CN107304166B - Industrial preparation method of 1-naphthylamine - Google Patents
Industrial preparation method of 1-naphthylamine Download PDFInfo
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- CN107304166B CN107304166B CN201610262021.XA CN201610262021A CN107304166B CN 107304166 B CN107304166 B CN 107304166B CN 201610262021 A CN201610262021 A CN 201610262021A CN 107304166 B CN107304166 B CN 107304166B
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Abstract
The invention discloses an industrial production method of 1-naphthylamine, which is prepared by hydrogenation reduction of 1-nitronaphthalene, wherein the reaction is continuously carried out in catalytic hydrogenation kettles which are connected in series, and a reaction solvent and a catalyst Raney nickel are respectively added into each catalytic hydrogenation kettle which is connected in series; replacing the reaction device system with nitrogen and then hydrogen; heating each reaction kettle; continuously introducing hydrogen into each catalytic hydrogenation kettle; then continuously introducing 1-nitronaphthalene and a solvent into a first catalytic hydrogenation kettle connected in series; and while continuously feeding the materials into the first catalytic hydrogenation kettle, discharging the materials from the previous catalytic hydrogenation kettle to the next catalytic hydrogenation kettle, discharging the materials from the last catalytic hydrogenation kettle connected in series to a catalyst settling tank, settling the materials after reaction, feeding the reaction solution into a desolventizing device, feeding the separated crude product into a distilling device, and distilling to obtain the product 1-naphthylamine. The invention solves the industrialization problem of continuously preparing the 1-naphthylamine by a catalytic hydrogenation method.
Description
Technical Field
The invention relates to a preparation method of 1-naphthylamine, in particular to an industrial preparation method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene.
Background
1-naphthylamine (also called as menaphthylamine) is used as an analytical reagent, a fluorescent indicator and a gas chromatography stationary liquid; also used for organic synthesis, is an intermediate for producing various dyes, and is also a main raw material of the rubber antioxidant.
At present, the method for industrially producing 1-naphthylamine at home and abroad mainly comprises the steps of reducing 1-nitronaphthalene by sodium polysulfide consisting of sodium sulfide and sulfur, washing the reduced material with water and distilling to obtain a finished product. The reduction method has low yield (the yield is about 85 percent), and a large amount of sulfide-containing wastewater is generated in the production process, so the post-treatment cost is high.
The nitro compound can be reduced into the amino compound through catalytic hydrogenation, but the existing method for preparing 1-naphthylamine through catalytic hydrogenation of 1-nitronaphthalene still stays in a pilot plant stage of batch production, and no industrial report exists. In addition, the research on the catalytic hydrogenation reduction process mainly focuses on the adaptability of the catalyst.
For example, chinese patent document CN 101434550B (application No. 200810174591.9) discloses a method for preparing 1-naphthylamine from 1-nitronaphthalene, wherein 1-nitronaphthalene, ethanol and a supported nickel catalyst are added into a reaction kettle, hydrogenation reaction is performed for 3-8 hours, and solid-liquid separation is performed after the reaction is completed; the supported nickel catalyst used is prepared by a series of steps: preparing nickel into nitrate and preparing into 1M aqueous solution, taking a nickel salt aqueous solution with the nickel amount being 45-58% of the mass of a catalyst finished product, adding a silica sol aqueous solution containing 20% of silicon dioxide, heating a system, adding diatomite subjected to acid treatment in advance under the stirring condition, adjusting the pH value of the system, stirring for 12-16 hours, cooling, carrying out solid-liquid separation, washing the obtained solid with water, granulating, drying, reducing with hydrogen at 500-700 ℃, and passivating with mixed inert gas containing air with the volume ratio of 5% under the cooling condition to obtain the catalyst finished product. The technical feature claimed in this patent document is the preparation method of the supported nickel catalyst for catalytic hydrogenation.
For example, chinese patent document CN 102304053 a (application No. 201110205790.3) discloses a method for synthesizing naphthylamine by catalytic hydrogenation, which comprises preparing a nickel-copper composite catalyst for catalytic hydrogenation synthesis, and then adding 1-nitronaphthalene, ethanol and the nickel-copper composite catalyst into a reaction kettle to start hydrogenation reduction reaction. The technical solution claimed in this patent document is distinguished from the prior art by the catalyst used and the method for preparing the catalyst.
The preparation of the catalysts claimed in the two patent documents mentioned above is complicated and the preferred embodiments of each are laboratory bench tests.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an industrial production method for preparing 1-naphthylamine with higher yield and product purity by continuous catalytic hydrogenation.
The technical scheme for realizing the aim of the invention is an industrial preparation method of 1-naphthylamine, which is prepared by hydrogenation reduction of 1-nitronaphthalene, and the reaction is carried out in 2-4 catalytic hydrogenation kettles connected in series, and comprises the following steps:
① adding reaction solvent and Raney nickel catalyst into each serial catalytic hydrogenation kettle, the adding amount of the solvent is 50-70% of the volume of each catalytic hydrogenation kettle, and the adding amount of the catalyst is 0.5-3% of the solvent mass.
② the reactor system was purged with nitrogen and then with hydrogen.
③ opening the stirring device and temperature control system of each catalytic hydrogenation kettle, heating each reaction kettle and keeping the temperature in each reaction kettle at 90-140 ℃.
④, continuously introducing hydrogen into each catalytic hydrogenation kettle at 90-140 ℃ until the pressure in each catalytic hydrogenation kettle is 0.8-2 Mpa, and keeping the pressure in each catalytic hydrogenation kettle 1 at 0.8-2 Mpa.
And then continuously introducing 1-nitronaphthalene and a solvent into the first catalytic hydrogenation kettle connected in series, wherein the volume ratio of the introduced 1-nitronaphthalene to the solvent is 0.5-2: 1, and the introduction speed of the solvent is determined by the retention time of the solvent in the first catalytic hydrogenation kettle being 2.5-5.5 hours.
⑤ when continuously feeding materials into the first catalytic hydrogenation kettle, the former catalytic hydrogenation kettle discharges materials to the latter catalytic hydrogenation kettle, the last catalytic hydrogenation kettle in series discharges materials to the catalyst settling tank, the materials flowing out from the last catalytic hydrogenation kettle settle in the catalyst settling tank, the reaction liquid enters the desolventizing device through the liquid outlet, the solvent and the crude product are separated in the desolventizing device, the solvent obtained by separation is stored in the solvent recovery storage tank, the crude product obtained by separation enters the distilling device (7), and the product 1-naphthylamine is obtained after distillation.
The solvent in step ① is methanol or ethanol.
In the step ②, the reaction device system is first replaced with nitrogen gas for 2-3 times, the pressure of the nitrogen gas is controlled to be 0.2-0.6 MPa each time, and then replaced with hydrogen gas for 2-3 times, and the pressure of the hydrogen gas is controlled to be 0.2-0.6 MPa each time.
Heating each reaction kettle in the step ③, keeping the temperature in each reaction kettle at 100-120 ℃, and continuously introducing hydrogen into each catalytic hydrogenation kettle at 90-140 ℃ in the step ④ until the pressure in each catalytic hydrogenation kettle is 1-2 Mpa.
The solvent residence time in step ④ is inversely proportional to the number of catalytic hydrogenation vessels in series, with the greater the number of catalytic hydrogenation vessels in series, the shorter the residence time.
The purity of the 1-nitronaphthalene continuously introduced into the first catalytic hydrogenation kettle connected in series in the step ④ is more than 94%.
And ⑤, settling the catalyst at the bottom of the catalyst settling tank, opening a solid outlet at the bottom to recover the catalyst, loading the recovered catalyst into a catalyst replenishing tank, and returning the catalyst to the system for recycling.
When the volume of the solvent recovered in the recovered solvent storage tank reaches more than 20 percent of the volume of the storage tank, introducing the solvent into the catalytic hydrogenation kettle from the recovered solvent storage tank; the volume of the recovered solvent storage tank is 1-8 times of the volume of the catalytic hydrogenation kettle.
Optionally, when the hydrogen suction speed of each catalytic hydrogenation kettle is reduced, adding a catalyst into the catalytic hydrogenation kettle through a catalyst adding tank, wherein the adding amount of the catalyst is 1-5% of the initial adding amount; or after the reaction starts, catalysts are supplemented into the catalytic hydrogenation kettles every hour, the catalyst supplementation amount from the first catalytic hydrogenation kettle to the last catalytic hydrogenation kettle is gradually reduced, the catalyst supplementation amount of the first catalytic hydrogenation kettle per hour is 10% -18% of the initial mass, and the catalyst supplementation amount of the last catalytic hydrogenation kettle per hour is 6% -11% of the initial mass.
The invention has the positive effects that: (1) the invention applies the liquid phase continuous hydrogenation method to the preparation of the 1-naphthylamine, and solves the industrial problem of preparing the 1-naphthylamine by the catalytic hydrogenation method; in the preparation process of the 1-naphthylamine, nitronaphthalene is reacted in the first catalytic hydrogenation kettle and then enters the subsequent catalytic hydrogenation kettles connected in series for further catalytic hydrogenation, so that the 1-nitronaphthalene is completely reduced. The method uses Raney nickel as a catalyst, does not need to use a supported nickel catalyst or a nickel-copper composite catalyst in the background technology, can recycle the catalyst recovered in the production process, and conveys the catalyst to a waste material factory for recycling treatment after losing activity.
(2) Compared with the sodium sulfide reduction process, the industrial preparation method of the 1-naphthylamine is green and environment-friendly, and solves the treatment problem of waste water and waste residue caused by the sodium sulfide reduction process. Therefore, compared with the existing industrial preparation method of the 1-naphthylamine, the post-treatment cost is low, thereby reducing the production cost of the 1-naphthylamine.
(3) Compared with the traditional sodium sulfide reduction method, the continuous catalytic hydrogenation method adopted by the invention has the advantage of high reaction yield which can reach more than 97%.
(4) The invention adopts a liquid phase continuous hydrogenation method, does not need to carry out frequent nitrogen and hydrogen replacement on equipment, has high production efficiency and strong operation safety, reduces the labor intensity of workers, saves energy and reduces the production cost.
Drawings
FIG. 1 is a schematic view of the structure of an apparatus for industrially producing 1-naphthylamine in example 1.
FIG. 2 is a schematic view showing the structure of an apparatus used for the industrial production of 1-naphthylamine in example 7.
FIG. 3 is a schematic view of the structure of an apparatus for industrial production of 1-naphthylamine according to example 8.
The reference numbers in the above figures are as follows: a catalytic hydrogenation kettle 1, a first catalytic hydrogenation kettle 11, a second catalytic hydrogenation kettle 12, a third catalytic hydrogenation kettle 13 and a fourth catalytic hydrogenation kettle 14; a nitronaphthalene storage tank 2; a solvent storage tank 3; a catalyst replenishment tank 4, a first catalyst replenishment tank 41, a second catalyst replenishment tank 42, a third catalyst replenishment tank 43, and a fourth catalyst replenishment tank 44; a catalyst settling tank 5; a desolventizing device 6; a distillation apparatus 7; and a recovered solvent storage tank 8.
Detailed Description
(example 1)
Referring to fig. 1, the apparatus used in the industrial preparation method of 1-naphthylamine of this example includes a catalytic hydrogenation kettle 1, a nitronaphthalene storage tank 2, a solvent storage tank 3, a catalyst replenishment tank 4, a catalyst settling tank 5, a desolventizing apparatus 6, a distillation apparatus 7, and a recovered solvent storage tank 8.
The catalytic hydrogenation kettle 1 comprises a first catalytic hydrogenation kettle 11 and a second catalytic hydrogenation kettle 12 which are connected in series and have the same volume, the nitronaphthalene storage tank 2 is communicated with a feeding hole, located at the top, of the first catalytic hydrogenation kettle 11 through a pump and a pipeline, and the pump used in the embodiment is a metering pump. The upper part of the kettle body of the first catalytic hydrogenation kettle 11 is provided with a discharge hole, the upper part of the kettle body of the second catalytic hydrogenation kettle 12 is provided with a feed inlet and a discharge hole, and the connecting line of the feed inlet and the discharge hole of the second catalytic hydrogenation kettle 12 is crossed with the axis of the second catalytic hydrogenation kettle 12. The inside draft tube that sets up of each catalytic hydrogenation cauldron 1, the stirring vane of catalytic hydrogenation cauldron 1's agitating unit is located inside the draft tube. The top of each catalytic hydrogenation kettle 1 is provided with a hydrogen interface which is respectively communicated with a hydrogen storage tank through a pipeline.
The solvent storage tank 3 is communicated with a feed inlet at the top of the catalytic hydrogenation kettle 1 through a metering pump and a solvent conveying pipeline. Solvent pipeline includes trunk line and two branch road pipelines, and the feed inlet of trunk line is connected with the discharge gate of pump, and trunk line and first catalytic hydrogenation cauldron 11 are connected to first branch road pipeline, and trunk line and second catalytic hydrogenation cauldron 12 are connected to second branch road pipeline, are equipped with the valve on each branch road pipeline.
The catalyst replenishment tank 4 includes a first catalyst replenishment tank 41 and a second catalyst replenishment tank 42. A catalyst replenishing tank 4 is arranged above each catalytic hydrogenation kettle 1, and the discharge port of each catalyst replenishing tank 4 is communicated with the corresponding catalyst feed port above the catalytic hydrogenation kettle 1 through a pipeline.
The catalyst settling tank 5 is provided with a feed inlet, a liquid outlet and a solid outlet. The feed inlet and the liquid outlet are arranged above the wall of the catalyst settling tank 5, and the liquid outlet is arranged above the feed inlet. The solids outlet is arranged at the bottom of the catalyst settling tank 5. The discharge hole of the second catalytic hydrogenation kettle 12 is communicated with the feed inlet of the catalyst settling tank 5 through a pipeline.
The liquid outlet of the catalyst settling tank 5 is communicated with the lower feed inlet of the desolventizing device 6 through a pipeline. The desolventizing device 6 is also provided with a solvent outlet at the top and a crude product outlet at the bottom. The solvent outlet at the top is communicated with a recovered solvent storage tank 8 through a pipeline. The crude product outlet at the bottom of the desolventizing device 6 is communicated with a distilling device 7 through a pipeline.
The recovered solvent storage tank 8 is communicated with an upper end feed inlet of the catalytic hydrogenation kettle 1 through a pump and a solvent conveying pipeline, and the recovered solvent storage tank 8 is communicated with a main pipeline of the solvent storage tank 3 through a section of pipeline. The volume of the recovered solvent storage tank 8 is 1-8 times of the volume of the catalytic hydrogenation kettle.
The industrial preparation method of 1-naphthylamine of this example includes the following steps:
① opening metering pump and valves on the pipeline between the solvent storage tank 3 and the catalytic hydrogenation kettle 1, the solvent in the solvent storage tank 3 is methanol, and the volume of the solution is 10m35500L of reaction solvent methanol is respectively added into the first catalytic hydrogenation kettle 11 and the second catalytic hydrogenation kettle 12, then the switch of the catalyst replenishing tank 4 above each catalytic hydrogenation kettle 1 is opened, and 70kg of Raney nickel is respectively added into the first catalytic hydrogenation kettle 11 and the second catalytic hydrogenation kettle 12.
② the reaction system is replaced by nitrogen gas for 3 times, wherein the nitrogen pressure is controlled to be 0.2-0.6 MPa (0.3 MPa in this embodiment) each time, and then replaced by hydrogen gas for 3 times, and the hydrogen pressure is controlled to be 0.2-0.6 MPa (0.4 MPa in this embodiment) each time.
③, opening the stirring devices and the temperature control systems of the first catalytic hydrogenation kettle 11 and the second catalytic hydrogenation kettle 12, heating each reaction kettle and keeping the temperature in each reaction kettle at 110 ℃.
④ at 110 deg.C, continuously introducing hydrogen into the first catalytic hydrogenation reactor 11 and the second catalytic hydrogenation reactor 12 respectively until the pressure in each catalytic hydrogenation reactor 1 is 1.5 MPa, and keeping the pressure in each catalytic hydrogenation reactor 1 at 1.5 MPa.
Then, a metering pump connected with the nitronaphthalene storage tank 2 and a metering pump connected with the methanol storage tank 3 are started, the materials are continuously fed into the first catalytic hydrogenation kettle 11, the volume ratio of the introduced nitronaphthalene to the methanol is 1: 0.8, and the introduction speed of the methanol is 4 hours when the residence time of the methanol in the first catalytic hydrogenation kettle 11 is 4 hours.
The material contained in the nitronaphthalene storage tank 2 is 1-nitronaphthalene, and is prepared by nitrating naphthalene through mixed acid, wherein the purity of the 1-nitronaphthalene is 96.5%.
⑤ when continuously feeding materials into the first catalytic hydrogenation kettle 11, the first catalytic hydrogenation kettle 11 discharging materials into the second catalytic hydrogenation kettle 12, the second catalytic hydrogenation kettle 12 discharging materials into the catalyst settling tank 5, after the reacted materials flowing out of the second catalytic hydrogenation kettle 12 settling in the catalyst settling tank 5, the reaction liquid above the reaction liquid enters the desolventizing device 6 through the liquid outlet, methanol and crude products are separated in the desolventizing device 6, the separated methanol is stored in the recovery solvent storage tank 8, the separated crude products enter the distilling device 7, 1-naphthylamine with the purity of 96.3% is obtained through the distilling process, the total amino value is 99.5%, and the yield (calculated by nitronaphthalene) of the 1-naphthylamine is 98%.
The catalyst settles at the bottom of the catalyst settling tank 5, and a solid outlet at the bottom is opened to recover the catalyst. And (4) loading the recovered catalyst into a catalyst replenishing tank 4, and returning the recovered catalyst to the system for recycling.
When the hydrogen suction speed of the first catalytic hydrogenation kettle 11 and the second catalytic hydrogenation kettle 12 is reduced, the catalyst is supplemented into the catalytic hydrogenation kettle through the catalyst supplementing tank 4, and the adding amount of the catalyst is 1% -15% of the initial adding amount.
When the solvent recovered in the recovered solvent storage tank 8 reaches 25% of the storage tank volume, the solvent methanol is introduced into the catalytic hydrogenation kettle 1 from the recovered solvent storage tank 8.
(example 2)
The industrial production method of 1-naphthylamine in this example was otherwise the same as in example 1 except that:
in the step ①, the solvent introduced into the catalytic hydrogenation kettle 1 is ethanol, in the step ⑤, 1-naphthylamine with the purity of 96.5% is obtained through a distillation process, the total amino value is 99.37%, and the yield of the 1-naphthylamine (calculated by nitronaphthalene) is 97.6%.
(example 3)
The industrial production method of 1-naphthylamine in this example was otherwise the same as in example 1 except that:
at step ①, the distance to 10m36000L of reaction solvent methanol are respectively added into the first catalytic hydrogenation kettle 11 and the second catalytic hydrogenation kettle 12, then the switch of the catalyst replenishing tank 4 above each catalytic hydrogenation kettle 1 is opened, and 75kg of Raney nickel is respectively added into the first catalytic hydrogenation kettle 11 and the second catalytic hydrogenation kettle 12.
④, continuously introducing hydrogen into the first catalytic hydrogenation kettle 11 and the second catalytic hydrogenation kettle 12 respectively at 120 ℃ until the pressure in each catalytic hydrogenation kettle 1 is 1.3 MPa, and keeping the pressure in each catalytic hydrogenation kettle 1 at 1.3 MPa.
Then, a metering pump connected with the nitronaphthalene storage tank 2 and a metering pump connected with the methanol storage tank 3 are started, the materials are continuously fed into the first catalytic hydrogenation kettle 11, the volume ratio of the introduced nitronaphthalene to the methanol is 1: 1, and the introduction speed of the methanol is determined by the retention time of the methanol in the first catalytic hydrogenation kettle 11 being 5 hours.
In step ⑤, 8kg of catalyst is added into the first catalytic hydrogenation reactor 11 and the second catalytic hydrogenation reactor 12 through the catalyst addition tank 4 every hour.
The 1-naphthylamine with the purity of 96.5 percent is obtained through the distillation process, the total amino group value is 99.43 percent, and the yield of the 1-naphthylamine (calculated by nitronaphthalene) is 97.4 percent.
(example 4)
The industrial production method of 1-naphthylamine in this example was otherwise the same as in example 3 except that:
in the step ①, the solvent introduced into the catalytic hydrogenation kettle 1 is ethanol, in the step ⑤, 1-naphthylamine with the purity of 96.3% is obtained through a distillation process, the total amino value is 99.63%, and the yield of the 1-naphthylamine (calculated by nitronaphthalene) is 97.8%.
(example 5)
The industrial production method of 1-naphthylamine in this example was otherwise the same as in example 1 except that:
in the step ④, the material in the nitronaphthalene storage tank 2 is 1-nitronaphthalene (industrial product nitronaphthalene) with the purity of 94%.
Step ⑤ is carried out by distillation to obtain 1-naphthylamine (industrial 1-naphthylamine) with purity of 94.72%, total amino group value of 99.48% and yield of 1-naphthylamine (calculated by nitronaphthalene) of 97.6%.
(example 6)
The industrial production method of 1-naphthylamine in this example was otherwise the same as in example 3 except that:
in step ④, the material contained in the nitronaphthalene storage tank 2 is 1-nitronaphthalene (refined nitronaphthalene) having a purity of 99.9%.
The distillation step ⑤ gave 99.91% purity 1-naphthylamine (refined 1-naphthylamine) with a total amino group value of 99.93% and a yield of 1-naphthylamine (based on nitronaphthalene) of 97.64%.
(example 7)
Referring to FIG. 2, the apparatus used in the industrial production process of 1-naphthylamine according to this example was the same as that used in example 1 except that:
the catalytic hydrogenation kettle 1 comprises a first catalytic hydrogenation kettle 11, a second catalytic hydrogenation kettle 12 and a third catalytic hydrogenation kettle 13 which are connected in series and have the same volume, and a discharge hole of the third catalytic hydrogenation kettle 13 is communicated with a feed hole of the catalyst settling tank 5 through a pipeline. A third catalyst replenishing tank 43 is arranged above the third catalytic hydrogenation kettle 13, and the third catalytic hydrogenation kettle 13 is communicated with the solvent storage tank 3 and the recovered solvent storage tank 8 through pipelines.
The industrial production method of 1-naphthylamine in this example was otherwise the same as in example 1 except that:
at step ①, the distance to 10m36000L of methanol are respectively added into the first catalytic hydrogenation kettle 11, the second catalytic hydrogenation kettle 12 and the third catalytic hydrogenation kettle 13, then the switch of the catalyst replenishing tank 4 above each catalytic hydrogenation kettle 1 is opened, and 75kg of Raney nickel is respectively added into each catalytic hydrogenation kettle 1.
In step ③, each reaction vessel was heated and the temperature in each vessel was maintained at 120 ℃.
In step ④, hydrogen is continuously introduced into the first catalytic hydrogenation reactor 11, the second catalytic hydrogenation reactor 12 and the third catalytic hydrogenation reactor 13 at 120 ℃ until the pressure in each catalytic hydrogenation reactor 1 is 1.3 Mpa, and the pressure in each catalytic hydrogenation reactor 1 is kept at 1.3 Mpa.
Then, a metering pump connected with the nitronaphthalene storage tank 2 and a metering pump connected with the methanol storage tank 3 are started, the materials are continuously fed into the first catalytic hydrogenation kettle 11, the volume ratio of the introduced nitronaphthalene to the methanol is 1: 1, and the introduction speed of the methanol is determined by the retention time of the methanol in the first catalytic hydrogenation kettle 11 being 3 hours.
In step ⑤, while continuously feeding materials into the first catalytic hydrogenation reactor 11, discharging the materials from the first catalytic hydrogenation reactor 11 into the second catalytic hydrogenation reactor 12, discharging the materials from the second catalytic hydrogenation reactor 12 into the third catalytic hydrogenation reactor 13, discharging the materials from the third catalytic hydrogenation reactor 13 into the catalyst settling tank 5, settling the reacted materials from the third catalytic hydrogenation reactor 13 in the catalyst settling tank 5, introducing the reaction solution above the reaction solution into the desolventizing device 6 through the liquid outlet, separating methanol from the crude product in the desolventizing device 6, storing the separated methanol in the recovery solvent storage tank 8, introducing the separated crude product into the distilling device 7, and distilling to obtain 1-naphthylamine with a purity of 96.5%, a total amino value of 99.43%, and a yield (in terms of nitronaphthalene) of 1-naphthylamine of 98.4%.
In the preparation process, catalysts are supplemented into the first catalytic hydrogenation kettle 11, the second catalytic hydrogenation kettle 12 and the third catalytic hydrogenation kettle 13 through the catalyst supplementing tank 4 every hour, and the adding amount is respectively 10 kg, 8kg and 5 kg.
(example 8)
Referring to FIG. 3, the apparatus used in the industrial production process of 1-naphthylamine according to this example was the same as that used in example 7 except that:
the catalytic hydrogenation kettle 1 comprises a first catalytic hydrogenation kettle 11, a second catalytic hydrogenation kettle 12, a third catalytic hydrogenation kettle 13 and a fourth catalytic hydrogenation kettle 14 which are connected in series and have the same volume, and a discharge hole of the fourth catalytic hydrogenation kettle 14 is communicated with a feed inlet of the catalyst settling tank 5 through a pipeline. A fourth catalyst replenishing tank 44 is arranged above the fourth catalytic hydrogenation kettle 14, and the fourth catalytic hydrogenation kettle 14 is communicated with the solvent storage tank 3 and the recovered solvent storage tank 8 through pipelines.
The industrial production method of 1-naphthylamine in this example was otherwise the same as in example 5 except that:
at step ①, the distance to 10m36000L of methanol are respectively added into the first catalytic hydrogenation kettle 11, the second catalytic hydrogenation kettle 12, the third catalytic hydrogenation kettle 13 and the fourth catalytic hydrogenation kettle 14, then the switch of the catalyst replenishing tank 4 above each catalytic hydrogenation kettle 1 is opened, and 75kg of Raney nickel is respectively added into each catalytic hydrogenation kettle 1.
In step ③, each reaction vessel was heated and the temperature in each vessel was maintained at 120 ℃.
In step ④, hydrogen is continuously introduced into the first catalytic hydrogenation reactor 11, the second catalytic hydrogenation reactor 12, the third catalytic hydrogenation reactor 13 and the fourth catalytic hydrogenation reactor 14 at 120 ℃ until the pressure in each catalytic hydrogenation reactor 1 is 1.3 Mpa, and the pressure in each catalytic hydrogenation reactor 1 is kept at 1.3 Mpa.
Then, a metering pump connected with the nitronaphthalene storage tank 2 and a metering pump connected with the methanol storage tank 3 are started, the materials are continuously fed into the first catalytic hydrogenation kettle 11, the volume ratio of the introduced nitronaphthalene to the methanol is 1: 1, and the introduction speed of the methanol is determined by the retention time of the methanol in the first catalytic hydrogenation kettle 11 being 2.5 hours.
In step ⑤, while continuously feeding the raw materials into the first catalytic hydrogenation reactor 11, the first catalytic hydrogenation reactor 11 discharges into the second catalytic hydrogenation reactor 12, the second catalytic hydrogenation reactor 12 discharges into the third catalytic hydrogenation reactor 13, the third catalytic hydrogenation reactor 13 discharges into the fourth catalytic hydrogenation reactor 14, the fourth catalytic hydrogenation reactor 14 discharges into the catalyst settling tank 5, the reacted materials flowing out of the fourth catalytic hydrogenation reactor 14 settle in the catalyst settling tank 5, the reaction liquid above the precipitated materials enters the desolventizing device 6 through the liquid outlet, methanol is separated from the crude product in the desolventizing device 6, the separated methanol is stored in the recovered solvent storage tank 8, the separated crude product enters the distilling device 7, and the distillation process is performed to obtain 1-naphthylamine with a purity of 96.5%, a total amino value of 99.57%, and a yield (in terms of nitronaphthalene) of 1-naphthylamine of 98.8%.
In the preparation process, catalysts are supplemented into the first catalytic hydrogenation kettle 11, the second catalytic hydrogenation kettle 12, the third catalytic hydrogenation kettle 13 and the fourth catalytic hydrogenation kettle 14 through the catalyst supplementing tank 4 every hour, and the adding amount is respectively 13 kg, 10 kg, 8kg and 5 kg.
Claims (7)
1. An industrial preparation method of 1-naphthylamine is prepared by hydrogenation reduction of 1-nitronaphthalene, and is characterized in that the reaction is carried out in 2-4 catalytic hydrogenation kettles (1) connected in series, and comprises the following steps:
① adding reaction solvent and catalyst Raney nickel into each serial catalytic hydrogenation kettle (1), wherein the adding amount of the solvent is 50-70% of the volume of each catalytic hydrogenation kettle (1), and the adding amount of the catalyst is 0.5-3% of the mass of the solvent;
② replacing the reaction device system with nitrogen and then hydrogen;
③, opening the stirring devices and the temperature control systems of the catalytic hydrogenation kettles (1), heating the reaction kettles and keeping the temperature in the reaction kettles at 90-140 ℃;
④, continuously introducing hydrogen into each catalytic hydrogenation kettle (1) at 90-140 ℃ until the pressure in each catalytic hydrogenation kettle (1) is 0.8-2 Mpa, and keeping the pressure in each catalytic hydrogenation kettle (1) at 0.8-2 Mpa;
continuously introducing 1-nitronaphthalene and a solvent into a first catalytic hydrogenation kettle connected in series, wherein the volume ratio of the introduced 1-nitronaphthalene to the solvent is 1-1.25: 1, and the purity of the 1-nitronaphthalene is more than 94%; the introduction speed of the solvent is determined by the retention time of the solvent in the first catalytic hydrogenation kettle to be 2.5-5.5 hours;
⑤, when continuously feeding materials into a first catalytic hydrogenation kettle, discharging materials from the former catalytic hydrogenation kettle to the latter catalytic hydrogenation kettle, discharging materials from the last catalytic hydrogenation kettle in series to a catalyst settling tank (5), settling the materials flowing out of the last catalytic hydrogenation kettle in the catalyst settling tank (5), allowing the reaction liquid to enter a desolventizing device (6) through a liquid outlet, separating the solvent from the crude product in the desolventizing device (6), storing the separated solvent in a recovered solvent storage tank (8), allowing the separated crude product to enter a distilling device (7), and distilling to obtain the product 1-naphthylamine;
and (2) replenishing catalysts into the catalytic hydrogenation kettles every hour after the reaction starts, wherein the catalyst replenishment amount from the first catalytic hydrogenation kettle to the last catalytic hydrogenation kettle is gradually reduced, the catalyst replenishment amount of the first catalytic hydrogenation kettle per hour is 10-18% of the initial mass, and the catalyst replenishment amount of the last catalytic hydrogenation kettle per hour is 6-11% of the initial mass.
2. The method of claim 1, wherein the solvent used in step ① is methanol or ethanol.
3. The industrial preparation method of 1-naphthylamine as claimed in claim 1, wherein in step ②, the reaction device system is first replaced with nitrogen gas for 2-3 times, the pressure of nitrogen gas is controlled to be 0.2-0.6 MPa each time, and then replaced with hydrogen gas for 2-3 times, and the pressure of hydrogen gas is controlled to be 0.2-0.6 MPa each time.
4. The industrial preparation method of 1-naphthylamine according to claim 1, wherein the reaction vessels are heated in step ③ to maintain the temperature in each reaction vessel at 100-120 ℃, and hydrogen is continuously introduced into each catalytic hydrogenation vessel (1) at 90-140 ℃ until the pressure in each catalytic hydrogenation vessel (1) is 1-2 MPa in step ④.
5. The method for industrially producing 1-naphthylamine according to claim 1, wherein the solvent residence time in step ④ is inversely proportional to the number of catalytic hydrogenation reactors (1) connected in series, and the larger the number of catalytic hydrogenation reactors (1) connected in series, the shorter the residence time.
6. The industrial preparation method of 1-naphthylamine as claimed in claim 1, wherein in step ⑤, the catalyst is settled at the bottom of the catalyst settling tank (5), the solid outlet at the bottom is opened to recover the catalyst, and the recovered catalyst is loaded into the catalyst replenishing tank (4) and returned to the system for recycling.
7. The industrial production method of 1-naphthylamine according to claim 6, characterized in that: when the volume of the solvent recovered in the recovered solvent storage tank (8) reaches more than 20 percent of the volume of the storage tank, introducing the solvent into the catalytic hydrogenation kettle from the recovered solvent storage tank (8); the volume of the recovered solvent storage tank (8) is 1-8 times of the volume of the catalytic hydrogenation kettle.
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| US5410085A (en) * | 1992-10-27 | 1995-04-25 | Bayer Aktiengesellschaft | Process for the preparation of chlorine-substituted aromatic amines and of catalysts |
| CN101434550A (en) * | 2008-11-07 | 2009-05-20 | 甘肃中科药源生物工程有限公司 | Method for preparing 1-naphthylamine from 1-nitronaphthalene |
| CN101906046A (en) * | 2010-07-01 | 2010-12-08 | 江苏科圣化工装备工程有限公司 | Method and device for producing o-phenylenediamine by continuous liquid phase hydrogenation |
| CN102304053A (en) * | 2011-07-22 | 2012-01-04 | 湖南化工研究院 | Preparation method for synthesizing naphthylamine by catalytic hydrogenation |
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| US5410085A (en) * | 1992-10-27 | 1995-04-25 | Bayer Aktiengesellschaft | Process for the preparation of chlorine-substituted aromatic amines and of catalysts |
| CN101434550A (en) * | 2008-11-07 | 2009-05-20 | 甘肃中科药源生物工程有限公司 | Method for preparing 1-naphthylamine from 1-nitronaphthalene |
| CN101906046A (en) * | 2010-07-01 | 2010-12-08 | 江苏科圣化工装备工程有限公司 | Method and device for producing o-phenylenediamine by continuous liquid phase hydrogenation |
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