CN113880112B - 一种制备二硝酰胺铵水溶液的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 23
- MJVUDZGNBKFOBF-UHFFFAOYSA-N n-nitronitramide Chemical compound [O-][N+](=O)N[N+]([O-])=O MJVUDZGNBKFOBF-UHFFFAOYSA-N 0.000 title claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000779 smoke Substances 0.000 claims abstract description 25
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 19
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- YNKVVRHAQCDJQM-UHFFFAOYSA-P diazanium dinitrate Chemical compound [NH4+].[NH4+].[O-][N+]([O-])=O.[O-][N+]([O-])=O YNKVVRHAQCDJQM-UHFFFAOYSA-P 0.000 claims abstract description 10
- 239000005457 ice water Substances 0.000 claims abstract description 10
- 230000001546 nitrifying effect Effects 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 5
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 claims description 5
- CGDXUTMWWHKMOE-UHFFFAOYSA-N difluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)F CGDXUTMWWHKMOE-UHFFFAOYSA-N 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- SAPIQCCFEBULSH-UHFFFAOYSA-M lithium;sulfamate Chemical compound [Li+].NS([O-])(=O)=O SAPIQCCFEBULSH-UHFFFAOYSA-M 0.000 claims description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- BRUFJXUJQKYQHA-UHFFFAOYSA-O ammonium dinitramide Chemical compound [NH4+].[O-][N+](=O)[N-][N+]([O-])=O BRUFJXUJQKYQHA-UHFFFAOYSA-O 0.000 abstract description 44
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000006396 nitration reaction Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000003380 propellant Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000000802 nitrating effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- -1 beta-nitro-beta-iminopropionitrile Chemical compound 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- AGSPXMVUFBBBMO-UHFFFAOYSA-N beta-aminopropionitrile Chemical compound NCCC#N AGSPXMVUFBBBMO-UHFFFAOYSA-N 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种制备二硝酰胺铵水溶液的方法,属于含能材料领域。该方法以氨基磺酸盐为原料,红烟硝酸为硝化试剂,在催化剂作用下,高效制备二硝酰胺铵水溶液的方法。本发明方法包括以下步骤:首先,在反应器中加入红烟硝酸和催化剂,冷却到‑30℃至‑50℃后,缓慢加入氨基磺酸盐,充分搅拌反应;结束后,用冰水淬灭反应,通入氨气中和反应,采用活性炭纯化获得二硝酰胺铵水溶液。本发明原料易得,合成与纯化工艺简单,能够高效制备二硝酰胺铵水溶液,适宜于工业化应用。
Description
技术领域
本发明涉及一种制备二硝酰胺铵水溶液的方法,尤其是一种以氨基磺酸盐为原料,红烟硝酸为硝化试剂,在催化剂作用下,高效制备二硝酰胺铵水溶液的方法,属于含能材料领域。
背景技术
高氯酸铵(AP)是固体推进剂中最广泛使用的氧化剂,占推进剂总质最的60%-90%,在固体火箭发动机工作时,排放的燃气中含有大量的氯化氢气体,对发射场的环境造成严重污染。因此,各国研究机构均致力于发展一种新型洁净氧化剂来减少其燃烧产物对环境的危害(熊文慧,隋九龄,刘科,无氯氧化剂在洁净固体推进剂中的应用,化学推进剂与高分子材料,2019,17,1-9)。
二硝酰胺铵(Ammonnium Dinitramide,简写为ADN)是一种新型高能环保型氧化剂,分子式为NH4N(NO2)2,具有+25.8%的氧平衡,生成热为-149.6kJ/mol,晶体密度为1.82g/cm3,分子中不含碳和氯,有望替代AP应用于航天飞机和空间运输动力***。该物质于1971年被苏联科学家首次制备出来,直到1989年美国科学家公开报道ADN合成路线及性能后,引起世界各国研究人员的广泛关注,成为当今含能材料领域研究热点之一(彭翠枝,郑斌,张培,范夕萍,任晓雪,国外二硝酰胺铵的发展现状,火***学报,2014,37,1-5;王学敏,刘海洲,许华新,陈兴强,王连心,ADN的性质及其在单元推进剂中的应用,化学推进剂与高分子材料,2014,12,9-13;周晓杨,唐根,庞爱民,ADN推进剂国外研究进展,飞航导弹,2017,2,87-92.)。二硝酰胺铵的主要合成路线如下:
方程1:
方程2:
方程3:
X:CONH2,SO3NH4,SO3K
ADN的合成方法主要有两种:无机法和有机法(S.Venkatachalam,G.Santhosh,K.N.Ninan,An overview on the synthetic routes and properties of ammoniumdinitramide(ADN)and other dinitramide salts.Propellants ExplosivesPyrotechnics,2004,3,178-187)。有机方法首先以五氧化二氮和四氟硼硝酰等为硝化剂的强硝化体系合成二硝胺基有机化合物,然后通过氨解反应使C-N键断裂,生成ADN(图1,方程1)。如专利US5198204A和WO9119670A1采用的将氨基甲酸酯硝化的方法,专利WO9119669A1和US5254324采用的N-烷氧羰基-N-硝酰胺硝化路线,俄罗斯采用β-硝基-β-亚氨基丙腈硝化的路线(O.A.Lukyanov,V.P.Gorelik,V.A.Tartakovskii,Dinitramide and its salts1.synthesis of dinitramide salts by decyanoethylation of N,N-dinitro-β-aminopropionitrile,Russian Chemical Bulletin,1994,43,89-92),西安近代化学研究所王伯周团队开发的氨基丙腈和丙烯腈路线(ADN的合成及性能研究(I),含能材料,1999,7,145-148;ADN的合成及性能研究(II),含能材料,2001,9,97-99;氨基甲酸乙酯法合成ADN,火***学报,2005,28,49-51;ADN无机法合成及分离纯化研究,含能材料,2006,14,358-360)。这类硝化合成ADN的反应步骤较多,五氧化二氮和四氟硼硝酰等硝化试剂制备条件复杂且价格昂贵,大都停留在实验室研制阶段,限制了其工程化应用。
无机法合成ADN主要以氨基磺酸盐、氨气等无机物为起始原料(图1,方程2和方程3),在低温下用硝硫混酸硝化,接着氨气中和,分离纯化得到ADN。如公开的专利US5976483和文献(H.Jang,M.J.Sul,J.S.Shim,Y.C.Park,S.J.Cho,Scalable synthesis of highpurities ammonium dinitramide and its decomposition characteristics,Journalof Industrial and Engineering Chemistry,2018,63,237-244),以及黎明化工研究院王学敏团队开发的氨基磺酸铵-混酸硝化路线(混酸法合成ADN的分离纯化工艺研究,化学推进剂与高分子材料,2009,7,47-61;混酸硝化法合成二硝酰胺铵及其机理探讨,化学推进剂与高分子材料,2011,9,74-77)。这类硝化合成ADN的步骤少,硝硫混酸配制简单,使用方便,原料便宜易得。然而,合成工序仍然存在一些缺点:(1)必须使用大量浓硫酸作为脱水剂,使发烟硝酸解离出足够量的硝酰正离子,实现氨基磺酸盐硝化反应,因而伴随生成大量硫酸铵副产物;(2)硫酸铵和浓硫酸的废水排放污染环境,无害化处理难度大;(3)均为无溶剂反应,放热剧烈,绝热温升接近127K,(朱勇,王玉,刘建利,李普瑞,张志刚,ADN合成过程的热效应,含能材料,2012,20,735-738),对***冷却能力要求苛刻,控温不当易发生各种副反应甚至冲料,有安全隐患;(4)ADN分离纯化困难,需要经过多次活性炭柱吸附分离,产品收率偏低。这些问题限制了ADN的工程化应用。因此,开发一种高效制备ADN的方法具有重要的工业价值和学术意义。
发明内容
针对现有无机法合成ADN存在的技术问题,本发明提供一种以氨基磺酸盐为原料,不使用硝硫混酸,以红烟硝酸为硝化试剂,在催化剂和惰性溶剂作用下,高效制备ADN水溶液的方法。本发明在反应过程中添加的催化剂能够明显提高反应收率,可使ADN收率达到82%,远高于现有技术水平(40-60%收率)。本发明反应原料易得,避免使用浓硫酸,合成与纯化工艺简单,收率高,宜于工业化生产。
为了达到上述目的,本发明采用的技术方案如下:
一种制备二硝酰胺铵水溶液的方法,以氨基磺酸盐为原料,红烟硝酸为硝化试剂,在催化剂作用下,能够高效制备二硝酰胺铵水溶液,包括以下步骤:
(1)在反应器中加入红烟硝酸作为硝化试剂,冷却至-30℃至-50℃后,加入催化剂和适量溶剂,充分搅拌30分钟;其中,催化剂与红烟硝酸的摩尔比为1:10-100;红烟硝酸与溶剂的体积比为1:1-5。
(2)分批缓慢加入氨基磺酸盐,进行硝解反应,控制反应温度在-30℃至-40℃之间,加料完毕后,继续搅拌反应0.5-3小时;其中,氨基磺酸盐与红烟硝酸的摩尔比为1:3-15。
(3)将步骤(2)反应后的反应液倒入冰水混合物中,控制反应温度在-5℃至5℃之间,通入氨气进行中和反应;
(4)将中和反应液经过活性炭柱分离,去除硝酸铵杂质,即可得到目标产物二硝酰胺铵的水溶液。
进一步的,所述步骤(1)中红烟硝酸中四氧化二氮的质量分数为15-30%。
进一步的,所述步骤(1)中催化剂为甲基磺酸、三氟甲基磺酸、三氟乙酸、三氯乙酸、二氟甲基磺酸、苯磺酸、对硝基苯磺酸、对甲基苯磺酸中的一种。
进一步的,所述步骤(1)中溶剂为二氯甲烷、二硫化碳、四氯化碳中的一种。
进一步的,所述步骤(2)中氨基磺酸盐为氨基磺酸铵、氨基磺酸锂、氨基磺酸钠、氨基磺酸钾中的一种。
本发明与现有技术相比,本发明的有益效果为:
(1)首次使用红烟硝酸为硝化试剂,不使用硝硫混酸,实现氨基磺酸盐硝化反应合成ADN,避免生成硫酸铵副产物;(2)开发了液体酸催化剂,提高了红烟硝酸硝化效率,进而显著提高ADN收率,解决了ADN收率偏低问题;(3)采用惰性溶剂稀释反应,分批缓慢加料,绝热温升可控,反应过程相对温和,对***冷却能力要求不高;(4)ADN分离纯化方便,经过一次活性炭柱吸附分离,产品纯度为99.95%,收率达到82%。本发明方法原料易得,合成与纯化工艺简单,具有工业应用价值。
附图说明
图1为本发明实施例1制备的ADN水溶液紫外吸收光谱图;
图2为本发明实施例1制备的ADN红外光谱图;
图3为本发明实施例1制备的ADN热分解曲线图;
图4为本发明实施例1制备的ADN离子色谱图。
具体实施方式
下面结合附图和具体实施方式对本发明做进一步说明。
如图1所示,本发明制备的ADN水溶液紫外吸收特征峰为218nm,282nm;图2给出了本发明合成的ADN红外谱图,结果显示:NH4 +的N-H伸缩振动(3130),-NO2伸缩振动(1535,1400),-NO2对称伸缩振动(1175),-N3对称伸缩振动(1022),-NO2弯曲振动(731,762,827);图3中热分解曲线表明ADN的熔点为92℃,在94℃附近有一个明显的吸热峰,此时ADN晶体由固相转变为液相,约在150℃左右开始放热,放热峰温为197℃;ADN分子式为H4N4O4,元素分析(%),理论值:H,3.25;N,45.16;实测值:H,3.20;N,45.12;实测值与理论值吻合较好。这些表征数据与文献报道一致(ADN的合成及性能研究(I),含能材料,1999,7,145-148),本发明制备的目标产物ADN结构完全正确。图4离子色谱仪显示本发明合成的ADN水溶液具有较高的纯度(99.95%)。本发明未使用浓硫酸作脱水剂,因此没有硫酸铵杂质生成,经过一次活性炭柱纯化,ADN纯度可达99.95%,显著高于公开报道的硝硫混酸工艺(99.5%)。
实施例1
在250mL反应器中加入30g红烟硝酸(含四氧化二氮20%),冷却至-30℃,加入5.2g三氟乙酸和18mL二氯甲烷,充分搅拌30分钟;分批缓慢加入17.3g氨基磺酸铵,进行硝解反应,控制反应温度在-30℃至-40℃之间,加料完毕后,继续搅拌反应0.5小时;将反应液倒入冰水混合物中,控制反应温度在-5℃至5℃之间,通入氨气进行中和反应;将中和反应液经过活性炭柱分离,去除硝酸铵杂质,即可得到目标产物二硝酰胺铵的水溶液,收率为73%。
实施例2
在250mL反应器中加入30g红烟硝酸(含四氧化二氮20%),冷却至-40℃,加入0.7g三氟甲基磺酸和36mL二氯甲烷,充分搅拌30分钟;分批缓慢加入3.5g氨基磺酸铵,进行硝解反应,控制反应温度在-30℃至-40℃之间,加料完毕后,继续搅拌反应0.5小时;将反应液倒入冰水混合物中,控制反应温度在-5℃至5℃之间,通入氨气进行中和反应;将中和反应液经过活性炭柱分离,去除硝酸铵杂质,即可得到目标产物二硝酰胺铵的水溶液,收率为82%。
实施例3
在250mL反应器中加入30g红烟硝酸(含四氧化二氮30%),冷却至-40℃,加入0.4g甲基磺酸和90mL四氯化碳,充分搅拌30分钟;分批缓慢加入10.4g氨基磺酸钾,进行硝解反应,控制反应温度在-30℃至-40℃之间,加料完毕后,继续搅拌反应3小时;将反应液倒入冰水混合物中,控制反应温度在-5℃至5℃之间,通入氨气进行中和反应;将中和反应液经过活性炭柱分离,去除硝酸铵杂质,即可得到目标产物二硝酰胺铵的水溶液,收率为64%。
实施例4
在250mL反应器中加入60g红烟硝酸(含四氧化二氮30%),冷却至-50℃,加入0.6g二氟甲基磺酸和36mL二硫化碳,充分搅拌30分钟;分批缓慢加入15.6g氨基磺酸钾,进行硝解反应,控制反应温度在-30℃至-40℃之间,加料完毕后,继续搅拌反应2小时;将反应液倒入冰水混合物中,控制反应温度在-5℃至5℃之间,通入氨气进行中和反应;将中和反应液经过活性炭柱分离,去除硝酸铵杂质,即可得到目标产物二硝酰胺铵的水溶液,收率为72%。
实施例5
在250mL反应器中加入60g红烟硝酸(含四氧化二氮15%),冷却至-50℃,加入2.1g三氟乙酸和36mL四氯化碳,充分搅拌30分钟;分批缓慢加入13.2g氨基磺酸钾,进行硝解反应,控制反应温度在-30℃至-40℃之间,加料完毕后,继续搅拌反应2小时;将反应液倒入冰水混合物中,控制反应温度在-5℃至5℃之间,通入氨气进行中和反应;将中和反应液经过活性炭柱分离,去除硝酸铵杂质,即可得到目标产物二硝酰胺铵的水溶液,收率为76%。
实施例6
在250mL反应器中加入60g红烟硝酸(含四氧化二氮20%),冷却至-35℃,加入0.5g三氟乙酸和37mL四氯化碳,充分搅拌30分钟;分批缓慢加入22.6g氨基磺酸钠,进行硝解反应,控制反应温度在-30℃至-40℃之间,加料完毕后,继续搅拌反应1小时;将反应液倒入冰水混合物中,控制反应温度在-5℃至5℃之间,通入氨气进行中和反应;将中和反应液经过活性炭柱分离,去除硝酸铵杂质,即可得到目标产物二硝酰胺铵的水溶液,收率为65%。
实施例7
在250mL反应器中加入30g红烟硝酸(含四氧化二氮20%),冷却至-30℃,加入18mL二氯甲烷,充分搅拌30分钟;分批缓慢加入17.3g氨基磺酸铵,进行硝解反应,控制反应温度在-30℃至-40℃之间,加料完毕后,继续搅拌反应0.5小时;将反应液倒入冰水混合物中,控制反应温度在-5℃至5℃之间,通入氨气进行中和反应;将中和反应液经过活性炭柱分离,去除硝酸铵杂质,即可得到目标产物二硝酰胺铵的水溶液,收率为41%,远低于实施例1的73%收率。实验结果表明,液体酸催化剂的加入可以促进红烟硝酸解离出更多真正起硝解作用的硝酰正离子,显著提高ADN收率。
以上所述实施例仅表达本发明的实施方式,但并不能因此而理解为对本发明专利的范围的限制,应当指出,对于本领域的技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些均属于本发明的保护范围。
Claims (3)
1.一种制备二硝酰胺铵水溶液的方法,其特征在于,由以下步骤组成:
(1)在反应器中加入红烟硝酸作为硝化试剂,冷却至-30 ℃至-50 ℃后,加入催化剂和适量溶剂,充分搅拌30分钟;其中,催化剂与红烟硝酸的摩尔比为1:10-100;红烟硝酸与溶剂的体积比为1:1-5;所述催化剂为甲基磺酸、三氟甲基磺酸、三氟乙酸、三氯乙酸、二氟甲基磺酸中的一种;所述溶剂为二氯甲烷、二硫化碳、四氯化碳中的一种;
(2)分批缓慢加入氨基磺酸盐,进行硝解反应,控制反应温度在-30 ℃至-40 ℃之间,加料完毕后,继续搅拌反应0.5-3小时;其中,氨基磺酸盐与红烟硝酸的摩尔比为1:3-15;
(3)将步骤(2)反应后的反应液倒入冰水混合物中,控制反应温度在-5 ℃至5℃之间,通入氨气进行中和反应;
(4)将中和反应液经过活性炭柱分离,去除硝酸铵杂质,即可得到目标产物二硝酰胺铵的水溶液。
2.根据权利要求1所述的一种制备二硝酰胺铵水溶液的方法,其特征在于,所述步骤(1)中红烟硝酸中四氧化二氮的质量分数为15-30%。
3.根据权利要求1或2所述的一种制备二硝酰胺铵水溶液的方法,其特征在于,所述步骤(2)中氨基磺酸盐为氨基磺酸铵、氨基磺酸锂、氨基磺酸钠、氨基磺酸钾中的一种。
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