Formaldehyde

ADAM W. FRANZ, BASF SE, Ludwigshafen, Germany

HELMUT KRONEMAYER, BASF SE, Ludwigshafen, Germany
DANIEL PFEIFFER, BASF SE, Ludwigshafen, Germany
ROMAN D. PILZ, BASF SE, Ludwigshafen, Germany
GÄNTHER REUSS, BASF Aktiengesellschaft, Ludwigshafen, Germany
WALTER DISTELDORF, BASF Aktiengesellschaft, Ludwigshafen, Germany
ARMIN OTTO GAMER, BASF Aktiengesellschaft, Ludwigshafen, Germany
ALBRECHT HILT, Ultraform GmbH, Ludwigshafen, Germany

1. Introduction . . . . . . . . . . . . . . . . 1 6. Quality Specifications and Analysis 17

2. Physical Properties . . . . . . . . . . . 2 6.1. Quality Specifications. . . . . . . . . . 17
2.1. Monomeric Formaldehyde . . . . . . 2 6.2. Analysis . . . . . . . . . . . . . . . . . . . 17
2.2. Aqueous Solutions . . . . . . . . . . . . 3 7. Storage and Transportation . . . . . 18
3. Chemical Properties. . . . . . . . . . . 5 8. Uses . . . . . . . . . . . . . . . . . . . . . . 19
4. Production . . . . . . . . . . . . . . . . . 6 9. Economic Aspects . . . . . . . . . . . . 20
4.1. Silver Catalyst Processes . . . . . . . 7 10. Toxicology and Occupational
4.1.1. Complete Conversion of Methanol Health. . . . . . . . . . . . . . . . . . . . . 21
(BASF Process) . . . . . . . . . . . . . . 8 11. Low-Molecular-Mass Polymers. . . 22
4.1.2. Incomplete Conversion and 11.1. Linear Polyoxymethylenes . . . . . . 22
Distillative Recovery of Methanol . . 9 11.2. Cyclic Polyoxymethylenes. . . . . . . 25
4.2. Formox Process . . . . . . . . . . . . . . 10 11.2.1. Trioxane . . . . . . . . . . . . . . . . . . . 25
4.3. Comparison of Process Economics 12 11.2.2. Tetraoxane . . . . . . . . . . . . . . . . . . 28
4.4. Distillation of Aqueous 11.2.3. Higher Cyclic Polyoxymethylenes . . 28
Formaldehyde Solutions. . . . . . . . 13 12. Formaldehyde Cyanohydrin . . . . . 29
4.5. Preparation of Liquid Monomeric References. . . . . . . . . . . . . . . . . . 30
Formaldehyde . . . . . . . . . . . . . . . 14
5. Environmental Protection . . . . . . 14

1. Introduction gas-fired boilers, and even in cigarette smoke.

Formaldehyde is an important industrial chemi-
Formaldehyde occurs in nature and is formed cal and is employed in the manufacture of many
from organic material by photochemical pro- industrial products and consumer articles. More
cesses in the atmosphere as long as life contin- than 50 branches of industry now use formal-
ues on earth. Formaldehyde is an important dehyde, mainly in the form of aqueous solutions
metabolic product in plants and animals (includ- and formaldehyde-containing resins. In 2011,
ing humans), where it occurs in low but mea- the demand for formaldehyde (based on 37 wt%
surable concentrations. It has a pungent odor aqueous solution) in the three major markets —
and is an irritant to the eye, nose, and throat even Northern America, Western Europe, and Asia
at a low concentration; the threshold concentra- Pacific — was 31.4 × 106 t/a [1, 2]. This
tion for odor detection is 0.05–1 ppm. Formal- corresponds to 89% of the world’s demand.
dehyde is also formed when organic material is
incompletely combusted; therefore, formalde- History. Formaldehyde was first synthesized in
hyde is found in combustion gases from, for 1859, when BUTLEROV hydrolyzed methylene
example, automotive vehicles, heating plants, acetate and noted the characteristic odor of

 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a11_619.pub2
2 Formaldehyde

the resulting solution. In 1867, HOFMANN con- UV absorption spectra of formaldehyde, see
clusively identified formaldehyde, which he [3]. Structural information about the formalde-
prepared by passing methanol vapor and air hyde molecule is provided by its fluorescence
over a heated platinum spiral. This method, [4], IR [5], Raman [6], and microwave spectra
but with other catalysts, still constitutes the [7]. Following are some of the thermodynamic
principal method of manufacture. The prepara- properties of gaseous formaldehyde:
tion of pure formaldehyde was described later
by KEKULÉ in 1882.
Industrial production of formaldehyde Heat of formation at 25°C 115.9 ± 6.3 kJ/mol
Gibbs energy at 25°C 109.9 kJ/mol
became possible in 1882, when TOLLENS dis- Entropy at 25°C 218.8 ±
covered a method of regulating the methanol 0.4 kJ mol 1 K 1
vapor : air ratio and affecting the yield of the Heat of combustion at 25°C 561.5 kJ/mol
reaction. In 1886, LOEW replaced the platinum Heat of vaporization at 19.2°C 23.32 kJ/mol
Specific heat capacity at 25°C, cp 35.425 J mol 1 K 1
spiral catalyst by a more efficient copper gauze. Heat of solution at 23°C
The German firm, Mercklin und Lösekann, in water 62 kJ/mol
started to manufacture and market formalde- in methanol 62.8 kJ/mol
hyde on a commercial scale in 1889. Another in 1-propanol 59.5 kJ/mol
in 1-butanol 62.4 kJ/mol
German firm, Hugo Blank, patented the first use Cubic expansion coefficient 2.83 × 10 3 K 1

of a silver catalyst in 1910. Specific magnetic susceptibility 0.62 × 106

Industrial development continued from 1900 Vapor density relative to air 1.04
to 1905, when plant sizes, flow rates, yields, and
efficiency were increased. In 1905, Badische
Anilin & Soda-Fabrik started to manufacture The vapor pressure p of liquid formaldehyde
formaldehyde by a continuous process employ- has been measured from 109.4 to 22.3°C [8]
ing a crystalline silver catalyst. Formaldehyde and can be calculated for a given temperature T
output was 30 kg/d in the form of an aqueous 30 (K) from the following equation:
wt% solution.
The methanol required for the production of p…kPa† ˆ 10‰5:0233 …1429=T †‡1:75 log T 0:0063T Š

formaldehyde was initially obtained from the

timber industry by carbonizing wood. The Polymerization in either the gaseous or the
development of the high-pressure synthesis of liquid state is influenced by wall effects, pres-
methanol by Badische Anilin & Soda-Fabrik in sure, traces of humidity, and small quantities of
1925 allowed the production of formaldehyde formic acid. Formaldehyde gas obtained by
on a true industrial scale. vaporization of paraformaldehyde or more
highly polymerized α-polyoxymethylenes,
which is ca. 90–100% pure, must be stored at
2. Physical Properties 100–150°C to prevent polymerization. Chemi-
cal decomposition is insignificant below 400°C.
2.1. Monomeric Formaldehyde Formaldehyde gas is flammable, its ignition
temperature is 430°C [9]; mixtures with air are
Formaldehyde [50-00-0], CH2O, Mr 30.03, is a explosive. At ca. 20°C the lower and upper
colorless gas at ambient temperature that has a explosive limits of formaldehyde are ca. 7
pungent, suffocating odor, and an irritant action and 72 vol% (87 and 910 g/m3), respectively
on the eyes and skin. [10]. Flammability is particularly high at a
Formaldehyde liquefies at 19.2°C, the den- formaldehyde concentration of 65–70 vol%.
sity of the liquid being 0.8153 g/cm3 at 20°C At a low temperature, liquid formaldehyde is
and 0.9172 g/cm3 at 80°C. It solidifies at miscible in all proportions with nonpolar sol-
118°C to give a white paste. The liquid and vents such as toluene, diethyl ether, chloroform,
gas polymerize readily at low and ordinary or ethyl acetate. However, solubility decreases
temperatures up to 80°C. Pure formaldehyde with increasing temperature and at room tem-
gas does not polymerize between 80 and perature polymerization and volatilization
100°C and behaves as an ideal gas. For the occur, leaving only a small amount of dissolved
 Formaldehyde 3

gas. Solutions of liquid formaldehyde in acetal- Table 1. Calculated distribution of oligomers of methylene glycol,
dehyde behave as ideal solutions [11]. Liquid HO(CH2O)nH, in an aqueous 40 wt% formaldehyde solution at
35°C [13]
formaldehyde is slightly miscible with petro-
leum ether and p-cymene [12]. n Proportion, % n Proportion, %
Polar solvents, such as alcohols, amines, or 1 26.80 7 3.89
acids, either catalyze the polymerization of 2 19.36 8 2.50
formaldehyde or react with it to form methylol 3 16.38 9 1.59
compounds or methylene derivatives. 4 12.33 10 0.99
5 8.70 > 10 1.58
6 5.89
2.2. Aqueous Solutions

At room temperature, pure aqueous solutions

contain formaldehyde in the form of methylene formaldehyde concentration of up to 60 wt%
glycol HOCH2OH [463-57-0] and its oligo- [14]. Table 1 gives the calculated oligomer
mers, namely the low-molecular-mass poly distribution in an aqueous 40 wt% solution of
(oxymethylene) glycols with the following formaldehyde.
structure A kinetic study of the formation of methyl-
ene glycol from dissolved formaldehyde and
HO…CH2 O†n H …n ˆ 1 8† water shows that the reverse reaction is 5×103
to 6×103 times slower than the forward reaction
Monomeric, physically dissolved formalde- [16], and that it increases greatly with the acidity
hyde is only present in low concentrations of up of the solution. This means that the distribution
to 0.1 wt%. The polymerization equilibrium of the higher mass oligomers (n > 3) does not
change rapidly when the temperature is
HOCH2 OH ‡ n CH2 O „ HO…CH2 O†n‡1 H increased or the solution is diluted; the methyl-
ene glycol content then rises at the expense of
is catalyzed by acids and is shifted toward the the smaller oligomers (n = 2 or 3). In aqueous
right at lower temperature and/or higher form- solutions containing  2 wt% formaldehyde,
aldehyde concentrations, and toward the left if formaldehyde is entirely monomeric.
the system is heated and/or diluted [13, 14] (see Methylene glycol can be determined by the
also Section 11.1 Linear Polyoxymethylenes). bisulfite method [17] or by measuring the partial
Dissolution of formaldehyde in water is exo- pressure of formaldehyde [18]. Molecular
thermic, the heat of solution ( 62 kJ/mol) being masses and monomer contents can be deter-
virtually independent of the solution concentra- mined by NMR spectroscopy [14, 19].
tion [15]. Clear, colorless solutions of formal- The approximate amount of monomeric
dehyde in water can exist at a formaldehyde formaldehyde present as formaldehyde hemi-
concentration of up to 95 wt%, but the tempera- formal and methylene glycol in aqueous solu-
ture must be raised to 120°C to obtain the tions containing formaldehyde and methanol,
highest concentrations. Concentrated aqueous can be calculated from data at 25–80°C [20] by
solutions containing more than 30 wt% formal- using the following equation:
dehyde become cloudy on storage at room pffiffiffiffi
temperature, because larger poly(oxymethy- Monomer …mol%† ˆ 100 12:3 F ‡ …1:44 0:0164F †M
lene) glycols (n  8) are formed which then
precipitate out (the higher the molecular mass of where F is the formaldehyde concentration
the polymers, the lower their solubility). (7–55 wt%) and M is the methanol concentra-
Equilibrium constants have been determined tion (0–14 wt%).
for the physical dissolution of formaldehyde in The partial pressure pF of formaldehyde
water and for the reaction of formaldehyde to above aqueous solutions has been measured
give methylene glycol and its oligomers [13]. by LEDBURY and BLAIR and computed by
These parameters can be combined with other WALKER and LACY [21]. The parameter pF for
data to calculate the approximate equilibria at solutions in which F is in the range 0–40 wt%
any temperature from 0 to 150°C and at a can be calculated with a relative error of 5–10%
4 Formaldehyde

Table 2. Partial pressure pF of formaldehyde (kPa) above aqueous formaldehyde solutions

t, °C Formaldehyde concentration, wt%

1 5 10 15 20 25 30 35 40

5 0.003 0.011 0.016 0.021 0.025 0.028 0.031 0.034 0.037

10 0.005 0.015 0.024 0.031 0.038 0.043 0.049 0.053 0.056
15 0.007 0.022 0.036 0.047 0.057 0.066 0.075 0.083 0.090
20 0.009 0.031 0.052 0.069 0.085 0.099 0.113 0.125 0.137
25 0.013 0.044 0.075 0.101 0.125 0.146 0.167 0.187 0.206
30 0.017 0.061 0.105 0.144 0.180 0.213 0.245 0.275 0.304
35 0.022 0.084 0.147 0.203 0.256 0.305 0.353 0.398 0.442
40 0.028 0.113 0.202 0.284 0.360 0.432 0.502 0.569 0.634
45 0.037 0.151 0.275 0.390 0.499 0.604 0.705 0.803 0.899
50 0.047 0.200 0.371 0.531 0.685 0.833 0.978 1.119 1.258
55 0.059 0.262 0.494 0.715 0.929 1.137 1.341 1.541 1.740
60 0.074 0.340 0.652 0.953 1.247 1.536 1.820 2.101 2.378
65 0.093 0.437 0.852 1.258 1.657 2.053 2.443 2.831 3.218
70 0.114 0.558 1.104 1.645 2.182 2.717 3.250 3.780 4.310

in the temperature range T = 273–353 K by Aqueous Formaldehyde – Methanol Solutions.

using the following equation: Technical-grade formaldehyde solutions con-
tain a small amount of methanol as a result of
pF …kPa† ˆ 0:1333Fe F …a0 ‡a1 =T‡a2 =T † the incomplete methanol conversion during
α 2

α ˆ 0:08760  0:00950 formaldehyde production. The amount of meth-

a0 ˆ 12:0127  0:0550
a1 ˆ 3451:72  17:14
anol present depends on the production process
a2 ˆ 248257:3  5296:8 employed. The presence of methanol is often
desirable in aqueous solutions containing more
Results of such calculations are given in than 30 wt% formaldehyde because it inhibits
Table 2 and agree well with the measured the formation of insoluble, higher mass poly-
values. mers. Methanol concentrations of up to 16 wt%
Table 3 gives the partial pressures and con- stabilize the formaldehyde.
centrations of formaldehyde in the liquid and The approximate density ϱ (in grams per
gaseous phases of aqueous formaldehyde solu- cubic centimeter) of aqueous formaldehyde
tions. The partial pressures and concentrations solutions containing up to 13 wt% methanol
were measured at the boiling points of the at a temperature of 10–70°C can be calculated
solutions at a pressure of 101.3 kPa [22]. by using the following equation [23]:

Table 3. Concentration and partial pressure of formaldehyde ρ ˆ a ‡ 0:0030…F b† 0:0025…M c† 104 ‰0:055…F 30†
measured at the boiling points (101.3 kPa) of aqueous formaldehyde ‡5:4Š…t 20†
solutions [22]

Formaldehyde concentration, wt% Partial pressure where

Liquid phase Gaseous phase (pF), kPa F formaldehyde concentration
(Fl) (Fg)
in wt%
3.95 3.68 2.35 M methanol concentration in wt%
8.0 7.3 4.75
t temperature in °C
12.1 10.6 7.0
15.3 13.2 8.65 a, b, and c constants
20.1 16.95 11.2
25.85 21.45 14.45
30.75 24.9 16.8
35.65 27.4 18.8 The following values can be assumed when
42.0 30.5 21.4 F is in the range 0–48: a = 1.092, b = 30, and c
47.5 33.1 23.4 = 0. The corresponding values in the range F =
49.8 34.0 24.1
48–55 are a = 1.151, b = 50.15, and c = 1.61.
 Formaldehyde 5

The boiling points of pure aqueous solutions Polymerization. Anhydrous monomeric form-
containing up to 55 wt% formaldehyde are aldehyde cannot be handled commercially. Gas-
between 99 and 100°C at atmospheric pressure eous formaldehyde polymerizes slowly at
[24]. In dilute aqueous solutions, formaldehyde temperatures below 100°C, polymerization
lowers the freezing point of water. If solutions being accelerated by traces of polar impurities
containing more than 25 wt% formaldehyde are such as acids, alkalis, or water (see para-
cooled, polymer precipitates out before the formaldehyde, Section 11.1 Linear Polyoxy-
freezing point is reached. According to NATTA methylenes). Thus, in the presence of steam
[23], the approximate refractive index n18 D of and traces of other polar compounds, the gas is
aqueous 30–50 wt% formaldehyde solutions stable at ca. 20°C only at a pressure of 0.25–0.4
containing up to 15 wt% methanol can be kPa, or at a concentration of up to ca. 0.4 vol%
calculated from the following equation: at ca. 20°C and atmospheric pressure.
Monomeric formaldehyde forms a hydrate
D ˆ 1:3295 ‡ 0:00125F ‡ 0:000113M
n18 with water; this hydrate reacts with further
formaldehyde to form polyoxymethylenes
where F and M are wt% concentrations of (see Section 2.2 Aqueous Solutions). Methanol
formaldehyde and methanol, respectively. or other stabilizers, such as guanamines
In close agreement with measurements of [45] or alkylene bis(melamines) [46], are
commercial solutions, the dynamic viscosity η generally added to commercial aqueous formal-
of aqueous formaldehyde–methanol solutions dehyde solutions (37–57 wt%) to inhibit
may be expressed by the following equation [25]: polymerization.

η …mPa
s† ˆ 1:28 ‡ 0:039F ‡ 0:05M 0:024t Reduction and Oxidation. Formaldehyde is

readily reduced to methanol with hydrogen
This equation applies to solutions containing over a nickel catalyst [39, 47]. For example,
30–50 wt% formaldehyde and 0–12 wt% meth- formaldehyde is oxidized by nitric acid, potas-
anol at a temperature t of 25–40°C. sium permanganate, potassium dichromate, or
Detailed studies on chemical reactions, oxygen to give formic acid or CO2 and water
vapor–liquid equilibria and caloric properties [39, 48].
of systems containing formaldehyde, water, In the presence of strong alkalis [49] or when
and methanol are available [26–36]. heated in the presence of acids [50], formalde-
hyde undergoes a Cannizzaro reaction with
formation of methanol and formic acid [51].
3. Chemical Properties In the presence of aluminum or magnesium
methylate, paraformaldehyde reacts to form
Formaldehyde is one of the most reactive
methyl formate (Tishchenko reaction) [39].
organic compounds known and, thus, differs
greatly from its higher homologues and ali-
Addition Reactions. The formation of spar-
phatic ketones [37, 38]. Only the most important
ingly water-soluble sodium formaldehyde
of its wide variety of chemical reactions are
bisulfite is an important addition reaction of
treated in this article; others are described in
formaldehyde [52]. Hydrocyanic acid reacts
[39]. For a general discussion of the chemical
with formaldehyde to give glycolonitrile [107-
properties of saturated aldehydes, see → Alde-
16-4] [39]. Formaldehyde undergoes an acid-
hydes, Aliphatic.
catalyzed Prins reaction in which it forms
Decomposition. At 150°C, formaldehyde under- α-hydroxymethylated adducts with olefins [25].
goes heterogeneous decomposition to form Acetylene undergoes a Reppe addition reaction
mainly methanol and CO2 [40]. Above 350°C, with formaldehyde [53] to form 2-butyne-1,
however, it tends to decompose into CO and H2 4-diol [110-65-6]. Strong alkalis or calcium
[41]. Metals such as platinum [42], copper [43], hydroxide convert formaldehyde to a mixture
chromium, and aluminum [44] catalyze the for- of sugars, in particular hexoses, by a multiple
mation of methanol, methyl formate, formic acid, aldol condensation which probably involves a
CO2, and methane. glycolaldehyde intermediate [54, 55]. Mixed
6 Formaldehyde

aldols are formed with other aldehydes; the aromatic sulfonamides, amines, and phenols
product depends on the reaction conditions. to give a wide range of resins (→ Amino Resins;
Acetaldehyde, for example, reacts with formal- → Phenolic Resins; → Resins, Synthetic).
dehyde to give pentaerythritol, C(CH2OH)4
[115-77-5] and isobutyric aldehyde reacts
with formaldehyde to form neopentyl glycol
(→ Alcohols, Polyhydric). 4. Production
Formaldehyde is produced industrially from
Condensation Reactions. Important condensa- methanol [67-56-1] by the following three
tion reactions are the reaction of formaldehyde processes:
with amino groups to give Schiff’s bases, as
well as the Mannich reaction [39]. Amines react
with formaldehyde and hydrogen to give meth- 1. Partial oxidation and dehydrogenation
ylamines. Formaldehyde reacts with ammonia with air in the presence of silver crystals,
to give hexamethylenetetramine, and with steam, and excess methanol at 650–720°C
ammonium chloride to give monomethylamine, (BASF process, methanol conversion =
dimethylamine, or trimethylamine and formic 97–98%).
acid, depending on the reaction conditions [56]. 2. Partial oxidation and dehydrogenation with
Reaction of formaldehyde with diketones and air in the presence of crystalline silver or
ammonia yields imidazoles [57]. silver gauze, steam, and excess methanol at
Formaldehyde reacts with many compounds 600–650°C [59] (primary conversion of
to produce methylol ( CH2OH) derivatives. It methanol = 77–87%). The conversion is
reacts with phenol to give methylolphenol, with completed by distilling the product and recy-
urea to give mono-, di-, and trimethylolurea, cling the unreacted methanol.
with melamine to give methylolmelamines, and 3. Oxidation only with excess air in the pres-
with organometallic compounds to give metal- ence of a modified iron–molybdenum–vana-
substituted methylol compounds [39]. dium oxide catalyst at 250–400°C (methanol
Aromatic compounds such as benzene, ani- conversion = 98–99%).
line, and toluidine combine with formaldehyde
to produce the corresponding diphenylme-
Processes for converting propane, butane
thanes. In the presence of hydrochloric acid
[60], ethylene, propylene, butylene [61], or
and formaldehyde, benzene is chloromethylated
ethers (e.g., dimethyl ether) [62] into formalde-
to form benzyl chloride [100-44-7] [58]. The
hyde are not of major industrial significance for
possible formation of bis(chloromethyl)ether
economic reasons. Processes that employ partial
[542-88-1] from formaldehyde and hydro-
hydrogenation of CO [63] or oxidation of meth-
chloric acid and the toxicity of this compound
ane [64] do not compete with methanol conver-
are reported elsewhere (→ Ethers, Aliphatic).
sion processes because of the lower yields of the
Formaldehyde reacts with hydroxylamine,
former processes.
hydrazines, or semicarbazide to produce
The specifications of the methanol, used for
formaldehyde oxime (which is spontaneously
formaldehyde production according to pro-
converted to triformoxime), the corresponding
cesses 1–3 are listed in Table 4. However,
hydrazones, and semicarbazone, respectively.
crude aqueous methanol obtained by high-
Double bonds are also produced when
[65], medium-, or low-pressure [66] synthesis
formaldehyde is reacted with malonates or
can also be used for process 1. This methanol
with primary aldehydes or ketones possessing
contains low concentrations of inorganic
a CH2 group adjacent to the carbonyl
impurities and limited amounts of other
group.
organic compounds. The methanol must be
first subjected to purification processes and
Resin Formation. Formaldehyde condenses preliminary distillation to remove low-boiling
with urea, melamine, urethanes, cyanamide, components.
 Formaldehyde 7

Table 4. Specifications of commercial methanol (grade AA) used 500°C and to 99% at 700°C. The temperature
for the production of formaldehyde [67] dependence of the equilibrium constant for this
Parameter Specification reaction Kp is given by
Methanol content >99.85 wt% log K p ˆ …4600=T † 6:470
Relative density, d 20
4 0.7928 g/cm3
Maximum boiling point range 1°C For detailed thermodynamic data of reactions
Acetone and acetaldehyde content <0.003 wt%
Ethanol content <0.001 wt%
(1)–(6) see [68]. Kinetic studies with silver on a
Volatile iron content <2 μg/L carrier show that reaction (1) is a first-order
Sulfur content <0.0001 wt% reaction [69]. Therefore, the rate of formalde-
Chlorine content <0.0001 wt% hyde formation is a function of the available
Water content <0.15 wt%
pH 7.0
oxygen concentration and the oxygen residence
KMnO4 test, minimum 30 min time on the catalyst surface:
decolorization time
dcF
ˆ kcO
dt

where
4.1. Silver Catalyst Processes
cF = formaldehyde concentration
The silver catalyst processes for converting cO = oxygen concentration
methanol to formaldehyde are generally carried k = rate constant
out at atmospheric pressure and at 600–720°C. t = time
The reaction temperature depends on the excess
of methanol in the methanol–air mixture. The A complete reaction mechanism for the con-
composition of the mixture must lie outside the version of methanol to formaldehyde over a
explosive limits. The amount of air that is used silver catalyst has not yet been proposed. How-
is also determined by the catalytic quality of the ever, some authors postulate that a change in
silver surface. The following main reactions mechanism occurs at ca. 650°C [70]. New
occur during the conversion of methanol to insight into the reaction mechanism is available
formaldehyde: from spectroscopic investigations [71–73],
which demonstrate the influence of different
CH3 OH „ CH2 O ‡ H2 ΔH ˆ ‡84 kJ=mol …1† atomic oxygen species on reaction pathway
and selectivity. The synthesis of formaldehyde
H2 ‡ 1=2 O2 ! H2 O ΔH ˆ 243 kJ=mol …2† over a silver catalyst is carried out under strictly
adiabatic conditions. Temperature measure-
CH3 OH ‡ 1=2 O2 ! CH2 O ‡ H2 O ΔH ˆ 159 kJ=mol …3† ments both above and in the silver layer show
that sites still containing methanol are separated
The extent to which each of these three from sites already containing predominantly
reactions occurs, depends on the process data. formaldehyde by only a few millimeters.
Byproducts are also formed in the following The oxygen in the process air is shared between
secondary reactions: the exothermic reactions, primarily reaction (2)
and, to a lesser extent depending on the process
CH2 O ! CO ‡ H2 ΔH ˆ ‡12:5 kJ=mol …4† used, the secondary reactions (5) and (6). Thus, the
amount of process air controls the desired reaction
CH3 OH ‡ 3=2 O2 ! CO2 ‡ 2 H2 O ΔH ˆ 674 kJ=mol …5† temperature and the extent to which the endother-
mic reactions (1) and (4) occur.
CH2 O ‡ O2 ! CO2 ‡ H2 O ΔH ˆ 519 kJ=mol …6† Another important factor affecting the yield
of formaldehyde and the conversion of metha-
Other important byproducts are methyl for- nol, besides the catalyst temperature, is the
mate, methane, and formic acid. addition of inert materials to the reactants.
The endothermic dehydrogenation reaction Water is added to spent methanol–water-evapo-
(1) is highly temperature-dependent, conver- rated feed mixtures, and nitrogen is added to air
sion increasing from 50% at 400°C to 90% at and air–off-gas mixtures, which are recycled to
8 Formaldehyde

dilute the methanol–oxygen reaction mixture.

The throughput per unit of catalyst area provides
another way of improving the yield and affect-
ing side reactions. These two methods of pro-
cess control are discussed in [74].
The theoretical yield of formaldehyde
obtained from Reactions (1)–(6) can be calcu-
lated from actual composition of the plant off-
gas by using the following equation:

Yield …mol%†
  1
…% CO2 † ‡ …% CO†
ˆ 100 1 ‡ r ‡
0:528…% N2 † ‡ …% H2 † 3…% CO2 † 2…% CO†

Percentages signify concentrations in vol%

and r is the ratio of moles of unreacted methanol
to moles of formaldehyde produced [75]. The
equation takes into account the hydrogen and
oxygen balance and the formation of by
products.

4.1.1. Complete Conversion of Methanol

(BASF Process)

The BASF process for the complete conversion

of methanol to formaldehyde is shown schemat-
ically in Figure 1 [76]. A mixture of methanol
and water is fed into the evaporating column.
Fresh process air and, if necessary, recycled off-
gas from the last stage of the absorption column
enter the column separately [75]. A gaseous Figure 1. Flowchart of formaldehyde production by the
BASF process
mixture of methanol in air is thus formed in a) Evaporator; b) Blower; c) Reactor; d) Boiler; e) Heat
which the inert gas content (nitrogen, water, and exchanger; f) Absorption column; g) Steam generator; h)
CO2) exceeds the upper explosive limit. A ratio Cooler; i) Superheater
of 60 parts of methanol to 40 parts of water with Recycling schemes: –
–
– off-gas, –––– formaldehyde
or without inert gases is desired. The packed solution.
evaporator constitutes part of the stripping
cycle. The heat required to evaporate the meth- corresponding to that of the pressurized steam
anol and water is provided by a heat exchanger, (0.5 MPa). The almost dry gas from the gas
which is linked to the first absorption stage of cooler passes to the first stage of a four-stage
the absorption column [77]. After passing packed absorption column, where the gas is
through a demister, the gaseous mixture is cooled and condensed. Formaldehyde is eluted
superheated with steam and fed to the reactor, countercurrent to water or to the circulating
where it flows through a 25–30 mm thick bed of formaldehyde solutions whose concentrations
silver crystals. The crystals have a defined range increase from stage to stage.
of particle sizes [78] and rest on a perforated The product circulating in the first stage may
tray, which is covered with a fine corrugated contain 55 wt% formaldehyde if the temperature
gauze, thus permitting optimum reaction at the of the gas leaving this stage is kept at ca. 75°C;
surface. The bed is positioned immediately this temperature provides sufficient evaporation
above a water boiler (cooler), which produces energy for the feed stream in the heat exchanger.
superheated steam and simultaneously cools the The final product contains 40–55 wt% formal-
hot reaction gases to a temperature of 150°C dehyde, as desired, with an average of 1–2 wt%
 Formaldehyde 9

methanol and 0.01 wt% formic acid. The formaldehyde plant increases in proportion to
yield of the formaldehyde process is 86.5– the diameter of the reactor. The largest known
90.5 mol%. Some of the off-gas is removed reactor appears to be that of BASF in the
at the end of the fourth stage of the column [75] Germany; it has an overall diameter of 3.2 m
and is recycled due to its extremely low form- and a production capacity of 90 000 t/a (calcu-
aldehyde content (Fig. 1, route indicated by lated as 100 wt% formaldehyde).
dashed-dotted lines). The residual off-gas is
fed to a steam generator, where it is combusted 4.1.2. Incomplete Conversion and Distillative
[79] (net calorific value = 1970 kJ/m3). Prior to Recovery of Methanol
combustion the gas contains ca. 4.8 vol% CO2,
0.3 vol% CO, and 18.0 vol% H2 as well as Formaldehyde can be produced by partial oxi-
nitrogen, water, methanol, and formaldehyde. dation and distillative recovery of methanol.
The combusted off-gas contains no environ- This process was and is used in numerous
mentally harmful substances. The total steam companies (e.g., ICI, Borden, and Degussa)
equivalent of the process is 3 t per ton of 100 wt [81]. As shown in Figure 2, a feed mixture of
% formaldehyde. pure methanol vapor and freshly blown-in air is
In an alternative procedure to the off-gas generated in an evaporator. The resulting vapor
recycling process (Fig. 1, dashed lines) the is combined with steam, subjected to indirect
formaldehyde solution from the third or fourth superheating, and then fed into the reactor. The
stage of the absorption tower is recycled to the reaction mixture contains excess methanol and
evaporator; a certain amount of steam is used in
the evaporation cycle. The resulting vapor is
combined with the feed stream to the reactor to
obtain an optimal methanol : water ratio [80]. In
this case, the temperature of the second stage of
the absorption column is ca. 65°C.
The yields of the two processes are similar
and depend on the formaldehyde content of the
recycled streams.
The average life time of a catalyst bed
depends on impurities such as inorganic materi-
als in the air and methanol feed; poisoning
effects caused by some impurities are partially
reversible within a few days. The life time of the
catalyst is also adversely affected by long expo-
sure to excessively high reaction temperatures
and high throughput rates because the silver
crystals then become matted and cause an
increase in pressure across the catalyst bed.
This effect is irreversible and the catalyst bed
must be changed after three to eight months
[25]. The catalyst is regenerated electrolytically.
Since formaldehyde solutions corrode car-
bon steel, all parts of the manufacturing equip-
ment that are exposed to formaldehyde solutions
must be made of a corrosion-resistant alloy, e.g.,
certain types of stainless steel. Furthermore,
tubes that convey water or gases must be
made of alloys to protect the silver catalyst Figure 2. Flowchart of formaldehyde production with
recovery of methanol by distillation
against metal poisoning. a) Evaporator; b) Blower; c) Reactor; d) Boiler; e) Distilla-
If the throughput and reaction temperature tion column; f) Absorption column; g) Steam generator; h)
have been optimized, the capacity of a Cooler; i) Superheater; j) Anion-exchange unit
10 Formaldehyde

steam and is very similar to that used in the recycled to the reactor. This inert gas, with
BASF process (cf. Section 4.1.1 Complete Con- additional steam, can reduce the excess metha-
version of Methanol (BASF Process)). The nol needed in the reactor feed, consequently
vapor passes through a shallow catalyst bed providing a more concentrated product with
of silver crystals or through layers of silver less expenditure on distillation. The yield of
gauze. Conversion is incomplete and the the process is 87–92 mol%.
reaction takes place at 590–650°C, undesirable Process variations to increase the incomplete
secondary reactions being suppressed by this conversion of methanol employ two-stage oxi-
comparatively low temperature. Immediately dation systems [82]. The methanol is first partly
after leaving the catalyst bed, the reaction gases converted to formaldehyde, using a silver cata-
are cooled indirectly with water, thereby gener- lyst at a comparatively low temperature (e.g.,
ating steam. The remaining heat of reaction is 600°C). The reaction gases are subsequently
then removed from the gas in a cooler and is fed cooled and excess air is added to convert the
to the bottom of a formaldehyde absorption remaining methanol in a second stage employ-
column. In the water-cooled section of the ing either a metal oxide (cf. Section 4.2 Formox
column, the bulk of the methanol, water, and Process) or a further silver bed as a catalyst.
formaldehyde separate out. At the top of the Formaldehyde solutions in methanol with a
column, all the condensable portions of the relatively low water content can be produced
remaining formaldehyde and methanol are directly by methanol oxidation and absorption
washed out of the tail gas by countercurrent in methanol [83]. Anhydrous alcoholic formal-
contact with process water. A 42 wt% formal- dehyde solutions or alcoholic formaldehyde
dehyde solution from the bottom of the absorp- solutions with a low water content can be
tion column is fed to a distillation column obtained by mixing a highly concentrated form-
equipped with a steam-based heat exchanger aldehyde solution with the alcohol (ROH) and
and a reflux condenser. Methanol is recovered distilling off an alcohol – water mixture with a
at the top of the column and is recycled to the low formaldehyde content. The formaldehyde
bottom of the evaporator. A product containing occurs in the desired solutions in the form of the
up to 55 wt% formaldehyde and less than 1 wt% hemiacetals RO(CH2O)nH.
methanol is taken from the bottom of the distil-
lation column and cooled. The formaldehyde 4.2. Formox Process
solution is then usually fed into an anion-
exchange unit to reduce its formic acid content In the Formox process, a metal oxide (e.g., iron,
to the specified level of less than 50 mg/kg. molybdenum, or vanadium oxide) is used as a
If 50–55 wt% formaldehyde and no more catalyst for the conversion of methanol to form-
than 1.5 wt% methanol are required in the aldehyde. Many such processes have been
product, steam addition is restricted and the patented since 1921 [84]. Usually, the oxide
process employs a larger excess of methanol. mixture has an Mo : Fe atomic ratio of 1.5–2.0,
The ratio of distilled recycled methanol to fresh small amounts of V2O5, CuO, Cr2O3, CoO, and
methanol then lies in the range 0.25–0.5. If a P2O5 are also present [85]. Special conditions
dilute product containing 40–44 wt% formalde- are prescribed for both the process and the
hyde is desired, the energy-intensive distillation activation of the catalyst [86]. The Formox
of methanol can be reduced, leading to savings process has been described as a two-step oxida-
in steam and power as well as reductions in tion reaction in the gaseous state (g) which
capital cost. The off-gas from the absorption involves an oxidized (KOX) and a reduced
column has a similar composition to that (Kred) catalyst [87]:
described for the BASF process (in Section CH3 OH…g† ‡ KOX → CH2 O…g† ‡ H2 O…g† ‡ Kred
4.1.1 Complete Conversion of Methanol
(BASF Process)). The off-gas is either released Kred ‡ 1=2 O2…g† → KOX ΔH ˆ 159kJ=mol
into the atmosphere or is combusted to generate CH2 O ‡ 1=2 O2 „ CO ‡ H2 O ΔH ˆ 215 kJ=mol
steam, thus avoiding environmental problems
caused by residual formaldehyde. Alternatively, In the temperature range 270–400°C, con-
the tail gas from the top of the absorber can be version at atmospheric pressure is virtually
 Formaldehyde 11

complete. However, conversion is temperature- absorption tower are mixed and, if necessary,
dependent because at >470°C the following side preheated by means of the product stream in a
reaction increases considerably: heat exchanger before being fed into the evap-
orator. The gaseous feed passes through cata-
CH2 O ‡ 1=2 O2 „ CO ‡ H2 O ΔH ˆ 215 kJ=mol lyst-filled tubes in a heat-exchanging reactor. A
typical reactor for this process has a shell with a
The methanol oxidation is inhibited by water diameter of ca. 2.5 m that contains tubes only
vapor. A kinetic study describes the rate of 1.0–1.5 m in length. A high-boiling heat-trans-
reaction to formaldehyde by a power law kinetic fer oil circulates outside the tubes and removes
rate expression of the form [88] the heat of reaction from the catalyst in the
tubes. The process employs excess air and the
r ˆ kPxCH3 OH PvO2 PzH2 O temperature is controlled isothermally to a value
of ca. 340°C; steam is simultaneously generated
where x = 0.94 ± 0.06; y = 0.10 ± 0,05 and z = in a boiler. The air–methanol feed must be a
0.45 ± 0.07. The rate is independent of the flammable mixture, but if the oxygen content is
formaldehyde partial pressure. The measured reduced to ca. 10 mol% by partially replacing air
activation energy is 98 ± 6 kJ/mol. with tail gas from the absorption tower, the
As shown in Figure 3, the methanol feed is methanol content in the feed can be increased
passed to a steam-heated evaporator. Freshly without forming an explosive mixture [89].
blown-in air and recycled off-gas from the After leaving the reactor, the gases are cooled
to 110°C in a heat-exchange unit and are passed
to the bottom of an absorber column. The
formaldehyde concentration is regulated by
controlling the amount of process water added
at the top of the column. The product is removed
from the water-cooled circulation system at the
bottom of the absorption column and is fed
through an anion-exchange unit to reduce the
formic acid content. The final product contains
up to 55 wt% formaldehyde and 0.5–1.5 wt%
methanol. The resultant methanol conversion
ranges from 95–99 mol% and depends on the
selectivity, activity, and spot temperature of the
catalyst, the latter being influenced by the heat
transfer rate and the throughput rate. The overall
plant yield is 88–92 mol%.
Well-known processes using the Formox
method have been developed by Perstorp/
Reichhold (Sweden, United States, Great Brit-
ain) [90, 91], Lummus (United States) [92],
Montecatini (Italy) [93], and Hiag/Lurgi
(Austria) [94].
The tail gas does not burn by itself because it
consists essentially of N2, O2, and CO2 with a
few percent of combustible components such as
dimethyl ether, carbon monoxide, methanol,
and formaldehyde. Combustion of Formox
Figure 3. Flowchart of formaldehyde production by the tail gas for the purpose of generating steam is
Formox process not economically justifiable [95]. Two alterna-
a) Evaporator; b) Blower; c) Reactor; d) Boiler; e) Heat tive methods of reducing atmospheric emission
exchanger; f) Formaldehyde absorption column; g) Circula-
tion system for heat-transfer oil; h) Cooler; i) Anion- have been developed. The off-gas can be burned
exchange unit either with additional fuel at a temperature of
12 Formaldehyde

700–900°C or in a catalytic incinerator at credits for steam production. According to the

450–550°C. However, the latter system employs resulting data the silver process, without the
a heat exchanger and is only thermally self- recovery of methanol (cost of formaldehyde
sufficient if supplementary fuel for start-up is $ 259/t), offers the most favorable production
provided and if an abnormal ratio of oxygen: costs, followed by the Formox process ($ 278/t)
combustible components is used [96]. and the silver process with recovery ($ 287/t).
The two latter processes produce a product
with < 1% methanol whereas the methanol con-
4.3. Comparison of Process Economics tent in the silver process without recovery lies
between 1–5%.
Considering the economic aspects of the three The study [2] takes into consideration the
formaldehyde processes in practice, it becomes benefit of the production of steam only in the
obvious that the size of the plant and the cost of case of the Formox process at a steam price of $
methanol are of great importance. Generally, 18/t. In Table 5, the production of steam is also
the Formox process proves to be advantageous included in the silver processes. The proven
regarding the attainable formaldehyde yield. capacity limits of a plant with only one reactor
The silver process requires lower investment at are about 54 × 103 t/a (calculated 100%) with
same plant size. In consequence, the silver the metal oxide process and about 90 × 103 t/a
process demands a larger plant size to com- with the silver process.
pensate the disadvantage of lower raw material The key feature of the BASF process for the
yield. For the purpose of a cost comparison, a production of 50 wt% formaldehyde is a liquid
study was undertaken based on the cost of circulation system in which heat from the absorp-
methanol being $ 443/t and a plant production tion unit of the plant is transferred to a stripper
capacity of 54 × 103 t/a of 37% formaldehyde column to vaporize the methanol–water feed.
(calculated 100%) [2]. Table 5 summarizes the Therefore, the process produces excess steam,
economic data additionally taking into account with simultaneous savings in cooling water.

Table 5. Comparison of economic factors in formaldehyde production processes [2] 54 × 103 plant producing 37% formaldehyde in the US
gulf coast

Unit Silver catalyst Silver catalyst with Formox process

(complete conversion) methanol recycle

Technology features
Total project investment $ millions 11 15 16
Methanol consumption t/t 0.46 0.45 0.43
Steam demand t/t 0.2 0.5 0.2
Steam production t/t 1.1 0.6 0.5
Reactor temperature °C 600–720 590–650 250–400
Methanol yield % 86% 87% 92%
Production cost calculation
Methanol cost $/t 204 202 190
Catalyst and other chemicals $/t 3 3 3
Raw material $/t 207 204 193
Steam cost $/t 4 9 4
Steam credit $/t 20 10 9
Other utilities $/t 5 5 7
Utilities $/t 11 4 1
Fixed costs $/t 21 24 25
Cash cost $/t 216 232 219
Depreciation $/t 18 24 26
Cost of production $/t 235 256 245
10 ROCE $/t 25 31 33
Cost of production + 10% ROCE $/t 259 287 278
 Formaldehyde 13

Plant operation and start-up are simple; the obtained in the silver-catalyzed processes, a
plant can be restarted after a shutdown or after a Formox plant must burn the tail gas with
short breakdown, as long as the temperatures in sulfur-free fuel, with or without partial regen-
the stripping cycle remain high. The BASF eration of energy by means of steam produc-
process has several other advantages. Formal- tion. Advantages of the process are its very
dehyde is obtained from a single pass of the low reaction temperature, which permits high
methanol through the catalyst. If a lower form- catalyst selectivity, and the very simple
aldehyde concentration is needed (e.g., 40 wt%) method of steam generation. All these aspects
the yield can be increased by employing a mean an easily controlled process. Plants
feedstock of suitably pretreated crude based on this technology can be very small
aqueous methanol instead of pure methanol with annual capacities of a few thousand tons.
(cf. Section 4.1.1 Complete Conversion of As a result, plants employing Formox metha-
Methanol (BASF Process)). Deacidification nol oxidation are most commonly encountered
by means of ion exchangers is not necessary. throughout the world. However, if higher
The off-gas does not present any problems capacities are required and a small number
because it is burned as a fuel gas in power of reactors must be arranged in parallel, the
stations to generate steam or steam and power. economic data favor the processes employing a
The catalyst can be exchanged within 8–12 h of silver catalyst.
plant shutdown to restart and can be regenerated It is difficult to be precise as to what the share
completely with little loss. The plant is compact of each of the three technologies is with respect
due to the small volume of gas that is used and to the global formaldehyde capacity. However,
the low space requirements; both factors result it is fair enough to state that all three technol-
in low capital investment costs. ogies are relevant for the current production of
Formaldehyde production processes based formaldehyde.
on incomplete methanol conversion employ a
final distillation column to recover the methanol
and concentrate the formaldehyde. As shown in 4.4. Distillation of Aqueous
Table 5, this means that more steam and cooling Formaldehyde Solutions
water is consumed than in the BASF process.
The BASF process has a somewhat lower yield Since formaldehyde polymerizes in aqueous
but all other aspects are roughly comparable. solutions, the monomer content and thus the
Other distinctive features of the incomplete vapor pressure of formaldehyde during distilla-
conversion of methanol are the relatively large tion are determined by the kinetics of the asso-
amount of direct steam introduced into the feed- ciated reactions.
stock and the lower reaction temperature, which Vacuum distillation produces a more con-
give a somewhat larger amount of hydrogen centrated bottom product and can be carried out
in the off-gas with a net calorific value of at a low temperature, an extremely low vapor
2140 kJ/m3. The additional ion-exchange unit pressure, and an acid pH value of 3–3.4 [97].
also increases production costs. However, the distillation rates are low, making
The Formox process uses excess air in the this procedure uneconomical.
methanol feed mixture and requires at least 13 High-pressure distillation at 0.4–0.5 MPa
mol of air per mole of methanol. A flammable and above 130°C with long columns produces
mixture is used for the catalytic conversion. a relatively concentrated overhead product. Effi-
Even with gas recycling, the process must ciency is high, but yields are limited due to the
handle a substantial volume of gas, which is formation of methanol and formic acid via the
3–3.5 times the gas flow in a silver-catalyzed Cannizzaro reaction [98].
process. Thus, the equipment must have a large If formaldehyde solutions are subjected to
capacity to accommodate the higher gas flow. slow distillation at atmospheric pressure with-
The main disadvantage of the Formox process out refluxing, the distillate has a lower formal-
is that the off-gas is noncombustible, causing dehyde content than the bottom product [22]. If
substantial costs in controlling environmental the condensate is refluxed, the ratio of conden-
pollution. To reduce air pollution to the levels sate (reflux) to distillate determines the
14 Formaldehyde

formaldehyde content of the distillate removed

[97].
In the case of aqueous formaldehyde solu-
tions that contain methanol, a virtually metha-
nol-free product can be obtained by using
distillation columns with a large number of
plates and a relatively high reflux ratio. The
product is taken from the bottom of the column
[99].

4.5. Preparation of Liquid Monomeric

Figure 4. Apparatus for the preparation of liquid mono-
Formaldehyde meric formaldehyde
a) Distillation flask; b) Glass tube with hairpin turns; c)
Two methods have been described for the prep- Condenser; d) Glass wool
aration of liquid monomeric formaldehyde from
paraformaldehyde, the first was developed by F.
WALKER [12] and the second by R. SPENCE [100].
In WALKER’s method, liquid formaldehyde is condenser flask is cooled in liquid air, a color-
prepared by vaporizing alkali-precipitated less solid product condenses. The inlet and
α-polyoxymethylene. The resultant vapor is outlet tubes of the condenser flask are then
then condensed and the crude liquid condensate sealed with a flame. The contents of the con-
is redistilled. The process is performed in an densing flask liquefy when carefully warmed.
apparatus made of Pyrex glass. A vaporizing The procedure can be repeated to obtain an even
tube is charged to about one-half its height with purer substance. The liquid formaldehyde that is
the polymer. The thoroughly dried system is prepared does not polymerize readily and, when
then flushed with dry nitrogen. The vaporizing vaporized, leaves only very small traces of
tube is heated to 150°C in an oil bath and the polymeric product.
condensing tube is chilled in a bath of solid
carbon dioxide and methanol. The polymer is
vaporized in a slow stream of nitrogen by 5. Environmental Protection
gradually raising the temperature. Formation
of polymer on the tube walls is minimized by As already stated, formaldehyde is ubiqui-
winding wire round the tubes and heating with tously present in the atmosphere [101]. It is
electricity. The crude liquid product, which is released into the atmosphere as a result of the
opalescent due to precipitated polymer, is then combustion, degradation, and photochemical
distilled in a slow current of nitrogen. decomposition of organic materials. Formalde-
According to the method of SPENCE, para- hyde is also continuously degraded to carbon
formaldehyde is dried over sulfuric acid in a dioxide in processes that are influenced by
vacuum desiccator and introduced into a distil- sunlight and by nitrogen oxides. Formalde-
lation flask. This flask is connected to a glass hyde washed out of the air by rain is degraded
condenser via glass tubes with relatively long by bacteria (e.g., Escherichia coli, Pseudomo-
hairpin turns designed to separate traces of nas fluorescens) to form carbon dioxide and
water (Fig. 4). The system is first evacuated water [102].
by means of a mercury diffusion pump, and The major source of atmospheric formalde-
the distillation flask is then heated to 110°C in hyde is the photochemical oxidation and
an oil bath to remove traces of oxygen. The incomplete combustion of hydrocarbons (i.e.,
distillate is heated electrically to 120°C when methane or other gases, wood, coal, oil, tobacco,
it flows through the upper parts of the hairpin and gasoline). Accordingly, formaldehyde is a
turns; in the lower parts of the loops, it is component of car and aircraft exhaust fumes and
cooled to 78°C by means of a cooling bath. is present in considerable amounts in off-gases
After the valve to the pump is shut and the from heating plants and incinerators. The main
 Formaldehyde 15

Table 6. Sources emitting formaldehyde into the atmosphere [103] Formaldehyde in confined areas comes from
Emission source Formaldehyde level
the following sources:
Natural gas combustion
Home appliances and 1. Smoking of cigarettes and tobacco products
industrial equipment 2400–58 800 μg/m3 [104, 106, 107]
Power plants 15 000 μg/m3
2. Urea–, melamine–, and phenol–formalde-
Industrial plants 30 000 μg/m3
Fuel-oil combustion 0.0–1.2 kg/barrel oil hyde resins in particle board and plywood
Coal combustion furniture
Bituminous < 0.005–1.0 g/kg coal 3. Urea–formaldehyde foam insulation
Anthracite 0.5 g/kg coal
Power plant, industrial, 4. Open fireplaces, especially gas fires and
and commercial stoves
combustion 2.5 mg/kg coal
Refuse incinerators
5. Disinfectants and sterilization of large sur-
Municipal 0.3–0.4 g/kg refuse faces (e.g., hospital floors)
Small domestic 0.03–6.4 g/kg refuse
Backyard (garden refuse) up to 11.6 g/kg refuse Sources generating formaldehyde must be
Oil refineries
Catalytic cracking units 4.27 kg/barrel oil
differentiated into those which release formal-
Thermoform units 2.7 kg/barrel oil dehyde for a defined period, cases (1), (4), and
Automotive sources (5) and those which release formaldehyde gas
Automobiles 0.2–1.6 g/L fuel continuously, i.e., decomposition of resins as in
Diesel engines 0.6–1.3 g/L fuel
Aircraft 0.3–0.5 g/L fuel
cases (2) and (3). Many regulations have been
issued to limit pollution of the atmosphere with
formaldehyde in both general and special appli-
cations [108]. Protection against pollution of
emission sources of formaldehyde are summa- the environment with formaldehyde must be
rized in Table 6. enforced with due attention to its sources.
The formaldehyde in the exhaust gases of The most effective limitation of atmospheric
motor vehicles is produced due to incomplete pollution with formaldehyde is the strict obser-
combustion of motor fuel. Formaldehyde may vation of the maximum allowable concentration
be produced directly or indirectly. In the indirect indoors and outdoors. A maximum workplace
route, the unconverted hydrocarbons undergo concentration of 0.37 mg/m3 (0.3 ppm) has, for
subsequent photochemical decomposition in the example, been established in the Germany
atmosphere to produce formaldehyde as an [109]. Other limit values and guide values
intermediate [104]. The concentration of form- have been specified for formaldehyde levels
aldehyde is higher above densely populated in outdoor and indoor air. Emission limits for
regions than above the oceans as shown in stationary installations have also been estab-
Table 7 [105]. lished and regulations for specific products
have been formulated. Table 8 gives a survey
of regulations valid in some countries in 2010.
In Germany, formaldehyde levels and emis-
Table 7. Geographical distribution of formaldehyde in ambient air sions are subjected to stringent regulations.
Location Formaldehyde Plants operating with formaldehyde must con-
concentration (max.), ppm∗ form to the plant emission regulations intro-
Air above the oceans 0.005 duced in 2015 which limit formaldehyde in
Air above land 0.012 off-gases to a maximum of 5 mg/m3 for mass
Air in German cities flow rates of 0.1 kg/h or more [111]. The
normal circumstances 0.016 national emission limits will thereby have to
high traffic density 0.056
Air in Los Angeles (before 0.165 follow the European Industrial Emission Direc-
the law on catalytic com- tive (IED) Guideline and different BREF (Best
bustion of exhaust gases available technique Reference Document)
came into effect) [112]. Due to the organization into horizontal
∗
1 ppm = 1.2 mg/m3 and vertical BREF different emission level will
16 Formaldehyde

Table 8. International regulations restricting formaldehyde levels [110]

Country Eight hour exposure limit, ppm Short term limit, ppm Ceiling limit, ppm

Australia 1 2 -
Argentina - - 0.3
Belgium - - 0.3
Brazil - - 1.6
Canada – Alberta 0.75 - 2
Canada – British Columbia 0.3 - 1
Canada – Manitoba - - 0.3
Canada – Newfoundland - - 0.3
Canada – Nova Scotia - - 0.3
Canada – Ontario - 1 1.5
Canada – Quebec - - 2
Denmark - - 0.3
Finland 0.3 - 1
France 0.5 1 -
Germany (MAK∗) 0.3 0.6 1
Italy - - 0.3
Japan 0.1 - 0.2
Netherlands 1 1.5 -
Norway 0.5 1.5 -
South Africa 2 2 -
Spain - 0.3 -
Sweden 0.5 - 1
Switzerland 0.5 1 -
United Kingdom (HSE∗) 2 2 -
USA (ACGIH∗) - - 0.3

USA – NIOSH∗ 0.016 0.1 -

USA – OSHA∗ 0.75 2 -
∗
According to MAK values – Maximale Arbeitsplatz-Konzentration (Threshold Limit Value); HSE-Health, Safety, Environmental; ACGIH-
American Conference of Governmental Industrial Hygienists; NIOSH – National Institute for Occupational Safety and Health; OSHA –
Occupational Safety and Health Administration

be defined for formaldehyde production plants German Institute for Structural Engineering has
(LVOC-BREF 241) and upstream process (e.g., issued guidelines for classifying particle board
Wood-based panel BREF [113]). into emission categories E1, E2, and E3, class
This presupposes a closed handling proce- E3 having the highest emission [118]. The low-
dure. For example, industrial filling and transfer est class (E1) is allowed a maximum formalde-
of formaldehyde solutions is carried out by hyde emission of 0.1 ppm and a maximum
using pressure compensation between commu- formaldehyde content of 10 mg per 100 g of
nicating vessels. Discharge of formaldehyde absolutely dry board (as measured by the DIN
into wastewater in Germany is regulated by EN 120 perforator method) [119]. Furthermore,
law since it endangers water and is toxic to the uses and applications of urea–formaldehyde
small animals [114]. Formaldehyde is, however, foams, which are used to some extent for the
readily degraded by bacteria in nonsterile, nat- heat insulation of cavity walls, have been con-
ural water [115]. trolled by DIN 18 159 [119] since 1978. No
A maximum limit of 0.1 ppm formaldehyde formaldehyde emission is permitted after the
in indoor living and recreation areas has been construction has dried.
recommended by the BGA (German Federal Cigarette smoke contains 57–115 ppm of
Health Office) [116] and confirmed by the ad- formaldehyde and up to 1.7 mg of formaldehyde
hoc-AG in 2006 [117]. To avoid unacceptable can be generated while one cigarette is smoked.
formaldehyde concentrations in room air, the If five cigarettes are smoked in a 30 m3 room,
 Formaldehyde 17

with a low air-change rate of 0.1 (i.e., 10%) per exchangers. Typical product specifications for
hour, the formaldehyde concentration reaches formulations on the European market are listed
0.23 ppm [104, 107]. in Table 9. Other manufacturers’ specifications
The best protection against accumulation of are described in [121–127].
formaldehyde in confined spaces is, however,
proper ventilation. The strong smell of formal-
dehyde is perceptible at low concentration and 6.2. Analysis
thus provides adequate warning of its presence.
If all manufacturing and application regulations The chemical reactivity of formaldehyde pro-
are strictly observed, possible emission of form- vides a wide range of potential methods for its
aldehyde from consumer products is very low qualitative and quantitative determination in
and will not therefore constitute a human health solutions and in the air.
hazard.
Qualitative Methods. Qualitative detection of
Formaldehyde concentrations in cosmetic
formaldehyde is primarily provided by colori-
products have been limited since 1977, they
metric methods, e.g., [129, 130], Schiff’s fuch-
must be appropriately labeled if they contain
sin–bisulfite reagent is a general reagent used
> 0.05 wt% formaldehyde [120]. Below this
for detecting aldehydes. In the presence of
level, formaldehyde does not cause allergic
strong acids, it reacts with formaldehyde to
reactions even in sensitive subjects.
form a specific bluish violet dye. The detection
limit is ca. 1 mL/m3. Further qualitative detec-
6. Quality Specifications and tion methods are described in [131].
Analysis Quantitative Methods. Formaldehyde can be
quantitatively determined by either physical
6.1. Quality Specifications
or chemical methods.
Formaldehyde is commercially available pri- Physical Methods. Quantitative determination
marily in the form of an aqueous (generally of pure aqueous solutions of formaldehyde can
30–55 wt%) solution, and in solid form as be carried out rapidly by measuring their spe-
paraformaldehyde or trioxane (cf. Chap. 11 cific gravity [39]. Gas chromatography [132,
Low-Molecular-Mass Polymers). Formalde- 133] and high-pressure liquid chromatography
hyde solutions contain 0.5–12 wt% methanol (HPLC) [134–136] can also be used for direct
or other added stabilizers (see Chap. 7 Storage determination.
and Transportation). They have a pH of
2.5–3.5, the acid reaction being due to the Chemical Methods. The most important chem-
presence of formic acid, formed from formal- ical methods for determining formaldehyde are
dehyde by the Cannizzaro reaction. The solu- summarized in [131]. The sodium sulfite
tions can be temporarily neutralized with ion method is most commonly used. This method

Table 9. Typical specifications of commercial formaldehyde solutions [128]

Formaldehyde Methanol content Formic acid Iron content Density Added stabilizer
content, wt% (max), wt% content (max), mg/kg (max), mg/kg t, °C g/mL

30 1.5 150 0.8 20 1.086–1.090

37 1.8 200 1 20 1.107–1.112
37 8–12 200 1 20 1.082–1.093 Methanol
37 1.8 200 1 20 1.108–1.112 Isophthalobisguanamine,
100 mg/kg
50 2.0 200 1 55 1.126–1.129
50 2.0 200 1 40 1.135–1.138 Isophthalobisguanamine,
200 mg/kg
18 Formaldehyde

was developed by LEMMÉ [137] and was subse- Table 10. Storage temperatures for commercial formaldehyde
quently improved by SEYEWETZ and GIBELLO solutions
[138], STADTLER [139], and others. It is based Formaldehyde Methanol Storage
on the quantitative liberation of sodium hydrox- content, wt% content, wt% temperature, °C
ide produced when formaldehyde reacts with 30 1 7–10
excess sodium sulfite: 37 <1 35
37 7 21
CH2 O ‡ Na2 SO3 ‡ H2 O→ HOCH2 SO3 Na ‡ NaOH 37 10–12 6–7
50 1–2 45∗
50 1–2 60–65
The stoichiometrically formed sodium
∗
hydroxide is determined by titration with acid Stabilized with 200 mg/kg of isophthalobisguanamine.
[39].
Formaldehyde in air can be determined down The many compounds used for stabilizing
to concentrations in the μL/m3 range with the formaldehyde solutions include urea [146], mel-
aid of gas sampling apparatus [140, 141]. In this amine [147], hydrazine hydrate [148], methyl-
procedure, formaldehyde is absorbed from a cellulose [149], guanamines [150], and
defined volume of air by a wash liquid and is bismelamines [45]. For example, by adding as
determined quantitatively by a suitable method. little as 100 mg of isophthalobisguanamine
The quantitative determination of formaldehyde [5118-80-9] per kilogram of solution, a 40 wt
in air by the sulfite/pararosaniline method is % formaldehyde solution can be stored for at
described in [142]. least 100 d at 17°C without precipitation of
A suitable way of checking the workplace paraformaldehyde, and a 50 wt% formaldehyde
concentration of formaldehyde is to take a solution can be stored for at least 100 d at 40°C
relevant sample to determine the exposure of [44].
a particular person and to use this in combina- Formaldehyde can be stored and transported
tion with the pararosaniline method. The liquid in containers made of stainless steel, aluminum,
test solution is transported in a leakproof wash enamel, or polyester resin. Iron containers lined
bottle [131]. A commercial sampling tube [143, with epoxide resin or plastic may also be used,
144] can also be used, in which the formalde- although stainless steel containers are preferred,
hyde is converted to 3-benzyloxazolidine during particularly for higher formaldehyde concentra-
sampling. Evaluation is carried out by gas tions. Unprotected vessels of iron, copper,
chromatography. nickel, and zinc alloys must not be used.
Continuous measurements are necessary to The flash point of formaldehyde solutions is
determine peak exposures, e.g., by the para- in the range 55–85°C, depending on their con-
rosaniline method as described in [145]. centration and methanol content. According to
German regulations for hazardous substances
(Gefahrstoffverordnung, Appendix 6) and
7. Storage and Transportation Appendix 1 of the EEC guidelines for hazardous
substances, aqueous formaldehyde solutions
With a decrease in temperature and/or an used as working materials that contain  1 wt
increase in concentration, aqueous formalde- % of formaldehyde must be appropriately
hyde solutions tend to precipitate para- labeled. The hazard classifications for the trans-
formaldehyde. On the other hand, as the port of aqueous formaldehyde solutions with a
temperature increases, so does the tendency to flash point between 21 and 55°C containing > 5
form formic acid. Therefore, an appropriate stor- wt% formaldehyde and < 35 wt% methanol are
age temperature must be maintained (Table 10). as follows [151]:
The addition of stabilizers is also advisable (e.g.,
methanol, ethanol, propanol, or butanol). How- GGVS/GGVE, ADR/RID Class 8, number 63 c
ever, these alcohols can be used only if they do CFR 49: 172.01 flammable
not interfere with further processing, or if they liquid
can be separated off; otherwise, effluent prob- IMDG Code (GGVSee) Class 3.3
UN No. 1198
lems may be encountered.
 Formaldehyde 19

Formaldehyde solutions with a flash point > separate keywords. In this respect, formalde-
61°C and aqueous formaldehyde solutions with hyde is irreplaceable as a C1 building block. It
a flash point > 55°C that contain > 5 wt% is, for example, used to synthesize 1,4-butane-
formaldehyde and < 35 wt% methanol are diol [110-63-4], trimethylolpropane [77-99-6],
classified as follows: and neopentyl glycol [126-30-7], which are
employed in the manufacture of polyurethane
GGVS/GGVE, ADR/RID Class 8, number 63 c and polyester plastics, synthetic resin coatings,
CFR 49: 172.01 combustible
liquid
synthetic lubricating oils, and plasticizers. Other
IMDG Code (GGVSee) Class 9 compounds produced from formaldehyde
UN No. 2209 include pentaerythritol [115-77-5] (employed
chiefly in raw materials for surface coatings
and in permissible explosives) and hexa-
methylenetetramine [100-97-0] used as a
8. Uses cross-linking agent for phenol–formaldehyde
condensates and permissible explosives).
Formaldehyde is one of the most versatile chem- The complexing agents nitrilotriacetic acid
icals and is employed by the chemical and other [139-13-9] (NTA) and ethylenediaminetetraace-
industries to produce a virtually unlimited num- tic acid [60-00-4] (EDTA) are derived from
ber of indispensable products used in daily life formaldehyde and are components of deter-
[152]. gents. The demand for formaldehyde for the
Resins. The highest amounts of formaldehyde production of 4,4´ -diphenylmethane diisocya-
are used for producing condensates (i.e., resins) nate [101-68-8] (MDI) is steadily increasing.
with urea, melamine, and phenol and, to a small This compound is a constituent of polyur-
extent, with their derivatives (see also Amino ethanes used in the production of soft and rigid
Resins; → Phenolic Resins; → Resins, Syn- foams and, more recently, as an adhesive and for
thetic). The main part of these resins is used bonding particle boards.
for the production of adhesives and impregnat- The so-called polyacetal plastics (→ Poly-
ing resins, which are employed for the manu- oxymethylenes) produced by polymerization of
facture of particle boards, plywood, and formaldehyde are increasingly being incorpo-
furniture. These condensates are also employed rated into automobiles to reduce their weight
for the production of curable molding materials and, hence, fuel consumption. They are also
→ Plastics Processing, 2. Processing of Ther- used for manufacturing important functional
mosets; as raw materials for surface coating → components of audio and video electronics
Paints and Coatings, 2. Types; Chapter 12. equipment [153].
Urea, Benzoguanamine, and Melamine Resins Formaldehyde is also a building block for
for Coatings and as controlled-release nitrogen products used to manufacture dyes, tanning
fertilizers → Fertilizers, 2. Types; Section 2.4 agents, dispersion and plastics precursors,
Slow- and Controlled-Release Fertilizers. They extraction agents, crop protection agents, animal
are used as auxiliaries in the textile, leather, feeds, perfumes, vitamins, flavorings, and
rubber, and cement industries. Further uses drugs.
include binders for foundry sand, rockwool
and glasswool mats in insulating materials, Direct Use. Only a very small amount of form-
abrasive paper, and brake linings. A very small aldehyde is used directly without further proc-
amount of urea–formaldehyde condensates are essing. It is used directly as a corrosion
used in the manufacture of foamed resins (→ inhibitor, in the metal industry as an aid in
Foamed Plastics) that have applications in the mirror finishing and electroplating, in the elec-
mining sector and in the insulating of buildings. trodeposition of printed circuits, and in the
photographic industry for film development.
Use as an Intermediate. About 40% of the total However, formaldehyde as such is used mainly
formaldehyde production is used as an interme- for preservation and disinfection, for example,
diate for synthesizing other chemical com- in medicine for disinfecting hospital wards,
pounds, many of which are discussed under preserving specimens, and as a disinfectant
20 Formaldehyde

against athlete’s foot (→ Disinfectants, Section Table 11. Worldwide formaldehyde production capacities (based
6.2 Aldehydes). on 100 wt%) in 2011 [2, 154]
Modern hygiene requires preservatives and Region/country Total capacity, 103 t/a
disinfectants to prevent the growth of micro-
Asia Pacific 9463
organisms which can produce substances that China 5088
may be extremely harmful to man. As an Japan 675
antimicrobial agent, formaldehyde displays Indonesia 427
very few side effects, but has a broad spectrum India 279
Malaysia 250
of action → Biocides; Section 4.2 Aldehydes South Korea 191
und Formaldehyde-Releasing Compounds. All Taiwan 159
alternative agents have unpleasant or even Thailand 143
dangerous side effects. Moreover, their toxic- Others 2251
Western Europe 3435
ity has not been as thoroughly investigated as Germany 1005
that of formaldehyde, and their spectrum of Italy 464
action is limited (i.e., they do not provide Netherlands 352
comprehensive disinfectant protection). Spain 335
United Kingdom 294
Another advantage of formaldehyde is that it Belgium 220
does not accumulate in the environment since Sweden 157
it is completely oxidized to carbon dioxide Others 608
within a relatively short time. In the cosmetics Central and Eastern Europe 1547
Russia 807
industry, formaldehyde is employed as a pre- Poland 174
servative in hundreds of products, for example, Others 566
soaps, deodorants, shampoos, and nail-harden- North America 2440
ing preparations; in some of these items, upper United States 2088
Canada 265
limits have been set for the formaldehyde Mexico 87
concentration due to its sensitizing effect (cf. South America 623
Table 8). Formaldehyde solutions are also used Brazil 360
as a preservative for tanning liquors, disper- Chile 118
Argentina 65
sions, crop protection agents, and wood pres- Others 80
ervatives. Furthermore, formaldehyde is Middle East 385
required in the sugar industry to prevent bac- Africa 79
terial growth during syrup recovery.

Momentive Specialties Chemicals 1.5 × 106 t/a

9. Economic Aspects BASF 0.5 × 106 t/a
Dynea 0.4 × 106 t/a
Formaldehyde is one of the most important
basic chemicals and is required for the manu-
facture of thousands of industrial and consumer The three leading countries with a formalde-
products. It is the most important industrially- hyde capacity (based on 100 wt%) share of
produced aldehyde. about 45% are:
Formaldehyde can seldom, if ever, be
replaced by other products. Substitutes are gen- China 5.09 × 106 t/a
erally more expensive; moreover, their toxicities United States 2.09 × 106 t/a
have been less thoroughly investigated than that Germany 1.01× 106 t/a
of formaldehyde.
Worldwide capacity [2, 154] for formalde-
hyde 100 wt% is approximately ~18 × 106 t/a in Formaldehyde consumption is ca. 13.1 × 106
2011 (see Table 11; the values are based on 100 t/a, based on 100 wt% formaldehyde. The global
wt% formaldehyde); the three largest manufac- demand by area of application and by region is
turers of this capacity are [2]: summarized in Table 12.
 Formaldehyde 21

Table 12. Global consumption of formaldehyde by area of Table 13. Dose – response relationship following human exposure
application and by region in 2011 [2] to gaseous formaldehyde [162, 163]

Global use by area of application % Effect Exposure level, ppm

Amino resins 34 Odor threshold 0.05–1.0

Phenolic resins 12 Irritation threshold in eyes, 0.2–1.6
Polyacetal resins 9 nose, or throat
Acetylenics chemicals 8 Stronger irritation of upper 3–6
MDI 6 respiratory tract, coughing,
Paraformaldehyde 6 lacrimation, extreme discomfort
Pentaerythritol 4 Immediate dyspnea, burning in 10–20
Hexamine 4 nose and throat, heavy coughing and
Others 17 lacrimation
Necrosis of mucous membranes, > 50
Global use by region % laryngospasm, pulmonary edema

Asia Pacific 50.2

Western Europe 22.3
North America 16.2 sensitization. There is no evidence for formal-
Central and Eastern Europe 5.2 dehyde to cause respiratory allergy [161].
South America 3.6 In chronic inhalation studies with rats, mice,
Middle East 2.0
hamsters, and monkeys no systemic toxicity
Africa 0.5
occurred in irritant concentrations. Upper respi-
ratory tract irritation ceased at concentrations <
ca. 1 ppm. At concentrations above 1–2 ppm
Formaldehyde and its associated products are changes in the nasal mucosa (respiratory epi-
used in ca. 50 different branches of industry, as thelium) occur. At high concentrations (15–20
described in Chapter 8 Uses. ppm) olfactory epithelium, laryngeal mucosa,
and proximal parts of the tracheal epithelium
might also be affected. The lesions are charac-
10. Toxicology and Occupational terized by epithelial hyperplasia and metaplasia.
Health Studies using other routes of administration also
failed to show systemic toxicity or reproductive
Formaldehyde toxicity was investigated exten- effects.
sively during the last decades and comprehen- Formaldehyde was genotoxic in several in
sive reviews are available [155–160]. vitro test systems. In animals, there are some
Formaldehyde is an essential intermediate in indications of in vivo genotoxicity in tissues of
cellular metabolism in mammals and humans, initial contact (portal of entry) but not in remote
serving as a precursor for the biosynthesis of organs or tissues. In workers exposed to form-
amino acids, purines and thymine. Exogenously aldehyde no systemic genotoxicity and no con-
administered formaldehyde is readily metabo- vincing evidence of local genotoxicity was
lized by oxidation to formic acid or reacts with found.
biomolecules at the sites of first contact. Inha- No evidence of systemic carcinogenicity was
lation exposure of rats, monkeys, and humans to found after oral, dermal, and inhalative admin-
irritant concentrations did not increase blood istration of formaldehyde. Several chronic inha-
formaldehyde levels, which were found to be lation studies in rats showed development of
around 80 mM (= 2.4 ppm) in these species. nasal tumors starting at concentrations at or
Formaldehyde gas is toxic via inhalation above 6 ppm, causing in addition severe chronic
and causes irritation of the eyes and the epithelial damage in the nasal epithelium [164].
mucous membranes of the respiratory tract. The nonlinear concentration response curve
Concentration–response relationship following shows a disproportionately high increase in
human exposure is given in Table 13. Aqueous tumor incidence at concentrations of 10 and
formaldehyde solutions cause concentration 15 ppm. The same nonlinear concentration
dependent corrosion or irritation and skin response was observed for DNA protein
22 Formaldehyde

cross-link (DPX) formation in nasal mucosa, mass representatives of this group are the sug-
which is a surrogate of formaldehyde tissue ars. Although these substances can be made by
“dose”, and for increase in cell proliferation aldol condensation of formaldehyde, they do not
in nasal epithelium. This leads to the suggestion revert to formaldehyde on cleavage, and are not
that increased cell proliferation is a prerequisite discussed in this article.
for tumor development [164]. Chronic inhala- The representatives of group (1), the real
tion studies in mice failed to show statistically formaldehyde polymers (polyoxymethylenes),
significant increases in tumor incidences at sim- revert to formaldehyde on cleavage and, there-
ilar concentrations while in hamsters no nasal fore, can be considered as a solid, moisture-free
tumors were found. This may be attributed to form of formaldehyde. If these linear or cyclic
differences in local formaldehyde tissue dose or compounds contain no more than eight formal-
lower susceptibility of the species for nasal dehyde units, they are defined as low-molecu-
tumor formation. lar-mass polymers. The high-molecular-mass
Over a long period of time, numerous epi- substances are the real polymers (para-
demiological studies failed to give convincing formaldehyde, acetal plastics, see also →
evidence of carcinogenicity [157]. But based on Polyoxymethylenes). Chemical and physical
newer data of the cohort analyses for naso- analyses of these low- and high-molecular-
pharyngeal cancer mortality of the National mass compounds as well as investigation of
Cancer Institute (NCI) [165], the International their chemical reactions led to the elucidation
Agency for Research on Cancer IARC [156, of the molecular structure of polymers in gen-
166] had to classify formaldehyde as “known eral [171].
human carcinogen (Group 1)”. On the contrary,
the ECHA adopted the opinion of the Commit-
tee for Risk Assessment of the European Chem- 11.1. Linear Polyoxymethylenes
ical Agency and chose the lower protective
category “presumed human carcinogen (Class Apart from the poly(oxymethylene) glycols,
1B)”. The incorporation of the new classifica- also called poly(oxymethylene) dihydrates or
tion in the 6th Adaptation to Technical Progress simply polyoxymethylenes, of the formula
(ATP) [167] entered into force in 2015. HO-(CH2O)n-H, derivatives such as poly
Current occupational exposure limits in dif- (oxymethylene) diacetates CH3COO(CH2O)n
ferent countries vary between 0.1 and 1 ppm COCH3 and poly(oxymethylene) dimethyl
[110, 168] for long-term and between 0.1 and 2 ethers CH3O(CH2O)nCH3 should be mentioned.
ppm for short-term exposure. Nevertheless the Some of their physical properties are given in
limit values for indoor air of 0.1 ppm proposed Table 14. The n values of the real low-molecu-
in 1992 [169] were confirmed in 2010 [170] and lar-mass polyoxymethylenes are 2–8; the n
later on by the WHO. values of paraformaldehyde are 8–100. How-
ever, high polymers with a degree of polymeri-
zation n  3000 are also obtained. The
11. Low-Molecular-Mass Polymers polyoxymethylenes are also classified as α, β,
γ, δ, and ε polymers which are of historical
The ability of formaldehyde to react with itself importance. They differ in their degrees of
to form polymers depends directly on the polymerization and in their chemical structures
reactivity of formaldehyde as a whole. Two (Table 15). Their toxicology is the same as that
different types of formaldehyde polymers are of formaldehyde (see Chap. 10 Toxicology and
possible and are based on the following struc- Occupational Health).
tural elements: The lower poly(oxymethylene) glycols are
colorless solids with melting points between 80
1. -CH2-O- and 120°C (Table 14). In contrast to the high-
2. -CH(OH)- molecular-mass materials, they dissolve in ace-
tone and diethyl ether without or with only
The polyhydroxyaldehydes consist of the slight decomposition; they are insoluble in
structural unit (2). The highest molecular petroleum ether. When dissolved in warm
 Formaldehyde 23

Table 14. Physical properties of low-molecular-mass poly(oxymethylene) glycols HO-(CH2O)n-H and their derivatives

n Poly(oxymethylene) glycols Poly(oxymethylene) diacetates Poly(oxymethylene) dimethyl ethers

fp, °C Solubility in acetone fp, °C bp, °C ρ, g/m (13 Pa, 24°C)

3
fp, °C bp, °C (101.3 kPa) ρ, g/cm3(25°C)

2 23 39–40 1.128
3 82–85 Very soluble in the cold 13 60–62 1.158 69.7 105.0 0.9597
4 82–85 Very soluble in the cold 3 84 1.179 42.5 155.9 1.0242
5 95–105 Very soluble in the cold 7 102–104 1.195 9.8 201.8 1.0671
(decomp.)
6 17 124–126 1.204 18.3 242.3 1.1003
7 Soluble in the cold ca. 15 180–190
8 Soluble in the cold ca. 15 180–190
9 115–120 Soluble when heated 32–34 1.216∗
(decomp.)
∗
Value at 13 Pa and 36°C.

Table 15. Structure and synthesis of α–ε polyoxymethylenes [172]

Polymer Formula Synthesis

Paraformaldehyde HO(CH2O)nH from aqueous formaldehyde solution [173]

n = 8–100
α-Polyoxymethylene HO(CH2O)nH from aqueous formaldehyde solution [173]
n > 100
β-Polyoxymethylene HO(CH2O)nH by heating paraformaldehyde [174]
n > 200
γ-Polyoxymethylene H3CO(CH2O)nCH3 from a methanolic paraformaldehyde solution in the presence of
n = 300–500 sulfuric acid [175]
δ-Polyoxymethylene H3CO[CH2OC(OH)HO]nCH3 by prolonged boiling of γ-polyoxymethylene with water [174]
n = 150–170
ε-Polyoxymethylene HO(CH2O)nH by sublimation of 1,3,5-trioxane [174]
n > 300

water, they undergo hydrolysis to give a form- molecular mass when the system is heated.
aldehyde solution. The low-molecular-mass The polymers partially separate out, crystallize,
polymers constitute a homologous series, whose and slowly undergo further condensation
properties change continuously with the degree polymerization [176]. The low-molecular-
of polymerization. mass substances can be further precipitated
A freshly prepared, aqueous formaldehyde and isolated by concentrating the solution at
solution polymerizes to the lower polymers low temperature under vacuum conditions; the
when allowed to stand (see also Section 2.2 polymers can be further precipitated by evapo-
Aqueous Solutions). Indeed, formaldehyde ration [177]. The resulting mixture can be sepa-
exists in dilute solution as dihydroxymethylene rated into the individual substances by
(formaldehyde hydrate), which in turn under- exploiting their varying solubilities in different
goes polycondensation to yield low-molecular- solvents [171].
mass poly(oxymethylene) glycols: The transformation of poly(oxymethylene)
dihydrates to diacetates and, above all, to dieth-
CH2 O ‡ H2 O Û HO-CH2 -OH ‡ n HOCH2 OH ers produces a remarkable increase in thermal
Û HO-CH2 O-…CH2 O†n -H ‡ n H2 O and chemical stability. This is because the
unstable hemiacetals at the ends of the chains
Equilibrium is attained under the influence of are eliminated through saturation of the
a hydrogen ion catalyst. At a low temperature hydroxyl groups. The diethers are stable up to
and a high concentration, equilibrium favors 270°C in the absence of oxygen and up to 160°C
formation of high-molecular-mass polymers. in the presence of oxygen. These diethers and
However, the major product is of lower diacetates are resistant to hydrolysis under
24 Formaldehyde

neutral conditions, the diethers are also stable in Table 16. Vapor pressure of formaldehyde (p) released from
the presence of alkali. Similar to the dihydrates, paraformaldehyde
the properties of the diacetates and diethers also t, °C 10 21 25 33 37
change continuously as the degree of polymeri- p, kPa 0.112 0.165 0.193 0.408 0.667
zation increases (see Table 14).
t, °C 43 47 51 58 65
Poly(oxymethylene) diacetates are produced p, kPa 0.943 1.096 1.376 1.808 20.8
by the reaction of paraformaldehyde with acetic
anhydride [171]. Pure products are isolated by t, °C 80 90 100 110 120
vacuum distillation, solvent extraction, and p, kPa 32.8 44.1 49.6 53.5 78.3
crystallization. ∗
Values up to 58°C according to [179] and from 65–120°C according
The formation of poly(oxymethylene) to [180].
dimethyl ethers involves the reaction of poly-
(oxymethylene) glycols or paraformaldehyde
with methanol at 150–180°C in the presence of individual molecules. The rate of decomposition
traces of sulfuric or hydrochloric acid in a closed therefore depends on the number of end groups,
vessel [171]. Alternatively, they can be synthe- i.e., on the degree of polymerization.
sized by the reaction of formaldehyde dimethyl Paraformaldehyde contains only a few ace-
acetal with either paraformaldehyde or a concen- tone-soluble components (lower diglycols). It
trated formaldehyde solution in the presence of dissolves slowly in cold water, but readily in
sulfuric acid. This synthesis can be varied by warm water where it undergoes hydrolysis and
substituting other formaldehyde dialkyl acetals depolymerization to give a formaldehyde solu-
for the dimethyl compound [178]. tion. Although this solution is generally cloudy
as a result of impurities, these can be removed
Paraformaldehyde [30525-89-4] was first pro- by filtration. Indeed, the resulting solution is
duced in 1859. This polymer, at first mistakenly identical with the solution obtained on dissolv-
called dioxymethylene and trioxymethylene, ing gaseous formaldehyde in water. Not only
consists of a mixture of poly-(oxymethylene) heat, but also dilute alkali or acid increase the
glycols HO-(CH2O)n-H with n = 8–100. The solubility of paraformaldehyde. Alkali catalyzes
formaldehyde content varies between 90 and formaldehyde cleavage at the chain ends, acid
99% depending on the degree of polymerization causes additional splitting at the oxygen
n (the remainder is bound or free water). It is an bridges. The rate constant of dissolution passes
industrially important linear polyoxymethylene. through a minimum between pH 2 and 5, it
increases rapidly above and below this pH range
Properties. Paraformaldehyde is a colorless, [181]. The situation becomes more complex at
crystalline solid with the odor of monomeric higher concentrations of formaldehyde in the
formaldehyde. It has the following physical solution due to the incipient back reaction.
properties: fp 120–170°C, depending on the Solubility in nonaqueous solvents is also
degree of polymerization; heat of combustion improved in the presence of acidic or alkaline
16.750 kJ/kg (product containing 98 wt% form- agents as a result of the onset of de-
aldehyde); energy of formation 177 kJ/mol polymerization. Paraformaldehyde also dis-
formaldehyde (product containing 93 wt% solves in alcohols, phenols, and other polar
formaldehyde); flash point 71°C; ignition tem- solvents, in which depolymerization and solva-
perature of dust 370–410°C; lower explosion tion can occur.
limit of dust 40 g/m3 (the last three values
strongly depend on the particle size); minimum Production. Paraformaldehyde is prepared
ignition energy 0.02 J. industrially in continuously operated plants by
Even at ambient temperature, paraformal- concentrating aqueous formaldehyde solutions
dehyde slowly decomposes to gaseous formal- under vacuum conditions. At first, colloidal,
dehyde (Table 16), a process which is greatly waxy gels are obtained, which later become
accelerated by heating. Depolymerization is brittle. The use of a fractionating column
based on a chain “unzipping” reaction which through which gases were passed dates from
starts at the hemiacetal end groups of the about 1925 [182, 183].
 Formaldehyde 25

Paraformaldehyde is produced in several paraformaldehyde condenses with resorcinol

steps which are carried out at low pressure in an alkaline medium is measured [199]. The
and various temperatures [184–186]. Highly formaldehyde content is measured by using the
reactive formaldehyde is produced under vac- sodium sulfite method (cf. Section 6.2 Analysis)
uum conditions starting with solutions that con- and the water content by the Karl Fischer
tain 50–100 ppm of formic acid and also 1–15 method.
ppm of metal formates where the metals have an
atomic number of 23–30 (e.g., Mn, Co, and Cu) Transport and Storage. Paraformaldehyde is
[187]. The solutions are processed in thin-layer stored and transported as granules or a free-
evaporators [188] and spray dryers [189]. flowing coarse powder in bags, containers, and
Other techniques such as fractional conden- in silos or silo wagons. Cool, dry conditions
sation of the reaction gases in combination with must be maintained.
the formaldehyde synthesis process [190] and
very rapid cooling of the gases [191] are also Uses. Paraformaldehyde is used in place of
applied. Alternatively, formaldehyde-contain- aqueous formaldehyde solutions, especially in
ing gas is brought into contact with para- applications where the presence of water inter-
formaldehyde at a temperature that is above feres, e.g., in the plastics industry for the prepa-
the dew point of the gas and below the decom- ration of phenol, urea, and melamine resins,
position temperature of paraformaldehyde varnish resins, thermosets, and foundry resins.
[192]. The product is obtained in the form of Other uses include the synthesis of organic
flakes when a highly concentrated formalde- products in the chemical and pharmaceutical
hyde solution is poured onto a heated metal industries (e.g., Prins reaction, chloromethyla-
surface. The hardened product is subsequently tion, Mannich reaction), the production of tex-
scraped off and thoroughly dried [193]. tile auxiliaries (e.g., for crease-resistant
Paraformaldehyde beads are produced by finishes), and the preparation of disinfectants
introducing a highly concentrated melt into a and deodorants.
cooling liquid (e.g., benzene, toluene, cyclo-
hexane [194]. Acids [195] and alkalis [184,
196] are also added; they apparently accelerate 11.2. Cyclic Polyoxymethylenes
polymerization and lead to the formation
of higher-molecular-mass but less reactive 11.2.1. Trioxane
paraformaldehyde.
Highly soluble, highly reactive para- 1,3,5-Trioxane [110-88-3], trioxymethylene, or
formaldehyde with a low degree of polymeriza- 1,3,5-trioxycyclohexane, C3H6O3, Mr 90.1, is
tion is very much in demand. It is produced from the cyclic trimer of formaldehyde and was
concentrated, aqueous–alcoholic formaldehyde first produced and identified in 1885. A labora-
solutions [197, 198]. tory oddity for many years, this substance is
Stabilizing agents include hydantoins [199], very important today, especially as an interme-
nicotinamide, and succinamide [200]. diate in the production of acetal resins
(polyoxymethylenes).
Quality Specifications. An important factor
regarding the quality of paraformaldehyde is
its tendency to “age”, especially under the influ-
ence of heat, which results in decreased
reactivity. The paraformaldehyde loses its resid-
ual water and becomes brittle. This may be
prevented by storage below 10°C; in a moist
atmosphere, regeneration is possible. After pro-
duction, the residual moisture in the product Physical Properties. Trioxane is a white crys-
should therefore be retained. talline solid with a characteristic odor resem-
Reactivity is determined with the aid of the bling that of chloroform. Other physical
resorcinol test in which the rate at which properties are as follows (see also [201]):
26 Formaldehyde

fp 62–63°C this reason, the usual detection methods for

bp 115°C formaldehyde, such as the sodium sulfite
Density of crystals 1.39 kg/m3
Density of liquid at 65°C 1.17 kg/m3 method, cannot be applied directly. Formalde-
Refractive index n20
D at 65°C 1.3891 hyde in acetals, and thus trioxane, can be deter-
Specific heat 1.23 kJ kg 1K 1 mined by heating in water in the presence of a
Heat of fusion 222 kJ/kg strong acid (e.g., sulfuric acid) to convert the
Heat of evaporation 452 kJ/kg
Trouton constant 25 product to monomeric formaldehyde. The form-
Heat of formation 180 kJ/mol formaldehyde aldehyde can then be determined by the sulfite
Heat of combustion 16.850 kJ/kg method (see Section 6.2 Analysis).
Vapor pressure The acid-catalyzed hydrolysis of trioxane is
accelerated by using stronger acids, higher acid
concentrations, and nonaqueous solvents. When
trioxane is heated in nonaqueous systems in the
t, °C 25 37.5 86 87 90 114.5 129 presence of either strong acids (sulfuric acid,
p, kPa 1.69 4.16 37.7 39.5 44.0 101.2 161.8 hydrochloric acid, zinc chloride, iron chloride
etc.) or comonomers, it is converted to high-
molecular-mass oxymethylene homopolymers
or oxymethylene copolymers, respectively.
Flash point 45°C This method is applied today in the large-scale
Ignition temperature 410°C production of acetal resins. If additional sub-
Lower explosion limit (38°C) 3.57 vol%
Upper explosion limit (75°C) 28.7 vol%
stances which react with formaldehyde (e.g.,
Dynamic viscosity η phenols, melamine) are also present during
at 65°C 2.05 mPa s these hydrolytic or moisture-free reactions,
at 85°C 0.91 mPa s then the nascent formaldehyde reacts very vig-
Dielectric constant
at 20°C 3.2–3.4
orously with them.
at 70°C 8
Conductance at 78°C <1 μS Production. Trioxane is prepared by the trime-
rization of formaldehyde. In the beginning of
the industrial production, the starting materials
For the spectroscopic analytical identifica- used were paraformaldehyde or polyoxymethy-
tion of trioxane, see [201]. The compound forms lenes which were heated with acid, usually
an azeotropic mixture with 30 wt% water, sulfuric acid [202]. As, in the first half of the
bp 91.3°C. 20th century, the commercial importance of
Trioxane is soluble in water (0.172 g/cm3 at trioxane grew, aqueous formaldehyde solutions
18°C, 0.211 g/cm3 at 25°C and completely solu- and higher formaldehyde concentrations [203]
ble at 100°C), alcohol, ketones, organic acids, were introduced.
ethers, esters, phenols, aromatic hydrocarbons, The main application for trioxane is the use
and in chlorinated hydrocarbons; however, it is as a monomer in the cationic copolymerization
only sparingly soluble in aliphatic hydrocarbons. with acetals or cyclic ethers for the manufacture
Like dioxane and other cyclic ethers, melted of polyacetal copolymer.
trioxane (mixed with water if necessary) is an Therefore, the world capacity for trioxane
excellent solvent for organic substances. It strongly corresponds to the global capacity of
forms addition compounds with phenol and cyclic polyoxymethylenes (C-POM), which was
1,3,5-trinitrobenzene. about 200 000 t for Europe, 100 000 t for
Studies of vapor-liquid equilibria of systems NAFTA, 680 000 t for Asia and 450 000 t
containing formaldehyde, water, methanol, and for Mainland China for 2015. In comparison
trioxane are available [30, 34, 36]. the world production in 1987 was 250 000 t, in
1997 about 380 000 t.
Chemical Properties. Trioxane is stable up to The preferred process for trioxane produc-
224°C. Like acetals, it is hydrolyzed by aqueous tion is illustrated in Figure 5 (see also
solutions of strong acids. However, trioxane is [204]). Commercial aqueous formaldehyde is
inert under neutral and alkaline conditions. For concentrated to 60–65 wt% in a column (a)
 Formaldehyde 27

Figure 5. Trioxane production

a) Concentration column; b) Reactor; c) Extraction column; d, e) Distillation columns; f) Solvent purification

under vacuum conditions. The 60–65% form- Impurities and byproducts (formic acid,
aldehyde solution is fed into the reactor (b). A methyl formate, dimethylformal, and formalde-
dilute (6–10%) formaldehyde solution is hyde) can be eliminated by washing with
removed and, if necessary, can be reconcen- sodium hydroxide solution after the extraction
trated by pressure distillation and returned to step [214]. Emulsification of the reaction mix-
the process. In the reactor (b), formaldehyde is ture in an inert, nonvolatile liquid, e.g., paraffin
trimerized in the presence of a catalyst (e.g., oil, may reduce the formation of para-
sulfuric acid, phosphoric acid, ion exchanger formaldehyde in the reactor [215]. Addition
[205], or heteropoly acid [206]) which is pres- of inert organic substances with low dielectric
ent at a concentration of up to 25 wt% [207]. constants to the trimerization mixture increases
Technical and kinetic experiments designed to conversion [216]. Special processes in a syn-
achieve optimal reactor conditions are thesis reactor have also been described [217].
described in [208]. A mixture of trioxane, Crystallization of liquid trioxane and contact
formaldehyde, and water is distilled off and, with an inert gas stream can be used for further
if necessary, concentrated in a distillation col- purification, especially from higher homologues
umn [209]. In the extraction column (c) [210], of bis(methoxymethyl) ether [218].
the trioxane is extracted from the aqueous In the 1990s, a new method was proposed to
mixture by using methylene dichloride remove trioxane from the mixture of trioxane,
[75-09-2] [203] or another inert, water- formaldehyde, and water. After trimerization,
immiscible solvent (benzene [211], 1,2- formaldehyde is separated by pervaporation, e.g.,
dichloroethane [212], or nitrobenzene [213]). with a polyether block amide membrane
The formaldehyde–water mixture is returned [219, 220].
to the concentrating column (a). The trioxane– Since water is added with the aqueous form-
methylene dichloride mixture is separated in aldehyde solution, the energy requirement for
the distillation column (d). The crude trioxane trioxane production is very high (14–17 t of
is obtained at the bottom of the column and the steam per ton of trioxane). This may be reduced
methylene dichloride as overhead product. The by using a process based on the trimerization of
trioxane is subsequently purified by distillation gaseous formaldehyde with Lewis acids [221]
in column (e). The solvent methylene dichlor- and catalyzed by vanado- and/or molybdo and/
ide is freed of impurities in the solvent purifi- or wolframo-phosphoric acids [222–224].
cation step (f) and recycled to the extraction Trioxane can also be produced by recycling
column (c). of polyoxymethylenes (POM) [225, 226].
28 Formaldehyde

Producers. The main producers of trioxane are Mr 120, is the cyclic tetramer of formaldehyde
Celanese (Germany and United States), BASF and is a crystalline solid (fp 112°C). Tetraoxane
(Germany), Polyplastics (owned by Celanese vapors are stable even at 200°C (bp at 101.3
and Daicel, Japan), Mitsubishi Gas Chemical kPa, 163–165°C).
(Japan), Asahi (Japan), Korean Engineering Tetraoxane is produced by heating a water-
Plastics and Kolon Plastics (both Korea), Yun insoluble, high-molecular-mass poly(oxy-
Tian Hua, Tianye Chemicals, Shenhua and methylene) diacetate [202]. In the tetrameriza-
PTM (China). The world capacity in 2015 tion of formaldehyde, metal sulfates may be
was above 1.4 × 106 t/a. used as catalyst [228].
Tetraoxane accumulates as a high-boiling
Uses. The production of plastics (polyoxy- substance in the distillation residue obtained
methylene plastics, POM) is the most important during the production of trioxane. It is also
commercial application of trioxane and requires obtained in the polymerization of trioxane and
extremely pure material. Since trioxane depo- can be isolated by extraction with, for example,
lymerizes to produce formaldehyde, it can be ethylbenzene [229]. The formation of tetraox-
used in almost all formaldehyde reactions, espe- ane by irradiation of carbon monoxide and
cially when anhydrous formaldehyde is desired. hydrogen has also been described [230].
Trioxane is used, e.g., as a textile auxiliary; in Because of its higher boiling point tetraoxane
various cross-linking agents, for instance for is a more favorable textile auxiliary than triox-
pitch fibers in manufacturing of carbon fibers; ane for achieving crease resistance, e.g., for
for stabilization and reinforcement of wood to cellulose fibers. Like trioxane, tetraoxane can
produce musical instruments; and in distillable also be employed in the production of acetal
binders in ceramic compositions for shaped plastics.
articles, e.g., in an injection moulding process.
It is also employed in the stabilization and 11.2.3. Higher Cyclic Polyoxymethylenes
deodorization of waxes, as an anticorrosive
additive for metals (especially when corrosion Higher cyclic polyoxymethylenes can also
is caused by chlorinated hydrocarbons) [227], as undergo polymerization. The tendency to
an additive in photographic developers, as a polymerize in the melt decreases with increasing
solid fuel, in coating removers and, because ring size.
of its hydrolysis to formaldehyde in presence
of acid, in disinfectants. 1,3,5,7,9-Pentoxecane
Storage and Transportation. Liquid trioxane
is stored and transported in heated tanks. Solid
trioxane is transported in drums, trioxane flakes
are transported in drums and bags.
Toxicology. Trioxane is not known to display
any special toxic reactions; its oral LD50 value [16528-92-0], pentaoxane, pentaoxacyclode-
in rats is > 3200 mg/kg. Hydrolysis in the cane, or pentaoxymethylene, C5H10O5, the
presence of acid produces formaldehyde (see cyclic pentamer of formaldehyde, is a crystal-
Chap. 10 Toxicology and Occupational Health). line product (fp 55–56°C). The polymerization
of trioxane with the aid of a tin tetrachloride
catalyst produces several cyclic homologues
11.2.2. Tetraoxane including pentoxecane [231].
The fractional distillation and subsequent
preparative gas chromatography of residues
from the commercial trioxane polymerization
affords 1,3,5,7,9-pentoxecane [232].
Although hexoxecane (six formaldehyde
1,3,5,7-Tetraoxane [293-30-1], tetraoxy- units) has not clearly been identified in the
methylene, or 1,3,5,7-tetroxocane, C4H8O4, residue, pentadecoxane (15 formaldehyde units)
 Formaldehyde 29

has been unambiguously detected (fp 68–70°C). primary, secondary, and tertiary β-hydroxyethy-
Pentoxecane is used in addition to tetraoxane in leneamines [237]
patent formulations for the shrinkproofing of The hydroxyl group of formaldehyde cyano-
cotton [233]. hydrin can be replaced by other electronegative
groups. For example, reaction with ammonia
gives amino nitriles including nitrilotriacetoni-
12. Formaldehyde Cyanohydrin trile N(CH2CN)3 which is an intermediate in the
synthesis of nitrilotriacetic acid (NTA) [238].
Ethylenediaminetetraacetonitrile is similarly
synthesized from formaldehyde cyanohydrin
and ethylene diamine in the presence of sulfuric
Formaldehyde cyanohydrin [107-16-4], acid as a catalyst. Subsequent hydrolysis yields
CH2(OH)CN, Mr 57.05, is also known as ethylenediaminetetraacetic acid (EDTA) [238].
hydroxyacetonitrile, glycolonitrile, or glycolic The reaction of cyanohydrins with ammonia is a
nitrile. It is less commercially important than step in the Strecker synthesis of amino acids.
acetone cyanohydrin (→ Acetone) but of about Hydration of formaldehyde cyanohydrin and
the same importance as the cyanohydrin deriv- subsequent treatment with an aqueous solution
atives of acetaldehyde, benzaldehyde, and of sodium cyanide and ammonia (Bucherer
ethylene. reaction, a variant of the Strecker synthesis)
leads to DL-serine [239].
Physical Properties. Formaldehyde cyanohy- Formaldehyde cyanohydrin reacts with
drin is a colorless liquid with an odor similar hydrogen halides or phosphorus pentachloride
to that of hydrogen cyanide. It is soluble in to form α-halonitriles. In aqueous solutions at
water, ethanol, and diethyl ether but insoluble in pH 8 and a temperature of 10°C or less, it
chloroform and benzene. For IR spectrum see trimerizes to form 4-amino-2,5-bis(hydroxy-
[234]. Other physical properties follow: methyl)pyrimidin-5-ol [240]. Hydantoin can
be synthesized by reacting formaldehyde cya-
mp 72°C nohydrin with carbon dioxide, ammonia, or
bp at ammonium carbonate at high pressure [241,
101.3 kPa 183°C (slight 242].
decomp.)
3.2 kPa 119°C
0.4 kPa 76.5–78°C Production. Formaldehyde cyanohydrin is
Relative density d 19
4 1.1039 formed in 79.5% yield when 37% formaldehyde
n20
D 1.4112 is mixed with a stoichiometric amount of aque-
Electrolytic dissociation constant k at 0.843 × 10 5 ous hydrogen cyanide for 1 h at 2°C in the
25°C
Dielectric constant 178 presence of sodium hydroxide as a catalyst
[243]. Patents also describe synthesis by (1)
heating formaldehyde with hydrogen cyanide
at 250°C [244] or in the presence of sulfur
Chemical Properties. Like all cyanohydrins, dioxide at pH 1.5–2.0 in an aqueous medium
reactions can occur at both the nitrile and the [245] and (2) by reacting acetonitrile with
hydroxyl groups of formaldehyde cyanohydrin. oxygen and with or without water at high
Heating at 100°C with water yields hydroxy- pressure in the presence of various vanadium
acetamide, acid-catalyzed hydrolysis yields oxides [246–248].
hydroxyacetic acid. Reaction with absolute Formaldehyde cyanohydrin is generally
ethanol in the presence of hydrochloric acid handled as an aqueous solution but it can also
produces ethyl hydroxyacetate [235]. N-Substi- be isolated in the anhydrous state by ether
tuted amides can be synthesized by heating extraction, drying, and vacuum distillation
formaldehyde cyanohydrin with amines in [249]. Although the extremely pure product is
water [236]. Catalytic hydration (Ni–Al cata- reported to be very stable [250], addition of a
lysts) of the nitrile group gives amines. The small amount of stabilizer (e.g., monochloro-
resulting mixtures can be separated into acetic, mercaptoacetic, lactic, sulfonilic, and
30 Formaldehyde

phosphoric acids) is advisable [251]. Mono- Dangl, J.R. (1949) Infrared Determination of Organic Struc-
chloroacetic acid is especially suitable because tures, D. Van Nostrand Company, New York, p. 49 51, 53, 55,
56; Schneider, W.G. and Bernstein, H.J. (1956) Trans. Faraday
it codistills with the product. Cyanohydrin with Soc., 52, 13–18; Singer, W.E. (1947) Phys. Rev., 71, 531–533.
a lower degree of purity is not very stable, 6 Hibben, J.H. (1939) The Raman Effect and its Chemical
especially at high pH values, this should be Applications, Reinhold Publ. Co., p. 187.
borne in mind when handling anhydrous form- 7 Bragg, J.K. and Sharbaugh, A.H. (1949) Phys. Rev., 75,
1774–1775; Lawrance, R.B. and Strandberg, M.W.P. (1951)
aldehyde cyanohydrin (see also [240]). Phys. Rev., 83, 363; Oka, T., Hirakawa, H., and Shimoda, K.
(1960) J. Phys. Soc. Japan, 15, 2265–2279.
Transport and Storage. Formaldehyde cyano- 8 Spence, R. and Wild, W. (1935) J. Chem. Soc., 506–509.
hydrin is used almost exclusively as an inter- 9 Legrand, J., Delbourgo, R., and Lafitte, P. (1959) C. R. Hebd.
mediate and is normally produced at the site Seances Acad. Sci., 249, 1515–1516; Vanpée, M. (1955) Bull.
Soc. Chim. Belg., 64, 235–263.
where it is to be processed. However, it is also
10 National Fire Protection Association (1973) Fire Protection
supplied as a 70% aqueous solution and is Guide on Hazardous Materials, 5th edn,49 Hazardous Chem.
transported in steel containers and tank cars. Data, Boston, p. 150.
Attention should be paid to stabilization dur- 11 Sapgir, S. (1929) Bull. Soc. Chim. Belg., 38, 392–408.
12 Walker, J.F. (1933) J. Am. Chem. Soc., 55, 2821–2825.
ing transport and storage. Impure formalde-
13 Bezzi, S. and Iliceto, A. (1951) Chim. Ind. (Milan), 33,
hyde cyanohydrin can decompose to give 212–217; Iliceto, A. (1951) Gazz. Chim. Ital., 81, 915–932,
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should therefore be paid to explosion and fire edn, Reinhold Publ. Co., New York, p. 62; Koberstein, E.,
hazards. Müller, K.P., and Nonnenmacher, G. (1971) Ber. Bunsenges.
Phys. Chem., 75, 549–553.
14 Walker, J.F. (1931) J. Phys. Chem., 35, 1104–1113.
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101 (1984) Formaldehyd, in Gemeinsamer Bericht des Bundesge- 126 Formox Process for Producing Formaldehyde, Product Bulle-
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 Formaldehyde 33

153 Eckenberger, J. (1996) Kunststoffe, 86 (10),1514. 183 Du Pont (1947) 2 527 654 (C. Pyle, J. A. Lane); 2 527 655,
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155 WHO International Program on Chemical Safety (IPCS) (1989) Lane).
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156 WHO international Agency for Research on Cancer (IARC) 185 Cities Service Oil Co. (1948) 2 498 206 (B. W. Greenwald, R.
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160 Nielsen, G.D. et al. (2013) Recent trend in risk assessment of 193 Sumitomo (1959) 3 001 235 (D. Komiyama, T. Takaki, T.
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161 Hilton, J. et al. (1996) Experimental assessment of the sensi- 195 Heyden Newport Chem. Corp. (1957) 2 915 560 (D. Steinhardt,
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aldehyde. Interantional Program on Chemical Safety (IPS), 197 Degussa (1951) 884 947 (H. Leyerzapf).
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163 Henschler, D. (1987) Formaldehyd, MAK-Nachtrag 1987, McCants).
VCH Verlagsgesellschaft, Weinheim, Germany. 199 Du Pont (1948) 2 481 981 (R. L. Craven); 2 519 550, 1948 (R.
164 Monticello, T.M. et al. (1996) Correlation of regional and L. Craven).
nonlinear formaldehyde induced nasal cancer with proliferating 200 Mitsubishi Gas Chemical (1973) 73 21 082 (M. Katayama, S.
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165 Hauptmann, M. et al. (2004) Mortality from solid cancers 201 Beilstein, 19 (34),4710.
among workers in formaldehyde industries. Am J Epidemiol, 202 Staudinger, H. and Luthy, H. (1925) Helv. Chim. Acta, 8, 65.
159, 1117–1130. 203 Du Pont (1940) 2 304 080 (C. E. Frank).
166 WHO international Agency for Research on Cancer (IARC) 204 Mahieux, J. (1969) Hydrocarbon Process., 48 (5),163.
(2012) IARC Monographs on the Evaluation of Carcinogenic 205 Rotta, G. (1972) 2 225 267.
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167 European Union, “Verordnung Nr. 605/2014 der Kommission”, J. Masamoto, K. F. Hamanaka et al.).
Amtsblatt der Europäischen Union. 207 BASF (1966) 1 543 340 (H. Buchert, H. Sperber).
168 NIOSH Registry of Toxic Effects of Chemicals, July 1996. 208 Bartholomé, E., Köhler, W., Schecker, H.G., and Schulz, G.
169 Bundesgesundheitsblatt 9, 1992, p. 482–483; WHO Air Quality (1971) Chem. Ing. Tech., 43, 597.
Guidelines (in press). 209 ICI (1963) 1 012 372 (W. R. Bamford).
170 World Health Organization, “WHO Guidelines for Indoor Air 210 BASF (1968) 1 668 867 (H. Sperber, H. Fuchs).
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171 Staudinger, H. (1932) Die hochmolekularen organischen Ver- 212 BASF (1968) 1 668 867 (H. Sperber, H. Fuchs, H. Libowitzky).
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172 Houben-Weyl, E 20, 1390. 215 Degussa (1963) 1 377 169.
173 Houben-Weyl, XIV/1 a, 408–410, 413–421. 216 Polyplastics (1971) 3 732 252 (H. Komazawa, O. Matsumo).
174 Walker, J.F. (1964) Formaldehyde, 3rd edn, Reinhold Publish- 217 Hoechst (1978) 2 853 091 (K. F. Mück, G. Sextro, K. H. Burg);
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177 Houben-Weyl, 7/1, 429. et al.).
178 Du Pont (1948) 2 449 469 (W. F. Gresham, R. E. Brooks). 219 Asahi (1995) 95 33 762 (J. Masamoto).
179 Nordgren, G. (1939) Acta Pathol. Microbiol. Scand., 40, 220 Hoechst (1994) 596 381 (D. Arnold).
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J. Wimmer). F. Kern).
34 Formaldehyde

225 Fleischer, D., Mueck, K.F., and Reuschel, G. (1992) Kunst- 243 Dow Chemical 2 890 238 (1959) (A.R. Sexton).
stoffe, 82 (9),763–766. 244 Monsanto (1953) 2 752 383 (S.F. Belt).
226 Hoechst (1992) 484 786 (K.-F. Mueck, G. Reusch, D. 245 Mitsubishi Chemical (1976) JP-Kokai 76 100 027 (Y. Ono).
Fleischer). 246 Standard Oil Co. (1987) 4 634 789 (R.G. Teller, J.F. Brazdil, L.
227 Solvay (1971) 2 142 920 (A. Ryckaert); Péchiney-Saint- C. Glaeser).
Gobain, (1968) 1 793 235 (Y. Correia). 247 Brazdil, J.F. et al. (1986) J. Catal., 100 (2),516.
228 Toyo Koatsu Industries (1965) 3 426 041 (Y. Miyake, S. 248 Standard Oil Co. (1985) 4 515 732 (J.F. Brazdil, W.A. Marrit,
Adachi, N. Yamanchi, T. Hayashi et al.). M.D. Ward).
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230 Sugimoto, S. et al. (1983) Int. J. Appl, Radiat. Isot., 34 (11),559. 250 Rohm and Haas Co. (1962) 3 057 903 (J.W. Nemec, C.H.
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232 Burg, K.H. et al. (1968) Makromol. Chem., 111, 181. (H. Beier).
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237 Du Pont (1948) 598984.
Further Reading
238 Hampshire Chemical (1958) 2 855 428 (J. J. Singer, M. Gerberich, H.R. and Seaman, G.C. Formaldehyde, in Kirk Othmer
Weisberg). Encyclopedia of Chemical Technology, 5th edn, John Wiley &
239 Hampshire Chemical (1984) 3 242 748 (A. Kleemann, B. Sons, Hoboken, NJ, online DOI.
Lehman, K. Deller). Lippmann, M. (ed.) (2009) Environmental Toxicants, 3rd edn, John
240 Lake, D.B. and Londergan, T.E. (1954) J. Org. Chem., 19, Wiley & Sons, Hoboken, NJ.
2004.
241 Mitsui Toatsu Chem. (1986) 61 72 761 (H. Inagaki et al.).
242 Mitsui Toatsu Chem. (1986) 61 83 164 (K. Takeuchi et al.).