647
1 INTRODUCTION
One of the toughest problems researchers and
engineers are facing while dealing with the
exploitationofminera ldepositslocatedonthebottom
oftheseasandoceansatgreatdepthsisthetransport
ofexcavatedmaterialtothesurface.Thisproblemhas
been addressed by academic institutions and
indust
rial consortia (Depowski et al. 1998, Sobota et
al. 2005). This is due to huge interest in the
exploitation of underwater deposits due to an
increase in demand for some mineral resources and
the depletion of their deposits on land. Wide
operation areas of shelves in the sea mining (Karlic
1984; Depowski et al. 1998) and int
erest in
polymetallic nodules and massive sulphide
polymetallic (SMS) (SPC 2013) occurring in huge
areas led to the creation of many concepts and
Research on the Application of Controlled Pyrotechnic
Reaction with the Use of Ammonium Nitrate for
Transport from Seabed
W.Filipek&K.Broda
A
GHUniversityofScienceandTechnology,Krakow,Poland
ABSTRACT:Theincreasinginterestintheexploitationofunderwatermineraldepositsisduetotheincreasein
demandforsomemineralresourcesbecauseofthedepletionoftheirdepositsonland.Thereforeworldwide
researchisaimedatdevelopingefficienttechnologiesexploitationofmineralsfromthebottomoftheseasand
oceans.
Thebiggestprobleminthedevelopmentofunderwater systemsoperatingatgreatdepthsistra
nsportfromthe
seabedtothesurface.Previoussolutionsrepresentvariousassumptionsandtechnicalconcepts.Un‐fortunately,
theirbiggestdrawbackishighenergyconsumptionandthushighcosts.
Theaut
horsproposedtheuseofanewmethodwhichinvolvestheuseofpyrotechnicsasthesourceofenergy
intransportfromtheseabedatgreatdepths(Filipek&Broda,2016,2017)presentingtheresultsoftheoretical
andexperimentalresearchofpyrotechnicreactioninvolvingpotassiumnitrate.
Thispaperexplainstheconceptoftheuseofpyrotechnicma
terialsinvolvingammoniumnitratetransportfrom
greatdepthsin theaquaticenvironment.Itpresents the resultsofexperimentalverifica tion of possibilityof
ammoniumnitrateuseinpyrotechnicreactionsasasourceofenergyneededtoraisetheexcavatedmaterial
fromtheseabedto the surface.Theaut
horsusedpreviouslydeveloped method of control for the effects of
pyrotechnicreaction, i.e. mechanicaldampingof theshock wave inorder to limit its harmful effects on the
housingofthetransportdeviceperformedalsobycontrollingthetimeofpyrotechnicreaction.Intheoretical
research, particular attention was pa
id to determine the depth to which one can apply this method and
determinetheenergyneededfortransportdependingonthedensityofthetransportedmaterial(spoil).
Wecomparedtheresultsof the reaction usingpotassiumnitrate in thereaction with the use ofammonium
nitrate.Theresults confirmthe possibilit
yoftheuseof pyrotechnic materialsfor the transportationof large
depths.
http://www.transnav.eu
the International Journal
on Marine Navigation
and Safety of Sea Transportation
Volume 11
Number 4
December 2017
DOI:10.12716/1001.11.04.11
648
solutions. They have their advantages and
disadvantages, the largest of which is energy
consumption.
In previous publications (Filipek & Broda 2016,
2017)theauthorsproposedtheuseofanewmethod
whichinvolvestheuseofpyrotechnicsasasourceof
energy in transport from the seabed with depths
presenting
the theoretical results (Filipek & Broda
2016)andtheexperimentalpyrotechnicreactionswith
theparticipationofblackpowder(potassiumnitrate)
(Filipek&Broda2017).Thispublicationpresentsthe
resultsofthecontinuationofresearch–thistimewith
the use of ammonium nitrate in the controlled
pyrotechnicreaction.
2 COURSE
OFTHERMALDECOMPOSITIONOF
AMMONIUMNITRATE
NH
4NO3 ammonium nitrate has a molecular weight
of80.05g/molanditsnaturaloccurrenceinanatural
environmentisrare.Forthefirsttimeitwasreceived
in1659byGlauber(Błasiaketal.1956). Ammonium
nitrateundernormalconditionsisasolid,crystalline
body which is readily soluble in
water. The solid
NH
4NO3absorbsH2Ofromtheair.At169.5C(442.5
K)pureammoniumnitratemelts.Theheatoffusion
ofNH4NO
3equals68kJ/kg.Incontrast,at210C(483
K)pureammoniumnitrateboils.
Ammonium nitrate is an unstable substance on
heating and its decomposition may take pla ce
according to different patterns depending on the
temperature(Cagninaetal.2013,Chaturvedi&Dave
2013):
NH
4NO3NH3+HNO3–712kJ/kg (1)
NH
4NO3N2O+H2O+559kJ/kg (2)
4NH
4NO33N2+2NO2+8H2O+1256kJ/kg (3)
NH
4NO3N2+2H2O+½O2+1450kJ/kg (4)
8NH
4NO35N2+4NO+2NO2+16H2O+555kJ/kg(5)
Reaction(1)occursatatemperaturebelow160C
(433K)(Urbański,1985),leadingtodecompositionof
ammonium nitrate into ammonia NH
3 and HNO3
nitricacid.Thisprocessstartsinambienttemperature
butisveryslow.
Properdistributionofammoniumnitratebeginsat
185°C(458K)accordingtothereaction(2)(Urbański
1985, Błasiak 1956). In its course ammonium nitrate
decomposesintonitrousoxide,N
2Oand water H2O.
Above280 °C (553K) decomposition proceeds more
rapidly according to reaction (3) (Urbański1955,
Błasiak 1956), wherein the breakdown products of
NH
4NO3arenitrogenN2,nitrogendioxideNO2,and
waterH
2O.Whileathigher temperaturesthan400°C
(673K)decompositionto‐atedwithastrongburstof
thedistributionofproceedsaccordingtoreaction(4)
(Urbański 1955, Błasiak 1956). Temperature of
explosion amounts to about 1500 °C (1773 K)
(Urbański1955,Błasiak1956),thepulseof
pressure–
approximately 200 MPa for 0.5 10
‐5
s and
approximately0.98m
3
ofgasisemittedfromonekg
of NH
4NO3. According to recent data, ammonium
nitratemayalsobedecomposedduringtheexplosion
inaccordancewithequation(5)(Saunders1922).
It should be emphasized that the indicated
temperatures, at which the initiation of the process
occursreferstonormalpressureandpureammonium
nitrate.Inthecaseofimpurities,the
decompositionof
NH
4NO3 may occur at much cooler temperature.
According to the authors of the equation, (1) is an
unfavourable reaction from the viewpoint of use in
the transport of seabed due to the fact that both
reactionproducts(ammoniaandnitricacid)areliquid
and therefore have a relatively high density. The
problem of the appearance of these decomposition
productsofammoniumnitrateaccordingtoequation
(1)canbedisregardedsincetherateofthisreactionat
atemperatureofapprox.169
o
C(442K)isverysmall
(accordingtod)andduringthedayonly6%oftotal
weightwilldecompose).
Anotherunfavourableoptionofdecompositionof
ammoniumnitrateis(3).Oneof the productsof the
decomposition of nitrogen dioxide NO
2 which is a
highly toxic gas and as a result of the reaction with
water, a nitric acid and nitrous acid emerge, a
compound which is chemically unstable and nitric
acidisoneofitsbreakdownproducts.
2NO
2+H2OHNO3+HNO2 (6)
Consequently,wefoundthatthedecompositionof
theammoniumnitrate isto be carriedbytheoption
(2)and(4)or(5).
3 EXPERIMENTALEXAMINATIONOF
PERFORMANCEOFPYROTECHNICREACTION
OFAMMONIUMNITRATEDECOMPOSITION
USINGʺGEOMETRICʺSUPPRESSION
In order to investigate the suitability of the use of
pyrotechnicsto
transportintheaquaticenvironment
ready‐madespecialteststandwasused(Fig.1)which
was constructed by the authors (Filipek & Broda,
2017).Itconsistsofthecombustionchamber(1)witha
pyrotechniccharge,whichisconnectedto the radio‐
controlled ignition. The chamber is connected to the
tank(2)
which istheexpansionspaceofthegas,i.e.
pyrotechnic reaction products. The volume of the
reservoir(2)wasapproximately310
‐4
m
3
10
‐5
m
3
.The
volume was not determined exactly beca use the
experiments were aimed at determining the quality
and not the quantity of pressure distribution over
time. A pressure gauge (3), thermometer (4) and a
checkvalve(5)forinstallationfillingandleaktesting
areconnectedtothereservoir(2),attheend
ofwhich
there is a valve (6) closed during the experiment or
theleaktestposition.Inordertoemptytheposition
of the gas being the reaction product after the
completionoftheexperiment,thevalve(6)isturned
open.
649
Startofthe experiment wasmade byloading the
load chamber (1). Chamber (1) was then connected
with the tank (2), the connection being sealed. Next
stepwastoconductaleaktest.Itconsistedofraising
pressure to 0.59 MPa using pump connected to the
valve(5)andthen
afteradjustingthetemperatureof
compressed air (4) the ambient temperature for 1
hour,itwasbeingcheckedwhetherthepressurewas
not falling. After confirming the leak tightness, the
pressurewasbeingloweredto0.1MPa.Thispressure
wasthebaselinefortheexperiments.Thentheradio
initiated pyrotechnic
reaction followed. Pressure
changes indicated by the pressure gauge (3) were
recorded using a camera with a frequency of 25
framespersecond.Aftertheexperimentgasproducts
ofthe reaction were removed from theinside of the
stand by opening the valve (6). Experiments and
removal of the gas from
the installation were
performed in the open air. Because – as already
mentioned – experiments aimed at determination of
qualitative rather than quantitative distribution of
pressure in time, the works on the quantitative
analysis of the resulting products of combustion are
continued.
Figure1. Laboratory test stand for the examination of the
performance of pyrotechnic reaction with ”geometric”
suppression.(Filipek&Broda2017)
Asaresultofexperimentsconductedwithoutthe
useofgeometricsuppressionweobtainwaveformsin
the form of a harmonic oscillator which is a non‐
preferredfrom the viewpointof use in the transport
of seabed and future operation of the tool based on
this method due to the local
sudden changes in
stressesofthestructurewithinashorttimeofafew
dozenmilliseconds.
Figure2. Comparison of pressure distribution during the
pyrotechnicreactionwithandwithoutsuppression.
After applying suppression we get the desired
effectofsuppressionofoscillations.Asampleselected
from the many results we present in Figure 2. The
Solid line shows the waveformʹs recorded without
suppression,andthebrokenlineshowstherecorded
waveformwiththeuseoftheinsulationmaterial.
4 EXPERIMENTAL
VERIFICATIONOFTHE
SUITABILITYOFCONTROLLED
DECOMPOSITIONOFAMMONIUMNITRATE
FORTRANSPORTFROMTHESEABED
In the reaction according to the option (2) to two
products: nitrous oxide and water. Wherein under
normalconditionsofnitrousoxideisacolourlessgas
with a sweet odour. It is used, among others
in
anaesthesia.Fromourpointofview,moreinteresting
istheuseofgasinthecartuningandasanoxidizerin
rocketengines(Herdy2016).However,thisgasisnot
indifferenttotheenvironmentbecauseitisoneofthe
main greenhouse gases. Therefore, in industry the
reactionsof
thermaldecompositionofnitrousoxideis
used wherever it arises in technological processing.
Thereactionlooksasfollows:
2N
2O2N2+O2 (7)
Unfortunately, the process of natural
decompositiontakesplaceataveryhightemperature
ofabout1600°C(1873K).However,withtheuseof
catalysts, we are able to lower the temperature to
about200°C(473K)(Bryan&Pederson. 1995,Lohner
et al. 2008). Since this gas has strong oxidizing
properties,itcanbeusedinthecombustionreaction.
An exemplary process includes the coal combustion
process:
C+2N
2O2N2+CO2 (8)
Thestartingpointforcarryingouttheabove(7.8)
combustion of the decomposition reactions is to
obtain the nitrous oxide decomposition of the
ammonium nitrate according to reaction (2). This
process is one of the fundamental processes
producingnitrousoxidefortechnicalpurposes.
Experiment with nitrous oxide from the
thermal
decompositionofammoniumnitratewascarriedout
650
using a laboratory stand constructed by the authors
Figure3(Filipek&Broda,2017).Thestandcomprises
a combustion chamber (reactor) (1) connected to a
pressuregauge(3)throughatube(2)inwhichthegas
generated during the reaction is cooled in order to
prevent damage to the pressure
gauge (3). Tube (2)
alsoservesasanexpansionchamber.Weusevalve
(4)forleaktestingpositionandtoremovegasesafter
theexperiment.
Figure3. Stand for laboratory research with control of
reaction.(Filipek&Broda,2017)
The experiment was started by filling the load
chamber (1). After checking leak tightness tool at 5
Barthevalve(4)wasopenedtoalignthepressureof
the chamberatmospheric pressure and after it had
reached the level, the valve (4) was closed and the
reactionwasinitiated.
As a
result of experiments we received a
monotonic increase in pressure over time which is
presentedinthegraph(Fig.4).
The experiment was performed in two stages. In
the first stage, decomposition of ammonium nitrate
wascarriedoutat200°C(473K)(curve1inFig.4).
Theprocess
lasteduntilitreachedthevaluesmarked
with P point on the graph (Fig. 4). Then
decomposition process of ammonium nitrate was
interrupted,whichautomaticallyledtoadecreasein
temperature (up to the ambient temperature), and
hence the pressure (curve 2 on Fig 4). The
decomposition process of ammonium nitrate
was
resumed after about 43200s (12 hours), wherein the
decomposition temperature was adjusted to 250 °C
(523K).Itshowed an increaseinpressure uptothe
point P (curve 3). The process of decomposition
carried on according to curve 4. In the diagram in
orderto avoidexcessive elongation
of the time axis,
and thereby reduce the transparency (readability) of
figure waveforms obtained before and after cooling
werecombinedinpointP.
Figure4. Pressure distribution during the reaction with
performancecontrol
Thereare methods to reducethesuddenincrease
in pressure over time in the event of the use of
decomposition of ammonium nitrate in accordance
with (4) and (5), but then additional compounds in
theformofthesocalledinhibitorsmustbeemployed.
Thismethodcanreducetherateof
decompositionof
ammoniumnitrate(4.5).However,aftertheinitiation
ofthisreactionitisstillaself‐sustainingreactionwith
nopossibilityofstoppingorchangingthespeedofits
course.
5 IDENTIFICATIONOFDEPTHDOWNTO
WHICHTHEMETHODOFOUTPUT
TRANSPORTEXCAVATEDFROMTHESEABED
BASEDONPYROTECHNIC
REACTIONWITH
AMMONIUMNITRATECANBEUSED
For the analysis we chose three options of chemical
reactions, two for ammonium nitrate (distribution‐
distribution, distribution‐combustion) and one for
potassium nitrate (combustion) reaction which is a
comparative reaction. In the case of thermal
decomposition of ammonium nitrate reactions occur
in two stages.
The first step is the thermal
decomposition of ammonium nitrate in accordance
withequation(2).Next,thenitrousoxideisburnedin
accordance with equation (9) or decomposed as in
equation(10).
C+N
2O+2H2ON2+CO2+2H2O (9)
2N
2O+4H2O2N2+O2+4H2O (10)
However, in the case of potassium nitrate we
chosereaction(Filipek&Broda2016,2017):
4KNO
3+5C2K2CO3+2N2+3CO2 (11)
Reason for the choice and the reaction course is
describedindetailintheabovecitedpublication.
Wemadeouranalysisassuming thatproductsin
the gas phase include nitrogen and oxygen in the
liquid phase include water and carbon dioxide and
calcium carbonate present in the solid phase.
This
assumption entailed the necessity of analysis at
temperatures below condensation temperature (CO
2,
H
2O)foragivenpressure.Thereforeweassumedthat
wewouldconducttheanalysisofthepressurevalues
above5MPafortwotemperaturesof5°C(278K)and
15°C(288K).Undertheseconditions,bothCO
2and
H
2Oareinliquidstate. Inaddition,weassumedthat
in the case of nitrogen and oxygen being in the gas
phase Amagat’s law is satisfied (Szewczyk 2009),
which states that the volume occupied by the gas
mixtureisequaltothesumofthevolumesoccupied
by individual ingredients in
the solution, assuming
that each of the components has the same
temperature and pressure. We used it also for the
mixtureofCO
2andH2Oduetothefactthatwedid
notfindanyindicationintheliteraturethatthislawis
notfulfilledforthismixture.Inouranalysis,thereare
two‐phase mixtures (gas‐liquid), and obviously the
dissolution of part of the vapour phase in liquid
phase takes place, the mechanism
of which is
quantitatively described as a function of pressure
(Henryʹs law) in a wide variety of literature (Carrol
651
1991,1999). In contrast, there is no clear information
on the dependence of the volume of the two‐phase
mixture on the amountof the soluble component in
thegasphase.ItforcedustoapplytheAmagat’slaw
alsoforthis case.Letus schematically introducethe
symbolsasshown
below(Fig.5)where
isdensity
of the mixture, V
volume of the mixture,
Iis i‐
densityofthei‐componentinthemixture,thevolume
V
iofthei‐componentinthemixture
Figure5.Conceptdiagramfordetermination
Ifweconsiderthethree‐componentmixturewitha
mass m
, the density of suspension matter can be
determinedfromtheequation:
11 2 2
12
ii i i i i
ii i
mV V V
VVVV
(12)
Introducinganothervariable
1
1
22
ii
ii
ii
VV
and
VV
(13)
equation(12)takesanewform(14).
11 2 2
1
1
ii i i i i
ii
(14)
Due to the possibility of replacing m
i component
mass of mixture with the product of the number of
molesofthen
icomponentanditsMimolarmasswe
obtain:
22
222
ii ii i
i
ii i i i
mnM
mnM
(15)
Substitutingtheaboveequationin(14)formulawe
obtain:
11
2
22 22
11
2
22 221
1
11
1
ii i i
i
ii ii
ii i i
i
iiiiii
nM n M
nM nM
nM n M
nM nM
(16)
Whenconsideringamixtureofi‐components,the
aboveformulacanberepresentedas:
1
11
1
11
1
nn
ii ii
nn n
nn nn
ii
nn
ii n ii n
nni nni
ii
nM nM
nM nM
nM nM
nM nM
(17)
On the Internet at http://www.peacesoftware.de/
einigewerte_e.htmlwecanfindanalgorithm‐atool
whichhasbeenusedtodeterminethedesireddensity
of nitrogen, oxygen, carbondioxide and water, both
forliquidphaseandgasphase.Inordertodetermine
themaximumdepthdowntowhichthemethodcan
beusedtotransporttheexcavatedmaterialfromthe
seabed based on the pyrotechnic reaction using
ammoniumnitrate it is assumedthat themodel isa
multi‐phasesystem.Thegasphaseincludesnitrogen
andoxygen,theliquidphaseincludescarbondioxide
andwaterandthesolidphase–potassiumcarbonate
(in the case of the comparative reaction). The
maximum depth at which the transport will be
possible is determined from the comparison of
relativedensityofthefluidsurroundingthetransport
system
p to the density of the multiphase
as a
functionofpressure:
11
2
22 22
11
2
22 221
() 1
()
11
() 1
() ()
ii i i
i
ii ii
ii i i
i
iii iii
nM n M
p
nM nM
p
nM n M
p
nM p nM p
(18)
If the ratio is greater than 1, then the process of
ascent would be theoretically possible. When
=
p
theprocessofascentwillnotbepossible.Thevalues
ofdensitynecessarytodesignatethe
dependingon
the pressure were calculated using the available
Internet (http://www.peacesoftware.de/einigewerte_
e.html)application.Theresultingamountsareshown
in Figure 6. The results presented were obtained at
two temperatures. The dashed line shows the
waveformsfor the temperature of 5°C (278K), while
the solid line shows the waveforms implemented at
15°C(288K).
Figure6. Comparison of the three courses of reactions as
consideredfortheascent.
Presentedin the graph above, the pressurefalls
within the range of 5 MPa (liquid phase of carbon
dioxide and water) to 50 MPa (the critical point for
oxygen). Unfortunately, the Internet application
(http://www.peacesoftware.de/einigewerte_e.html)
doesnotallowthecalculationofthepressuresabove
the critical point for oxygen. However, accepted
pressure
range covers the depth on Clarion‐
ClippertonzoneinthePacific.
652
6 CONCLUSIONS
With the ability to determine the density
we are
able to determine the the energy E needed to lift
transport module, which amounts to (Filipek &
Broda,2016):
p
p
p
EE
(19)
whereE
pisthetheoreticalpotentialenergyneededto
move the weight between two points immersed in
liquid
p(e.g.thebottomofthesea,thesurfaceofthe
sea). From the above formula we can conclude that
the most significant amount responsible for the
processoftheascent is
parameter. The changeof
thisparameterasafunctionofpressureandhencethe
depthwasshowninFig6forthethreecases.Itcanbe
seen that the reactions (2) and (10) arethe most
effective, from the point of view of transportation
fromtheseabed,whichis
thethermaldecomposition
ofammoniumnitratetonitrousoxideandwater,and
thenthethermaldecompositionofnitrousoxide.The
reactioncourseinaccordancewith(2)and(9),which
isthethermaldecompositionofammoniumnitrateto
nitrous oxide and water and then burning the
resultingnitrousoxideisaless
favourablereactionin
viewofequation(19)butbothdiscussedcasescanbe
successfully applied to the depth at which
polymetallicnodulesoccurontheClipperton‐Clarion
zone.
Unfortunately, the third method of using the
potassium nitrate would not allow us to achieve a
satisfactorydepth.Also,atthesmaller
depths(upto
about 1 km) it is less energetically favourable.
Althoughthebestresultsareachievedusing(2)and
(10), however, due to the need to ensure adequate
temperature of thermal decomposition of nitrous
oxide it may become the method technically more
difficulttoimplement thanthe method based on
(2)
and (9) wherein the combustion process of nitrogen
dioxide appears to be simpler for implementation.
This aspect must be analysed in detail, which the
authorswillpresentinsubsequentpublicationsafter
completion.
ACKNOWLEDGMENTS
This article was written within Statutes Research
AGH,No.11.11.100.005
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