Special Report

1,4-Butanediol: A Techno-commercial profile

1,

Abstract
4-Butanediol (BDO) is commercially 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 production of products like tetrahydrofuran (THF), polybutylene terephthalate (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. Demand in China is expected to grow at
5% per year, the fastest in the world.
Asian countries are the main contributors for expansion of BDO production.

Introduction
1,4-Butanediol (BDO) [CAS: 11063-4], also called as 1,4-hydroxy butane is a colourless liquid with the formula 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 because of its hygroscopic nature.

cal and industrial safety risk. The only

precaution to be taken is for its inflammable 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 manufacture of tetrahydrofuran (THF),
gamma-butyrolactone (GBL) and polyvinylpyrrolidinone (PVP). BDO is also
used as a chain extender for polyurethanes 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 1930s. The raw material used was
acetylene. This process is still widely
used by global BDO producers.
Mitsubishi Chemical Industries introduced its new technology of production of BDO using butadiene[1, 2] in
late 1970s: This involves reaction of
butadiene and acetic acid, followed by
hydrogenation and hydrolysis to form
BDO.

In polar solvents such as lower alcohols, ketones, esters, water and also
in glycol ethers and its acetates, BDO
is completely miscible. However, it
is immiscible or slightly miscible in
hydrocarbons.

BASF has also patented a similar 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 practiced 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.

BDO is neither corrosive, explosive

nor pyrophoric in nature, so it can be
handled without any great physiologi-

In 1980s, ARCO introduced another

production technology for BDO via
propylene oxide.

Chemical Weekly January 18, 2011

B.G. SAMPAT
bgsampat@gmail.com
The process of BDO production
from maleic anhydride was introduced by Davy. In this process, maleic anhydride is esterified with ethanol. 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 possibilities.
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, ventilated 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 (vapours, liquid).
Since BDO solidifies at temperatures below 19C, appropriate storage
temperatures are required; however,
reliquefaction does not alter its properties.
BDO can be shipped and stored
in mild steel; however, coated tanks
or stainless steel will prolong product
consistency. Upon longer storage, water and iron should be avoided. It is also
advisable to store under a pad of dry
nitrogen.
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Special Report
logy to a Chinese company called Sichuan Tianhua Co. (Luzhou). This is the
first time Investa licensed there technology to a third party.
Reppe process from acetylene and
formaldehyde
Since first commercialization the
Reppe process has been the major manufacturing method for preparation of
BDO, with all US & Western European
producers employing the process.

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.

The most prevalent route is BASFs

Reppe process. Also widely used is
Kvaerner John Browns new butane
to maleic anhydride route known as
the Davy process. ISP uses BP/Lurgis
Geminox technology for production of
BDO directly from butane, whereas
Mitsubishi Chemicals uses the butadiene/acetic acid process. In 2003 Investa
licensed there acetylene-based techno-

The production process is divided

in two parts.
Reaction of formaldehyde & acetylene to form 1,4-butynediol; and
Hydrogenation to form BDO.
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 diacetate, 1,4-diacetoxy-2-butene, which
is hydrogenated and hydrolyzed to
form BDO.
This is a three step process:
In first step, the catalytic reaction
of butadiene and acetic acid gives
1,4-diacetoxy-2-butene;
In the second step, subsequent hydrogenation gives 1,4-diacetoxybutane; and
In third and last step, hydrolysis
leads to BDO.
Around 80-85% of the theoretical
yield, based on butadiene, has been obtained.
Selective amounts of THF can be
produced as by-product by partial hydrolysis of the intermediate diacetate
and its further deacetocyclisation.

Fig. 2: Reaction scheme: Butadiene-acetic acid process

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Propylene oxidation to BDO

Kuraray Company (Japan) deveChemical Weekly January 18, 2011

Special Report
loped this process, which was commercialized 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%.

However, in this case, allyl alcohol is

derived from propylene via allyl acetate. The chemistry is similar to vinyl
acetate production using propylene
acetoxylation. Allyl acetate is converted to allyl alcohol via dehydration, with
the recovered co-product acetic acid recycled.

Analogous to this process is the

Dairen process operated in Taiwan.

From maleic anhydride

In this process n-butane is oxidized

Fig. 3: Reaction scheme: Propylene oxide process

Fig. 4: Reaction scheme: Maleic anhydride process

Fig. 5: Reaction scheme: Dichlorobutene process

Chemical Weekly January 18, 2011

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-1990s, Sisas, 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 requirements.
Dichlorobutene process
In this process butadiene is chlorinated to form mixture of 1,4-dichlorobutene & 3,4-dichlorobutene. The
3,4-dichlorobutene can be isomerised to
1,4-dichlorobutene. This 1,4-dichlorobutene is hydrogenated to form BDO.
Bio-Based BDO
Founded in 2000 by research scientists 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 produce BDO at high levels from sucrose
as well as from xylose, a five-carbon
sugar. Development is primarily focused on sucrose because it is a readily
available feedstock with a tradable forward market and with less pricing volatility compared to hydrocarbon feedstocks currently in use to make BDO.
The ability to produce BDO from
both six-and five carbon sugars now
opens the way to possible second-generation BDO processes that use carbohydrates derived from lignocellulosic
biomass, such as wood residue, municipal 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
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Special Report
microbes can produce, approaching the
commercial levels needed to manufacture large volumes of BDO at reduced
cost. With a cost advantage over traditional 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
was roughly 1.37-mtpa. The global market 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 balanced, 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 introduction of new capacity based on technology employing maleic anhydride as
feedstock. Due to this process the traditional issue of safely handling acetylene is removed.
New BDO projects in Asia include:
SK Corps 40,000-tpa unit at Ulsan,
South Korea;
Nan Ya Plastics 40,000-tpa in Taiwan;
Dairen Chemicalss plant at MaiLian, which came online with
120,000-tpa capacity, making the
208

company one of the largest BDO

producers in world.
Investa, a world leader in chemical
intermediates, polymers and fibres,
has signed a technology licensing
agreement with Markor Chemicals
headquartered in Urumqi (Xinjiang Province, China) for butanediol manufacturing technology.
The licensing agreement covers the
manufacturing process, required
technology,
product
formulation and engineering service for
100,000-tpa BDO plant.
Chinaq Chemicals (based in Zibo,
China) has completed their expansion of a maleic anhydride production facility and started development
for a 50,000-tpa BDO facility, which
is expected to be completed in 2012.

Arabia). The project includes a 50,000tpa BDO plant. Now Osos is seeking for
another partner for the project.

In the Middle East, demand for BDO

is growing at the rate of 1%, but there is
no expansion in this region. Sabic recently 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

Tetrahydrofuran
THF is the largest use for BDO accounting 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

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 outlet is polybutylene terephthalate. Also
good amount of BDO goes into the manufacturing of the gamma butyarolactone
which is used in the electronic goods,
pharmaceuticals, agrochemicals and
high performance polymers.
Uses of BDO
Two-third of the total BDO is consumed captively for producing the
value-added products.

Total 1.37 mt
PU
9%

Others
5%

THF 45 %

GBL
15%

PBT
26%

Fig 6: Global BDO demand by application

Chemical Weekly January 18, 2011

Special Report
Producers of BDO
Country
USA

Saudi Arabia
Germany
Netherlands
China

Malaysia
Taiwan

Korea
Japan

Company
BASF
Invista
International Specialty products
Lyondell chemicals
Gulf advance chemicals al Jubail
BASF
International Specialty products
Lyondell Chemicals
Shanxi Sanwei group
Xinjiang Markor Chemical Industry
China National Bluestar Group
Dairen Chemicals
Sinopec Shengli Oil
Shangdong Jiatal Petrochemicals
Sichuan Tianhua
BASF Petronas
Dairen Chemicals
TCC Chemicals
Nan Ya Plastics
BASF
Korea PTG
BASF
Mitsubishi Chemicals

elastomers, polyurethane stretch fibres

and high performance copolyester polyether elastomers [14]. A smaller amount
of THF is used as a solvent in polyvinyl
chloride cements and resin-based coatings, in precision magnetic tape manufacturing and as a reaction solvent.
THF dissolves virtually all plastics
with the exception for certain polyamides and polyfluoroethylene. Some
of the most important are polyvinyl
chloride, polyethylene, polystyrene,
polyesters resins, phenol formaldehyde
resins, epoxy resins, a number of natural resins and certain polyurethanes.
Gamma-butyrolactone
GBL is derived from BDO by deChemical Weekly January 18, 2011

Process
Reppe/acetylene
Reppe/acetylene
Butane/Maleic anhydride
Propylene oxide
Butane/Maleic anhydride
Reppe/acetylene
Reppe/acetylene
Propylene oxide
Reppe/acetylene
Reppe
Kvaerner
Reppe/Acetylene
Butane
Kvaerner/Maleic anhydride/n-butane
Reppe/acetylene
Maleic anhydride/Kvaerner
Allyl acetate
Kvaerner/n-butane
Butadiene
Butadiene
Kvaerner/Maleic anhydride/n-butane
Reppe/Acetylene
Butadiene

Capacity [ktpa]
136
109
63
55
75
190
90
125
155
60
55
36
60
13
25
66
220
30
60
30
30
25
100

Others
27%

PTMEG
46%

Solvent
27%

Fig. 7: Asian THF demand by end-use

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Special Report
hydrogenation and cyclisation, preferably 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 important 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 intermediate in the synthesis of herbicides
like 2-methyl-4-chlorophenoxybutyric
acid (MCPB), growth regulators [-(4methylbenzylidene)--butyrolactone],
gamma acetobutyrolactone (a vitamin
B1 intermediate) and the rubber additive thiodibutyric acid. GBL is also
used as a polymerization catalyst in
hairwave compositions and sun lotions
and in pharmaceuticals. It is also used
in printing inks, e.g. for ink-jet printing;
as an extractant in the petroleum industry; as a stabilizer for chlorohydrocarbons; and as a nematicide.
Other methods for production of
GBL are hydrogenation of maleic anhydride, 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 fatal), 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 unconscious very quickly. GHB is classified 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 methamphetamines.
Polybutylene terephthalate
PBT is a strong and highly crystalline synthetic resin, produced by the
polymerization of BDO and terephthalic 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, owing 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 rigidity 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 mechanically strong, heat-resistant up to 150C
(or 200C with glass-fibre reinforcement) 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 extenders and long-chain polyols. Most

conventional TPUs are based on either

polyester or polyether polyols, 4,4-diphenylmethane 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:
Excellent abrasion resistance;
Outstanding low-temperature performance;
Excellent mechanical properties,
combined with a rubber-like elasticity;
Very good tear strength;
High elasticity;
High transparency; and
Good oil and grease resistance.
Copolyester-ether
Copolyester-ether elastomer markets and production are still predominantly 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 applications. Consumption of copolyesterether 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. Underthe-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
Polybutylene
Terephthalate

1,4-Butanediol

Copolyester
Ethers

Tetrahydrofuran

Polytetramethylene
Ether Glycol
Solvent
Uses

Thermoplastic
Polyurethanes
Spandex
Fibers

g-Butyrolactone

Pharmaceuticals
Intermediates
Herbicides
Foundry Resins

N-Methyl2-Pyrrolidone

2-Pyrrolidone

N-Vinyl2-Pyrrolidone

Extraction Solvent
Polyaramide
Cleaning Agents
Electronics

Pharmaceuticals
Intermediates

Polyvinyl
Pyrrolidone

Fig. 8: BDO derivatives & their applications

Reference: Nexant: Butanediol/THF PERP 06/07-4

automotive applications, growth will

be moderated from 2007 to 2012. In
other Asia consumption will be driven
by increasing use in all applications,
particularly automotive, hose and tubing, and wire and cable.
Dupont is the worlds largest producer of copolyester-ether elastomers,
with plants in the United States, Luxembourg and Japan. Other important
producers include Eastman Chemical
Chemical Weekly January 18, 2011

and Ticona (a business of Celanese

Corporation) in the United States; DSM
Engineering Plastics in the Netherlands; P Group in Italy; and Toyobo
Co. and Mitsubishi in Japan.
Other applications
Miscellaneous uses as solvent, a
coating resin raw material and an intermediate in chemicals and pharmaceutical production account for about 2% of
global BDO demand.

References
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Chemical Technology, John Wiley
& Sons, Inc. 1996.
2. Mitsubishi Chem., DE-OS 2345160,
1974; DE-OS 2424539, 1974;
DE-OS 2504637, 1975; DE-OS
2510088, 1975; DE-OS 2510089,
1975; DE-OS 2505749, 1975.
3. Y. Tanabe, Hydrocarbon Process.
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4. Quaker Oats, US 3074964, 1961
(A. P. Dunlop, E. Sherman). H.
Hara, JP-Kokai 7887347, 1978.
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Pinkos, R. Fischer)
6. BASF, WO9707111, 1995 (M.
Heider et al.)
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Heider, T. Ruehl, J. Henkelmann,
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75154237, 1975 (Y. Okumura, Y.
Nagashima)
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US4247467, 1978 (J. H. Murib)
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US4247467, 1978 (J. H. Murib)
12. Encyclopaedia Britannica
13. Supplier data by Goodfellow
14. Polyethers, Tetrahydrofuran and
Oxetane Polymers by Gerfried
Pruckmayr, P. Dreyfuss, M. P.
Dreyfuss. Kirk Othmer Encyclopedia of Chemical Technology.
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15. H. G. Hoppe and H. G. Wussow in
Polyurethane Handbook, G. Oertel
editor, 2nd edition, Hanser Publishers (1994), p. 421.
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market), Chemical Week, 12 April
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17. Malaysia: New BDO plant used
below capacity, Asian Textile
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