CN109776330B - Method for preparing 1,2, 4-butanetriol trinitrate by using microchannel reactor - Google Patents
Method for preparing 1,2, 4-butanetriol trinitrate by using microchannel reactor Download PDFInfo
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Abstract
The invention discloses a method for preparing 1,2, 4-butanetriol trinitrate by using a microchannel reactor, belonging to the technical field of organic synthesis application. The method is a new process for synthesizing 1,2, 4-butanetriol trinitrate by nitration in a micro-channel reactor in a short reaction time of dozens of seconds to a few minutes by using 1,2, 4-butanetriol and nitric acid-sulfuric acid as raw materials. After materials are introduced into a micro-channel reactor through a metering pump, 1,2, 4-butanetriol trinitrate product is obtained through preheating, mixing, reacting and post-treating.
Description
Technical Field
The invention belongs to the technical field of organic synthesis application, and particularly relates to a method for preparing 1,2, 4-butanetriol trinitrate by nitration of 1,2, 4-butanetriol serving as a raw material, and more particularly relates to a process for preparing 1,2, 4-butanetriol trinitrate in a high-throughput microchannel continuous flow reactor.
Background
1,2, 4-butanetriol trinitrate, BTTN for short, is an energetic plasticizer, is mainly applied to equipment with high-performance NEPE propellant at present, is not easy to freeze due to excellent low-temperature performance, and can effectively avoid the low-temperature embrittlement of the solid propellant, so that the solid propellant is widely applied.
Currently, the 1,2, 4-butanetriol trinitrate in the industry is produced mainly in the following ways: batch kettle type nitrification, kettle type continuous nitrification and jet nitrification. Although the nitrobutanetriol is good in stability, the nitrobutanetriol is also an explosive and has high potential safety hazard.
The reaction of the continuous microchannel reactor is carried out in the microchannel, the continuous mode is adopted for feeding, the materials are uniformly distributed in a high-efficiency mixing state, the accurate control of the reaction can be realized, and the occurrence of side reactions is reduced. Meanwhile, the microchannel reactor has low liquid holdup, so that the safety risk of a reaction zone is greatly reduced, and the safe synthesis of BTTN can be realized.
Disclosure of Invention
The invention aims to provide a process for preparing 1,2, 4-butanetriol trinitrate by nitration of 1,2, 4-butanetriol in a high-throughput micro-channel continuous flow reactor, compared with the existing process, the process has the advantages of precise control of reaction conditions, reduction of discharge of organic waste liquid, continuous and safe production, high conversion rate of 1,2, 4-butanetriol in extremely short time and great improvement of selectivity of 1,2, 4-butanetriol trinitrate.
A method for preparing 1,2, 4-butanetriol trinitrate by nitration of 1,2, 4-butanetriol in a microchannel reactor comprises the following steps:
1) materials 1,2, 4-butanetriol solution and nitric acid-sulfuric acid solution required in the reaction are firstly respectively introduced into each straight channel module in the microchannel reactor for preheating, the set temperature is controlled by an external heat exchanger, the heat exchange medium is heat conduction oil, and then the 1,2, 4-butanetriol solution is changed through flow control: the molar ratio of nitric acid is 1: 3-1: 10, preferably 1: 3-1: 6; the mass fraction of nitric acid in the mixed acid is 10-100%, the nitric acid synchronously enters a mass transfer enhanced module through respective metering pumps to carry out mixing reaction, and the mixing temperature is also controlled by an external heat exchanger.
2) After being mixed and reacted in the module, the mixture continuously passes through a series of mass transfer enhanced micro-channel modules and straight-flow micro-channel modules, and after the reaction process is finished, a product flows out from an outlet of the reactor and enters a cooling post-treatment process; the reaction residence time of the reaction process in the microchannel reactor is 50-150 s, preferably 80-100 s, and the reaction temperature is 10-100 ℃, preferably 20-80 ℃.
3) And (3) passing a product obtained from the outlet of the microchannel reactor through an ice water bath of a cooling coil, then entering a collector filled with ice water, standing, layering, neutralizing, washing with water, and distilling under reduced pressure to obtain a light yellow oily liquid with the yield of 80-95%.
The reactor system is formed by assembling a plurality of modules, wherein the modules can be assembled in parallel or in series, and the heat exchange passage and the reaction passage are integrated into a whole or only comprise the reaction passage and are immersed in a temperature-control heat-conducting medium. The thermocouple is arranged in the heat exchange passage or the heat-conducting medium and can be used for measuring the actual temperature of the heat exchange medium in the heat exchange passage or the external heat-conducting medium. The thermocouple is arranged in the heat exchange passage or the heat-conducting medium and can be used for measuring the actual temperature of the heat exchange medium in the heat exchange passage or the external heat-conducting medium. The module is made of stainless steel or metal alloy coated with a corrosion-resistant coating, polytetrafluoroethylene and the like. The reaction system can resist corrosion and pressure, and the pressure resistance is different according to different materials. The micro-channel structure in the module is divided into a straight-flow channel structure and an enhanced mixed channel structure, the straight-flow channel is of a tubular structure, the enhanced mixed channel structure is of a heart-shaped structure, and the hydraulic diameter of the channel is 0.5-10 mm.
The mass transfer enhanced microchannel reactor system for carrying out nitration on 1,2, 4-butanetriol comprises three parts, namely 1,2, 4-butanetriol, mixed nitric-sulfuric acid, preheating, mixing reaction and nitration, so that a raw material preheating module, a mixing module and a certain number of reaction modules are required, and the specific number is determined by the reaction residence time.
Compared with the prior art, the invention has the following main characteristics:
1. the invention adopts the continuous flow micro-channel reactor, shortens the reaction time from the traditional hours to dozens of seconds to several minutes, and obviously improves the reaction efficiency.
2. Because the raw materials are mixed well in the micro-channel, the temperature is controlled accurately, the consumption of concentrated sulfuric acid and nitric acid can be greatly reduced in the reaction process, the generation of waste acid is reduced, and the selectivity of the product is obviously improved.
3. In the microchannel reactor, the whole process of feeding, preheating, mixing and reaction is continuous flow reaction, so that the problems that an additional device needs to be configured and leakage occurs in transfer in the conventional batch reaction are avoided, the reactor is environment-friendly and safe, and the production efficiency is high.
Drawings
FIG. 1 is a flow chart of the process for preparing 1,2, 4-butanetriol trinitrate by nitration of 1,2, 4-butanetriol according to the invention;
FIG. 2 is a block diagram of a corning microchannel module type and enhanced hybrid geometry feature size microchannel reactor module and structure used in the present invention; 1-a straight channel functional module, 2-an enhanced mixed structure functional module;
FIG. 3 is a schematic flow diagram of a microchannel reactor used in the present invention; 1. 2-raw material tank, 3, 4-raw material pump, 5, 6-pressure gauge, 7-straight channel module, 8, 9-enhanced mixing module, and 10-raw material collection.
Detailed Description
Referring to FIG. 1, the process of the present invention utilizes the apparatus diagram of FIG. 3, according to the following steps: (1) firstly, respectively pumping 1,2, 4-butanetriol solution and mixed acid of nitric acid and sulfur in storage tanks 1 and 2 into a straight channel module 7 (a straight channel structure is shown as No. 1 in figure 2) according to a certain proportion through metering pumps 3 and 4 for preheating, and monitoring the system pressure through pressure gauges 5 and 6 in the whole process; (2) preheating the 1,2, 4-butanetriol solution and the mixed acid of the nitric acid and the sulfuric acid, and then introducing the preheated solution into a micro mixer enhanced mixing module 8 (the structure is shown in No. 2 and No. 3 in FIG. 2) for mixing; (3) the mixed raw materials enter the next group of enhanced mixing modules 9 for reaction; (4) and (3) after the product obtained through the microchannel reaction passes through a cooling coil pipe ice-water bath, standing, layering and washing with water, drying under reduced pressure, and obtaining the final product 1,2, 4-butanetriol trinitrate in a collection bottle 10.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
(1) The device used is as follows: the high-flux microchannel reactor (the straight channel module and the enhanced mixed channel module) determines the connection mode of the microchannel reactor by referring to fig. 3, the number of the mixed reaction modules is determined according to the flow speed and the reaction residence time, and the heat exchange medium is heat conduction oil.
(2) Preparing a 1,2, 4-butanetriol solution in the material tanks 1 and 2; the mass concentration of the nitric acid is 10 percent. The flow control of each metering pump 3 and pump 4 is set to change the 1,2, 4-butanetriol solution: respectively injecting the materials into each straight channel preheating module according to the molar ratio of nitric acid being 1:3, and controlling the reaction temperature to be 10 ℃; the 1,2, 4-butanetriol solution and the mixed acid of the nitric acid and the sulfuric acid are respectively pumped into a micro mixer mixing module 8 by metering pumps 3 and 4 to be mixed, and the mixed raw materials enter a lower group mixing module 9 to react. The reaction residence time was 150s, and the reaction product flowed out of the reactor in a high dispersion phase continuous flow state after passing through a cooling coil in an ice water bath (see FIG. 3) into a collector containing ice water.
(3) The product is subjected to standing, layering, neutralization and water washing, and then is subjected to reduced pressure distillation to obtain light yellow oily liquid with the yield of 80%.
Example 2
(1) The device used is as follows: the high-flux microchannel reactor (the straight channel module and the enhanced mixed channel module) determines the connection mode of the microchannel reactor by referring to fig. 3, the number of the mixed reaction modules is determined according to the flow speed and the reaction residence time, and the heat exchange medium is heat conduction oil.
(2) Preparing a 1,2, 4-butanetriol solution in the material tanks 1 and 2; the mass concentration of the nitric acid is 35 percent. The flow control of each metering pump 3 and pump 4 is set to change the 1,2, 4-butanetriol solution: respectively injecting the materials into each straight channel preheating module according to the molar ratio of nitric acid being 1:10, and controlling the reaction temperature to be 40 ℃; the 1,2, 4-butanetriol solution and the mixed acid of the nitric acid and the sulfuric acid are respectively pumped into a micro mixer enhanced mixing module 8 by metering pumps 3 and 4 to be mixed, and the mixed raw materials enter a next group of mixing modules 9 to react. The reaction residence time was 50s, and the reaction product flowed out of the reactor in a high dispersion phase continuous flow state after passing through a cooling coil ice-water bath (see FIG. 3) into a collector filled with ice water.
(3) The product is subjected to standing, layering, neutralization and water washing, and then is subjected to reduced pressure distillation to obtain light yellow oily liquid with the yield of 93%.
Example 3
(1) The device used is as follows: the high-flux microchannel reactor (the straight channel module and the enhanced mixed channel module) determines the connection mode of the microchannel reactor by referring to fig. 3, the number of the mixed reaction modules is determined according to the flow speed and the reaction residence time, and the heat exchange medium is heat conduction oil.
(2) Preparing a 1,2, 4-butanetriol solution in the material tanks 1 and 2; the mass concentration of the nitric acid is 100 percent. The flow control of each metering pump 3 and pump 4 is set to change the 1,2, 4-butanetriol solution: respectively injecting the materials into each straight channel preheating module according to the molar ratio of nitric acid being 1:4, and controlling the reaction temperature to be 100 ℃; the 1,2, 4-butanetriol solution and the mixed acid of the nitric acid and the sulfuric acid are respectively pumped into a reinforced mixing module 8 of a micro mixer by metering pumps 3 and 4 to be mixed, and the mixed raw materials enter a next reinforced mixing module 9 to react. The reaction residence time was 80s, and the reaction product flowed out of the reactor in a high dispersion phase continuous flow state after passing through a cooling coil in an ice water bath (see FIG. 3) and into a collector containing ice water.
(3) The product is subjected to standing, layering, neutralization and water washing, and then is subjected to reduced pressure distillation to obtain a light yellow oily liquid with the yield of 95%.
Claims (1)
1. A method for preparing 1,2, 4-butanetriol trinitrate by nitration of 1,2, 4-butanetriol in a microchannel reactor is characterized by comprising the following steps:
1) materials 1,2, 4-butanetriol solution and nitric acid-sulfuric acid solution required in the reaction are firstly respectively introduced into each straight channel module in the microchannel reactor for preheating, the set temperature is controlled by an external heat exchanger, the heat exchange medium is heat conduction oil, and then the 1,2, 4-butanetriol solution is changed through flow control: the molar ratio of nitric acid =1: 4-1: 10; the mass fraction of nitric acid in the mixed acid is 35-100%, the nitric acid synchronously enters a mass transfer enhanced module through respective metering pumps to carry out mixing reaction, the mixing temperature is also controlled by an external heat exchanger,
2) after being mixed and reacted in the module, the mixture continuously passes through a series of mass transfer enhanced micro-channel modules and straight-flow micro-channel modules, and after the reaction process is finished, a product flows out from an outlet of the reactor and enters a cooling post-treatment process; the reaction residence time in the microchannel reactor in the reaction process is 50-80 s, and the reaction temperature is 40-100 ℃;
3) and (3) passing a product obtained from the outlet of the microchannel reactor through an ice water bath of a cooling coil, then entering a collector filled with ice water, standing, layering, neutralizing, washing with water, and carrying out reduced pressure distillation to obtain a light yellow oily liquid, namely the 1,2, 4-butanetriol trinitrate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0154215B1 (en) * | 1995-10-10 | 1998-12-01 | 김용구 | Process for producing 1,2,4-butanetrioltrinitrate |
| WO2005068642A2 (en) * | 2003-10-01 | 2005-07-28 | Board Of Trustees Operating Michigan State University | Bacterial synthesis of 1,2,4-butanetriol enantiomers |
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| US8658818B2 (en) * | 2010-11-23 | 2014-02-25 | Alliant Techsystems Inc. | Methods of producing nitrate esters |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0154215B1 (en) * | 1995-10-10 | 1998-12-01 | 김용구 | Process for producing 1,2,4-butanetrioltrinitrate |
| WO2005068642A2 (en) * | 2003-10-01 | 2005-07-28 | Board Of Trustees Operating Michigan State University | Bacterial synthesis of 1,2,4-butanetriol enantiomers |
Non-Patent Citations (4)
| Title |
|---|
| Synthesis and Characterization of 1,2,4-Butanetrioltrinitrate;FARIDEH GOURANLOU等;《Asian Journal of Chemistry》;20101231;第22卷(第6期);第4224页第2段 * |
| 微通道反应器的发展研究进展;凌芳等;《上海化工》;20170430;第42卷(第4期);第35页右栏第2段，第36页右栏第3段 * |
| 微通道反应器连续法合成硝酸异辛酯;刘卫孝等;《高校化学工程学报》;20170831;摘要 * |
| 甘油／1，2，4-丁三醇混合醇连续喷雾硝化技术研究;王振江等;《火炸药》;19971231(第1期);第6-9页 * |
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