Formaldehyde
(systematic name
methanal) is an organic compound
with the formula CH2O
and structure H−CHO. The compound is a pungent, colorless gas that polymerizes spontaneously into paraformaldehyde. It is stored as aqueous
solutions (formalin), which consists mainly of the hydrate CH2(OH)2.
It is produced commercially as a precursor to many other materials and chemical
compounds. In 2006, the global production rate of formaldehyde was estimated at
12 million tons per year. It is mainly used in the production of
industrial resins, e.g., for particle boards and coatings. Small amounts also occur naturally.
Formaldehyde is produced
industrially by the catalytic oxidation of methanol. The most common catalysts are silver metal, iron(III) oxide, iron molybdenum oxides
[e.g. iron(III) molybdate] with a molybdenum-enriched surface or vanadium oxides.
In the commonly used formox process,
methanol and oxygen react at c. 250–400 °C in the presence of iron oxide
in combination with molybdenum and/or vanadium to produce formaldehyde
according to the chemical equation:
2 CH3OH + O2 → 2 CH2O
+ 2 H2O
The silver-based catalyst usually
operates at a higher temperature, about 650 °C. Two chemical reactions on
it simultaneously produce formaldehyde: shown above and the dehydrogenation reaction:
CH3OH → CH2O + H2
In principle, formaldehyde could be
generated by oxidation of methane, but this route is
not industrially viable because the methanol is more easily oxidized than
methane.
In Biochemistry - Formaldehyde is produced via
several enzyme-catalyzed routes. Living beings, including humans, produce
formaldehyde as part of their metabolism. Formaldehyde is key to several
bodily functions (e.g. epigenetics), but its
amount must also be tightly controlled to avoid self-poisoning.
Occurrence
Processes in the upper atmosphere contribute
up to 90% of the total formaldehyde in the environment. Formaldehyde is an
intermediate in the oxidation (or combustion) of methane, as well as of other carbon compounds,
e.g. in forest fires, automobile exhaust, and tobacco smoke. When produced in the atmosphere by
the action of sunlight and oxygen on atmospheric methane
and other hydrocarbons, it becomes
part of smog. Formaldehyde has also been detected in
outer space.
Formaldehyde and its adducts are ubiquitous in nature. Food may
contain formaldehyde at levels 1–100 mg/kg. Formaldehyde, formed in the
metabolism of the amino acids serine and threonine, is found in the bloodstream of humans
and other primates at concentrations of approximately 50 micromolar.
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,
converting it to formic acid, so it does
not accumulate. It nonetheless presents significant health concerns, as a contaminant.
Formaldehyde is classified as a carcinogen (agents in the environment capable of contributing to cancer growth).
Additionally, it can cause respiratory and skin irritation upon exposure.
Industrial applications
Formaldehyde is a common precursor to more complex compounds
and materials. In approximate order of decreasing consumption, products
generated from formaldehyde include urea formaldehyde
resin, melamine resin, phenol formaldehyde
resin, polyoxymethylene
plastics, 1,4-butanediol, and methylene
diphenyl diisocyanate. The textile industry uses formaldehyde-based resins
as finishers to
make fabrics crease-resistant.
When treated
with phenol, urea, or melamine, formaldehyde produces, respectively, hard
thermoset phenol formaldehyde resin, urea formaldehyde resin, and melamine
resin. These polymers are permanent adhesives used in plywood and carpeting. They are also foamed to make insulation, or cast into molded products. Production of
formaldehyde resins accounts for more than half of formaldehyde consumption.
Disinfectant and biocide
An aqueous solution of formaldehyde
can be useful as a disinfectant as it kills most bacteria and fungi (including their spores). It
is used as an additive in vaccine manufacturing to inactivate toxins and
pathogens. Formaldehyde releasers
are used as biocides in personal care products such as cosmetics. Although
present at levels not normally considered harmful, they are known to cause
allergic contact dermatitis
in certain sensitized individuals.
Aquarists use formaldehyde as a
treatment for the parasites Ichthyophthirius
multifiliis and Cryptocaryon irritans.
Formaldehyde is one of the main disinfectants recommended for destroying anthrax.
Formaldehyde
is also approved for use in the manufacture of animal feeds in the US. It is an
antimicrobial agent used to maintain complete animal feeds or feed ingredients Salmonella
negative for up to 21 days.
Formaldehyde
is commonly used to disinfect (via fumigating, sprinklers, and spray sleds)
poultry and swine confinement buildings, egg hatcheries, rooms, railway cars,
mushroom houses, tools, and equipment. Formaldehyde is a valuable packaged
preservative in the food and beverage industry.
Safety
Because of its widespread use, toxicity, and volatility, formaldehyde poses a significant
danger to human health. In 2011, the US National
Toxicology Program described formaldehyde as "known to be a
human carcinogen".
Chronic inhalation
However,
concerns are associated with chronic (long-term) exposure by inhalation as may
happen from thermal or chemical decomposition
of formaldehyde-based resins and the production of formaldehyde resulting from
the combustion of a variety of organic compounds (for
example, exhaust gases). As formaldehyde resins are used in many construction materials,
it is one of the more common indoor air pollutants. At concentrations above 0.1 ppm
in air, formaldehyde can irritate the eyes and mucous membranes. Formaldehyde inhaled at this
concentration may cause headaches, a burning sensation in the throat, and
difficulty breathing, and can trigger or aggravate asthma symptoms.
In the residential
environment, formaldehyde exposure comes from several routes; formaldehyde
can be emitted by treated wood products, such as plywood
or particle board, but it is produced by paints, varnishes, floor finishes, and cigarette smoking as well. In July 2016, the U.S.
EPA released a prepublication version of its final rule on Formaldehyde
Emission Standards for Composite Wood Products. These new rules impact
manufacturers, importers, distributors, and retailers of products containing
composite wood, including fiberboard, particleboard, and various laminated
products, who must comply with more stringent record-keeping and labeling
requirements.
In the building
environments, formaldehyde levels are affected by several factors. These
include the potency of formaldehyde-emitting products present, the ratio of the
surface area of emitting materials to volume of space, environmental factors,
product age, interactions with other materials, and ventilation conditions.
Formaldehyde is emitted from a variety of construction materials, furnishings, and
consumer products.
Other routes
Formaldehyde
occurs naturally, and is "an essential intermediate in cellular metabolism
in mammals and humans." According to the American Chemistry
Council, "Formaldehyde is found in every living system—from
plants to animals to humans. It metabolizes quickly in the body, breaks down
rapidly, is not persistent, and does not accumulate in the body."
In humans,
ingestion of as little as 30 milliliters (1.0 US fl oz) of 37%
formaldehyde solution can cause death. Other symptoms associated with ingesting
such a solution include gastrointestinal damage (vomiting, abdominal pain), and
systematic damage (dizziness). Testing for formaldehyde is done by blood and/or
urine by gas
chromatography–mass spectrometry. Other methods include infrared
detection, gas detector tubes, etc., of which high-performance
liquid chromatography is the most sensitive.
Contaminant in food
Scandals have broken in both the 2005 Indonesia food
scare and 2007 Vietnam food
scare regarding the addition of formaldehyde to foods to extend
shelf life. In 2011, after a four-year absence, Indonesian authorities found
foods with formaldehyde being sold in markets in a number of regions across the
country. In August 2011, at least at two Carrefour supermarkets, the Central Jakarta Livestock and Fishery Sub-Department
found cendol containing 10 parts per million of formaldehyde. In 2014, the
owner of two noodle factories in Bogor, Indonesia, was arrested
for using formaldehyde in noodles. 50 kg of formaldehyde was confiscated.
Foods known to be contaminated included noodles, salted fish, and tofu. Chicken
and beer were also rumored to be contaminated. In some places, such as China, manufacturers
still use formaldehyde illegally as a preservative in foods, which exposes
people to formaldehyde ingestion. In the early 1900s, it was frequently added
by US milk plants to milk bottles as a method of pasteurization due to the lack
of knowledge and concern regarding formaldehyde's toxicity.
In 2011 in Nakhon Ratchasima, Thailand, truckloads of rotten
chicken were treated with formaldehyde for sale in which "a large
network", including 11 slaughterhouses run by a criminal gang, were
implicated. In 2012, 1 billion rupiah (almost US$100,000) of fish imported
from Pakistan to Batam,
Indonesia, were found laced with formaldehyde.