃ and 500 ℃; cooling to room temperature in the third section;
(4) placing the baked powder into a tubular furnace for programmed temperature rise reduction: in the first stage, the temperature is increased at the temperature of 30-500 ℃ at the temperature increasing rate of 5 ℃/min under the protection of nitrogen; the second section is reduced for 2h under the hydrogen condition of 500 ℃ and 500 ℃; cooling to room temperature under the protection of nitrogen in the third section to obtain Ni2Zn1Ti1。
Example 7
0.1g of Ni was weighed1Ti1Adding 20mL of N, N-dimethylformamide and 1g of 1-nitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 70 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 0.6MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction liquid is subjected to liquid chromatography analysis, and the conversion rate of 1-nitronaphthalene is improved40.04 percent and the selectivity of 1-naphthylamine is 84.64 percent.
Example 8
0.1g of Ni was weighed0.2Zn0.8Ti1Adding 20mL of N, N-dimethylformamide and 1g of 1-nitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 70 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 0.6MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction solution is analyzed by liquid chromatography, the conversion rate of 1-nitronaphthalene is 46.24%, and the selectivity of 1-naphthylamine is 86.61%.
Example 9
0.1g of Ni was weighed0.33Zn0.67Ti1Adding 20mL of N, N-dimethylformamide and 1g of 1-nitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 70 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 0.6MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction solution was subjected to liquid chromatography, and the conversion of 1-nitronaphthalene was 84.4% and the selectivity of 1-naphthylamine was 73.56%.
Example 10
0.1g of Ni was weighed0.67Zn0.33Ti1Adding 20mL of N, N-dimethylformamide and 1g of 1-nitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 70 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 0.6MPa of reaction pressure, and recording the reaction starting time; after 5 hours, the reaction was completed, the electric heating kettle and hydrogen were shut offA main valve of the bottle is used for naturally cooling the reaction kettle to room temperature; the obtained reaction solution was subjected to liquid chromatography, and the conversion of 1-nitronaphthalene was 92.3% and the selectivity of 1-naphthylamine was 75.56%.
Example 11
0.1g of Ni was weighed0.8Zn0.2Ti1Adding 20mL of N, N-dimethylformamide and 1g of 1-nitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 70 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 0.6MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction solution was subjected to liquid chromatography, and the conversion of 1-nitronaphthalene was 83.83% and the selectivity of 1-naphthylamine was 91.21%.
Example 12
0.1g of Ni was weighed0.5Zn0.5Ti1Adding 20mL of N, N-dimethylformamide and 1g of 1-nitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 70 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 0.6MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction solution was subjected to liquid chromatography, and the conversion of 1-nitronaphthalene was 99.57% and the selectivity of 1-naphthylamine was 93.56%.
Example 13
0.1g of Ni was weighed0.5Zn0.5Ti1Adding 20mL of N, N-dimethylformamide and 1g of 1-nitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 80 ℃, opening the main valve and the air inlet valve of the hydrogen cylinder, and adding pressureUntil the reaction pressure is 0.6MPa, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction solution is subjected to liquid chromatography analysis, the conversion rate of the 1-nitronaphthalene is 100 percent, and the selectivity of the 1-naphthylamine is 100 percent.
Example 14
0.1g of Ni was weighed0.5Zn0.5Ti1Adding 20mL of ethanol and 1g of 1-nitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 80 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 0.6MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction solution is subjected to liquid chromatography analysis, the conversion rate of the 1-nitronaphthalene is 100 percent, and the selectivity of the 1-naphthylamine is 100 percent.
Example 15
0.1g of Ni was weighed0.5Zn0.5Ti1Adding 20mL of ethanol and 1g of nitrobenzene into a catalyst in a high-pressure reaction kettle, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 70 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 1.0MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction solution was subjected to liquid chromatography, and the nitrobenzene conversion was 100% and the aniline selectivity was 100%.
Example 16
0.1g of Ni was weighed0.5Zn0.5Ti1Adding 20mL of ethanol and 1g of o-chloronitrobenzene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; opening the kettle when the temperature in the kettle reaches 70 DEG CA main valve of a hydrogen cylinder and an air inlet valve, wherein the pressure is increased to 1.0MPa of reaction pressure, and the reaction starting time is recorded; after 7 hours, the reaction is finished, the electric heating kettle and the hydrogen cylinder main valve are closed, and the reaction kettle is naturally cooled to the room temperature; the obtained reaction solution is subjected to liquid chromatography analysis, the conversion rate of o-chloronitrobenzene is 100 percent, and the selectivity of o-chloroaniline is 97.2 percent.
Example 17
0.1g of Ni was weighed0.5Zn0.5Ti1Adding 20mL of ethanol and 1g of m-chloronitrobenzene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 70 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 1.0MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction solution is subjected to liquid chromatography analysis, the conversion rate of m-chloronitrobenzene is 100 percent, and the selectivity of m-chloroaniline is 98.8 percent.
Example 18
0.1g of Ni was weighed0.5Zn0.5Ti1Adding 20mL of ethanol and 1g of p-chloronitrobenzene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 70 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 1.0MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction solution was subjected to liquid chromatography, and the conversion of p-chloronitrobenzene was 100% and the selectivity of p-chloroaniline was 98.0%.
Example 19
0.1g of Ni was weighed0.5Zn0.5Ti1Adding 20mL of N, N-dimethylformamide and 1g of 1, 5-dinitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; sealing the kettle, replacing air in the kettle with hydrogen for 4 times, and then using a vacuum pump to replace the kettleVacuumizing the inner part, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 100 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 1.0MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction liquid is analyzed by liquid chromatography, the conversion rate of the 1, 5-dinitronaphthalene is 100 percent, and the selectivity of the 1, 5-diaminonaphthalene is 100 percent.
Example 20
0.1g of Ni was weighed0.5Zn0.5Ti1Adding 20mL of N, N-dimethylformamide and 1g of 1, 8-dinitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 100 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 1.0MPa of reaction pressure, and recording the reaction starting time; after 8 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction liquid is analyzed by liquid chromatography, the conversion rate of the 1, 8-dinitronaphthalene is 100 percent, and the selectivity of the 1, 8-diaminonaphthalene is 100 percent.
Example 21
0.1g of Ni was weighed2Zn1Ti1Adding 20mL of N, N-dimethylformamide and 1g of 1-nitronaphthalene into a high-pressure reaction kettle by using a catalyst, and then adding magnetons; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 60 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 0.6MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; the obtained reaction solution was subjected to liquid chromatography, and the conversion rate of 1-nitronaphthalene was 99.99% and the selectivity of 1-naphthylamine was 99.99%.
Example 22
0.1g of Ni was weighed0.5Zn0.5Ti1Adding 20mL of N, N-bis in a high-pressure reaction kettleMethyl formamide and 1g 1-nitronaphthalene, and then magnetons are added; after the kettle is sealed, replacing air in the kettle with hydrogen for 4 times, vacuumizing the kettle by using a vacuum pump, and putting the kettle into a jacket of an electric heating kettle for heating; when the temperature in the kettle reaches 80 ℃, opening a main valve of a hydrogen cylinder and an air inlet valve, increasing the pressure to 0.6MPa of reaction pressure, and recording the reaction starting time; after 5 hours, closing the electric heating kettle and the hydrogen cylinder main valve, and naturally cooling the reaction kettle to room temperature; performing liquid chromatography analysis on the obtained reaction solution, wherein the conversion rate of the 1-nitronaphthalene is 99.99 percent, and the selectivity of the 1-naphthylamine is 99.99 percent; centrifugally filtering out the catalyst, directly carrying out a second reaction on the recovered catalyst under the same reaction conditions without any treatment, and carrying out liquid chromatography on the obtained reaction liquid to obtain a reaction liquid with the 1-nitronaphthalene conversion rate of 99.99 percent and the 1-naphthylamine selectivity of 96.2 percent; centrifugally filtering out the catalyst, directly carrying out a third reaction on the recovered catalyst under the same reaction conditions without any treatment, and carrying out liquid chromatography analysis on the obtained reaction liquid to obtain a product with the 1-nitronaphthalene conversion rate of 72.6% and the 1-naphthylamine selectivity of 92.5%; centrifugally filtering out the catalyst, directly carrying out fourth reaction on the recovered catalyst under the same reaction conditions without any treatment, and carrying out liquid chromatography analysis on the obtained reaction liquid to obtain the product with the 1-nitronaphthalene conversion rate of 64% and the 1-naphthylamine selectivity of 51.5%; and (3) centrifugally filtering out the catalyst, calcining the recovered catalyst for 2 hours at 500 ℃ in a hydrogen atmosphere, carrying out a fifth reaction under the same reaction conditions, and carrying out liquid chromatography analysis on the obtained reaction liquid to obtain the product with the 1-nitronaphthalene conversion rate of 95.8% and the 1-naphthylamine selectivity of 97.5%.

Claims (10)

1. The method for preparing the NiZnTi catalyst by coprecipitation is characterized in that the NiZnTi catalyst is obtained by coprecipitation reaction of nickel salt, zinc salt and titanium salt.
2. A method for preparing a NiZnTi catalyst by coprecipitation according to claim 1, characterized in that it comprises the following steps:
(1) dissolving nickel salt, zinc salt and titanium salt in water to obtain a mixed solution of metal salt;
(2) slowly adding an alkaline solution into the mixed solution obtained in the step (1) under the stirring condition until the pH value is 9-11, then continuously stirring for 12-36 hours at 70-100 ℃, centrifuging the obtained turbid solution, washing to be neutral, and drying;
(3) roasting the dried solid obtained in the step (2);
(4) and (4) reducing the solid roasted in the step (3) to obtain a final product, namely the NiZnTi catalyst.
3. The method for preparing the NiZnTi catalyst by coprecipitation according to claim 1, wherein in the step (1), the nickel salt is one or more of nickel nitrate, nickel chloride, nickel bromide, nickel sulfate and nickel acetate; the zinc salt is one or more than two of zinc nitrate, zinc sulfate, zinc chloride and zinc sulfate; the titanium salt is one or more than two of titanium sulfate, tetrabutyl titanate, titanyl sulfate and titanium tetrachloride.
4. The coprecipitation method of claim 1, wherein in step (1), the amount ratio of the nickel salt, the zinc salt, and the titanium salt is 0.5 to 6:0.8 to 1.2, wherein the amount ratio of the zinc to the nickel is 0 to 4:0 to 4, and 0 is excluded.
5. The method for preparing the NiZnTi catalyst by coprecipitation according to claim 1, wherein in the step (2), the alkaline solution is a sodium carbonate solution or/and a sodium hydroxide solution; when the alkaline solution is a mixed solution of sodium carbonate and sodium hydroxide, the mass ratio of the sodium carbonate to the sodium hydroxide is 2-3: 3-5.
6. The method for preparing the NiZnTi catalyst by coprecipitation according to claim 1, wherein in the step (3), the roasting temperature is 350-550 ℃, and the roasting time is 1-4 hours; roasting is carried out in a muffle furnace; the roasting adopts a programmed heating method to heat.
7. The method for preparing the NiZnTi catalyst by coprecipitation according to claim 1, wherein in the step (4), the temperature of reduction is 400-550 ℃, and the time of reduction is 1-4 hours; the reduction is carried out in a tube furnace; the reduction adopts a programmed heating method to heat.
8. The use of the NiZnTi catalyst obtained by the method of claims 1 to 7 in the hydrogenation of nitroarenes or halogenated nitroarenes to produce aromatic amines or halogenated aromatic amines.
9. The application according to claim 8, characterized in that it comprises the following steps: adding a NiZnTi catalyst with the mass of 5-20% of that of the nitroaromatic or the halogenated nitroaromatic and the nitroaromatic or the halogenated nitroaromatic into a high-pressure reaction kettle, adding an organic solvent, then adding magnetons, sealing the high-pressure kettle, replacing the air in the kettle with nitrogen for 2-5 times, heating to 50-80 ℃, introducing hydrogen, pressurizing to 0.5-0.8MPa, and reacting for 4-8 hours.
10. The application of claim 8, wherein the organic solvent is one or more of N, N-dimethylformamide, methanol or ethanol, and the dosage ratio of the organic solvent to the nitroaromatic or the halogenated nitroaromatic is 10-30 ml: 0.5 to 2 g.
CN202110518702.9A 2021-05-12 2021-05-12 Method for preparing NiZnTi catalyst by coprecipitation and application of NiZnTi catalyst in hydrogenation reaction of nitroaromatic or halogenated nitroaromatic Pending CN113181923A (en)

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US20100280294A1 (en) * 2007-10-19 2010-11-04 Peter Birke Catalyst for the hydrogenation of unsaturated hydrocarbons and process for its preparation
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Publication number Priority date Publication date Assignee Title
US20100280294A1 (en) * 2007-10-19 2010-11-04 Peter Birke Catalyst for the hydrogenation of unsaturated hydrocarbons and process for its preparation
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