Butanols 1
Butanols
Heinz-Dieter Hahn, Ruhrchemie Aktiengesellschaft, Oberhausen, Federal Republic of Germany
(Chaps. 1 – 8)
Georg Dämbkes, Ruhrchemie Aktiengesellschaft, Oberhausen, Federal Republic of Germany (Chaps. 1 – 8)
Norbert Rupprich, Hoechst Aktiengesellschaft, Frankfurt/Main, Federal Republic of Germany (Chap. 9)
1. Introduction . . . . . . . . . . . . . . .
2. Physical Properties . . . . . . . . . .
3. Chemical Properties . . . . . . . . . .
4. Production . . . . . . . . . . . . . . . .
5. Quality Requirements and Control
6. Storage and Transportation . . . . .
7. Uses . . . . . . . . . . . . . . . . . . . .
1. Introduction
Butanols (butyl alcohols) are aliphatic saturated
C4 alcohols (C4 H9 OH, M r 74.12). There are
four structural isomers of the alcohols: two pri-
mary, one secondary, and one tertiary; as there is
an asymmetric C atom in the secondary alcohol,
there are two stereoisomers of 2-butanol.
In addition to the systematic IUPAC nomen-
clature, other, nonsystematic names for the var-
ious butanols are in common use.
1-Butanol (n-butanol) occurs in nature in
compound form. It also occurs, sometimes in
high concentrations, in fusel oils obtained by fer-
mentation. The first industrial production of 1-
butanol, around 1912, was based on the discov-
ery of the bacterium Clostridium acetobutylicum

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a04 463
. 1 8. Economic Aspects . . . . . . . . . . . . 9
. 2 9. Toxicology and Occupational Health 9
. 2 9.1. 1-Butanol . . . . . . . . . . . . . . . . . . 9
. 4 9.2. 2-Butanol . . . . . . . . . . . . . . . . . . 10
. 7 9.3. 2-Methyl-1-propanol . . . . . . . . . . 10
. 7 9.4. 2-Methyl-2-propanol . . . . . . . . . . 11
. 7 10. References . . . . . . . . . . . . . . . . . 11
Weizmann, which causes carbohydrates to fer-
ment to give mainly acetone and 1-butanol.
The continually increasing demand for 1-bu-
tanol could only be met by developing new man-
ufacturing processes, such as the hydrogenation
of crotonaldehyde formed by the aldolization of
acetaldehyde; the Reppe synthesis (propylene
carbonylation); and, in particular, the process by
which most 1-butanol is produced, the hydro-
genation of n-butyraldehyde, easily obtainable
by the hydroformylation of propylene.
2-Methyl-1-propanol (isobutanol) occurs in
natural products as well as in fusel oils (74 % of
the total alcohol in the product of molasses fer-
mentation), from which it can be isolated. The
isobutyl oil synthesis, a reaction related to meth-
anol synthesis from CO and H2 , first made it pos-
sible to produce larger quantities of 2-methyl-1-
propanol. In the 1980s, nearly all 2-methyl-1-
propanol is produced by the oxo synthesis (pro-
pylene hydroformylation). This straight forward
production process and the attractive prices have
led to a considerable expansion of the market for
isobutanol.
The secondary and tertiary butanols are ob-
tained by hydration of the corresponding unsatu-
rated hydrocarbons, the butenes, whereas dehy-
dration of the butanol yields the corresponding
butene.
Thus, 2-butanol (sec-butanol), the simplest
alcohol with an asymmetric carbon atom, can
be obtained by the acid-catalyzed hydration
2 Butanols

of 1- and 2-butene whereas hydration of 2- (isobutanol)/water and 2-butanol/2-methyl-2-

methylpropene (isobutene) yields 2-methyl-2-
propanol (tert-butanol). The ready availability
of 1- and 2-butene and 2-methylpropene from
olefins derived from petroleum cracking has
made the commercial application of these reac-
tions possible. Most 2-butanol produced is fur-
ther processed to 2-butanone (methyl ethyl ke-
tone).
The rapid development of 2-methyl-2-propyl
methyl ether as an additive for low-lead gaso-
lines has increased the availability of 2-methyl-
2-propanol, from which it can be derived as by-
product.
propanol (tert-butanol)/water cf. [22] and [23].
Table 2 shows the composition of some bi-
nary azeotropic mixtures. For other azeotropes
see [24–26].
3. Chemical Properties
The chemical properties of butanols are mainly
those of primary, secondary, and tertiary alco-
hols. In particular the reactive primary alcohols
serve as starting materials for a wide range of re-
actions. The following deserve special mention:

Dehydration. The catalytic dehydration of

2. Physical Properties alcohols for the preparation of olefins is a
well-established reaction [27]. Of the buta-
With the exception of 2-methyl-2-propanol (mp
nols 2-methyl-2-propanol (tert-butanol) under-
25.6 ◦ C) butanols are colorless liquids. Butanols
goes this reaction most readily. Even with di-
exhibit a characteristic odor; their vapors have
lute sulfuric acid water is split off on warm-
an irritant effect on mucous membranes and a
ing, leading to the formation of very pure 2-
narcotic effect in higher concentrations.
methylpropene (isobutene) [115-11-7] [28]. As
All butanols are completely miscible with
2-methylpropene is readily obtainable from the
common organic solvents. Only 2-methyl-2-
C4 -fractions of olefins from cracked petroleum
propanol is completely miscible with water. The
this reaction is no longer of industrial impor-
major characteristic physical properties of buta-
tance, however. See Chap. 4 for the manufacture
nols are compiled in Table 1.
of pure 2-methylpropene. The dehydration of 2-
See Chapter 6 for safety data, such as flash
methyl-1-propanol (isobutanol) similarly leads
points, ignition temperatures, and lower explo-
to the formation of 2-methylpropene.
sive limits.
The dehydration of 2-methyl-1-propanol to
For further physical properties of butanols see
2-methylpropene is carried out in the pres-
also [1]. The thermodynamic properties of all
ence of γ-Al2 O3 catalyst at about 300 – 350 ◦ C
butanols have been examined in detail; cf. [2],
with practically quantitative conversion and a 2-
[3] for 1-butanol; [4] for 2-methyl-1-propanol;
methylpropene selectivity of over 90 %. In an
[5–7] for 2-butanol; [8], [9] for 2-methyl-2-
analogous manner 1-butanol can be dehydrated
propanol.
to a mixture of 1-butene [106-98-9] and cis-
References [10–12] give an outline of
and trans-2-butene [624-64-6], [590-18-1] [29],
liquid – vapor equilibria for the distillation of bu-
[30].
tanols. H. A. Rizk and N. Youssef [13] as well
Selective dehydration of 1-butanol in mix-
as G. E. Rajala and J. Crossley [14] have in-
tures with 2-methyl-1-propanol can be carried
vestigated the dielectric properties of butanol in
out with calcium zeolite molecular sieves [31],
detail. D. Davis [15] has set up nomograms for
due to the difference in the spatial structure of
the densities of aqueous solutions of 1-butanol,
the two butanols.
2-methyl-1-propanol, and 2-methyl-2-propanol.
Also, at lower temperature dibutyl ether
Further physical properties of the systems
[142-96-1] can be formed from 1-butanol in
comprising water with the various butanols have
the presence of dehydration catalysts [30]. The
been described by several authors; cf. [16–18]
branched butanols show little tendency to un-
for 1-butanol/water, [19], [20] for 2-butanol, and
dergo this reaction.
[21] for 2-methyl-2-propanol.
For the phase equilibria of the ternary
systems isobutyraldehyde/2-methyl-1-propanol
 Butanols 3
Table 1. Physical properties of butanols

1-Butanol 2-Methyl- 2-Butanol 2-Methyl-

1-propanol 2-propanol

mp, ◦ C − 89.3 − 107.9 − 114.7 + 25.6

bp, ◦ C 117.7 107.9 99.5 82.55
Density d 20
4 0.8098 0.8027 0.8065 0.7867
Refractive index n20
D 1.3991 1.3959 1.39719 1.3841
Viscosity at 20 ◦ C, mPa · s 3.0 4.0 4.2 (15 ◦ C) 3.3 (30 ◦ C)
Specific heat, J g−1 K−1 2.437 2.5263 2.81 3.035
at 30 – 80 ◦ C at 30 – 80 ◦ C at 20 ◦ C
Heat of vaporization, J/g 591.64 578.83 562.75 535.78
Heat of fusion, J/g 125.2 91.61
Heat of combustion, kJ/g 36.111 35.981 35.588
Critical pressure, hPa 48.4 48
Critical temperature, ◦ C 287 265 265 235
Surface tension at room temp., mN/m 22.3 23.0 23.5
Dielectric constant at room
temperature 17.8 18.8 15.5 11.4
Evaporation number
(ether = 1) 33 24
Solubility in water
at 20 ◦ C, wt % 7.7 8.5 12.5 miscible
at 30 ◦ C, wt % 7.08 7.5 18 miscible
Solubility of water
in butanol
at 20 ◦ C, wt % 20 15 miscible
at 30 ◦ C, wt % 20.62 17.3 36.5 miscible
Rotation [α]20D (+) (S)-2-butanol
+ 13.73◦
(−) (R)-2-butanol
− 13.79◦

Table 2. Azeotropic mixtures [24], [25], [26]

Compound A Compound B bp, ◦ C bp, ◦ C wt % butanol in

comp. B azeotrope azeotrope

1-Butanol water 100 92.7 [26] 57.5 [26], 55.5 [24]

93.0 [24] 63.0 [25]
1-Butanol acetic acid 1-butyl ester 126.2 117.6 67.2
1-Butanol 2-methyl-1-propanol 99.5 no azeotrope
1-Butanol cyclohexane 81.4 79.8 10.0
1-Butanol toluene 110.6 105.6 27.0
2-Methyl-1-propanol water 100 89.8 67 [26], 70 [24]
2-Methyl-1-propanol acetic acid 2-methylpropyl ester 116.5 107.6 92/95 [26], 55 [24]
2-Methyl-1-propanol cyclohexane 81.4 78.1 14.0
2-Methyl-1-propanol toluene 110.6 101.2 44.5
2-Butanol water 100 87.0 [26], 88.5 [24] 73.2 [26], 68 [24]
2-Butanol acetic acid 2-methylpropyl ester 112.2 no azeotrope
2-Butanol 2-butanone 79.6 no azeotrope
2-Butanol cyclohexane 81.4 76.0 18.0
2-Butanol toluene 110.6 95.3 55.0
2-Methyl-2-propanol water 100 79.9 88.24
2-Methyl-2-propanol cyclohexane 81.4 71.3 37.0

Oxidation. As primary and secondary alco-
hols 1-butanol, 2-methyl-1-propanol, and 2-bu-
tanol can be dehydrogenated to the correspond-
ing carbonyl compounds. Dehydrogenation can
be carried out even at low reaction temperatures
with oxidizing agents such as manganese(IV)
oxide in sulfuric acid, nitric acid, chromic acid,
or selenium dioxide [32].
Even without oxidizing agents the use of suit-
able catalysts (e.g., Cu) at higher temperatures
enables the alcohols to be dehydrogenated to al-
dehyde or ketone until the thermodynamic equi-
librium has been established [33–36]. 2-Butanol
dehydrogenates to 2-butanone (methyl ethyl ke-
tone) [78-93-3] at about 350 ◦ C [37].
As a tertiary alcohol 2-methyl-2-propanol
cannot be selectively dehydrogenated; splitting
4 Butanols
of the molecule occurs under extreme condi-
tions.
Primary alcohols can be oxidized to car-
boxylic acids under other reaction conditions.
In addition to the standard oxidizing agents, this
oxidation can be accomplished by the reaction
of the alcohol with alkali hydroxide at 275 ◦ C.
In this reaction, which is based on the observa-
tions of Guerbert, the alkali salt of butyric acid
[107-92-6] is formed together with hydrogen
and 2-ethylhexanol [104-76-7] (cf. also [38]).
The Koch-Haaf reaction can be used to pre-
pare trimethylacetic acid [75-98-9] from 2-
methyl-1-propanol and 2-methyl-2-propanol by
the addition of carbon monoxide in the pres-
ence of sulfuric acid [39]. With readily available
2-methyl-1-propanol (isobutanol) from the oxo
synthesis, trimethylacetic acid can be obtained
in 89 % yield [40].
Alkylation. Butanols can be employed in a
wide variety of alkylation reactions. N-alkyl-,
N,N-dialkyl-, or N,N,N-trialkylamines are ob-
tainable with ammonia and amines. The use of
isomeric mixtures of alcohols leads to the corre-
sponding mixed amines. Ring alkylation of aro-
matic hydrocarbons proceeds with butanol in the
presence of Friedel-Crafts catalysts [41].
Esterification. Butanols can be converted in
the usual manner into butyl esters with inorganic
and organic acids. The reaction is generally car-
ried out in the presence of acid catalysts. In cer-
tain cases excess of acid which is to be esteri-
fied can serve as the catalyst. The rate of ester
formation greatly depends on the structure of
the carboxylic acid and of the alcohol. The pri-
mary butanols react more rapidly than 2-butanol,
which in turn reacts more quickly than 2-methyl-
2-propanol. For the formation of esters with acid
chlorides and acid anhydrides, as well as other
esterification processes, see [42].
4. Production
Of the many available processes for the prepa-
ration of butanols, the following have achieved
industrial importance:
1-Butanol:
propylene hydroformylation (oxo synthesis)
Reppe synthesis
crotonaldehyde hydrogenation
2-Methyl-1-propanol:
propylene hydroformylation
catalytic hydrogenation of carbon monoxide
homologization reaction
2-Butanol:
n-butene hydration
2-Methyl-2-propanol:
2-methylpropene hydration
byproduct of propylene oxide and methyl
tert-butyl ether production
Oxo Synthesis. The most important process
for the manufacture of 1-butanol and 2-methyl-
1-propanol is propylene hydroformylation with
subsequent hydrogenation of the aldehydes
formed.
In the oxo reaction (hydroformylation)
carbon monoxide [630-08-0] and hydrogen
[1333-74-0] are added to a carbon – carbon dou-
ble bond in the liquid phase in the presence of
catalysts (hydrocarbonyls or substituted hydro-
carbonyls of Co, Rh, or Ru) (→ Oxo Synthe-
sis) [43]. In the first reaction step aldehydes are
formed with one more C-atom than the origi-
nal olefins. For olefins with more than two C-
atoms, isomeric aldehyde mixtures are normally
obtained. In the case of propylene these consist
of 1-butanal and 2-methylpropanal.
There are several variations of the hydro-
formylation process, the differences being in
the reaction conditions (pressure, temperature)
as well as the catalyst system used. The clas-
sic high-pressure process exclusively used until
the beginning of the 1970s operates at pressures
of 20 – 30 MPa (200 – 300 bar) CO/H2 and tem-
peratures of 100 – 180 ◦ C. The catalyst is Co. It

leads to about 75 % 1-butanol and about 25 %
2-methyl-1-propanol.
The new process developments of the past
few years have led to a clear shift in the range of
products. The processes operating at relatively
low pressures (1 – 5 MPa , 10 – 50 bar) use mod-
ified Rh-catalysts. The isomeric ratios achieved
are about 92 : 8 [44] or 95 : 5 [45] 1-butanol to
2-methyl-1-propanol. However, by the use of
unmodified Rh the percentage of 2-methyl-1-
propanol can be increased to about 50 %. For
details on the oxo synthesis and propylene hy-
droformylation see [25], [38], [46] and → Oxo
Synthesis.
Catalytic hydrogenation of the aldehydes
leads to the formation of the corresponding al-
cohols.
As only primary alcohols can be obtained via
the oxo synthesis, it is not possible to produce
2-butanol and 2-methyl-2-propanol by this pro-
cess.
Reppe Process. 1-Butanol and 2-methyl-1-
propanol can also be produced on a commer-
cial scale by the carbonylation of propylene
[115-07-1] developed by Reppe. In this process,
developed in 1942, [47], [48], olefins, carbon
monoxide, and water are made to react under
pressure in the presence of a catalyst (tertiary
ammonium salt of polynuclear iron carbonyl
hydrides). The difference between this process
and the classic Co-catalyzed hydroformylation
is that at low temperature (about 100 ◦ C) and
low pressure (0.5 – 2 MPa, 5 – 20 bar) alcohols
are formed directly from the olefin.
As with the oxo synthesis the carbon monox-
ide can be added to both C-atoms of the double
bond which means that, when propylene is used,
1-butanol and 2-methyl-1-propanol are obtained
in a ratio of 86 : 14.
The catalyst is sensitive both to air and to
higher temperatures at which, in the presence
of water and CO2 , it decomposes into iron car-
bonate. To achieve adequate reaction rates the
catalyst, carbonyl triferrate, must be present in
concentrations of  10 % in the reaction solu-
Butanols 5
tion; this is attained by the presence of dissolving
agents (N-alkylpyrrolidine); see [49], [50], [51]
for details of the process.
The Reppe process has not been as success-
ful as propylene hydroformylation with Co cat-
alysts despite favorable n/iso ratios in the re-
action products and milder reaction conditions
[52]. This can be attributed to the more expen-
sive process technology.
Hydrogenation of Crotonaldehyde
[4170-30-3]. Until the mid 1950s the manu-
facture of 1-butanol based on acetaldehyde was
the preferred process. With the development of
the oxo synthesis, however, it has lost its im-
portance even in Japan and the USA and is no
longer in use.
The individual steps of the process are as fol-
lows:
aldol condensation
2 CH3 CHO −→ CH3 CH(OH)CH2 CHO
splitting off of water
CH3 CH(OH)CH2 CHO −→ CH3 CH = CHCHO + H2 O
hydrogenation
CH3 CH = CHCHO + 2 H2 −→ CH3 CH2 CH2 CH2 OH
Acetaldehyde is aldolized to acetaldol at nor-
mal temperature and pressure in the presence
of alkaline catalysts. With conversions of about
60 % the acetaldol yield is about 95 %. Unre-
acted acetaldehyde can be distilled off and re-
cycled. The removal of water and formation of
aldehyde is brought about by acidification of the
acetaldol with acetic acid or phosphoric acid and
subsequent distillation, whereby the crotonalde-
hyde is obtained almost quantitatively as the top
product.
Various gas- and liquid-phase processes have
proved their value for the hydrogenation of cro-
tonaldehyde to 1-butanol. Copper catalysts are
particularly useful. About 1000 kg of 1-butanol
can be obtained from 1350 kg of acetaldehyde
[53].
The future economic importance of the cro-
tonaldehyde hydrogenation process will depend
to a large extent on developments in the raw ma-
terials market. As “crude oil” raw material be-
comes scarcer and more expensive as a basis
6 Butanols
for the oxo synthesis, the alternative route based
on ethanol from fermentation will become in-
creasingly competitive. The biomass substrate
for ethanol production is almost inexhaustible.
The ethanol is first dehydrogenated to form acet-
aldehyde, from which the synthesis can proceed.
Such a process route is an increasingly in-
teresting alternative for tropical countries with
large supplies of cheap biomass as well as for
the more developed countries of the third world
which do not have their own oil resources [54].
Catalytic Hydrogenation of Carbon
Monoxide. In addition to the CO/H2 -based
methanol synthesis developed commercially
in the 1920s, other analogous processes were
developed for the manufacture of higher alco-
hols. Compared with the methanol synthesis,
however, these processes found only limited ap-
plication. Nowadays they have no commercial
importance.
The most significant process for the pro-
duction of 2-methyl-1-propanol was the BASF
isobutanol oil synthesis. Reaction products with
about 50 % methanol [67-56-1] and 11 – 14 %
2-methyl-1-propanol as well as various other
components were obtained from CO and H2
at temperatures of about 430 ◦ C and pressures
of about 30 MPa (300 bar) in the presence of a
KOH-modified methanol synthesis catalyst [55],
[56]. BASF ceased its isobutyl oil synthesis in
1952 when 2-methyl-1-propanol and its sec-
ondary product 2-methylpropene could be ob-
tained more economically using the oxo synthe-
sis or via a petrochemical route. Further compre-
hensive experiments to obtain the desired buta-
nol from the cheap raw materials methanol and
ethanol with the homologization reaction have
so far proved fruitless. Butanols have so far only
been obtained in small amounts as byproducts.
A review is given in [57].
Olefin Hydration. 2-Butanol (sec-butanol)
and 2-methyl-2-propanol (tert-butanol) can be
obtained by the acid-catalyzed addition of wa-
ter to 1- or 2-butene [106-98-9], [107-01-7]
and 2-methylpropene [115-11-7] respectively.
The water adds at the double bond in accor-
dance with the Markovnikov rule. The differ-
ence in olefin reactivity can be used for the se-
lective manufacture of 2-butanol or 2-methyl-2-
propanol from technical C4 -fractions where the
two alcohols are prepared in turn and isolated.
2-Methylpropene can be completely converted
to 2-methyl-1-propanol with 65 % sulfuric acid.
Hydration of n-butene, on the other hand, re-
quires 75 – 80 % H2 SO4 [58]. Because of the
tendency of the olefins to polymerize readily,
the requisite reaction temperatures must not be
exceeded.
In addition to this indirect hydration another
process variant is known to industry in which the
olefins are hydrated directly at elevated temper-
atures (about 200 – 300 ◦ C) and higher pressures
(10 – 35 MPa, 100 – 350 bar) [59], [60].
Various catalysts have been described for di-
rect hydration, such as tungsten oxide [61] and
aqueous aluminum hydroxide gel suspensions
[62]. For the hydration of 1-butene and 2-butene
the best results are obtained at temperatures
between 220 and 300 ◦ C or in the case of 2-
methylpropene, at 190 – 245 ◦ C [63]. Direct hy-
dration of the olefins has not yet established itself
as a serious competitor to indirect hydration. For
process improvement see [64].
Other Processes. 2-Methyl-2-propanol
(tert-butanol) is formed during the manufac-
ture of propylene oxide from 2-methylpropane
[75-28-5] in an amount of about 1.2 t per ton
of propylene oxide [27, pp. 834, 1005]. In an
intermediate stage tert-butyl hydroperoxide
[75-91-2] is formed from isobutane. Another
process, in which 2-methyl-2-propanol is ob-
tained as a by-product, is the splitting of methyl
tert-butyl ether to highly pure 2-methylpropene
or 2-methyl-2-propanol. Similarly the methyl
tert-butyl ether synthesis with slight traces of
water in the feedstock (methanol and C4 -olefins)
produces 2-methyl-2-propanol as a byproduct
[65].
In the literature a number of other methods
for the preparation of butanol are cited which are
generally of no significance other than for lab-
oratory preparation. A comprehensive review is
to be found in B. Cornils and E. Zilly [38].

5. Quality Requirements and Control
On an industrial scale the four different butanols
are generally marketed as pure substances and
not as isomer mixtures. Because of their many
applications both as commodities and as materi-
als for the manufacture of special fine chemicals
a high standard of purity is demanded for the bu-
tanols.
The quality is mainly controlled by determin-
ing the physical and chemical properties of the
alcohols, such as density, refractive index, color,
water content, hydroxyl value, acid value, car-
bonyl value, and distillation range. The charac-
teristic values are normally determined accord-
ing to the ASTM [66], DIN [67], or the BS meth-
ods [68].
Table 3 lists the standard specifications which
are stipulated by the American Society for Test-
ing and Materials for 1-butanol, 2-butanol, and
2-methyl-1-propanol.
The B. S. I. (British Standards Institution)
has issued specifications for 1-butanol (BS 508:
1966) and 2-butanol (BS 1993: 1968).
The best way to verify isomer purity
and detect traces of impurities is by gas-
chromatographic analysis. Such analyses can be
carried out rapidly and with good reproducibil-
ity, on a routine basis, enabling the use of a high
sampling frequency.
Separation can be effected by the use of both
polar and non-polar packed columns or appro-
priate capillary columns.
For general purity analyses a thermal conduc-
tivity detector system is used; trace (impurity)
analysis is carried out using a flame ionization
detector system. Experience has shown that ni-
trogen, hydrogen, and helium are suitable carrier
gases.
The degree of purity of commercial 1-bu-
tanol, 2-methyl-1-propanol, and 2-butanol is at
least 99 wt %. 2-Methyl-2-propanol is supplied
both as a product of at least 99.8 wt % purity
and as an azeotropic mixture with 11 to 12 wt %
water.
In addition to characteristic value determina-
tion and gas-chromatographic analysis a num-
ber of special analyses and tests may be car-
ried out depending on the intended application,
such as esterification tests with phthalic anhy-
dride and color tests with concentrated sulfuric
acid or KMnO4 .
Butanols 7
6. Storage and Transportation
Butanols can be stored or dispatched in untreated
mild steel or enamelled steel drums provided
that ingress of moisture is prevented. Stainless
steel containers are also suitable. The butanols
are transported in rail and road tank cars, and in
drums as well as in tanker vessels and containers.
It is important to observe the national and inter-
national safety regulations relating to aviation,
ocean-going and inland waterway shipping, rail
and road transport as well as the particular safety
requirements for butanols.
Some important data relating to the safe han-
dling, storage, and transport of butanols are com-
piled in Table 4.
7. Uses
1-Butanol. 1-Butanol is used principally in
the field of surface coating. In the USA, for in-
stance, approx. 85 % of 1-butanol production
finds an outlet in this sector of the market. It is
used either directly as a solvent for varnishes or
it is converted into derivatives which then serve
as solvents or monomer components.
1-Butanol cannot be used directly as a solvent
in the production of nitrocellulose lacquers; in
admixture with toluene, ethanol, or various es-
ters, however, it is an excellent thinner.
The addition of 5 – 10 % of 1-butanol is also
valuable in overcoming “blushing” (unwanted
white opacity) which may arise when large quan-
tities of thinners, particularly volatile solvents,
are used.
1-Butanol is also useful for regulating the vis-
cosity and improving the flow properties of var-
nishes and for the prevention of “streaking” in
paints and lacquers based on spirit-soluble gums
and resins.
Although not itself a solvent for substances
such as polystyrene and chlorinated rubber, 1-
butanol can be successfully used in quantities
up to 20 % as a diluent for the commonly used
solvents for these substances, which are mainly
the esters of the saturated carboxylic acids; in
particular, the acetates.
The acrylic ester of 1-butanol has become
increasingly important during the last decade.
8 Butanols
Table 3. ASTM Specifications for butanols [66]

1-Butanol 2-Methyl-1- 2-Butanol ASTM

propanol Standard
ASTM-Standard: D 304-80 D 1719-81 D 1007-80

Sampling D 268-80
Specific gravity 0.810 – 0.813 0.802 – 0.804 0.807 – 0.809 D 268-80
Color (platinum – cobalt scale) < 10 < 10 < 10 D 1209
Distillation range 117.7 ◦ C within a 107.9 ◦ C within a 98.0 – 101.0 ◦ C D 1078
range of 1.5 ◦ C range of 2 ◦ C
Nonvolatile matter < 0.005 g/100 mL < 0.005 g/100 mL < 0.005 g/100 mL D 1353
Odor characteristic, characteristic, characteristic, D 1296
nonresidual nonresidual nonresidual
Water (Karl Fischer) < 0.1 wt % < 0.2 wt % < 0.5 wt % D 1364
Miscibility with vol% heptane 19 19 19 D 1476
(99 %) at 20 ◦ C

Acidity (as free acetic acid) < 0.005 wt % = 0.047 mg < 0.003 wt % = 0.028 mg < 0.002 wt % = 0.019 mg D 1613
KOH/g sample KOH/g sample KOH/g sample

Table 4. Safety data for butanols [25], [69–71]

UN- Flash point, Ignition limits in Ignition Danger class, MAK a , ppm TLV b , ppm TWA c ,
◦
No. C air, vol% temperature, IMDG-code ppm
◦
C

1-Butanol 1120 + 34 1.4 – 11.3 380 3.3 100 50 100

2-Methyl-1-propanol
(isobutanol) 1212 + 28 1.7 – 10.9 430 3.3 100 75 100
2-Butanol (sec-butanol) 1121 + 24 390 3.3 100 150 150
2-Methyl-2-propanol
(tert-butanol) 1122 + 11 2.3 – 8 470 3.2 100 150 100
a
For the Federal Republic of Germany.
b
Threshold Limit Value.
c
Time-weighted average concentration.

It has become an essential component of latex
paints since such coatings are not only robust
but can also be produced relatively cheaply. The
1-butyl esters of phthalic, adipic, sebacic, oleic,
azelaic, stearic, and phosphoric acids are used as
plasticizers and additives for surface coatings.
The most important of these products is di-1-
butyl phthalate (DBP). Consumption is, how-
ever, stagnating and in some countries it de-
creased slightly within the last years.
In the USA in particular, but also in the Fed-
eral Republic of Germany and Belgium, 1-buta-
nol is used for the manufacture of butylamines.
1-Butanol has numerous applications in the
plastics and textile sector. It is used as a coagu-
lation bath for spinning acrylic fibers and in the
dyeing of poly(vinyl alcohol) fibers.
2-Methyl-1-propanol. The fields of applica-
tion of 2-methyl-1-propanol (isobutanol) closely
resemble those of 1-butanol. Indeed, because
of its lower price it can often replace 1-buta-
nol and is accordingly used as a solvent, dilu-
ent, and additive for nitrocellulose and synthetic
resins; wetting agent; cleaner additive; and com-
ponent of printing inks and related products. Its
capacity for dissolving resins (ketone, phthalate,
urea, and melamine – formaldehyde resins) is of
commercial importance. As a solvent for phe-
nol – formaldehyde resins, however, 2-methyl-
1-propanol is not as effective as 1-butanol.
Several esters exhibit excellent solvent prop-
erties; in particular, isobutyl acetate is a
very good solvent for fats, chlorinated rubber,
polystyrene, and coumarone resins. The esters
of phthalic acid, adipic acid, some dicarboxylic
acids as well as phosphoric acid are used as plas-
ticizers, particularly for PVC and its copolymers
and for cellulose derivatives.
The isobutyl esters of 2,4-dichloro- and 2,4,5-
trichlorophenoxyacetic acid exhibit herbicidal
activity. For the anti-freezing properties of 2-
methyl-1-propanol in gasoline see [72].
 Butanols 9
Table 5. Butanol capacities in the leading producer countries in 1984
Also of interest is the use of 2-methyl-1-
propanol as an extracting agent in the recovery 1-Butanol/∗ 2-Butanol,
of ammonium phosphate [73]. 2-methyl-
1-propanol,
1000 t 1000 t
2-Butanol. Practically all of the 2-buta-
United States 700
nol produced is dehydrogenated to 2-butanone F.R. of Germany 300 60
(MEK or methyl ethyl ketone) which has found Western Europe 422 ∗∗
considerable application because of its good sol- Japan 206 146

vent properties and its favorable boiling point ∗ Any 1-butanol production plant also can be used for the
(79.57 ◦ C). 2-Butanol itself is also used as a sol- manufacture of 2-methyl-1-propanol;
∗∗ 1982
vent: in particular, when mixed with aromatic
hydrocarbons it is especially suitable as a sol-
vent for alkyd resins and ethylcellulose lacquers. Plant utilization was approx. 60 – 70 % in
The ability of 2-butanol to dissolve both water 1983.
and oils is applied in the manufacture of brake The uses can vary considerably from one re-
fluids and cleaning agents. gion to another. As well as direct use as a sol
2-Butanol is converted into amines by treat- vent the main areas of application are in plas-
ment with ammonia. The acetate is recom- ticizers, butyl acetate, acrylic esters, and glycol
mended as a good solvent for nitrocellulose; esters (see Table 6).
the xanthate is used in ore flotation. 2-Butanol Table 6. Butanol consumption by end use, %
also finds application in the manufacture of per-
fumes, dyestuffs, fruit essences, and wetting Japan USA
(1982) (1980)
agents.
Plasticizers 13 8
Solvents 18 17
2-Methyl-2-propanol. Consumption of 2- Butyl acetate 20 9
methyl-2-propanol is small in comparison with Butyl acrylate 24 29
Glycol ethers and esters 13 23
the other butanols, although its use appears to be Miscellaneous 12 14
growing. The solvent sector is again the major
field of application. 2-Methyl-2-propanol is also
used as an agent for introducing the tert-butyl
group into organic compounds (e.g., tert-butyl-
phenol for the preparation of oil-soluble resins 9. Toxicology and
and antioxidants, trinitro-tert-butyltoluene as ar- Occupational Health [74–78]
tificial musk) and as a starting material for the
preparation of peroxides (polymerization cata- The main effects of exposure to excessive con-
lysts). centrations of all butanols are irritation of the
2-Methyl-2-propanol competes with 2- mucous membranes and depression of the cen-
propanol as a gasoline additive to prevent car- tral nervous system. Animal studies have shown
buretor freezing. The methylether can be used low acute oral, dermal, and inhalation toxicity.
as an antiknock agent in gasoline. Its use as a There is insufficient data to make a reliable as-
fuel additive increased from 175 000 t in 1982 sessment of the long-term effects in animals. The
to 400 000 t in 1983. limited amount of documented experience in hu-
mans suggests that excessive exposure can cause
irritation, headache, nausea, fatigue, and dizzi-
ness.
8. Economic Aspects
Both in the industrialized countries and world-
wide, there is considerable excess capacity for
9.1. 1-Butanol
the manufacture of 1-butanol and 2-methyl-1-
The lowest median lethal dose (LD50 ) published
propanol, the two major products in this group
in the literature is 790 mg/kg (rat, oral) and
of substances (Table 5).
4200 mg/kg (rabbit, dermal) [74]. Inhalation of
10 Butanols
high concentrations of 1-butanol by experimen-
tal animals results in pulmonary and eye irri-
tation, incoordination, and narcosis. The low-
est LC50 published in the literature is 8000 ppm
(rats, inhal., 4 h) [74]. Application of drops of
1-butanol into the rabbit eye produces severe
corneal irritation. 1-Butanol has a slight to mod-
erate irritating effect on rabbit skin [75]. 1-
Butanol was found to be non-mutagenic in the
Ames test [75].
Conjunctivitis and keratitis, sometimes ac-
companied by small intracorneal vacuoles, were
reported among workers exposed to 1-butanol
vapors. Intracorneal vacuoles proved to be re-
versible after exposure had ceased [76]. In a
ten-year-study, workers exposed to 1-butanol at
concentrations of 200 ppm and above developed
corneal inflammation associated with a burning
sensation, blurring of the vision, lacrimation,
and photophobia. The mean erythrocyte count
was slightly lowered. There were only rare com-
plaints of irritation when the concentration was
100 ppm [75].
Further data indicate that eye irritation may
be expected when the concentration of 1-buta-
nol is above 50 ppm [76]. According to another
study humans exposed to 1-butanol showed
mild irritation already at 25 ppm, followed by
headaches at 50 ppm [77]. Workers exposed
to 80 ppm experienced a greater hearing loss
(hypoacusia) in comparison with an unexposed
group [77]. Dermatitis of the fingers and hands
upon exposure to 1-butanol is also reported [76].
Exposure limits:
TLV (ceiling limit) 50 ppm (skin) [77],
OSHA air standard (TWA) 100 ppm [74],
MAK value 100 ppm.
9.2. 2-Butanol
The lowest LD50 published in the literature is
4400 mg/kg (rat, oral) [77]. 2-Butanol, like the
other butanols, is a depressant to the central ner-
vous system. The lowest lethal concentration
published in the literature is 10670 ppm for mice
exposed for 225 min; repeated exposure of mice
to 5330 ppm produced narcosis without death;
and no acute signs of intoxication were observed
in mice exposed to 1650 ppm for 420 min [75].
2-Butanol caused severe corneal injury when
applied to the rabbit eye but was not found to be
irritating to the rabbit skin [75].
According to one report industrial exposure
to about 100 ppm has not resulted in any diffi-
culties [77]. Another study concludes that irri-
tation of the eyes, nose, and throat, headache,
nausea, fatigue, and dizziness have been expe-
rienced from excessive exposure to 2-butanol
[75].
Exposure limits:
TLV 100 ppm (TWA); 150 ppm (STEL) [77],
OSHA air standard 150 ppm (TWA),
MAK value 100 ppm.
9.3. 2-Methyl-1-propanol
The lowest published LD50 is 2460 mg/kg (rat,
oral) [75]. A dermal LD50 of 4250 mg/kg in the
rabbit indicates a low toxicity due to local ap-
plication [75]. The lowest LC50 for 2-methyl-1-
propanol is 8000 ppm (rats, inhal., 4 h) [77]. The
compound produces narcosis in mice that had
been intermittently exposed to 6400 ppm for a
total of 136 h. The narcotic dosage is followed
by slight organic changes in the liver and kid-
neys. Repeated exposure of mice to 2125 ppm
for 9.25 h did not cause any adverse effect [76].
Application of 2-methyl-1-propanol to the
rabbit eye causes moderate to severe irritation.
A moderate irritation was observed after 24-h
exposure of the rabbit skin [74].
The results of long-term studies in which a
small number of rats received the material either
orally or subcutaneously suggest that 2-methyl-
1-propanol may have a carcinogenic potential
[75]. Exposure of E. coli bacteria resulted in mu-
tagenesis [74].
In humans, there was no evidence of eye irri-
tation during repeated 8-h exposure to levels in
the order of 100 ppm [75]. Industrial exposure
to mixed vapors of butyl acetate and 2-methyl-
1-propanol has caused vacuolar keratitis in sev-
eral workers but it is not known which of the
substances was responsible [76]. Application of
2-methyl-1-propanol to human skin resulted in
slight erythema and hyperemia [76].

Exposure limits:
TLV 50 ppm (TWA), 75 ppm (STEL) [77],
OSHA air standard 100 ppm (TWA) [74],
MAK value 100 ppm.
9.4. 2-Methyl-2-propanol
The lowest LD50 is reported to be 3500 mg/kg
(rat, oral) [74]. The acute effect of the bad-
smelling 2-methyl-2-propanol is that of a nar-
cotic. Prolonged contact with rabbit skin failed
to cause irritation [75]. The testing of the com-
pound by NTP (National Toxicology Programm,
U.S. Department of Health and Human Services)
for carcinogenesis bioassay began in June 1983
[74].
Following application to human skin there
was no reaction other than slight erythema and
hyperemia. Irritating effects, headache, nausea,
fatigue, and dizziness are reported as symptoms
of excessive exposure [75].
Exposure limits:
TLV 100 ppm (TWA), 150 ppm (STEL) [77],
OSHA air standard 100 ppm (TWA) [74],
MAK value 100 ppm.
10. References
1. R. W. Gallant, Hydrocarbon Process. 46
(1967) no. 1, 183 – 189. R. W. Gallant:
Physical Properties of Hydrocarbons, vol. 1,
Gulf Publ. Comp., Houston, Texas, 1968,
pp. 84 – 91.
2. H. A. Gundry, A. J. Head, G. B. Lewis, Trans.
Faraday Soc. 58 (1962) 1309 – 1312.
3. C. Mosselman, H. Dekker, Recl. Trav. Chim.
Pays-Bas 88 (1969) no. 3, 257 – 265.
4. J. F. Counsell, E. B. Lees, J. F. Martin, J.
Chem. Soc. A 1968, no. 8, 1819 – 1823.
5. N. S. Berman, Doctoral Thesis (1962), Univ.
of Texas, University Microfilms, Ann Arbor,
Michigan; Chem. Eng. Prop. 59 (1963) no. 1,
85.
6. R. J. L. Andou, J. E. Connett, J. F. Counsell,
E. B. Lees, J. F. Martin, J. Chem. Soc. A 1971,
no. 4, 661 – 664.
7. D. Ambrose, C. H. S. Sprake, J. Chem. Soc.
1971, no. 9, 1261 – 1262.
Butanols 11
8. E. T. Beynon, Jr., J. J. McKetta, J. Phys. Chem.
67 (1963) 2761 – 2765.
9. E. T. Beynon, University Microfilms, Ann
Arbor, Michigan, Order no. 65-8025, 75 pp.;
Diss. Abstr. 26 (1965) no. 2, 930; Chem. Abstr.
63 (1965) no. 12, 16196.
10. W. B. Kay, W. E. Donham, Chem. Eng. Sci. 4
(1955) 1 – 16.
11. M. Hirata, Kagaku To Seibutsu 2 (1964)
311 – 316; Chem. Abstr. 64 (1966) 12203.
12. E. P. Ageev, G. M. Pančenkov, V. A. Spivak,
Zh. Fiz. Khim. 41 (1967) no. 5, 1155 – 1157.
13. H. A. Rizk, N. Youssef, Z. Phys. Chem.
Frankfurt/M 58 (1/4) (1968) 100 – 113; Z.
Phys. Chem. Leipzig NF 244 (1970) no. 3/4,
165 – 172.
14. G. E. Rajala, J. Crossley, Can. J. Chem. 49
(1971) no. 22, 3617 – 3622.
15. D. Davis, Ind. Chem. 39 (1963) no. 2, 75.
16. J. J. Kipling, J. Colloid Sci. 18 (1963)
502 – 511.
17. D. Hessel, G. Geiseler, Z. Phys. Chem. Leipzig
229 (1965) no. 314, 199 – 209.
18. V. M. Komarov, B. K. Kricevcov, Zh. Prikl.
Khim. Leningrad 39 (1966) 2604 – 2606.
19. A. I. Alzybejewa, W. P. Beloussow, N. W.
Owtracht, A. G. Moratschewski, J. Phys.
Chem. (Moscow) 38 (1964) 1242 – 1247.
20. G. Schneider, C. Russo, Ber. Bunsenges. Phys.
Chem. 70 (1966) no. 9/10, 1008 – 1014.
21. H. Arm, Helv. Chim. Acta 45 (1962)
1803 – 1806.
22. A. G. Moračevskij, N. A. Smirnova, R. V.
Lyzlova, Zh. Prikl. Khim. Leningrad 38
(1965) 1212 – 1267.
23. A. G. Moračevskij, Z. P. Popovic, Zh. Prikl.
Khim. Leningrad 38 (1965) 2129 – 2131.
24. Handbook of Chemistry and Physics, 55th ed.,
CRC Press, Inc., Cleveland, Ohio, 1974 /75.
25. Hoechst AG/Ruhrchemie AG: Oxo Synthesis
Products (Aldehydes, Alcohols, Acids), 2nd
ed., 1971.
26. L. H. Horsley, W. S. Tamplin: “Azeotropic
Data III,” Adv. Chem. Ser. 116 (1973) .
27. F. Asinger: Die Petrochemische Industrie,
Akademie-Verlag, Berlin 1971, p. 302.
28. B. C. Gates, J. S. Wisnouskas, H. W. Heath, J.
Catal. 24 (1972) no. 2, 320 – 327.
29. H. Pines, W. O. Haag, J. Am. Chem. Soc. 82
(1960) 2471.
30. H. Knözinger, R. Köhne, J. Catal. 5 (1966)
264 – 270.
31. P. B. Weisz, Erdöl Kohle Erdgas Petrochem.
18 (1965) no. 7, 525 – 527.
12 Butanols
32. L. Bexten, J. Weber in: Methodicum
Chimicum, vol. 5 (1975) p. 277.
33. E. Buckley, J. D. Cox, Trans. Faraday Soc. 63
(1967) 895.
34. A. Amariglio, X. Duval, Bull. Soc. Chim. Fr.
1966, 2100 – 2106.
35. K. J. Miller, J. L. Wu, J. Catal. 27 (1972)
no. 1, 60 – 63.
36. U. R. Rao, R. Kumar, N. R. Kuloor, Ind. Eng.
Chem. Process Des. Dev. 8 (1969) 9.
37. Hydrocarbon Process. Pet. Refin. 44 (1965)
no. 11, 234.
38. B. Cornils, E. Zilly in: Methodicum Chimicum,
vol. 5 (1975) p. 84.
39. H. Koch, W. Haaf, Justus Liebigs Ann. Chem.
618 (1958) 251 – 266.
40. Ruhrchemie AG, DE-OS 1793369, 1968 (J.
Falbe, B. Cornils, J. Meis, H. Tummes, J.
Weber).
41. L. M. Kozlova, I. A. Romaan, Izv. Akad. Nauk
Latv. SSR Ser. Khim. 1968, no. 6, 727 – 730.
42. Methodicum Chimicum, vol. 5 (1975) p. 637.
43. J. Falbe: Carbon Monoxide in Organic
Synthesis, Springer Verlag,
Berlin-Heidelberg-New York 1970.
44. UCC, DE-AS 2062703, 1970. Johnson
Matthey Ltd., DE-AS 1939322, 1969.
45. RP-Industries, DE 2627354, 1976.
Stamicarbon, EP 40891, 1980.
46. Ullmann, 3rd ed., supplement vol., p. 87.
47. W. Reppe, H. Vetter, Justus Liebigs Ann.
Chem. 582 (1953) 133.
48. N. V. Kutepow, H. Kindler, Angew. Chem. 72
(1960) 802.
49. H. Kindler, K. Eisfeld, Ind. Chim. Belge 32
(1967) 650.
50. Ullmann, 3rd ed., vol. 5, p. 134.
51. BASF, DE-AS 1114796, 1960; DE-AS
1114797, 1960.
52. Hydrocarbon Process. 50 (1971) no. 11, 138.
53. Kyowa Hakko Kogyo, Hydrocarbon Process.
48 (1969) no. 11, 160.
54. W. Swodenk, Chem. Ing. Tech. 55 (1983) 683.
55. Winnacker-Küchler, 3rd ed., vol. 3, pp. 349,
386.
56. H. Friz, Chem. Ing. Tech. 40 (1968) 999.
57. H. Bahrmann, W. Lipps, B. Cornils, Chem.
Ztg. 106 (1982) 249.
58. H. Kropf, Chem. Ing. Tech. 38 (1966) 837.
59. ICI, US 2815391, 1953.
60. M. Sittig: Chemicals from C4 -Hydrocarbons,
Noyes Development Corp., Park Ridge 1966,
pp. 73 – 79.
61. ICI, US 3164641, 1959.
62. Montecatini, US 3164641, 1959.
63. Gulf Research & Development Co., US
3006970, 1958.
64. Jap. Oil, DE-OS 1944392, 1968 (T. Horie).
65. CWH AG, DE 2629769, 1976 (F. Obenaus et
al.); Hydrocarbon Process. 61 (1982) no. 3,
121 – 123. Hydrocarbon Process. 60 (1981)
no. 8, 101 – 106.
66. Annual Book of ASTM Standards, Section 6,
vol. 06.03: “Paint-Fatty Oils and Acids,
Solvents, Miscellaneous; Aromatic
Hydrocarbons; Naval Stores,” American
Society for Testing and Materials, Philadelphia
1984.
67. DIN-Taschenbuch 30, Beuth-Vertrieb GmbH,
Berlin-Köln-Frankfurt 1971.
68. British Standard Yearbook, British Standards
Institution, Inc., Royal Charter, London 1971.
69. Hoechst AG: “Lösemittel Hoechst,” VOC L,
Frankfurt 1984. Hoechst AG: “Hoechst
Solvents, Manual for Laboratory and
Industry,” 5th ed., Frankfurt 1975.
70. G. Sorbe, GIT-Fachz. Lab. 16 (1972) no. 5,
598.
71. K. Nabert, G. Schön: Sicherheitstechnische
Kennzahlen brennbarer Gase und Dämpfe,
2nd ed., Deutscher Eichverlag, Berlin 1963.
72. T. Hammerich, H. Schildwächter, Erdöl Kohle
Erdgas Petrochem. 18 (1965) no. 12,
972 – 976.
73. Chem. Eng. Int. Ed. 79 (1972) 32 – 36.
74. R. J. Lewis, R. L. Tatken (eds.): Registry of
toxic effects of chemical substances, National
Institute for Occupational Safety and Health
(RTECS ONLINE data base) DIMDI,
10. 01. 84.
75. V. K. Rowe, S. B. McCollister in G. D.
Clayton, F. E. Clayton (eds.): Patty’s Industrial
Hygiene and Toxicology, 3rd ed., vol. 2 C,
Wiley Interscience, New York 1982,
pp. 4571-4588.
76. E. Browning: Toxicity and Metabolism of
Industrial Solvents, Elsevier,
Amsterdam-London-New York 1965,
pp. 342 – 355.
77. American Conference of Governmental
Industrial Hygienists: Documentation of
Threshold Limit Values for substances in
workroom air, Cincinnati, Ohio 1980, vol. 4,
pp. 54, 55, 235.
78. A. I. Cederbaum, G. Cohen, Biochem. Biophys.
Res. Commun. 97 (1980) no. 2, 730 – 736.