Special Report
1,4-Butanediol: A Techno-commercial profile
1,
Abstract
4-Butanediol (BDO) is commer-
cially produced by a number of
routes, of which the major one is
the Reppe Process in which acetylene
and formaldehyde are reacted.
Having terminal primary hydroxyl
groups, BDO is widely used for pro-
duction of products like tetrahydro-
furan (THF), polybutylene terephtha-
late (PBT) resins, gamma-butyrolactone
(GBL), polyurethanes, pharmaceuticals
products and other compounds. Another
major use of BDO is as solvent.
Global BDO demand is expected to
grow at the rate of 2.8-3% per year for
the next two years to about 1.6-mt. De-
mand in China is expected to grow at
5% per year, the fastest in the world.
Asian countries are the main con-
tributors for expansion of BDO pro-
duction.
Introduction
1,4-Butanediol (BDO) [CAS: 110-
63-4], also called as 1,4-hydroxy bu-
tane is a colourless liquid with the for-
mula HOCH2CH2CH2CH2OH. It is one
of the stable isomer of butanediol. This
slightly viscous liquid is odourless and
solidifies below 20oC and is classified
as readily biodegradable chemical. On
standing in air, it absorbs moisture be-
cause of its hygroscopic nature.
In polar solvents such as lower al-
cohols, ketones, esters, water and also
in glycol ethers and its acetates, BDO
is completely miscible. However, it
is immiscible or slightly miscible in
hydrocarbons.
BDO is neither corrosive, explosive
nor pyrophoric in nature, so it can be
handled without any great physiologi-
Chemical Weekly January 18, 2011
cal and industrial safety risk. The only
precaution to be taken is for its inflam-
mable nature. As for consumer use, this
chemical is used as an ingredient in
deodorants in European countries, and
marketed as dietary supplement in the
US.
BDO is primarily used in the manu-
facture of tetrahydrofuran (THF),
gamma-butyrolactone (GBL) and poly-
vinylpyrrolidinone (PVP). BDO is also
used as a chain extender for polyure-
thanes and in the manufacture of poly-
(butylene terephthalate) (PBT).
Historical background
The first process for the production
of BDO was introduced by Dr. Reppe
in 1930’s. The raw material used was
acetylene. This process is still widely
used by global BDO producers.
Mitsubishi Chemical Industries in-
troduced its new technology of produc-
tion of BDO using butadiene[1, 2] in
late 1970’s: This involves reaction of
butadiene and acetic acid, followed by
hydrogenation and hydrolysis to form
BDO.
BASF has also patented a simi-
lar process, in which acetic acid first
adds to butadiene; the product then
isomerizes to 1,4-diacetoxy-2-butene
[18, 19]. According to a process prac-
ticed by Toyo Soda[20] chlorine first
adds to butadiene to form a mixture of
1,4-dichloro-2-butene [764-41-0] and
3,4-dichloro-1-butene [760-23-6]. This
mixture reacts with sodium acetate to
form 1,4-diacetoxy-2-butene, which is
subsequently hydrogenated directly to
BDO.
In 1980’s, ARCO introduced another
production technology for BDO via
propylene oxide.
B.G. SAMPAT
bgsampat@gmail.com
The process of BDO production
from maleic anhydride was intro-
duced by Davy. In this process, ma-
leic anhydride is esterified with etha-
nol. This ethyl ester is hydrogenated
to diethyl succinate and further to
BDO; THF will be a by-product. This
process is relatively flexible as to the
three products formed in the reaction
are BDO, THF and GBL, providing
scope for downstream business possi-
bilities.
Genomatica (a San Diego-based
company) has genetically engineered
E. coli bacteria to metabolise sugar into
BDO. They expect to build and begin
operating a pilot plant by the end of
2009.
Storage and handling
BDO needs to be stored in a tightly
closed container, in a cool, dry, venti-
lated area, away from sources of heat
or ignition. It is stored separately from
reactive or combustible materials, and
out of direct sunlight. Containers of the
material may be hazardous when empty,
since they retain product residues (va-
pours, liquid).
Since BDO solidifies at tempera-
tures below 19°C, appropriate storage
temperatures are required; however,
reliquefaction does not alter its proper-
ties.
BDO can be shipped and stored
in mild steel; however, coated tanks
or stainless steel will prolong product
consistency. Upon longer storage, wa-
ter and iron should be avoided. It is also
advisable to store under a pad of dry
nitrogen.
205
 Special Report
Reaction of formaldehyde & acety-
Hydrogenation to form BDO.
Fig. 1: Reaction scheme: Reppe process
Process for BDO production
BDO is currently produced by the
following processes:
Reppe process from acetylene and
formaldehyde;
Butadiene-acetic acid process;
Propylene oxidation to BDO;
From maleic anhydride;
Dichlorobutene process; and
Bio-based BDO.
In first step, the catalytic reaction
In the second step, subsequent hy-
In third and last step, hydrolysis
Fig. 2: Reaction scheme: Butadiene-acetic acid process
206
The most prevalent route is BASF’s
Reppe process. Also widely used is
Kvaerner John Brown’s new butane
to maleic anhydride route known as
the Davy process. ISP uses BP/Lurgi’s
Geminox technology for production of
BDO directly from butane, whereas
Mitsubishi Chemicals uses the butadi-
ene/acetic acid process. In 2003 Investa
licensed there acetylene-based techno-
logy to a Chinese company called Sich-
uan Tianhua Co. (Luzhou). This is the
first time Investa licensed there tech-
nology to a third party.
Reppe process from acetylene and
formaldehyde
Since first commercialization the
Reppe process has been the major manu-
facturing method for preparation of
BDO, with all US & Western European
producers employing the process.
The production process is divided
in two parts.
lene to form 1,4-butynediol; and
The typical yield of the process is
around 90% of the theoretical yield
based on acetylene.
Butadiene-acetic acid process
The reaction of butadiene with
acetic acid and oxygen in presence of
catalysts like palladium on carbon or
tellurium on carbon produces the di-
acetate, 1,4-diacetoxy-2-butene, which
is hydrogenated and hydrolyzed to
form BDO.
This is a three step process:
of butadiene and acetic acid gives
1,4-diacetoxy-2-butene;
drogenation gives 1,4-diacetoxy-
butane; and
leads to BDO.
Around 80-85% of the theoretical
yield, based on butadiene, has been ob-
tained.
Selective amounts of THF can be
produced as by-product by partial hy-
drolysis of the intermediate diacetate
and its further deacetocyclisation.
Propylene oxidation to BDO
Kuraray Company (Japan) deve-
Chemical Weekly January 18, 2011
 Special Report

loped this process, which was commer-
cialized by ARCO Chemical Company.
Allyl alcohol is produced by catalytic
isomerisation of propylene oxide and
this alcohol is hydroformaylated using
catalysts like rhodium. The resultant
product is reduced to BDO. The yield is
very high at around 93%.
Analogous to this process is the
Dairen process operated in Taiwan.
However, in this case, allyl alcohol is
derived from propylene via allyl ace-
tate. The chemistry is similar to vinyl
acetate production using propylene
acetoxylation. Allyl acetate is convert-
ed to allyl alcohol via dehydration, with
the recovered co-product acetic acid re-
cycled.
From maleic anhydride
In this process n-butane is oxidized
to produce maleic anhydride, which is
then hydrogenated to give GBL, with
THF as by-product. The GBL is further
reduced to BDO. In the mid-1990’s, Si-
sas, a small Italian company, developed
and operated a process that converts
malic anhydride to GBL in one step.
The GBL is then converted to BDO,
THF or NMP depending on market re-
quirements.
Dichlorobutene process
In this process butadiene is chlori-
nated to form mixture of 1,4-dichloro-
butene & 3,4-dichlorobutene. The
3,4-dichlorobutene can be isomerised to
1,4-dichlorobutene. This 1,4-dichloro-
butene is hydrogenated to form BDO.

Fig. 3: Reaction scheme: Propylene oxide process
Bio-Based BDO
Founded in 2000 by research scien-
tists and engineers from the University
of California, San Diego, Genomatica
has developed technologies for a range
of biologically produced industrial
chemicals from a variety of renewable
feedstock.

Genomatica first produced BDO

from glucose in February 2008, and has
since demonstrated the ability to pro-
duce BDO at high levels from sucrose
as well as from xylose, a five-carbon
sugar. Development is primarily fo-
cused on sucrose because it is a readily
available feedstock with a tradable for-
ward market and with less pricing vola-
Fig. 4: Reaction scheme: Maleic anhydride process
tility compared to hydrocarbon feed-
stocks currently in use to make BDO.

The ability to produce BDO from

Fig. 5: Reaction scheme: Dichlorobutene process
both six-and five carbon sugars now
opens the way to possible second-gene-
ration BDO processes that use carbo-
hydrates derived from lignocellulosic
biomass, such as wood residue, mu-
nicipal paper waste, agricultural waste
or energy crops like switchgrass. At the
same time, company researchers have
demonstrated 20,000-fold increases
in the concentrations of BDO that

Chemical Weekly January 18, 2011 207

 Special Report
microbes can produce, approaching the
commercial levels needed to manufac-
ture large volumes of BDO at reduced
Investa, a world leader in chemical
cost. With a cost advantage over tra-
ditional manufacturing processes, this
bio-manufacturing method for BDO
will release chemical producers from
the fluctuations of the hydrocarbon
markets and lower their overall carbon
footprint, while meeting the growing
demand for sustainably manufactured
products.
Global scenario
Global capacity for BDO in 2009
Chinaq Chemicals (based in Zibo,
was roughly 1.37-mtpa. The global mar-
ket in 2008 was estimated to be about
1.25-mt, worth approximately $ 4.0-bn.
Demand will grow at about 6-7% per
annum and will reach roughly 1.6-mt
by 2011. In Europe demand will grow
at the rate of 2-3% whereas US demand
will grow at 1%/year. Demand in China
is growing the fastest, i.e. about 10%.
Growth in Asia is at roughly 8%, even
as demand in the western hemisphere is
growing at 3-4%. Demand in Japan is
declining by 0.5-0.7% and the slump is
expected to continue at least until 2011.
As the supply and demand is well bal-
anced, producers have maintained a
reasonable margin in the face of rising
raw material prices.
The last few years have seen some
dramatic changes in the global BDO
industry brought about by the introduc-
tion of new capacity based on techno-
logy employing maleic anhydride as
feedstock. Due to this process the tra-
ditional issue of safely handling acety-
lene is removed.
New BDO projects in Asia include:
SK Corp’s 40,000-tpa unit at Ulsan,
South Korea;
Nan Ya Plastics 40,000-tpa in Tai-
wan;
Dairen Chemicals’s plant at Mai-
Lian, which came online with
120,000-tpa capacity, making the
208
company one of the largest BDO
producers in world.
another partner for the project.
intermediates, polymers and fibres,
has signed a technology licensing
agreement with Markor Chemicals
headquartered in Urumqi (Xinji-
ang Province, China) for butane-
diol manufacturing technology.
The licensing agreement covers the
manufacturing process, required
technology, product formula-
tion and engineering service for
100,000-tpa BDO plant.
high performance polymers.
China) has completed their expan-
sion of a maleic anhydride produc-
tion facility and started development
for a 50,000-tpa BDO facility, which
is expected to be completed in 2012.
In the Middle East, demand for BDO
is growing at the rate of 1%, but there is
no expansion in this region. Sabic recent-
ly decided that they are not going to take
a 35% stake in a previously announced
PBT and related intermediates complex
planned by Osos Petrochemicals (Saudi
Total 1.37 mt
Others
5%
PU
9%
GBL
15%
PBT
26%
Fig 6: Global BDO demand by application
Arabia). The project includes a 50,000-
tpa BDO plant. Now Osos is seeking for
The largest consumption of BDO
is tetrahydrofuran (THF) used to make
polytetra methylene ether glycol which
goes in fibers, urethane elastomers and
copolyester ethers. The next largest out-
let is polybutylene terephthalate. Also
good amount of BDO goes into the manu-
facturing of the gamma butyarolactone
which is used in the electronic goods,
pharmaceuticals, agrochemicals and
Uses of BDO
Two-third of the total BDO is con-
sumed captively for producing the
value-added products.
Tetrahydrofuran
THF is the largest use for BDO ac-
counting for 45% of BDO demand. The
major use of THF is as a monomer in
the production of polytetramethylene
ether glycol (PTMEG), a component
of cast and thermoplastic polyurethane
THF 45 %
Chemical Weekly January 18, 2011
 Special Report

Producers of BDO
Country Company Process Capacity [ktpa]
USA BASF Reppe/acetylene 136
Invista Reppe/acetylene 109
International Specialty products Butane/Maleic anhydride 63
Lyondell chemicals Propylene oxide 55
Saudi Arabia Gulf advance chemicals al Jubail Butane/Maleic anhydride 75
Germany BASF Reppe/acetylene 190
International Specialty products Reppe/acetylene 90
Netherlands Lyondell Chemicals Propylene oxide 125
China Shanxi Sanwei group Reppe/acetylene 155
Xinjiang Markor Chemical Industry Reppe 60
China National Bluestar Group Kvaerner 55
Dairen Chemicals Reppe/Acetylene 36
Sinopec Shengli Oil Butane 60
Shangdong Jiatal Petrochemicals Kvaerner/Maleic anhydride/n-butane 13
Sichuan Tianhua Reppe/acetylene 25
Malaysia BASF Petronas Maleic anhydride/Kvaerner 66
Taiwan Dairen Chemicals Allyl acetate 220
TCC Chemicals Kvaerner/n-butane 30
Nan Ya Plastics Butadiene 60
Korea BASF Butadiene 30
Korea PTG Kvaerner/Maleic anhydride/n-butane 30
Japan BASF Reppe/Acetylene 25
Mitsubishi Chemicals Butadiene 100

elastomers, polyurethane stretch fibres

and high performance copolyester poly- Others
ether elastomers [14]. A smaller amount 27%
of THF is used as a solvent in polyvinyl
chloride cements and resin-based coat-
ings, in precision magnetic tape manu-
facturing and as a reaction solvent. PTMEG
46%
THF dissolves virtually all plastics
with the exception for certain poly-
amides and polyfluoroethylene. Some
of the most important are polyvinyl
chloride, polyethylene, polystyrene,
polyesters resins, phenol formaldehyde Solvent
resins, epoxy resins, a number of natu- 27%
ral resins and certain polyurethanes.

Gamma-butyrolactone
GBL is derived from BDO by de- Fig. 7: Asian THF demand by end-use

Chemical Weekly January 18, 2011 209

 Special Report
hydrogenation and cyclisation, prefer-
ably in the gas phase and generally over
o
copper catalyst at 200-250 C to yield up
to 93% GBL. GBL is a solvent as well
as precursor of another industrially im-
portant solvent N-Methylpyrollidone
(NMP), which is used as a solvent for
extraction of acetylene, butadiene and as
solvent for polyphenylene sulphide and
as a substitute for chlorofluorocarbons.
The main use of GBL is as an inter-
mediate in the synthesis of herbicides
Excellent abrasion resistance;
like 2-methyl-4-chlorophenoxybutyric
Outstanding low-temperature per-
acid (MCPB), growth regulators [α-(4-
methylbenzylidene)-γ-butyrolactone],
Excellent mechanical properties,
gamma acetobutyrolactone (a vitamin
B1 intermediate) and the rubber ad-
ditive thiodibutyric acid. GBL is also
Very good tear strength;
used as a polymerization catalyst in
High elasticity;
hairwave compositions and sun lotions
High transparency; and
and in pharmaceuticals. It is also used
Good oil and grease resistance.
in printing inks, e.g. for ink-jet printing;
as an extractant in the petroleum indus-
try; as a stabilizer for chlorohydrocar-
bons; and as a nematicide.
Other methods for production of
GBL are hydrogenation of maleic anhy-
dride, hydrogenation of maleic esters,
process via THF[4], dihydrofuran[5],
acetylene[6, 7], butynediol[8], olefins
[9, 10, 11], which are not industrially
important.
Due to its property of being a
prodrug of gamma-hydroxybutyrate
(GHB), GBL was sold as a nutritional
supplement after the scheduling of
GHB, under the names Revivarant and
Renewtrient in the U.S. at least until the
end of 1999.
GBL (as well as GHB), when taken
internally in therapeutic doses without
the presence of other drugs (especially
alcohol, as mixing the two can be fa-
tal), has been shown to elevate growth
hormone levels in humans to at least
five times the baseline. GHB and GBL
are often used as recreational drugs.
210
GHB has two effects, at low doses it
has a euphoric effect (which is why
it is sometimes referred to as liquid
Ecstasy). At higher doses it acts like
a sedative and can make the user un-
conscious very quickly. GHB is classi-
fied as a dangerous drug and is legally
available in the U.S. only as part of an
FDA-approved investigational study.
Penalties under Texas law for illegal
possession or sale of GHB are the
same as for heroin and methamphet-
amines.
Polybutylene terephthalate
PBT is a strong and highly crystal-
line synthetic resin, produced by the
polymerization of BDO and terephtha-
lic acid[12]. PBT is highly suitable
for injection-molding into solid parts.
Either unmodified or reinforced with
glass fibres or mineral fillers, it is used
in numerous applications, especially
electrical and small machine parts, ow-
ing to its excellent electrical resistance,
surface finish and toughness. Pipe made
with PBT was formerly popular for
residential plumbing as a low-cost and
easily handled substitute for copper, but
it was found to degrade after prolonged
contact with oxidizing chemicals such
as chlorine in municipal water supplies,
so it is no longer used. PBT lends ri-
gidity and thermoplastic properties to a
synthetic rubber known as copolyester
elastomer.
PBT is used as an insulator in the
electrical and electronics industries
[13]. It is resistant to solvents, shrinks
very little during forming, is mechani-
cally strong, heat-resistant up to 150°C
(or 200°C with glass-fibre reinforce-
ment) and can be treated with flame
retardants to make it non-combustible.
Thermoplastic polyurethanes
Thermoplastic polyurethanes (TPUs)
are formed by the addition reaction
of difunctional isocyanates, chain ex-
tenders and long-chain polyols. Most
conventional TPUs are based on either
polyester or polyether polyols, 4,4’-di-
phenylmethane diisocyanate (MDI) as
the isocyanate component and BDO
(BDO) as a chain extender[15]. Only a
limited amount of BDO can be added to
the formulation. As a result, TPUs can
be prepared only with hard-segment
content not exceeding about 25%.
Features of commercially available
TPU include:
formance;
combined with a rubber-like elasti-
city;
Copolyester-ether
Copolyester-ether elastomer mar-
kets and production are still predomi-
nantly concentrated in the United
States, Europe and Japan. However,
the fastest growing market is in Asia
(excluding Japan), where demand is
currently growing at approximately
10% per year and is forecast to grow at
7-10% per year through 2012.
This market accounts for about 3%
of global BDO demand.
Copolyester-ether elastomers are
used in automotive, hose and tubing,
medical, and wire and cable applica-
tions. Consumption of copolyester-
ether elastomers in the United States is
fairly mature and is expected to grow
at a moderate rate during 2007-2012.
In Europe, consumption is projected to
grow at a slightly faster rate. Under-
the-hood automotive applications,
where there is an increasing need to
meet higher temperature requirements,
will promote this growth. In Japan,
where consumption is also driven by
Chemical Weekly January 18, 2011
 Special Report

References
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1,4-Butanediol Terephthalate Chemical Technology, John Wiley
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Copolyester
2. Mitsubishi Chem., DE-OS 2345160,
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Dreyfuss”. Kirk Othmer Encyclo-
Fig. 8: BDO derivatives & their applications pedia of Chemical Technology.
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Chemical Weekly January 18, 2011 211