Article No : a12_013

Formic Acid
WERNER REUTEMANN, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic
of Germany
HEINZ KIECZKA, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic
of Germany

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . 13 8. Storage and Transportation. . . . . . . . . . . . 27

2. Physical Properties . . . . . . . . . . . . . . . . . . 13 9. Legal Aspects. . . . . . . . . . . . . . . . . . . . . . . 27
3. Chemical Properties . . . . . . . . . . . . . . . . . 15 10. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4. Production . . . . . . . . . . . . . . . . . . . . . . . . . 17 11. Economic Aspects . . . . . . . . . . . . . . . . . . . 28
4.1. Methyl Formate Hydrolysis . . . . . . . . . . . . 18 12. Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.1.1. Kemira – Leonard Process . . . . . . . . . . . . . . 20 12.1. Esters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.1.2. BASF Process . . . . . . . . . . . . . . . . . . . . . . . 21 12.1.1. Methyl Formate. . . . . . . . . . . . . . . . . . . . . . 28
4.1.3. USSR Process . . . . . . . . . . . . . . . . . . . . . . . 21 12.1.2. Ethyl Formate . . . . . . . . . . . . . . . . . . . . . . . 29
4.1.4. Scientific Design – Bethlehem Steel Process. 23 12.1.3. Isobutyl Formate . . . . . . . . . . . . . . . . . . . . . 29
4.2. Other Processes . . . . . . . . . . . . . . . . . . . . . 23 12.1.4. Miscellaneous Esters . . . . . . . . . . . . . . . . . . 29
4.2.1. Oxidation of Hydrocarbons . . . . . . . . . . . . . 23 12.2. Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.2.2. Hydrolysis of Formamide. . . . . . . . . . . . . . . 23 12.2.1. Alkali-Metal and Alkaline-Earth Metal
4.2.3. Production of Formic Acid from Formates . . 24 Formates . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.2.4. Direct Synthesis from Carbon Monoxide and 12.2.2. Ammonium Formate . . . . . . . . . . . . . . . . . . 30
Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 12.2.3. Aluminum Formate . . . . . . . . . . . . . . . . . . . 30
4.2.5. Use of Carbon Dioxide . . . . . . . . . . . . . . . . 25 12.2.4. Nickel Formate . . . . . . . . . . . . . . . . . . . . . . 30
4.3. Concentration of Formic Acid . . . . . . . . . . 25 12.2.5. Copper Formate . . . . . . . . . . . . . . . . . . . . . 30
4.4. Construction Materials . . . . . . . . . . . . . . . 25 13. Toxicology and Occupational Health . . . . . 30
5. Environmental Protection . . . . . . . . . . . . . 26 References . . . . . . . . . . . . . . . . . . . . . . . . . 31
6. Quality Specifications. . . . . . . . . . . . . . . . . 26
7. Chemical Analysis . . . . . . . . . . . . . . . . . . . 27

1. Introduction 1995 [1]. Formic acid is produced by hydrolysis

of methyl formate or formamide or from its salts.
Formic acid [64-18-6] HCOOH, M r 46.03, is a In addition, formic acid is a byproduct of acetic
colorless liquid with a pungent odor, which is acid production by liquid-phase oxidation of
completely miscible with water and many polar hydrocarbons.
solvents but only partially miscible with hydro-
carbons. Formic acid derived its name from the
red ant, Formica rufa, in which it was discovered 2. Physical Properties
around 1670. Formic acid has been detected in
the poison or defense systems of ants, bees, and Formic acid, mp 8.3
C [2], bp 100.8
C (at
other insects and also of cnidarians. 101.3 kPa) [3], is a colorless, clear, very corro-
Formic acid is used primarily in dyeing, in the sive liquid with a pungent odor. With a pKa of
textile and leather industries; in rubber produc- 3.739, formic acid is the strongest unsubstituted
tion; and as an intermediate in the chemical and fatty acid, about ten times stronger than acetic
pharmaceutical industries. The use of formic acid acid [4]. Pure formic acid is hygroscopic.
as an aid in the ensilage of green forage has The temperature dependence of the density of
increased sharply. formic acid is given in Table 1. The density of
The worldwide production of formic acid is formic acid – water binary mixtures, as a function
about 260 000 t/a in 1987 and 390 000 t/a in of formic acid concentration, is shown in Table 2.

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a12_013.pub2
14 Formic Acid Vol. 16

Table 1. Density of pure formic acid as a function of temperature [5] Table 4. Vapor pressure of pure formic acid [7]

t, C r , g/cm 3
t, C r, g/cm 3
Liquid Solid
*
0 1.244 40 1.195 t,
C p, kPa t,
C p, kPa
10 1.232 50 1.182
15 1.226 60 1.169 5.23 1.083 5.07 0.664
20 1.220 70 1.156 0.00 1.488 0.00 1.096
25 1.214 80 1.143 8.25 2.392 8.25 2.392
30 1.207 90 1.130 12.57 3.029
100 1.117 20.00 4.473
* 29.96 7.248
Supercooled liquid.
39.89 11.357
49.93 17.347
Table 2. Density of aqueous formic acid solutions at 20
C [6] 59.98 25.693
70.04 37.413
Formic acid Formic acid 79.93 52.747
content, wt % r , g/cm3 content, wt % r, g/cm 3 100.68 101.667
110.62 135.680
2 1.003 50 1.118
5 1.011 60 1.141
10 1.024 70 1.163
20 1.048 80 1.185 The enthalpy of the gas-phase dimerization is
30 1.072 90 1.204 63.8 kJ/mol [8]. The thermodynamic proper-
40 1.095 100 1.221
ties of monomeric and dimeric formic acid have
been investigated by WARING [9].
The freezing point diagram for the formic The ring-type dimeric structure exists both in
acid – water binary mixture exhibits a eutectic the vapor phase and in solution. Liquid formic
point (Table 3) at 48.5
C and 41.0 mol % of acid consists of long chains of molecules linked
formic acid [2]. Formic acid does not increase in to each other by hydrogen bonds. Solid formic
volume when it solidifies and has a tendency to acid can also be isolated in two polymorphic
undergo supercooling. forms (a and b) [10]:
Table 4 shows the vapor pressure curve of
pure formic acid. The vapor of formic acid
deviates considerably in behavior from an ideal
gas because the molecules dimerize partially in
the vapor phase. At room temperature and normal
pressure, 95 % of the formic acid vapor consists
of dimerized formic acid [8]:

The thermodynamic properties of monomeric

Table 3. Freezing points of various formic acid – water mixtures [2]
and dimeric formic acid have been investigated
Formic acid Formic acid [10].
molar fraction, % fp,
C molar fraction, % fp,
C Vapor – liquid equilibrium data for formic
100.0 8.3 41.0 48.5 acid – water mixtures and for mixtures of formic
80.0 5.6 39.8 46.8 acid with organic compounds have been collect-
74.8 8.2 37.0 43.0 ed in [11]. Formic acid and water form a maxi-
69.5 13.0 31.7 33.5 mum-boiling azeotropic mixture whose boiling
64.5 17.3 28.0 29.3
59.0 23.2 23.1 22.8 point is 107.6
C at 101.3 kPa; it consists of
54.2 28.3 20.0 19.7 77.6 wt % formic acid and 22.4 wt % water. The
50.0 35.3 12.0 10.3 composition and boiling point of formic acid –
44.6 42.0 water azeotropic mixtures are shown as a func-
42.0 46.7
tion of pressure in Table 5. Formic acid can form
Vol. 16 Formic Acid 15

Table 5. Azeotropic data for the formic acid – water system heat capacity of formic acid – water mixtures
p, bar bp of azeo- Formic acid Reference
decreases approximately linearly as the concen-
tropic mixture,
C content, wt % tration of formic acid increases [6].
The physical properties of formic acid are
0.093 48.6 66.2 [12]
0.267 72.3 70.5 [12]
listed below:
1.013 107.6 77.6 [12]
2.026 128.7 84 [13]
3.140 144 85 [13] Heat of fusion 276 J/g [7]
Heat of vaporization (at bp) 483 J/g [7]
Dielectric constant
Liquid (at 20
C) 57.9 [21]
Solid (at 10.1
C) 11.7
Refractive index n20 D 1.37140 [19]
Surface tension s
Table 6. Dynamic viscosity of pure formic acid as a function of

(at 20 C) 37.67103 N/m [20]
temperature [16]
(at 40
C) 35.48103 N/m
(at 60
C) 33.28103 N/m
t,
C h, mPa  s
(at 80
C) 31.09103 N/m
10 2.262 Heat of formation D H H0f
20 1.804 Liquid (at 25
C) 425.0 kJ/mol [22]
30 1.465 Vapor (at 25
C, monomer) 378.57 kJ/mol [8]
40 1.224 (at 25
C, dimer) 820.94 kJ/mol
50 1.025 Heat of combustion DH0c
Liquid (at 25
C) 254.8 kJ/mol [22]
Entropy S 0
Liquid (at 25
C) 129.0 J K1 mol1 [10]
azeotropic mixtures with many other substances Vapor (at 25
C, monomer) 248.88 J K1 mol1 [8]
[14]. (at 25
C, dimer) 332.67 J K1 mol1 [8]
Heat of neutralization 56.9 kJ/mol [23]
The variation of dynamic viscosity with tem- Critical data pcrit 7.279 MPa [18]
perature is shown in Table 6. The dynamic vis- T crit 581 K [18]
cosity of formic acid – water mixtures decreases r crit 0.392 g/cm3 [18]
approximately linearly as the water content of Thermal conductivity l
Liquid (at 20
C) 0.226 W m1 K1 [18],
formic acid increases [15]. The thermal conduc- [24]
tivity of formic acid is markedly higher than that (at 60
C) 0.205 W m1 K 1
of comparable liquids, because of its pronounced (at 100
C) 0.185 W m1 K1
polarity. Vapor (at 50
C) 0.0136 W m1 K1
(at 100
C) 0.0176 W m1 K1
The variation of specific heat capacity with (at 200
C) 0.0267 W m1 K1
temperature is shown in Table 7. The specific Electrical conductivity (at 25
C) 6.08105 W 1 cm1
[25]
Coefficient of cubic expansion a 0.001 [3]
Table 7. Specific heat capacity of formic acid as a function of (at 30
C)
temperature at constant pressure [17]

t,
C cp, J g1K1 t,
C cp, J g1 K1 In 1968, GALLANT reported the important physi-
Solid Vapor cal properties of formic acid and other low
150 0.921 25 1.058 molecular weight fatty acids as a function of
100 1.114 100 1.192 temperature [18].
75 1.193 200 1.348
50 1.285 300 1.480
25 1.411 400 1.589
0 1.800 600 1.757 3. Chemical Properties
800 1.870
1000 1.953
1200 2.037
To some extent, formic acid reacts differently
Liquid from its higher homologues because it is both a
20 2.169 carboxylic acid and an aldehyde.
50 2.202
100 2.282
Aldehyde Reactions. In some reactions,
formic acid behaves like an aldehyde. Thus if
16 Formic Acid Vol. 16

an aqueous solution of formic acid is heated with Table 8. Volume of carbon monoxide produced per liter of formic acid
(99 wt %) as a function of storage time and temperature [33]
a silver nitrate solution, metallic silver is depos-
ited. Mercury, gold or platinum ions are reduced Time, d V, L
in solution, as are organic compounds. For ex-
ample, formic acid reduces triphenylmethanol to at 20
C at 30
C at 40
C
triphenylmethane. The reduction of imines 15 0.012 0.064 0.303
(Schiff bases) by formic acid has been known 30 0.024 0.128 0.597
for a long time. Primary amines can be prepared 60 0.049 0.255 1.161
90 0.073 0.381 1.700
from ketones, ammonia, and formic acid (Leuck-
art reaction). Like other aldehydes, formic acid
has bactericidal properties.
oxide properties [31]. The reactions of formic
Carboxylic Acid Reactions. Magnesium,
acid were summarized by GIBSON in 1969 [32].
zinc, and iron dissolve in formic acid with the
Although formic acid is not very stable, it can
evolution of hydrogen. Because of its strongly
be distilled at atmospheric pressure in the
acidic nature, many alcohols can be esterified by
absence of catalysts. Formic acid may decom-
formic acid, without the addition of mineral
pose into either carbon monoxide and water
acids. Primary and secondary alcohols are esteri-
(dehydration) or carbon dioxide and hydrogen
fied in pure formic acid 15 000 – 20 000 times
(dehydrogenation); the nature of the decomposi-
more rapidly than in pure acetic acid [26]. The
tion and the reaction rate depend strongly on the
rate of esterification of primary, secondary, and
presence of catalysts, the temperature, and the
tertiary alcohols in formic acid has been deter-
concentration of formic acid. Dehydrogenation
mined [27], [28]. Because of its extremely reac-
is catalyzed preferentially by metals (platinum
tive carboxyl group, amines can be formylated by
sponge, copper, nickel, silver). Dehydration, on
formic acid, with high yields, for example, the
the other hand, is catalyzed by aluminum oxide,
yield of N-methylformanilide [93-61-8] is 93 –
silicon dioxide, and charcoal. Dehydration is
97 %. Formic acid adds to the double bonds of
promoted by mineral acids but inhibited by wa-
olefins to form esters. Acetylenes react with
ter; it also occurs on activated metal surfaces
formic acid in the vapor phase to yield vinyl
which must be considered during the preparation
formates [29].
and processing of formic acid, as well as during
Formic acid may also be used as a source of
transportation and storage of the highly concen-
carbon monoxide. Thus, carboxylic acids can be
trated acid. Tables 8 and 9 show the formation of
prepared from olefins and formic acid in the
carbon monoxide as a function of formic acid
presence of sulfuric or hydrofluoric acid (Koch
concentration and temperature [33]. A summary
carboxylic acid synthesis). Formic acid and ter-
of the catalytic decomposition of formic acid has
tiary organic bases form addition compounds
been published by MARS [34], along with an
(3 : 1 and 2 : 1 ratio of formic acid : base). If, for
extensive list of references. The temperature
instance, 1 mole of gaseous triethylamine is
dependence of formic acid decomposition at low
passed in 3 moles of anhydrous formic acid, the
temperature (between 40 – 100
C) has been
addition product is obtained in quantitative yield.
investigated [35].
In these compounds formic acid is present in an
extremely active form. Addition compounds of
formic acid and trimethylamine or triethylamine
can be used as liquid reducing agents in many Table 9. Volume of carbon monoxide produced per liter of aqueous
formic acid as a function of storage time and concentration [33]
selective reductions. The reduction of sulfur
dioxide to sulfur is approximately quantitative [30]. Time, d V, L (t ¼ 40
C)
Formic acid reacts with hydrogen peroxide in
the presence of an acidic catalyst to form unsta- 90 wt % 98 wt % 99 wt %
ble performic acid [107-32-4] (HCOOOH); per- 15 0.010 0.110 0.303
formic acid (! Peroxy Compounds, Organic) 30 0.019 0.220 0.597
may decompose explosively when heated to 60 0.039 0.437 1.161
90 0.058 0.653 1.700
80 – 85
C. Performic acid exhibits typical per-
Vol. 16 Formic Acid 17

4. Production 1970s, the hydrolysis of methyl formate [ 107-

31-3] to methanol and formic acid was developed
The worldwide installed capacity for producing commercially by various firms into an economi-
formic acid was about 330 000 t/a in 1988. The cally feasible method. This process involves
installed formic acid processes can be classified carbonylation of methanol and subsequent
in four groups: hydrolysis of the methyl formate produced. The
methanol resulting from this process is returned
1. methyl formate hydrolysis, to the first stage. Formic acid plants based on this
2. oxidation of hydrocarbons, process were started up at BASF (Federal Re-
3. hydrolysis of formamide, and public of Germany) in 1981 and Kemira (Fin-
4. preparation of free formic acid from formates. land) in 1982 [37]. Most of the formic acid plants
begun in recent years employ this principle of
The significance of individual processes has methyl formate hydrolysis.
shifted considerably in the last decade because Table 10 shows the world capacity for various
the economic data for production and raw formic acid production processes in 1986.
products have changed and new processes have Although other methods for producing formic
been developed. In the past, a large amount of the acid have been patented, they do not appear to
formic acid utilized was a byproduct in the have been implemented industrially. Direct syn-
manufacture of acetic acid. However, the pro- thesis of formic acid from carbon monoxide and
portion of formic acid produced by dedicated water cannot be carried out economically because
processes has increased. of the unfavorable position of the equilibrium.
Formic acid is a byproduct in the production In recent years, various ways of producing
of acetic acid [64-19-7] by liquid-phase oxida- formic acid from carbon dioxide and hydrogen
tion of butane or naphtha (! Acetic Acid, Sec- have been investigated extensively, but this meth-
tion 4.2.). For many years, oxidation of hydro- od has not yet been applied industrially. The
carbons was the most important method of oxidation of methyl tert-butyl ether [1634-04-4]
producing acetic acid. Over the past decade, how- with oxygen to form tert-butyl formate [762-75-4]
ever, the preferred process in the establishment of and formic acid has been described [38]. Various
new acetic acid plants has been the carbonylation methods have been developed for the electrochem-
of methanol [36], which is expected to remain the ical production of formic acid, but they have not
preferred method in the future. As a result, the been used commercially [3], [39]. The combined
proportion of formic acid produced worldwide, production of formic acid and acetic acid from
which results as a byproduct in the manufacture methyl formate, carbon monoxide, and water with
of acetic acid, will continue to decrease. methyl iodide [74-88-4] as promoter and anhy-
The production of formic acid by hydrolysis drous rhodium chloride [13569-65-8] as catalyst,
of formamide [75-12-7 ] played an important role has been described by BP [40].
in Europe; in 1972, about one-third of the world
production was obtained by this process [3].
However, the consumption of ammonia and
sulfuric acid, along with the unavoidable produc- Table 10. Formic acid production capacity in 1986 (without standby
plants; BASF assessment)
tion of ammonium sulfate, have in many cases
made this process economically inferior. As a Percentage of
result, the direct hydrolysis of methyl formate is Process Capacity, t/a total capacity, %
currently preferred. Hydrolysis of 160 000 49
Another industrial production method in- methyl formate
volves formation of the free acid from its salts. Byproduct in 74 000 22
Sodium formate [141-53-7] and calcium formate hydrocarbon
oxidation
[544-17-2] are used for this purpose. Hydrolysis 10 000 3
The economic disadvantages of the methods of formamide
discussed led to the development of a process Acidolysis of 86 000 26
specifically dedicated to the production of formic alkali formates
Total 330 000
acid, with no undesirable byproducts. In the
18 Formic Acid Vol. 16

4.1. Methyl Formate Hydrolysis stage involves carbonylation of methanol in the

liquid phase with carbon monoxide, in the pres-
Synthesis of formic acid by hydrolysis of methyl ence of a basic catalyst:
formate is based on a two-stage process: in the
first stage, methanol is carbonylated with carbon CH3 OHþCO!HCOOCH3 DH 0R ¼ 29 kJ=mol
monoxide; in the second stage, methyl formate is
hydrolyzed to formic acid and methanol. The This reaction was first described by BASF in
methanol is returned to the first stage: 1925 [41]. As a rule, the catalyst is sodium
methoxide [124-41-4]. Potassium methoxide
CH3 OHþCO!HCOOCH3
[865-33-8] has also been proposed as a catalyst;
it is more soluble in methyl formate and gives a
CH3 OOCHþH2 O!CH3 OHþHCOOH higher reaction rate [44]. Although fairly high
pressures were initially preferred, carbonylation
COþH2 O!HCOOH is carried out in new plants at lower pressure.
Under these conditions, reaction temperature and
Although the carbonylation of methanol is catalyst concentration must be increased to
relatively problem-free and has been carried out achieve acceptable conversion. According to
industrially for a long time [3], [41], only recently published data, ca. 4.5 MPa, 80
C, and 2.5 wt %
has the hydrolysis of methyl formate been devel- sodium methoxide are employed. About 95 %
oped into an economically feasible process. The carbon monoxide, but only about 30 % methanol,
main problems are associated with work-up of the is converted under these circumstances. Nearly
hydrolysis mixture. Because of the unfavorable quantitative conversion of methanol to methyl
position of the equilibrium, reesterification of formate can, nevertheless, be achieved by recy-
methanol and formic acid to methyl formate cling the unreacted methanol. The carbonylation
occurs rapidly during the separation of unreacted of methanol is an equilibrium reaction, and
methyl formate. Problems also arise in the selec- Table 11 specifies the equilibrium concentra-
tion of sufficiently corrosion-resistant materials. tions of methyl formate.
Older publications suggest the reaction of The reaction rate can be raised by increasing
methyl formate and a dicarboxylic acid, with the temperature, the carbon monoxide partial
subsequent distillation of formic acid from the pressure, the catalyst concentration, and the in-
higher-boiling esters [3]. Degussa suggested hy- terface between gas and liquid:
drolyzing methyl formate at 200
C above atmo-
spheric pressure and then reducing the pressure r ¼ CaeE=RT cpCO
suddenly to less than 0.1 MPa. Separation of the where
methyl formate –methanol mixture flash-evapo- r ¼ reaction rate,
rated from the aqueous formic acid can then take C ¼ proportionality coefficient,
place in a liquid separator [5]. a ¼ interface between gas and liquid,
Industrial methods involving carbonylation of E ¼ activation energy,
methanol and hydrolysis of methyl formate,
followed by isolation of the formic acid, were
Table 11. Maximum methyl formate concentration (in weight percent)
developed by (1) the Leonard Process Company achievable by carbonylation of methanol (unpublished BASF data)
(United States), (2) BASF (Federal Republic of
Germany), (3) Halcon – Scientific Design – t,
C p, MPa
Bethlehem Steel (United States), and (4) the
1 5 9 17
Scientific Research Institute for the Chlorine
Industry of the Ministry of the Chemical Industry 50 59 95 98 99
(former Soviet Union). 60 43 91 96 99
70 31 85 94 98
Key patents relating to the carbonylation of 80 21 78 90 96
methanol and the hydrolysis of methyl formate 90 15 69 85 94
are listed in [43]. 100 10 59 79 91
110 7 49 71 87
Basic Principles. Carbonylation of Metha-
120 5 39 62 82
nol. In the four processes mentioned, the first
Vol. 16 Formic Acid 19

R ¼ molar gas constant, of 1 : 1, the conversion is only 30 %, but if the

c ¼ catalyst concentration in solution, and molar ratio of water to methyl formate is increased
pCO ¼ CO partial pressure in the gas phase [45]. to 5 – 6, the conversion of methyl formate rises to
60 %. However, a dilute aqueous solution of formic
This equation reveals the dependence of reac- acid is obtained this way, and excess water must be
tion rate on the partial pressure of carbon mon- removed from the formic acid with the expenditure
oxide. Therefore, to synthesize methyl formate, of as little energy as possible.
gas mixtures with a low proportion of carbon Another way to overcome the unfavorable
monoxide must first be concentrated; this can be position of the equilibrium is to hydrolyze methyl
achieved by low temperature distillation, pres- formate in the presence of a tertiary amine, e.g.,
sure-swing adsorption, prism separators (Mon- 1-(n-pentyl)imidazole [19768-54-8], [49]. The
santo), or the Cosorb process (Tenneco). base forms a salt-like compound with formic
acid; therefore, the concentration of free formic
In a side reaction, sodium methoxide reacts acid decreases and the hydrolysis equilibrium is
with methyl formate to form sodium formate and shifted in the direction of products. In a subse-
dimethyl ether, and becomes inactivated: quent step formic acid can be distilled from the
NaOCH3 þ HCOOCH3 !HCOONa þ CH3 OCH3
base without decomposition.
A two-stage hydrolysis has been suggested, in
which a water-soluble formamide is used in the
The substances used must be anhydrous; oth- second stage [50]; this forms a salt-like com-
erwise, sodium formate is precipitated to an pound with formic acid. It also shifts the equi-
increasing extent: librium in the direction of formic acid.
To keep undesirable reesterification as low as
NaOCH3 þ H2 O þ HCOOCH3 !2 CH3 OH þ NaOOCH
possible, the time of direct contact between
methanol and formic acid must be as short as
Sodium formate is considerably less soluble in possible, and separation must be carried out at the
methyl formate than in methanol. The risk of lowest possible temperature. Introduction of
encrustation and blockage due to precipitation of methyl formate into the lower part of the column
sodium formate can be reduced by adding poly in which lower boiling methyl formate and meth-
(ethylene glycol) [46]. The carbon monoxide anol are separated from water and formic acid,
used must contain only a small amount of carbon has also been suggested. This largely prevents
dioxide; otherwise, the catalytically inactive car- reesterification because of the excess methyl
bonate is precipitated. formate present in the critical region of the
Basic catalysts may reverse the reaction, and column [51].
methyl formate decomposes into methanol and The hydrolysis of methyl formate is catalyzed
carbon monoxide. Therefore, undecomposed so- by strong acids, but the efficiency of strong
dium methoxide in the methyl formate must be mineral acids [52] is restricted because they also
neutralized [47]. promote the decomposition of formic acid. In the
Hydrolysis of Methyl Formate. In the second processes described by BASF, Leonhard, and
stage, the methyl formate obtained is hydrolyzed: Halcon – Scientific Design – Bethlehem Steel,
autocatalysis by formic acid is therefore used. In
HCOOCH3 þH2 OCH3 OHþHCOOH DH 0R ¼ 16:3 kJ=mol
the Soviet Union, a process has been described in
which hydrolysis is carried out in a vertical
The equilibrium constant for methyl formate column reactor divided into two zones [53]; the
hydrolysis depends on the water: ester ratio [48]. upper zone is filled with a strongly acidic cation
With a molar ratio of 1, the constant is 0.14, but exchanger which partially hydrolyze methyl for-
with a water: methyl formate molar ratio of 15, it is mate. In the lower part of the reactor, hydrolysis
0.24. Because of the unfavorable position of this is carried out with autocatalysis by formic acid
equilibrium, a large excess of either water or produced in the upper section.
methyl formate must be used to obtain an econom- Dehydration of the Hydrolysis Mixture. For-
ically worthwhile methyl formate conversion. If mic acid is marketed in concentrations exceeding
methyl formate and water are used in a molar ratio 85 wt %; therefore, dehydration of the hydrolysis
20 Formic Acid Vol. 16

mixture is an important step in the production of during flash-evaporation. methanol are separated
formic acid from methyl formate. For dehydra- under vacuum. Although the reverse reaction is
tion, the azeotropic point must be overcome. The attenuated further as a result, condensation of the
concentration of formic acid in the azeotropic low-boiling methyl formate in vacuo presents a
mixture increases if distillation is carried out problem. The formic acid is dehydrated by distil-
under pressure (Table 5), but the higher boiling lation. If 85 wt % formic acid is desired, dehy-
point at high pressure also increases the decom- dration must be carried out at ca. 0.3 MPa. Even
position rate of formic acid. At the same time, the higher concentrations can be achieved by con-
selection of sufficiently corrosion-resistant ma- necting an additional dehydration column down-
terials presents considerable problems. A num- stream under atmospheric pressure, and formic
ber of entrainers have been proposed for azeo- acid concentrations up to ca. 98 wt % can then be
tropic distillation [43]. drawn off as the distillate.
BASF describes various energy-saving pro- Process Description [57–60] (Fig. 1). Com-
cesses for the dehydration. One process involves pressed carbon monoxide and methanol are con-
extractive distillation with N-formylmorpholine verted into methyl formate in reactor (a). Catalyst
[4394-85-8] [54]. Another method of increasing is fed into the reactor in a methanol solution. The
formic acid concentration in dilute solutions amount of methanol introduced in this way
without a considerable input of energy is to makes up for methanol losses in the process. The
extract formic acid from water by liquid – liquid discharge from reactor (a) is flashed and fed into
extraction. Secondary amides have been pro- the methyl formate column (b) from which meth-
posed [55] as extractive agents. Formic acid yl formate is drawn off as the distillate. Methanol
binds weakly to the amide; therefore, water can and the dissolved catalyst are returned to the
be distilled to overcome the azeotropic point. In a reactor; inactivated catalyst (primarily sodium
subsequent column, formic acid can then be formate) is crystallized and discharged.
distilled from the extractant in vacuo. The energy Off-gas from column (b) and waste gas from
consumed can be reduced further by optimizing reactor (a) are burned. Methyl formate reacts
the exchange of heat [56]. partially with water in the preliminary reactor
(c), and discharge from the preliminary reactor is
fed into the main reactor (d) along with recycled
4.1.1. Kemira – Leonard Process methyl formate, methanol, and water. The con-
tact time in this reactor is largely sufficient for
A 20 000-t/a formic acid plant based on a method equilibrium to be established. Reactor discharge
developed by the Leonard Process Co. [57] was is flashed to approximately atmospheric pressure
built at Kemira in Finland and put into operation in the flash tank (e); methyl formate, methanol,
in 1982. The process has been developed further and small quantities of formic acid evaporated in
by Kemira, and licences for it have been issued in this process are recycled to the main reactor (d).
Korea, India and Indonesia. Methyl formate and methanol are distilled in
In the Kemira – Leonard process, Methyl for- vacuo in the acid separation column (g). Contact
mate and carbonylation is carried out at about time is minimized by internals with a small liquid
4 MPa and a temperature of approximately holdup. The distillate is separated into methyl
80
C, with additive-containing alkoxides used formate and methanol in the recycle column (f).
as catalyst [58]. Hydrolysis is carried out in two Formic acid can be concentrated under pressure
reactors with different operating conditions. in a column; if the pressure is ca. 0.3 MPa, 85 %
Methyl formate and water react in the preliminary formic acid is drawn off as the bottom product.
reactor in approximately equimolar proportions. Distillation in two columns is more industrially
The formic acid produced catalyzes the hydroly- controllable. Water is distilled overhead in the
sis in the main reactor. An excess of methyl first product column (h). The bottom product is
formate is employed in the main reactor, and concentrated further in the second product col-
hydrolysis is carried out at ca. 120
C and umn (i), and formic acid with a maximum con-
0.9 MPa. The reactor discharge is brought to centration of ca. 98 wt % is drawn off as distil-
atmospheric pressure in a flash tank; reesterifica- late. The bottom product is recycled to the first
tion is largely prevented by the cooling that occurs product column.
Vol. 16 Formic Acid 21

Figure 1. Production of formic acid (Kemira – Leonard process)

a) Methyl formate reactor; b) Methyl formate column; c) Preliminary reactor; d) Main reactor; e) Flash tank; f) Recycle column;
g) Acid separation column; h) First product column; i) Second product column

4.1.2. BASF Process (a); catalyst decomposition products are discharged

by crystallization. In reactor (c), methyl formate is
A 100 000-t/a formic acid plant began operating hydrolyzed with excess water at elevated tempera-
in Ludwigshafen (Federal Republic of Germany) ture and increased pressure. The reaction product is
in 1981. In this plant, a technology for the hydro- flashed into the low-boiler column (d). Methyl
lysis and dehydration was used for the first time. formate is removed as the distillate, with methanol
The production of methyl formate by carbon- as a side stream, and dilute aqueous formic acid is
ylation of methanol has been carried out on a drawn off from the bottom into the extraction unit
large scale for many years at BASF [41], [61]. (e). Here, the formic acid and some of the water are
The carbonylation stage is largely identical to extracted by the secondary amide. Most of the
that of the Kemira – Leonard process, but the water (largely free of formic acid) is recycled to
hydrolysis stage and the dehydration of formic reactor (c). The extract–a mixture of extractant,
acid are noticeably different. formic acid, and some water–is distilled in the
In the BASF process, hydrolysis is carried out dehydration column (f). Enough water is distilled
with a large excess of water (about 5 mol of water via the head for the required formic acid concen-
per mole of methyl formate) to shift the equilib- tration to be obtained in the pure acid column (g).
rium in the direction of formic acid. Much of the This column is operated in vacuo. The extraction
water is separated by liquid – liquid extraction agent is recycled from the bottom of column (g) to
with a secondary amide. the extraction unit.
Process Description (Fig. 2) Carbon monox-
ide and methanol react in the methyl formate
reactor (a) in the presence of sodium methoxide. 4.1.3. USSR Process
Methyl formate is fed, as a distillate, from the
methyl formate column (b) into the formic acid A 40 000-t/a formic acid plant based on a process
reactor (c) together with recycled methyl formate. [53] developed in the former Soviet Union is
Methanol and dissolved catalyst are drawn off from being built in Saratov (Ukraine) [62] and is
the bottom of column (b) and returned to reactor expected to be operational in 1989.
22 Formic Acid Vol. 16

Figure 2. Production of formic acid (BASF process)

a) Methyl formate reactor; b) Methyl formate column; c) Hydrolysis reactor; d) Low-boiler column, e) Extraction unit;
f) Dehydration column; g) Pure acid column

According to published material, this formic prevented by decompressing and cooling to

acid process differs from the above-mentioned about 45
C. Formic acid is produced in a pres-
processes [63], [64] in the hydrolysis stage. sure column as an azeotropic mixture with water
Hydrolysis is carried out at 80
C and 0.6 MPa which contains 85 wt % formic acid.
in a fixed-bed reactor equipped with bubble-cap Process Description [63], [64] (Fig. 3). Car-
trays in the upper section. Reesterification is bon monoxide reacts with methanol in column

Figure 3. Production of formic acid (USSR process)

a) Methyl formate reactor; b) Methyl formate column; c) Hydrolysis reactor; d) Low-boiler column; e) Formic acid column;
f) Fixed-bed catalyst
Vol. 16 Formic Acid 23

reactor (a), in the presence of the catalyst and a States, butane [106-97-8] is used as the hydro-
stabilizer, at about 3 MPa, to yield methyl for- carbon, and ca. 50 kg of formic acid is produced
mate. Separation into methyl formate (distillate) per ton of acetic acid. In Europe, the oxidation of
and methanol plus catalyst takes place in the naphtha is preferred, and up to 250 kg of formic
methyl formate column (b) at 0.2 MPa. The acid is produced per ton of acetic acid in this
exhaust gas produced is partially recycled. In process. For the mechanism of formic acid pro-
reactor (c), methyl formate is hydrolyzed with duction, see [59].
water in two stages; in the first stage, packed Unreacted hydrocarbons, volatile neutral con-
acidic cation exchanger is used as catalyst (f), stituents, and water are separated first from the
which partially hydrolyzes the methyl formate. In oxidation product. Formic acid is separated in the
the second stage, hydrolysis is carried out with next column; azeotropic distillation is generally
autocatalysis by the formic acid produced in stage used for this purpose. The entrainers preferred in
one. Methanol and methyl formate are distilled this process are benzene or chlorinated hydro-
from the hydrolysis product in the low-boiler carbons. The formic acid contains about 2 wt %
column (d); these compounds are separated, along acetic acid, 5 wt % water, and 3 wt % benzene
with the carbonylation reaction mixture, in the [59]. Formic acid with a content of about 98 wt %
methyl formate column (b). Aqueous formic acid can be produced by further distillation.
is drawn off the bottom of column (d) and further
dehydrated in the formic acid column (e) under
pressure. Formic acid with a content of 85 wt % is 4.2.2. Hydrolysis of Formamide
drawn off in the side stream, and the concentration
can be increased to about 98 wt % in the column In 1972, 35 % of the formic acid produced world-
situated downstream. wide was still made by the formamide process
developed by BASF. However, because of the
direct hydrolysis of methyl formate, this process
4.1.4. Scientific Design – Bethlehem Steel has lost much of its significance (see Table 10).
Process Formic acid is produced this way in a three-
stage process. In the first stage, methanol is
The process developed jointly by Scientific De- carbonylated to yield methyl formate:
sign and Bethlehem Steel [65] has not yet been
implemented industrially on a large scale. COþCH3 OH!HCOOCH3 DH 0R ¼ 29 kJ=mol
The carbonylation stage is essentially similar
to the processes described previously. If the In the second stage, formamide is produced by
concentration of carbon monoxide is higher than ammonolysis of ethyl formate:
90 mol %, a single back-mixed reactor is provid-
ed, but if the carbon monoxide concentration is HCOOCH3 þNH3 !HCONH2 þCH3 OH DH 0R ¼ 72 kJ=mol
between 50 and 90 mol %, a two-stage, counter-
current, back-mixed reactor system is recom- In the third stage, sulfuric acid is used to
mended. If the carbon monoxide concentration hydrolyze formamide to formic acid and ammo-
is low, however, the total pressure must be nium sulfate:
increased considerably [66]. The hydrolysis is
catalyzed by formic acid, and the dehydration is HCONH2 þ1=2 H2 SO4 þH2 O!HCOOHþ1=2 ðNH4 Þ2
carried out by distillation alone. SO4 DH 0R ¼ 48 kJ=mol

Methanol is carbonylated as in the first stage

4.2. Other Processes of the processes already described (Section 4.1).
Conversion to formamide is usually carried out at
4.2.1. Oxidation of Hydrocarbons 0.4 – 0.6 MPa and 80 – 100
C; methanol is
distilled and recycled to the methyl formate stage
Formic acid is produced as a byproduct in the (see ! Formamides). Formamide is hydrolyzed
liquid-phase oxidation of hydrocarbons to acetic continuously in the third stage by using 68 – 74 %
acid (! Acetic Acid, Section 4.2.). In the United sulfuric acid at temperatures between 85
C and
24 Formic Acid Vol. 16

the boiling point of formic acid [3]. This reaction Carbon monoxide is mixed countercurrently
is carried out preferably in stirred containers and with aqueous sodium hydroxide, for example, in
provides the heat for the distillation of formic a tower reactor at 1.5 – 1.8 MPa and 180
C
acid. A hot slurry consisting essentially of am- [59]. Sodium formate crystallizes and reacts with
monium sulfate and formic acid flows out of the strong mineral acids, (e.g., concentrated sulfuric
stirred container into a rotary kiln where the acid) at normal pressure in a cooled, stirred
residual formic acid is distilled so that dry, pure reactor at 35
C:
ammonium sulfate is produced at the kiln end.
2 HCOONaþH2 SO4 !2 HCOOHþNa2 SO4
The yield of formic acid exceeds 90 %. The
economic efficiency of this process is determined
by the commercial value of ammonium sulfate. The reaction mixture is separated, for exam-
Hydrochloric acid, nitric acid, or phosphoric ple, in a thin-film evaporator at normal pressure
acid can also be used to hydrolyze formamide [3]. and 100 – 120
C, to produce formic acid and
dry sodium sulfate [67]. The suggestion has been
made that reaction with sulfuric acid be carried
4.2.3. Production of Formic Acid from out in two stages. In this case, the first stage takes
Formates place in vacuo in a horizontal tubular reactor with
rotating internals, and some of the formic acid is
The reaction of sodium formate [141-53-7] or evaporated at the same time. In the second stage,
calcium formate [544-17-2] with strong mineral the remaining formic acid is evaporated, also in
acids, such as sulfuric and nitric acids, is the vacuo, at 30 – 60
C in a smaller tubular reactor
oldest known process for producing formic acid [68].
commercially. If formates or sodium hydroxide Norsk Hydro describes the production of for-
are available cheaply or occur as byproducts in mic acid from calcium formate by reaction with
other processes, formic acid can still be produced nitric acid. The calcium nitrate produced may be
economically in this manner. used, for example, as a fertilizer.
Formates as Byproducts in the Production
of Polyhydric Alcohols. Sodium formate and 4.2.4. Direct Synthesis from Carbon
calcium formate occur as byproducts in the Monoxide and Water
production of pentaerythritol [115-77-5], trimethy-
lolpropane [77-99-6], and 2,2-dimethyl-1,3-propa- The simplest theoretically possible method of
nediol [126-30-7 ] (neopentyl glycol) (! Alco- producing formic acid is to react carbon monox-
hols, Polyhydric). The formates unavoidably ide with water:
produced in this manner are used in several plants
as feed for manufacturing formic acid. H2 OþCOHCOOH

Formates from Sodium Hydroxide and As pressure increases and temperature de-
Carbon Monoxide. The production of sodium creases, the equilibrium of this exothermic reac-
formate from sodium hydroxide and carbon mon- tion shifts in favor of formic acid. Below 150
C,
oxide once had considerable significance, but the reaction rate is very slow, and although
today this process is carried out simply to utilize equilibrium is reached rapidly at higher temper-
excess sodium hydroxide solution in low-capacity ature, the pressure must be increased drastically
plants. The economic efficiency of producing for- to obtain acceptable formic acid concentrations.
mic acid from its salts suffers because one equiva- Table 12 lists the calculated equilibrium concen-
lent of a low-value inorganic salt (e.g., sodium trations at various temperatures and pressures.
sulfate), is produced per mole of formic acid. Inorganic acids and salts have been described
Carbon monoxide reacts with alkaline com- as catalysts in the literature. Unless the reaction
pounds, even in aqueous solution, to yield the rate can be increased markedly by the develop-
corresponding formates: ment of new catalysts, direct synthesis cannot be
used for the economical production of formic
acid.
Vol. 16 Formic Acid 25

Table 12. Calculated equilibrium concentrations of formic acid at simple distillation (! Distillation, 1. Funda-
different temperatures and pressures [69]
mentals). Further dehydration is carried out by
Carbon monoxide pressure, MPa Formic acid ternary azeotropic distillation, extractive distil-
concentration, wt % lation, or extraction. Additional concentration
at 25
C at 100
C at 217.9
C can then be achieved by simple distillation.
0.027 0.63 6.95 1 Through suitable choice of distillation condi-
0.30 7.15 79.1 10 tions, formic acid with a content exceeding
0.72 16.95 187 20 99 wt % can be drawn off as distillate.
3.7 85.8 950 50
108 2540 28170 90
Azeotropic Distillation. Propyl and butyl
formates have been proposed as entrainers for
azeotropic distillation [3]. A particularly eco-
nomical separation of water from the water –
4.2.5. Use of Carbon Dioxide formic acid – acetic acid mixture obtained by
oxidizing butane is achieved by azeotropic dis-
Interesting developments in carbon dioxide chem- tillation with ethyl n-butyl ether [628-81-9] [77].
istry have resulted in formic acid syntheses, but so
far these have not been used industrially [70]. Extractive Distillation. In extractive distil-
Zinc selenide [1315-09-9] and zinc telluride lation, formic acid is extracted in a distillation
[1315-11-3 ] have been proposed as catalysts for column by means of a basic extracting agent
the hydrogenation of carbon dioxide [71]. If introduced countercurrently and fed into the
homogeneous transition-metal catalysts are em- bottom of the column. If this mixture is heated
ployed, carbon dioxide, hydrogen, and water can in a column downstream, the formic acid is
be converted to formic acid. If alcohol is used liberated from the salt-like compound and dis-
instead of water, the corresponding ester is pro- tilled. N-Formylmorpholine [4394-85-8] has
duced. Ruthenium and palladium complexes have been suggested as extractant [54], and various
proved particularly active; either inorganic bases sulfones have been described as auxiliary liquids
[72] or organic bases [73] (e.g., aliphatic tertiary for extractive distillation [78].
amines) can be used as the alkaline material.
BP Chemicals has developed a process in which Extraction. A number of extractants have
formic acid is produced from carbon dioxide and been proposed for extracting acetic and formic acids
hydrogen via several process stages [74–76]. In the [79]. According to BASF, secondary amides are
first stage, a nitrogen base such as triethylamine efficient extracting agents [55]; H€uls recommends
[121-44-8] reacts with carbon dioxide and hydro- compounds in the series tri-n-octylamine [1116-76-
gen in the presence of a noble-metal catalyst (e.g., a 3] to tri-n-dodecylamine [102-87-4 ] [80].
ruthenium complex) to yield the formate of the
nitrogen base. In the second and third stages, the
formate is separated from the catalyst and the low- 4.4. Construction Materials
boiling constituents. In the fourth stage, the for-
mate reacts with a high boiling base, for example, The use of sufficiently corrosion-resistant mate-
1-(n-butyl)imidazole [4316-42-1], to yield a for- rials in the individual process stages is part of the
mate that can be thermally decomposed. Simulta- expertise of formic acid production. Tests on
neously, the low-boiling base is liberated and materials under laboratory conditions do not
distilled. In the fifth stage, the formate is thermally always guarantee that corrosion resistance can
decomposed, formic acid distilled, and the high- be achieved in practice. A low impurity content
boiling base is returned to the fourth stage. or a change in concentration or temperature may
produce a decisive change in the corrosion resis-
tance of a material toward formic acid.
4.3. Concentration of Formic Acid If austenitic CrNi steels are used, those that
contain molybdenum are preferred to molybde-
Formic acid – water mixtures cannot be concen- num-free types [81]. Above 20
C, stainless steel
trated to more than the azeotropic composition by AISI 304 (Cr 18 wt %, Ni 8 wt %) has only
26 Formic Acid Vol. 16

adequate resistance, if the formic acid concen- additional carbon source is available, degrada-
tration is below 10 % or above 90 %. Stainless tion proceeds more quickly.
steel AISI 316 (Cr 18 wt %, Ni 10 wt %, Mo 2 Toxicity to fish was tested on the blue gill
wt %) is resistant up to ca. 50
C to formic acid sunfish (Lepomis macrochirus). The lethal dose
below 40 wt % or over 80 wt % [82]. For higher (TLm 24) was found to be 175 ppm [85]. Toxic-
temperatures and formic acid concentrations be- ity in invertebrates was determined on Daphnia
tween 40 and 80 wt %, steels with higher Cr, Ni, magna. The TLm 48 value was 120 ppm [86]. In
and Mo contents (for example, AISI 317 or the Federal Republic of Germany, formic acid is
317 L) or special nickel-rich alloys must be used. classified among the substances that slightly
Aluminum ist not sufficiently resistant to formic endanger water (Class 1 of water endangerment,
acid, except at concentrations below 30 wt % or WGK 1) [87].
above 80 wt % and at temperatures below 20
C Formic acid vapor can be removed from ex-
[82]. Titanium is resistant under oxidizing con- haust streams by washing with water. Fog results
ditions but is attacked very strongly under reduc- when formic acid vapor is emitted during periods
ing conditions [81]. The corrosion behavior of of high humidity. In the Federal Republic of
titanium is considerably improved by addition of Germany emission is controlled by the technical
platinum or palladium. The more exotic metals guidelines for air (TA Luft) [88]. Formic acid
tantalum, niobium, and zirconium are also cor- belongs to Class 1, which means that for emission
rosion resistant [81]. rates of 0.1 kg/h or higher, the formic acid con-
Of the nonmetallic materials, graphite and glass centration must be <20 mg/m3 in the exhaust
are sufficiently corrosion-resistant, but their use is gas. Upon filling of formic acid, the displaced air
limited because of their poor mechanical proper- is recycled via a gas-transfer line or it is emitted
ties. Among the common plastics, polyethylene is after purification (e.g., by water washing or
resistant up to about 50
C. Polytetrafluorethylene passage through an incinerator).
(PTFE) and poly(vinylidene fluoride) (PVDF) are
resistant to formic acid. Hard poly(vinyl chloride)
(PVC) is resistant only at room temperature, and 6. Quality Specifications
soft PVC should be used only for formic acid
concentration below 10 wt %. Formic acid is marketed in concentrations of 85,
Liquid-crystal polymers (LCP) are recom- 90, 95, 98, and >99 wt %. The impurity content
mended as packing materials for columns be- depends on the production process. Formic acid
cause their resistance to formic acid is reportedly produced by oxidation of hydrocarbons still con-
much better than that of ceramics. A survey of tains a small proportion of acetic acid. A typical
construction materials used in formic acid pro- specification for formic acid produced by hydro-
duction is given in [83]. lysis of methyl formate is given in Table 13; this
Table 13. Sales specification for formic acid [89]

5. Environmental Protection Specification Limits Analytical method

Content min. 85 wt % titrimetric,

Like most other simple organic acids, formic acid min. 90 wt % ISO 731/II, 5.2
can be degraded rapidly and completely by bio- 99 wt %
logical methods. For this reason, formic acid is Color number max. 10 APHA ASTM D 1209–79
Acetic acid max. 150 mg/kg ISO 731/VII
totally mineralized in a short time in purification Sulfate max. 1 mg/kg ISO 731/V
plants and streams. The ecological equilibrium of Chloride max. 1 mg/kg ISO 731/IV
the streams can, however, be disturbed by a Iron max. 1 mg/kg ISO 731/VI
change in pH. For formic acid, the theoretical Other heavy max. 1 mg/kg FCC III
metals
biological oxygen demand (BOD) is 350 mg/g. Evaporation max. 20 mg/kg DIN 53 172
The chemical oxygen demand has been deter- residue
mined to be 86 mg/g after 5 d (COD5) and Quality the formic acid
250 mg/g after 20 d (COD20). In the modified complies with
DAB 7
OECD screening test (OECD method 30 IE), and FCC III
formic acid is degraded to >90 % [84]. If an
Vol. 16 Formic Acid 27

Table 14. Safety data [93] for formic acid

Formic acid content, wt %

85 90 94 99 Method


Flashpoint, C 59 58 55 48 DIN 51 755
Autoignition point,
C 500 480 480 480 DIN 51 794
Flammable limits in air, vol % 15 – 47 14 – 44 14 – 38 12 – 38

acid meets the specifications required in the Food highly toxic carbon monoxide and water. For
Chemicals Codex (FCC) [90]. this reason, formic acid with a concentration of
99 wt % or higher is transported in canisters
without gastight seals [3]. Containers of highly
7. Chemical Analysis concentrated formic acid should be protected
against exposure to heat and stored in a well-
The concentration of formic acid is normally ventilated place. Before entering ship tanks or
determined by titration with sodium hydroxide storage tanks that have contained highly concen-
solution. Volatile impurities can be determined trated formic acid, personnel should monitor the
by gas chromatography on packed columns. carbon monoxide content of the air. The storage
Polyesters or Carbowax 20 M, both treated with method should ensure that contact with strong
phosphoric acid and adsorbed on chromosorb as a alkali solutions (evolution of heat) and strong
carrier, have proved successful as the stationary acids or oxidizing agents (decomposition) does
phase. Formic acid content is measured with a not occur. Table 14 contains important safety
thermal-conductivity cell because the substance data.
cannot be detected with flame ionization detec-
tors (FID).
Test methods for formic acid have been stan- 9. Legal Aspects
dardized by the International Organization for
Standardization (ISO) [91]. Other standard ana- Formic acid is marked according to the regula-
lytical methods for formic acid are described in tions of the European Economic Community
[92]. (council directive 76/907/EEC including the lat-
est amendment) and to the regulations of the
Federal Republic of Germany (Gef Stoff V)
8. Storage and Transportation [94] as: Corrosive, R34 (formic acid content
25 – 90 wt %), R35 (formic acid content > 90
Formic acid is stored in tanks made of austenitic wt %), and S 2–23–26. The EEC numbers of
CrNi steels (18 % Cr, 10 % Ni, 2 % Mo), for formic acid are 607–001–00–0 (formic acid con-
example, AISI 316 L. The use of other materials, tent >90 wt %) and 607–001–01–8 (formic acid
such as AISI 304 L, polyethylene-lined carbon content 25 – 90 wt %). Hazard classifications
steel, glass-lined carbon steel, and polypropyl- for the transport of formic acid are listed in the
ene, is restricted to specific concentrations and following:
low temperatures. Tank cars and tank trucks
made of AISI 316 L are used for transportation.
Small canisters may be made of polyethylene; RID/ADR class 8, item 32 b
glass bottles are used for laboratory quantities. Fed. Rep. of Germany: class 8, item 32 b
GGVE/GGVS
When aqueous formic acid mixtures are stored or
ADNR class 8; item 21 b
transported the melting points at various concen- IMDG Code (Fed. Rep. 8
trations (Table 3) should be considered. Tanks of Germany: GGVSee)
are best heated with hot water or subsidiary IATA-DGR 1779
UN Number 1779
electrical heating systems. To prevent corrosion,
DOT Hazard Classification (USA) corrosive material
even of AISI 316, wall temperatures above 50
C HazChem Code (UK) 2R
must be avoided. Formic acid decomposes to
28 Formic Acid Vol. 16

Table 15. Applications of formic acid (1988, BASF assessment) 11. Economic Aspects
Textiles, leather 25 %
Pharmaceuticals, crop-protection agents 10 % In 2000 the world consumption of formic acid
Latex, rubber auxiliaries 10 % was about 415 000 t, half of which was used in
Silage 35 % Europe. The main applications in Europe are in
Miscellaneous 20 %
the Silage and animal feed preparation market.
About 65% of the formic acid demand in Europe
are produced by BASF, Kemira, BP, and Per-
storp. Perstorp is the only company using sodium
10. Uses formate as starting material, whereas the other
three utilize the methyl formate process.
Because of its acidity, its aldehyde nature, and its
reducing properties, formic acid is used in a
variety of fields (Table 15). 12. Derivatives
In contrast to mineral acids, formic acid
evaporates without leaving any residue. The Among the derivatives of formic acid, amides
leather and textile industries, in particular, make (! Formamides), various esters, and salts are
use of its strongly acidic nature. Animal skins the most important.
and hides are acidified with a mixture of formic
acid, sulfuric acid, and sodium chloride before
chrome tanning (! Leather, Chap. 6. Chrome 12.1. Esters
Tanning).
Formic acid is used for adjusting the pH of Esters of formic acid have the typical physical
dye baths in dyeing of natural and synthetic and chemical properties of esters; they are readily
fibers. Use is made of its highly reactive nature volatile and flammable, and have a sweet, often
in the manufacture of pharmaceuticals and crop- fruity smell. They are only partially soluble in
protection agents [32], [43]. Formic acid plays water. A summary of their chemical properties
an important role in the coagulation of rubber has been published by GIBSON [32].
latex.
In Europe, most of the formic acid is used as a
12.1.1. Methyl Formate
silage aid. If freshly mown, damp grass is sprayed
with formic acid to establish a pH of ca. 4, such
Methyl formate [107-31-3], C2H 4O2, Mr 60.05, is
fodder can be used directly for silage. Formic
an intermediate in the production of formic acid
acid promotes the fermentation of lactic acid and
(Sections 4.1, 4.2) and formamide (! Forma-
suppresses the harmful formation of butyric acid.
mides) in large manufacturing plants. With in-
If formic acid is used, fermentation processes
creasing interest in the production of synthesis gas
occur more rapidly and at lower temperature so
by coal gasification, methyl formate will become
that fewer nutrients are lost [95], [96]. Mixtures
important as a versatile key intermediate. It can
of formic acid with formaldehyde or with am-
also be used as a starting material in the produc-
monium formate are also used as silage aids.
tion of high-purity carbon monoxide [99]. Physi-
Silage that utilizes formic acid is restricted large-
cal properties, safety data, and marking regula-
ly to Europe, but it should be of interest in all
tions for methyl formate are summarized below.
regions where climate makes green forage diffi-
cult to dry.
Other applications of formic acid are as an Boiling point (101.3 kPa) 31.7
C [17]
additive for cleaning agents (replacement of Melting point 99
C [17]
mineral acid for environmental reasons), in the Specific gravity d420 0.975 [17]
Refractive index n20D 1.3433 [99]
synthesis of the sweetener aspartame [22839-47- Flash point (open cup) 20
C [99]
0] [97] (! Amino Acids, Section 5.1.2.), and in Ignition temperature 450
C [99]
the desulfurization of flue gas by the Saarberg – Flammable limits in air 5.0 – 23 vol % [99]
H€olter process (pH stabilization of the wash MAK value 100 mL/m3; 250 mg/m3
(category I)
liquid) [98].
(Continued)
Vol. 16 Formic Acid 29
3 3
TLV—TWA 100 mL/m ; 250 mg/m
TLV—STEL 150 mL/m3 ; 375 mg/m3
[68-12-2 ] is produced by reacting methyl for-
UN number 1243 mate with dimethylamine [124-40-3] (! For-
EEC number 607–014–00–1 mamides). A new use has been found for methyl
Marking according to symbol : F R12, S 9–16–33 formate in the production of foundry molds. The
Gef Stoff V (FRG)
Hazchem Code (UK) 2 SE
mold is formed from granular refractory material
RID/ADR class 3, item I a and a binder consisting of phenol – formalde-
ADNR class 3, item I a hyde resin which is cured by exposure to methyl
IMDG Code 3.1 formate vapor. This process makes possible the
(F.R. of Germany GGVSee)
IATA-DGR 1243
production of rapidly cured foundry molds at low
DOT Hazard Classification flammable liquid temperature [104].
(USA) Small quantities of methyl formate are used as
solvents and insect control agents. With the
Production. Methyl formate is produced by anticipated extension of C1 chemistry, methyl
base-catalyzed carbonylation of methanol (Sec- formate may be used as an intermediate for a
tion 4.1). Processes have been developed for number of products [99], [100].
dehydrogenating methanol, but these have not
yet been implemented commercially [100]:
12.1.2. Ethyl Formate
2 CH3 OH!HCOOCH3 þ2 H2 DH 0R ¼ 98:9 kJ=mol
Ethyl formate [109-94-4], C3H6 O2, Mr 74.08, bp
Catalysts containing copper are used. 54.1
C, mp 80d420 0:923, flash point20
C,
Mitsubishi Gas Chemical (MGC) has devel- ignition point 440
C, UN number 1190, has a
oped highly active catalysts which contain Cu – sharp rumlike smell and taste.
Zr – Zn or Cu – Zr – Zn – Al. The conversion Ethyl formate is produced by carbonylation of
of methanol is approximately 50 %, with a meth- ethanol with carbon monoxide or by esterifica-
yl formate selectivity of ca. 90 % and a space – tion of ethanol with formic acid.
time yield of 3000 g L1 h1 [101]. Air Products Ethyl formate is a solvent for acetyl cellulose
uses a copper – chromite catalyst for the dehy- and nitrocellulose. Ethyl formate is used in alco-
drogenation of methanol [102]. Methyl formate hol-free drinks, ice cream, chewing gum, and
can also be produced by oxy-dehydrogenation of other confectionery as a component of apple-,
methanol: pineapple-, banana-, and peach-type flavors.

2 CH3 OHþO2 !HCOOCH3 þ2 H2 O DH 0R ¼ 472:8 kJ=mol

12.1.3. Isobutyl Formate
Soluble chromium compounds are used as
catalyst [103]. Isobutyl formate [542-55-2], M r 102.13, bp
The direct synthesis of methyl formate from 98
C, mp 96d420 0:88, flash point 5
C, ignition
synthesis gas has been investigated: point 320
C, UN number 2393, is produced by
carbonylation of isobutyl alcohol [78-83-1] with
2 COþ2 H2 !HCOOCH3 DH 0R ¼ 157:2 kJ=mol carbon monoxide or esterification of isobutyl
alcohol with formic acid. Isobutyl formate is
The high pressure of 100 – 200 MPa used as a solvent for colors, lacquers, adhesives,
(1000 – 2000 bar) required makes economical and cleansing agents.
implementation impossible [100]. The dimeriza-
tion of formaldehyde has likewise not been
exploited industrially [100]: 12.1.4. Miscellaneous Esters

2 CH2 O!HCOOCH3 DH 0R ¼ 146:4 kJ=mol A number of formates produced by esterification

of the corresponding alcohols with formic acid
Uses. Most of the methyl formate produced are used as perfumes and flavorings (! Flavors
is used as an intermediate for the production of and Fragrances). Some representative products
formic acid and formamide. Dimethylformamide are citronellyl formate [105-85-1], geranyl for-
30 Formic Acid Vol. 16

mate [61759-63-5], phenylethyl formate [104- (OOCH)(OOCCH 3), is also manufactured com-
62-1], benzyl formate [104-57-4], and isopentyl mercially. The various formates are produced
formate [110-45-2 ]. either directly from the metal or by reaction with
Orthoformates are used in the preparation of an aluminum compound, for example, aluminum
acetals and ketals. Chloroformic esters are used hydroxide [106].
as intermediates in organic syntheses. Aluminum formates are used to impregnate
textiles and to make paper water-resistant. For-
mates are also employed mordants in the textile
12.2. Salts industry. Because of the low toxicity and anti-
septic, astringent, and basic properties of the
12.2.1. Alkali-Metal and Alkaline-Earth aluminum salts, aluminum formates are used in
Metal Formates pharmaceuticals.

Sodium formate [141-53-7] and calcium formate

[544-17-2 ] are byproducts in the synthesis of 12.2.4. Nickel Formate
polyols such as pentaerythritol. However, they
are also produced directly from the correspond- Nickel(II) formate [15694-70-9] usually exists in
ing hydroxides and carbon monoxide (Sec- the form of a green crystalline dihydrate Ni
tion 4.2.3) [3]. (HCOO)2  2 H2O; it is prepared by dissolving
Sodium or calcium formate is used to produce nickel(II) hydroxide [12054-48-7] or nickel(II)
formic acid (Section 4.2.3). An important pro- carbonate [16337-84-1] in formic acid or by
cess for manufacturing sodium dithionite [7775- reaction of nickel(II) sulfate with sodium for-
14-6] starts with sodium formate. Oxalic acid mate. Nickel(II) formate is used for the produc-
[144-62-7] production employs sodium formate tion of nickel hydrogenation catalysts.
as an intermediate. Sodium formate is used in
chrome tanning and as a mordant in the dyeing
and printing of fabrics by the textile industry. The 12.2.5. Copper Formate (! Copper Com-
reducing power of sodium formate is utilized in pounds, Section 5.1.)
electroplating baths and photographic fixing
baths. Calcium formate is also used in tanning. Copper(II) formate [544-19-4] is produced by
Adding calcium formate to concrete reduces the reacting copper(II) hydroxide [20427-59-2],
setting time considerably. copper(II) oxide [1317-38-0], or copper(II) car-
bonate [12069-69-1] with formic acid. It is used
as an antibacterial agent for treating cellulose.
12.2.2. Ammonium Formate

Ammonium formate solutions are used as a low- 13. Toxicology and Occupational
corrosion silage aid; the complex salts ammoni- Health
um diformate [64165-14-6] and ammonium
tetraformate [70179-79-2] are stable in aqueous Formic acid occurs naturally in small amounts in
solution [105]. plants, animal poisons, and higher organisms. In
humans, it is formed in toxic amounts during
methanol poisoning. After intake of large
12.2.3. Aluminum Formate amounts of methanol, the metabolic capacity to
detoxify it to carbon dioxide is insufficient, and
Stepwise replacement of the hydroxyl groups in the high amount of formic acid that results leads
aluminum hydroxide [21645-51-2] yields dibasic to metabolic acidosis. Under physiological con-
aluminum formate [18748-09-9], (HO)2Al ditions, formic acid which is observed under
(OOCH); Almonobasic aluminum formate these conditions in low concentration is a com-
[51575-25-8 ], (HO)Al(OOCH)2; and aluminum ponent of human blood and tissues, and plays an
formate [22918-74-7], Al(OOCH)3. Aluminum important role in the transfer of C1 compounds
hydroxy acetate formate [34202-30-7] (HO)Al during intermediate metabolism. Most of the
Vol. 16 Formic Acid 31

formic acid taken up by the body is metabolized; Rats administered formic acid in concentra-
a small portion is excreted unchanged in the tions of 0.5 and 1.0 % in feed and drinking water,
urine. After oral intake, the biological half-life respectively, showed a slight increase in body
of formic acid is about 45 minutes in human weight gain. In addition the weights of liver,
blood plasma [107]. kidneys, adrenals, and (for the lower dose group)
The most prominent toxic property of this spleen were lower than those of control animals
compound is its corrosive effect upon skin and [111]. In rats, the administration of dosages of
mucous membrane. When applied to the clipped 8.2, 10, 25, 90, 160, and 360 mg kg1 d 1 in
skin of rabbits, formic acid causes necrosis, drinking water for 2 to 27 weeks led to a lower
which heals slowly [108]. Following oral intake intake of food and delay in body weight gain only
of aqueous dilutions of formic acid, corrosion of in the highest dose group [115].
the oral cavity and esophagus occurs even at The influence of formic acid on biochemical
concentrations as low as 6 % [108–110]. The parameters was investigated in rats by exposing
LD50 after oral administration is reported to be them for 6 h a day to vapors of 20 ppm for three
1830 mg/kg in rats [111] and 1076 mg/kg in or eight days [116]. This treatment led to a
mice [112]. Formic acid, whose solubility in decrease in the concentration of glutathione in
water is good, can be absorbed easily by the skin the liver and kidneys.
[107], [108] and causes serious local injuries Few experimental results are available regard-
upon inhalation. In rats, increasing concentra- ing the mutagenic effects of formic acid. The
tions of aqueous acid solutions, inhaled as satu- substance was weakly mutagenic when tested on
rated vapors (20
C), lead to death during de- Escherichia coli [117]. A mutagenic effect was
creasing exposure times: a 10 % aqueous solution also observed on the germ cells of drosophila
of formic acid is tolerated for 7 h. Eyelid closure [118]. However, no primary genotoxic mecha-
and watery nasal discharge as a result of pro- nism of action appears to be involved; rather, the
nounced irritation is no longer observed after mutagenicity is probably associated with the
termination of the exposure period. A 25 % acidity of the compound, which leads to radical
aqueous solution is lethal after an exposure of formation after inhibition of the enzyme catalase.
more than 3 h; a 50 % aqueous solution, after The TLV-TWA exposure limit (ACGIH) for
30 min; and undiluted (98 %) formic acid, formic acid is 5 ml/m3 (9 mg/m3); its MAK
after only 3 min inhalation. In rats, the LC50 is value is also 5 ml/m3 (9 mg/m3) (short term
7.4 mg/L after inhalation of the vapor [113]. The exposure maximum: category I). Formic acid
predominant symptoms of inhalative intake are has a PDK (former Soviet Union) of 0.5 ml/m3
irritation of the eyes, irritation and corrosion of (1 mg/m3).
the nasal mucous membranes, and corneal
opacity.
According to earlier investigations [108], for-
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