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Liquids Handling
Flammable
nite a flammable atmosphere. This flammable atmosphere
may be evolved from the liquid itself if the liquid is
flammable or combustible and is at or above its flash point
temperature, or in the form of a spray or mist.
Liquids Handling
Electrical Conductivity,
Liquid , pS/m
through the liquid, the dissipation of electrostatic charge is
Conductive liquids ( > 104 pS/m) limited by the insulating piping or lining. As a result, charge
Acetaldehyde (15C) 1.7 x 108 accumulates on both the liquid and the insulating piping or
Acetonitrile (20C) 7 x 108 lining. Even if the conductive substrate piping is electrically
Ethyl acetate (25C) 4.6 x 104 grounded, the insulating lining of a lined pipe will remain
Ethyl alcohol (25C) 1.35 x 105 electrostatically charged because the charge on it is not mo-
Ethylene glycol 1.16 x 108 bile. Thus, electrical grounding of conductive piping, while
Methyl alcohol (18C) 4.4 x 107 necessary, may not be enough to minimize the potential elec-
Methyl ethyl ketone (25C) 1 x 107 trostatic hazard posed by insulating liquids or liquids in con-
Methyl isobutyl ketone < 5.2 x 106 ductive piping with an insulating lining, and additional pre-
Phenol 1 x 106 cautions may be required.
Isopropyl alcohol (25C) 3.5 x 108
Mixing
Water, distilled ~1 x 109
The stirring and mixing of liquids can generate electro-
Semi-conductive liquids ( = 100104 pS/m)
static charge due to contact between the liquid and the vessel
Methylene chloride 4,300
walls and agitator, and between the liquid and any undis-
Trichloroethylene 800
solved or immiscible solids or liquids. When agitation is dis-
Non-conductive liquids ( < 100 pS/m) continued, an insulating liquid can remain electrostatically
Benzene, purified 5 x 103 charged, even if it is contained in a grounded conductive ves-
Carbon tetrachloride 4 x 104 sel. Charge can even continue to be generated on an insulat-
Heptane, purified 3 x 102 ing liquid as solids settle.
Hexane, purified 1 x 105 When all charge-generating operations have ceased, the
Styrene monomer 10 liquid will remain charged for a period of time corresponding
Toluene <1 to its charge-relaxation time as long as the liquid is in contact
Xylene 0.1 with electrical ground, e.g., a grounded metal vessel. The
for a substance is related to its electrical conductivity and is a
ardous level of static charge under certain conditions, such as measure of the time required for the electrostatic charge to be
when they: contain immiscible solids and liquids, e.g., in slur- dissipated by conduction to electrical ground. For conductive
ries, dispersions, suspensions, and emulsions; flow through liquids, the charge-relaxation time is typically much less than
strainers and filters; and are splashed or sprayed. A hazardous 1 s. For insulating liquids, it can be as long as 100 s.
level of electrostatic charge is evidenced by an electric field The dissipation of charge from the liquid in an insulating
strength exceeding 3 106 V/m, which is referred to as the or lined vessel will be primarily a factor of the charge-relax-
breakdown strength of air. For an electric field strength ex- ation time of the vessel or lining material rather than of the
ceeding this threshold, the air adjacent to a charged liquid or liquid itself. In this regard, the charge-relaxation time for
solid surface is ionized, a phenomenon that immediately pre- electrically insulating materials, such as plastics, is typically
cedes an electrostatic discharge. on the order of hours or even days.
Liquids Handling
MIEs generally decrease as the prevailing pressure increas- Propagating brush discharges
es because the flammable atmosphere has more potential Breakdown voltage, Vb, is the voltage at which the insulat-
energy at higher pressures; thus, less energy is required ing property of a material breaks down and an electrical arc
from the electrostatic discharge to create the activation en- is able to puncture or cause a pinhole in the material. In
ergy needed to initiate the combustion reaction. The pres- glass-lined vessels and PTFE-lined piping, if the potential
ence of an alternative oxidant such as pure oxygen, as op- difference between the liquid and the conductive substrate
posed to air, can also affect MIEs. For example, the MIE of vessel or piping exceeds the breakdown voltage of the lining,
diethyl ether is 0.19 mJ at a concentration of 5.1 vol.% in a propagating brush-type electrostatic discharge can occur.
air (21 vol.% oxygen), but only 0.0012 mJ in pure oxygen. These highly energetic discharges, which have effective ener-
gies of as much as 23 J, not only can cause leaks by punc-
Brush discharges turing glass and PTFE linings, but also ignite flammable at-
Brush-type electrostatic discharges arise from charged mospheres, including vapors evolved from flammable liq-
items made from materials that are insulating in electro- uids. Leaks can pose a risk of fire and explosion if the liquid
static terms, such as plastics, to proximate conductors at a is flammable or combustible, or a risk of injury to personnel
lower electrical potential (voltage), such as grounded con- and damage to equipment if the liquid is also corrosive.
ductive plant equipment and personnel. Brush discharges Piping made from plastics and other electrically insulat-
can have an effective energy (E) of as much as 4 mJ, and ing materials can also give rise to propagating brush dis-
thus can be sufficiently energetic to ignite vapors evolved charges. This can occur when the electric field associated
from flammable liquids, many of which have MIEs less with the charge generated by the flow of the material inside
than 4 mJ, as shown in Table 3. the piping is sufficiently strong to ionize the air outside the
Examples of plastic items that can become electrostatically piping i.e., if the electric field strength exceeds the
charged during the processing of liquids include piping, tub- breakdown strength of air (3 106 V/m). Upon ionization,
ing, containers, funnels, pumps, filter media and filter hous- opposite polarity ions are attracted by the electric field as-
ings. These items can become electrostatically charged: (a) by sociated with the charge inside the piping. These opposite-
contact with an electrically insulating liquid during filling, ly charged ions accumulate on the outside wall of the pip-
pouring (emptying), and stirring; and (b) when handled, ing, forming a double-layer charge with the charge on the
wiped or rubbed by personnel. For example, a plastic contain- inside wall. If the potential difference between the charge
er may become electrostatically charged during the pouring of layers exceeds the breakdown voltage of the pipe wall, or
an insulating liquid, such as toluene. The charged plastic con- if a conductor at a lower electrical potential approaches the
tainer could give rise to a brush discharge as it is brought layer of charge on the outside wall, a propagating brush-
close to the vessel into which the liquid is being poured. type electrostatic discharge can occur.
Unlike spark discharges, no satisfactory model has yet Both propagating and brush-type discharges arise from
been proposed for estimating the effective energy of brush electrostatically charged insulators. The difference is that
discharges, and their maximum effective energy (4 mJ) is brush discharges arise when there is a single-layer charge
known only empirically. The name of these discharges is on one side of the insulator, while propagating brush dis-
derived from the multiple brush-like discharge channels charges arise when there is a double-layer charge i.e.,
that are observed for brush discharges under low-light con- charge on both sides of the insulating surface. As shown in
ditions. This is attributed to the fact that the charge on an Figure 1, the second layer of charge can be provided either
insulating surface is not mobile and cannot form a singular by image charge or by ionization of the atmosphere on the
discharge channel. For this same reason, only a limited opposite side of the insulator. The image charge is the oppo-
area of the insulating surface is discharged during any one site-polarity charge attracted to the charge on an insulator
discharge event. Thus, a charged insulator can give rise to that results from the polarization of the otherwise balanced
multiple brush discharges until all of the charge on its sur- charge in the conductor. The double-layer charge enables
face(s) has been discharged or dissipated. more of the charge to propagate to the primary discharge
Operations during which flash fire incidents caused by channel, and accounts for the higher energy of propagating
brush discharges have occurred include: the use of plastic brush discharges. A propagating brush discharge under low
containers and funnels in the open transfer of flammable light conditions is shown in Figure 2.
liquids; the replacement of synthetic filter media; and the While no data on the dimensions of pinholes caused by
breaking (disconnecting or opening) of PTFE-lined pip- propagating brush discharges or the resulting leak rates
ing containing residual flammable liquid, among others. could be found, pinholes are often undetectable by the
Brush discharges can also pose an ignition hazard in the naked eye. They may appear as little more than discol-
event of a leak or spill around a plastic item, or when orations in the glass or on the surface of the insulator, as
plastic items such as containers, plastic sheeting, and shown in Figure 3. For this reason, pinholes are typically
drum pumps are used to clean up spills and leaks of detected through spark testing rather than visual inspec-
flammable liquids. tion. Spark testing involves the use of a conductive brush
Insulator,
Thickness < 8mm
Vb 4 kV)
Liquids Handling
on a particular droplet may become sufficient to overcome ditives is also highly empirical. That is, performance often
the breakdown strength of air and produce a discharge to cannot be predicted theoretically, and instead requires lab-
the vessel wall or to an adjacent droplet at a lower electri- oratory-scale testing to determine whether an additive will
cal potential. be effective at increasing the conductivity of a particular
While the discharge energy from any one droplet may liquid or mixture. Ultimately, testing of field samples also
be small, the effect may be to create a cascade of dis- may be required to verify that the additive is having the de-
charges from the others and thereby simultaneously release sired effect in full-scale equipment.
substantially more of the energy of the cloud. It has been One disadvantage of antistatic additives is that the
speculated that such a discharge may be sufficiently ener- salts, polymers, and other ingredients that comprise them
getic to ignite a flammable spray or mist. are sometimes incompatible with pharmaceutical and
Notably, lightning bolts during thunderstorms are pro- food applications. In these instances, the use of a conduc-
duced by clouds, millions of cubic meters in volume. In tive liquid, such as an alcohol or ketone, may be consid-
contrast, in industrial processes and even in large-scale ex- ered. However, these liquids have the disadvantage of
periments with clouds of sprays and mists as large as 60 needing to be added in much greater concentration (e.g.,
m3, there is no record that these theorized lightning-like on the order of 1020 vol.% or more), which may be dis-
discharges have ever been observed (17). Further, there is ruptive to the process chemistry. Further, these liquids
no record that these discharges have been observed from also must be miscible in the insulating liquid in order to
sprays or mists, even during the washing of 30,000 ft3 increase the liquids electrical conductivity. Lastly, if the
compartments in ocean-going tankers (18). Consequently, conductive liquids are flammable, they may increase the
the probability that lightning-like discharges from an elec- flammability of the insulating liquid, such as by lowering
trostatically charged spray or mist will occur in industrial- the flash point.
scale process vessels and equipment is considered remote.
Grounding plant equipment
CONTROLLING THE HAZARDS All conductive plant and equipment associated with the
A number of approaches are available for controlling elec- processing of flammable liquids should be electrically
trostatic hazards associated with liquid processing, including grounded in order to prevent the accumulation of electro-
raising the conductivity of the liquid, providing a pathway to static charge, and thereby minimize the probability of igni-
electrical ground to dissipate charge from the liquid, and lim- tion from spark-type electrostatic discharges. Conductive
iting the flow and agitation velocity, among others. plant and equipment that should be grounded include pip-
ing, vessels, containers, agitators, pumps, valves, other fit-
Increasing conductivity tings, flanges and couplings, among others.
The electrostatic hazard posed by insulating liquids, such as Suitable reference grounds for fixed conductive plant
toluene, hexane, heptane, xylene and other non-polar solvents, components, vessels and equipment are identified in the Na-
can be decreased dramatically by increasing their electrical tional Electrical Code (NEC) or NFPA 70 (20), and include
conductivity. The conductivity of an insulating liquid can be the plant superstructure. The grounding of conductive plant
increased through the addition of an antistatic additive or a and equipment should be verified regularly by measurement.
more-conductive liquid. These additives typically do not affect Efforts should be made to keep flammable liquids in
the rate of charge generation, rather the increased conductivity continuous contact with electrical ground, even in glass-
enables charge to be more readily dissipated from the liquid. lined vessels and PTFE-lined piping, in order to minimize
Antistatic additives, also known as conductivity im- the accumulation of electrostatic charge on the liquid. Only
provers, have the advantage of requiring the addition of only piping and hose made from antistatic or conductive materi-
a few parts-per-million (ppm) to increase the conductivity of als should be used with flammable liquids in order to mini-
an insulating liquid by several orders of magnitude (19). mize the probability of ignition from brush-type and propa-
While the chemistry of these additives is proprietary, it ap- gating brush-type electrostatic discharges. Such piping and
pears that there are principally two mechanisms by which hose should be electrically grounded during use.
they accomplish this feat. First, the additives contain multi-
ple salts that are dissolved within the insulating liquid, with Limiting flow and agitation velocity
at least one of the salts being sufficiently strong to remain The free fall of flammable and combustible liquids dur-
capable of providing free ions in the solution. The second ing the filling of vessels and containers causes splashing
mechanism is electron transfer. Certain polymers, such as and spraying, with the consequent generation of electro-
some sulfonic and acrylate polymers are capable of transfer- static charge on the liquid. Splashing of flammable and
ring electrons from the end of one chain to the end of an ad- combustible liquids can also result in the formation of
jacent chain. flammable and electrostatically charged sprays and mists.
While these mechanisms are believed common to com- To minimize the potential electrostatic hazard,
mercially available antistatic additives, the use of these ad- flammable and combustible liquids should instead be intro-
Liquids Handling