CN102659088B - Water-phase synthesis method of sodium azide - Google Patents
Water-phase synthesis method of sodium azide Download PDFInfo
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- CN102659088B CN102659088B CN2012101408998A CN201210140899A CN102659088B CN 102659088 B CN102659088 B CN 102659088B CN 2012101408998 A CN2012101408998 A CN 2012101408998A CN 201210140899 A CN201210140899 A CN 201210140899A CN 102659088 B CN102659088 B CN 102659088B
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- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 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 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 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 20
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 18
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 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
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 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
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 239000003125 aqueous solvent Substances 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
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 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
- 238000000034 method Methods 0.000 abstract description 16
- 239000000047 product Substances 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
- 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 group 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
- 239000000203 mixture Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 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
- 238000002156 mixing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003912 environmental pollution 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
- 238000011084 recovery 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
- 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
- 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
- 238000010189 synthetic method 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
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 thereaction 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, therebysaving 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 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-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 mostly to be the gas-liquid two-phase method in the ethanolic soln of nitrous acid ester gas feeding hydrazine hydrate and sodium hydroxide, the temperature of reaction of requirement is lower, and etoh solvent loss in removal process is bigger; 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 at the deficiency that exists in the existing sodiumazide synthetic 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 yield and the purity of environmental pollution and raising product in the entire reaction course, concrete technical scheme is as follows as far as possible:
A kind of water phase synthesis method of sodiumazide, comprise: liquid ethyl nitrite is added in the reaction system that is constituted by hydrazine hydrate, sodium hydroxide, phase-transfer catalyst and water, confined reaction, reclaim unreacted ethyl nitrite, byproduct second alcohol and water after reaction is finished, filtering reacting liquid gets sodiumazide then.
In the aforesaid method, liquid ethyl nitrite is to be made through further condensation by the common method for preparing the gas ethyl nitrite, being about to inorganic acid solution splashes in the mixed system that is made of ethanol and sodium nitrite solution, the gas ethyl nitrite that generates obtains liquid ethyl nitrite through further condensation, used inorganic acid solution generally is 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 to be stirred in the mixed system that splashes into Sodium Nitrite and ethanol composition down, the control temperature of reaction is at 20-40 ℃, 1.5-2 hour drip off sulfuric acid, after acid adds, 30-40 ℃ of insulation reaction 0.5-1h begins condensation 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, because these compositions are required material composition among the present invention simultaneously, therefore their recovery set can be used.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 for the preparation sodiumazide, and the ethanol cover of gained is used for the liquid ethyl nitrite of preparation, and the water jacket of gained is used as diluting concentrated sulfuric acid water or sodium hydroxide solution water or sodiumazide preparation solvent.Reclaim filtrate behind ethyl nitrite, the second alcohol and water filter sodiumazide, the filtrate of filtering reacting liquid gained is mother liquor, but mother liquor direct reuse to the solvent water circulation in the sodiumazide synthesis procedure instead of part reaction system is applied mechanically.
The reaction equation for preparing liquid ethyl nitrite and sodiumazide is as follows:
The present invention carries out in the water solvent system, replaces present ethanol system, has also alleviated the pressure of post-processed ethanol.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, 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 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 adding water again.In addition, also contain a large amount of water in the filtrate after filtering sodiumazide, the content of solute is very low in the filtrate (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, 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 when complete, system pressure is stablized constant gradually, under temperature of reaction of the present invention, the pressure of enclosed system is in the 0.1-1.0MPa(gauge pressure) about, under this pressure, react and can safe and effectively carry out.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 cyclodextrin.The add-on of phase-transfer catalyst adds the 0.02%-0.03% of weight for the raw material hydrazine hydrate.
Further, the mol ratio of hydrazine hydrate, 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 finishes by 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, liquid caustic soda, phase-transfer catalyst and water reaction generate sodiumazide.Compare with existing technology, present method is 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 and, product yield height, product purity product are on very good terms, and are suitable for suitability for industrialized production.In addition, capable of circulation applying mechanically such as the byproduct ethanol that reaction generates, unreacted ethyl nitrite, mother liquor have namely been saved cost, have been alleviated environmental stress, have further improved the yield of product again, are suitable for the industrialization cleaner production.
Embodiment
Further set forth below by the present invention of embodiment, should be understood that, following explanation only is in order to explain the present invention, its content not to be limited.
Embodiment 1
With the 66.0g(0.66 mole) 98% vitriol oil and pure water be configured to 50% sulphuric acid soln, the gained sulphuric acid soln stirs and to splash into the 90.6g(1.3 mole down) Sodium Nitrite and 64.4g(1.33 mole) in the mixed system of ethanol composition, the control temperature of reaction is at 25-40 ℃, and the beginning condensation collects the liquid ethyl nitrite, drips 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 the 62.5g(1.0 mole) hydrazine hydrate and 137.5g(1.1 mole) 32% liquid caustic soda is cooled to 10-15 ℃ after mixing, add 1wt% tetrabutyl phosphonium bromide ammonium solution 1.5g, in all adding systems of above-mentioned gained liquid ethyl nitrite, confined reaction, keep 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, sodium hydroxide and ethyl nitrite, react according to the step of embodiment 1, and reaction result sees Table 1:
From experimental result, hydrazine hydrate: 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 sees Table 2:
From experimental result, several catalyst effects do not have too big difference.
Embodiment 4
With the 87.5g(0.67 mole) phosphoric acid and pure water be configured to 50% phosphoric acid solution, the gained phosphoric acid solution stirs and to splash into the 90.6g(1.3 mole down) Sodium Nitrite and 66.3g(1.37 mole) in the mixed system of ethanol composition, the control temperature of reaction is at 20-40 ℃, the liquid ethyl nitrite is collected in condensation, drips 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 the 62.5g(1.0 mole) hydrazine hydrate and 143.8g(1.15 mole) 32% liquid caustic soda is cooled to 10-15 ℃ after mixing, add 1% tetrabutyl phosphonium bromide ammonium solution 1.5g, in all adding systems of gained liquid ethyl nitrite, confined reaction, keep 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, 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, the control temperature of reaction is at 25-40 ℃, and ethyl nitrite is collected in condensation, drips 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, 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, the control temperature of reaction is at 25-40 ℃, and ethyl nitrite is collected in condensation, drips 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, 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 sees Table 3.
As can be seen from the above table, the mother liquor recovery set yield that has obviously improved sodiumazide.
Claims (7)
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 is constituted by hydrazine hydrate, sodium hydroxide, phase-transfer catalyst and aqueous solvent, confined reaction, after reaction is finished, reclaim unreacted ethyl nitrite, byproduct second alcohol and water, filtering reacting liquid gets sodiumazide then;
Liquid ethyl nitrite is disposable to join confined reaction in the reaction system;
The mol ratio of hydrazine hydrate, 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 quality; System temperature is always 0-30 ℃ in the reaction process;
Phase-transfer catalyst is quaternary ammonium salt-type phase transfer catalyst or cyclic crown ether class phase-transfer catalyst.
2. water phase synthesis method according to claim 1, it is characterized in that: the preparation method of liquid ethyl nitrite is: inorganic acid solution is splashed in the mixed system that is made 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 in the hydrazine hydrate and the water in the aqueous sodium hydroxide solution.
4. according to the described water phase synthesis method of claim 1, it is characterized in that: the mol ratio of hydrazine hydrate, sodium hydroxide, liquid ethyl nitrite is 1:1.1-1.2:1.2-1.3.
5. water phase synthesis method according to claim 1, it is characterized in that: system temperature is always 10-20 ℃ in the reaction process.
6. water phase synthesis method according to claim 1, 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 cyclodextrin.
7. 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 filtrate 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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| 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 |
| CN104760939B (en) * | 2015-03-16 | 2017-10-10 | 浙江海蓝化工集团有限公司 | A kind of synthesis technique of the sodium azide aqueous phase of n-butanol recycled |
| CN110467161B (en) * | 2019-09-25 | 2021-07-06 | 山东省化工研究院 | Synthesis process of sodium azide |
| 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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| 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 |
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2012
- 2012-05-09 CN CN2012101408998A patent/CN102659088B/en active Active
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