CN112409185B - Method for synthesizing dinitroanthraquinone by continuous flow microchannel reactor - Google Patents
Method for synthesizing dinitroanthraquinone by continuous flow microchannel reactor Download PDFInfo
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- CN112409185B CN112409185B CN202011364202.6A CN202011364202A CN112409185B CN 112409185 B CN112409185 B CN 112409185B CN 202011364202 A CN202011364202 A CN 202011364202A CN 112409185 B CN112409185 B CN 112409185B
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- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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Abstract
The invention belongs to the field of organic synthesis, and particularly relates to a continuous reaction process method for synthesizing dinitroanthraquinone by nitration by using anthraquinone as a raw material and nitric acid as a nitrating agent. In particular to a process method for generating dinitroanthraquinone by continuously nitrifying anthraquinone serving as a substrate in a continuous flow microchannel reactor.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a continuous reaction process method for synthesizing dinitroanthraquinone by nitration by using anthraquinone as a raw material and nitric acid as a nitrating agent. In particular to a process method for generating 2-nitroanthraquinone by continuously nitrifying anthraquinone serving as a substrate in a continuous flow microchannel reactor.
Background
Dinitroanthraquinone is one of the most important anthraquinone derivatives, is an intermediate for synthesizing vat dyes, has wide application and high consumption, and can be used for producing disperse, vat, acid and active dyes, inks, coatings, polymer pigments and other applications. Although there are many routes to 1-aminoanthraquinone, the most competitive method currently produces 2-aminoanthraquinone by reduction or aminolysis after nitration of anthraquinone to dinitroanthraquinone.
The nitration of anthraquinone is mainly carried out by three methods, namely a pure nitric acid nitration method, a mixed acid nitration method and a solvent nitration method. In the pure nitric acid nitration method, the molar ratio of anthraquinone to nitric acid is about 1:19, the purity is not high, and the yield is 73%. The yield of the mixed acid nitration method is 75%, the reaction system is close to paste, the fluidity and the mixing property are poor, and the reaction time is long. The pure nitric acid nitration method and the mixed acid nitration method are almost eliminated due to large acid consumption, low yield and serious wastewater. The solvent method is the most widely used method in the current industrial production, the yield is about 75-83%, and meanwhile, some byproducts and impurities can be obtained and can be further applied after refining. Meanwhile, in an intermittent reaction kettle, nitration reaction inevitably causes local overheating to cause danger due to local uneven mixing, and the method has the advantages of long reaction time, unstable reaction process, high explosion risk and large production risk.
The invention provides a method for synthesizing dinitroanthraquinone by using a continuous flow microchannel reactor, which is a future production trend, and 1, 5-dinitroanthraquinone and 1, 8-dinitroanthraquinone are obtained by separating through a silica gel column.
Disclosure of Invention
The invention aims to provide a process method for preparing dinitroanthraquinone by anthraquinone nitration in a high-flux microchannel reactor. Compared with the prior art, the method can improve the yield and the product purity of the reaction, greatly shorten the reaction period, reduce the use of solvents and the generation of wastes, reduce potential safety hazards and realize continuous intelligent production.
The invention relates to a method for synthesizing dinitroanthraquinone by a continuous flow microchannel reactor, which comprises the following steps:
step 1, preheating an anthraquinone-concentrated sulfuric acid saturated solution, a mixed acid nitrating agent and an organic solvent respectively serving as three strands of materials, and then respectively introducing the materials into a continuous flow microchannel reactor through a metering pump;
step 2, controlling the flow of the materials by a metering pump, enabling the preheated anthraquinone-concentrated sulfuric acid saturated solution, the mixed acid nitrating agent and the organic solvent to synchronously enter a microchannel reactor module for mixing reaction according to set flow rates, controlling the reaction temperature by an external heat exchanger, enabling a heat exchange medium to be heat conduction oil, enabling the product to flow out of an outlet of the reactor, and enabling the product to enter a product collecting region for further treatment;
step 3, diluting the material obtained at the outlet of the microchannel reactor by ice water, standing and settling, and separating out sulfuric acid mother liquor; distilling and recovering an organic phase;
and 4, step 4: separating by a silica gel column separation silica gel column, wherein a mobile phase is a mixture solvent of methanol and water, and the mass ratio of the methanol to the water is 4: 6;
wherein the mass ratio of anthraquinone to concentrated sulfuric acid in the anthraquinone-concentrated sulfuric acid saturated solution in the step 1 is 1: 2-6, wherein the mass ratio of concentrated nitric acid to concentrated sulfuric acid in the mixed acid nitrating agent is 1: 1-5; wherein the concentration of the nitric acid is 85-98 percent, and the concentration of the sulfuric acid is 90-98 percent;
wherein the set flow rate of the anthraquinone-concentrated sulfuric acid saturated solution in the step 2 is 10-40ml/min, and the flow rate of the sulfuric acid-nitric acid solution is 8-15 ml/min; the flow rate of the organic solvent is 5-40 ml/min;
wherein the time for carrying out the mixing reaction in the microchannel reactor module in the step 2 is 40-300 s; the reaction temperature is 100-120 ℃; the reaction pressure is 0-10 bar.
In the method for preparing the dinitroanthraquinone, the organic solvent in the steps 1 and 2 is one or more selected from dichloroethane, chloroform, ethyl acetate, acetone, acetonitrile, cyclohexane, N-dimethylformamide and N, N-dimethylacetamide; wherein the volume ratio of the organic solvent to the anthraquinone is 1-10: 1.
Further, in the method for preparing dinitroanthraquinone, the mass ratio of anthraquinone to concentrated sulfuric acid in the saturated solution of anthraquinone-concentrated sulfuric acid in the step 1 is 1: 3-5; the mass ratio of the concentrated nitric acid to the concentrated sulfuric acid in the mixed acid nitrating agent is 1: 2-4; the flow rate of the anthraquinone-concentrated sulfuric acid saturated solution of the material in the step 2 is set to be 10-20 ml/min; the flow rate of the material sulfuric acid-nitric acid solution is 10-14 ml/min; the flow rate of the organic solvent solution is 10-20 ml/min; the time for carrying out the mixing reaction in the microchannel reactor module in the step 2 is 60-150 s; the reaction temperature is 100 ℃; the reaction pressure is 0-5 bar.
The above reactions are all carried out in a continuous flow microchannel reactor with a certain structure, and the reaction system comprises a metering device, a reaction device, a product collecting and processing device and other different functional device areas.
The microchannel reactor module is divided into a direct-current channel structure and an enhanced mass transfer structure, wherein the direct-current channel structure is in a tubular structure and the like, and the enhanced mass transfer structure is in a heart shape or other shapes and the like.
The invention has the beneficial effects that:
the invention provides a method for synthesizing dinitroanthraquinone by a continuous flow microchannel, which is used for separating 1, 5-dinitroanthraquinone and 1, 8-dinitroanthraquinone by a silica gel column. The method is carried out in a continuous flow microchannel reactor, the reaction time is only dozens of seconds to several minutes, the reaction time is greatly reduced, the generation of side reactions is reduced, and the production efficiency is greatly improved.
The adopted equipment has accurate temperature control, rapid reaction, excellent heat transfer performance, temperature runaway prevention, and higher safety and reliability.
The adopted equipment is made of special glass, ceramics, silicon carbide and the like, and has stable performance and long service life. The continuous production quality is stable, manual operation is reduced, and intelligent production is convenient to realize. Can realize that one production line produces a plurality of nitroanthraquinone derivatives, and saves the configuration of production equipment for enterprises.
Drawings
FIG. 1 is a structural unit diagram of a microchannel reactor used in the present invention, wherein a is a straight flow channel with a tubular structure, and b is an enhanced mass transfer channel with a heart-shaped structure.
FIG. 2 is a simplified flow chart of the present invention.
FIG. 3 is a diagram of a simple apparatus of the present invention, in which 1, 2, 3, 4, 5 are raw material tanks, 6, 7, 8, 9, 10 are raw material weighing devices, 11, 12, 13 are mixing and preheating devices, 14, 15, 16 are metering pumps, 17, 18, 19 are pressure gauges, 20 is a reaction device, and 21 is a product collecting region.
Detailed Description
The present invention will be specifically illustrated below with reference to examples, but is not limited thereto.
Example 1
(1) The connection mode is determined by referring to fig. 2, the channel structure of the reactor is a in fig. 1, the molar ratio is determined according to the volume of the channel and the set flow rate, and the heat exchange medium of the heat exchanger is heat conduction oil.
(2) Mixing 150g of anthraquinone and 900g of sulfuric acid, and stirring to form an anthraquinone-sulfuric acid saturated solution; 92.5g of nitric acid and 370g of sulfuric acid are prepared into a mixed acid solution, and the solvent is dichloroethane. Preheating the three systems, and pumping into a metering pump respectively, wherein the anthraquinone-sulfuric acid saturated solution is pumped into a microchannel reactor at a flow rate of 14ml/min, the mixed acid solution is pumped into the microchannel reactor at a flow rate of 10ml/min and dichloroethane at a flow rate of 15ml/min, and the molar ratio of anthraquinone to nitric acid is 1: 2.1, controlling the reaction temperature at 120 ℃, the retention time at 40s, diluting the product with ice water, settling and absorbing acid, distilling out an organic phase, washing to obtain a crude dinitroanthraquinone product, and detecting by liquid chromatography, wherein the conversion rate of anthraquinone is 99%; separating the crude product by a silica gel column, wherein a mixture solvent of methanol and water is used as a mobile phase for separation, and the mass ratio of the methanol to the water is 4: 6; 1. the content of 5-dinitroanthraquinone is 70 percent, and the HPLC purity is 99.8 percent; 1. The content of 8-dinitroanthraquinone is 29 percent, and the HPLC purity is 99.6 percent.
Example 2
And (3) determining a connection mode by referring to FIG. 2, wherein the channel structure of the reactor is b in FIG. 1, the molar ratio is determined according to the volume of the channel and the set flow rate, and the heat exchange medium of the heat exchanger is heat conduction oil.
Mixing 150g of anthraquinone and 600g of sulfuric acid, and stirring to form an anthraquinone-sulfuric acid saturated solution; 92.5g of nitric acid and 370g of sulfuric acid are prepared into a mixed acid solution, and the solvent is dichloroethane. Preheating the three systems, and pumping into a metering pump respectively, wherein the anthraquinone-sulfuric acid saturated solution is pumped into a microchannel reactor at a flow rate of 14ml/min, the mixed acid solution is pumped into the microchannel reactor at a flow rate of 14ml/min and dichloroethane at a flow rate of 15ml/min, and the molar ratio of anthraquinone to nitric acid is 1: 2.1, controlling the reaction temperature to be 110 ℃, keeping the reaction temperature for 200s, diluting the product with ice water, settling and absorbing acid, distilling out an organic phase, washing to obtain a crude dinitroanthraquinone product, detecting by liquid chromatography, wherein the conversion rate of anthraquinone is 99.4 percent, separating the crude dinitroanthraquinone product by a silica gel column, and separating by using a mixture solvent of methanol and water as a mobile phase, wherein the mass ratio of methanol to water is 4: 6; 1. the content of 5-dinitroanthraquinone is 69 percent, and the HPLC purity is 99.7 percent; 1. the content of 8-dinitroanthraquinone is 30.4%, and the HPLC purity is 99.6%.
Example 3
The connection mode is determined by referring to fig. 2, the channel structure of the reactor is a in fig. 1, the molar ratio is determined according to the volume of the channel and the set flow rate, and the heat exchange medium of the heat exchanger is heat conduction oil.
Mixing 150g of anthraquinone and 600g of sulfuric acid, and stirring to form an anthraquinone-sulfuric acid saturated solution; 92.5g of nitric acid and 277.5g of sulfuric acid are prepared into a mixed acid solution, and the solvent is dichloroethane. Preheating the three systems, and pumping into a metering pump respectively, wherein an anthraquinone-sulfuric acid saturated solution is pumped into a microchannel reactor at a flow rate of 14ml/min, a mixed acid solution is pumped into the microchannel reactor at a flow rate of 15ml/min and dichloroethane at a flow rate of 15ml/min, and the molar ratio of anthraquinone to nitric acid is 1: 2.3, controlling the reaction temperature to be 100 ℃, keeping the reaction temperature for 300s, diluting the product with ice water, settling and absorbing acid, distilling out an organic phase, washing to obtain a crude dinitroanthraquinone product, detecting by liquid chromatography, wherein the conversion rate of anthraquinone is 99.8 percent, separating the crude dinitroanthraquinone product by a silica gel column, and separating by using a mixture solvent of methanol and water as a mobile phase, wherein the mass ratio of methanol to water is 4: 6; 1. the content of 5-dinitroanthraquinone is 71 percent, and the HPLC purity is 99.8 percent; 1. The content of 8-dinitroanthraquinone is 28.8%, and the HPLC purity is 99.7%.
Example 4
And (3) determining a connection mode by referring to FIG. 2, wherein the channel structure of the reactor is b in FIG. 1, the molar ratio is determined according to the volume of the channel and the set flow rate, and the heat exchange medium is heat conduction oil.
Mixing 150g of anthraquinone and 600g of sulfuric acid, and stirring to form an anthraquinone-sulfuric acid saturated solution; 92.5g of nitric acid and 185g of sulfuric acid are prepared into mixed acid solution, and the solvent is chloroform. Preheating the three systems, pumping into the systems through metering pumps respectively, pumping an anthraquinone-sulfuric acid saturated solution at 14ml/min, pumping a mixed acid solution at 10ml/min and chloroform at a flow rate of 15ml/min into a microchannel reactor, wherein the molar ratio of anthraquinone to nitric acid is 1: 2.1, controlling the reaction temperature to be 110 ℃, keeping the reaction temperature for 60s, diluting the product with ice water, settling and absorbing acid, distilling out an organic phase, washing to obtain a crude dinitroanthraquinone product, detecting by liquid chromatography, wherein the conversion rate of anthraquinone is 99.2%, separating the crude dinitroanthraquinone product by a silica gel column, and separating by using a mixture solvent of methanol and water as a mobile phase, wherein the mass ratio of methanol to water is 4: 6; 1. the content of 5-dinitroanthraquinone is 68 percent, and the HPLC purity is 99.8 percent; 1. the content of 8-dinitroanthraquinone is 31.2%, and the HPLC purity is 99.5%.
Example 5
The connection mode is determined by referring to fig. 2, the channel structure of the reactor is a in fig. 1, the molar ratio is determined according to the volume of the channel and the set flow rate, and the heat exchange medium of the heat exchanger is heat conduction oil.
Mixing 150g of anthraquinone and 600g of sulfuric acid, and stirring to form an anthraquinone-sulfuric acid saturated solution; 92.5g of nitric acid and 185g of sulfuric acid are prepared into a mixed acid solution, and the solvent is ethyl acetate. Preheating the three systems, pumping in the three systems through metering pumps respectively, pumping a quinone-sulfuric acid saturated solution at 14ml/min, pumping a mixed acid solution at 15ml/min and ethyl acetate at a flow rate of 15ml/min into a microchannel reactor, wherein the molar ratio of anthraquinone to nitric acid is 1: 2.3, controlling the reaction temperature to be 100 ℃, keeping the reaction temperature for 100s, diluting the product with ice water, settling and absorbing acid, distilling out an organic phase, washing to obtain a crude dinitroanthraquinone product, detecting by liquid chromatography, wherein the conversion rate of anthraquinone is 99.5 percent, separating the crude dinitroanthraquinone product by a silica gel column, and separating by using a mixture solvent of methanol and water as a mobile phase, wherein the mass ratio of methanol to water is 4: 6; 1. the content of 5-dinitroanthraquinone is 70.5 percent, and the HPLC purity is 99.7 percent; 1. the content of 8-dinitroanthraquinone is 29 percent, and the HPLC purity is 99.5 percent.
Claims (1)
1. A method for synthesizing dinitroanthraquinone by a continuous flow microchannel reactor is characterized by comprising the following steps:
step 1, preheating an anthraquinone-concentrated sulfuric acid saturated solution, a mixed acid nitration solution of mercuric sulfate and an organic solvent respectively serving as three strands of materials, and then respectively introducing the materials into a continuous flow microchannel reactor through a metering pump;
step 2, controlling the flow of the materials by a metering pump, enabling the preheated anthraquinone-concentrated sulfuric acid saturated solution, the mixed acid nitration solution of mercury sulfate and the organic solvent to synchronously enter a micro-channel reactor module for mixing reaction according to set flow rates, controlling the reaction temperature by an external heat exchanger, enabling a heat exchange medium to be heat conduction oil, enabling a product to flow out of an outlet of the reactor, and enabling the product to enter a product collecting region for further treatment;
step 3, diluting the material obtained at the outlet of the microchannel reactor by ice water, standing and settling, and separating out sulfuric acid mother liquor; distilling and recovering an organic phase;
step 4, separating by a silica gel column, wherein a mobile phase is a mixture solvent of methanol and water, and the mass ratio of the methanol to the water is 4: 6;
wherein the mass ratio of anthraquinone to concentrated sulfuric acid in the anthraquinone-concentrated sulfuric acid saturated solution in the step 1 is 1:3-5, and the mass ratio of concentrated nitric acid to concentrated sulfuric acid in the mixed acid nitration solution of mercury sulfate is 1: 2-4; wherein the concentration of the nitric acid is 85-98 percent, and the concentration of the sulfuric acid is 90-98 percent; the mass of the mercuric sulfate and the anthraquinone is 0,03-0, 05: 1; the organic solvent is one or more selected from dichloroethane, chloroform, ethyl acetate, acetone, acetonitrile, cyclohexane, N-dimethylformamide and N, N-dimethylacetamide; the volume ratio of the organic solvent to the anthraquinone is 1-10: 1;
wherein the set flow rate of the anthraquinone-concentrated sulfuric acid saturated solution in the step 2 is 10-20ml/min, and the flow rate of the sulfuric acid-nitric acid solution is 10-14 ml/min; the flow rate of the organic solvent is 10-20 ml/min;
wherein the time for carrying out the mixing reaction in the microchannel reactor module in the step 2 is 60-150 s; the reaction temperature is 100 ℃; the reaction pressure is 0-5 bar.
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