REPORT: 1

T.R.
EGE UNIVERSITY
D E P ART M ENT O FC H E M
IC A L ENGINE ERING
KM Y 401 CHE M CI A L ENGINEERING DESIGN

PROJECT: FORMALIN
PRODU CTION

1.0
SUM MARY
INTRODUCTION
i

2.0
RESULTS
3
Submitted to: Prepared by:
2.1 PHY SICA L PROPERTIES
Prof. Dr. H. Ferhan ATALAY
5 05057361 Günter KULEŞOĞLU
Prof. Dr. Firuz BALKA 05057274 Duygu BAYRAKTAR
Assist. Dr. Zehra ÖZÇELĐK 05057288 Sinem ARMA Y
2.2 CHEMICAL REACTIONS 05057330 Ayça ATA
7
08.10.2008
2.1.1 DECOMPOSITION
BORNOV A/IZMIR
7

2.1.2 POLYMERIZATION
7
 7

2.1.4 AD DITION REACTIONS

8

8 C
2.1.5 CONDENSATION REACTIONS
ONTENTS
2.1.6 RESIN FORMATION
9

2.3 U S A G EARE A
9

2.4 S T ORA G E A N DTRANSPORTATION

11

2.5 TOXICOLOGY, OPERATIONAL HEALTH A N DPROCE S S SAFETY

13

2.5.1 A CU T ETOXICITY
14

2.5.2 C ANCE R EPIDEMIOLOGY

16

2.5.3 ANIMAL C ANCE R STUDIES

19

2.5.4 GENOTOXICITY
19

2.5.5 FIR E AN D E XPL O SIO N HAZARD

20

2.5.6 REACTIVITY
20

2.5.7 E M ERG E NCY AN D FIRST AID PROCEDURES

20

2.5.8 sp?ll, leak and d?sposal procedures

21

2.5.9 mon?tor?ng and measur?ng procedures

21

2.5.10 protect?ve equ?pment and cloth?ng

22

2.5.1 1 eng?neer?ng and controls

 2.5.12 med?cal surve?ll ance
23

2.5.13 env?ronmental ?ssues

24 SUMMARY

Formalin2.6
is econom?c
the aqueous aspects
form (37 wt%) of formaldeyhde produced mostly from
25 process. Because formaldehyde is highly water soluble, it is usually
methanol by an oxidation
marketed as a liquid solution, typically at 37 weight percent formaldehyde solution, combined
2.7 d?sposal
with water and up to 16 percent methanol. Recently, the production volume of formaldehyde
31
has grown rapidly with increasing demand in manufacturing sector for resins including
3.0
phnolic, urea, melamin, acetal many additives. Other additional application areas of
formaldehyde D ISCU S SIO
include N & CONCLUSIONS
surface coating, leather tanning, bindery applications, laminates,
insulation materials, etc. Also, formaldehyde is a preservative disinfection of bacteria.
32

4.0
Formalin is mainly manufactured by methanol oxidation of which processes are “
REFERENCES
excess methanol process” and “excess air process” and “combined cataylst process.” The
basic difference between
37them is the catalyst applied. The methanol excess process, called the
silver process, employs silver as the catalyst while the air excess process (molybdenum
5.0
process) uses metallic oxides of iron and molybdenum. In considering higher investment cost
apPend?CES
and more complicated operation than the silver process, it is recommended to use the silver
process. 38-45

Uses of formalin can be summarized as follows:

Phenol resin and adhesives, urea and melamine adhesives
Urea resin, melamine resin, hexamethy lenetetramine
Pentaerythritol, paraformaldehyde
Medicines and agricultural chemicals
Polyacetal resin
Hemiformal

Moreover, use of formaldeyhde derivatives and formalin are explained comprehensively

in Results part. Manufacturing processes of formalin are studied and the flow sheets of the
processes are given in the Appendix part. Also, there are known effects of formaldehyde and
its derivatives, therefore the needed information about its toxicology, exposure even
occupatioanl health and environmental issues are given in the Results section.
 1.0 INTRODUCTION
Since Blum’s proposal of formalin as a useful general biological fixative in 1893 it has
become an unsurpassed standard. For 119 years zoologists, botanists, histologists, and
pathologists have used formalin to preserve their materials for a detailed anatomical,
histological or cytological study. To pathologists it represents until now the only admissible
standard, in spite of the denounced toxicity of the product.
Formalin is an aqueous solution of formaldehyde. The typical concentration is 37 - 40
%. That is, it is expected that a commercial formalin has 370 - 400 g of formaldehyde in each
1000 g of commercial solution. The intended dilution is w/w, not vol/vol. Formaldehyde is a
nearly colorless gas with a pungent, irritating odor even at very low concentrations (below 1
ppm). Its vapors are flammable and explosive. Because the pure gas tends to polymerize, it is
commonly used and stored in solution. Formalin, the aqueous solution of formaldehyde (30%
to 50% formaldehyde), typically contains up to 15% methanol as a stabilizer. As
formaldehyde is self-reactive, and continues to oxidize in aqueous solution producing formic
acid, and in older solutions may even form a precipitate of paraformaldehyde (a solid
polymerized formaldehyde). Formalin solutions thus really contain formaldehyde,
paraformaldehyde, formic acid, and methanol.
Formaldehyde is used in the manufacture of plastics; urea-formaldehyde foam
insulation; and resins used to make construction materials (e.g., plywood), paper, carpets,
textiles, paint, and furniture.
The first industrial process for production of formalin, an aqueous solution of
formaldehyde, was based on oxidative dehydrogenation of methanol over a copper catalyst.
Improvements in catalyst technology resulted in substitution of the copper catalyst for an
unsupported silver catalyst, which is the formula still used today. In the 1950s a competing
process for production of formaldehyde was developed. This process was based on selective
(partial) oxidation of methanol over an Fe-Mo (molybdenum and iron) oxide catalyst. The
two processes, (Oxidation-dehydrogenation using a silver catalyst involving either the
complete or incomplete conversion of methanol; and the direct oxidation of methanol to
formaldehyde using metal oxide catalysts (Formox process)), referred to as silver and oxide
processes respectively, are used today for the production of formalin on the industrial scale.
Each process accounts for about 50% of the total production of formalin, which today
amounts to about 20Mton per annum, expressed as 37 wt% HCHO in water.
 In the silver process, vapourised methanol with air and steam is passed over a thin bed
o
of silver-crystal catalyst at about 650 C. Formaldehyde is formed by the dehydrogenation of
methanol. The heat required for the endothermic reaction is obtained by burning hydrogen
contained in the off-gas produced from the dehydrogenation reaction. The other process,
oxide process, involves the oxidation of methanol over a catalyst of Fe-Mo oxide. A mixture
of air and methanol is vapourised and passed into catalyst-packed reactor tubes. The reaction
o
which takes place at 350 C is highly exothermic and generates heat to provide steam for
turbines and process heating. Yields from both processes are around 90% to 92% but the
oxide process has a lower reaction temperature and the metal catalyst is cheaper than silver.
However, the silver process is still the most prevalent.
A wide range of alternative feedstocks have been considered but not found to be
economic. For example, a tiny amount is produced from the non-catalytic oxidation of
propane-butane mixtures. Formaldehyde can be produced from methane but a mixture of
products needs to be separated. It is also a byproduct of the oxidation of naphtha to acetic
acid.
Formaldehyde can cause irritation of the eyes, nose, and throat, even at low levels for
short periods. Longer exposure or higher doses can cause coughing or choking. Severe
exposure can cause death from throat swelling or from chemical burns to the lungs. Direct
contact with the skin, eyes, or gastrointestinal tract can cause serious burns. Drinking as little
as 30 mL (about 2 tablespoons) of formalin can cause death. Formate, a formaldehyde
metabolite, can cause death or serious systemic effects. Generally, more serious the exposure
to formaldehyde is the more severe are the symptoms. Previously sensitized persons may
develop a skin rash or breathing problems from very small exposures.
Formaldehyde has low cost, high purity, and variety of chemical reactions, so it has
become one of the world’s most important industrial and reasearch chemicals. More than 50
branches of industry now use formaldehyde, mainly in the form of aqueous solutions and
6
formaldehyde-containing resins. Worldwide production of formaldehyde is 3 ×10 t / a .
 2.0 RESULTS

Formaline process description information and other related information found in

literature during feasibility study is composed in a logical order. Firstly process description is
given as a result:
The direct synthesis of formaldehyde from hydrocarbons has not yet resulted in cost
reductions and because of the reactivity of formaldehyde, its handling and separation, as well
as its direct preparation from hydrocarbons, are difficult. These factors, in the past, have
exerted considerable influence on the pattern of formaldehyde growth.
Currently, the only and competing production technologies for formaldehyde of
commercial significance are based on the partial oxidation and dehydrogenation of methanol
using a silver catalyst, or partial oxidation of methanol using a metal oxide-based catalyst
since nearly all of the world's formaldehyde is made from methanol.
In the silver catalyst route, which is also known as Methanol Excess Process,
vaporized methanol with air and steam is passed over a thin bed of silvercrystal catalyst at
about 650°C. Formaldehyde is formed by the dehydrogenation of methanol. The heat required
for the endothermic reaction is obtained by burning hydrogen contained in the off-gas
produced from the dehydrogenation reaction.
The other route, which is also known as Air Excess Process, involves the oxidation of
methanol over a catalyst of molybdenum and iron oxide (Formox Process - developed and
licensed by Reichhold Chemicals). A mixture of air and methanol is vaporized and passed
into catalyst-packed reactor tubes. The reaction which takes place at 350ºC is highly
exothermic and generates heat to provide steam for turbines and process heating.
A high pressure version of the Formox Process called as Perstorp Process also exists,
which can be retrofitted to existing plants to boost capacity. The high conversion rate of the
process eliminates the need for methanol recovery via distillation, and it can produce
formaldehyde at concentrations up to 57%.

SILVER CATALYST PROCESS: The silver catalyst process employs two main reactions,
which are given below, to convert methanol to formaldehyde: Dehydrogenation and Partial
Oxidation.
CH 3OH → HCHO + H 2
CH 3OH + 1 → HCHO + H 2O
2
O2
 The equilibrium conversion in the dehydrogenation reaction is highly temperature
dependent. The amount of process air controls the temperature by supplying oxygen to the
exothermic reactions, including oxidation of hydrogen. The addition of inert materials such as
water or nitrogen can also aid conversion by permitting the use of higher methanol
concentrations relative to oxygen without entering the explosive region. These techniques
permit variations in the process:

Incomplete conversion plus separation and recycle of unreacted methanol,

Complete conversion.

The usual commercial form of the silver catalyst process involves incomplete
conversion of methanol at lower temperatures, which minimizes byproducts, followed by
distillation to remove and recycle the methanol. This allows the fine-tuning of the amount of
methanol in the final product.
Formaldehyde product may be produced at concentrations of up to 52- 55% by
adjusting the amount of water added in formaldehyde absorption. Methanol concentrations
can be adjusted as required (normally less than 1%) by distillation. In some cases, an ion
exchange unit is needed to reduce the formic acid concentrations, but most commercial
processes claim a figure of 0.06% without ion exchange.
The methanol conversion per pass is typically 75- 85%, and overall process yield of
formaldehyde from methanol is 90- 92 mol percent.
Impurities, particularly iron, determine the catalyst life. The catalyst bed has a
tendency to become matted under conditions of high temperature and throughput. Catalyst life
is typically one year and it may be electrolytically regenerated.
Although steam is generated internally, with most designs there is a net steam import
requirement. At a temperature of around 700°C, methanol conversion is sufficiently high to
dispense with the final distillation column.
A complete conversion process plant is similar to that described for incomplete
conversion, described above, in most other respects.

METAL OXIDE CATALYST PROCESS: The basis of the metal oxide catalyst process is the
vapor-phase oxidation of methanol with excess oxygen (from air) at temperatures of 250-
400°C.
 Metal oxides in the catalyst are typically molybdenum and iron at a molar ratio of 1.5
to 2.0 (Mo:Fe). Small amounts of oxides of vanadium, cobalt, phosphorus, chromium and
copper may also be included.

Further reactions can occur to some extent, depending on temperature. These include
the continued oxidation of formaldehyde to formic acid and carbon monoxide, and
dehydration of methanol to dimethyl ether.

A significant variation on this process is the absorption of the formaldehyde into a

urea solution to make urea-formaldehyde precondensate. This can be used for the production
of urea-formaldehyde resins, the largest single use of formaldehyde.

Recycle of inerts permits the use of relatively high methanol concentrations without
creating an explosive mixture. Oxygen concentration is kept to approximately 10%, whereas
methanol is around 6- 9%, both on a molar basis.

The Fe/Mo oxide catalyst is relatively insensitive to impurities such as iron carbonyls
in the methanol feedstock. In a typical design, the catalyst is supplied as rings, and a very
constant temperature profile is maintained by the use of a number of layers with different
catalytic activities. A typical catalyst life is 18 months.

Export steam from the process is around 0.5 pound per pound of product. Licensors
claim methanol conversion per pass of 92- 94%. Therefore, no distillation column is required
to recover and recycle methanol in the product stream. Maximum methanol content ranges
from between 0.5 and 1.0 percent for 37 weight percent product to 1.5 percent for 50 weight
percent product. The formaldehyde solution typically contains 0.02- 0.04 percent formic acid.
If required, the formic acid concentration can be further reduced in an ion exchangers.

2.1 PHYSICAL PROPERTIES

Formaldehyde, CH2O, formula weight 30.03 is the first member of the series
of aliphatic aldehydes, is a colorless gas at ambient temperature that has a pungent,
suffocating odor and an irritant action on the eyes and skin.
 Formaldehyde gas is flammable, its ignition temperature is 430 °C; mixtures with air
are explosive. At ca. 20 °C the lower and upper explosive limits of formaldehyde are ca. 7
and
3
72vol% (87 and 910 g/m ), respectively. Flammability is particularly high at a
formaldehyde
concentration of 65-70 vol %.
At a low temperature, liquid formaldehyde is miscible in all proportions with
nonpolar solvents such as toluene, ether, chloroform, or ethyl acetate. Polar solvents, such
as alcohols, amines or acids, either catalyze the polymerization of formaldehyde or react
with it to form methylol compounds or methylene derivatives.
Since pure formaldehyde is a gas at ordinary temperatures and cannot be readily
isolated or handled in this state, it is marketed chiefly in the form of its aqueous solutions.
Monomeric physically dissolved formaldehyde is only present in low concentrations
of up to 0.1 wt%. At ordinary temperatures, formaldehyde gas is readily soluble in water,
alcohols and other polar solvents. Dissolution of formaldehyde in water is exothermic, the
heat of solution (62 kJ/mol) being virtually independent of the solution concentration. Clear,
colorless solutions of formaldehyde in water can exist at a formaldehyde concentration up to
% wt 95, but the temperature must be raised to 120° C to obtain the highest concentrations.
Concentrated aqueous solutions containing more than 30 wt% formaldehyde becomes cloudy
on storage at room temperature, because larger poly glycols are formed which then precipitate
out. The partial pressure of formaldehyde in equilibrium with the solution is low, due to
solvation, and is a function of methylene glycol concentration rather than the total
formaldehyde content. Formaldehyde is apparently not appreciable associated in the gaseous
state, and its partial pressure may be regarded as the decomposition pressure of the dissolved
hydrate. These factors explain the fact that formaldehyde solutions may be concentrated by
vacuum evaporation at low temperatures, whereas pressure distillation at high temperatures
makes its possible to obtain concentrated distillates from dilute solutions. On distillation at
ordinary pressures without rectification, the still residue is always somewhat more
concentrated than the distillate solution. Fractional condensation of the vapors of boiling
solutions results in increasing ratio of formaldehyde to water in uncondensed vapors since
water is the least volatile constituent of the mixed vapor.
For more information on physical properties of formalin, see the MSDS given in
Appendix.
2.2 CHEMICAL REACTIONS

Formaldehyde is one of the most reactive organic compounds known and, thus, differs
greatly from its higher homologues and aliphatic ketones. Formaldehyde will
combine chemically with practically every type of organic chemical with the exception of
paraffin. It can be employed as in the form of monomer, solution or polymer with essentially
equivalent result. In general, the form used is of importance chiefly in its effect on the rate
of reaction. Monomeric and polymeric forms are of special value where the presence of
water is undesirable. Solutions and polymers are less reactive than the monomer, since they
represent lower energy potentials in which the aldehyde has already reacted with itself or
water. The most important reactions are treated as below:

2.2.1 DECOMPOSITION

At 150 °C, formaldehyde undergoes heterogeneous decomposition to form

mainly methanol and CO2. Above 350°C, however, it tends to decompose into CO and H2.
Metals such as platinum, copper, chromium, and aluminum catalyze the formation of
methanol, methyl formate, formic acid, CO 2, and methane.

2.2.2 POLYMERIZATION

Anhydrous monomeric formaldehyde cannot be handled commercially.

Gaseous formaldehyde polymerizes slowly at temperatures below 100 °C,
polymerization being accelerated by traces of polar impurities such as acids, alkalis, or water.
Thus, in the presence of steam and traces of other polar compounds, the gas is stable at ca.
20 °C only at a pressure of
0.25-0.4 kPa, or at a concentration of up to ca. 0.4 vol% at ca. 20 °C and atmospheric pressure.
Monomeric formaldehyde forms a hydrate with water; this hydrate reacts with
further formaldehyde to form polyoxymethylenes. Methanol or other stabilizers, such as
guanamines or melamines, are generally added to commercial aqueous formaldehyde
solutions (37-55 wt%) to inhibit polymerization.

2.2.3 REDUCTION AND OXIDATION

Formaldehyde is readily reduced to methanol with hydrogen over a nickel catalyst.

For example, formaldehyde is oxidized by nitric acid, potassium permanganate,
potassium dichromate, or oxygen to give formic acid or CO, and water,
In the presence of strong alkalis or when heated in the presence of acids,
formaldehyde undergoes a Cannizzaro reaction with formation of methanol and formic acid.
In the presence
of aluminum or magnesium methylate, paraformaldehyde reacts to form methyl formate
(Tishchenko reaction).

2.2.4 ADDITION REACTIONS

The formation of sparingly water-soluble sodium formaldehyde bisul-fite is an

important addition reaction of formaldehyde. Hydrocyanic acid reacts with formaldehyde
to give glycolonitrile. Formaldehyde undergoes an acid-catalyzed Pnns reaction in which it
forms a-hydroxy-methylated adducts with olefms .Acetylene undergoes a Reppe addition
reaction with formaldehyde to form 2-butyne-l,4-diol. Strong alkalis or calcium
hydroxide convert formaldehyde to a mixture of sugars, in particular hexoses, by a
multiple aldol condensation which probably involves a glycolaldehyde intermediate. Mixed
aldols are formed with other aldehydes; the product depends on the reaction conditions.
Acetaldehyde, for example, reacts with formaldehyde to give pentaerythritol, C(CH,OH)4 .

2.2.5 CONDENSATION REACTIONS

Important condensation reactions are the reaction of formaldehyde with amino groups
to give Schiff s bases, as well as the Mannich reaction. Amines react with formaldehyde
and hydrogen to give methyl-amines. Formaldehyde reacts with
ammonia to give hexamethylenetetramine, and with
ammonium chloride to give monomethylamine, dime- thylamine, or trimethylamine and
formic acid, depending on the reaction conditions. Reaction of formaldehyde with diketones
and ammonia yields imidazoles.
Formaldehyde reacts with many compounds to produce methylol (-CH2OH)
derivatives. It reacts with phenol to give methylolphenol, with urea to give mono-, di-, and
trimethylolurea, with melamine to give methylolmelamines, and with
organometallic compounds to give metal-substituted methylol compounds.
Aromatic compounds such as benzene, aniline, and toluidine combine
with formaldehyde to produce the corresponding diphenyl-methanes. In the
presence of hydrochloric acid and formaldehyde, benzene is chloromethylated to form
benzyl chloride.
Formaldehyde reacts with hydroxylamine, hydrazines, or semicarbazide to
produce formaldehyde oxime (which is spontaneously converted to triformoxime), the
corresponding hydrazones, and semicarbazone, respectively. Double bonds are also
produced when formaldehyde is reacted with malonates or with primary aldehydes or
ketones possessing a CH2 group adjacent to carbonyl group.
 2.2.6 RESIN FORMATION

Formaldehyde condenses with urea, melamine, urethanes, cyanamide, aromatic

sulfonamides and amines and phenols to give a wide range of resins.

2.3 USAGE AREA

Formalin is an aqueous solution of formaldehyde. Formaldehyde has been used for

many years in consumer goods to deter spoilage caused by microbial contamiantion. It has
been used as a preservative in household cleaning agents, dishwashing liquids, fabric
softeners, shoe-care agents, car shampoos and waxes, and carpet cleaning agents. Generally
the formaldehyde content in these products is less than 1%.
Formaldehyde is commercially offered as a 37 wt% to 50 wt% aqueous solution, with
37 wt% (known as formalin or formol) being the most widely used grade which may also
contain 0-15 wt% methanol and a polymerisation inhibitor. As formaldehyde is self-reactive,
and continues to oxidize in aqueous solution producing formic acid, and in older solutions
may even form a precipitate of paraformaldehyde (a solid polymerized formaldehyde).
Formalin solutions thus really contain formaldehyde, paraformaldehyde, formic acid, and
methanol.
Formaldehyde is used as a chemical intermediate in the manufacture of a large variety
of organic compounds, ranging from amino and phenolic resins to slow release fertilizers.
Products manufactured using organic compounds, where formaldehyde is used as a chemical
intermediate in their production, include: plywood adhesives, abrasive materials, insulation,
foundry binders, and brake linings made from phenolic resins, surface coatings, molding
compounds, laminates and wood adhesives made from melamine resins; phenolic
thermosetting, resins curing agents and explosives made from hexamethylenetetramine;
urethanes, lubricants, alkyd resins and multifunctional acrylates made from
trimethylolpropane; plumbing components from polyacetal resins; and controlled-release
fertilizers made from urea formaldehyde concentrates. Polyacetal plastics produced by
polymerization of formaldehyde are incorporated into automobiles to reduce weight and fuel
consumption. They are also used in the manufacture of functional components of audio and
video electronics equipment.
Formaldehyde solutions have also been used for disinfecting dwellings, ships, storage
houses, utensils, and clothing. Solutions containing 28% formaldehyde have been used as
germicides to disinfect inanimate objects. Formaldehyde is used as a tissue preservative and
disinfectant in embalming fluids.
In agricultural industry, formaldehyde has been used as a fumigant, as a preventative
for mildew and spelt in wheat, and for rot in oats. It has been used as a preplanting soil
sterilant in mushroom houses. Formaldehyde has been used as a germicide and a fungicide for
plants and vegetables; as an insecticide for destroying flies and other insects; and in the
manufacture of slow-release fertilizers. Approximately 80% of the slow-release fertilizer
market is based on urea-formaldehyde-containing products.
Formaldehyde continues to be used in the manufacture of glass mirrors, explosives,
artificial silk and dyes; for waterproofing fabrics; for preserving and coagulating rubber latex;
and for tanning and preserving animal hides. In photography industry, formaldehyde has been
used for hardening gelatin plates and papers, toning gelatin-chloride papers, and for chrome
printing and developing.
Formaldehyde is used as an antimicrobial agent in many cosmetic products, including
soaps, shampoos, hair preparations, deodorants, lotions, make-up, mouthwashes, and nail
products. Formaldehyde is incompatible with ammonia; alkalies; tannin; iron preparations;
and salts of copper, iron, silver, potassium permanganate, iodine, and peroxide. When it is
used as a preservative in shampoos, formaldehyde may interact unfavorably with both
fragrance components and color additives. Some cosmetics have reportedly contained 0.6%
formaldehyde, while concentrations as high as 4.5% have been detected in nail hardeners.
Formaldehyde concentrations in dry-skin lotions, creme rinses, and bubble bath oils have
reportedly ranged from 0.4 to 0.5%. Formaldehyde has also been found in sun-tan lotion and
hand cream, bath products, mascara and eye make-up, cuticle softeners, nail creams, vaginal
deodorants, and shaving creams. Trace amounts of formaldehyde found in cosmetic products
could also result from its use as a disinfectant of the manufacturing equipment.

Compared to its use in product manufacturing, the use of formaldehyde in the medical
fields is relatively small. Consumption in this area averages approximately 1.5% of the total
production volume. Some of the earlier, minor, medicinal applications for formaldehyde
included its use during vasectomies, as a foot antiperspirant or as a preservative in such
products, as a treatment for athlete’s foot, and as a sterilant for echinococcus cysts prior to
their surgical removal. In veterinary medicine, formaldehyde has been used therapeutically as
an antiseptic and as a fumigant. It has also been used to treat tympany, diarrhea, mastitis,
pneumonia, and internal bleeding in animals. In animal nutrition, formaldehyde is used to
protect dietary protein in ruminants. It is used as a food additive to improve the handling
characteristics of animal fat and oilseed cattle food mixtures.
Other industries using formaldehyde in their processes include the sugar industry
where formaldehyde is used as an infection inhibitor in producing juices; the rubber industry
where it is used as a biocide for latex, an adhesive additive, and an anti-oxidizer additive for
synthetic rubber; and the food industry where it is used for preserving dried foods,
disinfecting containers, preserving fish and certain oils and fats, and modifying starch for cold
swelling. It has been use as a bacteriostatic agent in some foods, such as cheese. In the
petroleum industry, formaldehyde is used as a biocide in oil well-drilling fluids and as an
auxiliary agent in refining. Formaldehyde has been used as an anti- corrosive agent for
metals. In the plastics industry, for the preparations of phenol, urea, and melamine resins,
where the presence of water could interfere with the production process, paraformaldehyde
may be used in place of aqueous formaldehyde solutions. In addition to its use in selected
pesticide applications, paraformaldehyde has also been used in making varnish resins,
thermosets, and foundry resins, the synthesis of chemical and pharmaceutical products, the
preparation of disinfectants and deodorants, and the production of textile products.
Formaldehyde was used in the textile industry as early as the 1950s when formaldehyde-
based resins were initially used to produce crease-resistant fabrics. Postproduction
analysis indicated that these early resins contained a substantial amount of extractable
formaldehyde (more than 0.4% by weight of the fabric. With the introduction of new
resins and other process modifications in the 1970s, the level of extractable formaldehyde
in crease-resistant fabrics gradually decreased to 0.01–0.02%.

2.4 STOR AGE AND TRANSPORTATION

With a decrease in temperature and/or an increase in concentration, aqueous

formaldehyde solutions tend to precipitate paraformaldehyde. On the other hand, as the
temperature increases, so does the tendency to form formic acid. Therefore, an appropriate
storage temperature must be maintained.
Table 2.1: Storage temperatures for commercial formaldehyde solutions.

Formaldehyde content, Methanol content, wt% Storage Temperature, °C

wt%

30 ≤1 7-10

37 <1 35

37 7 21

37 10-12 6-7

50 1-2 45*

50 1-2 60-65

*Stabilized with 200 mg/kg of isophthalobisguanamine.

The addition of stabilizers is also advisable (e.g., methanol, ethanol, propanol, or
butanol). However, these alcohols can be used only if they do not interfere with further
processing, of if they can be separated off; otherwise, effluent problems may be encountered.
The many compounds used for stabilizing formaldehyde solutions include urea,
melamine, hydrazine hydrate, methylcellulose, guanamines, and bismelamines. For example,
by adding as little as 100 mg of isophthalobisguanamine per kg of solution, a 40 wt%
formaldehyde solution can be stored for at least 100 days at 17 °C without precipitation of
paraformaldehyde, and a 50 wt% formaldehyde solution can be stored for at least 100 days at
40 °C.
Formaldehyde can be stored and transported in containers made of stainless steel,
aliminum, enamel, or polyester resin. Iron container lined with epoxide resin or plastic may
also be used, although stainless steel containers are preferred, particularly for higher
formaldehyde concentrations. Unprotected vessels of iron, copper, nickel, and zinc alloys
must not be used.
The flash point of formaldehyde solution is in the range 55-85 °C, depending on their
concentrations and methanol content. According to German regulations for hazardous
substances (Gefahrstoffverordnung, Appendix 6) and Appendix 1 of the EEC (European
Economic Community) guidelines for hazardous substances, aqueous formaldehyde solutions
used as working materials that contain ≥1 wt% of formaldehyde must be appropriately
labeled.
Formaldehyde should be stored in a cool, dry, well-ventilated area and properly
labeled. Formaldehyde should never be stored in vehicles except to transport to and from
field during sampling operations. Used formaldehyde, either from spill clean-up or from
activities generated from the process of change-out of sample containers must be stored in a
properly labeled hazardous waste container and made available for recycling under Resources
Conservation Recovery Act (RCRA) protocols. Storage of waste formaldehyde should be in
an area not frequented by the general population or duty workers and should be in an area not
subject to heat cycles and well ventilated.
Formaldehyde should be transported only in original container, fully labeled and
stored properly within the vehicle to prevent shifting, spillage or breakage. Formaldehyde
should never be opened, mixed or transferred to sample vials at any time inside a closed
vehicle. A Materials Safety Data Sheet (MSDS) should be in the possession of the user and
made available to those working with this chemical.
During operational use and/or during transportation where an accidental spill is likely
to occur, each field unit should have as part of their required emergency equipment, sufficient
absorbent material to handle small spills. Clean, 1 gallon plastic Nalgene containers with
Teflon screw caps, or equivalent, clearly labeled, should be available for small spills and for
transporting used formalin from the field to the laboratory for proper disposal. Care should be
exercised during clean-up that no person becomes dermally exposed to formaldehyde. If,
during the emergency, the spill occurs where there is insufficient ventilation to proceed with
clean-up, the area should be vacated immediately and others should be prevented from
entering the spill area unless properly suited and with a self- contained air supply. Proper
authorities should be notified if the spill occurs on a roadway or has potential to do harm by
entering a water supply or other bodies of water where there is a greater exposure potential to
humans and/or an aquatic ecosystem. A record of how much of the chemical was spilled and
the method of clean-up and proper disposal should be under-taken once the spill has been
contained and dealt with, not during the emergency. If exposed to formaldehyde, flush
exposed skin with copious amounts of water and remove contaminated clothing as quickly as
possible to prevent continued exposure.

2.5 TOXICOLOGY, OC CUPATIONAL HEAL T H AND PRO C ESS SAFETY

Formaldehyde is a colorless, pungent gas which polymerizes slowly at room

temperature. The four basic uses for formaldehyde include use as a bactericide or fungicide,
in the production of resins, as intermediates in the production of chemicals, and as a
component of end-use consumer items. Formaldehyde is also used as embalming fluid and in
textile treating to impart wrinkle-resistance to clothing.
Facilities reporting the highest exposures (0.1 to above 1.0 ppm) to formaldehyde
include those producing hardwood plywood, particle board, fiberboard and resins as well as
foundries, laboratories and funeral services. Industries in textile finishing, apparel
manufacturing, formaldehyde production and plastic molding have the next highest exposures
ranging from 0.1 to 1.0 ppm. A long list of facilities have exposures to low concentrations
(0.1 - 0.5 ppm), among them being pulp, paper and paperboard mills , softwood plywood
manufacturers, manufacturers of various cardboard and paper products, paint, pigment and
dye manufacturers, photo finishing labs, hemodialysis units, biology and veterinary labs, and
various facilities dealing with electrical devices.
Formaldehyde is an essential intermediate in cell metabolism in mammals and
humans. All tissues contain measurable amounts of formaldehyde, e.g., human blood 2-3
ppm.
Formaldehyde does not accumulate in the environment or in the human body because
it is rapidly oxidized or biodegraded. In the body, exogeneous formaldehyde is metabolized
with a half-life of 1.5 minutes into formic acid and carbon dioxide.

2.5.1 A CUT E TOXICITY

Formalin (aqueous formaldehyde) is highly acutely toxic with deaths occurring with as
little as 30 milliliters (ml, about one once) ingested. The inhalation of high concentrations of
formaldehyde is also extremely dangerous, with the IDLH (Immediately Dangerous to Life
and Health) concentration being 100 ppm. Accidental splash exposures into the eyes may
cause blindness especially in cases where immediate flushing of the eyes with water does not
occur.
Irritation of eyes, nose, throat and chest is an acute response to formaldehyde that
diminishes rapidly upon removal from exposure. OSHA (Occupational Safety and Health
Administration) reports that irritation complaints occur from employees manufacturing
particle board and molded plastics at levels of 0.4 to 1.0 ppm, by foundry care room workers
exposed to more than 1 ppm, by dialysis nurses exposed to 0.26 to 0.4 ppm, by embalmers
exposed to 0.25 to 1.39 ppm, by carpenters exposed to formaldehyde treated wood at 0.35
ppm, by textile finishers exposed at 0.16 to 1.2 ppm, and by garment workers with exposures
of 0.42 to 0.50 ppm. In an independent clinical study, irritation at concentrations up to 0.04
ppm in 2% to 4% of those tested was reported.
A major effect of formaldehyde on the skin is dermatitis, both irritant dermatitis and
"allergic" contact dermatitis which results in a small percentage of the population.
Formaldehyde had also been reported to cause hives. Although there is some absorption of
formaldehyde through the skin, it is not considered significant.
Formaldehyde has also been reported to cause asthma which may develop within
minutes of exposure or several hours after the exposure, either during the latter part of the
work day or after returning home. The development of asthma may be influenced by
continuous or intermittent exposures. Exposures to high concentrations for a short period
may be more hazardous in causing asthma than exposure to low concentrations over an
extended period.
Ingestion (Swallowing): Liquids containing 10 to 40% formaldehyde cause severe irritation
and inflammation to the mouth, throat, and stomach. Severe stomach pains will follow
ingestion with possible loss of consciousness and death. Ingestion of dilute formaldehyde
solutions (0.03-0.04%) may cause discomfort in the stomach and pharynx.
Inhalation (Breathing): Formaldehyde is highly irritating to the upper respiratory tract and
eyes. Concentrations of 0.5 to 2.0 ppm may irritate the eyes, nose, and throat of some
individuals. Concentrations of 3 to 5 ppm also cause tearing of the eyes and are intolerable to
some persons. Concentrations of 10 to 20 ppm cause difficulty in breathing, burning of the
nose and throat, cough, and heavy tearing of the eyes; 25 to 30 ppm causes severe respiratory
tract injury leading to pulmonary edema and pneumonitis. A concentration of 100 ppm is
immediately dangerous to life and health. Deaths from accidental exposure to high
concentrations of formaldehyde have been reported.
Skin (Dermal): Formalin is a severe skin irritant and a sensitizer. Contact with formalin
causes white discoloration, smarting, drying, cracking, and scaling. Prolonged and repeated
contact can cause numbness and a hardening or tanning of the skin. Previously exposed
persons may react to future exposure with an allergic eczematous and dermatitis or hives.
Eye Contact: Formaldehyde solutions splashed in the eye can cause injuries ranging from
transient discomfort to severe, permanent corneal clouding and loss of vision. The severity of
the effect depends on the concentration of formaldehyde in the solution and whether or not the
eyes are flushed with water immediately after the accident.
Note: The perception of formaldehyde by odor and eye irritation becomes less sensitive with
time as one adapts to formaldehyde. This can lead to overexposure if a worker is relying on
formaldehyde's warning properties to alert him or her to the potential for exposure.

2.5.2 CANC E R EPIDEMIOLOGY

Lung Cancer:
Several recently published epidemiological studies have been instrumental in the
development of the new formaldehyde regulations. Perhaps the most important as well as
controversial study was conducted and published by the National Cancer Institute (NCI). In
one of the largest cohort mortality analyses, 26561 workers employed prior to January 1, 1966
were studies for excess lung cancer. Investigators compared the mortality of formaldehyde-
exposed workers with that of the United States population, the local population and non-
exposed workers.
Although a significant increase in lung cancer was observed in the worker population,
the investigators (Blair, et al.) concluded that "these data provide little evidence that mortality
from cancer is associated with formaldehyde exposures at levels experienced by workers in
this study" primarily due to a lack of correlation between increased cancer risk and increased
dose (as measured by cumulative exposure). The investigators' comments were met with
much criticism from other scientists who reviewed the raw data from the study.
A five member Advisory Panel to the study concluded that, "The finding of a
significant increase in the risk for lung cancer...makes up particularly hesitant to characterize
this as a study with evidence to exonerate formaldehyde as a carcinogen." Likewise, the
National Institute for Occupational Safety and Health (NIOSH -- the research branch
affiliated with OSHA) concluded that, "Sufficient evidence exists...to conclude that there are
significant excesses of lung cancer...The absence of anexposure-response trend is not
sufficient cause to discount the observed lung cancer excesses..."
Federal OSHA agreed with both the Advisory Panel and NIOSH stating that a
significant increase in lung cancer can determine carcinogenicity even if the study failed to
establish a dose-response curve.
Two independent researchers (Sterling and Weikam) proceeded to statistically
reexamine the data from the NCI study. The researchers reconfirmed a significant lung
cancer excess. Among the criticisms submitted primarily by the Formaldehyde Institute and
Dupont, their analyses failed to correct for cigarette smoking as well as other items. OSHA
defined their analyses by noting that the percentages of deaths resulting from lung cancer in
formaldehyde-exposed workers were excessively high and significant.
Another independent researcher (Sielken) took the raw data from the NCI study and
correlated the formaldehyde exposure data with the likelihood of dying from cancer of the
respiratory system and lung cancer.
The United Auto Workers (UAW) reanalyzed a section of the NCI study and
concluded an increasing likelihood of death due to lung cancer. They also discovered that
persons exposed at the highest cumulative doses were less likely to smoke because of
formaldehyde's irritant effects.
In summary, OSHA's position was that there was no dose-response relationship in the
NCI study due to exposure misclassifications and due to the fact that cigarette smoking was
not evident in workers with the highest cumulative doses. OSHA supported the study's
finding that there was a significant increase in lung cancer in workers with 20 or more years
of latency. They also noted the probability of a trend of an increased risk of lung cancer with
an increase in the average level of formaldehyde exposure.
OSHA also noted a British study of lung cancer which concluded a significant excess
of lung cancer among workers at the highest exposure level (greater than 2.0 ppm) after
comparison with national rates of lung cancer. A significant increase in risk of death from
chronic bronchitis was also observed. A possible dose-response relationship was noted.
Although the authors downplayed the validity of their cancer results due to the high national
rates of lung cancer, OSHA discounted their downplay and supported the study's findings.
Nasopharyngeal Cancer:
The NCI study also noted an "increased risk of death from cancer of nasopharynx with
an increased cumulative exposure to formaldehyde (however) a not statistically significant
(but) a striking dose-response gradient was observed by the authors." OSHA supported the
importance of the study in relating formaldehyde concentration to nasopharyngeal cancer.
Excursions to levels exceeding 4 ppm were noted. Cancer was also observed in workers
exposed to high concentration for less than 1 year. The Formaldehyde Institute and
Cyanamid Company criticized the study stating that the formaldehyde exposure was
mixed with a particulate exposure, that there were only 3 cancer cases of the 7 total who
were exposed for less than 1 year and that there were no cases observed in workers with the
highest cumulative exposure. OSHA regarded the criticisms as insignificant.
In another study conducted by an independent researcher (Vaughan et al.) in the state
of Washington, residents living in mobile homes exposed to formaldehyde through
formaldehyde-treated building materials, as well as occupations dealing with resin and glue
work (i.e., carpenters with less than a 0.5 ppm exposure, and furniture assemblers, cabinet
makers and sewing machine operators having exposures greater than 0.5 ppm) were studied.
Due to the extremely low exposure potential and cancer risk observed in most of the workers,
OSHA concluded that is was inappropriate to conclude that the occupational study was
negative even though excess cancer was not observed.
On the other hand, the residential exposures were greater than the workplace
exposures from the standpoint of cumulative dose. Exposures lasting up to 168 hours
(compared to typical 40 hour a week work exposures) were observed with concentrations in
new mobile homes of years ago averaging as much as 0.5 ppm. OSHA determined that
formaldehyde exposure is probably associated with the development of nasopharyngeal
cancer in humans. Although rare, nasopharyngeal cancer existed with a background rate of
approximately half of that seen in home residents.
Oral Cancer:
The National Institute of Occupational Safety and Health (NIOSH) conducted a study
on workers exposed to formaldehyde in the garment industry manufacturing permanent press
garments. Workers were exposed for at least 3 months to concentrations of o.14 to 0.17 ppm.
The investigators reported excess oral cancer. OSHA, however, severely criticized the study
stating that "some evidence of an association between formaldehyde exposure and oral cancer
(existed) but not necessarily a causal relationship." OSHA criticized the study for limited
latency periods, a middle-aged female population and a low percentage (5.5%) of deaths from
cancer.
Brain Cancer:
Brain cancer has been reported in pathologists, anatomists, morticians, embalmers and
funeral directors exposed to embalming fluid or other tissue preservatives containing
formalin. Exposure concentrations were not given. OSHA stated that the exposure
"probably" contributed to the excess risk of brain cancer observed in professional workers but
was unable to reach a determination that brain cancer is caused by exposure to formaldehyde.
Other Cancers:
Leukemia has been reported in embalmers. OSHA's position was similar to that stated
above for reports of brain cancer.
 2.5.3 ANIMAL C ANCER STUDIES

Several laboratories have studied cancer in animals. The one of greatest interest was
conducted by Battelle Columbus Laboratories for the Chemical Industry Institute of
Toxicology (CIIT). 120 male and female animals of each of two species, one rat and one
mouse, were exposed for 6 hours/day, 5 days a week at concentrations averaging 2.0, 5.6, and
14.3 ppm in an inhalation experiment for 24 months (the average lifespan of a rodent). In the
rats, there was a significant increase in nasal cancers at the highest concentration. The
numbers of nasal cancers in mice was insufficient to show statistical significance, but were
considered formaldehyde related due to pathological examination. No increases in leukemia,
lymphomas, or brain cancer were observed.
Other studies support their finding of nasal cancer. New York University conducted
studies in which formaldehyde was administered in a strain of rats different from that used in
the CIIT study. OSHA concluded that the NYU studies confirmed that exposure to
formaldehyde can cause cancer in animals. An independent inhalation animal study (Tobe et
al.) also reported nasal cancer after formaldehyde exposure even though only a small number
of animals were used in the experiment. An inhalation hamster study conducted by yet
another independent laboratory reported no tumors, but due to the many scientific flaws in the
study (decreased rodent survival time, limited experience at detecting tumors) OSHA
discounted the study.
Other studies have been conducted demonstrating that formaldehyde applied topically
to the skin of laboratory animals does not cause cancer.
OSHA concluded that the finding of nasal cancer in two strains of rats in three
independent studies on formaldehyde alone to be extremely strong and reproducible evidence
that formaldehyde is an animal carcinogen. Evidence of a dose-response relationship, finding
cancers of identical cell-type and location in two species and evidence that formaldehyde is
genotoxic strengthens the scientific relationship of formaldehyde exposure causing cancer.

2.5.4 GENOTOXITY

Formaldehyde appears to be capable of binding to DNA, a well known mechanism by which

chemicals cause cancer. Formaldehyde appears to be both an initiator and a late stage cancer
causing chemical.
 2.5.5 FIRE AND EXPLOSION HAZARD

Moderate fire and explosion hazard when exposed to heat or flame. The flash point of
37% formaldehyde solutions is above normal room temperature, but the explosion range is
very wide, from 7 to 73% by volume in air. Reaction of formaldehyde with nitrogen dioxide,
nitromethane, perchloric acid and aniline or peroxyformic acid yields explosive compounds.

Extinguishing Media: Use dry chemical "alcohol foam", carbon dioxide, or water in
flooding amounts as fog. Solid streams may not be effective.

2.5.6 REACTIVITY

Stability: Formaldehyde solutions may self-polymerize to form white precipitates.

Incompatibility (Materials to Avoid): Strong oxidizing agents, caustics, strong alkalis,
isocyanates, anhydrides, oxides, and inorganic acids. Formaldehyde reacts with hydrochloric
acid to form the potent carcinogen, bis-chloromethyl ether. Formaldehyde reacts with nitrogen
dioxide, nitromethane, perchloric acid and aniline, or peroxyformic acid to yield explosive
compounds. A violent reaction occurs when formaldehyde is mixed with strong oxidizers.
Hazardous Combustion or Decomposition Products: Oxygen from the air can oxidize
formaldehyde to formic acid, especial when heated. Formic acid is corrosive.

2.5.7 EMERGENCY AND FIRST AID PROCEDURES

Employees and students must notify their immediate supervisor or instructor of all
illness and injuries related to exposure to hazardous chemicals. Contact your supervisor if you
have any questions regarding the procedure for treating a non-serious injury or illness.
Ingestion (Swallowing): If the victim is conscious, dilute, inactivate, or absorb the ingested
formaldehyde by giving milk, activated charcoal, or water. Any organic material will
inactivate the formaldehyde. Keep affected person warm and at rest. Get medical attention
immediately. If vomiting occurs, keep head lower than hips.
Inhalation (Breathing): Remove the victim from the exposure area to fresh air
immediately. Do not enter areas with high levels of formaldehyde. Wait for rescuers with
appropriate respiratory protection equipment. If breathing has stopped, give artificial
respiration. Keep the affected person warm and at rest until ambulance arrives.
Skin Contact: Remove contaminated clothing (including shoes) immediately. Wash the
affected area of your body with soap or mild detergent and large amounts of water until no
evidence of the chemical remains (at least 15 to 20 minutes). Get medical attention after
washing affected area.
Eye Contact: Wash the eyes immediately with large amounts of water occasionally lifting
lower and upper lids, until no evidence of chemical remains (at least 15 to 20 minutes). Get
medical attention immediately. If you have experienced appreciable eye irritation from a
splash or excessive exposure, you should be referred promptly to an ophthalmologist for
evaluation.

2.5.8 SPILL, L EAK , AND DISPOSAL PROCEDURES

Occupational Spill: Take up small spills with absorbent material and place the waste
into properly labeled containers for later disposal. In the event of a large spill, alert personnel
in the area that a spill has occurred. Do not attempt to handle a large spill of formaldehyde.
Vacate the laboratory immediately and call for assistance.

2.5.9 MONITORIG AND MEASUREMENT PROCEDURES

Monitoring Requirements: If the exposure to formaldehyde exceeds 0.5 ppm action level
or the 2 ppm STEL, employer must monitor the exposure. Employer need not measure every
exposure if a "high exposure" employee can be identified. This person usually spends the
greatest amount of time nearest the process equipment. If you are a "representative
employee", you will be asked to wear a sampling device to collect formaldehyde. This device
may be a passive badge, a sorbent tube attached to a pump, or an impinger containing liquid.
You should perform your work as usual, but inform the person who is conducting the
monitoring of any difficulties you are having wearing the device.
Evaluation of 8-hour Exposure: Measurements taken for the purpose of determining time-
weighted average (TWA) exposures are best taken with samples covering the full shift.
Samples collected must be taken from the employee's breathing zone air.
Short-term Exposure Evaluation: If there are tasks that involve brief but intense exposure to
formaldehyde, employee exposure must be measured to assure compliance with the STEL.
Sample collections are for brief periods, only 15 minutes, but several samples may be needed
to identify the peak exposure.
Monitoring Techniques: OSHA's only requirement for selecting a method for sampling and
analysis is that the methods used accurately evaluate the concentration of formaldehyde in
employees' breathing zones. Sampling and analysis may be performed by collection of
formaldehyde on liquid or solid sorbents with chemical analysis. Sampling and analysis may
also be performed by passive diffusion monitors and short-term exposure may be measured by
instruments such as real-time continuous monitoring systems and portable direct reading
instruments.
Notification of Results: Your employer must inform you of the results of exposure
monitoring representative of your job. You may be informed in writing, but posting the results
where you have ready access to them constitutes compliance with the standard.

2.5.10 PROTECTIE EQUIMENT AND CLOTHING

Clothing: Material impervious to formaldehyde is needed if the employee handles

formaldehyde solutions of 1% or more. Other employees may also require protective clothing
or equipment to prevent dermatitis.
Respiratory Protection: Contact Supervision if you believe respirators are required.
Protective Gloves: Wear protective (impervious) gloves provided by your employer, at no
cost, to prevent contact with formalin. Y our employer should select these gloves based on the
results of permeation testing and in accordance with the ACGIH Guidelines for Selection of
Chemical Protective Clothing.
Eye protection: If you might be splashed in the eyes with formalin, it is essential that you
wear goggles or some other type of complete protection for the eye. You may also need a face
shield if your face is likely to be splashed with formalin, but you must not substitute face
shields for eye protection. (This section pertains to formaldehyde solutions of 1% or more.)
Other Protective Equipment: You must wear protective (impervious) clothing and
equipment provided by your employer at no cost to prevent repeated or prolonged contact
with formaldehyde liquids. If you are required to change into whole-body chemical protective
clothing, your employer must provide a change room for your privacy and for storage of your
street clothing. If you are splashed with formaldehyde, use the emergency showers and
eyewash fountains provided by your employer immediately to prevent serious injury. Report
the incident to your supervisor and obtain necessary medical support.
 2.5.11 ENGINEERING CONTROLS

Ventilation is the most widely applied engineering control method of reducing the
concentration of airborne substances in the breathing zones of workers. There are two distinct
types of ventilation.
Local Exhaust: Local ventilation is designed to capture airborne contaminants as near to the
point of generation as possible. To protect you, the direction of contaminant flow must always
be toward the local exhaust system inlet and away from you.
General (Mechanical): General dilution ventilation involves continuous introduction of
fresh air into the workroom to mix with the contaminated air and lower your breathing zone
concentration of formaldehyde. Effectiveness depends on the number of air changes per hour.
Where devices emitting formaldehyde are spread out over a large area, general dilution
ventilation may be the only practical method of control.
Work Practices: Work practices are an important part of a control system. If you are asked
to perform a task in a certain manner to limit your exposure to formaldehyde, it is extremely
important that you follow these procedures.

2.5.12 MEDICAL SURVEILLANCE

Medical surveillance helps to protect employees' health. Your employer must make a
medical surveillance program available at no expense to you and at a reasonable time and
place if you are exposed to formaldehyde at concentrations above 0.5 ppm as an 8-hour
average or 2 ppm over any 15 minute period. You will be offered medical surveillance at the
time of your initial assignment and once a year afterward as long as your exposure is at least
0.5 ppm (TWA) or 2 ppm (STEL). Even if your exposure is below these levels, you should
inform your employer if you have signs and symptoms that you suspect, through your
training, are related to your formaldehyde exposure because you may need medical
surveillance to determine if your health is being impaired by your exposure.
The surveillance plan includes: (a) A medical disease questionnaire. (b) A physical
examination if the physician determines this is necessary. If you are required to wear a
respirator, your employer must offer you a physical examination and a pulmonary function
test every year. The physician must collect all information needed to determine if you are at
increased risk from your exposure to formaldehyde. At the physician's discretion, the medical
examination may include other tests, such as a chest x-ray, to make this determination. After a
medical examination the physician will provide your employer with a written opinion which
includes any special protective measures recommended and any restrictions on your exposure.
The physician must inform you of any medical conditions you have which would be
aggravated by exposure to formaldehyde. All records from your medical examinations,
including disease surveys, must be retained at your employer's expense.

2.5.13 ENVIRONMENTAL ISSUES

Formaldehyde is a naturally occurring substance in the environment made of carbon,

hydrogen and oxygen. According to the U.S. Environmental Protection Agency, natural
processes in the upper atmosphere may contribute up to 90 percent of the total formaldehyde
in the environment (WHO, International Programme on Chemical Safety, Concise
International Chemical Assessment Document: Formaldehyde). Since formaldehyde is a by-
product of combustion, cars and trucks emit formaldehyde, as does burning wood.
Formaldehyde does not accumulate in the environment, because it is broken down within a
few hours by sunlight or by bacteria present in soil or water. Humans metabolize
formaldehyde quickly, so it does not accumulate in the body.
Formaldehyde manufacture and use represent only a partial source of formaldehyde in
the environment. Formaldehyde in the atmosphere results primarily from incomplete
combustion of hydrocarbons, as well as photochemical oxidation of unconverted
hydrocarbons from combustion sources.
Table 2.2 - Contribution to atmospheric formaldehyde

Emission Source Percent

Motor vehicle and aircraft exhausts 53-63

Photochemical reactions (largely from hydrocarbons in 19-32

exhausts)

Combustion plants, incinerators 13-15

Petrochemical refineries 1-2

Formaldehyde production plants 1

 Indoor formaldehyde levels are also of concern. It is known that formaldehyde-based
products such as resins and UF foam insulations contribute small amounts of formaldehyde to
the air. Some representative products include carpeting, floor and ceiling tiles, pressed wood
products, and linedair ducts. With time, formaldehyde decomposes in both the atmosphere
and normal nonsterile water. The initial oxidation product, formic acid, is a component of
acid rain. Because of its high solubility there will be efficient transfer into rain and surface
water which may be an important sink. Additional quantities are removed by dry deposition or
by dissolving in the ocean and other surface waters.
Although discharges to watercourses are strictly limited in most countries,
formaldehyde is not subject to the stringent controls that apply to bioaccumulating substances.
Specific concerns about formaldehyde are largely focused on the health impact on humans of
atmospheric formaldehyde in the workplace or home.
The International Agency for Research on Cancer (IARC), part of the World Health
Organization, recently has reclassified formaldehyde from group 2A “probably carcinogenic
to humans” to group 1 “carcinogenic to humans”. This move was made based on a finding of
“sufficient evidence that formaldehyde causes nasopharyngeal cancer in humans”, affecting
the nasal cavity and paranasal inuses.
As a result of health concerns, most countries in the developed world classify
formaldehyde as a toxic compound and require strict handling procedures and labeling of
products. Many countries have imposed stringent limits on the concentration of
formaldehyde, both in the workplace and home, and have also imposed standards on products
such as particle board. The product standards may be expressed as a direct limit on the
formaldehyde concentration, or as a maximum emission value for the product.

2.6 ECONOMIC ASPECTS:

Formaldehyde is one of the most important basic chemicals and is required for the
manufacture of thousands of industrial and consumer products. It is the most important
industrially produced aldehyde.
The formaldehyde industry provides thousands of jobs where workers are employed
directly in producing the chemical and managing its marketing, sale and distribution. These
workers operate and maintain the formaldehyde production facilities, and have responsibility
for management, research and development, sales and marketing. Beyond these jobs derived
direcly from formaldehyde, hundreds of thousands of workers are supported indirectly
through formaldehyde.
 Formaldehyde’s chemistry makes it an extremely versatile contributor to the
production of hundreds of items that improve everday life. Some studies have made and the
results shows that, in the United States, production of formaldehyde and formaldehyde-
containing goods accounts for more than five percent of the yearly U.S. Gross National
Product (GNP) –or about $500 billion out of a GNP exceeding $10 trillion. Formaldehyde’s
wide-ranging use makes it essential to operations of nearly 50,000 U.S. facilities in 17 major
industries, and it serves as a basic raw material in another 70 industries. Annual U.S.
formaldehyde production exceeds five million metric tons.
Formaldehyde is the most important commercially aldehyde (class of highly reactive
organic chemical compounds obtained by oxidation of primary alcohol), according to the
most recent CEH Marketing Research Report on Formaldehyde from SRI International. More
than half of all formaldehyde is used primarily to make urea-, phenol-, melamine-
formaldehyde (UF, PF and MF) resins and polyacetal resins- altogether a business valued at
nearly $ 10 billion. If urea formaldehyde resins were not available to the industries that use
them, the additional cost to consumers in the United States and Canada would approach $3.5
billion annually.
If phenol formaldehyde resins were not available to the building, construction,
automotive and other industries that use them, the additional cost to consumers in the United
States and Canada would approach $4.65 billion annually.
If melamine formaldehyde resins were not available to the textile, surface coatings and
other industries that use them, the additional cost to consumers in the United States and
Canada would approach $365 million annually.
If polyacetal resins were not available to the numerous industries that use them, the
additional cost to consumers in the United States and Canada would approach $220 million
annually.
Manufacturing Regions of Formalin:
• China (mainland), • Indonesia, • Hungary,
• Iran, • Japan, • Myanmar
• India, • Pakistan, • Netherlands,
• South Korea, • Russian • Singapore
Federation,
• Taiwan,
• Turkey,
• United Arab Emirates,
• Ukraine,
• Vietnam,
• Egpyt
• Philippines,
• Germany,
 Main Export Markets:

• Western Europe,
• North America,
• Africa,
• South America,
• Mid East,
• Southeast Asia,
• Eastern Asia,
• Eastern Europe,
• Ocenia

Some formaldehyde manufacturers in the U.S. are:

Borden Chemical,
Georgia-Pacific Resins, Inc.,
Capital Resin Corporation,
GEO Specialty Chemicals, Inc.,
Celenase Ltd. Chemicals Division,
Hercules Incorporated,
Perstorp Polyols,
D.B. Western, Inc.,
Praxair, Inc.,
Dupont Chemical Solutions Enterprise,
Solutia Inc.,
Dynea USA, Inc.,
Wright Chemical Corporation.
 Table 2.3 - Producers and their capacities

PRODUCER CAPACITY*
Borden Chemical, (18 sites) 4,600
Capital Resin, Columbus, OH 100
Celanese, Bishop, TX; Rock Hill, SC 1,730
D.B. Western, Virginia, MN 40
Degussa, Theodore, AL 215
DuPont, LaPorte, TX; Parkersburg, WV 900
Geo Specialty Chemicals, (Trimet) Allentown, PA 135
Georgia-Pacific (14 sites) 2,510
Hercules (Aqualon), Louisiana, MO 170
ISP, Calvert City, Ky.; Texas City, TX 200
Neste Resins (5 sites) 900
New Mexico Adhesives, Las Vegas, NM 50
Perstorp, Toledo, OH 450
Praxair, Geismar, LA 140
Solutia, Alvin, TX 200
Wright Chemical, Riegelwood, NC 160
Total 12,500

*Millions of pounds per year on a 37 percent basis. Commercial production is from methanol
either by silver catalyst or metal oxide catalyst processes. 70 to 80 percent of formaldehyde
output is used captively.

In 1998 Geo Specialty Chemicals purchased Trimet from Mallinckrodt and Borden
Chemical acquired Spurlock Industries and its plants in Waverly, VA, and Malvern, AR,
adding another 275 million pounds of capacity. In 2000, Borden Chemicals and Plastics sold
its formaldehyde business, including the recently upgraded, 1,470 million pound Geismar, LA
facility, to Borden Chemical.

In 1999, International Specialty Products ended formaldehyde production in Calvert

City, KY, and closed the Texas City, TX plant the next year, eliminating 200 million pounds
per year in total.

Perstorp expanded its Toledo plant by 140 million pounds, increasing capacity at the
site to 450 million pounds in 1999.
 In 2000, Georgia-Pacific acquired the formaldehyde of Celanese, but not the
production facility at Rock Hill, SC According to a long-term manufacturing agreement,
Georgia-Pacific will utilize the formaldehyde output of the Rock Hill plant to supply third
parties including former customers of Celanese.

Subsequent to the formaldehyde acquisition from Celanese, Georgia-Pacific

announced it is divesting its chemicals division and intends to sell the division as a single
unit. The business includes formaldehyde and its derivative resins. No buyer has thus far been
identified.

Seven producers in Canada have combined total capacity for about 1,800 million
pounds per year of formaldehyde; Mexico's capacity totals about 510 million pounds from
eleven producers.
Demand in 1999: 9,623 million pounds; 2000: 9,702 million pounds; 2004: 10,096 million
pounds, projected. Demand equals production plus imports (1999: 82 million pounds; 2000:
62 million pounds) less exports (1999: 21 million pounds; 2000: 18 million pounds).

GROWTH Historical (1995 - 2000): 1.8 percent per year; 1.0 percent per year through 2004.

PRICE Historical (1995 - 2000): High, $0.24 per pound, 37 percent methanol-free
(uninhibited) tanks, f.o.b. Gulf; low, $0.13, same basis. Current: $0.21, same basis.

STRENGTH: Formaldehyde use in production of acetylenic chemicals (butanediol), MDI and

acetal resins continues growing at about 5 percent. These uses currently account for one-third
of formaldehyde demand.

WEAKNESS: In March, housing starts fell another 1.3%, to an annual rate of 1.61 million
units. In 2000, the rate stood approximately at 1.70 million units. This decrease depresses
demand for formaldehyde in urea- and phenol-formaldehyde resins used in particleboard and
plywood, respectively. These two classes of thermosetting resins consume more than one-
third of formaldehyde demand.

OUTLOOK: Formaldehyde demand is softening as housing and construction have declined.

Most large-volume formaldehyde contracts are tied to methanol and natural gas pricing, so
major customers are generally paying twice what they did a year ago, even though list pricing
for 37 percent material is $0.21 per pound. Natural gas remains around $5.25 to $5.50 per
million BTUs, down substantially from its high of $9 to $10 winter in 2000, but still around
twice its traditional value. Some analysts expect gas prices to continue falling, but others warn
that a summer surge in electricity demand could send gas back up around $7. Formaldehyde
capacity has always exceeded demand by a substantial margin, and this situation will continue

Prices of formaldehyde are closely linked to and generally track its methanol
feedstock. In Europe, formaldehyde is usually traded regionally over small distances and so
prices vary according to country and are unofficially set on a quarterly contract basis. In the
US, most large volume formaldehyde contracts are tied to methanol and natural gas pricing,
sometimes leading to a large delta between contract and spot prices. Companies in
formaldehyde sector in Turkey are:

Çağlayan Kimya San.Tic.LTD.ŞTĐ.,

Topçu Kimya Nak. ve Tic.,
Saf Su Oya Kimya,
Turca Kimyevi Maddeler Tic. LTD.,
Mars Kimya,
Kur Kimya,
Söz Kimya LTD.ŞTĐ.,
Joco Kimya,

But, for production of formaldehyde there are totally 6 registered companies in

Turkey: 1 in Bursa, Hatay, Đstanbul, Kastamonu and 2 producers in Kocaeli. Datas from
TOBB;

Production
Workers Area (m2)
Registered Capacity
City
Producer
Closed Open
E T F W AD Total TO%S
Area Area
BURSA 1 16 12 6 73 13 120 17,157 104,980 *
HATAY 1 2 0 4 32 9 47 2,000 24,743 *
ISTANBUL 1 4 0 0 23 3 30 2,805 7,148 *
KASTAMONU 1 1 2 2 9 2 16 1,673 7,779 *
KOCAELI 2 17 16 13 388 82 516 122,444 335,222 *
TOTAL 6 40 30 25 525 109 729 146,079 479,872 292,765
 E: Engineer; T: Technician; F: Foreman;W: Worker; AD: Administrative;

2.7 DISPOSAL

The Resource Conservation and Recovery Act (RCRA) identifies formaldehyde as a

toxic waste if it discarded as a commercial product, manufacturing intermediate, or off-
spicification commercial chemical product. Formaldehyde is identified as the hazardous
constituent in waste assigned the hazardous wate number U122 under RCRA.
Spilled or used formaldehyde is considered a hazardous waste and must be handled as
a solid waste under RCRA. The generator-be it in the field office or the district office-must
contact a hazardous waste contractor for appropriate disposal under RCRA regulations. An
Environmental Protection Agency (EPA) identification number must be obtained for each site
from which disposal of a regulated material or waste will be made and records must be
maintained on the amounts of waste formaldehyde, storage time, and the contractor involved
in the hazardous waste recycling.
 3.0 DISCUSSION & CONCLUSIONS
At ambient temperatures, formaldehyde exists in a gaseous state, emitting a familiar
sharp odor, irritating the eyes and skin. This gas is relatively stable at temperatures between
80°C and 100°C, but slowly polymerizes at lower temperatures, and is not sold commercially.
Because formaldehyde is highly water soluble, it is usually marketed as a liquid solution,
typically at 37 weight percent formaldehyde solution, combined with water and up to 16
percent methanol. Besides, pure formaldehyde is a gas at ordinary temperatures and cannot be
readily isolated or handled in this state, it is marketed chiefly in the form of its aqueous
solutions. Therefore, and all production comparisons shown in this report are made on a 37
percent basis.

However, higher concentrations are sold and are required for the production of some
derivative products such as polyacetal resins. The market trend is to sell solutions at higher
concentrations to reduce shipping costs. Stabilizers are usually required when shipping higher
concentrations of formaldehyde solutions. Unreacted methanol in solution helps inhibit
formaldehyde polymerization; however, this is highly time and temperature dependent. Other
product impurities include formic acid (less than 0.03 percent) and iron compounds (less than
0.5 ppm) in a 37 percent solution.

For the manufacture of formaldehyde; a wide range of alternative feed stocks have
been considered but not found to be economic. For example, a tiny amount of formaldehyde is
produced from the non-catalytic oxidation of propane butane mixtures. Formaldehyde can be
produced from methane but a mixture of products needs to be separated. It is also a byproduct
of the oxidation of naphtha to acetic acid.

Yields for both processes (Oxidation-dehydrogenation using a silver catalyst involving

either the complete or incomplete conversion of methanol; and the direct oxidation of
methanol to formaldehyde using metal oxide catalysts (Formox process)) are around 90 to 92
percent but the oxidation route has a lower reaction temperature and the metal catalyst is
cheaper than silver. However, the partial oxidation dehydrogenation route is still the most
prevalent.

The basic difference between them is the catalyst applied. The methanol excess
process, called the silver process, employs silver as the catalyst while the air excess
process (molybdenum process) uses metallic oxides of iron and molybdenum. In considering
higher investment cost and more complicated operation than the silver process, we
recommend that our clients use the silver process But, in considering higher investment
cost and more complicated operation than the silver process, it is recommend to use the silver
process.

Recent improvements in the metal oxide catalyst process have aimed at process
simplification, more extensive use of carbon steel equipment to reduce capital investment, and
modifications of the catalyst to increase catalyst life.

The most radical improvements in the silver catalyst process have been made by
BASF and are now used commercially. A different form of the catalyst, a higher reaction
temperature, and changes in reactor feed composition have made possible a high methanol
conversion; thus, it is no longer necessary to recover unreacted methanol. Maximum size of a
production unit has also been increased by these changes.

Silver-catalyzed processes for making formaldehyde from methanol can be

characterized according to the number of catalytic stages used to effect the conversion. Single
stage operation is quite widely used but suffers from the disadvantage that rather high
amounts of unconverted methanol are contained in the product emerging from the catalyst
bed. This phenomenon is customarily referred to as methanol leakage. Since for many
applications methanol is an undesirable contaminant, it must be separated from the
formaldehyde solution. This entails a substantial investment in distillation facilities and
energy to carry out such separations.

Because of the nature of the process, methanol and air concentrations are strictly
controlled to avoid potential explosions. An excess of methanol is used in production to
maintain concentration levels above the explosive limits.

A concentrated aqueous solution of formaldehyde can only be used for certain

applications, since it can neither be stored, nor transported, for extended periods. The most
usual concentration is of the order of magnitude of from 30 to 37% by weight, especially the
latter figure, since this represents a solution of optimum concentration which proves stable
over extended periods, without precipitation of paraformaldehyde. Such solutions are required
for the manufacture of phenolic resins.

On the other hand, solutions of maximum concentration have advantages for other
applications, e.g. to save transport costs, if the time for transport is relatively long and to save
 lion pounds per year capacity)

evaporation costs in subsequent processes, e.g. the manufacture of urea-formaldehyde

condensation resins or the manufacture of butynediol by reaction with acetylene.

There has been significant research activity to develop new processes for producing
formaldehyde. Even though this work has been extensive, no commercial units are known to
exist based on the technologies discussed in the following.
One possible route is to make formaldehyde directly from methane by partial oxidation.
This process has been extensively studied. The incentive for such a process is reduction of
raw material costs by avoiding the capital and expense of producing the methanol from
methane.
Another possible route for producing formaldehyde is by the dehydrogenation of
methanol which would produce anhydrous or highly concentrated formaldehyde solutions.
For some formaldehyde users, minimization of the water in the feed reduces energy costs,
effluent generation, and losses while providing more desirable reaction conditions.
A third possible route is to produce formaldehyde from methylal that is produced from
methanol and formaldehyde. The incentive for such a process is twofold. First, a higher
concentrated formaldehyde product of 70% could be made by methylal oxidation as opposed
to methanol oxidation, which makes a 55% product .This higher concentration is desirable for
some formaldehyde users. Secondly, formaldehyde in aqueous recycle streams from other units
could be recovered by reacting with methanol to produce methylal as opposed to recovery
by other more costly means, eg. distillation and evaporation. Development of this process
is complete.

ECONOMICS AND COMPARISON OF THE PROCESSES: The production costs of 37%

aqueous formaldehyde solution by the production processes (metal oxide catalyst process, the
silver catalyst process) are summarized in the following figure.

Figure 3.1 - Formaldehyde production cost comparison, 37% basis, U.S. Gulf Coast, 1st Qtr 2005 (120
mil
 The higher capital cost of the metal oxide catalyst plant is compensated for by better
process yields from methanol. The silver catalyst process without recycle has the next lowest
estimated cost plus return on capital employed (ROCE); however, the product has a higher
methanol content than the product resulting from the metal oxide and silver catalyst with
recycle processes.
The price of methanol has a dramatic effect on formaldehyde economics, since cost for
methanol feedstock represents 80 to 86 percent of cash cost and 67 to 72 percent of cost plus
ROCE for the commercial processes studied. Sensitivities show the effect of methanol price
over the range 45 to 125 cents per gallon.
Concentration of the formaldehyde solution is an important consideration for three
reasons: downstream derivative requirements, shipping costs, and energy requirements to
remove excess water. Polyacetal resins, for example, are direct polymers of formaldehyde,
and require as concentrated a solution as possible to achieve polymerization. Resins are
usually supplied as a solution of 60 percent solids or more, for which formaldehyde feedstock
at more than 50 percent concentration is desirable.
Where concentrated formaldehyde is required, the metal oxide process has the
advantage. Conversely, in some cases, such as the highly exothermic production of phenol
formaldehyde resins, a more dilute solution is actually desirable.
The silver process with distillation offers a certain amount of flexibility which is
appropriate for a plant supplying a complex and varied market. On the other hand, the metal
oxide process has an advantage in serving the single largest formaldehyde market in its ability
to form urea-formaldehyde precondensate directly in the absorption column. Existing
production capacity is dominated by the silver catalyst process, whereas the majority of new
plants being built employ the metal oxide process. This is due to the higher formaldehyde
yields on methanol and higher product concentration achieved.

DEMAND: The current consumption of formaldehyde stands at around 20 million metric tons
per year (37 wt. percent basis), representing the largest use of methanol globally. The
substantial costs associated with movement of formaldehyde over larger distances have
caused almost all of the formaldehyde plants globally to be integrated with appropriate
downstream plants. This has been possible owing to the versatility of formaldehyde end uses.
As can be seen in Figure 3.2, amino resins, which include mainly urea- and melamine-
formaldehyde resins, currently constitute slightly more than one-third of the total global
formaldehyde consumption. Phenolic resins are the second largest area of consumption.
Figure 3.2 - Breakdown of Global Formaldehyde End Uses (2005).
Global consumption growth is estimated for nine end use categories through 2015.

SUPPLY: Figure 3.3 shows the dominance of Western Europe in formaldehyde capacity. The
producers in the developed countries tend to have larger capacities distributed over a number
of production lines.
The producers in developing
countries tend to have much smaller
production capacities, and the
production tends to be
opportunistic. When margins are
good the plants operate flat out, but
when margins are poor, the plants
operate only to support the
consumption in the downstream
plants.

Figure 3.3 - Share of Key Regions in Overall Formaldehyde Capacity (2005).

SUPPLY-DEMAND BALANCE: The overall operating rate of the plants globally is expected
to increase from the upper 70s in 2005 to the lower 90s by 2015. Fragmentation in the
market that has led to poor margins in the past is expected to reduce with the closure of
some of the small, relatively uneconomical facilities.

Individual supply/demand balances are also provided for North America, Western
Europe, China, Japan, and Rest of the World.
In Turkey, just 6 companies produce totally, 292765 tons of formaldehyde in a year.
These values are too small when compared with the formaldehyde production in Canada and
United States. Also, there are many distributors in Turkey, so it can be understood that
formaldehyde production in Turkey does not meet the all requirements.

4.0 REFERENCES

[1] Ullmann, Ullmann’s Encyclopedia of Industrial Chemistry, Fifth Completely Revised

Edition, Volume A11, page 619-647.

[2] Othmer K., Kirk Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol
11, page 929-947.

[3] www.formaldehyde.org

[4] www.the-innovation-group.com

[5] http://www.microscopy-uk.org.uk/mag/indexmag.html
uk.org.uk/mag/artoct02/toptips12.html

[6] http://www.sefsc.noaa.gov/HTMLdocs/appendix-I.htm

[7] http://cameochemicals.noaa.gov/chemical/17291

[8] http://www.sriconsulting.com/PEP/Reports/Phase_77/RP023A/RP023A.html

[9] http://www.freepatentsonline.com/4119673.html

[10] http://www.dsir.gov.in/reports/techreps/tsr137.pdf

[11] http://www.mechatropia.or.kr/bbs/jck99/sp_3_034.pdf
 2 m

5.0 APPENDICES
APPENDIX A – SILVER C ATALYST PR OC ESS IN DETAIL
The following process produces 50000 tons/year of formalin from methanol
using the Silver Catalyst Process given in Figure A.1.

Formaldehyde and water required for the production are formed in the following
reaction:

CH 3OH + 1 → HCHO + H ∆H rxn = −37.3 kcal / mol

2
2O
O2

Reaction rate expression can be simplified to:

k1 p m
− r [mole / gr catalyst hour ]
= m
1+k p
where where p is a partial pressure in atm, and m refers to methanol. The rate expression is
3
only valid when oxygen is present in excess. The catalyst bulk density is 100 lb/ft and the
above constants are defined as:
7040
log k1 = 11.43 − log k = 10.79 −
3810 2 T
T
where T is in Kelvin.

Fresh methanol, Stream 2, at 30°C and 14.7 psia mixes with recycled methanol,
Stream 15, at 68.3°C and 16 psia. Stream 3 (recycled and fresh methanol) is at 35.4°C and
14.7 psia. Pump, P-101, raises the pressure up to 35 psia. Stream 4 enters a heat exchanger
where the methanol is vaporized. Stream 5 is then at 150°C and 29 psia. Fresh air is available
at 25°C and 14.7 psia in Stream 1. Compressor, C-101, raises the pressure to 35 psia in
Stream 5. This stream is then heated by medium-pressure steam. The temperature is raised to
150°C in Stream 7. Stream 6 and Stream 7 mix at a pressure of 29 psia. The combined
mixture is at 149.6°C and 28 psia in Stream 8. The reactor converts 87.4% of the methanol.
The exit reactor temperature is 343°C. Heat is removed by making high-pressure steam from
boiler feed water. The outlet, Stream 9, is at 343°C and 25 psia. A valve drops the pressure of
this stream to 5 psia before it enters the absorber, T-101. Fresh water is sent through the T-
101 at 30°C and 20 psia. T-101 is set to absorb 99% of the formaldehyde that enters. Stream
13 is then heated to 102°C before entering T-102, the formalin distillation column. T-101
recovers a 37 wt% solution of formaldehyde in water. Most of the methanol is recovered in
the distillate. Stream 15, the distillate, is recycled back to the inlet of fresh methanol at 68.3°C
and 16 psia. The bottoms, Stream 16 is pumped, by P- 103, up to 38.5 psia for storage.
Deionized water at 30°C in Stream 18 is added to achieve the 37 wt% solution of
formaldehyde in water. Storage of formalin is tricky. At high temperatures, undesirable
polymerization of formaldehyde is inhibited, but formic acid formation is favored. At low
temperatures, acid formation is inhibited, but polymerization is favored. With ≤ 2 wt%
methanol, the storage tank contents must be maintained between 35°C and 45°C.

Equipment description for the process described in Figure A.1 can be made as: P-101:
Methanol Pump, E-101: Methanol Vaporizer, C-101: Air Compressor, E-102: Air Heater
R-101: Fluid Bed Reactor, T-101: Formalin Absorber, E-103: Heater, T-102: Formalin
Distillation Column, E-104: Methanol Condenser, E-105: Formalin Reboiler, P-102: Reflux
Pump, V-101: Reflux Drum, P-103: Formalin Pump, E-106: Formalin Cooler.
Table A.1 – Stream table for the production of formalin
Table A.1 (Continued) – Stream table for the production of formalin

Process flowsheet of the diagram is given in the following page:

Figure A.1 – Production of formalin from methanol us ing silver catalyst process
 APPENDIX B –A SAMPLE FORMALIN PRODUCTION PLANT

Characteristic properties for a formalin production plant are gathered together and given in this section. For the process flow diagram
of the plant see Figure B.1 first.

Figure B.1 – Process flow diagram for a sample formalin production plant with a production capacity of 4000 m3 formalin/day
 Typical equipments that will be needed for such a plant are listed below:
Reactor, Absorber, Air Filter, Suction Filter, Gas Mixer,
Gas-Water Separator, FML Filter, Drain Separator,
Evaporator, Mixed Gas Filter, M.V. Preheater, Air Preheater,
Formalin Cooler, Start-Up Heater, Flame Arrester, Air Blower,
Air Compressori RG Blower, RG Preheater, Cooling Tower,
Various Tanks for Raw Feed Materials and Products,
Various Pumps.

3
Production capacity of the plant is 4000 m /day and working condition is 12
hours/day. Raw material and utility consumption for the plant and for the production of one
tone of 37% formalin is given in the following table:

Table B.1 – Raw material and utility consumption

Assuming that no unexpected complications are faced, such a plant is built in 18

months after the beginning of the construction scheadule. Required land area for a plant of the
2 2
given capacity is 3000 m and 1000 m of that area is covered by facilities and buildings
requred for manufacturing.

Plant layout for the sample formalin production plant is given in Figure B.2 in the
following page:
Figure B.2 – Plant layout
 Operation manpower for the sample plant is also estimated and given to be such as in
the following table:
Table B.2 – Raw material and utility consumption