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AALTO

UNIVERSITY
SCHOOL OF CHEMICAL TECHNOLOGY
Ke42.6500 Unit Operations in Environmental Technology


Report on

UNSYMMETRICAL DIMETHYL HYDRAZINE


POLLUTION OF ENVIRONMENT. SOURCES
AND ABATEMENT METHODS


Submitted to
Sergei Preis




Submitted by

Mohammed Refaat (466851)






February 2015

Contents
Abstract .................................................................................................................................................... 3
Introduction ............................................................................................................................................ 4
Chemical and physical properties of UDMH ................................................................................ 4
Environment issues concerning UDMH ......................................................................................... 5
Treatment techniques ......................................................................................................................... 6
References ............................................................................................................................................... 9

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Abstract

UnsymmetricDimethylhydrazine(UDMH)isacolorless,volatileliquidthatcontainstwo
nitrogenatomsbondedbyacovalentbond.UDMHsmellsasammoniaanditishighlyreactive.
Itissparinglyharmfulifitexposuretohumanitcausesthroatandnoseirritation,vomitingand
liverdamage.Moreoverirritatingtotheskinandtheeyes.AlsoCarcinogeniceffects(isanagent
directlyinvolvedincausingcancer).
UDMHisusedinHighenergyfuelinmilitaryapplication(rocketpropellant),spacecraftandthe
spaceshuttle,InProductionofchemicalandinthetreatmentofwaterboilerstoprevent
corrosion.
Sincethemainusageisintherocketpropellant,itischallengingtocontrolthepollutionfrom
theproductionstageuntiltheusageinthemilitaryapplicationandotherapplication.

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Introduction

UnsymmetricDimethylhydrazine(UDMH)ismodernchemicalthatenternatureprincipallyby
emanationsfromtheirutilizationasshuttlefuelsandtheprocessorutilizethesechemicals.
NeverthelessUDMHisverytoxicandhascarcinogenicproperties.Itcausesnegativeeffectto
theenvironment.ThetransformationofUDMHtotoxiccompounds.
ThemostcriticalisthatfallofrocketisaccompaniedbythespillofunburnedUDMHwhichis
toxicandriskytohumanhealthandtheenvironment.
InthisarticlewepresentstateoftheartknowledgeaboutUDMHpollutionsourcesandthe
abatementmethods.TheinformationmayhelpindevelopinformationontheUDMH.

Chemical and physical properties of UDMH

Chemicalformula:

CASNumber:57147
Color:Colorless
PhysicalState:liquid
Meltingpoint:58oC
Boilingpoint:63.9oC
Thevaporpressure:157mmHgat25oC

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Environment issues concerning UDMH

TheproblemcanbedividedintotwomajorfirstleakageintheproductionofUDMH;Rocket
manufacturestage.Andinthefallprocessresidualfuelremainsinthefueltank,itevaporate,
spilledtotheenvironment.TheUDMHisconvertedintodifferenthighlytoxiccompounds.

Air:
AswementionbeforeUDMHishighlyreactive.Itreactinairwithozoneandrapidlydegraded
anditisoneofthemainreaction.Thereactionratedependonwhetherthereisexcessozone
thanthestoichemetricamountornot.Themainproductofthisreactionishydrogenperoxide
anddimethylnitrosamine(NDMA).Sothemainfactoraffectingrateofthereactioniswhether
thereisexcessozoneornot.
Intheperiodofozonepollutionthereactionwasveryrapidcomparedtonormalconditions.

Water:
TherateofdegradationofUDMHinwaterdependonmanyfactorssuchPH(rateof
degradationishigherinalkalinesolution),presentoforganicmatter,oxygenconcentration,
hardness,temperatureandmetalions.

Soil:
TherateofdegradationofUDMHinsoilisquickerthaninwater.Itdependmainlyon
autoxidation.Themainfactorresponsibleofdisappearanceofthechemicals.Moreoverthe
bacteriainthesoilplaysanimportantrule.

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Treatment techniques

TreatmentofairandwatercontainingUDMHbyoxidationisverychallengingsincethereaction
produceundesiredproductnitrosodimethylamine(NDMA)whichisevenmoretoxic.To
overcomethisproblemwhichhappenedusingozoneorcatalyticoxidationinthepresenceof
CuandFe.Advancedoxidationprocessisusedsuchasphotocatalysiswhichminimizethe
formationofNDMA.MoreoverthereactiondependonthepHofthesolution.
Oneofthecommonformsofadvancedoxidationprocessishydrodynamiccavitationwhich
extentthedegradationofUDMH.

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DevelopeanEfficientprocessesfordisposalanddestructionofUDMHisverychallanging.There
isnoreliabletreatmenttechnologiesthatmeetstheenvironmentaldemandsandenergysaving
critiria.Also,waysofconvertingUDMHintoproductsintheindustrialscaleisnotyet
developed.Butrecentlytheproblemcanbesolvedbyintegratingatreatmentsectionfor
oxidationofUDMHintheProductionplantofmilitaryapplication,spacecraftandthespace
shuttle.AlsoinProductionofchemicalandinthetreatmentofwaterboilers.
Theoxidationreactiontakeplaceinafluidizedbedreactorusingcatalystwhichhashigh
selectivityandactivity.Moreoverthereactormusthavelargeheattransferareatogetridof
thelargeamountofheatcomimgoutoftheoxidationreaction.

Fig 1 process of UDMH catalytic destruction


Fluidized bed reactor (1); water heat exchanger (2); cyclone (3); reactor(4); jet scrubbers (5, 6);
absorber-condenser (7); aerosol filter (8); pumps (9); storage tank of UDMH (10)



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Figure1showstheflowsheetofprocessofUDMHcatalyticdestruction.Firsttank(10)isthe
storagetankofUDMHisfedtothefluidizedbedreactor(1)andairisaddedtothereactorfor
completeoxidation.Anelectriccoilisusedforpreheatingthebedreactor.Alsotheproduct
gasesofreactorpassthroughaheatexchangerforheatintegration.
Thenthegasespassesthroughcyclone(3)toseparatelargeparticlessincethegasescontains
solidparticles.Secondstepisthecatalyticreactorandforfurtherpurification.Thegasespasses
throughtwostagesscrubbers(5,6)tomakesureofcompleteremovalofUDMHparticles.
Moreoverapowdercatalystisaddedtothescrubberliquidforcompleteoxidation.Thenthe
gasenterstheabsorbercondenser(7)forlastpurificationstep.
ThisprocessshowshighefficiencyforUDMHdestructionandoneofthemainadvantageisthat
theprocesscanbeuseasamobileunit;itiseasytotransportittodifferentlocations.

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References

1. Z.R. Ismagilov, M.A. Kerzhentsev, I.Z. Ismagilov, V.A. Sazonov, V.N. Parmon, G.L. Elizarova, O.P.
Pestunova, V.A. Shandakov, Yu.L. Zuev, V.N. Eryomin, N.V. Pestereva, F. Garin, H.J. Veringa
Oxidation of unsymmetrical dimethylhydrazine over heterogeneous catalysts: Solution of
environmental problems of production, storage and disposal of highly toxic rocket fuels
Catalysis Today, Volume 75, Issues 14, 3 July 2002, Pages 277-285

2. Lars Carlsen, Olga A. Kenesova, Svetlana E. Batyrbekova


A preliminary assessment of the potential environmental and human health impact of
unsymmetrical dimethylhydrazine as a result of space activities
Chemosphere, Volume 67, Issue 6, April 2007, Pages 1108-1116

3. Lars Carlsen, Bulat N. Kenessov, Svetlana Ye. Batyrbekova


A QSAR/QSTR study on the human health impact of the rocket fuel 1,1-dimethyl hydrazine and its
transformation products: Multicriteria hazard ranking based on partial order methodologies
Environmental Toxicology and Pharmacology, Volume 27, Issue 3, May 2009, Pages 415-423

4. Gangadhar Choudhary, Hugh Hansen


Human health perspective of environmental exposure to hydrazines: A review
Chemosphere, Volume 37, Issue 5, August 1998, Pages 801-843

5. Bulat N. Kenessov, Jacek A. Koziel, Tim Grotenhuis, Lars Carlsen


Screening of transformation products in soils contaminated with unsymmetrical dimethylhydrazine
using headspace SPME and GCMS
Analytica Chimica Acta, Volume 674, Issue 1, 26 July 2010, Pages 32-39

6.

Mahmood Torabi Angaji, Reza Ghiaee


Decontamination of unsymmetrical dimethylhydrazine waste water by hydrodynamic cavitationinduced advanced Fenton process
Ultrasonics Sonochemistry, Volume 23, March 2015, Pages 257-265

7.

P.A. Kolinko, D.V. Kozlov, A.V. Vorontsov, S.V. Preis


Photocatalytic oxidation of 1, 1-dimethyl hydrazine vapours
Catalysis Today, Volume 122, Issues 12, 15 April 2007, Pages 178-185

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8.

Oxana P. Pestunova, Galina L. Elizarova, Zinfer R. Ismagilov, Mikhail A. Kerzhentsev, Valentin N.


Parmon
Detoxication of water containing 1, 1-dimethylhydrazine by catalytic oxidation with dioxygen and
hydrogen peroxide over Cu- and Fe-containing catalysts
Catalysis Today, Volume 75, Issues 14, 3 July 2002, Pages 219-225

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