CN105777550A - Method for continuously synthesizing 2,4-dimitroanisole - Google Patents
Method for continuously synthesizing 2,4-dimitroanisole Download PDFInfo
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- CN105777550A CN105777550A CN201610317074.7A CN201610317074A CN105777550A CN 105777550 A CN105777550 A CN 105777550A CN 201610317074 A CN201610317074 A CN 201610317074A CN 105777550 A CN105777550 A CN 105777550A
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- dinitroanisol
- continuously
- washing
- dnan
- methanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for continuously synthesizing 2,4-dimitroanisole, and relates to the field of synthesis of chemical raw materials. The method mainly comprises the following five steps of synthesis, recovery of methyl alcohol, washing, drying, and flaking and packaging. The method has the advantages that by adopting the continuous synthesis method, the recovery rate of solvent is high, the pollution is little, the cost is low, and the safety, reliability and stability are realized in the process; the total yield of product is more than 90%, and the purity is more than 99.2%.
Description
Technical field
The present invention relates to chemical raw material synthesis field, be specifically related to one and be continuously synthesizing to 2,4-
The method of dinitroanisol.
Background technology
2,4-dinitroanisols (DNAN) are the molten of a kind of function admirable recently reported
Casting explosive carrier.Molecular formula is C7H6N3O5, and density is 1.341g/cm3, a kind of fulvescent
To light yellow crystalline solid, it is slightly soluble in water, is dissolved in most of organic solvent, including methanol, second
Alcohol, also ether.
2015, one " a kind of 2,4-is declared and authorized in Zhejiang Dibang Chemical Co., Ltd.
The synthesis technique of dinitroanisol " invention patent mandate, Patent No.
CN201310325839.8.The synthetic method of the 2,4-dinitroanisol mentioned in this patent is
Composite inorganic alkali is dissolved in methanol and obtains methanol alkali liquor, then carbinol base drop is added in CDB
Carry out synthetic reaction, reactant liquor decrease temperature crystalline, filter, wash and obtain product dna N.This
Bright patent is a kind of method being interrupted synthetic DNA N.
At present, the domestic synthetic method industrial about DNAN has two kinds.The first be with
Chlorobenzene is raw material, and with nitric-sulfuric acid at 40 DEG C, nitrification prepares 1-chlorine DNFB
(CDB) intermediate.CDB prepares with methanol solution alkali reaction after product purification processes and contains
The reactant liquor of DNAN；The second is with CDB as raw material, in methanol solution, passes through first
Alcohol liquid caustic soda solution carries out nucleophilic displacement of fluorine and prepares DNAN reactant liquor.Two kinds of methods are interruption and close
One-tenth method, the prepared reactant liquor containing DNAN is after solid-liquid separation, containing the liquid of first alcohol and water
Carrying out Methanol Recovery process mutually, the DNAN of solid phase and a small amount of impurity can be through washings continuously
Obtain product dna N.The above-mentioned interruption producer that the producer of domestic production DNAN all uses
Method, the production of this product not yet realizes serialization.
Summary of the invention
It is an object of the invention to solve 2,4-dinitroanisol (DNAN) product cannot
The problems such as the high cost that causes continuously, cycle length, wastewater flow rate are bigger, it is provided that a kind of continuous print,
Synthesis cycle is short, production cost is low, wastewater flow rate is little 2,4-dinitroanisol (DNAN)
Industrial preparative method.
To achieve these goals, the technical scheme that the present invention takes by: provided a kind of even
Continuous it is combined to 2, the method for 4-dinitroanisol, including following processing step:
(1) DNFB (CDB) connects by a certain percentage with methanol liquid caustic soda mixed liquor
The continuous synthesis reactor that enters is synthesized the 2 of liquid, 4-dinitroanisol (DNAN), reactant liquor
Carry lifting system by synthesis reactor to continuously enter aging machine and synthesize further；
(2) reactant liquor continuously enters in vaporizer by aging machine lifting bucket, substantial amounts of methanol
Continuously enter in methanol rectifying tower with water continuous evaporation, formed the first of recoverable by rectification
Alcohol, rectifying column and vaporizer atmospheric operation；Water and 2,4-dinitroanisol (DNAN)
And sodium chloride then continuously enters in washing machine from the vaporizer other end；
(3) carrying out hot water by the washing kettle of three series connection to wash continuously, mode of washing is inverse
Stream washing, washes enters wastewater disposal basin；
(4), after the moisture during drying machine hot air drying controls product, product continuously enters film-making
In machine；
(5) forming lamellar 2,4-dinitroanisol (DNAN), product continuously enters material
Bucket, automatic Weighing, packaging.
Preferably, in described step (1), the raw material situation of feeding intake is: DNFB
(CDB): liquid caustic soda: methanol quality is than for 1:(0.65～0.72): (5～8), wherein, liquid
The mass fraction of alkali is 30%.
Preferably, in described step (1), synthesis reactor, the reaction temperature of aging machine are 62～67 DEG C,
Pressure is normal pressure.
Preferably, in described step (2), the pressure in vaporizer, rectifying column is normal pressure.
Preferably, in described step (3), in washing process, the temperature of hot wash-water is 95～98 DEG C,
Slurry amount is 2,2～4 times of 4-dinitroanisol (DNAN) volume.
Preferably, in described step (3), countercurrent washing regime is 2,4-dinitroanisol
(DNAN) flow direction of material is 1# washing kettle → 2# washing kettle → 3# washing kettle, hot wash-water stream
To being then 3# washing kettle → 2# washing kettle → 1# washing kettle.
Preferably, in described step (4), hot air drying temperature is 110～120 DEG C.
Use technical scheme, the method using continuous synthesis, solvent high-efficiency reclaims,
Polluting little, low cost, process safety is reliable, steadily.Total yield of products more than 90%, purity
More than 99.2%.
Accompanying drawing illustrates:
Fig. 1 is that this is continuously synthesizing to DNAN general flow chart.
Detailed description of the invention
Below by specific embodiment and combine a kind of serialization in the accompanying drawing narration present invention
Synthesis 2, the method for 4-dinitroanisol (DNAN).Unless stated otherwise, the present invention
Technological means used by is method known in those skilled in the art.It addition, embodiment party
Case is interpreted as illustrative, and unrestricted the scope of the present invention, the spirit and scope of the invention
It is limited only by the claims that follow.To those skilled in the art, without departing substantially from the present invention
On the premise of spirit and scope, carry out the material component in these embodiments and consumption is each
Plant to change or change and fall within protection scope of the present invention.
Embodiment 1:
(1) by the DNFB (CDB) of 65 DEG C of molten states, the methanol of 20 DEG C
And the liquid caustic soda solution that 20 DEG C of mass fractions are 30% in mass ratio for 1:0.69:6 be continuously added to
In reactor, keeping temperature constant in reactor is 65 DEG C；
(2), in synthesis reaction solution continuously enters vaporizer, methanol enters from vaporizer gaseous phase outlet
Enter rectifying column, from rectifying column top to returnable bottle, containing 2,4-dinitroanisol (DNAN),
Sodium-chloride water solution continuously enters in sink from vaporizer liquid-phase outlet；
(3) through 95 DEG C of hot washes in sink, enter standing separation in separator, separate
Wastewater collection be uniformly processed, product 2,4-dinitroanisol (DNAN) is collected laggard
Row is dried, weighs, analyzes test；
Tested by analysis, draw lamellar 2, total receipts of 4-dinitroanisol (DNAN)
Rate is 91%, and purity is 99.4%, and fusing point is 96.2 DEG C.
Embodiment 2:
(1) by the DNFB (CDB) of methanol, liquid caustic soda, molten state respectively
It is delivered to continuously in corresponding raw material head tank；
(2) alkali liquor, methanol and DNFB (CDB) are 1:0.72 in mass ratio:
5 are continuously added in reactor from head tank, and reactor design temperature is 65 DEG C, normal pressure, reaction
Liquid promotes system by reactor and continuously enters aging machine, and aging machine design temperature is 65 DEG C,
Normal pressure；
(3) mixed material in aging machine continuously enters vaporizer by lifting system, evaporation
Device uses autoclave self-circulation mode, and the reactant liquor after methanol removal continuously enters from vaporizer side
First washing kettle, the methanol of evaporator evaporation, water vapour continuously enter methanol rectifying tower, tower
Operating at ambient pressure, top gaseous phase is by condensation, and one backflow, one extraction enters methanol and returns
Store up groove；
(4) washing unit is mainly composed in series by the washing kettle of three band separators, its material
Being counter flow series washing with washings, hot wash-water uses 96 DEG C of hot water of hot water storgae, washing
It is then 3# washing kettle → 2# washing kettle → 1# washing kettle → liquid medicine separator → waste water that hot water flows to
Sedimentation tank；2,4-dinitroanisols (DNAN) flow direction of material is that 1# washing kettle → 2# washes
Wash still → 3# washing kettle → liquid medicine separator → drying unit；
(5) 2,4-dinitroanisol (DNAN) continuously enter in hot-air drier, logical
Crossing steam contact drying, baking temperature is 110 DEG C, blasts air bottom exsiccator, utilizes sky
Moisture in material is taken away by gas, and dried 2,4-dinitroanisol (DNAN) are even
Continuous entrance pelleter；
(6) logical cold water in the roller interlayer of pelleter, makes the 2 of roller surface, 4-dinitro benzene
Methyl ether (DNAN) solidify, scraped by scraper and make lamellar, fall into hopper, through automatic weighing,
Send dress automobile after barrelling, be transported to DNAN warehouse for finished product.
Tested by analysis, draw lamellar 2, total receipts of 4-dinitroanisol (DNAN)
Rate is 92%, and purity is 99.3%, and fusing point is 96.0 DEG C.
Embodiment 3:
(1) by the DNFB (CDB) of methanol, liquid caustic soda, molten state respectively
It is delivered to continuously in corresponding raw material head tank；
(2) alkali liquor, methanol and DNFB (CDB) are 1:0.72 in mass ratio:
8 are continuously added in reactor from head tank, and reactor design temperature is 62 DEG C, normal pressure, reaction
Liquid promotes system by reactor and continuously enters aging machine, and aging machine design temperature is 62 DEG C,
Normal pressure；
(3) mixed material in aging machine continuously enters vaporizer by lifting system, evaporation
Device uses autoclave self-circulation mode, and the reactant liquor after methanol removal continuously enters from vaporizer side
First washing kettle, the methanol of evaporator evaporation, water vapour continuously enter methanol rectifying tower, tower
Operating at ambient pressure, top gaseous phase is by condensation, and one backflow, one extraction enters methanol and returns
Store up groove；
(4) washing unit is mainly composed in series by the washing kettle of three band separators, its material
Being counter flow series washing with washings, hot wash-water uses 98 DEG C of hot water of hot water storgae, washing
It is then 3# washing kettle → 2# washing kettle → 1# washing kettle → liquid medicine separator → waste water that hot water flows to
Sedimentation tank；2,4-dinitroanisols (DNAN) flow direction of material is that 1# washing kettle → 2# washes
Wash still → 3# washing kettle → liquid medicine separator → drying unit；
(5) 2,4-dinitroanisol (DNAN) continuously enter in hot-air drier, logical
Crossing steam contact drying, baking temperature is 115 DEG C, blasts air bottom exsiccator, utilizes sky
Moisture in material is taken away by gas, and dried 2,4-dinitroanisol (DNAN) are even
Continuous entrance pelleter；
(6) logical cold water in the roller interlayer of pelleter, makes the 2 of roller surface, 4-dinitro benzene
Methyl ether (DNAN) solidify, scraped by scraper and make lamellar, fall into hopper, through automatic weighing,
Send dress automobile after barrelling, be transported to DNAN warehouse for finished product.
Tested by analysis, draw lamellar 2, total receipts of 4-dinitroanisol (DNAN)
Rate is 93%, and purity is 99.5%, and fusing point is 96.1 DEG C.
Embodiment 4:
(1) by the DNFB (CDB) of methanol, liquid caustic soda, molten state respectively
It is delivered to continuously in corresponding raw material head tank；
(2) alkali liquor, methanol and DNFB (CDB) are 1:0.70 in mass ratio:
7 are continuously added in reactor from head tank, and reactor design temperature is 67 DEG C, normal pressure, reaction
Liquid promotes system by reactor and continuously enters aging machine, and aging machine design temperature is 67 DEG C,
Normal pressure；
(3) mixed material in aging machine continuously enters vaporizer by lifting system, evaporation
Device uses autoclave self-circulation mode, and the reactant liquor after methanol removal continuously enters from vaporizer side
First washing kettle, the methanol of evaporator evaporation, water vapour continuously enter methanol rectifying tower, tower
Operating at ambient pressure, top gaseous phase is by condensation, and one backflow, one extraction enters methanol and returns
Store up groove；
(4) washing unit is mainly composed in series by the washing kettle of three band separators, its material
Being counter flow series washing with washings, hot wash-water uses 96 DEG C of hot water of hot water storgae, washing
It is then 3# washing kettle → 2# washing kettle → 1# washing kettle → liquid medicine separator → waste water that hot water flows to
Sedimentation tank；2,4-dinitroanisols (DNAN) flow direction of material is that 1# washing kettle → 2# washes
Wash still → 3# washing kettle → liquid medicine separator → drying unit；
(5) 2,4-dinitroanisol (DNAN) continuously enter in hot-air drier, logical
Crossing steam contact drying, baking temperature is 120 DEG C, blasts air bottom exsiccator, utilizes sky
Moisture in material is taken away by gas, and dried 2,4-dinitroanisol (DNAN) are even
Continuous entrance pelleter；
(6) logical cold water in the roller interlayer of pelleter, makes the 2 of roller surface, 4-dinitro benzene
Methyl ether (DNAN) solidify, scraped by scraper and make lamellar, fall into hopper, through automatic weighing,
Send dress automobile after barrelling, be transported to DNAN warehouse for finished product.
Tested by analysis, draw lamellar 2, total receipts of 4-dinitroanisol (DNAN)
Rate is 92%, and purity is 99.3%, and fusing point is 96.0 DEG C.
Obviously the present invention implements and is not subject to the restrictions described above, if the present invention of have employed
Method design and the improvement of various unsubstantialities that carries out of technical scheme, or the most improved incite somebody to action this
Design and the technical scheme of invention directly apply to other occasion, all at the protection model of the present invention
Within enclosing.
Claims (7)
1. one kind is continuously synthesizing to 2, the method for 4-dinitroanisol, it is characterised in that bag
Include following step:
(1) DNFB (CDB) connects by a certain percentage with methanol liquid caustic soda mixed liquor
The continuous synthesis reactor that enters is synthesized the 2 of liquid, 4-dinitroanisol (DNAN), reactant liquor
Carry lifting system by synthesis reactor to continuously enter aging machine and synthesize further；
(2) reactant liquor continuously enters in vaporizer by aging machine lifting bucket, substantial amounts of methanol
Continuously enter in methanol rectifying tower with water continuous evaporation, formed the first of recoverable by rectification
Alcohol, rectifying column and vaporizer atmospheric operation；Water and 2,4-dinitroanisol (DNAN)
And sodium chloride then continuously enters in washing machine from the vaporizer other end；
(3) carrying out hot water by the washing kettle of three series connection to wash continuously, mode of washing is inverse
Stream washing, washes enters wastewater disposal basin；
(4), after the moisture during drying machine hot air drying controls product, product continuously enters film-making
In machine；
(5) forming lamellar 2,4-dinitroanisol (DNAN), product continuously enters material
Bucket, automatic Weighing, packaging.
One the most according to claim 1 is continuously synthesizing to 2,4-dinitroanisol
Method, it is characterised in that: in described step (1), the raw material situation of feeding intake is: 2,4-dinitros
Base chlorobenzene (CDB): liquid caustic soda: methanol quality is than for 1:(0.65～0.72): (5～8), its
In, the mass fraction of liquid caustic soda is 30%.
One the most according to claim 1 is continuously synthesizing to 2,4-dinitroanisol
Method, it is characterised in that: in described step (1), synthesis reactor, the reaction temperature of aging machine are
62～67 DEG C, pressure is normal pressure.
One the most according to claim 1 is continuously synthesizing to 2,4-dinitroanisol
Method, it is characterised in that: in described step (2), the pressure in vaporizer, rectifying column is
Normal pressure.
One the most according to claim 4 is continuously synthesizing to 2,4-dinitroanisol
Method, it is characterised in that: in described step (3), in washing process, the temperature of hot wash-water is
95～98 DEG C, slurry amount is 2, the 2～4 of 4-dinitroanisol (DNAN) volume
Times.
One the most according to claim 1 is continuously synthesizing to 2,4-dinitroanisol
Method, it is characterised in that: in described step (3), countercurrent washing regime is 2,4-dinitro benzene
Methyl ether (DNAN) flow direction of material is 1# washing kettle → 2# washing kettle → 3# washing kettle, washing heat
Current direction is then 3# washing kettle → 2# washing kettle → 1# washing kettle.
One the most according to claim 1 is continuously synthesizing to 2,4-dinitroanisol
Method, it is characterised in that: in described step (4), hot air drying temperature is 110～120 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114507141A (en) * | 2021-12-23 | 2022-05-17 | 中北大学 | Method for controlling crystal form of 2,4-dinitroanisole |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114507141A (en) * | 2021-12-23 | 2022-05-17 | 中北大学 | Method for controlling crystal form of 2,4-dinitroanisole |
| CN114507141B (en) * | 2021-12-23 | 2024-01-23 | 中北大学 | Method for controlling 2,4-dinitroanisole crystal form |
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