CN114957107A - Method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine by micro-channel - Google Patents
Method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine by micro-channel Download PDFInfo
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- CN114957107A CN114957107A CN202210672465.6A CN202210672465A CN114957107A CN 114957107 A CN114957107 A CN 114957107A CN 202210672465 A CN202210672465 A CN 202210672465A CN 114957107 A CN114957107 A CN 114957107A
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- 238000000034 method Methods 0.000 title claims abstract description 29
- ZLJZDCVHRYAHAW-UHFFFAOYSA-N 3,5-dinitropyridine-2,6-diamine Chemical compound NC1=NC(N)=C([N+]([O-])=O)C=C1[N+]([O-])=O ZLJZDCVHRYAHAW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 148
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 64
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002253 acid Substances 0.000 claims abstract description 46
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 230000000802 nitrating effect Effects 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000012530 fluid Substances 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000005457 ice water Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000006396 nitration reaction Methods 0.000 claims abstract description 16
- 239000012043 crude product Substances 0.000 claims abstract description 14
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 238000005086 pumping Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 31
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- -1 tetrafluoroborate nitrate Chemical compound 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HLTDBMHJSBSAOM-UHFFFAOYSA-N 2-nitropyridine Chemical compound [O-][N+](=O)C1=CC=CC=N1 HLTDBMHJSBSAOM-UHFFFAOYSA-N 0.000 description 1
- TZEVSKPZTQIPLS-UHFFFAOYSA-N 3-nitropyridine-2,6-diamine Chemical compound NC1=CC=C([N+]([O-])=O)C(N)=N1 TZEVSKPZTQIPLS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine (DADNP) by a microchannel, which comprises the following steps: taking DMSO as a solvent, mixing and pumping 2, 6-diaminopyridine serving as a raw material and a mixed acid nitrating agent consisting of sulfuric acid and nitric acid into a microchannel reactor for nitration reaction, and sending a crude product output by the microchannel reactor into ice water to obtain a DADNP crude crystal product; wherein, at least one shell-and-tube feeding device is arranged on the microchannel reactor along the flowing direction of the fluid, and the fluid entering the microchannel reactor sequentially flows into the microchannel reactor after passing through a shell-side inlet and an outlet of the shell-and-tube feeding device; the tube side of the shell-and-tube feeding device is continuously filled with bisulfate, a plurality of notches are uniformly distributed on the tube wall of the tube side, and the bisulfate is in contact with shell side fluid in a soaking way at the notches. According to the method, the selectivity of the DADNP in a mild nitration system can be quickly realized to be more than or equal to 98%, the yield is more than or equal to 95%, and the method is green, economic, safe and efficient.
Description
Technical Field
The invention relates to the technical field of synthesis of nitropyridine type high-end chemicals, in particular to a method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine by using a micro-channel.
Background
Poly (2, 5-dihydroxy-1, 4-phenylenepyridobisimidazole) (PIPD) is a high-performance synthetic fiber, and plays an important role in many advanced fields due to excellent properties such as high strength, high thermal stability and the like. 2, 6-diamino-3, 5-dinitropyridine (DADNP) is an important intermediate for synthesizing PIPD fibers, and is mainly prepared by dinitration of 2, 6-Diaminopyridine (DAP) in a mixed acid system of concentrated sulfuric acid and concentrated nitric acid. However, due to the side reaction caused by strong heat release or the high water content of the concentrated acid system and the formation of water during the reaction, the dinitration of DAP is inhibited and the yield is generally low (the by-product is mainly mononitrated product, i.e. 2, 6-diamino-3-nitropyridine (DANP)). Therefore, a superacid system (fuming nitric acid/fuming sulfuric acid) is often employed to obtain higher yields of DADNP.
Patent US5945537A reports that 300.1g DAP was added dropwise to 1200mL of 20% fuming sulfuric acid at 25 ℃ over 90min while ensuring that the system temperature was less than 5-10 ℃, stirring for 15 min after the addition was completed, and then 240mL of 100% concentrated nitric acid was added continuously at 20 ℃ over 130min, with the yield of dapdp being 90.3%. Patent US8115007B2 likewise reports that the DADNP yield reaches 90% after a reaction time of 2h at 21 ℃ with the addition of 20% oleum and 98% concentrated nitric acid under similar procedures. Patent CN101314589A reports that DAP and 20% fuming sulfuric acid are mixed at 0 ℃ in a molar ratio of 1:20, and then reacted at 30 ℃ for 2-5 hours, and then 95% concentrated nitric acid is dropwise added to react at 15 ℃ for 3-6 hours, and DADNP yield is 95%. DADNP high-level documents (bulletin of explosives and powders, 2009,32(3): 9-11; chemical and adhesion, 2009,31(5): 4-6; Advanced Materials Research,2011,236-The synthesis conditions of yield (80-95%) all require fuming sulfuric acid and fuming nitric acid (or 100% concentrated nitric acid) to be used as mixed acid nitrating agents, and meanwhile, the total reaction time is not less than 4-6 hours. The safety of the above operation greatly restricts the synthesis scale of the industrial nitration reaction. At present, the combination of a mild sulfonation reagent and a nitration reagent (bisulfate and tetrafluoroborate nitrate) is adopted to replace concentrated sulfuric acid and concentrated nitric acid to realize the isothermal and nitration reaction of toluene, but the precondition is that inorganic salt is dissolved in a water environment system to release bisulfate anions and nitro cations, and the dinitration process is difficult to initiate in the water environment system. In addition, the strong exothermic effect of the nitration by the concentrated acid system causes the system to have a remarkable temperature runaway, and although the mono-nitration reaction of the system is promoted, the di-nitration reaction is easily inhibited, and the raw materials of the reactants of the system are consumed. Therefore, the development of a continuous, safe and efficient DADNP synthesis process under a mild nitration system has great significance. The microfluidic technology has been successfully applied to the synthesis of a high-risk nitration reaction system, but the DADNP continuous synthesis process by DAP dinitration under a sulfuric acid-nitric acid mixed acid system is not reported. Only patent CN1093695518A adopts a microchannel reactor filled with HZSM5 catalyst, and DAP and N are introduced 2 O 5 The reaction was carried out in methylene chloride to obtain a yield of DADNP of 95%. But in view of N 2 O 5 The product is easy to decompose, highly toxic and explosive, and the production safety requirement is much higher than that of a mixed acid system, so that the scale application is difficult to realize.
Disclosure of Invention
In view of the above problems, the invention provides a method for continuously synthesizing DADNP by a microchannel under a mild mixed acid system, which can quickly realize that the selectivity of DADNP in a mild nitration system is more than or equal to 98 percent and the yield is more than or equal to 95 percent.
The technical scheme of the invention is as follows: a method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine (DADNP) by a microchannel comprises the following processes: taking DMSO as a solvent, respectively pumping a raw material 2, 6-Diaminopyridine (DAP) and a mixed acid nitrating agent consisting of sulfuric acid and nitric acid into a microchannel reactor for nitration reaction, and then sending a crude product output by the microchannel reactor into ice water to obtain a DADNP crude crystal product; wherein the content of the first and second substances,
the sulfuric acid is fuming sulfuric acid or concentrated sulfuric acid with the concentration of 70-98%, and the nitric acid is fuming nitric acid or concentrated nitric acid with the concentration of more than or equal to 65%;
at least one shell-and-tube feeding device is arranged on the microchannel reactor along the flowing direction of the fluid, a shell-side inlet and a shell-side outlet of the shell-and-tube feeding device are respectively communicated to the upstream and the downstream of the microchannel reactor, and the fluid entering the microchannel reactor enters the shell-and-tube feeding device through the shell-side inlet and is discharged into the microchannel reactor through the shell-side outlet; the shell-and-tube feeding device is characterized in that a tube pass of the shell-and-tube feeding device is filled with bisulfate continuously, a plurality of notches communicated with the shell pass are uniformly distributed on the tube wall of the tube pass, and the bisulfate is in contact with shell pass fluid at the notches in a soaking manner.
According to the invention, the micro shell-and-tube spiral feeding device is arranged on the microchannel reactor, so that the bisulfate is circularly conveyed in a tube pass, and the cut is formed on the tube wall of the tube pass of the shell-and-tube spiral feeding device, so that the bisulfate is continuously infiltrated into a shell pass fluid at the cut to fully adsorb water produced by a reaction system, and the hydroscopic property of the bisulfate provides bisulfate ions while the water content of the system is reduced, so that the concentration of a nitrification active phase is improved, and the nitrification reaction under a mild condition is promoted. And (3) directly introducing the primary product output by the microchannel reactor into ice water to separate out the target product DADNP in a crystallization mode.
The invention further provides that the bisulphate salt comprises sodium bisulphate or potassium bisulphate.
The mixed acid nitrating agent comprises fuming sulfuric acid or fuming nitric acid, the number of the shell-and-tube feeding devices is 1, the shell-and-tube feeding devices are installed at 6-8/10 of the total residence time period of the microchannel reactor, and the pressure difference between a shell side inlet and a shell side outlet of each shell-and-tube feeding device is 0.1-0.25 MPa.
The mixed acid nitrating agent further comprises at least 2 shell-and-tube feeding devices when the mixed acid nitrating agent does not comprise fuming sulfuric acid or fuming nitric acid, wherein the first-stage shell-and-tube feeding device and the last-stage shell-and-tube feeding device which are arranged along the fluid flowing direction of the microchannel reactor are respectively arranged at 1-3/10 and 6-8/10 of the total residence time period of the microchannel reactor, and the pressure difference between the shell side inlet and the shell side outlet of the first-stage shell-and-tube feeding device and the pressure difference between the shell side inlet and the shell side outlet of the last-stage shell-and-tube feeding device are respectively 0.3-0.5 MPa and 0.1-0.25 MPa.
Preferably, the first stage shell-and-tube feed device and the last stage shell-and-tube feed device, which are arranged along the fluid flow direction of the microchannel reactor, are respectively installed at 2/10 and 7/10 of the total residence time period of the microchannel reactor,
the method is further set in such a way that a DMSO solution of the DAP is used as a strand of feed, the concentration of the solution is 1-6 mol/L, and the flow rate is 4-10 mL/min; the DMSO solution of the mixed acid nitrating agent is fed into the other strand of the mixed acid nitrating agent, wherein the volume ratio of the sulfuric acid to the nitric acid to the DMSO solvent is 1-4: 1: 0.4-2, and the flow rate is 1-4 mL/min; the reaction temperature in the microchannel reactor is 20-40 ℃, and the total reaction residence time is 20-40 minutes.
The invention further provides that the diameter of the microchannel reactor is 1/8 inches or 1/16 inches.
Preferably, the reaction temperature is 30 ℃, the total residence time is 40 minutes, and the diameter of the micro-reaction channel is 1/16 inches.
The method is further provided that when the sulfuric acid is 90% -98% concentrated sulfuric acid, the volume ratio of the sulfuric acid to the nitric acid to the DMSO solvent in the DMSO solution of the mixed acid nitrating agent is 1-2: 1: 1.
The invention is further set that the sulfuric acid is 70% -90% concentrated sulfuric acid, and the volume ratio of the sulfuric acid to the nitric acid to the DMSO solvent in the DMSO solution of the mixed acid nitrating agent is 2-4: 1: 0.5.
The method is further set that the concentration of the DMSO solution of the DAP is 2-4 mol/L, and the flow rate is 4-6 mL/min.
The shell-and-tube feeding device is further provided with a shell pass and a tube pass which are both U-shaped, a shell pass inlet and a shell pass outlet are respectively arranged at the tops of the outer walls of the two ends of the shell pass, the two ends of the tube pass are communicated to a closed storage tank, the closed storage tank is used for storing the bisulfate, a U-shaped spiral feeding rod is arranged in the tube pass in a matched manner, and the two ends of the spiral feeding rod penetrate through the closed storage tank and are connected to a motor so as to drive the spiral feeding rod to move.
The shell-and-tube feeding device is further provided with a pressure difference controller for detecting the pressure difference between the shell pass inlet and the shell pass outlet, and the pressure difference controller controls the conveying speed of the circular feeding of the spiral feeding rod to realize the full infiltration and contact of the bisulfate and the fluid in the shell pass.
The invention is further set that the ratio of the shell pass diameter to the tube pass diameter is 1.5-3: 1, and the aperture of the notch is phi 0.4-1.0 mm.
Preferably, the total length of the shell pass is 100 +/-10 mm, the diameter of the shell pass is phi 8-10 mm, the diameter of the tube pass is phi 4-6 mm, and the number of uniformly distributed notches is 20-30.
The invention has the following beneficial effects:
(1) the invention designs a miniature shell-and-tube spiral circulating feeding device based on the water-solubility and organic acid insolubility characteristics of bisulfate, and the bisulfate powder is extruded out through tube side tube wall cuts to force fluid to continuously infiltrate the bisulfate powder, so that the hydroscopic property of inorganic salt replaces soluble bisulfate ions while the water content of a system is reduced, and the concentration of a nitration active phase is improved; the pressure drop of the spiral feeding system is controlled, so that the powder is prevented from blocking a pipeline, and the fluid can smoothly pass through the pipeline.
(2) The invention combines the bisulfate and the shell-and-tube spiral feeding device to control the water content in the reaction system, and simultaneously adopts the organic solvent to dilute the concentrated acid, thereby reducing the overall viscosity of the system and improving the operation safety, so that the high-yield synthesis of the DADNP under the conventional concentrated acid system becomes possible, and the invention is favorable for industrial large-scale production.
(3) According to the invention, the shell-and-tube feeding device is arranged at the position of the microchannel reactor, so that the high selectivity and yield of a nitration reaction system are realized, the DADNP selectivity is not less than 98% and the yield is not less than 95% in a mixed acid system of 70-98% concentrated sulfuric acid and 65% concentrated nitric acid sold in the market can be ensured, and the consumption of the mixed acid is reduced to the maximum extent.
Drawings
FIG. 1 is a schematic flow diagram of the continuous synthesis of DADNP by the microchannel of the present invention.
FIG. 2 is a structural diagram of a shell-and-tube type feeding apparatus in the embodiment of the present invention.
The device comprises a T-shaped mixer 100, a T-shaped mixer 200, a microchannel reactor 300, an ice water crystallizer 400, a shell-and-tube feeding device 410, a shell pass 420, a tube pass 411, a shell pass inlet 412, a shell pass outlet 421, a cut 430, a closed storage tank 440, a spiral feeding rod 450, a motor 500 and a pressure difference controller.
Detailed Description
The technical solutions in the examples of the present invention will be described in further detail below, and it should be understood that the described examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention. Based on the embodiments of the present invention, those skilled in the art can make insubstantial improvements and modifications to the present invention without creative efforts to protect the present invention.
As shown in the flow chart of fig. 1 and fig. 2, the method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine (DADNP) by the microchannel provided by the embodiment of the invention comprises the following processes: mixing a mixed acid nitrating agent consisting of sulfuric acid and nitric acid and a DMSO (dimethyl sulfoxide) solvent into one feed, mixing DAP and DMSO into a DAP solution into the other feed, pumping the two feeds into a microchannel reactor 200 through a T-shaped mixer 100 for nitration reaction, inputting a crude product output by the microchannel reactor 200 into an ice water crystallizer 300 to obtain a DADNP crude crystal product, wherein ice water is filled in the ice water crystallizer 300; wherein the content of the first and second substances,
the sulfuric acid is fuming sulfuric acid or concentrated sulfuric acid with the concentration of 70-98%, and the nitric acid is fuming nitric acid or concentrated nitric acid with the concentration of more than or equal to 65%;
at least one shell-and-tube feeding device 400 is arranged on the microchannel reactor 200 along the fluid flow direction, a shell-side inlet 411 and a shell-side outlet 412 of the shell-and-tube feeding device 400 are respectively communicated to the upstream and the downstream of the microchannel reactor 200, and fluid entering the microchannel reactor 200 is discharged into the microchannel reactor 200 through the shell-side inlet 411 and the shell-side outlet 412 in sequence;
the tube side 420 of the shell-and-tube feeding device 400 is continuously filled with bisulfate powder, the tube wall of the tube side 420 is uniformly distributed with a plurality of notches 421 communicated with the shell side 410, and the bisulfate powder is in wetting contact with shell side fluid at the notches 421.
It should be noted that, with respect to the shell-side inlet 411 and the shell-side outlet 412 of the shell-and-tube feed device 400 being connected to the upstream and downstream of the microchannel reactor 200, respectively, the upstream and downstream are merely intended to represent the relative positions at which the shell-side inlet 411 and the shell-side outlet 412 are connected to the shell-and-tube feed device 400.
Further, in the embodiment of the present invention, the shell-and-tube feeding device 400 is a micro shell-and-tube flexible screw feeding device, the shell pass 410 and the tube pass 420 are both U-shaped, the shell pass inlet 411 and the shell pass outlet 412 are respectively disposed at the top of the outer wall at the two ends of the shell pass 410, the top at the two ends of the tube pass 420 are communicated to the sealed storage tank 430, and the sealed storage tank 430 is used for storing the bisulfate; a U-shaped spiral feeding rod 440 matched with the tube pass 420 is arranged in the tube pass 420, and two ends of the spiral feeding rod 440 penetrate through the closed storage tank 430 to be connected to a motor 450 so as to drive the spiral feeding rod 440 to move.
A pressure difference controller 500 for detecting the pressure difference between the shell-side inlet 411 and the shell-side outlet 412 is arranged between the shell-side inlet 411 and the shell-side outlet 412 of the shell-and-tube feeding device 400, and the pressure difference controller 500 controls the feeding circulation conveying speed of the spiral feeding rod 440. The dimensions of the shell-and-tube feed device in the examples of the invention are preferably: the total length of the shell pass 410 is 100mm, the diameter phi of the shell pass 410 is 10mm, the diameter phi of the tube pass 420 is 6mm, the diameter phi of the tube wall cut 421 of the tube pass is 0.8mm, and the number of the uniformly distributed cuts is 24.
The following examples further illustrate the process of the present invention.
Example 1
The concentration of the DMSO solution for preparing DAP is 4mol/L, and the flow rate is 4 mL/min. The mixed acid nitrating agent consists of commercially available 98% concentrated sulfuric acid, 65% concentrated nitric acid and a DMSO solvent, wherein the volume ratio of the commercially available 98% concentrated sulfuric acid to the commercially available 65% concentrated nitric acid to the commercially available DMSO solvent is 1:1:2, and the flow rate of the commercially available mixed acid nitrating agent to the commercially available mixed acid nitrating agent is 1 mL/min. The microchannel reaction temperature was 30 ℃, the total reaction residence time was 30 minutes, and the microchannel was 1/16 inches. In this embodiment, two shell-and-tube feeding devices are sequentially arranged along the fluid flowing direction of the microchannel reactor, and are respectively installed at the position where the residence time is 6 minutes and the position where the residence time is 21 minutes, the pressure difference between the shell side inlet and the shell side outlet of the two shell-and-tube feeding devices is respectively controlled at 0.3Mpa and 0.1Mpa, the crude product at the outlet of the microchannel reactor is directly introduced into ice water, and the crystallization product and the solution are taken out to determine the selectivity and the yield of DADNP, and as a result, the selectivity of DADNP is 99.4% and the yield is 97.7%.
Comparative example 1
The concentration of the DMSO solution for preparing DAP is 4mol/L, and the flow rate is 4 mL/min. The mixed acid nitrating agent consists of commercially available 98% concentrated sulfuric acid, 65% concentrated nitric acid and a DMSO solvent, wherein the volume ratio of the commercially available 98% concentrated sulfuric acid to the commercially available 65% concentrated nitric acid to the commercially available DMSO solvent is 1:1:2, and the flow rate of the commercially available mixed acid nitrating agent to the commercially available mixed acid nitrating agent is 1 mL/min. The microchannel reaction temperature was 30 ℃, the total reaction residence time was 30 minutes, and the microchannel was 1/16 inches. The crude product at the outlet of the microchannel reactor was directly passed into ice water, and the crystallized product and the solution were taken out to determine the selectivity and yield of DADNP, resulting in a selectivity of DADNP of 94.4% and a yield of 73.2%.
Example 2
The concentration of a DMSO solution for preparing DAP is 2mol/L, and the flow rate is 6 mL/min. The mixed acid nitrating agent consists of commercially available 70% concentrated sulfuric acid, 65% concentrated nitric acid and a DMSO solvent, wherein the volume ratio of the commercially available 70% concentrated sulfuric acid to the commercially available 65% concentrated nitric acid to the commercially available DMSO solvent is 4:1:0.5, and the flow rate is 4 mL/min. The microchannel reaction temperature was 40 ℃, the total reaction residence time was 40 minutes, and the microchannel was 1/8 inches. In this embodiment, two shell-and-tube feeding devices are sequentially arranged along the fluid flowing direction of the microchannel reactor, and are respectively installed at a position where the residence time is 4 minutes and a position where the residence time is 24 minutes, and the pressure difference between the shell side inlet and the shell side outlet of the two shell-and-tube feeding devices is respectively controlled at 0.4Mpa and 0.15Mpa, the crude product at the outlet of the microchannel reactor is directly introduced into ice water, and the selectivity and the yield of DADNP are determined by taking out the crystallized product and the solution, and as a result, the selectivity of DADNP is 98.9%, and the yield is 96.3%.
Example 3
The concentration of a DMSO solution for preparing DAP is 6mol/L, and the flow rate is 10 mL/min. The mixed acid nitrating agent consists of commercially available 90% concentrated sulfuric acid, 65% concentrated nitric acid and a DMSO solvent, wherein the volume ratio of the commercially available 90% concentrated sulfuric acid to the commercially available 65% concentrated nitric acid to the commercially available DMSO solvent is 2:1:2, and the flow rate of the commercially available mixed acid nitrating agent is 6 mL/min. The microchannel reaction temperature was 20 ℃, the total reaction residence time was 40 minutes, and the microchannel was 1/8 inches. In this embodiment, two shell-and-tube feeding devices are sequentially arranged along the fluid flowing direction of the microchannel reactor, and are respectively installed at the position where the residence time is 12 minutes and the position where the residence time is 30 minutes, the pressure difference between the shell side inlet and the shell side outlet of the two shell-and-tube feeding devices is respectively controlled at 0.5Mpa and 0.2Mpa, the crude product at the outlet of the microchannel reactor is directly introduced into ice water, and the crystallization product and the solution are taken out to determine the selectivity and the yield of DADNP, and as a result, the selectivity of DADNP is 98.1%, and the yield is 95.0%.
Example 4
The concentration of a DMSO solution for preparing DAP is 1mol/L, and the flow rate is 4 mL/min. The mixed acid nitrating agent consists of commercially available 98% concentrated sulfuric acid, 65% concentrated nitric acid and a DMSO solvent, wherein the volume ratio of the commercially available 98% concentrated sulfuric acid to the commercially available 65% concentrated nitric acid to the commercially available DMSO solvent is 3:1:0.5, and the flow rate is 2 mL/min. The microchannel reaction temperature was 40 ℃, the total reaction residence time was 30 minutes, and the microchannel was 1/16 inches. In this embodiment, two shell-and-tube feeding devices are sequentially arranged along the fluid flowing direction of the microchannel reactor, and are respectively installed at the position where the residence time is 9 minutes and the position where the residence time is 21 minutes, the pressure difference between the shell side inlet and the shell side outlet of the two shell-and-tube feeding devices is respectively controlled at 0.3Mpa and 0.10Mpa, the crude product at the outlet of the microchannel reactor is directly introduced into ice water, and the crystallized product and the solution are taken out to determine the selectivity and the yield of DADNP, and as a result, the selectivity of DADNP is 98.8%, and the yield is 95.7%.
Example 5
The concentration of a DMSO solution for preparing DAP is 3mol/L, and the flow rate is 6 mL/min. The mixed acid nitrating agent consists of commercially available 70% concentrated sulfuric acid, 65% concentrated nitric acid and a DMSO solvent, wherein the volume ratio of the commercially available 70% concentrated sulfuric acid to the commercially available 65% concentrated nitric acid to the commercially available DMSO solvent is 4:1:2, and the flow rate of the commercially available mixed acid nitrating agent is 4 mL/min. The microchannel reaction temperature was 40 ℃, the total reaction residence time was 30 minutes, and the microchannel was 1/16 inches. In this embodiment, two shell-and-tube feeding devices are sequentially arranged along the fluid flowing direction of the microchannel reactor, and are respectively installed at a position where the residence time is 7 minutes and a position where the residence time is 18 minutes, and the pressure difference between the shell side inlet and the shell side outlet of the two shell-and-tube feeding devices is respectively controlled at 0.5Mpa and 0.25Mpa, the crude product at the outlet of the microchannel reactor is directly introduced into ice water, and the selectivity and the yield of DADNP are determined by taking out the crystallized product and the solution, with the result that the selectivity of DADNP is 98.0% and the yield is 95.1%.
Comparative example 2
The concentration of a DMSO solution for preparing DAP is 3mol/L, and the flow rate is 6 mL/min. The mixed acid nitrating agent consists of commercially available 70% concentrated sulfuric acid, 65% concentrated nitric acid and a DMSO solvent, wherein the volume ratio of the commercially available 70% concentrated sulfuric acid to the commercially available 65% concentrated nitric acid to the commercially available DMSO solvent is 4:1:2, and the flow rate of the commercially available mixed acid nitrating agent is 4 mL/min. The microchannel reaction temperature was 40 ℃, the total reaction residence time was 30 minutes, and the microchannel was 1/16 inches. The crude product at the outlet of the microchannel reactor was directly passed into ice water, and the crystallized product and the solution were taken out to determine the selectivity and yield of DADNP, which was 86.0% and 68.2%.
Example 6
The concentration of a DMSO solution for preparing DAP is 2mol/L, and the flow rate is 4 mL/min. The mixed acid nitrating agent consists of 20% fuming sulfuric acid, 65% concentrated nitric acid and DMSO solvent, the volume ratio of the fuming sulfuric acid to the concentrated nitric acid is 1:1:2, and the flow rate is 1 mL/min. The microchannel reaction temperature was 30 ℃, the total reaction residence time was 30 minutes, and the microchannel was 1/16 inches. In this example, the microchannel reactor was equipped with 1 shell-and-tube feeder, and was installed at a residence time of 12 minutes, and the pressure difference between the inlet and outlet of the shell side was controlled at 0.1Mpa, and the crude product at the outlet of the microchannel reactor was directly introduced into ice water, and the selectivity and yield of DADNP were measured by taking out the crystallized product and the solution, and as a result, the selectivity of DADNP was 99.6%, and the yield was 98.0%.
Example 7
The concentration of a DMSO solution for preparing DAP is 2mol/L, and the flow rate is 4 mL/min. The mixed acid nitrating agent consists of commercially available 90% concentrated sulfuric acid, 100% concentrated nitric acid and DMSO solvent, the volume ratio of the commercially available 90% concentrated sulfuric acid to the commercially available 100% concentrated nitric acid to the commercially available DMSO solvent is 1:1:2, and the flow rate of the commercially available mixed acid nitrating agent is 1 mL/min. The microchannel reaction temperature was 30 ℃, the total reaction residence time was 30 minutes, and the microchannel was 1/16 inches. In this example, the microchannel reactor was equipped with 1 shell-and-tube feeder, and was installed at a residence time of 18 minutes, and the pressure difference between the inlet and outlet of the shell side was controlled at 0.15Mpa, and the crude product at the outlet of the microchannel reactor was directly introduced into ice water, and the selectivity and yield of DADNP were measured by taking out the crystallized product and the solution, and as a result, the selectivity of DADNP was 99.7%, and the yield was 98.6%.
Comparative example 3
The concentration of a DMSO solution for preparing DAP is 2mol/L, and the flow rate is 4 mL/min. The mixed acid nitrating agent consists of commercially available 90% concentrated sulfuric acid, 100% concentrated nitric acid and DMSO solvent, the volume ratio of the commercially available 90% concentrated sulfuric acid to the commercially available 100% concentrated nitric acid to the commercially available DMSO solvent is 1:1:2, and the flow rate of the commercially available mixed acid nitrating agent is 1 mL/min. The microchannel reaction temperature was 30 ℃, the total reaction residence time was 30 minutes, and the microchannel was 1/16 inches. The crude product at the outlet of the microchannel reactor was directly passed into ice water, and the crystallized product and the solution were taken out to determine the selectivity and yield of DADNP, with the result that the selectivity of DADNP was 96.5% and the yield was 83.5%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present application.
Claims (10)
1. A method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine by a micro-channel is characterized by comprising the following steps: taking DMSO as a solvent, respectively pumping raw materials of 2, 6-diaminopyridine and a mixed acid nitrating agent consisting of sulfuric acid and nitric acid into a microchannel reactor for nitration reaction, and then sending a crude product output by the microchannel reactor into ice water to obtain a crude crystal product of the 2, 6-diamino-3, 5-dinitropyridine; wherein the content of the first and second substances,
the sulfuric acid is fuming sulfuric acid or concentrated sulfuric acid with the concentration of 70-98%, and the nitric acid is fuming nitric acid or concentrated nitric acid with the concentration of more than or equal to 65%;
at least one shell-and-tube feeding device is arranged on the microchannel reactor along the flowing direction of the fluid, a shell-side inlet and a shell-side outlet of the shell-and-tube feeding device are respectively communicated to the upstream and the downstream of the microchannel reactor, and the fluid entering the microchannel reactor enters the shell-and-tube feeding device through the shell-side inlet and is discharged into the microchannel reactor through the shell-side outlet; the shell-and-tube feeding device is characterized in that a tube pass of the shell-and-tube feeding device is filled with bisulfate continuously, a plurality of notches communicated with the shell pass are uniformly distributed on the tube wall of the tube pass, and the bisulfate is in contact with shell pass fluid at the notches in a soaking manner.
2. The method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine by the microchannel, according to claim 1, wherein when the sulfuric acid is fuming sulfuric acid or the nitric acid is fuming nitric acid, the number of the shell-and-tube feeding devices is 1, the shell-and-tube feeding devices are installed at 6 to 8/10 of the total residence time period of the microchannel reactor, and the pressure difference between the shell-side inlet and the shell-side outlet of each shell-and-tube feeding device is 0.1 to 0.25 Mpa.
3. The method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine by the microchannel, according to claim 1, is characterized in that when the mixed acid nitrating agent does not include fuming sulfuric acid or fuming nitric acid, the number of the shell-and-tube feeding devices is at least 2, wherein the first stage shell-and-tube feeding device and the last stage shell-and-tube feeding device which are arranged along the fluid flowing direction of the microchannel reactor are respectively arranged at 1-3/10 and 6-8/10 of the total residence time period of the microchannel reactor, and the pressure difference between the shell-side inlet and the shell-side outlet of the first stage shell-and-tube feeding device and the pressure difference between the shell-side inlet and the shell-side outlet of the last stage shell-and-tube feeding device are respectively 0.3-0.5 Mpa and 0.1-0.25 Mpa.
4. The method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine by the micro-channel according to claim 1, wherein a DMSO solution of 2, 6-diaminopyridine is used as a feed, the concentration of the solution is 1-6 mol/L, and the flow rate is 4-10 mL/min; the DMSO solution of the mixed acid nitrating agent is fed into the other strand of the mixed acid nitrating agent, wherein the volume ratio of the sulfuric acid to the nitric acid to the DMSO solvent is 1-4: 1: 0.4-2, and the flow rate is 1-4 mL/min; the reaction temperature in the microchannel reactor is 20-40 ℃, and the total reaction residence time is 20-40 minutes.
5. The method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine through the microchannel, according to claim 4, is characterized in that the sulfuric acid is 90% -98% concentrated sulfuric acid, and the volume ratio of the sulfuric acid to the nitric acid to the DMSO solvent in the DMSO solution of the mixed acid nitrating agent is 1-2: 1: 1.
6. The method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine through the microchannel, according to claim 4, is characterized in that the sulfuric acid is 70% -90% concentrated sulfuric acid, and the volume ratio of the sulfuric acid to the nitric acid to the DMSO solvent in the DMSO solution of the mixed acid nitrating agent is 2-4: 1: 0.5.
7. The method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine through the micro-channel according to claim 4, wherein the DMSO concentration of the 2, 6-diamino-pyridine is 2-4 mol/L, and the flow rate is 4-6 mL/min.
8. The method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine through the micro-channel according to claim 1, wherein the shell side and the tube side of the shell-and-tube feeding device are both U-shaped, the shell side inlet and the shell side outlet are respectively arranged on the tops of the outer walls at the two ends of the shell side, the two ends of the tube side are communicated to a closed storage tank, the closed storage tank is used for storing the bisulfate, a U-shaped spiral feeding rod is arranged in the tube side in a matching manner, and the two ends of the spiral feeding rod pass through the closed storage tank and are connected to a motor to drive the spiral feeding rod to move.
9. The method for continuously synthesizing the 2, 6-diamino-3, 5-dinitropyridine through the micro-channel according to the claim 8, wherein a pressure difference controller for detecting the pressure difference between the shell side inlet and the shell side outlet of the shell-and-tube feeding device is arranged between the shell side inlet and the shell side outlet, and the pressure difference controller controls the conveying speed of the circular feeding of the spiral feeding rod.
10. The method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine by the micro-channel according to claim 1, wherein the ratio of the shell-side diameter to the tube-side diameter is 1.5-3: 1, and the aperture of the notch is phi 0.4-1.0 mm.
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