CN109289249A - The recovery method of plasticizer and stabilization agent in a kind of high-energy propellant - Google Patents

The recovery method of plasticizer and stabilization agent in a kind of high-energy propellant Download PDF

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Publication number
CN109289249A
CN109289249A CN201811498304.XA CN201811498304A CN109289249A CN 109289249 A CN109289249 A CN 109289249A CN 201811498304 A CN201811498304 A CN 201811498304A CN 109289249 A CN109289249 A CN 109289249A
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CN
China
Prior art keywords
supercritical
plasticizer
propellant
stabilization agent
recycling
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Pending
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CN201811498304.XA
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Chinese (zh)
Inventor
边利峰
朱宏春
王吉强
苗建波
张翠珍
张宇
王凌菲
郑晓林
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Inner Mongolia Synthetic Chemical Research Institute
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Inner Mongolia Synthetic Chemical Research Institute
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Priority to CN201811498304.XA priority Critical patent/CN109289249A/en
Publication of CN109289249A publication Critical patent/CN109289249A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D11/00Solvent extraction
    • B01D11/02Solvent extraction of solids
    • B01D11/0203Solvent extraction of solids with a supercritical fluid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D11/00Solvent extraction
    • B01D11/02Solvent extraction of solids
    • B01D11/0292Treatment of the solvent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/80Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/20Waste processing or separation

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The present invention relates to the recovery methods of plasticizer and stabilization agent in a kind of high-energy propellant, using supercritical CO2As solvent, the safe and efficient recycling of plasticizer, stabilization agent component in high-energy propellant is realized.The present invention uses CO2Secondary pollution is not generated as extractant, recycling component is not necessarily to complicated last handling process, and simple process is easy to implement, and is very suitable to scrap the recycling of active principle in the dangerous explosive wastewater waste such as solid propellant.

Description

The recovery method of plasticizer and stabilization agent in a kind of high-energy propellant
Technical field
The present invention relates to the recovery methods of plasticizer and stabilization agent in a kind of high-energy propellant, are specifically faced using super Boundary carbon dioxide (CO2) it is safe and efficient handle discarded high-energy propellant, therefrom recycle active principle plasticizer and stabilization agent.
Background technique
Solid propellant occupies status of crucial importance in military field, and the power source that it is used as engine is remarkably improved Weapon survival ability and operational exertion ability.Active service solid propellant is mostly high molecular material, such as double base propellant, complex solid Propellant, composite double base propellant etc., these propellants all have after curing molding aging rapidly and are unable to lacking for long term storage Point.Once exceeding storage period, if continuing to use the tactical qualities that can not only seriously affect guided missile, and safe thing may be led to Therefore.Therefore, how effectively, safe and pollution-free ground mass disposal is expired or the solid propellant scrapped, be that various countries are paid much attention to The problem of, and various discussions, research and practice are being carried out always.
Usually there are 3 kinds of ways in the world at present: first is that using conventional method, such as burning, explosion, recycling thermal energy;Second is that The various recovery and utilization technologies of active development mainly have at present with certain main components and portions additive (such as AP, heisuojin (RDX), octogen (HMX), aluminium (Al)) etc. centered on recovery technology with by properties of product and function conversion centered on return Receipts technology (such as re-works and switchs to civilian explosive wastewater product, industrial chemicals);Third is that just in the design of novel solid propellant Consider that its R3 (returns and receives/recirculate/huge profit use) characteristic and more meets green ring as the design object of novel propellant Factoring is read.
Patent US3,451,789 by dissolution, extraction ammonium perchlorate in the aqueous solution of heat, then from obtained solution Propellant is gradually handled by the solid residue after multistep separation extraction.It is disadvantageous in that in treatment process and forms solid The aggregation of residue, energy consumption is high, reduces recovery efficiency.
Patent US4,854,982 recycles ammonium perchlorate using Liquid Ammonia Treatment propellant.It is disadvantageous in that liquefied ammonia has poison Property, operating pressure is higher, and relative to cost of investment, and technology production capacity is lower.
Patent US4,909,868 uses near critical or supercritical CO2It is dissolved as solvent and separates biradical or be crosslinked biradical Plasticizer (such as nitroglycerine) and its stabilizer (such as diphenylamines and nitroaniline) in propellant, CO2It can be followed by processing Ring uses.
Chinese periodical " solid-rocket technology " the 6th phase in 2014 reports document, and " extracting RDX etc. from NC base propellant has Imitate the design of ingredient ", the document is using pressurized, heated extraction method (PLE) to black rope in retired nitrocotton (NC) base solid propellant Effective components such as modern (RDX) are recycled, and CH is used2Cl2Make extractant, extract and NC can be made to separate, extraction efficiency is high.
Chinese periodical " explosive wastewater journal " the 1st phase in 2016 reports document " in swelling/dissolution method recycling HTPB propellant The experimental study of AP component ", the document use tetrahydrofuran/aqueous solution swelling/dissolution method, carry out to the AP in HTPB propellant Leaching recycling, under specific process conditions, the AP rate of recovery is 95%, purity 96.1%.
Chinese periodical " explosive wastewater journal " the 1st phase in 2001 reports document and " handles composite solid with critical liquid abstraction technique The technical study of body propellant ", the document describe the process using critical liquefied ammonia separating and extracting AP from propellant.
Chinese periodical " explosive wastewater journal " the 6th phase in 2013 reports document, and " waste and old B Explosives are in overcritical titanium dioxide Dissolubility and its separating technology in carbon ", the document determine B Explosives TNT, RDX using High-pressure phase equilibria method and face super Boundary CO2Solubility in fluid proposes the technique of supercritical technology separating waste, worn B explosive.
Document disclosed above reflects the state of the art for scrapping that active principle recycles in explosive wastewater.Generally using organic Solvent swell/dissolution or supercritical fluid carry out the separating and extracting of component.It is recycled using organic solvents such as tetrahydrofuran, halogenated hydrocarbons The components such as AP, RDX in propellant consume a large amount of toxic and volatile solvents;Use overcritical liquefied ammonia as solvent, liquefied ammonia has poison Property, operating pressure is higher;Use supercritical CO2As solvent, be applied to double base propellant, in B explosive component recycling, with Double base propellant, B explosive are compared, and high-energy solid propellant matrix is high polymer cross-linked structure, and component is more complicated, therefore super Critical CO2Abstraction technique is not applied to the recycling of component in the high-energy propellant containing nitrate.
Summary of the invention
The technical problem to be solved in the present invention is to provide the recovery method of plasticizer and stabilization agent in a kind of high-energy propellant, Active principle plasticizer and stabilization agent are therefrom recycled to solve the problem of to handle discarded high-energy propellant safe and efficiently.
To solve, the technical solution adopted by the present invention are as follows: in a kind of high-energy propellant plasticizer and The recovery method of stabilization agent, using supercritical CO2The method of plasticizer, stabilization agent, specific to wrap in extraction, recycling high-energy propellant Include following steps:
(1) equipment and preparation of samples
High-energy propellant is prepared into graininess, partial size is no more than 5mm, is placed in extraction kettle;By supercritical CO2Feeding mechanism, Temperature, pressure control device, extraction kettle, recycling component collection device, CO2Recyclable device, using piping connection;
(2) supercritical extract
Supercritical CO is inputted into extraction kettle2It is extracted, supercritical CO2Pressure should be maintained within the scope of 10MPa ~ 30MPa, temperature Degree should be maintained within the scope of 40 DEG C ~ 60 DEG C, and extraction time is 2h ~ 4h;
(3) it separates and collects
The supercritical CO of extract will be dissolved with2Enter separator through pressure reducing valve, reduces pressure, supercritical CO2Gasification, extract Plasticizer, stabilization agent enter in collector;
(4) CO2Recycling
By gaseous state CO2It is re-compressed after drying, filtering, input extraction equipment is recycled.
Wherein, the high-energy propellant is the composite solidpropellant containing nitrate ester plasticizer, and the plasticizer is Nitrate can be nitroglycerine (NG), 1,2,4-butanetriol trisnitrate (BTTN), triethylene glycol dinitrate (TEGDN), one or more of diglycol dinitrate (DEGDN), the stabilization agent are phenyl amines, nitroaniline Type organic.
The beneficial effects of the present invention are:
The present invention is characterized in that using supercritical CO2Instead of organic solvent, plasticizer, stabilization agent group in high-energy propellant are realized The recycling divided.The advantage of the invention is that using CO2Secondary pollution is not generated as extractant, after recycling component is without complexity Treatment process, simple process are easy to implement, and are very suitable to scrap active principle in the dangerous explosive wastewater waste such as solid propellant Recycling.
Detailed description of the invention
Fig. 1 is supercritical CO2Recycle the process flow chart of plasticizer, stabilization agent in high-energy propellant.
Fig. 2 is the liquid chromatogram of high-energy propellant extract.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but does not limit the present invention.
In the following embodiments, as shown in Fig. 1, using supercritical CO2It recycles and increases in certain representative formula high-energy propellant Agent, stabilization agent are moulded, specific implementation step is as follows.
Step 1, equipment and preparation of samples.Propellant is prepared into the particle of partial size about 5mm, 20g sample is taken, is placed in capacity For in the extraction kettle of 50mL.By supercritical CO2Feeding mechanism, temperature, pressure control device, extraction kettle, recycling Fraction collection dress It sets, CO2Recyclable device, using piping connection.
Step 2, supercritical extract.CO is inputted into extraction kettle2, pressure is set as 20MPa, and temperature is 50 DEG C, extraction 2.5h。
Step 3, it separates and collects.The supercritical CO of extract will be dissolved with2Enter separator through pressure reducing valve, reduce pressure, Supercritical CO2Gasification, extract plasticizer, stabilization agent enter in collector.
Step 4, CO2Recycling.By gaseous state CO2It is re-compressed after drying, filtering, input extraction equipment is recycled.
Fig. 2 is the liquid chromatogram of selected high-energy propellant extract.Four chromatographic peaks correspond respectively to two kinds in spectrogram Plasticizer and two kinds of stabilization agents.
Calculate the extraction yield of four kinds of components, respectively plasticizer 1:95.4%;Plasticizer 2:91.8%;Stabilization agent 1:85.7%; Stabilization agent 2:88.9%.
The above described is only a preferred embodiment of the present invention, not making any form to technical solution of the present invention On limitation.According to the technical essence of the invention any simple modification to the above embodiments, equivalent variations and repair Decorations, fall within the protection scope of the present invention.

Claims (3)

1. the recovery method of plasticizer and stabilization agent, specific steps in a kind of high-energy propellant are as follows:
Step 1, equipment and preparation of samples
High-energy propellant is prepared into graininess, partial size is no more than 5mm, is placed in extraction kettle;By supercritical CO2Feeding mechanism, temperature Spend pressure control device, extraction kettle, recycling component collection device, CO2Recyclable device, using piping connection;
Step 2, supercritical extract
Supercritical CO is inputted into extraction kettle2It is extracted, supercritical CO2Pressure should be maintained within the scope of 10MPa ~ 30MPa, temperature Degree should be maintained within the scope of 40 DEG C ~ 60 DEG C, and extraction time is 2h ~ 4h;
Step 3, it separates and collects
The supercritical CO of extract will be dissolved with2Enter separator through pressure reducing valve, reduces pressure, supercritical CO2Gasification, extract Plasticizer, stabilization agent enter in collector;
Step 4, CO2Recycling
By gaseous state CO2It is re-compressed after drying, filtering, input extraction equipment is recycled.
2. recovery method according to claim 1, it is characterised in that: the high-energy propellant is to be plasticized containing nitrate The composite solidpropellant of agent.
3. recovery method according to claim 1, it is characterised in that: the plasticizer is nitrate, is nitroglycerine, 1, One or more of 2,4- butanetriol trinitrate, triethylene glycol dinitrate, diglycol dinitrate, institute Stating stabilization agent is phenyl amines, nitroaniline type organic.
CN201811498304.XA 2018-12-08 2018-12-08 The recovery method of plasticizer and stabilization agent in a kind of high-energy propellant Pending CN109289249A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110452124A (en) * 2019-06-13 2019-11-15 内蒙合成化工研究所 A method of TCTNB explosive is purified using supercritical extract

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1605235A (en) * 1968-05-06 1973-08-31 Thermal stabilisation of polyamide coated hexogen - by repeated extraction in refluxing inert solvent to remove impurities in the polyamide
US4909868A (en) * 1989-10-16 1990-03-20 The United States Of America As Represented By The Secretary Of The Army Extraction and recovery of plasticizers from solid propellants and munitions
NZ504394A (en) * 1997-10-14 2002-12-20 Boehringer Ingelheim Pharma Method of extracting undesirable materials from capsule surfaces by exposing the capsule to super critical fluid (SCF)
CN1993385A (en) * 2004-08-05 2007-07-04 马林克罗特贝克公司 Preparation of ultrapure polymeric articles
FR2918292A1 (en) * 2007-07-06 2009-01-09 Khanh Vien Tran Extracting natural products from plant sources using supercritical fluid, includes causing rapid, cyclic pressure variations to increase extraction yield
CN108467558A (en) * 2018-06-28 2018-08-31 多稳(太仓)智能科技有限公司 A kind of plastics firework barrel and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1605235A (en) * 1968-05-06 1973-08-31 Thermal stabilisation of polyamide coated hexogen - by repeated extraction in refluxing inert solvent to remove impurities in the polyamide
US4909868A (en) * 1989-10-16 1990-03-20 The United States Of America As Represented By The Secretary Of The Army Extraction and recovery of plasticizers from solid propellants and munitions
NZ504394A (en) * 1997-10-14 2002-12-20 Boehringer Ingelheim Pharma Method of extracting undesirable materials from capsule surfaces by exposing the capsule to super critical fluid (SCF)
CN1993385A (en) * 2004-08-05 2007-07-04 马林克罗特贝克公司 Preparation of ultrapure polymeric articles
FR2918292A1 (en) * 2007-07-06 2009-01-09 Khanh Vien Tran Extracting natural products from plant sources using supercritical fluid, includes causing rapid, cyclic pressure variations to increase extraction yield
CN108467558A (en) * 2018-06-28 2018-08-31 多稳(太仓)智能科技有限公司 A kind of plastics firework barrel and preparation method thereof

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Title
宋小兰: "《火炸药学报》", 30 December 2013 *
高拥军: "《山西化工》", 3 March 2017 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110452124A (en) * 2019-06-13 2019-11-15 内蒙合成化工研究所 A method of TCTNB explosive is purified using supercritical extract

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