CN107118152A - One kind production 2,6 pairs（Bitter amino）The industrial wastes regeneration and treatment technique of 3,5 di nitryl pyridine heat-resistant explosives - Google Patents
One kind production 2,6 pairs（Bitter amino）The industrial wastes regeneration and treatment technique of 3,5 di nitryl pyridine heat-resistant explosives Download PDFInfo
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- CN107118152A CN107118152A CN201710356592.4A CN201710356592A CN107118152A CN 107118152 A CN107118152 A CN 107118152A CN 201710356592 A CN201710356592 A CN 201710356592A CN 107118152 A CN107118152 A CN 107118152A
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- 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
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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Abstract
The invention belongs to energetic material field, it is related to a kind of production heat-resistant explosive 2,6 pairs of (bitter amino) 3, the regeneration and treatment technique of the industrial wastes of 5 di nitryl pyridines (PYX), to preparing heat-resistant explosive PYX intermediates N, N ' double (2,4,6 trinitrophenyls) 2, the waste liquid that 6 aminopyridines (PAP) process is produced has carried out reasonable utilization, regeneration mother liquor is disclosure satisfy that the technical requirements of reaction system, and be successfully used in the recycling of PAP condensation reactions；So as to efficiently control the discharge of industrial wastes, environmental pollution is reduced, intermediate PAP yield is improved, production cost is reduced；And PYX explosive productions waste liquid is no longer taken atmospheric distillation recycling design, eliminate the potential safety hazard of production process.
Description
Technical field
The invention belongs to energetic material field, and in particular to double (bitter amino) -3, the 5- di nitryl pyridines of 2,6- of one kind production
(PYX) the industrial wastes regeneration and treatment technique of heat-resistant explosive.
Background technology
PYX explosives, chemical name 2, double (bitter amino) -3, the 5- di nitryl pyridines of 6- are by U.S. Los Alamos countries
A kind of heat resistance explosive that laboratory is succeeded in developing in earlier 1970s, crystal density 1.77g/cm3, fusing point
360 DEG C, explosion velocity is 7274m/s (d=1.688g/cm3), vacuum stability is not more than 3.0ml/h.g (260 DEG C).PYX is comprehensive
One of best heat-resistant explosive of performance is closed, is usually used in manufacturing ultrahigh-temp perforating bullet powder charge, and open in Aero-Space, subsurface investigation
It is used widely in hair.
PYX explosives react, and being carried out in two steps first progress condensation reaction is：In the case where accelerator acts on, 2,4,6- trinitro- chlorine
Benzene and 2,6- diamino-pyridines react generation intermediate N, N '-bis- (2,4,6- trinitrophenyls) 2,6- amino pyrroles in a solvent
Pyridine (abbreviation PAP), reaction equation as shown below.
Then carrying out nitration reaction again, directly product PYX is made in nitrification in concentrated nitric acid by PAP.
But in current actual production, after filtering, the waste liquid of generation is to pass through to first step intermediate PAP reaction solution
Atmospheric distillation recycling design, it has the disadvantage that solvent recovering rate is low (only 50%), recycling design content only has 85%~
90%, it is impossible to meet the requirement of intermediate PAP condensation reactions.
And in the condensation reaction 2, the chlorine atom in 4,6- trinitro-chlorobenzene molecules is very active, in water plus
Partial hydrolysis, generation 2,4,6- trinitrophenols (I) can occur when hot.As can be seen here, this hydrolysis is with generation PAP's
Condensation reaction competes 2,4,6- trinitro-chlorobenzenes.It is therefore necessary to ensure this side reaction of generation hydrolysis is avoided as far as possible,
Otherwise 2,4,6- trinitro-chlorobenzenes that can be in consumption system.Meanwhile, if generating a large amount of 2,4,6- trinitro-s in reaction system
Phenol, because it is an acidity very strong compound, and necessarily consumption DAP and alkaline reaction accelerator,
So as to reduce the yield and purity of PAP products.
On the other hand, 2, the condensation reaction between 4,6- trinitro-chlorobenzenes and DAP is first order reaction and divided
What step was carried out, i.e. the DAP of the 2 of 1mol, 4,6- trinitro-chlorobenzenes and 1mol first generate 2- amino -6- (2,4,
6- trinitrophenyls) pyridine (II), then 2,4,6- trinitro-chlorobenzenes generation product N, N ' again with the second mole-bis- (-
2,4,6- trinitrophenyls) 2,6- aminopyridines.The presence of amino, will lead in PAP nitration reactions in compound (II) molecule
Cause violent oxidation reaction and cause and catch fire, produce potential safety hazard.Therefore, it should try one's best and avoid this pair of generation compound (II)
Product.
But in existing industrial production, condensation reaction is 2,4,6- trinitro-chlorobenzenes and DAP in promotion
The lower reaction generation PAP of agent effect, mixed solvent is as reaction medium, because selecting industrial solvent in actual production, reaction
Containing more than 5% moisture in system, so the generation of compound (I) is inevitable.And reaction system has a small amount of water in itself
Generation, therefore, the water in mother liquor is larger, and the carry out to reaction system is totally unfavorable, recycles mother liquor, it is necessary to
Moisture in mother liquor is rationally handled.
From the point of view of being analyzed more than, the mother liquor composition for preparing intermediate PAP is mainly, residual solvent, water and unreacted 2,
4,6- trinitro-chlorobenzenes, 2- amino -6- (2,4,6- trinitrophenyls) pyridine, 2,4,6- trinitrophenols and a small amount of PAP etc..
The content of 2,4,6- trinitro-chlorobenzenes there are about 5~8% in mother liquor, and 2,4,6- trinitro-chlorobenzenes belong to one-level explosive,
During high temperature distillation, compound (I) can be converted into the presence of water by having, and the material stability is poor, easily blast.Therefore,
Using the method recycling design of air-distillation, there is great potential safety hazard.In addition, the discharge of slops is not inconsistent cyclization yet
Guaranteed request, because containing substantial amounts of nitro compounds and undistilled solvent in waste liquid, certainly will cause serious environmental pollution.
The content of the invention
In view of the shortcomings of the prior art, the purpose of the present invention is PYX explosive production waste liquids is no longer taken atmospheric distillation
Recycling design, eliminates the potential safety hazard in production process.Recycled by the mother liquor in PAP condensation reactions, to improve
Intermediate PAP yield, and without drier, without cosolvent, no waste liquid is produced, and reduces the pollution to environment, reduction life
Cost is produced, the shortcoming in existing process is overcome
Step one：By 2,4,6- trinitro-chlorobenzenes and 2,6- diamino-pyridines, reacted reaction solution stirring is quiet in a solvent
Put, the solvent is chloroform and carbon tetrachloride mixed solvent, the two volume ratio is 1：1, because 2,4,6- trinitrophenols
Stability is very poor, explosive, in order to avoid potential safety hazard, stands sufficiently long time main purpose to allow 2,4,6- trinitro-s
Phenol fully reacts with alkali.Remove a hidden danger；
Step 2：Aqueous phase is layered with organic phase, and aqueous phase is located at upper strata, and organic phase is located at lower floor, and organic phase is chloroform
With carbon tetrachloride mixed liquor, because reaction can produce a variety of accessory substances, cotton-shaped floating can be formed in aqueous phase and organic phase interface
Thing analyzes predominantly 2,4,6- trinitrophenols and 2,4,6- trinitrophenols and reacts life with system neutral and alkali compound after tested
Into salt, its content in whole reaction solution is about 3%, so liquid interface need to will be taken to move down a segment distance, it is apart from d=
VReaction solutionUnder × 3% × 1.5/S (S is the organic phase-contact surface area of aqueous phase) collection organic phase to interface determined at d, it is
Mother liquor, mother liquor volume is VMother liquor；
Step 3：Chloroform and carbon tetrachloride mixed liquor, chloroform and four are added in the mother liquor described in step 2
Chlorination carbon volume ratio is 1：1, chloroform and the carbon tetrachloride volume V of addition1It is VMother liquor1/2nd；
2,4,6- trinitro-chlorobenzenes are added into above-mentioned mother liquor, additional amount are computed for rubbing to 2,4,6- trinitro-chlorobenzenes
Untill your concentration is 0.5mol/L.
Accelerator is added to above-mentioned mother liquor again, the accelerator is Na2CO3、NaHCO3、K2CO3、KHCO3Middle one kind, plus
The mol ratio of the accelerator entered and above-mentioned addition 2,4,6- trinitro-chlorobenzenes is 1:1~1.1, preferably 1:1.1
Finally, then to above-mentioned mother liquor add DAP, the DAP of addition with above-mentioned addition
The mol ratio of 2,4,6- trinitro-chlorobenzenes is 1:2.
Step 4：The mother liquor that step 3 is obtained comes into operation.
Beneficial effects of the present invention are as follows：
The present invention uses material；2,4,6- trinitro-chlorobenzenes, technical grade, 78~81 DEG C of fusing point, Shaanxi Kang Yuan chemical industry is limited
Responsible company；DAP, technical grade, fusing point >=117 DEG C, Shaanxi Kang Yuan chemical products Co., Ltd.It is industrial female
Liquid, Xi'an Inst. of Modern Chemistry；Accelerant N H, technical grade, Zhengzhou Kang Yuan chemical industry Co., Ltd；Chloroform, Xi'an
Chemical reagent factory；Carbon tetrachloride, Xi'an chemical reagent factory.TA Q200 type differential scanning calorimeters, TA companies of the U.S..
It is as follows using this influence of mother liquid recycling technique to PAP yields and quality in embodiment,
Influence of the Recycling Mother Solution number of times to PAP yields and quality
It can be seen that being carried out using this mother liquid recycling technique after ten circulations, PAP yields are stable in more than 95%,
And peak temperature (DSC) data stabilization is thermally decomposed, product quality is protected.And reduction production cost has been reached, has been improved whole
The security of individual production process.
Embodiment
The present invention is described in further detail with reference to embodiment, to more fully understand present disclosure.
Embodiment 1：
Step one：By 2,4,6- trinitro-chlorobenzenes and 2,6- diamino-pyridines, reacted reaction solution stirring is quiet in a solvent
Put, the solvent is chloroform and carbon tetrachloride mixed solvent, the two volume ratio is 1: 1, is layered to aqueous phase organic phase bright
It is aobvious,
Step 2：Organic phase after layering is separated from the water, organic phase is collected,
Step 3：In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, add
220 mL contain the industrial mother liquor of chloroform-carbon tetrachloride, add 110mL chloroform-carbon tetrachloride (1:1),
36.0g (0.145mol) 2,4,6- trinitro-chlorobenzene, 13.2g (0.157mol) NaHCO are added under agitation3, so
After 8.0g (0.073mol) 2,6- diamino-pyridines are added portionwise at room temperature.Temperature is raised to 35 DEG C, insulation after adding
30min. is warming up to reflux temperature again, and insulation 3h. coolings are filtered, filtration cakes torrefaction, at this moment resulting PAP, and yield 97.1% is pure
It is 317.8 DEG C to spend 98.1%, DSC.
Step 4：Filtrate input is collected to recycle.
Embodiment 2：
Step one：By 2,4,6- trinitro-chlorobenzenes and 2,6- diamino-pyridines, reacted reaction solution stirring is quiet in a solvent
Put, the solvent is chloroform and carbon tetrachloride mixed solvent, the two volume ratio is 1：1, it is layered to aqueous phase organic phase bright
It is aobvious,
Step 2：Organic phase after layering is separated from the water, organic phase is collected,
Step 3：Step 3：In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser
In, the industrial mother liquor that 220mL contains chloroform-carbon tetrachloride is added, 110mL chloroform-carbon tetrachloride is added
(1:1),
In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, add 220mL and contain
The industrial mother liquor of chloroform-carbon tetrachloride, adds 110mL chloroform-carbon tetrachloride (1:1), add under agitation
The trinitro-chlorobenzenes of 36.0g (0.145mol) 2,4,6-, 13.2g (0.157mol) NaHCO3, then it is added portionwise at room temperature
8.0g (0.073mol) 2,6- diamino-pyridines.Temperature is raised to 35 DEG C after adding, insulation 30min. is warming up to reflux temperature again,
3h. cooling filterings are incubated, filtration cakes torrefaction obtains 33.2gPAP, yield 97.1%, and purity 98.1%, DSC is 317.8 DEG C,
Step 4：Filtrate input is collected to recycle.
Embodiment 3：
A kind of industry of double (bitter amino) -3,5- di nitryl pyridine heat-resistant explosives of production 2,6- as claimed in claim 1
Spent solution regeneration handling process, it is characterised in that comprise the following steps：
Step one：By 2,4,6- trinitro-chlorobenzenes and 2,6- diamino-pyridines, reacted reaction solution stirring is quiet in a solvent
Put, the solvent is chloroform and carbon tetrachloride mixed solvent, the two volume ratio is 1：1, it is layered to aqueous phase organic phase bright
It is aobvious,
Step 2：Organic phase after layering is separated from the water, organic phase is collected,
Step 3：In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, add
220 mL contain the industrial mother liquor of chloroform-carbon tetrachloride, add 110mL chloroform-carbon tetrachloride (1:1),
In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, add 220mL and contain
The industrial mother liquor of chloroform-carbon tetrachloride, adds 110mL chloroform-carbon tetrachloride (1:1), add under agitation
The trinitro-chlorobenzenes of 36.0g (0.145mol) 2,4,6-, 16.7g (0.157mol) Na2CO3, 8.0g is then added portionwise at room temperature
(0.073mol) 2,6- diamino-pyridines.Temperature is raised to 35 DEG C after adding, insulation 30min. is warming up to reflux temperature again, protects
Warm 3h. cooling filtering, filtration cakes torrefaction obtains 32.8gPAP, yield 96.2%, and purity 98.3%, DSC is 317.4 DEG C,
Step 4：Filtrate input is collected to recycle.
Embodiment 4：
Step one：By 2,4,6- trinitro-chlorobenzenes and 2,6- diamino-pyridines, reacted reaction solution stirring is quiet in a solvent
Put, the solvent is chloroform and carbon tetrachloride mixed solvent, the two volume ratio is 1：1, it is layered to aqueous phase organic phase bright
It is aobvious,
Step 2：Organic phase after layering is separated from the water, organic phase is collected,
Step 3：Step 3：In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser
In, the industrial mother liquor that 220mL contains chloroform-carbon tetrachloride is added, 110mL chloroform-carbon tetrachloride is added
(1:1),
In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, add 220mL and contain
The industrial mother liquor of chloroform-carbon tetrachloride, adds 110mL chloroform-carbon tetrachloride (1:1), add under agitation
The trinitro-chlorobenzenes of 36.0g (0.145mol) 2,4,6-, 21.7g (0.157mol) K2CO3, 8.0g is then added portionwise at room temperature
(0.073mol) 2,6- diamino-pyridines.Temperature is raised to 35 DEG C after adding, insulation 30min. is warming up to reflux temperature again, protects
Warm 3h. cooling filtering, filtration cakes torrefaction obtains 32.6gPAP, yield 95.6%, and purity 98.1%, DSC is 317.8 DEG C,
Step 4：Filtrate input is collected to recycle.
Embodiment 5：
Step one：By 2,4,6- trinitro-chlorobenzenes and 2,6- diamino-pyridines, reacted reaction solution stirring is quiet in a solvent
Put, the solvent is chloroform and carbon tetrachloride mixed solvent, the two volume ratio is 1：1, it is layered to aqueous phase organic phase bright
It is aobvious,
Step 2：Organic phase after layering is separated from the water, organic phase is collected,
Step 3：Step 3：In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser
In, the industrial mother liquor that 220mL contains chloroform-carbon tetrachloride is added, 110mL chloroform-carbon tetrachloride is added
(1:1),
In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, add 220mL and contain
The industrial mother liquor of chloroform-carbon tetrachloride, adds 110mL chloroform-carbon tetrachloride (1:1), add under agitation
The trinitro-chlorobenzenes of 36.0g (0.145mol) 2,4,6-, 15.7g (0.157mol) KHCO3, 8.0g is then added portionwise at room temperature
(0.073mol) 2,6- diamino-pyridines.Temperature is raised to 35 DEG C after adding, insulation 30min. is warming up to reflux temperature again, protects
Warm 3h. cooling filtering, filtration cakes torrefaction obtains 32.8gPAP, yield 96.2%, and purity 98.3%, DSC is 317.6 DEG C,
Step 4：Filtrate input is collected to recycle.
Claims (6)
1. the industrial wastes regeneration and treatment technique of double (bitter amino) -3,5- di nitryl pyridine heat-resistant explosives of 2,6- of one kind production, its
It is characterised by, comprises the following steps：
Step one：2,4,6- trinitro-chlorobenzenes and 2,6- diamino-pyridines are reacted into generation N, N '-bis- (- 2,4,6- in a solvent
Trinitrophenyl) 2,6- aminopyridine reaction solutions stand obvious to the layering of aqueous phase organic phase, and the solvent is chloroform and four
Chlorination carbon mixed solvent, the two volume ratio is 1：1,
Step 2：Aqueous phase is layered with organic phase, and aqueous phase is located at upper strata, and organic phase is located at lower floor, and organic phase is chloroform and four
Chlorination carbon mixed liquor, determines that, apart from d under the interface of aqueous phase and organic phase, the relation between d and reaction volume V, collection has
Under the interface that machine is mutually extremely determined at d, it is apart from d=VReaction solution× 3% × 1.5/S, S are aqueous phase and organic phase-contact surface face
Product, by it as mother liquor, mother liquor volume is VMother liquor；
Step 3：Chloroform and carbon tetrachloride mixed liquor, chloroform and four chlorinations are added in the mother liquor described in step 2
Carbon volume ratio is 1：1, chloroform and the carbon tetrachloride volume V of addition1For VMother liquor1/2nd；
2,4,6- trinitro-chlorobenzenes are added into above-mentioned mother liquor, it is to the mole dense of 2,4,6- trinitro-chlorobenzenes to be computed additional amount
Spend untill for 0.5mol/L.
Accelerator is added to above-mentioned mother liquor again, the accelerator is Na2CO3、NaHCO3、K2CO3、KHCO3Middle one kind, the rush of addition
The mol ratio for entering agent and above-mentioned addition 2,4,6- trinitro-chlorobenzenes is 1:1~1.1；
Again to above-mentioned mother liquor add DAP, the DAP of addition with the above-mentioned nitre of addition 2,4,6- tri-
The mol ratio of base chlorobenzene is 1:2.
Step 4：The mother liquor that step 3 is obtained, which is put into, to be recycled.
2. a kind of Industry Waste of double (bitter amino) -3,5- di nitryl pyridine heat-resistant explosives of production 2,6- as claimed in claim 1
Liquid regeneration and treatment technique, it is characterised in that comprise the following steps：
Step one：By 2,4,6- trinitro-chlorobenzenes and DAP, reacted reaction solution stirring is stood in a solvent,
The solvent is chloroform and carbon tetrachloride mixed solvent, and the two volume ratio is 1：1, it is obvious to the layering of aqueous phase organic phase,
Step 2：Organic phase after layering is separated from the water, organic phase is collected,
Step 3：In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, 220mL is added
Industrial mother liquor containing chloroform-carbon tetrachloride, adds 110mL chloroform-carbon tetrachloride (1:1),
36.0g (0.145mol) 2,4,6- trinitro-chlorobenzene, 13.2g (0.157mol) NaHCO are added under agitation3, then in room
8.0g (0.073mol) 2,6- diamino-pyridines are added portionwise under temperature.Temperature is raised to 35 DEG C after adding, insulation 30min. rises again
Temperature to reflux temperature, insulation 3h. coolings is filtered, filtration cakes torrefaction, at this moment resulting PAP, yield 97.1%, purity 98.1%, DSC
For 317.8 DEG C,
Step 4：Filtrate input is collected to recycle.
3. a kind of Industry Waste of double (bitter amino) -3,5- di nitryl pyridine heat-resistant explosives of production 2,6- as claimed in claim 1
Liquid regeneration and treatment technique, it is characterised in that comprise the following steps：
Step one：By 2,4,6- trinitro-chlorobenzenes and DAP, reacted reaction solution stirring is stood in a solvent,
The solvent is chloroform and carbon tetrachloride mixed solvent, and the two volume ratio is 1：1, it is obvious to the layering of aqueous phase organic phase,
Step 2：Organic phase after layering is separated from the water, organic phase is collected,
Step 3：Step 3：In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, plus
Enter the industrial mother liquor that 220mL contains chloroform-carbon tetrachloride, add 110mL chloroform-carbon tetrachloride (1:1), exist
In 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, add 220mL contain chloroform-
The industrial mother liquor of carbon tetrachloride, adds 110mL chloroform-carbon tetrachloride (1:1) 36.0g, is added under agitation
(0.145mol) 2,4,6- trinitro-chlorobenzene, 13.2g (0.157mol) NaHCO3, 8.0g is then added portionwise at room temperature
(0.073mol) 2,6- diamino-pyridines.Temperature is raised to 35 DEG C after adding, insulation 30min. is warming up to reflux temperature again, is incubated
3h. cooling filterings, filtration cakes torrefaction obtains 33.2gPAP, yield 97.1%, and purity 98.1%, DSC is 317.8 DEG C,
Step 4：Filtrate input is collected to recycle.
4. a kind of Industry Waste of double (bitter amino) -3,5- di nitryl pyridine heat-resistant explosives of production 2,6- as claimed in claim 1
Liquid regeneration and treatment technique, it is characterised in that comprise the following steps：
Step one：By 2,4,6- trinitro-chlorobenzenes and DAP, reacted reaction solution stirring is stood in a solvent,
The solvent is chloroform and carbon tetrachloride mixed solvent, and the two volume ratio is 1：1, it is obvious to the layering of aqueous phase organic phase,
Step 2：Organic phase after layering is separated from the water, organic phase is collected,
Step 3：In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, 220mL is added
Industrial mother liquor containing chloroform-carbon tetrachloride, adds 110mL chloroform-carbon tetrachloride (1:1),
In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, add 220mL and contain trichlorine
The industrial mother liquor of methane-carbon tetrachloride, adds 110mL chloroform-carbon tetrachloride (1:1) 36.0g, is added under agitation
(0.145mol) 2,4,6- trinitro-chlorobenzene, 16.7g (0.157mol) Na2CO3, 8.0g is then added portionwise at room temperature
(0.073mol) 2,6- diamino-pyridines.Temperature is raised to 35 DEG C after adding, insulation 30min. is warming up to reflux temperature again, is incubated
3h. cooling filterings, filtration cakes torrefaction obtains 32.8gPAP, yield 96.2%, and purity 98.3%, DSC is 317.4 DEG C,
Step 4：Filtrate input is collected to recycle.
5. a kind of Industry Waste of double (bitter amino) -3,5- di nitryl pyridine heat-resistant explosives of production 2,6- as claimed in claim 1
Liquid regeneration and treatment technique, it is characterised in that comprise the following steps：
Step one：By 2,4,6- trinitro-chlorobenzenes and DAP, reacted reaction solution stirring is stood in a solvent,
The solvent is chloroform and carbon tetrachloride mixed solvent, and the two volume ratio is 1：1, it is obvious to the layering of aqueous phase organic phase,
Step 2：Organic phase after layering is separated from the water, organic phase is collected,
Step 3：Step 3：In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, plus
Enter the industrial mother liquor that 220mL contains chloroform-carbon tetrachloride, add 110mL chloroform-carbon tetrachloride (1:1),
In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, add 220mL and contain trichlorine
The industrial mother liquor of methane-carbon tetrachloride, adds 110mL chloroform-carbon tetrachloride (1:1) 36.0g, is added under agitation
(0.145mol) 2,4,6- trinitro-chlorobenzene, 21.7g (0.157mol) K2CO3, 8.0g is then added portionwise at room temperature
(0.073mol) 2,6- diamino-pyridines.Temperature is raised to 35 DEG C after adding, insulation 30min. is warming up to reflux temperature again, is incubated
3h. cooling filterings, filtration cakes torrefaction obtains 32.6gPAP, yield 95.6%, and purity 98.1%, DSC is 317.8 DEG C,
Step 4：Filtrate input is collected to recycle.
6. a kind of Industry Waste of double (bitter amino) -3,5- di nitryl pyridine heat-resistant explosives of production 2,6- as claimed in claim 1
Liquid regeneration and treatment technique, it is characterised in that comprise the following steps：
Step one：Will reacted reaction solution stirring be quiet in a solvent by 2,4,6- trinitro-chlorobenzenes and 2,6- diamino-pyridines
Put, the solvent is chloroform and carbon tetrachloride mixed solvent, the two volume ratio is 1：1, it is obvious to the layering of aqueous phase organic phase,
Step 2：Organic phase after layering is separated from the water, organic phase is collected,
Step 3：Step 3：In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, plus
Enter the industrial mother liquor that 220mL contains chloroform-carbon tetrachloride, add 110mL chloroform-carbon tetrachloride (1:1),
In the 500mL round-bottomed flasks equipped with water-bath, thermometer, mechanical agitation and reflux condenser, add 220mL and contain trichlorine
The industrial mother liquor of methane-carbon tetrachloride, adds 110mL chloroform-carbon tetrachloride (1:1) 36.0g, is added under agitation
(0.145mol) 2,4,6- trinitro-chlorobenzene, 15.7g (0.157mol) KHCO3, 8.0g is then added portionwise at room temperature
(0.073mol) 2,6- diamino-pyridines.Temperature is raised to 35 DEG C after adding, insulation 30min. is warming up to reflux temperature again, is incubated
3h. cooling filterings, filtration cakes torrefaction obtains 32.8gPAP, yield 96.2%, and purity 98.3%, DSC is 317.6 DEG C,
Step 4：Filtrate input is collected to recycle.
Priority Applications (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821983A (en) * | 2018-07-21 | 2018-11-16 | 信阳师范学院 | It is a kind of using phenyl ring as heat resistive compounds of parent and its preparation method and application |
| CN111909056A (en) * | 2020-08-06 | 2020-11-10 | 西安近代化学研究所 | Dimethyl sulfoxide industrial waste liquid regeneration treatment process for producing DIANP explosive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3678061A (en) * | 1971-03-26 | 1972-07-18 | Atomic Energy Commission | 2,6-bis(picrylamino)-3,5-dinitropyridine and a method for its preparation |
| EP0104717A1 (en) * | 1982-09-23 | 1984-04-04 | Chemtronics, Inc. | Method of preparing 2,6-bis(picrylamino)-3,5-dinitropyridine |
| PL186580B1 (en) * | 1997-08-06 | 2004-01-30 | Politechnika Warszawska | Method of obtaining 2,6-bis/picrylamino/3,4-dinitrilpyridine |
| PL186582B1 (en) * | 1997-08-06 | 2004-01-30 | Politechnika Warszawska | Method of obtaining 2,6-bis/picrylamino/3,4-dinitrilpyridine |
-
2017
- 2017-05-19 CN CN201710356592.4A patent/CN107118152A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3678061A (en) * | 1971-03-26 | 1972-07-18 | Atomic Energy Commission | 2,6-bis(picrylamino)-3,5-dinitropyridine and a method for its preparation |
| EP0104717A1 (en) * | 1982-09-23 | 1984-04-04 | Chemtronics, Inc. | Method of preparing 2,6-bis(picrylamino)-3,5-dinitropyridine |
| PL186580B1 (en) * | 1997-08-06 | 2004-01-30 | Politechnika Warszawska | Method of obtaining 2,6-bis/picrylamino/3,4-dinitrilpyridine |
| PL186582B1 (en) * | 1997-08-06 | 2004-01-30 | Politechnika Warszawska | Method of obtaining 2,6-bis/picrylamino/3,4-dinitrilpyridine |
Non-Patent Citations (5)
| Title |
|---|
| THOMAS M. KLAPOTKE，等: "Synthesis and Investigation of 2,6-Bis(picrylamino)-3,5-dinitropyridine(PYX) and Its Salts", 《CHEM. EUR. J.》 * |
| 王少林: "2,6-二苦氨基-3,5-二硝基吡啶的合成研究进展", 《化工中间体》 * |
| 程能林，等: "《溶剂手册》", 31 May 1986, 化学工业出版社 * |
| 邓明哲，等: "耐热炸药PYX制备工艺改进", 《应用化工》 * |
| 钟松，等: "《基础化学实验》", 31 October 2006, 中国环境科学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821983A (en) * | 2018-07-21 | 2018-11-16 | 信阳师范学院 | It is a kind of using phenyl ring as heat resistive compounds of parent and its preparation method and application |
| CN108821983B (en) * | 2018-07-21 | 2020-10-23 | 信阳师范学院 | Heat-resistant compound taking benzene ring as matrix and preparation method and application thereof |
| CN111909056A (en) * | 2020-08-06 | 2020-11-10 | 西安近代化学研究所 | Dimethyl sulfoxide industrial waste liquid regeneration treatment process for producing DIANP explosive |
| CN111909056B (en) * | 2020-08-06 | 2022-08-19 | 西安近代化学研究所 | Dimethyl sulfoxide industrial waste liquid regeneration treatment process for producing DIANP explosive |
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