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REVIEW

Safety of chlorine production


and chlorination processes
Most chlorine production is obtained by electrolysis of NaCl aqueous solution. Other processes to produce
chlorine involve the electrolysis of KCl or HCl aqueous solutions, the electrolysis of molten NaCl at high
temperature and the Deacon process. In most cases, chlorine is a by-product in the production of caustic
soda, potassium hydroxide, sodium metal or is recovered from HCl using HCl aqueous solution electrolysis
or gas–solid reaction in the Deacon process.
Chlorination reactions are part of various processes in the chemical industry, to manufacture heavy
chemicals, specialty chemicals, pesticides and pharmaceuticals, in inorganic and organic chemistry. They
are valuable tools in organic synthesis.
The hazards of chlorine production and chlorination processes involve:

- Gas phase explosion, i.e., self-ignition, deflagration and detonation in the gas phase.
- Runaway reaction or thermal explosion, deflagration and detonation in the condensed phase.

Gas phase explosion hazard with chlorine as an oxidizer is present in the production of chlorine by
electrolysis, in gas phase chlorination processes and in chlorination reactions carried out in the condensed
phase.
Gas phase chlorination processes are continuous processes operating either in the flammable range like
burners or outside the flammable range in loop reactors or loop processes where chlorine is the controlling
reactant.
When chlorination is carried out by chlorine injection in the liquid phase, gas phase explosion hazard
is related to chlorine evolution in the vapour phase, giving a flammable mixture with the solvent or
reaction mixture vapour. Hazard assessment is achieved by comparing the gas phase composition with the
flammable area of the gaseous mixture. Self-ignition is also considered because the self-ignition temperature
of gaseous fuels in chlorine atmosphere is lower than in air or oxygen and often close to the ambient
temperature.
The relevant flammability data is the flammability limits, LFL, UFL, minimum oxidizer concentration
(MOC), auto-ignition temperature (AIT), of fuels in chlorine and the explosion characteristics Pmax and KG
for deflagration in chlorine.
A collection of flammability data is given for the reader convenience, collected in the literature or obtained
in our own experimental facility, a specially designed 20 L Hastelloy C 276 sphere with 200 bar pressure
resistance, ambient to 300 8C initial temperature, easily opened for frequent cleaning. This apparatus allows
precise determination of the flammability limits, self-ignition temperature, explosion overpressure, rate of
pressure rise and flame speed.
Runaway reaction hazards in chlorination reactions are related to a series of dangerous process situations
or process deviations such as:

- Delay in reaction initiation.


- Reaction mixture instability.
- Production and accumulation of unstable species like chloramines, nitrogen tri-chloride, chloro-nitroso
compounds, alcohol hypo-chlorites.
- Demixing or separation of unstable species in case of chlorination reactions made in aqueous solution,
because the chlorinated compounds are less soluble in water than the initial reactant.
A full review of runaway reaction hazards in chlorination reactions is given with examples from the
literature and from the laboratory.

1074-9098/$30.00 ß Division of Chemical Health and Safety of the American Chemical Society 5
doi:10.1016/j.chs.2004.08.002 Elsevier Inc. All rights reserved.
By Jean-Louis Gustin cess is used for the recycling into chlor- a condenser. In between is a grey zone
ine of HCl aqueous solutions produced where the temperature is not carefully
INTRODUCTION—CHLORINE by chlorination processes. The HCl controlled, allowing NCl3 to accumu-
PRODUCTION AND USE produced by TiO2 chlorine processes late and subsequently decompose. This
may be recycled into chlorine using the processing step is subject to many pro-
Most chlorine production is obtained Deacon process. blems and accident case histories con-
by electrolysis of NaCl aqueous solu- The chlorine produced by electroly- cerning the disposal/destruction of the
tions. Different processes are also sis of NaCl, KCl, or HCl aqueous solu- NCl3 solutions.
used. Their importance depends on tions is obtained wet of water and is The gaseous chlorine is then lique-
the area considered. corrosive for current metallic materials fied by compression and cooling thus
In 1996, the mercury cell process of construction except titanium. The providing a further purification step for
accounted for 53% of the chlorine pro- wet gas is dried as soon as possible the liquid chlorine and allowing the
duction in France, 64% in Europe and by cooling to above 12 8C to prevent storage and transport of liquid chlor-
39% worldwide. The diaphragm cell chlorine hydrate formation, often by ine.
process accounted for 32% of the pro- direct contact with cold water, filtra- Total liquefaction of the chlorine
duction in France, 25% in Europe and tion of the water aerosol and washing produced is difficult and may cause
45% worldwide. The membrane cell with 98% sulphuric acid in a column, problems due to the presence of gas-
process accounted for 15% of the pro- to reach a water concentration of less eous impurities (H2, CO2, CO, O2, N2).
duction in France, 11% in Europe and than 20 mg/kg chlorine. Then carbon A fraction of the chlorine production is
16% worldwide. steel equipment dried to a dew point of not liquefied and is used on site at least
For environmental reasons, the 40 8C under atmospheric pressure for the production of bleach. This gas-
installation of new mercury cell plants may be used to process dry chlorine eous chlorine is rich in gaseous impu-
is not allowed in Europe and the exist- (see Process diagram 1). rities and called residual chlorine.
ing plants must meet the ever more The dry gaseous chlorine is then The chlorine consumer plants are
demanding regulation for mercury washed with liquid chlorine in a bub- best situated near the chlorine produc-
emission control. The importance of ble-cap tray column operated at tion plants, to limit chlorine transport.
the diaphragm cell process should 35 8C under atmospheric pressure However, this is not always so for his-
not increase as long as diaphragms to remove nitrogen tri-chloride from torical reasons or for small consumer
are made of asbestos. New plants are the gaseous chlorine and cool the gas plants. Therefore, a fraction of the
using the more environment friendly before compression. This column is chlorine produced is liquefied to
membrane cell process. also intended to separate chlorinated obtain good purity chlorine and allow
The process for the electrolysis of organic compounds from gaseous chlorine to be transported to remote
NaCl aqueous solutions to produce chlorine before compression in plants consumer plants. In France and in
caustic soda may apply to the electro- where this chlorinated organic con- Europe as well, the capacity of liquid
lysis of KCl aqueous solutions as well, centration is significant (see Process chlorine storage facilities is limited by
for the production of potassium hydro- diagram 2). the regulation. In France, chlorine sto-
xide. NCl3 and the chlorinated organic rage vessels as well as loading and
For the production of sodium metal, compounds condense or dissolve in unloading stations must be enclosed
the electrolysis of molten NaCl at 650 8C liquid chlorine in the column bottom, in a housing connected to a scrubber
is used. This process accounts for 2% of which is routinely admitted in a using caustic soda, to control acciden-
the chlorine production in France. so-called re-boiler where carbon tetra- tal releases. The capacity of the scrub-
The electrolysis of HCl aqueous chloride is often added to extract ber is typically 5,000 kg/hour chlorine
solutions using a diaphragm cell pro- nitrogen tri-chloride and allow its sub- in air destruction.
sequent disposal/destruction. Carbon Most chlorine storage facilities are
Jean-Louis Gustin is process safety tetrachloride is a suitable solvent to operated at or near ambient tempera-
consultant since 1984 within the for- extract NCl3 because it cannot be ture, under the liquid vapour pressure.
mer Rhône-Poulenc, Aventis, and now further chlorinated and has an atmo- There are limited examples of cryo-
Rhodia, working in the field of chem- spheric boiling point of 77 8C versus genic chlorine storage facilities oper-
istry and runaway reactions. He is 71 8C for NCl3. ated at 35 8C and atmospheric
affiliated with Rhoditech 24 Avenue The re-boiler is intended to allow pressure, as a buffer storage between
Jean-Jaurès, F69153 Décines-Char- chlorine to vaporize and return to chlorine production and local con-
pieu, France (Tel.: +4 72 93 57 14; the column. sumption. About 10% of the chlorine
fax +4 72 93 59 68; e-mail: jean-louis.- The re-boiler is either operated cold production is transported to a remote
gustin@eu.rhodia.com). (0 to 5 8C) in which case NCl3 is allowed consumer plant. Bulk chlorine trans-
A short version of this paper was pre- to accumulate in this vessel and must be port in Europe is by rail tanks. The use
sented to the Eurochlor seminar held further disposed, or the re-boiler is of road trucks is very limited. The use
in Leipzig, Germany, 1997, and was operated hot (45 to 60 8C) in which case of barges or boats was considered in
published by Eurochlor under the the re-boiler is intended to thermally northern Europe, it is more wide-
reference GEST 97/242. decompose NCl3 and is equipped with spread in the USA.

6 Chemical Health & Safety, January/February 2005


Process diagram 1. Chlorine line of an electrolysis plant.

One tonne cylinders and bottles are pounds to produce chlorinated pro- reactor, on a catalyst bed, solid /gas
used to supply chlorine to small con- ducts or intermediates. A wide range reactions in a fluid bed, gas/liquid
sumers and for water treatment. of useful products are obtained such reactions in a packed column, gas/
Chlorine is an important raw material as bleach, metallic chlorides, reactive liquid reactions by injecting chlorine
in the chemical industry. The main uses monomers to manufacture plastics, in a liquid phase in a semi-batch pro-
are in the production of PVC (40%), heat exchange fluids, chlorinated cess or in a continuous process. The
chlorinated solvents (25%), Phosgene solvents and intermediates in organic reaction of chlorine takes place with-
(10%), other organics (10%), inorganic synthesis to produce specialty out catalyst, in the presence of a cata-
and miscellaneous products (15%). chemicals, pesticides and pharmaceu- lyst or in photochemical reactions.
Quite similar to oxygen, chlorine is ticals. Compared to oxygen, chlorine is a
used as an oxidizer in a wide range of Chlorine is involved in a wide range more reactive gas because it is pro-
chemical processes where it is reacted of process situations including gas cessed as a pure gas whereas oxygen
with organic and inorganic com- phase reactions in a burner or in a loop is often reacted using air. More pro-
blems would occur with oxygen if the
use of pure oxygen was widespread in
the chemical industry.
Compared to pure oxygen, chlorine
is even more reactive. The self-ignition
temperature of gaseous mixtures of
organic vapours with chlorine is much
lower than that of their mixtures with
oxygen. Natural light can split the
chlorine molecule to produce reactive
chlorine radicals. Many reactions of
chlorine take place near the ambient
temperature. The combustion of iron
in chlorine can be initiated at tempera-
tures slightly above 100 8C.
Chlorine is toxic to man and ani-
mals. Many chlorinated compounds
are also toxic.
The TLVTWA is 0.5 ppm and the
STEL/C is 1 ppm. The effects of expo-
sure to chlorine may be described as
follows.

Below 1 ppm, detection of the smell by


Process diagram 2. Washing/cooling column and re-boiler. normal subject.

Chemical Health & Safety, January/February 2005 7


1 to 5 ppm, slight irritation of the upper ducts may be obtained. This process method and proposed other methods
breathing path. situation is dangerous in two cases: of solvent extraction to obtain those
5 to 8 ppm, irritation of the upper alcohol hypochlorites which cannot be
breathing path and of the eyes. - if a high concentration of unstable obtained directly using Sandmeyer’s
15 to 20 ppm, immediate severe irrita- chlorination product is obtained in method.
tion of the upper breathing path, strong the condensed phase and In most process instances, the forma-
cough and choking. - if a chlorinated liquid phase sepa- tion of alcohol hypochlorites is
30 ppm, breathing is difficult, pain to rates from the bulk liquid phase unwanted for process safety reasons.
breast, nausea, vomiting. ‘‘by segregation’’. However, the formation of alcohol
40–50 ppm, chemical tracheobronchi- The latter situation is frequent in the hypochlorites is possible in waste-water
tis, severe lung edema may appear up chlorination of aqueous solutions of treatments where alcohols are present,
to 72 hours later. organic reactants because the chlori- using chlorine or bleach. This is a very
Above 50 ppm, depending on the nated products are less soluble in water frequent process situation. The accu-
exposure time, loss of consciousness than the initial reactants. mulation of alcohol hypochlorite is pos-
and death. Examples of this dangerous process sible under alkaline conditions. The
For all the above reasons, the chemical situation are the synthesis of alcohol solubility limits of the hypochlorite in
processes where chlorine is involved hypo-chlorites by injecting chlorine in water depend on the alcohol chain
are submitted to careful safety studies an alkaline aqueous solution of alco- length. Methyl hypochlorite is soluble
where the specific chemical properties hol, the formation of nitrogen tri- in water and should not separate unless
of chlorine are considered. chloride by chlorination of certain the alcohol concentration in the waste
‘‘dangerous’’ nitrogen containing com- water is very high (of several percents by
pounds, the chlorination of oximes weight). Under acidic conditions, alco-
THERMAL EXPLOSION HAZARD IN in aqueous solution, the radical or hol hypochlorites are unstable and
THE CONDENSED PHASE should decompose readily or behave
photochemical chlorination of succi-
nimide. like chlorinating reagents, contributing
Chlorine is a strong oxidizer. Mixtures to the water treatment. One should take
of chlorine and organic fuels may have Alcohol Hypochlorites care if the yellow oil separates from the
a high energy content and are unstable. Traugott Sandmeyer described the bulk liquid. Methyl and ethyl hypo-
The thermal instability of condensed synthesis of methyl and ethyl hypo- chlorites may detonate in the liquid
phases containing chlorine can appear chlorites2,3 and suffered severe injuries phase.
in various process conditions. due to explosions during the experi-
ments. In Sandmeyer’s method to Nitrogen Trichloride
Example of Chlorine Accumulation Due obtain alcohol hypochlorites, chlorine The oxidation of organic compounds
to a Delay in the Chlorination Reaction is injected into an aqueous solution of containing nitrogen in their formula
Initiation alcohol and caustic soda with a mole (amines, amides, cyanides, urea) using
When chlorine is injected in a liquid ratio alcohol/sodium hydroxide of 1, chlorine, gives unstable chloramines.
reaction mixture, the chlorination under cooling at 0 8C. The alcohol The very unstable nitrogen trichloride
reaction may not start immediately hypochlorite separates by decantation. is finally obtained. NCl3 is only slightly
allowing chlorine to accumulate in When chlorine does not dissolve any soluble in water and can separate from
the reaction mixture. The reaction longer in the solution, chlorine injec- aqueous solutions giving a very sensi-
may start suddenly when a large con- tion must be interrupted to avoid the tive yellow dense oil. NCl3 can also be
centration of chlorine is present in the alcohol hypochlorite decomposition obtained by chlorination of aqueous
reaction mixture and give a severe run- under acidic conditions. The method solutions containing ammonium ions,
away reaction producing a large quan- was described for the synthesis ammonium nitrate, ammonium sul-
tity of insoluble HCl. An example of of methyl hypochlorite and ethyl phate, ammonium chloride or ammo-
such an induction period in chlorina- hypochlorite. Methyl hypochlorite is nia. The formation of nitrogen
tion is mentioned in the literature for a volatile yellow oil with a boiling point trichloride is possible in chlorination
the chlorination of ketones in metha- of 10 to 12 8C under 726 mmHg. Ethyl processes and in water treatment using
nol.1 To avoid this type of incident, the hypochlorite has an atmospheric boil- chlorine or bleach.
reaction onset should be checked ing point of 36 8C. The liquids are Due to the presence of ammonium
before allowing a large concentration flammable in air. They decompose ions and amine impurities in the salt,
of un-reacted chlorine to be dissolved slowly under alkaline conditions and and to the use of nitrogen containing
in the liquid phase. with violence under acidic conditions. flocculants for salt processing or to the
The Sandmeyer method may be contamination of the salt by dangerous
Examples of Dangerous Process applied to water soluble alcohols. nitrogen containing impurities, nitro-
Situation in Chlorination Reactions Roland Fort and Leon Denivelle4 gen trichloride is present in the crude
When chlorine is reacted with an described the synthesis and properties chlorine produced by electrolysis of
organic fuel in a liquid reaction mix- of a series of other alcohol hypochlor- NaCl or KCl brines. Nitrogen trichlor-
ture, highly unstable substitution pro- ites obtained following Sandmeyer’s ide may also be present in the chlorine

8 Chemical Health & Safety, January/February 2005


produced by electrolysis of HCl aqu- Between the lower limit and the in one tonne cylinders for use in the
eous solutions but is absent from the upper limit, the decomposition is Balard reaction, to produce bromine
chlorine produced by electrolysis of explosive and presents a flame propa- by chlorination of brine containing
molten NaCl due to the high tempera- gation phenomenon. In the dark, NCl3 sodium bromide. An operator felt that
ture conditions in this particular pro- decomposition flame has a pink colour a one tonne cylinder was self-heating
cess. at low concentration. Above the upper above ambient temperature. The cylin-
NCl3 compound was first obtained limit NCl3 vapour decomposes follow- der did not rupture but it was clear that
by Pierre Louis Dulong (1785–1838) ing a slow reaction mode. NCl3 is the NCl3 concentration in this residual
by chlorination of ammonium chloride thought to detonate also in the gas chlorine was not well controlled and
solutions. Dulong was seriously phase but the study of this detonation that this method of NCl3 disposal was
injured by several explosions of liquid in shock tubes is difficult due to the not safe.
NCl3.5 problem of obtaining a high vapour Further to this incident, the process
NCl3 is liquid under normal tem- concentration. was modified and carbon tetrachloride
perature and pressure conditions. The very low LEL of NCl3 makes was added to the chlorine purification
The theoretical atmospheric boiling possible the initiation of gas phase column re-boiler to allow NCl3 extrac-
point is 71 8C. The density of the liquid explosion of flammable chlorine + fuel tion. The NCl3 solution in liquid chlor-
is of 1.635 g/cm3 at ambient tempera- mixtures by NCl3 vapour at trace con- ine was continuously discharged from
ture, so the liquid may accumulate centration. the column bottom to the re-boiler,
undetected under water. The pungent Nitrogen trichloride is miscible with degassed and the NCl3 in CCl4 solution
odour of NCl3 is that of dirty chlori- liquid chlorine even at chlorine atmo- continuously decomposed in a carbon
nated swimming pools. The vapour spheric boiling point of 35 8C. NCl3 is steel vessel by raising the solution
pressure of the pure liquid is also soluble in carbon tetrachloride temperature to 45–60 8C. No serious
150 mmHg @ 20 8C and 80 mmHg @ and chloroform. Other solvents are incident occurred with this type of
0 8C. Due to its high vapour pressure sometimes mentioned like benzene, destruction process.
under ambient temperature, the liquid ether, carbon disulfide but one should In another example, NCl3 was
tends to evaporate quickly. NCl3 is avoid solvents which may be chlori- extracted by adding a mixture of car-
toxic. The recommended occupational nated by NCl3 or chlorine because the bon tetrachloride and chloroform to
exposure limit in France is of 0.1 ppm solution obtained may be unstable and the purification column re-boiler.
and the TLV-STEL is of 0.3 ppm. react violently. NCl3 is a chlorinating The NCl3 in liquid chlorine solution
Occupational exposure can occur in reactant. Solutions of 12–15 wt.% was admitted to the re-boiler, degassed
indoor swimming pool areas and in NCl3 in carbon tetrachloride or and withdrawn batch-wise to be sent
cleaning operations using bleach. chloroform are expected to be stable to incineration. No serious incident
The heat of decomposition was under ambient temperature but would occurred with this type of destruction
determined in carbon tetrachloride decompose above 60 8C. process.
solutions: DH = 54.7 kcal/mol or The decomposition exotherm However, the control of NCl3 con-
DH = 457 kcal/kg NCl3. In this obtained in DTA under temperature centration in the CCl4, chloroform and
decomposition, 1 mol of nitrogen and scan conditions, is influenced by the chlorinated organics solution is critical
3 mol of chlorine are produced per test cell wall material. The decomposi- since NCl3 may decompose violently on
2 mol of NCl3. The solvent is left unaf- tion pattern shows a chemical accel- heating. A runaway reaction accident is
fected in this decomposition. eration phenomenon in titanium or described on this process in a pamphlet
Liquid NCl3 can detonate in the stainless steel closed cell, and a slow by the American Chlorine Institute.6A
condensed phase. The constant decomposition exotherm in closed An off-line re-boiler used to degas chlor-
volume detonation of the liquid glass ampoule. In other words, the ine from a NCl3 in CCl4, chloroform and
produces a maximum pressure of decomposition of liquid NCl3 presents chlorinated organics solution before
5,500 bar and a maximum temperature an autocatalytic behaviour and is cat- its disposal, exploded on October 17,
of 2,128 8C. alyzed by metals like carbon steel, 1967 in a PPG facility at Lake Charles,
NCl3 vapour is also unstable and may stainless steel and titanium. This parti- Louisiana. The NCl3 concentration was
explode above 93 8C or under the influ- cular behaviour finds some industrial deduced from the concentration in the
ence of light. The limits of the gas phase application in NCl3 thermal destruc- column bottom after the incident, to be
explosive decomposition range in a P tion processes used in chlorine pro- only of 8.5 wt.% NCl3. This solution
versus T diagram are as follows: duction. could self-heat above the ambient tem-
perature of 22 8C and the decomposi-
Upper limit: 40 mmHg at 20 8C, Case Histories Concerning Nitrogen tion could runaway causing the re-
70 mmHg at 40 8C, 115 mmHg at 60 8C. Trichloride in Chlorine Purification boiler vessel rupture under an estimated
Lower limit: 10 3 mmHg at room Processes pressure of 51 bar and temperature of
temperature. A long time ago, the liquid chlorine 100 8C.
used to wash nitrogen trichloride from Another accident case history on the
The lower explosive limit is difficult gaseous chlorine in the bubble-cap tray same type of installation at an unspe-
to distinguish from the slow reaction. column described above, was collected cified location was also reported in a

Chemical Health & Safety, January/February 2005 9


letter of February 3, 1995 issued by the chemical reactor to decompose NCl3 chlorine injection to reduce their cya-
Chlorine Institute.6B if it is operated at high (45 to 60 8C) nide content. As the operators were
In this accident, a double block ball temperature. weeping very much, it was determined
valve system was installed on the liquid that cyanogen chloride, ClCN, was
chlorine line between the washing col- Recommended NCl3 Concentration evolving from the liquid. The forma-
umn bottom and the re-boiler, because Limits in Commercial Chlorine tion of cyanogen chloride is possible by
the previously installed single ball Trace concentration of NCl3 is also reaction of chlorine with inorganic
valve did not close properly. As the present in bulk liquid chlorine shipped cyanides under acidic conditions. It
plant was shut down for maintenance, to customers. Following Eurochlor was decided to replace chlorine injec-
shortly after the process modification, recommendations, the NCl3 concen- tion by the use of bleach to prevent this
the pipe between the two ball valves tration should not exceed 20 ppm in unwanted gas evolution. This sad story
and the ball valves themselves were 1,000 kg chlorine cylinders, 10 ppm in shows that oxidizing conditions are
destroyed by an explosion, causing a 20,000 and 50,000 kg rail tanks and not always obtained and that other
chlorine release which killed two 2 ppm above 300,000 kg chlorine volatile intermediates may also be
operators. inventory.7 formed.
The column drain pipe flange was The withdrawal of chlorine from the Bromination processes and the pro-
then sealed using a blind flange and it gaseous phase is forbidden for contain- cessing of bromine containing reac-
was a decided to pump a drum of ers of 1,000 kg and more to avoid con- tants produce waste solutions
carbon tetrachloride in the washing centrating NCl3 in the vessel. containing inorganic or organic bro-
column bottom. While this was imple- The accumulation of NCl3 in chlor- mides. The incineration of these wastes
mented a second explosion occurred ine vaporizers operating continuously would produce bromine which cannot
in the concrete trench below the is possible if the operating temperature be released as is in the atmosphere.
washing column where the NCl3 in is too low. If the vaporizer operating Some organic bromine product produ-
liquid chlorine solution from the col- temperature allows enough NCl3 cers offer the reprocessing of these
umn bottom had been collected. This decomposition, accumulation does wastes to recover bromine using the
second explosion severely injured one not occur. Balard reaction. The bromide contain-
operator. As the NCl3 concentration The recommended frequency of ing waste is chlorinated in a glass
was kept low in this plant column re- NCl3 control in chlorine production packed column where chlorine is
boiler, a fast increase of the NCl3 is given by Eurochlor depending on injected in the column bottom and
concentration in the crude chlorine the observed concentration.7 bromine is evolving in the column
was suspected due to an unexpected upper part where the liquid waste is
contamination of the salt, brine or Case Histories Concerning Nitrogen fed, as usual to carry out the Balard
chlorine itself. A possible source of Trichloride in Waste Treatments Using reaction. In this process, a very low
contamination was ammonia present Chlorine or Bleach level of contamination of the waste
in the cooling water used in direct At least one accident is known where by dangerous nitrogen containing
contact with gaseous chlorine from liquid NCl3 could separate in a waste- compounds is safety critical, either
the electrolysis room. Also, the deci- water treatment where bleach was for the organic and inorganic compo-
sion to install a double block valve used to oxidize cyanide ions. After an nents. In particular, the presence of
system and ball valves on the drain agitation failure, the actuation of a ammonium ions may cause explosions
pipe from the washing column bottom bottom valve triggered the detonation. due to the formation of nitrogen tri-
to the re-boiler was wrong since a NCl3 was suspected to have collected chloride in the glass column.
NCl3 decomposition could have been in a dense layer in the vessel bottom.
anticipated in this closed pipe and in Direct chlorination would lead to the Accumulation of Unstable Chlorinated
the ball valve bodies. The name given same dangerous situation. It was men- Compounds in The Bulk Liquid Phase
to the equipment may be misleading. tioned that the pH was not well con- The accumulation of unstable chlori-
Of course the washing column may trolled and became too acidic despite nated products in the bulk liquid phase
wash also chlorinated organics from the fact that bleach was used. This is most likely when a solvent is used
gaseous chlorine and it is also a pre- would be even easier if direct chlorina- where this product is soluble. The most
cooler for gaseous chlorine before tion had been used. One should take common example is nevertheless the
compression. However, it is impor- care that NCl3 may be obtained in accumulation of NCl3 produced by
tant to state that this equipment is waste-water treatments using chlorine electrolysis of KCl or NaCl salt con-
also designed to collect nitrogen tri- or bleach as an oxidizer if the water taining ammonium ions, in a NCl3
chloride, a very unstable detonating contains ammonium ions, cyanides, removal process using extraction in
compound. Also the column re-boiler amines, amides, urea, ammonia or carbon tetrachloride. If NCl3 is not
is designed to evaporate chlorine from any ‘‘dangerous’’ nitrogen containing continuously thermally decomposed,
the carbon tetrachloride solution, but compound. high NCl3 concentrations in the CCl4
it is also a purge tank or a buffer tank In another incident, the cyanide solution are obtained with a potential
before the solution disposal if it is kept containing sludge produced by a cal- runaway decomposition hazard as
at low (0 to 5 8C) temperature or a cium carbide oven was submitted to described above.

10 Chemical Health & Safety, January/February 2005


Miscellaneous Examples occurs, the process situation is safer, hydrogen in chlorine, allowing gas-
however it is necessary to check for phase explosion to occur. In case of
Example of unstable compound low concentration of unstable chlori- the gas-phase ignition in residual
obtained by chlorination of oximes in nated compounds (NCl3, alcohol hypo- chlorine containing H2, the combus-
aqueous solution chlorites, others, etc.) in the bulk liquid tion heat can initiate the combustion of
The chlorination of organic com- phase. carbon steel in chlorine, causing a
pounds with a N–O bound will leave chlorine release to the atmosphere.
this chemical bound unaffected. For Therefore, total liquefaction is avoided
example the chlorination of organic GAS PHASE EXPLOSION HAZARDS by sending residual chlorine to a
nitro-compounds does not affect the bleach production unit or to an on-site
nitro groups. The chlorination of oxi- Gas Phase Explosion Hazards in consumer unit.
mes gives chloro-oximes or chloro- Chlorine Production The hydrogen produced by electro-
nitroso compounds8,9 which can In chlorine production by electrolysis lysis processes must be washed with
demix from aqueous solutions giving of NaCl or KCl brine or HCl solutions, caustic soda and dried before use in
an unstable dense oil. For example, the chlorine is obtained in the anodic com- burners or in other processes. When
chlorination of acetaldoxime gives the partment and hydrogen is obtained in hydrogen with trace concentration of
water soluble chloro-acetaldoxime the cathode compartment of the elec- chlorine is released to the atmosphere,
which isomerises to chloro-nitro- trolysis cell. In the mercury cell pro- spontaneous ignition of the stack exit
soethane, both unstable compounds. cess, hydrogen is evolved in the may occur, especially by sunny
The latter gives an unstable dimer, a amalgam decomposer, allowing a bet- weather.
blue oil, which demix from aqueous ter separation between chlorine and The corrosion of carbon steel con-
solutions. This blue oil may decompose hydrogen. In the diaphragm or mem- tainers by wet chlorine may produce
violently. brane cell process the partial mixing of enough hydrogen to allow the hydrogen
This is another example of the the two gases is more straightforward concentration in the container to rise
demixion of an unstable chlorinated and the quality of the two gas separa- above the LFL in chlorine, making a
compound from aqueous solutions. tion relies on the pressure equilibrium gas-phase explosion possible. The
This ends in process situations similar between the cathode and anode com- hydrogen is produced by the reaction
to NCl3 formation and demixion. partments and on the tightness of the of carbon steel with hydrochloric acid
cell assembly. formed by hydrolysis of chlorine giving
Example of unstable solid obtained by As hydrogen is flammable in chlor- hydrochloric acid and hypochlorous
chlorination reaction ine, explosions may occur if the com- acid. For this reason, it is important to
N-bromosuccinimide is a very com- position of the two gases enters the keep the water concentration in chlor-
mon brominating reactant. But what flammable range of H2 + Cl2 mixtures. ine below the recommended limit.
about N-chlorosuccinimide? This pro- The lower flammability limit of hydro-
duct can be obtained by radical or gen in chlorine is: 3.5 vol.% H2. Above Gas Phase Explosion Hazards in
photochemical chlorination of succi- this limit, the mixture is flammable and Chlorination Reactions
nimide in aqueous solution. After crys- may give violent explosions in vessels.
tallization, the wet solid is recovered The upper flammability limit of Continuous or loop gas phase reactors
but it must be handled with care. The hydrogen in chlorine is: 89 vol.% Gas phase explosion hazard is present
solid explodes on contact with iron. hydrogen. Up to this concentration, when chlorine is mixed with a fuel in
The use of a plastic shovel is recom- the mixture of hydrogen and chlorine the gas phase. The fuel may be hydro-
mended to handle it. is flammable. These limits concern the gen, a solvent or organic vapour,
combustion and deflagration of the gas ammonia, etc.
Recommendations mixture. When chlorine is reacted with a fuel
When chlorine is reacted with organic The mixtures of hydrogen and chlor- in a burner, as in the manufacture of
reactants, especially if nitrogen con- ine are known to detonate. The lower HCl from hydrogen and chlorine most
taining compounds or ammonium ions limit for the detonation of hydrogen in incidents occur when the burner is set
are present, the possible formation chlorine is: 17.5 vol.% H2, the upper on-stream, either by lighting the burner
of unstable chlorinated compounds limit of the detonation range is: with a pilot flame or by preheating the
should be considered. Any segregation 83 vol.% hydrogen. gas and the burner. Of course the gas
of a separate phase from the bulk liquid Many severe explosions of H2 + Cl2 mixture is in the flammable range and
is potentially dangerous and should be mixtures occurred in the history of the explosions occur due to mal-opera-
investigated carefully. The separation of electrolysis process due to process fail- tion.
an unstable liquid phase may induce a ure or incorrect operation. The gas Loop reactors are used to react
high vapour pressure of the unstable phase explosion hazard makes the chlorine with organic reactants in the
product in the gas phase because the total liquefaction of chlorine a difficult gas phase. The substrate may be hydro-
gas phase is in equilibrium with the process since the hydrogen concentra- carbons or mixtures of hydrocarbons
separated unstable liquid. This problem tion in the residual chlorine may rise with chlorinated hydrocarbons. In this
should be considered. If no segregation above the lower flammability limit of type of process, chlorine is the control-

Chemical Health & Safety, January/February 2005 11


ling reactant and the reaction is ture with the reactant, product, solvent (1) Lowering the fuel vapour pressure
controlled by the chlorine to substrate or reaction mixture vapour. Here blan- below the Lower Flammability
mole ratio to obtain the desired keting is difficult as in other oxidation Limit in chlorine by lowering the
product. Under normal operating processes because the oxidizer is process temperature.
conditions, the reaction mixture is bubbled through the liquid reaction (2) Raising the fuel vapour pressure
not flammable, the fuel (substrate) mixture. above the Upper Flammability
concentration is above the upper As far as possible, it is recommended Limit in chlorine by raising the
flammability limit. On reactor start- to keep the reactor gas phase composi- process temperature.
up, the reactor is preheated to a tem- tion outside the flammable range. Var- (3) Blanketing the gas phase by flush-
perature above the auto-ignition tem- ious methods are used: ing the reactor gas phase with an
perature, where the slow reaction
of chlorine with the substrate is active.
The substrate vapour is circulated
in the loop and then chlorine is fed
to the loop reactor. The reaction
of chlorine must be initiated immedi-
ately. As the chlorination reaction
is exothermic, cooling is provided
in the loop to control the temperature.
Problems may arise if the chlorina-
tion reaction does not start immedi-
ately. The chlorine concentration
will increase in the loop, the gas phase
composition will enter the flammable
range and on reaction initiation, the
reactor will explode. Of course, inter-
locks are necessary to interrupt the
chlorine inlet flow and provide blan-
keting to the gas phase if the reaction
exotherm is not detected immediately
on chlorine injection.
Continuous gas phase reactors are
used for the chlorination of butadiene
to obtain dichlorobutenes, intermedi-
ates in the production of chloroprene.
The start-up procedure is similar to
that of gas phase loop reactors and
also the process conditions above the
upper flammable limit of butadiene at
the process temperature. A good con-
trol of the start-up conditions is also
necessary.
When chlorine is reacted with a fuel
on a catalyst bed, incorrect operation
will result in catalyst burn-out or gas
phase explosion before or after the
catalyst. Here the determination of
the fuel gas flammable limits in chlor-
ine are of interest if the feed gas is not
in the flammable range in normal pro-
cess conditions.

Semi-batch or continuous gas/liquid


reactors
When chlorine is injected or bubbled
in a liquid phase containing a reactant
and/or a solvent in a stirred reactor,
chlorine evolution in the reactor gas
phase may produce a flammable mix- Figure 1. 20 L sphere for gas explosion experiments, open.

12 Chemical Health & Safety, January/February 2005


inert gas such as nitrogen, CO2, mined flammable range. This phenom- self-ignitions were observed as if the
HCl. enon can be explained as follows: ignition delay was reduced by the pre-
vious ignitions. The reactor wall was
To keep the reactor gas phase below - The self-ignition temperature of gas- found to be covered with a soot deposit
the LFL in chlorine (method 1) is the eous mixtures is not a clear-cut limit. produced by the combustion of diox-
safer method where only proper tem- It is best represented by an induction ane in chlorine.
perature control is necessary. period versus temperature relation. Further to this incident, the self-igni-
To keep the reactor gas phase above Self-ignition will be observed at tion of gas phase mixtures of dioxane
the UFL in chlorine (method 2) may lower temperature if a longer induc- and chlorine was thoroughly investi-
not be quite safe. On start-up the tem- tion period is allowed. gated by F. Battin-Leclerc.11,12 Diox-
perature must be set to the process - Near the self-ignition temperature, ane is sometimes mentioned as a
normal value ensuring enough fuel the flammable area is enlarged to a solvent for chlorination processes13
vapour pressure before chlorine injec- wide range of equivalence ratios. whereas self-ignitions of dioxane +
tion. If a condenser is used where the - When long induction periods are chlorine mixtures are easily obtained
fuel vapour pressure is depleted, the necessary, weak ignition sources near the ambient temperature.
gas flow composition may enter the can initiate the explosion, such as The flammable limits of dioxane +
flammable range. Glass condensers light, wall effects, tar deposits, cata- chlorine mixtures were determined in
are better not used or protected from lyst deposits on the wall, NCl3 a 4.6 L explosion vessel together with
light. decomposition flame.5,10 the explosion overpressures and max-
Blanketing (method 3) is a difficult - The slow reaction of chlorine with imum rates of pressure rise.13 The
technique when the chlorine flow evol- organic fuels may modify the gas explosion overpressures obtained are
ving from the liquid reaction mixture phase composition allowing it to of the same order of magnitude of that
may change as the reaction goes to enter the flammable range. of explosion of gaseous fuel in air but
completion. half of the expected thermodynamic
If chlorine does not evolve in the gas A combination of these influences may explosion overpressures in chlorine.
phase in normal process conditions, an explain the above mentioned self-igni- The gas phase detonation of gaseous
inert gas flush in the reactor gas phase tion phenomenon outside the flamma- mixtures of dioxane and chlorine was
is recommended (see below). If a ble range. successfully investigated in shock tubes
chlorine flow evolves from the liquid by A. Elaissi.14,15 The detonation pro-
reaction mixture unreacted, enough Example of self-ignition of solvent ceeds in shock tubes leaving behind a
inert gas flush must be provided in vapour in chlorine soot deposit, with a velocity half of that
the reactor gas phase to lower the In a chlorination process using diox- expected from the Chapman-Jouguet
chlorine concentration below the ane as a solvent, the reactor gas phase theory. This mixture was shown to be
minimum oxidizer concentration was found to present a self-ignition very sensitive to detonation compared
(MOC) of the fuel flammable range. phenomenon if chlorine was allowed to mixtures of fuel in air or oxygen.
If HCl is released in the gas phase, to evolve in the reactor gas phase. After The full investigation of this example
this gas contributes to the reactor gas a first ignition, a series of subsequent shows that mixtures of organic fuels
phase blanketing. However, one
should take into account rapid
changes in the process conditions, if
the wanted chlorination reaction stops
due to catalyst depletion or reactant
consumption. More unreacted chlor-
ine can be released in the gas phase, the
HCl production can disappear. There-
fore, monitoring of the gas phase chlor-
ine concentration using a chlorine
analyzer is recommended.

Self-ignition, Deflagration and


Detonation in the Gas Phase
Self-ignitions of gaseous mixtures con-
taining chlorine and a fuel, near the
ambient temperature, are known. Self-
ignitions can turn into severe deflagra-
tions or detonations.
Self-ignition occurs in mixtures with
a composition both in the flammable
range and outside the previously deter- Figure 2. 20 L sphere for gas explosion experiments, closed.

Chemical Health & Safety, January/February 2005 13


with chlorine can exhibit self-ignition Table 1. Flammability Limits of Gaseous Fuels in Chlorine Data of Mal’tseva17,18
followed by deflagration and detona- Fuel Temperature (8C) LFL (vol.%) UFL (vol.%)
tion thus explaining violent explosions
observed in the past. Hydrocarbons
CH4 20–22 5.6 63.0
C2H6 20–22 4.95 55.4
EXPERIMENTAL SET-UP TO STUDY C3H8 20–22 4.30 50.0
EXPLOSION LIMITS, EXPLOSION C4H10 20–22 3.31 49.5
CHARACTERISTICS AND SELF- C5H12 20–22 2.42 43
IGNITION OF GASEOUS MIXTURES
Alcohols
CH3OH 70 13.8 73.5
A new explosion vessel, a 20 L sphere, C2H5OH 83 5.06 64.1
was built to investigate gas phase C3H7OH 102 3.03 51.5
explosions with special attention for C4H9OH 120 2.53 48.8
experiments using chlorine as an oxi- C5H11OH 143 1.98 37.6
dizer. See Figures 1 and 2.
This new facility allows the measure- Carboxylic acids
ment of: HCOOH 105 27.62 82.0
CH3COOH 122 15.83 56.0
- The flammability limits of gaseous C2H5COOH 145 9.33 50.8
mixtures using various ignition C3H7COOH 170 7.81 49.8
sources: single spark, fusing wire, C4H9COOH 190 5.84 48.8
chemical ignition sources.
Chloro-alkanes
- The explosion characteristics, i.e.,
CH3Cl 20 10.2 56.0
explosion overpressure and maxi-
CH2Cl2 50 16.7 52.9
mum rate of pressure rise.
CHCl3 Not combustible
- The laminar burning velocity
C2H5Cl 20 8.98 49.2
deduced from the pressure–time hist-
1,2-C2H4Cl2 100 16.4 36.8
ory of the explosion.16 The pressure
C2H3Cl3 Not combustible
is recorded at a rate of 20,000
C3H7Cl 60 6.88 41.8
Points/s.
C3H6Cl2 100 9.95 35.0
- The self-ignition temperature and
C3H5Cl3 Not combustible
induction period of gaseous mix-
C4H9Cl 100 5.42 44.5
tures, down to a few minutes. Sam-
pling is possible to check for gas NB compositions are in percents by volume. Isomers are not specified. Refer to the original
phase reaction. papers.
- Flash points in chlorine.
of 10 to 20 bar according to the ing is ensured before ignition using a
The main features of this explosion
expected explosion pressure. The ves- propeller mixer. Central ignition is
vessel are:
sel temperature can be set between made using spark, hot wire or a pyr-
- Hastelloy C276 walls to lower wall ambient temperature and 300 8C. Mix- otechnic ignition source.
effects, i.e., to prevent the reaction of
chlorine with fuel before ignition, Table 2. Flammability Limits of Gaseous Fuels in Chlorine Data Published by
catalysed by stainless steel. Dokter19 and Medard20
- The vessel is made of two half- Fuel Temperature (8C) LFL (vol.%) UFL (vol.%) Reference
spheres connected through a flange
H2 3.5 89 19
assembly kept tight by clamps.
CH4 5.51 63 19
CH4 100 3.6 66 19
The upper half-sphere is fixed, CH4 200 0.6 19
the lower half-sphere is movable, using CH3Cl 10.2 63 19
a pneumatic jack, to allow quick open- C2H6 4.95 58.8 19
ing of the vessel for frequent cleaning.
Combustion in chlorine produces soot H2 8 86 20
deposits on the walls, which may pro- CH4 20 5.6 70 20
mote or prevent ignition of subsequent CH4 100 3.6 20
mixtures. Cleaning after each positive CH4 200 0.6 20
test is necessary to obtain reliable flam- C2H6 6.1 58 20
mable limits in chlorine. C3H8 5 40 20
The vessel design pressure is CH3Cl 10 63 20
200 bar, thus allowing initial pressure CH2Cl2 16 53 20

14 Chemical Health & Safety, January/February 2005


Table 3. Flammability Limits of Gaseous Fuels in Chlorine Dokter19 and Medard20 published
Fuel Temperature (8C) LFL (vol.%) UFL (vol.%) Apparatus some more data collected in Table 2,
together with interesting discussions.
CH3Cl 25 7 65 (C) Further flammability data obtained
C3H8 70a 2 60 (S) either using our 4.6 L stainless steel
C3H6Cl2 200b 4.5 (S) cylinder described in Ref. 13 (C) or
(CH3)3COCH3 60 2 33 (C) our 20 L Hastelloy C sphere (S) are
1,4-Dioxane 80 2.5 41 (C) given in Table 3.
CH3COOH 120 5 36 (C) Miscellaneous data can be found in
Acetone 60 4.5 60 (C) the literature, like the flammability lim-
Chloro-benzene 130 7.5 43.5 (S) its of benzene in chlorine:21 LFL = 8
Toluene 160 3.5 50 (S) vol.%, UFL = 52 vol%.
2-Chloro-toluene 150 5 45 (C) The experimental data is given under
Chloro-toluene 160 4 (S) atmospheric initial pressure, unless
Di-chloro-toluene 160 6 (S) otherwise specified.
Tri-chloro-toluene 160 9 (S)
2-Fluoro-toluene 100 4 37 (C) Self-ignition Temperatures
a b
(C): 4.6 L cylinder; (S): 20 L sphere. Po = 1.7 atmosphere abs. Po = 1.3 atmosphere abs. Data on self-ignition temperature of
gaseous mixtures of fuel and chlorine
are given by Mal’tseva,18 Dokter19 and
REVIEW OF FLAMMABILITY DATA was introduced after evacuation, and others. A collection of data is given in
OF GASEOUS MIXTURES allowed to vaporize. Then chlorine Table 4.
CONTAINING CHLORINE was admitted in the explosion vessel.
Mixing was only by molecular diffusion
Flammability Limits (no stirring). A 10 min waiting time was CONCLUSION
A review of flammability limits of gas- observed before ignition by a spark.
eous mixtures containing chlorine was Our comment on this method is that Owing to the importance of chemical
first given by Mal’tseva, Roslovskii and the wall material is correct, mixing is reactions involving free chlorine in the
Frolov.17,18 The experimental set-up poor or not effective and the waiting chemical industry, the collection of
used to obtain these data was a dou- time before ignition is too long and experiences and experimental data is
ble-wall vertical glass cylinder, 80 mm may have allowed the mixture to react of great interest. This should contri-
in diameter and 120 mm high. The before ignition. The results are sum- bute more to process safety than infor-
experiment initial temperature was set marized in Table 1 for the reader con- mation on less dangerous chemicals or
by thermostating the vessel. The fuel venience. processes. It is surprising that only
limited effort or support is devoted to
collect safety data on chlorination
reactions. The literature on the safety
Table 4. Auto-ignition Temperature of Gaseous Fuels in Chlorine of chlorination reactions is very lim-
ited compared to the literature on oxi-
Fuel AIT in Chlorine (8C) Author
dation reactions using oxygen. The
CH4 318 18 author hopes that this contribution
C2H6 280 18 will promote further experimental
Dimethyl ether Ambient 18 work in this field. The new 20 L explo-
C1–C3 carboxylic acids 300–320 18 sion vessel, specially designed to study
C4–C7 carboxylic acids 230–190 18 the flammability of gaseous mixtures
C2–C4 carboxylic anhydrides 290–215 18 containing chlorine as an oxidizer will
C3–C5 ketones 325–205 18 allow the determination of reliable
C1–C8 alcohols 225–210 18 data at a reasonable cost, for a wide
C2–C7 aldehydes 110–160 18 range of initial conditions.
H2 207 19
CH3Cl 215 19
CH2Cl2 262 19 References
C2H6 205 19 1. Gallucci, R. R.; Going, R. Chlorination
C3H6 150–100 19 of aliphatic ketones in methanol. J. Org.
1,2-C3H6Cl2 180 19 Chem. 1981, 46, 2532–2538.
Dioxane (0.26 ATA) 100 10,11 2. Sandmeyer, T. Uber aethyl and methyl-
hypochlorit. Berichte D. Chem. Ge-
Chloro-benzene >165 20 L sphere
sellschaft, 1886, Jahrg. XIX, 857–861.
C3H8 (1.7 ATA) 165 20 L sphere 3. Sandmeyer, T. Uber den Aethylester
C3H6 (1.7 ATA) 60 20 L sphere der unterchlorigen Säure. Berichte D.

Chemical Health & Safety, January/February 2005 15


Chem. Gesellschaft, 1885, Jahrg. XVIII, explosion of nitrogen trichloride: Ap- Chlore en Phase Vapeur. Thesis dis-
1767–1769. plication to the safety of chlorine sertation, University of Orleans,
4. Fort, Roland; Denivelle, Leon Recher- plants and chlorination processes. 7th France, 14 March 1994.
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16 Chemical Health & Safety, January/February 2005