CN113429295B - Method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on fixed bed microreactor - Google Patents
Method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on fixed bed microreactor Download PDFInfo
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Abstract
The invention discloses a method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on a fixed bed microreactor, which comprises the following steps: (1) Dinitrochlorobenzene is used as a raw material, and is dissolved in a solvent to be used as a substrate solution to be hydrogenated; the dinitrochlorobenzene is at least one of 2,4-dinitrochlorobenzene, 2,6-dinitrochlorobenzene and 3,5-dinitrochlorobenzene; (2) Mixing a substrate solution to be hydrogenated and hydrogen in a micro mixer to form a gas-liquid mixture with a good gas-liquid micro dispersion state, and then reacting in a micro packed bed reactor filled with a solid particle catalyst; the reaction temperature is 40-160 ℃, and the pressure is 1-5 MPa; the retention time of the gas-liquid mixture in the micro packed bed reactor is 10-120 s; (3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained after the reaction is finished, and enabling the liquid product to enter a subsequent separation and purification system.
Description
Technical Field
The invention relates to the technical field of m-phenylenediamine preparation, in particular to a method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on a fixed bed microreactor.
Background
M-phenylenediamine is an important organic chemical raw material and intermediate, and is widely applied to synthesis of azo dyes, fur dyes, reactive dyes and sulfur dye intermediates in the dye industry, and can also be used for preparing materials such as hair dyes, color developing agents, petroleum additives, cement coagulants and the like. The m-phenylenediamine can also be synthesized with phthaloyl chloride to prepare high-temperature resistant aromatic polyamide resin and flame-retardant fiber, and is applied to the special fields of national defense, aerospace and the like. The prior m-phenylenediamine synthesis method mainly comprises an iron powder reduction method, an electrolytic reduction method and a catalytic hydrogenation method. Although the iron powder reduction method has simple process, a large amount of arylamine-containing iron mud and wastewater which are difficult to treat can be generated, the product quality is poor, and the yield is low; the electrolytic reduction method has high cost and complex device, and does not have the condition of large-scale production; therefore, the m-phenylenediamine is synthesized by adopting a catalytic hydrogenation production process at home and abroad at present.
More meta-oil, namely a mixture consisting of p-nitrochlorobenzene, o-nitrochlorobenzene and m-nitrochlorobenzene, is generated in the preparation process of nitrochlorobenzene, wherein the o-nitrochlorobenzene can be recovered by rectification, but the boiling points of the m-nitrochlorobenzene and the p-nitrochlorobenzene are only different by 2 ℃, so that the m-nitrochlorobenzene and the p-nitrochlorobenzene are difficult to separate, and therefore, the nitrochlorobenzene meta-oil is adopted in the industry to prepare 2,4-dinitrochlorobenzene, 2,6-dinitrochlorobenzene and 3,5-dinitrochlorobenzene by further nitration, but the application value of the dinitrochlorobenzene is low and the dinitrochlorobenzene is difficult to store in large quantities. CN110128278A discloses a method for synthesizing m-phenylenediamine by using 2,4-dinitrochlorobenzene as a raw material through hydrogenation in a batch type reaction kettle, which adopts noble metal palladium carbon as a catalyst, and an alkaline substance as an acid binding agent to complete hydrogenation reaction for 4 to 5 hours at the temperature of 80 to 100 ℃ and the pressure of 0.8 to 1.5MPa, so that fewer by-products are obtained in the reaction, the yield is high, and the development requirement of a clean process is met. However, the dinitrochlorobenzene hydrogenation preparation of m-phenylenediamine by using the hydrogenation kettle has the following defects: dinitrochlorobenzene catalytic hydrogenation is a typical gas-liquid-solid three-phase reaction, when the reaction is carried out in an intermittent kettle, high pressure and long reaction time are generally needed for ensuring the full contact between the three phases and the full progress of the hydrogenation reaction, the reaction efficiency is low, meanwhile, the generation of azo compounds and non-dechlorination byproducts can be caused by low mass transfer and reaction efficiency, further, the purity of products is greatly influenced, the post-treatment process is complex, 5% -10% of catalyst needs to be supplemented after each reaction, and the production cost is greatly improved.
Compared with an intermittent reaction kettle, the micro-reactor strengthens the mass transfer and heat transfer performance, greatly improves the production efficiency, has low liquid holdup in the micro-reactor and has the advantage of intrinsic safety. The method is applied to the field of organic synthesis, can realize the continuity of the reaction process, accurately control the reaction time, inhibit side reactions and improve the yield and selectivity of the reaction. Therefore, the method for continuously synthesizing m-phenylenediamine by catalytic hydrogenation based on the micro-reactor technology development can improve the safety of a reaction system, simplify the process flow, improve the product quality, reduce the discharge of three wastes and has extremely important economic, safe and environmental protection values.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on a fixed bed microreactor, which successfully converts dinitrochlorobenzene with high risk and low additional value into m-phenylenediamine with high additional value, and compared with the traditional batch kettle reactor, the method has the advantages of good mass transfer and heat transfer performance, continuous operation, accurate control of reaction conditions, small occupied area, easiness in amplification, intrinsic safety, environmental friendliness and the like. The method has the advantages of simple process flow, high economic benefit, short reaction period, high purity of the obtained product and low content of azo by-products and dechlorinated by-products.
A method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on a fixed bed microreactor comprises the following steps:
(1) Dinitrochlorobenzene is used as a raw material, and is dissolved in a solvent to be used as a substrate solution to be hydrogenated;
the dinitrochlorobenzene is at least one of 2,4-dinitrochlorobenzene, 2,6-dinitrochlorobenzene and 3,5-dinitrochlorobenzene;
(2) The substrate solution to be hydrogenated and hydrogen enter a micro mixer to be mixed to form a gas-liquid mixture with a good gas-liquid micro dispersion state, and then the gas-liquid mixture enters a micro packed bed reactor filled with a solid particle catalyst to react;
the reaction temperature is 40-160 ℃, and the pressure is 1-5 MPa;
the retention time of the gas-liquid mixture in the micro packed bed reactor is 10-120 s;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained after the reaction is finished, and enabling the liquid product to enter a subsequent separation and purification system.
The conception and the technical route of the invention are as follows: 1. firstly, mixing a substrate solution to be hydrogenated containing dinitrochlorobenzene with hydrogen in a micro mixer to form a gas-liquid mixture with good gas-liquid micro-dispersion state; 2. the obtained gas-liquid mixture enters a micro packed bed reactor filled with solid particle catalyst for reaction, the catalyst is not carried out by reaction liquid, the product is still the gas-liquid mixture, and the solid particle catalyst does not need to be separated; 3. the reaction temperature required by the micro packed bed reactor is lower, the generation of azo compounds can be effectively reduced, the yield and purity of the target product can be extremely high at the reaction temperature as low as 70 ℃, and the yield of the m-phenylenediamine can reach 98.7%.
On the basis of the conception and the technical route, aiming at the gas-liquid mixture and the fixed bed microreactor, the invention further optimizes and controls the reaction temperature, the reaction pressure and the residence time of the gas-liquid mixture in the fixed bed microreactor filled with the catalyst, which are adaptive to the gas-liquid mixture and the fixed bed microreactor, and realizes the maximum reaction efficiency, the product yield and the purity. In the method, high-yield m-phenylenediamine can be obtained in a short time at a reaction temperature as low as 70 ℃ in the catalytic hydrogenation reaction process in the fixed bed microreactor, and the energy consumption is obviously reduced on the premise of keeping high reaction efficiency.
The method utilizes the high-efficiency mass transfer performance of the micro packed bed reactor filled with the solid particle catalyst, effectively inhibits the generation of azo by-products and dechlorination-free by-products by strengthening gas-liquid-solid mass transfer in the hydrogenation reaction process, and reduces the reaction retention time to within 2 minutes from a plurality of hours required by the reaction kettle; meanwhile, the reaction residence time distribution, the reaction temperature and the reaction pressure are well controlled, the reaction conversion rate and the product purity are remarkably improved, the obtained reaction conversion rate is close to 100%, and the highest m-phenylenediamine yield can reach 99.4%. The method can effectively solve the problems of low production efficiency, poor product purity, complex device operation and the like in the hydrogenation kettle process, realizes continuous automatic operation in the reaction process, and has the advantages of high yield, good safety and the like.
In the step (1), the solvent is preferably at least one of methanol, ethanol, propanol, isopropanol, tetrahydrofuran and pyridine.
The concentration of dinitrochlorobenzene in the substrate solution to be hydrogenated influences the reaction conversion rate and the product purity. In the process system of the present invention, in the step (1), the mass concentration of the dinitrochlorobenzene in the solvent is preferably 2wt% to 20wt%, and more preferably 5wt% to 10wt%.
In the step (2), the micro mixer preferably comprises one of a membrane dispersion reactor, a micro-sieve pore reactor and a T-shaped reactor, and can also be other micro reactors capable of realizing uniform mixing of a gas-liquid system.
Preferably, in the step (2), the reaction temperature is 50-100 ℃, and the pressure is 2-3.5 MPa;
the residence time of the gas-liquid mixture in the micro packed bed reactor is 30-100 s. The method has the advantages of lower reaction temperature, extremely high reaction efficiency, product yield and purity at low reaction temperature and in short reaction time.
In the step (2), the molar ratio of dinitrochlorobenzene to hydrogen in the substrate solution to be hydrogenated is preferably 1.5 to 16, and more preferably 1:8 to 12.
In the technical scheme that the conventional catalyst and reaction liquid form suspension, the subsequent step of separating and recycling the catalyst is involved, and if the size of the catalyst is too small, the problems of incomplete separation of the catalyst and reaction products, high recycling difficulty and the like can be caused. The invention adopts a fixed bed micro-reactor, and does not relate to the subsequent separation process of the catalyst and the reaction product, so the size of the catalyst can be smaller, and the reaction efficiency, the product yield and the purity are higher. Preferably, in the step (2), the size of the solid particle catalyst is 50-1000 microns, and the solid particle catalyst can be matched with the parameter conditions of the catalytic hydrogenation process, such as reaction temperature, reaction pressure, residence time and the like, to perform synergistic action, so that the reaction efficiency, the product yield and the purity are further improved.
In the step (2), the solid particle catalyst is preferably at least one of palladium carbon catalyst, platinum carbon catalyst and ruthenium carbon catalyst.
In the method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on the fixed bed microreactor, in the step (1), an acid-binding agent can not be added into the substrate solution to be hydrogenated, and can also be added.
In a preferred example, in step (1) of the method, an acid-binding agent is further added to the substrate solution to be hydrogenated.
The molar ratio of the acid-binding agent to the dinitrochlorobenzene is preferably 1 to 2:1, and more preferably 1.2 to 1.6.
The acid-binding agent preferably comprises at least one of sodium acetate, sodium carbonate, sodium bicarbonate, potassium bicarbonate and triethylamine.
In the step (3), the yield of m-phenylenediamine in the gas-liquid mixture obtained after the reaction is finished is not lower than 98.3wt%.
In the step (3), the gas obtained by gas-liquid separation contains hydrogen, can enter a tail gas treatment system, and can be recycled, for example, the hydrogen can be used for mixing with the substrate solution to be hydrogenated in the step (2).
Compared with the prior art, the invention has the main advantages that:
1) Before and after the catalytic hydrogenation reaction, the conveyed materials are only gas-liquid mixtures all the time. In the process of continuously synthesizing m-phenylenediamine by catalytic hydrogenation, a specific noble metal catalyst is adopted, the gas-liquid-solid contact area in a fixed bed microreactor is large, and the occurrence of dechlorination is promoted.
2) The fixed bed microreactor has high mass transfer and heat transfer efficiency and can avoid catalyst deactivation caused by violent heat release.
3) The fixed bed microreactor requires lower reaction temperature and can effectively reduce the generation of azo by-products.
4) The reaction time is accurate and controllable, the generation of azo compounds is inhibited, the complete dechlorination is ensured, and the yield of the m-phenylenediamine can reach more than 98.3 percent.
5) The reactor has small volume and high safety.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on a fixed bed microreactor according to the present invention;
in the figure: 1-micro mixer; 2-a micro packed bed reactor packed with solid particulate catalyst; 3-gas-liquid separation tank.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
The invention relates to a method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on a fixed bed microreactor, which comprises the following steps:
(1) Dinitrochlorobenzene is taken as a raw material, and is dissolved in a solvent to be used as a substrate solution to be hydrogenated, namely a dinitrochlorobenzene solution;
the dinitrochlorobenzene is at least one of 2,4-dinitrochlorobenzene, 2,6-dinitrochlorobenzene and 3,5-dinitrochlorobenzene;
(2) The dinitrochlorobenzene solution and hydrogen enter a micro mixer 1 to be mixed to form a gas-liquid mixture with a good gas-liquid micro dispersion state, and then the gas-liquid mixture enters a micro packed bed reactor 2 filled with a solid particle catalyst to be reacted;
the reaction temperature is 40-160 ℃, and the pressure is 1-5 MPa;
the retention time of the gas-liquid mixture in the micro packed bed reactor is 10-120 s;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained after the reaction in a gas-liquid separation tank 3, wherein the gas containing hydrogen can enter a tail gas treatment system, and the liquid product containing m-phenylenediamine can enter a subsequent separation and purification system.
Example 1
According to the method, an ethanol solution of 2,4-dinitrochlorobenzene is prepared, the concentration is 10wt%, and the molar ratio of hydrogen to 2,4-dinitrochlorobenzene is controlled to be 10; the solution and hydrogen were mixed in an inlet T-type micromixer, the resulting gas-liquid mixture was passed through a microreactor packed with a palladium-carbon catalyst (catalyst size 50 μm), the reaction temperature was set at 90 ℃, the reaction pressure was 2.5MPa, the residence time was 80s, the reaction product was collected at the microreactor outlet, and the obtained product was analyzed to give 2,4-dinitrochlorobenzene with a conversion of 100%, m-phenylenediamine with a yield of 98.3%, azo-based substances with a yield of 1.2%, and non-dechlorinated substances with a yield of 0.4%.
Example 2
According to the method, an experiment is carried out, a methanol solution of 2,6-dinitrochlorobenzene is prepared, the concentration is 5wt%, triethylamine is added according to a molar ratio of 1.2 to 2,6-dinitrochlorobenzene, and the molar ratio of hydrogen to 2,6-dinitrochlorobenzene is controlled to be 8:1; the solution and hydrogen were mixed in an inlet membrane dispersion micromixer, the resulting gas-liquid mixture was passed through a microreactor packed with a platinum-carbon catalyst (catalyst size 200 μm), the reaction temperature was set at 70 ℃, the reaction pressure was 2.0MPa, the residence time was 70s, the reaction product was collected at the microreactor outlet, and the obtained product was analyzed to give 2,6-dinitrochlorobenzene with a conversion of 100%, m-phenylenediamine with a yield of 98.7%, azo-based substances with a yield of 0.84%, and non-dechlorinated substances with a yield of 0.23%.
Example 3
Experiments were carried out according to the method of the invention, 3,5-dinitrochlorobenzene in tetrahydrofuran was prepared, the concentration was 15wt%, sodium bicarbonate was added according to a molar ratio of 1:1.5, the molar ratio of hydrogen to 3,5-dinitrochlorobenzene was controlled to be 11; the solution and hydrogen are mixed in an inlet micromesh micromixer, the formed gas-liquid mixture passes through a microreactor filled with a palladium-carbon catalyst (the size of the catalyst is 800 microns), the reaction temperature is set to be 120 ℃, the reaction pressure is 3.0MPa, the residence time is 50s, reaction products are collected at the outlet of the microreactor, and the obtained products are analyzed, so that the conversion rate of 3,5-dinitrochlorobenzene is 100%, the yield of m-phenylenediamine is 99.4%, the content of azo substances is 0.14%, and the content of non-dechlorinated substances is 0.33%.
Example 4
Experiments were carried out according to the method of the invention, 2,4-dinitrochlorobenzene in methanol was prepared with a concentration of 10wt%, potassium bicarbonate was added in a molar ratio of 1.4 to 1, the molar ratio of hydrogen to 2,4-dinitrochlorobenzene was controlled to 11; the solution and hydrogen were mixed in an inlet T-type micromixer, the resulting gas-liquid mixture was passed through a microreactor packed with a platinum-carbon catalyst (catalyst size 1000 μm), the reaction temperature was set at 100 ℃, the reaction pressure was 4.0MPa, the residence time was 70s, the reaction product was collected at the microreactor outlet, and the obtained product was analyzed to give 2,4-dinitrochlorobenzene with a conversion of 100%, a yield of m-phenylenediamine of 99.0%, azo-based substances of 0.64%, and non-dechlorinated substances of 0.27%.
Example 5
According to the method, the experiment is carried out, the methanol solution of 2,4-dinitrochlorobenzene is prepared, the concentration is 10wt%, and the molar ratio of hydrogen to 2,4-dinitrochlorobenzene is controlled to be 10; the solution and hydrogen were mixed in an inlet T-type micromixer, the resulting gas-liquid mixture was passed through a microreactor packed with a ruthenium-carbon catalyst (catalyst size 200 μm), the reaction temperature was set at 100 ℃, the reaction pressure was 3.0MPa, the residence time was 80s, the reaction product was collected at the microreactor outlet, and the obtained product was analyzed to give 2,4-dinitrochlorobenzene with a conversion of 100%, m-phenylenediamine with a yield of 98.4%, azo-based substances with a yield of 0.82%, and non-dechlorinated substances with a yield of 0.57%.
Example 6
According to the method, an experiment is carried out, an isopropanol solution of 2,6-dinitrochlorobenzene is prepared, the concentration is 12wt%, and the molar ratio of hydrogen to 2,6-dinitrochlorobenzene is controlled to be 10; the solution and hydrogen were mixed in an inlet T-type micromixer, the resulting gas-liquid mixture was passed through a microreactor packed with a platinum-carbon catalyst (catalyst size 500 μm), the reaction temperature was set at 90 ℃, the reaction pressure was 3.5MPa, the residence time was 90s, the reaction product was collected at the microreactor outlet, and the product was analyzed, giving 2,6-dinitrochlorobenzene a conversion of 100%, m-phenylenediamine yield of 98.8%, azo-species of 0.32%, and non-dechlorinated species of 0.87%.
Example 7
Experiments were carried out according to the method of the invention, 2,4-dinitrochlorobenzene in methanol was prepared, with a concentration of 10wt%, sodium bicarbonate was added at a molar ratio of 1:1.5, the molar ratio of hydrogen to 2,4-dinitrochlorobenzene was controlled to 10; the solution and hydrogen were mixed in an inlet membrane dispersion micromixer, the resulting gas-liquid mixture was passed through a microreactor packed with a platinum-carbon catalyst (catalyst size 800 μm), the reaction temperature was set at 80 ℃, the reaction pressure was 3.0MPa, the residence time was 70s, the reaction product was collected at the microreactor outlet, and the obtained product was analyzed to give 2,4-dinitrochlorobenzene with a conversion of 100%, m-phenylenediamine with a yield of 98.8%, azo-based substances with a yield of 0.82%, and non-dechlorinated substances with a yield of 0.17%.
Example 8
Experiments were carried out according to the method of the invention, 3,5-dinitrochlorobenzene in methanol was prepared with a concentration of 10wt%, potassium bicarbonate was added at a molar ratio of 1.4 to 1, the molar ratio of hydrogen to 3,5-dinitrochlorobenzene was controlled to 10; the solution and hydrogen were mixed in an inlet membrane dispersion micromixer, the resulting gas-liquid mixture was passed through a microreactor packed with a palladium-carbon catalyst (catalyst size 200 μm), the reaction temperature was set at 90 ℃, the reaction pressure was 3.0MPa, the residence time was 80s, the reaction product was collected at the microreactor outlet, and the obtained product was analyzed to give 3,5-dinitrochlorobenzene with a conversion of 100%, m-phenylenediamine with a yield of 98.5%, azo-based substances 0.92%, and non-dechlorinated substances 0.34%.
Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention defined by the appended claims.
Claims (1)
1. A method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on a fixed bed microreactor is characterized by comprising the following steps:
(1) Dinitrochlorobenzene is taken as a raw material, and is dissolved in a solvent methanol to be used as a substrate solution to be hydrogenated; the mass concentration of the dinitrochlorobenzene in the solvent is 5wt%;
the dinitrochlorobenzene is 2,6-dinitrochlorobenzene;
adding an acid-binding agent triethylamine into the substrate solution to be hydrogenated;
the molar ratio of the acid-binding agent to the dinitrochlorobenzene is 1.2;
(2) The substrate solution to be hydrogenated and hydrogen enter a micro mixer to be mixed to form a gas-liquid mixture with a good gas-liquid micro dispersion state, and then the gas-liquid mixture enters a micro packed bed reactor filled with a solid particle catalyst to react;
the reaction temperature is 70 ℃, and the pressure is 2MPa;
the molar ratio of the dinitrochlorobenzene to the hydrogen in the substrate solution to be hydrogenated is 1:8;
the micro mixer is a membrane dispersion micro mixer;
the solid particle catalyst is a platinum carbon catalyst, and the size of the solid particle catalyst is 200 microns;
the residence time of the gas-liquid mixture in the micro packed bed reactor is 70s;
(3) After the reaction is finished, the gas-liquid mixture is subjected to gas-liquid separation, the liquid product enters a subsequent separation and purification system, the conversion rate of 2,6-dinitrochlorobenzene is 100%, the yield of m-phenylenediamine is 98.7%, the yield of azo substances is 0.84%, and the content of dechlorinated substances is 0.23%.
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| CN117466756B (en) * | 2023-11-09 | 2024-08-02 | 扬州博克莱生物医药科技有限公司 | Method for synthesizing 2-amino benzyl alcohol by utilizing micro-fixed bed liquid phase continuous hydrogenation |
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| CN107540554B (en) * | 2016-06-23 | 2020-04-24 | 南京大学 | Method for preparing m-phenylenediamine by hydrogenating m-dinitrobenzene |
| CN107382745B (en) * | 2017-09-08 | 2019-09-06 | 河北工业大学 | A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline |
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| CN110128278A (en) * | 2019-05-31 | 2019-08-16 | 济南和润化工科技有限公司 | A kind of method that 1-CHLORO-2,4-DINITROBENZENE catalytic hydrogenation prepares m-phenylene diamine (MPD) |
| CN110105220B (en) * | 2019-05-31 | 2022-05-06 | 济南和润化工科技有限公司 | Method for preparing m-phenylenediamine from meta-oil |
| CN110627650B (en) * | 2019-10-09 | 2021-02-12 | 清华大学 | Device for continuously synthesizing benzylamine substances through heterogeneous hydrogenation in microreactor |
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