CN102659088A - Water-phase synthesis method of sodium azide - Google Patents
Water-phase synthesis method of sodium azide Download PDFInfo
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- CN102659088A CN102659088A CN2012101408998A CN201210140899A CN102659088A CN 102659088 A CN102659088 A CN 102659088A CN 2012101408998 A CN2012101408998 A CN 2012101408998A CN 201210140899 A CN201210140899 A CN 201210140899A CN 102659088 A CN102659088 A CN 102659088A
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- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000001308 synthesis method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 68
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 40
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 21
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 5
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 18
- -1 cyclic crown ether Chemical class 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- 235000010288 sodium nitrite Nutrition 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical class 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical class [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical class [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical class [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 3
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000010413 mother solution Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- 235000011121 sodium hydroxide Nutrition 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 239000001117 sulphuric acid Substances 0.000 description 8
- 235000011149 sulphuric acid Nutrition 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ODJZWVFLHZHURI-UHFFFAOYSA-M [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] Chemical compound [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] ODJZWVFLHZHURI-UHFFFAOYSA-M 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 2
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a water-phase synthesis method of sodium azide, which comprises the following steps: adding liquid ethyl nitrite into a reaction system composed of hydrazine hydrate, sodium hydroxide, phase-transfer catalyst and solvent water to react under closed conditions; and after the reaction finishes, recycling unreacted ethyl nitrite, byproduct ethanol and water, and filtering the reaction liquid to obtain the sodium azide. The method uses water as the reaction solvent, carries out the reaction under pressurized conditions, and has the advantages of low energy consumption, mild reactions, high product yield and high product purity; and besides, the reaction byproduct ethanol, the unreacted ethyl nitrite, the centrifugal mother solution and the like can be recycled, thereby saving the cost, relieving the environmental pressure and further enhancing the product yield. Thus, the invention is suitable for industrialized clean production.
Description
Technical field
The present invention relates to a kind of water phase synthesis method of sodiumazide, belong to technical field of organic synthesis.
Background technology
Sodiumazide as a kind of Chemicals commonly used, is widely used in the automobile airbag gas propellant, medicine, explosive, industries such as agricultural chemicals and chemosynthesis.
The method of suitability for industrialized production sodiumazide mainly contains two kinds, and a kind of is the sodium Metal 99.5 method, and this method is a raw material with sodium Metal 99.5 and liquefied ammonia, and another kind is hydrazine-nitrous acid ester method.The sodiumazide production technique all adopts Hydrazine Hydrate 80-nitrous acid ester-sodium hydroxide process both at home and abroad at present, and the nitrous acid ester of use comprises methyl nitrite, ethyl nitrite, butyl nitrite, Isopentyl nitrite etc.Adopt the preparation technology of methyl nitrite and ethyl nitrite to be mostly that the temperature of reaction of requirement is lower, and etoh solvent loss in removal process is bigger with the gas-liquid two-phase method in the ethanolic soln of nitrous acid ester gas feeding Hydrazine Hydrate 80 and sodium hydroxide; The temperature of the arts demand of employing butyl nitrite and Isopentyl nitrite is higher, and reaction conversion ratio is lower.These technologies all exist reaction time long, and raw material nitrous acid ester utilization ratio is low, and energy consumption is higher, and quantity of three wastes is bigger, the problem that production cost is high.
Summary of the invention
The contriver through a large amount of creative works and experiment, provides a kind of water phase synthesis method of sodiumazide to the deficiency that exists in the existing sodiumazide compound method.Compare with existing technology, present method is reaction solvent with water, environmental pollution is little, cost is low, reaction temperature and, be suitable for suitability for industrialized production.
Present method is raw material, is the synthetic sodiumazide of reaction solvent with water that with liquid ethyl nitrite alleviate environmental pollution and the yield and the purity that improve product in the entire reaction course, concrete technical scheme is following as far as possible:
A kind of water phase synthesis method of sodiumazide; Comprise: liquid ethyl nitrite is added in the reaction system that constitutes by Hydrazine Hydrate 80, sodium hydroxide, phase-transfer catalyst and water; Confined reaction; Reclaim unreacted ethyl nitrite, sub product second alcohol and water after reaction is accomplished, filtering reacting liquid gets sodiumazide then.
In the aforesaid method; Liquid ethyl nitrite is to be made through further condensation by the domestic method for preparing the gas ethyl nitrite; Be about to inorganic acid solution and splash in the mixed system that is made up of ethanol and sodium nitrite solution, the gas ethyl nitrite of generation obtains liquid ethyl nitrite through further condensation, and used inorganic acid solution generally is a sulphuric acid soln; Concentration is about 40-60wt%, and the mol ratio of ethanol, sulfuric acid and Sodium Nitrite is: 1:1.05:1.05.More specifically; Adopt following method to prepare liquid ethyl nitrite: sulphuric acid soln is stirred in the mixed system that splashes into Sodium Nitrite and ethanol composition down, control reaction temperature is at 20-40 ℃, drips off sulfuric acid in 1.5-2 hour; After acid adds; 30-40 ℃ of insulation reaction 0.5-1h begins condensation and collection liquid ethyl nitrite from dripping sulfuric acid, to no longer receiving till the liquid ethyl nitrite.
In the reaction process, there is ethyl nitrite to fail to react completely, also has ethanol to generate,, therefore can their recovery set be used because these compositions are required material composition among the present invention simultaneously.Generally, reaction solution is heated to about 40 ℃ reclaims ethyl nitrite earlier, and then normal pressure steams ethanol, decompression steams water.The ethyl nitrite cover that reclaims gained is used to prepare sodiumazide, and the ethanol cover of gained is used to prepare liquid ethyl nitrite, and the water jacket of gained is used as diluting concentrated sulfuric acid water or sodium hydroxide solution water or sodiumazide preparation and uses solvent.Filtrating mistake behind recovery ethyl nitrite, the second alcohol and water filters sodiumazide, and the filtrating of filtering reacting liquid gained is mother liquor, but the solvent water circulation in mother liquor direct reuse to the sodiumazide synthesis procedure instead of part reaction system is applied mechanically.
The reaction equation for preparing liquid ethyl nitrite and sodiumazide is following:
The present invention carries out in the water solvent system, replaces present ethanol system, has also alleviated post-processed alcoholic acid pressure.Water only plays the effect of solvent in system, its consumption reaches in the system all raw materials and all dissolves to mix and get final product.In reaction raw materials, contain the water of part in the Hydrazine Hydrate 80, sodium hydroxide generally adds with the form of solution in addition, so that contact fully with other reactants, the concentration of solution does not influence the carrying out of reaction.Therefore; The strength of solution of suitable adjustment sodium hydroxide can satisfy the consumption requirement of aqueous solvent in the reaction system; General; The Hydrazine Hydrate 80 concentration of selling on the market is about 80wt%, and concentration sodium hydroxide is generally about 32-40wt%, in the case generally need not be in reaction system extra again adds entry.In addition, also contain a large amount of water in the filtrating after filtering sodiumazide, the content of solute is very low in the filtrating (being mother liquor); The water that can be used as reaction system is used, and for example can prepare sodium hydroxide solution with it, perhaps also can be used as the additional water of reaction system; Through experimental verification; Mother liquor of the present invention is capable of circulation to be applied mechanically more than 50 times, has avoided the waste of water, and entire reaction course meets the requirement that cleans production.
Preferably, liquid ethyl nitrite is disposable joins in the reaction system that Hydrazine Hydrate 80, sodium hydroxide, phase-transfer catalyst and water constitutes.
The present invention reacts under 0-30 ℃ air tight condition, and preferred temperature of reaction generally can react completely about 10h at 10-20 ℃.Carrying out along with reaction; Nitrogen gas generation is arranged in the system, thereby the pressure of system is constantly raise, in reaction near fully the time; System pressure is stablized constant gradually; Under temperature of reaction of the present invention, the pressure of enclosed system is about 0.1-1.0MPa (gauge pressure), and reaction can safe and effectively be carried out under this pressure.If system temperature is higher than temperature of reaction, cause system pressure to be higher than 1.0Mpa, this moment, there was potential safety hazard in reaction, and needing the people is pressure release.
Further; Used phase-transfer catalyst is quaternary ammonium salt-type phase transfer catalyst or cyclic crown ether class phase-transfer catalyst; Quaternary ammonium salt-type phase transfer catalyst is preferably Tetrabutyl amonium bromide, tetrabutylammonium chloride or tri-n-octyl methyl ammonium chloride, and cyclic crown ether class phase-transfer catalyst is preferably 18 hats, 6 ethers, 15 hat 5 ethers or Schardinger dextrins.The add-on of phase-transfer catalyst adds the 0.02%-0.03% of weight for the raw material Hydrazine Hydrate 80.
Further, the mol ratio of Hydrazine Hydrate 80, sodium hydroxide, liquid ethyl nitrite is 1:1-1.3:1.2-1.5, and preferred mol ratio is 1:1.1-1.2:1.2-1.3.
The present invention mainly accomplishes through two-step reaction, and the one, be that raw material reaction generates ethyl nitrite gas with ethanol, Sodium Nitrite, mineral acid, ethyl nitrite gas obtains liquid ethyl nitrite through condensation; The 2nd, liquid ethyl nitrite, Hydrazine Hydrate 80, liquid caustic soda, phase-transfer catalyst and water reaction generate sodiumazide.Compare with existing technology, present method is a reaction solvent with water, has alleviated consumption of ethanol; Waste gas is few, environmental pollution is little, cost is low, is reflected under the situation of pressurization to carry out, and energy consumption is low; Reaction temperature is high with, product yield, product purity article are on very good terms, and are suitable for suitability for industrialized production.In addition, capable of circulation applying mechanically such as the sub product ethanol that reaction generates, unreacted ethyl nitrite, mother liquor have promptly been practiced thrift cost, have been alleviated environmental stress, have further improved the yield of product again, are suitable for the industriallization cleaner production.
Embodiment
Through embodiment the present invention is further set forth below, should be understood that, following explanation only is in order to explain the present invention, its content not to be limited.
Embodiment 1
66.0g (0.66 mole) 98% vitriol oil and pure water are configured to 50% sulphuric acid soln; The gained sulphuric acid soln stirs in the mixed system that splashes into 90.6g (1.3 moles) Sodium Nitrite and 64.4g (1.33 moles) ethanol composition down; Control reaction temperature is at 25-40 ℃; And beginning condensation and collection liquid ethyl nitrite, dripped off sulfuric acid in about 2 hours.After acid adds, 30-40 ℃ of insulation reaction 0.5h, to no longer receiving till the liquid ethyl nitrite, altogether ethyl nitrite 90.6g.
With 62.5g (1.0 moles) Hydrazine Hydrate 80 be cooled to 10-15 ℃ after 137.5g (1.1 moles) 32% liquid caustic soda mixes; Add 1wt% tetrabutyl phosphonium bromide ammonium solution 1.5g; In all adding systems of above-mentioned gained liquid ethyl nitrite, confined reaction keeps temperature of reaction at 15-20 ℃; Reaction 10h, final system pressure reaches 0.32MPa.Open blow-off valve, slowly lay down pressure, reaction solution is heated to 40 ℃, reclaim ethyl nitrite, normal pressure steams ethanol then, and decompression dehydration is cooled to room temperature to solid occurring, and suction filtration gets sodiumazide.80 ℃ of vacuum-dryings of gained sodiumazide obtain sodiumazide product 54.3g, product yield 83.5%, and it is 99.6% that chemical analysis is measured purity.
Embodiment 2
Other conditions are constant, only change the mol ratio of Hydrazine Hydrate 80, sodium hydroxide and ethyl nitrite, react according to the step of embodiment 1, and reaction result is seen table 1:
From experimental result, Hydrazine Hydrate 80: sodium hydroxide: productive rate was better when the mol ratio of liquid ethyl nitrite was 1:1.1-1.2:1.2-1.3.
Embodiment 3
Other conditions are constant, the type of phase-transfer catalyst only, catalyzer all be configured to 1wt% solution, add-on is 1.5g, reacts according to the step of embodiment 1, reaction result is seen table 2:
From experimental result, several kinds of catalyst effects do not have too big difference.
Embodiment 4
87.5g (0.67 mole) phosphoric acid and pure water are configured to 50% phosphoric acid solution; The gained phosphoric acid solution stirs in the mixed system that splashes into 90.6g (1.3 moles) Sodium Nitrite and 66.3g (1.37 moles) ethanol composition down; Control reaction temperature is at 20-40 ℃; Condensation and collection liquid ethyl nitrite dripped off phosphoric acid in about 2 hours.After acid added, 30-40 ℃ of insulation reaction 0.5h was to no longer receiving till the liquid ethyl nitrite.Altogether ethyl nitrite 92.6g.
With 62.5g (1.0 moles) Hydrazine Hydrate 80 be cooled to 10-15 ℃ after 143.8g (1.15 moles) 32% liquid caustic soda mixes; Add 1% tetrabutyl phosphonium bromide ammonium solution 1.5g; In all adding systems of gained liquid ethyl nitrite, confined reaction keeps temperature of reaction at 15-20 ℃; Reaction 10h, final system pressure reaches 0.28MPa.Slowly lay down pressure, reaction solution is heated to 40 ℃, reclaim ethyl nitrite; Insulation reaction 0.5h, normal pressure steams ethanol then, and decompression dehydration is to solid occurring; Be cooled to room temperature, the centrifugal sodiumazide that gets, 80 ℃ of following vacuum-dryings obtain sodiumazide product 55.3g; Product yield 85.1%, it is 99.5% that chemical analysis is measured purity.
Embodiment 5
The 267.8g vitriol oil and pure water are configured to 50% sulphuric acid soln; The gained sulphuric acid soln stirs in the mixed system that splashes into 362.4g Sodium Nitrite and 264.4g ethanol composition down; Control reaction temperature is at 25-40 ℃, and the condensation and collection ethyl nitrite dripped off sulfuric acid in about 2 hours.After acid adds, 30-40 ℃ of insulation reaction 0.5h, to no longer receiving till the liquid ethyl nitrite, altogether ethyl nitrite 284g.
250g Hydrazine Hydrate 80,550g 32% liquid caustic soda solution are cooled to 10-15 ℃ after mixing, add 1% tetrabutyl phosphonium bromide ammonium solution 5.0g, in all adding systems of gained ethyl nitrite; Confined reaction; Keep temperature of reaction at 15-20 ℃, reaction 10h, final system pressure reaches 0.36MPa.Reaction solution is heated to 40 ℃, reclaims ethyl nitrite, insulation reaction 0.5h, normal pressure steams ethanol then, and decompression dehydration is cooled to room temperature to solid occurring, the centrifugal sodiumazide that gets.80 ℃ of following vacuum-dryings obtain sodiumazide product 221g, product yield 85%, and it is 99.7% that chemical analysis is measured purity.
Embodiment 6
The 206g vitriol oil and pure water are configured to 50% sulphuric acid soln; The gained sulphuric acid soln stirs in the mixed system that splashes into 278.8g Sodium Nitrite and 203.4g ethanol composition down; Control reaction temperature is at 25-40 ℃, and the condensation and collection ethyl nitrite dripped off sulfuric acid in about 2 hours.After acid added, 30-40 ℃ of insulation reaction 0.5h to no longer receiving till the liquid ethyl nitrite, merged with the ethyl nitrite that reclaims among the embodiment 3, altogether ethyl nitrite 284g.
225g Hydrazine Hydrate 80,440g 32% liquid caustic soda solution are cooled to 10-15 ℃ after mixing; Add 1% tetrabutyl phosphonium bromide ammonium solution 5.0g, merge with embodiment 3 gained solid-liquid separation mother liquors, in all adding systems of gained ethyl nitrite; Confined reaction; Keep temperature of reaction at 15-20 ℃, reaction 10h, final system pressure reaches 0.36 MPa.Reaction solution is heated to 40 ℃, reclaims ethyl nitrite, insulation reaction 0.5h, normal pressure steams ethanol then, and decompression dehydration is cooled to room temperature, the centrifugal sodiumazide that gets.80 ℃ of following constant pressure and dries obtain sodiumazide product 207g, and product is applied mechanically yield 88.5%, and it is 99.7% that chemical analysis is measured purity.
Embodiment 7
Other conditions are constant, and the solid-liquid separation mother liquor of each batch is inserted in next batch, react according to the step of embodiment 5, and reaction result is seen table 3.
Can find out that from last table the mother liquor recovery set is with the yield that has obviously improved sodiumazide.
Claims (10)
1. the water phase synthesis method of a sodiumazide; It is characterized in that comprising: liquid ethyl nitrite is added in the reaction system that constitutes by Hydrazine Hydrate 80, sodium hydroxide, phase-transfer catalyst and aqueous solvent; Confined reaction; Reaction is reclaimed unreacted ethyl nitrite, sub product second alcohol and water after accomplishing, and filtering reacting liquid gets sodiumazide then.
2. water phase synthesis method according to claim 1 is characterized in that: the preparation method of liquid ethyl nitrite is: inorganic acid solution is splashed in the mixed system that is made up of ethanol and sodium nitrite solution, obtain liquid ethyl nitrite through condensation.
3. water phase synthesis method according to claim 1 and 2 is characterized in that: sodium hydroxide adds with the form of the aqueous solution, and the water in the reaction system comes from water and the water in the aqueous sodium hydroxide solution in the Hydrazine Hydrate 80.
4. water phase synthesis method according to claim 1 and 2 is characterized in that: liquid ethyl nitrite is disposable to join confined reaction in the reaction system.
5. according to claim 1 or 2 described water phase synthesis methods; It is characterized in that; Reaction conditions is: the mol ratio of Hydrazine Hydrate 80, sodium hydroxide, liquid ethyl nitrite is 1:1-1.3:1.2-1.5, and the add-on of phase-transfer catalyst is the 0.02-0.03% of Hydrazine Hydrate 80 quality; System temperature is always 0-30 ℃ in the reaction process.
6. according to the described water phase synthesis method of claim 5, it is characterized in that: the mol ratio of Hydrazine Hydrate 80, sodium hydroxide, liquid ethyl nitrite is 1:1.1-1.2:1.2-1.3.
7. water phase synthesis method according to claim 5 is characterized in that: system temperature is always 10-20 ℃ in the reaction process.
8. water phase synthesis method according to claim 1 and 2 is characterized in that: phase-transfer catalyst is quaternary ammonium salt-type phase transfer catalyst or cyclic crown ether class phase-transfer catalyst.
9. water phase synthesis method according to claim 8; It is characterized in that: quaternary ammonium salt-type phase transfer catalyst is Tetrabutyl amonium bromide, tetrabutylammonium chloride or tri-n-octyl methyl ammonium chloride, and cyclic crown ether class phase-transfer catalyst is 18 hats, 6 ethers, 15 hat 5 ethers or Schardinger dextrins.
10. claim 1 or 2 described water phase synthesis methods is characterized in that: the ethyl nitrite, ethanol and the water difference recycled that reclaim gained; The filtrating that filters out the sodiumazide gained is designated as mother liquor, and the water cycle in the mother liquor instead of part reaction system is applied mechanically.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502337A (en) * | 2014-12-30 | 2015-04-08 | 山东艾孚特科技有限公司 | Method for quantitatively detecting various components in sodium azide aqueous-phase synthesis mother solution |
| CN104760939A (en) * | 2015-03-16 | 2015-07-08 | 浙江海蓝化工集团有限公司 | Aqueous-phase synthetic method of sodium azide with n-butyl alcohol circularly recycled |
| CN110467161A (en) * | 2019-09-25 | 2019-11-19 | 山东省化工研究院 | A kind of synthesis technology of sodium azide |
| CN111252746A (en) * | 2020-03-11 | 2020-06-09 | 青岛雪洁助剂有限公司 | Continuous sodium azide water-phase safe production device and process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06199507A (en) * | 1992-12-01 | 1994-07-19 | Mitsui Toatsu Chem Inc | Production of sodium azide |
| JPH0912309A (en) * | 1995-06-28 | 1997-01-14 | Toyo Kasei Kogyo Co Ltd | Production of sodium azide |
| CN101012055A (en) * | 2006-12-31 | 2007-08-08 | 安徽省郎溪县联科实业有限公司 | Method of preparing sodium azide |
-
2012
- 2012-05-09 CN CN2012101408998A patent/CN102659088B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06199507A (en) * | 1992-12-01 | 1994-07-19 | Mitsui Toatsu Chem Inc | Production of sodium azide |
| JPH0912309A (en) * | 1995-06-28 | 1997-01-14 | Toyo Kasei Kogyo Co Ltd | Production of sodium azide |
| CN101012055A (en) * | 2006-12-31 | 2007-08-08 | 安徽省郎溪县联科实业有限公司 | Method of preparing sodium azide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502337A (en) * | 2014-12-30 | 2015-04-08 | 山东艾孚特科技有限公司 | Method for quantitatively detecting various components in sodium azide aqueous-phase synthesis mother solution |
| CN104502337B (en) * | 2014-12-30 | 2017-02-22 | 山东艾孚特科技有限公司 | Method for quantitatively detecting various components in sodium azide aqueous-phase synthesis mother solution |
| CN104760939A (en) * | 2015-03-16 | 2015-07-08 | 浙江海蓝化工集团有限公司 | Aqueous-phase synthetic method of sodium azide with n-butyl alcohol circularly recycled |
| CN110467161A (en) * | 2019-09-25 | 2019-11-19 | 山东省化工研究院 | A kind of synthesis technology of sodium azide |
| CN110467161B (en) * | 2019-09-25 | 2021-07-06 | 山东省化工研究院 | Synthesis process of sodium azide |
| CN111252746A (en) * | 2020-03-11 | 2020-06-09 | 青岛雪洁助剂有限公司 | Continuous sodium azide water-phase safe production device and process |
| CN111252746B (en) * | 2020-03-11 | 2023-05-16 | 青岛雪洁助剂有限公司 | Continuous sodium azide water phase safety production device and process |
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|---|---|
| CN102659088B (en) | 2013-09-11 |
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