CN103183620A - Method for preparing nitroguanidine through guanidine sulfate nitrification in continuous-flow micro channel reactor - Google Patents
Method for preparing nitroguanidine through guanidine sulfate nitrification in continuous-flow micro channel reactor Download PDFInfo
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Abstract
The invention relates to a method for preparing nitroguanidine through guanidine sulfatenitrification in a continuous-flow micro channel reactor and belongs to the technical field of organic synthesis and application. The method is a new process for synthesizing the nitroguanidine within the reaction time from dozens of seconds to a few minutes through taking sulfuric acid solution and nitric acid of guanidine sulfate in the continuous-flow micro channel reactor as raw materials. After materials are introduced into the continuous-flow micro channel reactor by a measuring pump, a nitration product, namely the nitroguanidine is finally obtained through preheating, mixing and reaction. The method has the benefits that the operation is simple and safe, the yield is high, the continuous production of the nitroguanidine becomes possible, and the environmental pollution is less. According to the method, the product yield is 90-93 percent, and a melting point is 230-232 DEG C.
Description
Technical field
The invention belongs to the organic synthesis applied technical field, being specifically related to a kind of sulphuric acid soln with guanidine sulfate is the method that the nitrated dehydration of raw material prepares nitroguanidine, say so more specifically in high-throughput Continuous Flow micro passage reaction, utilize the sulphuric acid soln of nitric acid nitrating guanidine sulfate to prepare the technology of nitroguanidine.
Background technology
Nitroguanidine is a kind of organic synthesis raw material, on agricultural chemicals as the intermediate of Provado, acetamiprid, for the synthesis of next step intermediate N nitro imido imidazolyl alkane, in addition, it can aminoguanidine processed through reduction, for the synthesis of the angina drug trapymin etc., also can be used for the preparation of explosive and smokeless water medicine.Be used for organic synthesis, preparation aminoguanidine, medicine trapymin etc.Also can be used for the preparation of explosive and smokeless powder, is the admixture of nitrocotton gunpowder, nitroglycerine powder and diethylene glycol dinitrate, the important component of solid rocket propellant.
At present, the main production of nitroguanidine has thiocyanic acid method, fusing urea ammonium nitrate method, cyanamide ammonium nitrate method, Guanidinium nitrate method etc.
1. thiocyanic acid method
Process characteristic: this method yield height, but the sulfide impurities in the product and nitro-cotton effect, reducing with the nitroguanidine is the stability of the gunpowder of component.
2. fusing urea ammonium nitrate method
Process characteristic: this method takes full advantage of the heat energy of fusing urea, ammonium nitrate, and material moisture is low, but it is more to produce waste water.
3. cyanamide ammonium nitrate method
Process characteristic: reaction needs high temperature, high pressure, and reaction conditions is comparatively harsh.
4. Guanidinium nitrate method
Make Guanidinium nitrate generation nitration reaction with the vitriol oil, generate nitroguanidine, this is the main method of producing this product at present, also is most important method.Be raw material with the Guanidinium nitrate of purity more than 92%, making it with industrial sulphuric acid more than 92% is 1 by 1:2.5～3(Guanidinium nitrate) feed ratio 0～20 ℃ of reaction, can get Guanidinium nitrate, yield 80～85%.Bibliographical information be interrupter method, namely directly in reaction flask or still, carry out.With the frozen water dilution, filter after reaction is finished, filter cake gets pure product with the water recrystallization.
Process characteristic: this method does not need high temperature or condition of high voltage, and pollution is less relatively, but higher to temperature control requirement, scale effect is obvious, and accumulation of material is brought potential safety hazard easily; Next is to adopt interrupter method production, and the treatment times such as it is reinforced, discharging are long, and the reactor volume is huge, need take bigger factory building etc.
Up to now, Shang Weijian carries out the research that the nitric acid nitrating guanidine sulfate prepares nitroguanidine in the mode of Corning microchannel Continuous Flow.The invention provides a kind of operational path that in the Corning micro passage reaction, prepares nitroguanidine with the nitrated guanidine sulfate of the mode of Continuous Flow.This operational path advantage has been accurately to control the temperature of reaction, residence time of the mole of raw material and solvent reaction when etc., tens seconds to several minutes in the time higher yields obtain the nitration product nitroguanidine.
Summary of the invention
The purpose of this invention is to provide a kind of nitrated preparation nitroguanidine of sulphuric acid soln that in the continuous flow reactor of Corning high-throughput microchannel, carries out guanidine sulfate, compare with existing processes, this technology has reaction conditions and accurately controls, reduce the discharging of organic liquid waste, the mode of safety is produced continuously, and the guanidine sulfate transformation efficiency is very high in the extremely short time, and the nitroguanidine selectivity improves a lot.
The nitrated method for preparing nitroguanidine of guanidine sulfate in the Continuous Flow micro passage reaction of the present invention, carry out according to following step:
(1) sulphuric acid soln and the nitric acid of required material guanidine sulfate in the reaction, feed at first respectively and carry out preheating in the micro passage reaction in each straight channel, design temperature is controlled by external heat exchanger, heat transferring medium is thermal oil and water, changes the sulphuric acid soln of guanidine sulfate and the mol ratio of nitric acid by flow control again; The sulphuric acid soln flow velocity of control guanidine sulfate: 0.2mL/min ~ 10mL/min, preferred 0.8 ~ 2mL/min, control nitric acid flow velocity: 0.2mL/min ~ 10mL/min, preferred 0.8 ~ 2mL/min; Enter synchronously to strengthen in the quality transmission type reactor module via volume pump separately and carry out hybrid reaction, mixing temperature is controlled by external heat exchanger equally, and the sulphuric acid soln mass concentration of guanidine sulfate is 10%～45%, and the nitric acid mass concentration is 30%～50%;
(2) mol ratio by flow control guanidine sulfate and nitric acid, in this module after hybrid concurrency is given birth to reaction, continue by a series of enhancing quality transmission type microchannel modules and once-through type microchannel module, after reaction process is finished, product flows out from the outlet of reactor, enters the cooling last handling process; This reaction process is 50s～150s in the micro passage reaction internal reaction residence time, preferred 80～100s, and temperature of reaction is 40～120 ℃, preferred 80～100 ℃.
(3) will flow directly in the collector that frozen water is housed from the reaction solution that the micro passage reaction outlet obtains, stir on edge joint liquid limit, and solid is constantly separated out, after question response liquid stops to flow out, continue to stir 5min, filter, filter cake with water washing 2 times after, again with the water recrystallization, 35 ℃ of following drying under reduced pressure 6h, get the white powder solid, yield 90 ~ 93%, 230 ~ 232 ℃ of fusing points;
The sulphuric acid soln of guanidine sulfate in the step of the present invention (1): nitric acid mol ratio=1:0.9 ~ 1:100, the sulphuric acid soln mass concentration of guanidine sulfate is 10%～45%, preferred 20～30%; The nitric acid mass concentration is 30%～50%, preferred 35～45%.
Micro Channel Architecture is the once-through type channel architecture or strengthens the mixed type channel architecture in the enhancing quality transmission type micro passage reaction module described in the present invention.
Once-through type channel architecture of the present invention is tubular structure, and strengthening the mixed type channel architecture is T type structure, globosity, spherical band baffle arrangement, drops structure or heart-shaped structure, and the passage hydraulic diameter is 0.5mm ~ 10mm.
The used micro passage reaction of the present invention is enhancing quality transmission type micro passage reaction, and this reactive system is assembled by the polylith module.The material of this module is silicon single crystal, special glass, pottery, the stainless steel that scribbles the corrosion resistant coating or metal alloy, tetrafluoroethylene etc.Reactive system can be anticorrosion withstand voltage, and voltage endurance capability is looked the material difference and different, and reaction maximum safety pressure power is 15～30bar in the system.Micro Channel Architecture is divided the once-through type channel architecture and is strengthened two kinds of mixed type channel architectures in the module, the once-through type passage is tubular structure, strengthening the mixed type channel architecture is T type structure, globosity, spherical band baffle arrangement, drops structure, heart-shaped structure, and the passage hydraulic diameter is 0.5mm ~ 10mm.
The present invention carries out sulphuric acid soln preheating, hybrid reaction, nitrifying process three parts that the nitrated enhancing quality transmission type micro channel reactor system of Continuous Flow guanidine sulfate comprises guanidine sulfate, therefore the reaction module that needs raw material preheating module, mixing module and some amount, concrete quantity is determined by reaction time.
The selected micro passage reaction module material of the present invention comprises silicon single crystal, special glass, pottery, the stainless steel that scribbles the corrosion resistant coating or metal alloy, tetrafluoroethylene etc., this micro passage reaction is assembled by many pack modules, intermodule can in parallelly be assembled or the series connection assembling, module is with heat exchange path and the integrated and one of reaction path, or only contain the reaction path, and be immersed in the temperature control heat-conducting medium.Be furnished with thermopair in heat exchange path or heat-conducting medium, can be used for measuring the actual temperature of heat transferring medium in the heat exchange path or extraneous heat-conducting medium, the reaction channel of module is divided into straight type tubular channel and strengthens two kinds in quality transmission type passage.
The present invention has following principal feature compared with prior art:
1. the present invention adopts Continuous Flow microchannel continuous flow reactor, and reaction times from traditional a few hours shorten to tens seconds to several minutes, have significantly improved reaction efficiency.
2. because raw material mixes splendidly in the microchannel, and temperature is accurately controlled, in the reaction process, the consumption of the vitriol oil, nitric acid can significantly reduce, and reduced the generation of spent acid, and product selectivity improves obviously.
3. use Continuous Flow micro passage reaction material to be special glass among the present invention, the material of volume pump is tetrafluoroethylene and titanium, and excellent corrosion resistance has been avoided the serious problem of etching apparatus in the popular response device.
4. in micro passage reaction, omnidistance from charging, preheating, mixing and reaction process is the Continuous Flow reaction, needing in the conventional rhythmic reaction to have avoided the leakage of appearance in additional configuration device and the transfer, Environmental Safety, production efficiency height.
Description of drawings
Fig. 1 is the nitrated preparation nitroguanidine of guanidine sulfate of the present invention reaction process flow process schema;
Fig. 2 is Continuous Flow micro passage reaction setting drawing used in the present invention; 1,2 head tanks, 3, the 4-fresh feed pump, 5, the 6-tensimeter, the 7-microchannel, the 8-heat transferring medium, the 9-product is collected;
Fig. 3 is microchannel form figure used in the present invention; 1-straight channel functional module, 2-" heart type " structure function module, 3-T-type microchannel, the spherical microchannel of 4-, the spherical microchannel of 5-adds baffle plate, 6-droplet-shaped microchannel.
Embodiment
With reference to Fig. 1 technical process of the present invention, utilize the setting drawing of Fig. 2, according to following step: (1) earlier with the sulphuric acid soln of the guanidine sulfate in 1,2 storage tanks and nitric acid respectively through 3,4 volume pumps, squeeze into according to certain proportioning in the preheater (structure referring among Fig. 31, No. 5) of No. 7, microreactor and carry out preheating (No. 8 heat transferring mediums are water or thermal oil), whole process is by 5,6 tensimeter inspection system pressure; (2) sulphuric acid soln of guanidine sulfate and nitric acid are through carrying out hybrid reaction in the mixing tank that feeds No. 7, microreactor after the preheating again (structure referring among Fig. 32,3,4,5, No. 6); (3) product that should obtain through microchannel plate is by behind the spiral coil cooling tube ice-water bath, and after filtration, after the washing, carry out recrystallization, drying under reduced pressure obtains the final product nitroguanidine in receiving flask 9.
Do nearly step explanation below by the present invention of embodiment, but content not thereby limiting the invention.
Embodiment 1
(1) equipment therefor: Continuous Flow micro passage reaction (straight channel functional module+" heart type " structure function module), determine the micro passage reaction connection mode with reference to Fig. 3, the hybrid reaction number of modules determines that according to flow velocity and reaction time heat transferring medium is thermal oil.
(2) to configure the sulphuric acid soln mass concentration of guanidine sulfate be 10% to head tank 1,2; The nitric acid mass concentration is 30%.The flow control of setting each volume pump 3, pump 4 changes the sulphuric acid soln of guanidine sulfate: nitric acid mol ratio=1:0.9, the sulphuric acid soln flow velocity of control guanidine sulfate: 0.25mL/min, control nitric acid flow velocity: 0.2mL/min, material is squeezed into respectively in each straight channel warm-up block, and the temperature of reaction of controlling well is 40 ℃; The sulphuric acid soln of guanidine sulfate and nitric acid are squeezed into to mix in the heart-shaped mixing module with volume pump 3,4 respectively and are reacted.Reaction time is 50s, and reaction product goes out reactor (seeing accompanying drawing 2) by behind the spiral coil cooling tube ice-water bath with high dispersive phase Continuous Flow state flow.
(3) product after filtration, the washing after, carry out recrystallization, drying under reduced pressure gets the white powder solid, yield 90%, 230 ℃ of fusing points.Product structure characterizes:
1H NMR (CDCl3, δ: ppm) 7.49 (brs, 4H);
13C NMR (CDCl
3, δ: ppm) 161.0; MS (ESI+): 105[M+H
+], 127[M+Na
+], 159[M+CH
3OH+Na
+]; MS (ESI
-): 139,141[M+Cl
-], 166[M+NO
3-].
(1) equipment therefor: Continuous Flow micro passage reaction (straight channel functional module+droplet-shaped passage), determine the micro passage reaction connection mode with reference to Fig. 3, the hybrid reaction number of modules determines that according to flow velocity and reaction time heat transferring medium is thermal oil.
(2) to configure the sulphuric acid soln mass concentration of guanidine sulfate be 15% to head tank 1,2; The nitric acid mass concentration is 35%.The flow control of setting each volume pump 3, pump 4 changes the sulphuric acid soln of guanidine sulfate: nitric acid mol ratio=1:1, the sulphuric acid soln flow velocity of control guanidine sulfate: 0.2mL/min, control nitric acid flow velocity: 0.2mL/min, material is squeezed into respectively in each straight channel warm-up block, and the temperature of reaction of controlling well is 50 ℃; The sulphuric acid soln of guanidine sulfate and nitric acid are squeezed in the micro mixer droplet-shaped mixing module with volume pump 3,4 respectively and are reacted.Reaction time is 60s, and reaction product goes out reactor (seeing accompanying drawing 2) by behind the spiral coil cooling tube ice-water bath with high dispersive phase Continuous Flow state flow.
(3) product after filtration, the washing after, carry out recrystallization, drying under reduced pressure gets the white powder solid, yield 91%, 230 ℃ of fusing points.Product structure characterizes: with embodiment 1.
(1) equipment therefor: Continuous Flow micro passage reaction (straight channel functional module+ball-type shift-up template passage), determine the micro passage reaction connection mode with reference to Fig. 3, the hybrid reaction number of modules determines that according to flow velocity and reaction time heat transferring medium is thermal oil.
(2) to configure the sulphuric acid soln mass concentration of guanidine sulfate be 20% to head tank 1,2; The nitric acid mass concentration is 35%.The flow control of setting each volume pump 3, pump 4 changes the sulphuric acid soln of guanidine sulfate: nitric acid mol ratio=1:2, the sulphuric acid soln flow velocity of control guanidine sulfate: 0.2mL/min, control nitric acid flow velocity: 0.8mL/min, material is squeezed into respectively in each straight channel warm-up block, and the temperature of reaction of controlling well is 80 ℃; The sulphuric acid soln of guanidine sulfate and nitric acid are squeezed in the micro mixer ball-type shift-up template with volume pump 3,4 respectively and are reacted.Reaction time is 80s, and reaction product goes out reactor (seeing accompanying drawing 2) by behind the spiral coil cooling tube ice-water bath with high dispersive phase Continuous Flow state flow.
(3) product after filtration, the washing after, carry out recrystallization, drying under reduced pressure gets the white powder solid, yield 93%, 232 ℃ of fusing points.Product structure characterizes: with embodiment 1.
(1) equipment therefor: Continuous Flow micro passage reaction (straight channel functional module+ball-type passage), determine the micro passage reaction connection mode with reference to Fig. 3, the hybrid reaction number of modules determines that according to flow velocity and reaction time heat transferring medium is thermal oil.
(2) flow control of setting each volume pump 3, pump 4 changes the sulphuric acid soln of guanidine sulfate: nitric acid mol ratio=1:5, the sulphuric acid soln flow velocity of control guanidine sulfate: 0.2mL/min, control nitric acid flow velocity: 1mL/min, material is squeezed into respectively in each straight channel warm-up block, and the temperature of reaction of controlling well is 90 ℃; The sulphuric acid soln of guanidine sulfate and nitric acid are squeezed into volume pump 3,4 respectively and are carried out hybrid reaction in the micro mixer spherical channel.Reaction time is 90s, and reaction product goes out reactor (seeing accompanying drawing 2) by behind the spiral coil cooling tube ice-water bath with high dispersive phase Continuous Flow state flow.
(3) product after filtration, the washing after, carry out recrystallization, drying under reduced pressure gets the white powder solid, yield 93%, 231 ℃ of fusing points.Product structure characterizes: with embodiment 1.
(1) equipment therefor: Continuous Flow micro passage reaction (straight channel functional module+" heart type " structure function module), determine the micro passage reaction connection mode with reference to Fig. 3, the hybrid reaction number of modules determines that according to flow velocity and reaction time heat transferring medium is water.
(2) to configure the sulphuric acid soln mass concentration of guanidine sulfate be 30% to head tank 1,2; The nitric acid mass concentration is 40%.The flow control of setting each volume pump 3, pump 4 changes the sulphuric acid soln of guanidine sulfate: nitric acid mol ratio=1:10, the sulphuric acid soln flow velocity of control guanidine sulfate: 0.2mL/min, control nitric acid flow velocity: 2mL/min, material is squeezed into respectively in each straight channel warm-up block, and the temperature of reaction of controlling well is 100 ℃; The sulphuric acid soln of guanidine sulfate and nitric acid are squeezed in the heart-shaped mixing module of micro mixer with volume pump 3,4 respectively and are carried out hybrid reaction.Reaction time is 100s, and reaction product goes out reactor (seeing accompanying drawing 2) by behind the spiral coil cooling tube ice-water bath with high dispersive phase Continuous Flow state flow.
(3) product after filtration, the washing after, carry out recrystallization, drying under reduced pressure gets the white powder solid, yield 92%, 232 ℃ of fusing points.Product structure characterizes: with embodiment 1.
(1) equipment therefor: Continuous Flow micro passage reaction (ball-type shift-up template passage+T type craspedodrome passage), determine the micro passage reaction connection mode with reference to Fig. 3, the hybrid reaction number of modules determines that according to flow velocity and reaction time heat transferring medium is water.
(2) to configure the sulphuric acid soln mass concentration of guanidine sulfate be 45% to head tank 1,2; The nitric acid mass concentration is 50%.The flow control of setting each volume pump 3, pump 4 changes the sulphuric acid soln of guanidine sulfate: nitric acid mol ratio=1:50, the sulphuric acid soln flow velocity of control guanidine sulfate: 0.2mL/min, control nitric acid flow velocity: 10mL/min, material is squeezed into respectively in each straight channel warm-up block, and the temperature of reaction of controlling well is 120 ℃; The sulphuric acid soln of guanidine sulfate and nitric acid are squeezed in the micro mixer T shape craspedodrome passage with volume pump 3,4 respectively and are carried out hybrid reaction.Reaction time is 120s, and reaction product goes out reactor (seeing accompanying drawing 2) by behind the spiral coil cooling tube ice-water bath with high dispersive phase Continuous Flow state flow.
(3) product after filtration, the washing after, carry out recrystallization, drying under reduced pressure gets the white powder solid, yield 91%, 230 ℃ of fusing points.Product structure characterizes: with embodiment 1.
Claims (8)
1. the nitrated method for preparing nitroguanidine of guanidine sulfate in the Continuous Flow micro passage reaction is characterized in that carrying out according to following step:
(1) sulphuric acid soln and the nitric acid of required material guanidine sulfate in the reaction, feed at first respectively and carry out preheating in the micro passage reaction in each straight channel, design temperature is controlled by external heat exchanger, heat transferring medium is thermal oil and water, changes the sulphuric acid soln of guanidine sulfate and the mol ratio of nitric acid by flow control again; The sulphuric acid soln flow velocity of control guanidine sulfate: 0.2mL/min ~ 10mL/min, control nitric acid flow velocity: 0.2mL/min ~ 10mL/min; Enter synchronously to strengthen in the quality transmission type reactor module via volume pump separately and carry out hybrid reaction, mixing temperature is controlled by external heat exchanger equally, and the sulphuric acid soln mass concentration of guanidine sulfate is 10%～45%, and the nitric acid mass concentration is 30%～50%;
(2) mol ratio by flow control guanidine sulfate and nitric acid, in this module after hybrid concurrency is given birth to reaction, continue by a series of enhancing quality transmission type microchannel modules and once-through type microchannel module, after reaction process is finished, product flows out from the outlet of reactor, enters the cooling last handling process; This reaction process is 50s～150s in the micro passage reaction internal reaction residence time, and temperature of reaction is 40～120 ℃;
(3) will flow directly in the collector that frozen water is housed from the reaction solution that the micro passage reaction outlet obtains, stir on edge joint liquid limit, and solid is constantly separated out, after question response liquid stops to flow out, continue to stir 5min, filter, filter cake with water washing 2 times after, again with the water recrystallization, 35 ℃ of following drying under reduced pressure 6h, get the white powder solid, yield 90 ~ 93%, 230 ~ 232 ℃ of fusing points.
2. the nitrated method for preparing nitroguanidine of guanidine sulfate in the Continuous Flow micro passage reaction according to claim 1, the sulphuric acid soln that it is characterized in that guanidine sulfate in the step (1): nitric acid mol ratio=1:0.9 ~ 1:100, the sulphuric acid soln mass concentration of guanidine sulfate is 20～30%; The nitric acid mass concentration is 35～45%.
3. the nitrated method for preparing nitroguanidine of guanidine sulfate in the Continuous Flow micro passage reaction according to claim 1 is characterized in that Micro Channel Architecture is the once-through type channel architecture or strengthens the mixed type channel architecture in the described enhancing quality transmission type micro passage reaction module.
4. the nitrated method for preparing nitroguanidine of guanidine sulfate in the Continuous Flow micro passage reaction according to claim 1, it is characterized in that described once-through type channel architecture is tubular structure, strengthening the mixed type channel architecture is T type structure, globosity, spherical band baffle arrangement, drops structure or heart-shaped structure, and the passage hydraulic diameter is 0.5mm ~ 10mm.
5. the nitrated method for preparing nitroguanidine of guanidine sulfate in the Continuous Flow micro passage reaction according to claim 1 is characterized in that used micro passage reaction for strengthening the quality transmission type micro passage reaction, and this reactive system is assembled by the polylith module; The material of this module is silicon single crystal, special glass, pottery, the stainless steel that scribbles the corrosion resistant coating or metal alloy, tetrafluoroethylene;
Reactive system can be anticorrosion withstand voltage, and voltage endurance capability is looked the material difference and different, and reaction maximum safety pressure power is 15～30bar in the system; Micro Channel Architecture is divided the once-through type channel architecture and is strengthened two kinds of mixed type channel architectures in the module, the once-through type passage is tubular structure, strengthening the mixed type channel architecture is T type structure, globosity, spherical band baffle arrangement, drops structure, heart-shaped structure, and the passage hydraulic diameter is 0.5mm ~ 10mm.
6. the nitrated method for preparing nitroguanidine of guanidine sulfate in the Continuous Flow micro passage reaction according to claim 1, it is characterized in that selected micro passage reaction module material comprises silicon single crystal, special glass, pottery, the stainless steel that scribbles the corrosion resistant coating or metal alloy, tetrafluoroethylene etc., this micro passage reaction is assembled by many pack modules, intermodule can in parallelly be assembled or the series connection assembling, module is with heat exchange path and the integrated and one of reaction path, or only contain the reaction path, and be immersed in the temperature control heat-conducting medium;
Be furnished with thermopair in heat exchange path or heat-conducting medium, can be used for measuring the actual temperature of heat transferring medium in the heat exchange path or extraneous heat-conducting medium, the reaction channel of module is divided into straight type tubular channel and strengthens two kinds in quality transmission type passage.
7. the nitrated method for preparing nitroguanidine of guanidine sulfate in the Continuous Flow micro passage reaction according to claim 1 is characterized in that the sulphuric acid soln flow velocity 0.8 ~ 2mL/min of step (1) control guanidine sulfate, control nitric acid flow velocity 0.8 ~ 2mL/min.
8. the nitrated method for preparing nitroguanidine of guanidine sulfate in the Continuous Flow micro passage reaction according to claim 1 is characterized in that this reaction process of step (2) is 80～100s in the micro passage reaction internal reaction residence time, and temperature of reaction is 80～100 ℃.
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