CN111662183B - Method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using microchannel reactor - Google Patents
Method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using microchannel reactor Download PDFInfo
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Abstract
The invention relates to a method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using a microchannel reactor, which comprises the steps of respectively pumping a hydrochloric acid solution and o-chloroaniline into a microchannel salifying module for salifying reaction, and feeding the obtained o-chloroaniline hydrochloride solution into a microchannel condensation rearrangement module for condensation and rearrangement reaction with a formaldehyde solution; feeding the obtained condensation rearrangement reaction liquid into a micro-channel neutralization module to perform neutralization reaction with alkali liquor; performing continuous oil-water separation on the product, and enabling the separated oil layer to enter a micro-channel water washing module for water washing and then performing oil-water separation; the purity of the obtained MOCA product reaches more than 95 percent, and the chroma is stable. According to the invention, the microchannel reactor is utilized to sequentially and continuously perform homogeneous phase feeding on different microchannel reactor modules, so that continuous MOCA production is realized, the production efficiency is greatly improved, the product uniformity and stability are obviously improved, the full-process automatic operation is realized, and the method is suitable for industrial popularization and application.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using a microchannel reactor.
Background
3,3 '-dichloro-4, 4' -diaminodiphenylmethane is a commonly used aromatic diamine chain extender, commonly known as MOCA, can be used as a cross-linking agent, a curing agent and a vulcanizing agent, can also be used for preparing products with higher electric resistance, and is widely applied in a plurality of industrial fields of airplanes, automobiles, mining and the like.
In 1953, duPont, USA, who developed MOCA synthesis technology, first reacted o-chloroaniline with hydrochloric acid to generate o-chloroaniline hydrochloride, then condensed the salt solution with formaldehyde to generate MOCA hydrochloride, then neutralized the hydrochloric acid with NaOH, and finally obtained MOCA product through water washing, steam distillation and other steps. Most of the production processes adopt kettle type batch reactors, the reaction time is long, the operation is complex, the continuous production is difficult to realize, the treatment process after the reaction is long, the steps are complex, the energy consumption is high, and the quality of MOCA products is easy to reduce.
CN105294448B discloses a method for continuously preparing 4, 4-diaminodiphenylmethane derivatives by solid acid catalysis, which takes aniline derivatives and formaldehyde as raw materials, and carries out condensation reaction by solid acid catalysis in a first-stage or second-stage fixed bed reactor to obtain the 4, 4-diaminodiphenylmethane derivatives (MDA, MDT and MOCA). The method uses solid acid H beta, HY and HZSM-5 molecular sieves to replace traditional inorganic acid catalysts such as hydrochloric acid and sulfuric acid, and the process is simpler; however, the MOCA synthesized by the process has low yield, high unit consumption of o-chloroaniline, easy inactivation of the solid acid catalyst and difficult regeneration, and research stays in a laboratory pilot plant stage, so that industrialization is not realized.
CN205933698U discloses a 3,3 '-dichloro-4, 4' -diaminodiphenylmethane continuous condensation device, which comprises a microreactor, a tubular reactor and a neutralization kettle which are sequentially communicated, wherein a material inlet of the microreactor is respectively communicated with a raw material metering tank and the microreactor through a metering pump, the temperature of the microreactor is controlled after the materials enter the microreactor, the materials enter the neutralization kettle through the tubular reactor for neutralization, and a product MOCA is obtained after neutralization; the method has the advantages of low energy consumption and realization of continuous production in partial steps, but the tubular reactor adopts gravity to push materials to flow, so that the mixing effect is poorer than that of the traditional kettle type reactor, and the mass and heat transfer efficiency is low.
CN106986777B discloses a method for preparing 4, 4-diaminodiphenylmethane derivatives by using a microreactor, which comprises the steps of respectively conveying aniline derivative hydrochloride and formaldehyde solution into the microreactor through advection pumps to contact, mix and react, then cooling, dropwise adding sodium hydroxide solution to separate out white precipitate, filtering and drying to obtain crude 4, 4-diaminodiphenylmethane derivatives (MDA, MDT or MOCA), recrystallizing with ethanol, filtering and drying to obtain pure products. The method needs to be provided with a separate salifying kettle, the salifying liquid is a solid-liquid two-phase mixture, and the liquid-solid two-phase mixture is fed, so that the system can not continuously run due to the blockage of a micro-channel.
Therefore, improvement of the MOCA synthesis process, product quality enhancement, production efficiency improvement, raw material loss reduction and wastewater discharge reduction, and industrial large-scale production are urgently needed.
Disclosure of Invention
The invention aims to provide a method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using a microchannel reactor, which aims to solve the problems in the prior art, reduce side reactions, enhance the product quality, improve the production efficiency, reduce the raw material loss and the wastewater discharge so as to realize green and environment-friendly industrial scale-up production.
The technical scheme for solving the problems is as follows: a method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using a microchannel reactor comprises the following steps:
(1) Respectively and simultaneously pumping the hydrochloric acid solution and the o-chloroaniline into a microchannel salifying module to carry out salifying reaction to obtain an o-chloroaniline hydrochloride solution;
(2) Sending the o-chloroaniline hydrochloride solution obtained in the step (1) into a microchannel condensation rearrangement module, simultaneously pumping formaldehyde solution into the microchannel condensation rearrangement module, and carrying out condensation and rearrangement reaction in the microchannel condensation rearrangement module;
(3) Feeding the condensation rearrangement reaction liquid obtained in the step (2) into a micro-channel neutralization module, and simultaneously pumping alkali liquor into the micro-channel neutralization module to perform neutralization reaction in the micro-channel neutralization module;
(4) Feeding the neutralization reaction liquid obtained in the step (3) into a first delayer, carrying out oil-water separation, feeding an oil layer obtained by separation into a micro-channel washing module for washing, and carrying out steam stripping on a water layer obtained by separation to recover o-chloroaniline;
(5) And (5) feeding the product obtained after washing by the micro-channel washing module in the step (4) into a second layering device for oil-water separation, feeding the upper water layer obtained by separation into a distillation reactor for steam stripping to recover water, and feeding the lower oil layer obtained by separation into a product collecting tank for collection and drying to obtain the MOCA product.
Further, in the method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using a microchannel reactor, in the step (1), the concentration of hydrochloric acid in the hydrochloric acid solution is 10-25% by mass.
Further, in the method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using a microchannel reactor according to the present invention, in the step (1) and the step (2), the molar ratio of the hydrochloric acid to the o-chloroaniline to the formaldehyde is (1.5 to 1.1): 1: (0.4-0.7).
Further, in the method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using a microchannel reactor, in the step (2), the mass percentage concentration of formaldehyde in the formaldehyde aqueous solution is 10-37%.
Further, in the continuous preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using microchannel reactor of the present invention, in the step (2), the feeding mode of the formaldehyde solution is one feed or multiple feeds.
Further, in the method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using a microchannel reactor, in the step (2), there are n groups of the microchannel condensation rearrangement modules, the n groups of the microchannel condensation rearrangement modules are sequentially connected in series, and each group of the microchannel condensation rearrangement modules respectively and independently corresponds to one feed of the formaldehyde solution.
Further, in the method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using a microchannel reactor according to the present invention, in the step (1), the step (2) and the step (3), the temperature in the microchannel salt-forming module, the microchannel condensation rearrangement module and the microchannel neutralization module is 80 to 120 ℃.
Further, in the continuous preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using microchannel reactor of the present invention, in the step (3), the alkali solution is sodium hydroxide solution.
Further, in the method for continuously preparing the 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using the microchannel reactor, in the step (3), the molar ratio of the sodium hydroxide to the hydrochloric acid is (1.0-1.3): 1.
Further, in the method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using the microchannel reactor, the total reaction time of the step (1), the step (2) and the step (3) is 30-300 s.
Compared with the prior art, the invention has the beneficial effects that: the MOCA is creatively prepared by using the microchannel reactor, and the process design is optimized, so that the problems of poor heat transfer effect, poor material mixing effect, heterogeneous feeding, incapability of continuous production and the like in the prior art are effectively solved; the method has the advantages that materials are sequentially and continuously conveyed on different microchannel reactor modules by utilizing the microchannel reactor, so that continuous production of MOCA is realized, meanwhile, the raw materials are fully contacted through homogeneous feeding of reaction raw materials, the specific surface area is large, the heat and mass transfer efficiency is fully improved, so that the raw material mixing and contacting time is short, the reaction is fast and uniform, byproducts are few, the product quality uniformity and stability are remarkably improved, the purity of the obtained MOCA product can reach more than 95%, the chromaticity is stable, and the economic benefit is remarkably enhanced; in addition, because the mass transfer and the reaction process are completed in the micro-reaction channel, a conventional stirring device is not needed, the operation complexity is reduced, and meanwhile, the energy consumption such as acid consumption, alkali consumption and the like is greatly reduced; by using the microchannel reactor, the raw materials are fully and uniformly contacted, no local aggregation exists, the reaction safety is high, the full process is automatically operated, no amplification effect exists in the industrial process, and the method is suitable for large-scale popularization and application.
Drawings
FIG. 1 is a schematic flow diagram of a portion of the continuous process for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using a microchannel reactor according to the present invention;
FIG. 2 is a schematic diagram of the distribution flow of the microchannel condensation rearrangement module in the continuous preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using the microchannel reactor.
Detailed Description
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, the raw materials and reagents in the examples of the present invention were all purchased from commercial sources.
As shown in figure 1, the method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using the microchannel reactor comprises the following steps:
(1) Respectively and simultaneously pumping the hydrochloric acid solution and the o-chloroaniline into a microchannel salifying module to carry out salifying reaction to obtain an o-chloroaniline hydrochloride solution;
(2) Sending the o-chloroaniline hydrochloride solution obtained in the step (1) into a microchannel condensation rearrangement module, simultaneously pumping formaldehyde solution into the microchannel condensation rearrangement module, and carrying out condensation and rearrangement reaction in the microchannel condensation rearrangement module;
(3) Feeding the condensation rearrangement reaction liquid obtained in the step (2) into a micro-channel neutralization module, and simultaneously pumping alkali liquor into the micro-channel neutralization module to perform neutralization reaction in the micro-channel neutralization module;
(4) Feeding the neutralization reaction solution obtained in the step (3) into a first delayer for oil-water separation, feeding an oil layer obtained by separation into a micro-channel washing module for washing, and carrying out steam stripping on a water layer obtained by separation to recover o-chloroaniline;
(5) And (3) feeding the product obtained after the micro-channel washing module in the step (4) is washed by water into a second layer separator, carrying out oil-water separation, feeding the upper water layer obtained by separation into a distillation reactor for steam stripping to recover water, and feeding the lower oil layer obtained by separation into a product collecting tank for collection and drying to obtain the MOCA product.
In the method for continuously preparing the 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using the microchannel reactor, the MOCA preparation production thinking of the traditional batch process and other continuous processes is broken through, the microchannel reactor is innovatively adopted for continuously preparing the MOCA, and the overall process is optimally designed based on the combination of the characteristics of the microchannel reactor and the reaction process of the MOCA preparation, so that a plurality of microchannel reactor modules are combined into a system for continuously preparing the MOCA; in the microchannel salifying module, the microchannel condensation rearrangement module, the microchannel neutralization module and the microchannel water washing module, feeding materials such as hydrochloric acid solution, o-chloroaniline, formaldehyde solution, alkali liquor, water washing water and the like in a continuous flow mode through a micro pipeline of each microchannel reactor module respectively, and enabling the materials to enter reaction materials in each microchannel reactor module for rapid mixing; in the process, each material fluid is fully contacted with the wall of the corresponding microchannel reactor module, and the in-situ efficient heat exchange in the reaction process is realized based on the extremely large specific surface area of the microchannel reactor; the materials fed by the micro-pipeline continuous flow are uniformly distributed in a flow field in a laminar flow state, the contacted materials are uniformly and quickly mixed, and the reaction liquid is homogeneous at each reaction stage of MOCA, so that the retention time and the reaction temperature of the materials under the reaction condition can be accurately controlled, the initiation or termination of the reaction is facilitated, and the reaction safety is effectively controlled; therefore, MOCA is prepared by the process method designed by the invention, the uniformity of the obtained product is improved, the generated byproducts are reduced, the MOCA is green and safe, the side reactions are few, the mass production can be realized by adding a micro-reaction unit, the amplification effect is basically avoided, the full process is automatically operated, and the MOCA is suitable for large-scale industrial popularization and application.
In the above method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using a microchannel reactor, each material is fed homogeneously in a continuous flow manner through the microchannel of each microchannel reactor module, and after the reaction, the material is continuously fed into the next step stage as homogeneous output, specifically, in step (1), the following salt-forming reaction occurs:
in step (2), the following condensation and rearrangement reactions occur:
in step (3), the following neutralization reaction occurs:
in order to ensure the quality of MACA products such as purity, chromaticity and the like, preferably, in the step (1), the mass percentage concentration of hydrochloric acid in the hydrochloric acid solution is 10-25%; in the step (2), the mass percentage concentration of formaldehyde in the formaldehyde aqueous solution is 10-37%; in the step (1) and the step (2), the molar ratio of the hydrochloric acid to the o-chloroaniline to the formaldehyde is (1.5-1.1): 1: (0.4 to 0.7); in the step (3), in order to guarantee the neutralization effect, the alkali liquor is preferably sodium hydroxide solution, the molar ratio of the sodium hydroxide to the hydrochloric acid is (1.0-1.3): 1, so as to guarantee the neutralization efficiency; more preferably, in the step (1), the step (2) and the step (3), the temperature of the microchannel salifying module, the microchannel condensation rearrangement module and the microchannel neutralization module is controlled to be 80-120 ℃, so as to be beneficial to realizing homogeneous feeding, and particularly, the o-chloroaniline hydrochloride is dissolved in hydrochloric acid to provide guarantee for homogeneous continuous reaction; and (3) controlling the total reaction time of the step (1), the step (2) and the step (3) to be 30-300 s, and avoiding the problems of unstable chromaticity and the like caused by overlong reaction time.
In the above method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using a microchannel reactor, in the step (2), the feeding manner of the formaldehyde solution can be one feed or multiple feeds, and preferably, the feeding manner of the formaldehyde solution is multiple feeds; the number of the microchannel condensation rearrangement modules is n (n is more than or equal to 1), preferably, the number of the microchannel condensation rearrangement modules is more than two, and preferably, the number of the microchannel condensation rearrangement modules is 3-5; when the microchannel condensation rearrangement module has more than two groups, preferably, the n groups of microchannel condensation rearrangement modules are sequentially connected in series, each group of microchannel condensation rearrangement modules respectively and independently corresponds to one feed of the formaldehyde solution, and as shown in fig. 2, for example, 5 groups of microchannel condensation rearrangement modules are combined, that is, a first microchannel condensation rearrangement module, a second microchannel condensation rearrangement module, a third microchannel condensation rearrangement module, a fourth microchannel condensation rearrangement module and a fifth microchannel condensation rearrangement module are sequentially connected in series, when the module is specifically operated, the obtained adjacent chloroanilide hydrochloride solution in step (1) sequentially enters the first microchannel condensation rearrangement module, the second microchannel condensation rearrangement module, the third microchannel condensation rearrangement module, the fourth microchannel condensation rearrangement module and the fifth microchannel condensation rearrangement module, and simultaneously, the formaldehyde solution is equally divided into five feeds, and each feed respectively pumps the formaldehyde solution into each microchannel condensation rearrangement module, so that condensation and rearrangement reactions are performed in each microchannel condensation rearrangement module, and finally the reaction solution and the microchannel condensation rearrangement module are conveyed to the condensation rearrangement module through the fifth microchannel condensation rearrangement module; therefore, through the arrangement of the plurality of groups of microchannel condensation rearrangement modules, formaldehyde is fed in a plurality of strands in a segmented manner, the reaction is guaranteed, the concentration of formaldehyde in a single microchannel condensation rearrangement module is reduced, the self-polymerization of formaldehyde and the side reaction of impurities such as tripolymer and tetramer generated by the reaction of the formaldehyde and o-chloroaniline hydrochloride are reduced, and the purity and the yield of MOCA products are improved.
In the above-described continuous preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using a microchannel reactor, the MOCA product obtained in step (5), i.e., 3 '-dichloro-4, 4' -diaminodiphenylmethane, is subjected to a colorimetric test, preferably, using the MOCA colorimetric measurement method specified in the trade mark HG/T2711-2012, i.e.: preparing potassium chloroplatinate-hydrochloric acid colorimetric liquids with different contents to obtain colorimetric liquids with 1-8 # chromaticity, transferring the molten MOCA product into a nano colorimetric tube, and performing visual comparison on the molten MOCA product and the colorimetric liquids with the potassium chloroplatinate-hydrochloric acid colorimetric liquids to obtain the chromaticity of the product; test analysis shows that the color intensity of the MOCA product prepared by the invention meets the standard, is stable and is obviously superior to that of products obtained by the traditional intermittent and other continuous processes.
The present invention will be further described in more detail with reference to the following more specific application examples, but the present invention is not limited to any of these examples.
Example 1
(1) Simultaneously pumping 3406.7g of hydrochloric acid solution and 1276.3g of o-chloroaniline into a micro-channel salifying module respectively, and carrying out salifying reaction at 90 ℃ to obtain an o-chloroaniline hydrochloride solution; wherein, the mass percent concentration of the hydrochloric acid in 3406.7g of the hydrochloric acid solution is 15 percent, and the hydrochloric acid is 14mol;1276.3g o-chloroaniline is analytically pure, the purity is 99.9%;
(2) Sending the o-chloroaniline hydrochloride solution obtained in the step (1) into a microchannel condensation rearrangement module, simultaneously pumping 1650g of formaldehyde solution into the microchannel condensation rearrangement module, and carrying out condensation and rearrangement reaction in the microchannel condensation rearrangement module at 95 ℃; wherein, the mass percent concentration of the formaldehyde in 1650g of the formaldehyde solution is 10 percent, and the formaldehyde solution contains 5.5mol; the mol ratio of the hydrochloric acid to the o-chloroaniline to the formaldehyde is 1.4:1:0.55; the microchannel condensation rearrangement module is a group, 1650g of formaldehyde solution is pumped into the microchannel condensation rearrangement module in a single-strand feeding mode;
(3) Feeding the condensation rearrangement reaction liquid obtained in the step (2) into a micro-channel neutralization module, and simultaneously pumping 1987g of sodium hydroxide solution into the micro-channel neutralization module to perform neutralization reaction in the micro-channel neutralization module at 95 ℃; wherein the mass percent concentration of sodium hydroxide in the sodium hydroxide solution is 31 percent, the sodium hydroxide is 15.4mol, and the molar ratio of the sodium hydroxide to the hydrochloric acid is 1.1;
(4) Controlling the total reaction residence time of each material in the step (1), the step (2) and the step (3) to be 60s, then sending the neutralization reaction liquid obtained in the step (3) into a first layering device for continuous oil-water separation, enabling an oil layer obtained by separation to enter a micro-channel water washing module for continuous water washing, and performing steam stripping on a water layer obtained by separation to recover o-chloroaniline;
(5) Sending the product obtained after the micro-channel washing module in the step (4) is washed by water into a second layer separator for oil-water separation, sending the upper water layer obtained by separation into a distillation reactor for steam stripping to recover water, sending the lower oil layer obtained by separation into a product collecting tank for collection and drying to obtain an MOCA product; wherein the amount of the washing water is 0.7 times of the weight of the MOCA oil layer; the obtained MOCA product is 1277.3g, and the purity is 95.5%; and detecting the obtained MOCA product according to an MOCA chromaticity measurement method specified in the row standard HG/T2711-2012, wherein the detected chromaticity is 3.
Example 2
(1) Respectively and simultaneously pumping 5475g of hydrochloric acid solution and 1276.3g of o-chloroaniline into a micro-channel salifying module, and carrying out salifying reaction at 85 ℃ to obtain o-chloroaniline hydrochloride solution; wherein, the mass percent concentration of hydrochloric acid in 5475g of hydrochloric acid solution is 10%, and the hydrochloric acid content is 15mol;1276.3g o-chloroaniline is analytically pure, the purity is 99.9%;
(2) Sending the o-chloroaniline hydrochloride solution obtained in the step (1) into a microchannel condensation rearrangement module, simultaneously pumping 1500g of formaldehyde solution into the microchannel condensation rearrangement module, and carrying out condensation and rearrangement reaction in the microchannel condensation rearrangement module; wherein, the mass percentage concentration of the formaldehyde in 1500g of formaldehyde solution is 10 percent, and the formaldehyde solution contains 5mol of formaldehyde; the molar ratio of the hydrochloric acid to the o-chloroaniline to the formaldehyde is 1.5:1:0.5; the number of the microchannel condensation rearrangement modules is two, namely a first microchannel condensation rearrangement module and a second microchannel condensation rearrangement module, and the first microchannel condensation rearrangement module and the second microchannel condensation rearrangement module are sequentially connected in series; continuously conveying the o-chloroaniline hydrochloride solution obtained in the step (1) into the first microchannel condensation rearrangement module and the second microchannel condensation rearrangement module in sequence; the 1500g of formaldehyde solution is divided into two strands, and each strand of formaldehyde solution is respectively pumped into the first microchannel condensation rearrangement module and the second microchannel condensation rearrangement module; condensation and rearrangement reactions are sequentially carried out in the first microchannel condensation and rearrangement module and the second microchannel condensation and rearrangement module, specifically, the temperature of the first microchannel condensation and rearrangement module is controlled to be 85 ℃, the temperature of the second microchannel condensation and rearrangement module is controlled to be 90 ℃, and the condensation and rearrangement reactions are continuously carried out;
(3) Sending the condensation rearrangement reaction liquid obtained in the step (2) into a micro-channel neutralization module, simultaneously pumping 2032g of sodium hydroxide solution into the micro-channel neutralization module, and carrying out neutralization reaction in the micro-channel neutralization module at 90 ℃; wherein the mass percent concentration of sodium hydroxide in the sodium hydroxide solution is 31 percent, the sodium hydroxide is 15.75mol, and the molar ratio of the sodium hydroxide to the hydrochloric acid is 1.05;
(4) Controlling the total reaction residence time of each material in the step (1), the step (2) and the step (3) to be 120s, then sending the neutralization reaction liquid obtained in the step (3) into a first layering device for continuous oil-water separation, enabling an oil layer obtained by separation to enter a micro-channel water washing module for continuous water washing, and performing steam stripping on a water layer obtained by separation to recover o-chloroaniline;
(5) Sending the product obtained after the micro-channel washing module in the step (4) is washed by water into a second layer separator for oil-water separation, sending the upper water layer obtained by separation into a distillation reactor for steam stripping to recover water, sending the lower oil layer obtained by separation into a product collecting tank for collection and drying to obtain an MOCA product; wherein the amount of water used for washing is 1.0 time of the weight of the MOCA oil layer; the obtained MOCA product is 1286.4g, and the purity is 95.2%; and detecting the obtained MOCA product according to an MOCA chromaticity measurement method specified in the row standard HG/T2711-2012, wherein the detected chromaticity is 3.
Example 3
(1) 1898g of hydrochloric acid solution and 1276.3g of o-chloroaniline are respectively and simultaneously pumped into a micro-channel salifying module to carry out salifying reaction at 90 ℃ to obtain o-chloroaniline hydrochloride solution; wherein, 1898g hydrochloric acid solution contains 13mol hydrochloric acid, and the mass percentage concentration of hydrochloric acid is 25%; 1276.3g of o-chloroaniline is analytically pure, and the purity is 99.9%;
(2) Sending the o-chloroaniline hydrochloride solution obtained in the step (1) into a microchannel condensation rearrangement module, simultaneously pumping 800g of formaldehyde solution into the microchannel condensation rearrangement module, and carrying out condensation and rearrangement reaction in the microchannel condensation rearrangement module; wherein the mass percent concentration of formaldehyde in 800g of formaldehyde solution is 15%, and the formaldehyde content is 4mol; the mol ratio of the hydrochloric acid to the o-chloroaniline to the formaldehyde is 1.3:1:0.4; the microchannel condensation rearrangement module comprises four groups, namely a first microchannel condensation rearrangement module, a second microchannel condensation rearrangement module, a third microchannel condensation rearrangement module and a fourth microchannel condensation rearrangement module, wherein the first microchannel condensation rearrangement module, the second microchannel condensation rearrangement module, the third microchannel condensation rearrangement module and the fourth microchannel condensation rearrangement module are sequentially connected in series; continuously conveying the o-chloroaniline hydrochloride solution obtained in the step (1), and sequentially entering a first microchannel condensation rearrangement module, a second microchannel condensation rearrangement module, a third microchannel condensation rearrangement module and a fourth microchannel condensation rearrangement module; the 800g of formaldehyde solution is divided into four strands, and each strand of formaldehyde solution is respectively pumped into the first microchannel condensation rearrangement module, the second microchannel condensation rearrangement module, the third microchannel condensation rearrangement module and the fourth microchannel condensation rearrangement module; sequentially carrying out condensation and rearrangement reactions in the first microchannel condensation rearrangement module, the second microchannel condensation rearrangement module, the third microchannel condensation rearrangement module and the fourth microchannel condensation rearrangement module, specifically, controlling the reaction temperature in the first microchannel condensation rearrangement module to be 95 ℃, the reaction temperature in the second microchannel condensation rearrangement module to be 95 ℃, the reaction temperature in the third microchannel condensation rearrangement module to be 100 ℃ and the reaction temperature in the fourth microchannel condensation rearrangement module to be 100 ℃, and continuously carrying out condensation and rearrangement reactions;
(3) Sending the condensation rearrangement reaction liquid obtained in the step (2) into a micro-channel neutralization module, simultaneously pumping 1929g of sodium hydroxide solution into the micro-channel neutralization module, and carrying out neutralization reaction in the micro-channel neutralization module at 100 ℃; wherein the mass percent concentration of sodium hydroxide in the sodium hydroxide solution is 31 percent, the sodium hydroxide is 14.95mol, and the molar ratio of the sodium hydroxide to the hydrochloric acid is 1.15;
(4) Controlling the total reaction residence time of each material in the steps (1), (2) and (3) to 240s, then sending the neutralization reaction liquid obtained in the step (3) into a first layering device, carrying out continuous oil-water separation, feeding the separated oil layer into a micro-channel water washing module for continuous water washing, and carrying out steam stripping on the separated water layer to recover o-chloroaniline;
(5) Sending the product obtained after the micro-channel washing module in the step (4) is washed by water into a second layer separator for oil-water separation, sending the upper water layer obtained by separation into a distillation reactor for steam stripping to recover water, sending the lower oil layer obtained by separation into a product collecting tank for collection and drying to obtain an MOCA product; wherein the amount of water used for washing is 1.2 times of the weight of the MOCA oil layer; the obtained MOCA product is 1272.4g, and the purity is 95.9%; the obtained MOCA product is detected according to the MOCA chromaticity measurement method specified in the row standard HG/T2711-2012, and the detected chromaticity is 3+.
Example 4
(1) Respectively pumping 3088.5g of hydrochloric acid solution and 1276.3g of o-chloroaniline into a microchannel salt forming module at the same time, and carrying out salt forming reaction at 95 ℃ to obtain o-chloroaniline hydrochloride solution; wherein 3088.5g of hydrochloric acid solution contains 11mol of hydrochloric acid, and the mass percentage concentration of the hydrochloric acid is 13%; 1276.3g o-chloroaniline is analytically pure, the purity is 99.9%;
(2) Sending the o-chloroaniline hydrochloride solution obtained in the step (1) into a microchannel condensation rearrangement module, simultaneously pumping 720g of formaldehyde solution into the microchannel condensation rearrangement module, and carrying out condensation and rearrangement reaction in the microchannel condensation rearrangement module; wherein the mass percent concentration of formaldehyde in 720g of formaldehyde solution is 25 percent, and the formaldehyde solution contains 6mol of formaldehyde; the mol ratio of the hydrochloric acid to the o-chloroaniline to the formaldehyde is 1.1:1:0.6; the microchannel condensation rearrangement module comprises five groups, namely a first microchannel condensation rearrangement module, a second microchannel condensation rearrangement module, a third microchannel condensation rearrangement module, a fourth microchannel condensation rearrangement module and a fifth microchannel condensation rearrangement module, wherein the first microchannel condensation rearrangement module, the second microchannel condensation rearrangement module, the third microchannel condensation rearrangement module, the fourth microchannel condensation rearrangement module and the fifth microchannel condensation rearrangement module are sequentially connected in series; continuously conveying the o-chloroaniline hydrochloride solution obtained in the step (1), and sequentially entering a first microchannel condensation rearrangement module, a second microchannel condensation rearrangement module, a third microchannel condensation rearrangement module, a fourth microchannel condensation rearrangement module and a fifth microchannel condensation rearrangement module; the 720g of formaldehyde solution is divided into five parts, and each part of formaldehyde solution is respectively pumped into the first microchannel condensation rearrangement module, the second microchannel condensation rearrangement module, the third microchannel condensation rearrangement module, the fourth microchannel condensation rearrangement module and the fifth microchannel condensation rearrangement module; condensation and rearrangement reactions are sequentially carried out in the first microchannel condensation and rearrangement module, the second microchannel condensation and rearrangement module, the third microchannel condensation and rearrangement module, the fourth microchannel condensation and rearrangement module and the fifth microchannel condensation and rearrangement module, specifically, the reaction temperature in the first microchannel condensation and rearrangement module is controlled to be 95 ℃, the reaction temperature in the second microchannel condensation and rearrangement module is controlled to be 95 ℃, the reaction temperature in the third microchannel condensation and rearrangement module is controlled to be 100 ℃, the reaction temperature in the fourth microchannel condensation and rearrangement module is controlled to be 100 ℃, the reaction temperature in the fifth microchannel condensation and rearrangement module is controlled to be 105 ℃, and condensation and rearrangement reactions are continuously carried out;
(3) Sending the condensation rearrangement reaction liquid obtained in the step (2) into a micro-channel neutralization module, simultaneously pumping 1845.2g of sodium hydroxide solution into the micro-channel neutralization module, and carrying out neutralization reaction in the micro-channel neutralization module at 110 ℃; wherein the mass percent concentration of sodium hydroxide in the sodium hydroxide solution is 31 percent, the sodium hydroxide is 14.3mol, and the molar ratio of the sodium hydroxide to the hydrochloric acid is 1.3;
(4) Controlling the total reaction residence time of each material in the steps (1), (2) and (3) to be 300s, then sending the neutralization reaction liquid obtained in the step (3) into a first layering device, carrying out continuous oil-water separation, feeding the separated oil layer into a micro-channel water washing module for continuous water washing, and carrying out steam stripping on the separated water layer to recover o-chloroaniline;
(5) Sending the product obtained after the micro-channel washing module in the step (4) is washed by water into a second layer separator for oil-water separation, sending the upper water layer obtained by separation into a distillation reactor for steam stripping to recover water, sending the lower oil layer obtained by separation into a product collecting tank for collection and drying to obtain an MOCA product; wherein the amount of water used for washing is 1.3 times of the weight of the MOCA oil layer; the obtained MOCA product is 1241.6g, and the purity is 96.1%; and detecting the obtained MOCA product according to an MOCA chromaticity measurement method specified in the row standard HG/T2711-2012, wherein the detected chromaticity is 4.
Example 5
(1) Respectively pumping 2920g of hydrochloric acid solution and 1276.3g of o-chloroaniline into a microchannel salt forming module at the same time, and carrying out salt forming reaction at 80 ℃ to obtain o-chloroaniline hydrochloride solution; wherein, the mass percent concentration of the hydrochloric acid in the 2920g hydrochloric acid solution is 15 percent, and the hydrochloric acid is 12mol;1276.3g of o-chloroaniline is analytically pure, and the purity is 99.9%;
(2) Sending the o-chloroaniline hydrochloride solution obtained in the step (1) into a microchannel condensation rearrangement module, simultaneously pumping 567.6g of formaldehyde solution into the microchannel condensation rearrangement module, and carrying out condensation and rearrangement reaction in the microchannel condensation rearrangement module; wherein, 567.6g of formaldehyde solution contains 7mol of formaldehyde, and the mass percentage concentration of the formaldehyde is 37%; the mol ratio of the hydrochloric acid to the o-chloroaniline to the formaldehyde is 1.2:1:0.7 of the total weight of the mixture; the microchannel condensation rearrangement module comprises five groups, namely a first microchannel condensation rearrangement module, a second microchannel condensation rearrangement module, a third microchannel condensation rearrangement module, a fourth microchannel condensation rearrangement module and a fifth microchannel condensation rearrangement module, wherein the first microchannel condensation rearrangement module, the second microchannel condensation rearrangement module, the third microchannel condensation rearrangement module, the fourth microchannel condensation rearrangement module and the fifth microchannel condensation rearrangement module are sequentially connected in series; continuously conveying the o-chloroaniline hydrochloride solution obtained in the step (1), and sequentially entering a first microchannel condensation rearrangement module, a second microchannel condensation rearrangement module, a third microchannel condensation rearrangement module, a fourth microchannel condensation rearrangement module and a fifth microchannel condensation rearrangement module; the 567.6g of formaldehyde solution is equally divided into five strands, and each strand of formaldehyde solution is respectively pumped into the first microchannel condensation rearrangement module, the second microchannel condensation rearrangement module, the third microchannel condensation rearrangement module, the fourth microchannel condensation rearrangement module and the fifth microchannel condensation rearrangement module; sequentially carrying out condensation and rearrangement reactions in the first microchannel condensation rearrangement module, the second microchannel condensation rearrangement module, the third microchannel condensation rearrangement module, the fourth microchannel condensation rearrangement module and the fifth microchannel condensation rearrangement module, specifically, controlling the reaction temperature in the first microchannel condensation rearrangement module to be 95 ℃, the reaction temperature in the second microchannel condensation rearrangement module to be 95 ℃, the reaction temperature in the third microchannel condensation rearrangement module to be 105 ℃, the reaction temperature in the fourth microchannel condensation rearrangement module to be 105 ℃ and the reaction temperature in the fifth microchannel condensation rearrangement module to be 120 ℃, and continuously carrying out condensation and rearrangement reactions;
(3) Feeding the condensation rearrangement reaction liquid obtained in the step (2) into a micro-channel neutralization module, simultaneously pumping 1548.4g of sodium hydroxide solution into the micro-channel neutralization module, and carrying out neutralization reaction in the micro-channel neutralization module at 110 ℃; wherein the mass percent concentration of sodium hydroxide in the sodium hydroxide solution is 31%, the sodium hydroxide is 12mol, and the molar ratio of the sodium hydroxide to the hydrochloric acid is 1;
(4) Controlling the total reaction residence time of each material in the step (1), the step (2) and the step (3) to be 30s, then sending the neutralization reaction liquid obtained in the step (3) into a first layering device for continuous oil-water separation, enabling an oil layer obtained by separation to enter a micro-channel water washing module for continuous water washing, and performing steam stripping on a water layer obtained by separation to recover o-chloroaniline;
(5) Sending the product obtained after the micro-channel washing module in the step (4) is washed by water into a second layer separator for oil-water separation, sending the upper water layer obtained by separation into a distillation reactor for steam stripping to recover water, sending the lower oil layer obtained by separation into a product collecting tank for collection and drying to obtain an MOCA product; wherein the amount of water used for washing is 0.75 times of the weight of the MOCA oil layer; the obtained MOCA product is 1241.6g, and the purity is 96.1%; and detecting the obtained MOCA product according to an MOCA chromaticity measurement method specified in the row standard HG/T2711-2012, wherein the detected chromaticity is 4.
The embodiment shows that MOCA prepared by the method provided by the invention saves materials, reduces time consumption, and ensures that the purity of the obtained product can reach more than 95.2%, and the chroma meets the detection standard and is stable.
To further illustrate the preparation method of MOCA provided by the present invention, a number of comparisons were also made to prepare MOCA according to conventional procedures, one of which is listed below as a comparative example.
Comparative example 1
1800.9g of hydrochloric acid solution (the mass percent concentration of hydrochloric acid is 30.4 percent and contains 15mol of hydrochloric acid) and 1276.3g of o-chloroaniline (10 mol, analytically pure and purity of 99.9 percent) are dripped into a salt forming kettle, the temperature of the salt forming kettle is 45 ℃, the reaction time is 60min, and a large amount of white o-chloroaniline hydrochloride solid is separated after the salt forming is finished. Then, 405.4g of formaldehyde solution (the mass percentage concentration of formaldehyde is 37%, and the formaldehyde content is 5 mol) is dripped into the salt forming solution for condensation reaction, the molar ratio of hydrochloric acid to o-chloroaniline to formaldehyde is controlled to be 1.5, the condensation reaction temperature is 47.5 ℃, the reaction time is 4h, then the temperature is raised to 90 ℃, and the temperature is kept for 2h. After the heat preservation is finished, dropwise adding a sodium hydroxide solution into the reaction solution for neutralization, wherein the molar ratio of sodium hydroxide to hydrochloric acid is 1.5; after neutralization, layering and washing are carried out, the amount of washing water is 2.2 times of the weight of the MOCA oil layer, and finally the oil layer is dehydrated and dried by a drying kettle to obtain 1232.2g of MOCA product, wherein the purity of the MOCA product is 88.3 percent, and the chroma is 4+.
Compared with the traditional process, the process for preparing the MOCA by using the microchannel reactor is optimized, the MOCA is continuously produced by sequentially and continuously conveying materials on different microchannel reactor modules, and meanwhile, the raw materials are fully contacted by uniformly feeding the reaction raw materials, so that the heat and mass transfer efficiency is improved, the reaction is fast and uniform, the production time is greatly shortened, and the production efficiency is obviously improved; the homogeneous phase of the reaction is effectively controlled to be carried out, the side reaction is less, the quality uniformity and stability of the product are obviously improved, the purity of the MOCA product is improved by 7.8 percent, the appearance of the product has no color difference, the chromaticity is stable and meets the standard and is stable, and the product is obviously superior to the product obtained by the traditional process; in addition, because the mass transfer and the reaction process are completed in the micro-reaction channel, a conventional stirring device is not needed, the operation complexity is reduced, and meanwhile, the acid consumption is reduced by more than 10 percent, the alkali consumption is reduced by 10 to 15 percent, and the water washing consumption is reduced by more than 30 percent; in addition, the application process of the invention is safe and controllable, the whole process is operated automatically, and the industrial process has no amplification effect, thus being beneficial to increasing the economic benefit and being suitable for industrial large-scale popularization.
The present invention is not limited to the above-described embodiments, and any obvious modifications or alterations to the above-described embodiments may be made by those skilled in the art without departing from the spirit of the present invention and the scope of the appended claims.
Claims (8)
1. A method for continuously preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane by using a microchannel reactor is characterized by comprising the following steps:
(1) Respectively and simultaneously pumping the hydrochloric acid solution and o-chloroaniline into a micro-channel salifying module to carry out salifying reaction to obtain an o-chloroaniline hydrochloride solution;
(2) Sending the o-chloroaniline hydrochloride solution obtained in the step (1) into a microchannel condensation rearrangement module, simultaneously pumping formaldehyde solution into the microchannel condensation rearrangement module, and carrying out condensation and rearrangement reaction in the microchannel condensation rearrangement module;
(3) Feeding the condensation rearrangement reaction liquid obtained in the step (2) into a micro-channel neutralization module, and simultaneously pumping alkali liquor into the micro-channel neutralization module to perform neutralization reaction in the micro-channel neutralization module;
(4) Feeding the neutralization reaction solution obtained in the step (3) into a first delayer for oil-water separation, feeding an oil layer obtained by separation into a micro-channel washing module for washing, and carrying out steam stripping on a water layer obtained by separation to recover o-chloroaniline;
(5) Feeding the product obtained after the microchannel washing module in the step (4) is washed into a second delayer for oil-water separation, feeding the upper water layer obtained by separation into a distillation reactor for steam stripping to recover water, feeding the lower oil layer obtained by separation into a product collecting tank for collection and drying to obtain an MOCA product, wherein in the step (2), the microchannel condensation rearrangement modules comprise n groups, the n groups of the microchannel condensation rearrangement modules are sequentially connected in series, each group of the microchannel condensation rearrangement modules respectively and independently corresponds to one feed of the formaldehyde solution, and in the step (1), the microchannel salt formation module, the microchannel condensation rearrangement module and the microchannel neutralization module have the temperature of 80-120 ℃.
2. The continuous production method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using a microchannel reactor as claimed in claim 1, wherein in the step (1), the hydrochloric acid solution has a concentration of 10% to 25% by mass of hydrochloric acid.
3. The continuous production method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using microchannel reactor as claimed in claim 1, characterized in that in step (1) and step (2), the molar ratio of hydrochloric acid, o-chloroaniline and formaldehyde is (1.5-1.1): 1: (0.4-0.7).
4. The continuous production method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using a microchannel reactor as claimed in claim 1, wherein in the step (2), the concentration of formaldehyde in the aqueous formaldehyde solution is 10% to 37% by mass.
5. The continuous production method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using a microchannel reactor as claimed in claim 1, wherein in step (2), the feeding manner of the formaldehyde solution is one feed or a plurality of feeds.
6. The continuous process for preparing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using microchannel reactor as claimed in claim 1, characterized in that in step (3), the lye is sodium hydroxide solution.
7. The continuous preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using microchannel reactor as claimed in claim 6, characterized in that in step (3), the molar ratio of sodium hydroxide to hydrochloric acid is (1.0-1.3): 1.
8. The continuous production method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane using the microchannel reactor as claimed in any one of claims 1 to 7, wherein the total reaction time of the step (1), the step (2) and the step (3) is 30s to 300s.
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