SARVAJANIK EDUCATION SOCIETY

SARVAJANIK COLLEGE OF ENGINEERING & TECHNOLOGY

SURAT

CHEMICAL ENGINEERING DEPARTMENT

BACHELORS IN CHEMICAL ENGINEERING GUJARAT TECHNOLOGICAL
UNIVERSITY

PROPELLANTS & EXPLOSIVES

SUBJECT-CHEMICAL PROCESS INDUSTRIES-1 (2130505)
SEMESTER-3

MADE BY : SUBMITTED TO :
SHUBHAM DALAL - 160420105010 PROF. DR. SWATI SHARMA
ALAY DESAI - 160420105011 PROF. ANSHUL SHARMA
ARSHIT DOBARIYA - 160420105013

Academic Year 2017-18

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Introduction
 Exothermic reactions are capable of delivering energy for many purposes. In this section, only
chemical reactions and systems which release extremely large amounts of energy on a weight-time
basis will be considered. For e.g., energy systems of air-space vehicles.
 The knowledge of propulsion principles is necessary to understand energy requirements.
 Explosives and propellants are chemical compounds that undergo chemical decomposition reactions at
very fast speeds, producing gaseous products, and a great deal of heat.
 The major interest in developing energy systems for air-space vehicles is cantered on rocket propellants
although there is some need for high energy liquid fuel systems for manned aircraft

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Classification of Propellants
 They can be classified on the following basis:
1. Physical characteristics
 Solid propellants
1. Double base-monopropellant such as nitrocellulose with diphenylamine stabilizer and
nitroglycerine explosive
2. Composite-a mixture of finely ground oxidizer in a matrix of plastic

 Liquid propellants
(a)Monopropellant
 Homogeneous-methane

 Compound-liquid ammonia

(b)Bipropellant
 Hypergolic-spontaneously ignited

 Non-hypergolic-not self ignited

 Hybrid propellants-usually a mixture of solid fuel and liquid oxidizer.

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Classification of propellants
 They can be classified on the following basis:
 Chemical Reactant characteristics:
1. Monopropellants- a single chemical compound or a homogeneous mixture of compounds, each of
which is capable of sustaining an exothermic reaction when catalyzed
2. Bipropellants-consists of an oxidizer and reducer which will sustain an exothermic reaction when
mixed and ignited.

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Basic considerations in developing high
performance chemical propellants
 Ideal performances criteria for propellants
1. High heat of reaction
2. Low molecular weight combustion products
3. High density
4. Easily stored with no special handling problems
5. High reliability over wide storage temperature range
6. Non-corrosive
7. Low toxicity
8. Readily ignitable
9. Predicted and controllable burning rates

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Basic considerations in developing high
performance chemical propellants
 High specific impulse:
1. The first requisite is a high heat of reaction. The energy generated in combustion reaction is derived
from breaking of chemical valence bond forces, consulting energy of formation, in fuel and oxidation
molecules, and forming new and stronger valence bonds in the gaseous product molecules.
2. In selecting propellant combinations for high flame temratures,the choice of fuel and oxidizers will be
cantered on compounds formed from low strength chemical bond which will yield stable products of
high bond energies
3. The cheapest and most practical liquid bipropellant combination is oxygen-kerosene.
4. If cost is not considered, ultimate high performance rockets will use liquid bipropellants with fluorine
as oxidizer

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Basic considerations in developing high
performance chemical propellants
 Burning rate in liquid propellant systems
1. For bipropellant systems, the oxidizer and fuel are pumped at controlled rates through a premix
chamber into the combustion chamber.
2. The combustion rate is fixed by the dimensions of the chamber and the ability to cool the walls of the
chamber and the throat
3. Heat transfer of the chamber walls is accomplished by:
 Regenerative cooling in which one of the propellants is circulated through cooling jackets before
admittance to premix chamber
 Film or sweat cooling where the propellant is added through a porous wall to form a cool
protective film. Rocket performance is slightly decreased because the coolant film does not burn
effectively.

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Basic considerations in developing high
performance chemical propellants
 Burning rate control in solid propellant systems
1. The most significant design principle in the burning of solid propellants is that the burning proceeds in
a direction perpendicular to the burning surface
2. For a given chamber diameter and propellant composition, the burning rate is controlled by free area to
solid configurations.
3. The internal burning type will give higher thrust for a shorter duration.

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Basic considerations in developing high
performance chemical propellants
 Handling, storage and utilization of propellants
1. The liquid chemicals oxygen, fluorine and hydrogen are in cryogenic class.
 Hydrogen-ideal fuel in terms of Isp; has high diffusivity and chemical reactivity, giving smooth
combustion; high cooling capacity for regenerative or sweat cooling of thrust chamber. Its real
advantages are low storage temperature requirements and low density of the liquid.
 Fluorine-most promising of all oxidizers; very toxic, can be transported or stored in aluminium or
stainless steel tanks, jacketed for liquid nitrogen and the whole container insulated with a vacuum
jacket.
 Oxygen-most used cryogenic oxidizer with no corrosion or toxicity problems such as found with
fluorine; ultimate specific impulse x density is too low.

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Basic considerations in developing high
performance chemical propellants
Table no. : 1
Item Solid Liquid
Simplicity 3-4 moving parts 100 moving parts
Reliability 99% 97%
Safety Explosion hazard on Fire hazard, plus toxicity
blending composite and corrosiveness
mixture, fire hazard on
storage
Control of thrust Burning rate Complete
uncontrollable if initial
propellant temperature is
permitted to vary
Ultimate Isp 300 412
Cost versus size Low cost for small size Only adaptable to
rockets; launching expensive large size, long
systems inexpensive range rockets; launching
systems expensive
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Safety requirements
In addition to normal chemical plant hazards, the rocket and propellant industry handles potentially
high energy materials which can be explosive, toxic and corrosive. Some of the safety practices
encountered include:
1. Isolation-individual buildings where dangerous materials are processed are separated by distance
2. Ventilation and floor damage-must be considered for corrosive and toxic liquid propellants
3. Fire or explosion protection-automatic deluge sprinkler systems installed; buildings are fireproof
construction and often barricaded; floors are electrical conducting, all other materials are spark
proof and explosion proof
4. Transportation-isolation and shipment sizes are monitored interplant and regulated for cross
country shipment by the Interstate Commerce Commission.

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Nuclear Propulsion system
 Large interplanetary rockets are designed with a nuclear power plant and hydrogen as the propulsion
fluid because of its low mol. wt.
 The working fluid is pumped as a liquid from the storage tank through the nuclear reactor where the
hydrogen temperature may approach to 3573K.
 This high energy gas expands through a supersonic nozzle to give thrust.
 Materials of construction for hydrogen gas at high temperature are a prime consideration since
hydrogen diffuses into the lattice structure of materials and cause embrittlement.
 Much development work is reqired before a nuclear propulsion system is considered reliable.

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Hydrazine (N2H4)
 Pertinent properties
Mol. Wt. 32.05
M.P. 2.0°c
B.P. 113.5°c
Density 1.02 gm/cc
miscible with water and low mol. Wt. alcohols
Forms constant boiling (120.1 °c) mixture with 28.5 wt. % water

 Consumption pattern
Rocket fuels 90%
Miscellaneous 10%
antioxidant , plant growth retardant , drug manufacture

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Continue.
 Methods of production
Ammonia-sodium hypochlorite process
chemical reactions
(a) 2NaOH + Cl2 NaOCl + NaCl + H2O
(b)NH3 + NaOCl NH2Cl + NaOH
(c)NH2Cl + NH3 N2H4 + HCl
(d) salt production from reactions (b) & (c)
NaOH + HCl NaCl + H2O
(e)side reaction (avoided by temperature control and inhibitor)
2NH2Cl + N2H4 2NH4Cl + N2

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Continue.
 Quantitative requirements
Basis : 1ton of anhydrous hydrazine (98%)
Ammonia (including losses) 1.3 tons
Sodium hypochlorite 3.3 tons
inhibitor (glue or gelatin0 minor

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Continue.
 Process description
Caustic is continuously chlorinated at a temperature below 30°c to avoid hypochlorite decomposition.
Aqueous ammonia is mixed with the cold hypochlorite to produce chloramine in a mole ratio of
3NH3/1NH 2Cl with a glue inhibitor.
 Anhydrous NH3 is injected into the aqueous chloramine solution to give a molar excess of NH3. This
heats the reactants to 130°C, and optimizes temperature f high yields of hydrazine. The synthesis liquor
is separated via distillation, with the excess NH compressed and liquefied for recycle. The hydrazine
bottoms contain some salt from reaction (d) which must be separated in a crystallizing type evaporator
The overhead vapor is fractionated to produce a 65% constant boiling hydrazine hydrate .
 Anhydrous hydrazine is produced by an azeotropic distillation process using aniline which takes the
water overhead as an aniline-water azeotrope. A two-phase decantation of the condensed vapors returns
the aniline phase to the azeotrope column. The bottom containing 85-90% N2H4 can be stripped of
aniline and most of the remaining water in a still to yield 98 + % N2H4

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Continue.
 Economics
 Hydrazine is largely used as rocket fuel for military purposes, being in commercial development since
World War II (1945).
 At present prices, it is not attractive for commercial jet fuel or other non-fuel purposes.
 Limited military usage has restricted the production to two suppliers by the chloramine route.

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Boron-Hydrogen compounds
Table no. : 2 Physical property of given compound
Substances Heat of Normal state M.P. (°c) B.P. (°c) Density
combustion (gm/cc)
(Kcal/kg)
Diborane 17800 Colorless gas -164 -92 0.43

Pentaborane 16700 Colorless liquid -47 58 0.61

Decaborane 15300 White solid 103 213 0.94

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Methods of production
 Chemical reactions
(a) 3CH3OH + H3BO3 B(OCH3) + 3H2O
(B) Na + H NaH
(C) 7NaH + B(OCH3) NaBH4 + 6Na + 3CH3OH
sodium borohydride
(d) 3NaBH4 + BX3 2B2H6 + 3NaX ; X = F or Cl
(e) B2H6 + xH2 yB5H9 + zB5H11
(f) 2B5H9 B10H14 + 2H2
(g) B5H11 xB10H10 + yB4H10 + zH2

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Raw materials
 Methanol
 Sodium metal
 Boric acid
 Industrial grade hydrogen
 Boron trifluoride or trichloride
 Glycol ether
 Mineral oil

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Process description
 Methyl borate is prepared by the reaction of methanol with metaboric acid. Sodium hydride is
prepared as a dispersion of 5-25 micron crystals in inert oil.
 This dispersion is added to a jacketed reactor along with methyl and the resulting exothermic sodium
borohydride reaction is controlled by water-cooling the jacket.
 the sodium-oil dispersion and methanol vapor are recycled with the sodium borohydride mixed with
glycol ether in the diborane reactor. BF3 or BCI3 is added to produce diborane gas .
 The more desirable pentaborane is prepared by mixing dibonane and hydrogen and passing it through a
heated catalytic hydrogenerator . If the low vapor pressure decaborane powder is required, a mild
pyrolysis of the B5 boranes accomplishes this.

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Economics
 The high energy borane fuei program was initiated by the U.S. Department of Defense Development in
1946 to produce fuel for extremely long range manned aircraft .
 Development proceeded to the point where three plants totalling 100 million dollars investment 11
tons/day output were erected in 1956-58.
 Shortly after that, the decision was made to curtail projects for chemically fueled air-breathing engines
and concentrate on rocket missiles do not require expensive fuels of the borane type .
 As a result, the plants which were placed on standby with no immediate future needs-an example of
military obsolescence.

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EXPLOSIVES
 An explosive is defined as a substance which can undergo extremely rapid, self-propagating
decomposition with the formation of a large volume of gaseous products and evolution of heat.
 The explosive is generally prepared from one or several ingredients in solid form. Reaction may be
initiated by heat, impact, friction or a compression wave from another explosive.
 Explosives differ widely in degree of sensitivity for initiation and in ultimate force-time (Impulse)
characteristics.

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Classification of explosives
 Explosives differ widely in degree of sensitivity for initiation and in ultimate force-time(impulse)
characteristics
1. Initiators or Detonators-exothermic reaction as readily started by brief application of heat, friction
or impact. Small quantities used to initiate less sensitive higher power explosives.
2. Non-initiating high explosives-a high power explosive which requires an initiator to set off
explosive reaction.
3. Low explosives or propellants-materials whose reaction rates are relatively slow and controllable
4. Permissible explosives-must yield a low flame temperature of short duration as specified by the
U.S. Bureau of Mines.

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Properties of explosives
 Standard test are available to measure:
1. Power or brisance-combination of force x velocity to achieve shattering characteristics
2. Sensitivity-measured by impact loading , friction ,and initiating temperature
3. Explosion or adiabatic flame temperature
4. Velocity of detonation wave

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Cellulose nitrate
 It is obtained by treating purified, bleached and dried cotton
linters (cellulose) with a mixture of 12% HNO3, 63% H2SO4, 0.5%
N2O4 and 5.5% water.

[C6H7O2(OH)3]n + 3HNO3 ————> [C6H7O2(ONO2)3]n + 3H2O

 Cellulose also forms some sulfate which will lead to violent

explosion. This is to be overcome by removing sulphuric esters
by adding NH4OH or Na2CO3. some stabilizers in the form of
Fig : 1 (structure of cellulose nitrate)
diphenyl amine or diphenyl urea are added to cellulose nitrate to
arrest the formation of HNO2.

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Continue.
 Gun cotton is cellulose nitrate containing 13.2% nitrogen. It is obtained when cotton is steeped for 20
min in a cooled mixture of conc. HNO3 or conc. H2SO4. Dry gun cotton explodes very rapidly when
ignited. But, when it is wet, it is set of by a small amount of another explosive like mercury fulminate.
Dry gun cotton can also be ignited by shock. In the fiber form it is used in torpedoes and submarine
mines. It is also used as a propellants in rifles or artillery shells.

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Nitro glycerin
 Dynamites contains Nitro glycerin which is an oily
liquid which detonates spontaneously above 50 °C
is one of the principle components. The amount of
inert adsorbent such as wood pulp, starch meal, saw
dust etc are added to dynamite. Dynamites an
breaks rocks into fragment of usable size and also
pulverize it.
 Straight Dynamite - this contains 15-16% of GTN
in wood pulp coupled with NaNO3, the latter acting
as an oxidizing agent. It can be used for blasting
Fig : 2 (structure of nitro glycerin)
hard rocks, coals and other minerals and also in
demolition works etc.

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Continue.

Fig : 3 (flow chart of manufacturing of nitro glycerin)

• Blasting Dynamite(Gelatine dynamite) - in this formulation GTN is partly gelatinized by nitro

or colloidal cotton. It’s approximately composition is GTN 91.5%, nitrocotton 8% and CaCO3
0.5%. It is gel like, water proof, does not flow and sticks well into hole in which it has been
loaded. It can be used under wet conditions and thus demand for nonfreezing dynamites for
use in cold weather is increasing. Non freezing dynamites in the form of a mixture of GTN,
ethylene glycol dinitrate, saw dust and NaNO3 is as powerful as straight dynamite.
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Uses of explosives
 Government usage
1. High explosives for military usage-production depends on war or peace status
2. Propellants
 Military rockets
 Space travel developments

 Industrial usage
1. Coal mining
2. Metal mining
3. Non metallic mining and quarrying
4. Construction and road buildings

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Reference
• DRYDEN’S
OUTLINE OF CHEMICAL TECHNOLOGY
-FOR 21ST CENTURY
PAGE NO. (264-280)
THIRD EDITION (2011)
BY M. GOPALA RAO
AFFILIATED EAST-WAST PRESS PVT LTD

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Thank You

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