Nitroglycerin.

Nitroglycerin (NG), glyceryl trinitrate (55-63-0}, C3HsN309' is primarily used as

an explosive iu dynamites and as a plasticizer for nitrocellulose iu double- and multibase

propellants. It is very sensitive to shock, impact, and friction, and is employed only when

desensitized using other liquids or absorbent solids or when compounded with nitrocellulose.

\m1en desensitized with other liquids, such as triacetin [102-76-1} or dibutyl phthalate (84-74-

2}, it may be transported with care. N G is readily soluble in many organic solvents and acts as a

solvent for many explosive ingredients. It is completely miscible with homologous nitrate esters

such as ethylene and diethylene glycol dinitrates. Nitroglycerin is sufficiendy soluble in water

(0.18 g/100 g H 20 at 20C) to pose a contamination problem iu the disposal of process water

produced during its manufacture or used in fo=ulations.

The sensitivity of nitroglycerin decreases with decreasing temperature. Solid nitroglycerin is less

sensitive to high pressure shock than the liquid, although some tests iudicate it to be more

sensitive to friction because of intercrystalline contact. It has a relatively high (13.2C) freezing

point possibly accounting for the reported increase in accident rate in loading pure N G

dynamites and the significant decrease in mechanical properties of nitroglycerin-nitrocellulose

propellants at very low temperatures, unless freezing point depressants are added. Ethylene

glycol dinitrate (freezing point -22.8c C) is added to nitroglycerin-bearing dynamites for this

purpose.

Pure nitroglycerin is a stable liquid at temperate conditions. It decomposes above 60C to fo=

nitric oxides which in turn catalyze further decomposition. Moisture increases the rate of

decomposition under these conditions. Double- and multibase propellants containiug

nitroglycerin have substantially shorter stability lives at 65 and 80C than do single-base
propellants. The decomposition of nitroglycerin proceeds as A rate equation applicable to the

liquid phase is k = 10 20.2 e-46.000/RT

Unconfined nitroglycerin burns without exploding if present in thin layers and in small

quantities, but detonates if confined. Nitroglycerin, like other liquid explosives when aerated or

containiug microbubbles, is especially sensitive to shock. Nitroglycerin exhibits a low velocity

propagation regime and a detonation rate of about 2000 m/s compared to its high energy

detonation rate of about 7800 m/s. The low velocity detonation is associated with the propagation

of a precursor shock wave in the container wall, which causes cavitation bubbles to fo= in the

liquid. Low velocity detonation is uncommoniu high explosives, and is found primarily iu

nitroglycerin and its homologues, iu some gelatin dynamites, and in PETN, TNT, RDX, and

HMX in powder fo=. Absorption of nitroglycerin through the skiu or by vapor iuhalation

expands blood vessels and may result in severe headaches. The accumulation of condensed

pockets of nitroglycerin, as may occur in some propellant air-dryiug systems, should be

prevented because of potential hazard (104-110).

Manufacture. Although nitroglycerin has traditionally been made by the batch process

(106,107), the hazard of handling large quantities led to the development and wide use of

continuous processes. A number of continuous and semi-continuous processes are in use

including the Biazzi process, the Nitro Nobel injector process, and the Schmlid-Meissner

process. In general, the methods used to make nitroglycerin are applicable to the manufacture of

other liquid aliphatic polyhydroxy alcohol nitrates.

Nitroglycerin is made from pure glycerol [56-81-5) to ensure stability of the final product. Mixed

acid (90% nitric acid and 25-30% oleum) is used in both the batch and continuous processes. The

theoretical yield ratio of nitroglycerin from glycerol (qv) is 2.467: 1. The actual yield using
concentrated acid is about 2.36: 1 and slighdy higher in the continuous process than iu the batch

process. Affecting yields are solubility iu spent acid and wash waters, acid concentration and

composition, nitric acid-glycerol ratio, temperature stirring efficiency, and the efficiency of

separating the nitroglycerin from spent acid and wash fluids.

In the Biazzi continuous process, the equipment consists of a nitrator and acid separator with an

associated drowning tank, soda washers with a separator, and water washers each with an

additional separator. Emulsification of the nitroglycerin increases safety because emulsions

containiug three or more parts of water to nitroglycerin are relatively insensitive to initiation. The

stainless steel equipment is precision engineered and has highly polished inner surfaces.

Operations are totally automatic, include numerous fail-safe features, controls, and signaling

devices, and are monitored by a closed-television circuit from a remote control bunker. The

nitrator is a small cylindrical vessel equipped with a multiple bank of spiral, closely packed

cooling coils and a high speed turbostirrer. It has an outlet at the bottom for emergency drowning

of the contents, an inlet for entry of displacement acid, and an emulsion overflow pipe attached

ca 10 cm below the top. The nitrator cover has port holes for the impeller shaft, the glycerol

nozzle, the mixed-acid fed pipe, and a fume pipe. A 250-L capacity nitrator produces ca 1700

kg/h of nitroglycerin.

The mixed acid and glycerol are metered into the nitrator, quickly submerged, emulsified, and

forced up the nitrator past the cooling coils. Part of the nitroglycerin overflows iuto the separator,

and part returns to the vortex in the nitrator fluid. The temperature is kept at 1O-20C. The

emulsified mixture of nitroglycerin and spent acid enters the acid separator where a slight

rotating action imparted to the upper layer of the liquid breaks the emulsion and prevents

overheating. The spent acid flows continuously through an overflow from the bottom of the acid
separator to its storage tank. The nitroglycerin may also be separated in a specially designed

centrifuge. The remainiug acid is neutralized, and the product washed with water until it passes

the specification test for stability. The Biazzi process is also used for the manufacture of other

nitrate esters such as triethylene glycol dinitrate, butanetriol trinitrate, and trimethylolethane

trinitrate (metriol trinitrate), In the Nitro Nobel injector process, an injector is used to mix the

glycerol or other polyol with precooled nitration acid. The flow of the acid through the injector

creates a vacuum so that a metered ratio of the polyhydroxy alcohol is sucked in through the

throat, mixing the two quickly and thoroughly to fo= an emulsion. Increased safety is achieved

because the quantity of alcohol being nitrated is automatically dependent on the quantity of acid

entering the injector. Glycerol at about 48C is sucked into the injector where it reacts almost

instantaneously with the acid. The emulsion produced is rapidly cooled to 15C, and flows by

gravity to a centrifuge or gravity separator where the nitroglycerin is separated from the spent

acid on a continuous basis. The spent acid can be recycled or denitrated. The acidic-containiug

nitroglycerin is emulsified immediately with a water jet to fo= a nonexplosive mixture,

neutralized with sodium carbonate, and washed. The stabilized nitroglycerin is emulsified by

passage through an injector to fo= a nonexplosive water emulsion for safe temporary storage

(106,107,111-114).

EnvironmentalandSafety Considerations. Soda ash and water washes are the primary sources of

pollution from this process. These wastewaters may contain nitroglycerin, nitrates, and sulfates,

and vary iu pH from acid for the first wash after nitration to alkaline for the washes with soda

ash. The process water is first sent through catch basins to remove nonsoluble nitroglycerin. The

overflow may be discharged without further treatment or sent to percolation-evaporation ponds

or earthen sumps. Acidic wastewater may be neutralized by passage through crushed lime beds.
Caustic soda and sodium sulfide may also be used to decompose and dissolve nitroglycerin iu the

effluent, followed by use of an activated sludge system as the secondary treatment. Other

methods investigated include biodegradation of the nitroglycerin, reverse osmosis, absorption by

polymeric resins, treatment with lime and caustic, and oxidation with ozone and pe=anganate.

Safety has been gready increased by use of the continuous nitration processes. The quantity of

nitroglycerin iu process at anyone time is gready reduced, and emulsification of nitroglycerin

with water decreases the likelihood of detonation. Process sensors (qv) and automatic controls

minimize the likelihood of runaway reactions. Detonation traps may be used to decrease the

likelihood of propagation of an accidental initiation; eg, a tank of water into which the nitrated

product flows and settles on the bottom.