乙烯胺生产工艺Louisiana
乙烯胺生产工艺Louisiana
乙烯胺生产工艺Louisiana
Contents
Introduction ................................................3 Ethyleneamines Applications..................20
Product Profiles ..........................................4 Major End-Uses........................................21
Lubricant and Fuel Additives..................22
Ethylenediamine (EDA) ............................4
Polyamide Resins .....................................23
Diethylenetriamine (DETA) ......................4
Asphalt Additives and Emulsifiers...........24
Triethylenetetramine (TETA)....................4
Petroleum Production and Refining........24
Tetraethylenepentamine (TEPA) ..............4
Resins and Additives for
Heavy Polyamine (HPA) ............................5
Pulp and Paper .........................................25
Piperazine (PIP) .........................................5
Epoxy Curing Agents................................26
Aminoethylpiperazine (AEP)....................5
Bleach Activators......................................26
Aminoethylethanolamine (AEEA) ...........5
Chelates and Chelating Agents...............27
Metal Ore Processing...............................27
Typical Physical Properties .......................6
Surfactants and Emulsifiers ....................28
Ethyleneamines Anthelmintics (Dewormers) ...................28
Vapor Pressure vs. Temperature............8 Fabric Softeners........................................29
Viscosity vs. Temperature.......................9 Fungicides.................................................30
Specific Gravity vs. Temperature .........10 Textiles.......................................................31
Ethylenediamine Aqueous Solutions Polymers and Elastomers........................31
Freezing Point vs. Composition...........11 Other Applications ...................................31
Vapor-Liquid Equilibria
at 760 mm Hg.....................................12 Shipping Data............................................32
Heat of Solution at 22°C .......................13 Product Specifications .............................32
Specific Gravity vs. Temperature .........14
Piperazine Aqueous Solutions Product Availability ..................................33
Freezing Point vs. Composition...........15 Storage and Handling...............................34
Vapor-Liquid Equilibria
at 760 mm Hg.....................................16 Health Effects ............................................35
Ecological Fate and Effects ......................36
Reactions of Ethyleneamines ..................17
Product Safety...........................................37
Reaction Notes ..........................................18 References .................................................38
Emergency Service ...................................45
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Introduction
he Dow Chemical Company, pioneered ethyleneamines development in 1935,
T when the company was the first to commercialize production, and has been
the acknowledged world leader in the business ever since.
Today, Dow manufactures ethyleneamines in two world-scale facilities at its Taft,
Louisiana, petrochemicals complex. We are the only producer to use both the ethyl-
ene dichloride and reductive amination catalytic processes, thus providing unparal-
leled flexibility in meeting customer needs.
Unexcelled quality – in product, technology, and services – is the byword of
Dow’s ethyleneamines business. Another first for the company was receipt of ISO
9002 registration in 1990 for the Taft quality systems. Since then, registrations have
been received for raw material quality systems, including those for ethylene,
ethylene oxide, and ethanolamines, as well as for domestic and international
distribution systems.
In 1994, our ethyleneamines business won the Shingo Prize for Excellence in
Manufacturing. The award recognizes outstanding achievements in manufacturing
processes, quality enhancement, productivity improvement, and customer
satisfaction.
Helping to drive these evergreen quality programs is Dow’s technology
leadership. Dedicated research and development focused on the ethyleneamines
production processes has constantly improved product quality. Manufacturing
technicians employ advanced statistical process control and zone charting for
continuous improvement and reduced variability. Backing them is the in-plant
laboratory with dedicated equipment for each of the ethyleneamines covered in this
publication. And our applications scientists, unsurpassed in their knowledge of
ethyl-eneamine end uses, are always ready to assist customers with their needs.
Dow’s worldwide distribution network assures you of a readily available source
of ethyleneamines.
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Product Profiles
Ethylenediamine (EDA) (1,2-diaminoethane) is the lowest molecular weight
member of the ethyleneamines family. It contains two primary amine groups and
forms a maximum boiling azeotrope with water.
H2NCH2CH2NH2
Among the major end-uses for TEPA are the preparation of oil and fuel additives,
reactive polyamides, epoxy curing agents, and corrosion inhibitors.
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Heavy Polyamine (HPA) is a complex mixture of linear, branched, and cyclic ethyl-
eneamines, the structures of which can be deduced from the chemistry of manufacture
and a knowledge of the structures present in TETA and TEPA. The structures of the
principal components contain six or more nitrogen atoms per molecule.
The major end-use applications for HPA include oil and fuel additives, corrosion
inhibitors, and asphalt additives.
Piperazine (PIP) is the simplest cyclic member of the ethyleneamines family. The
product has two secondary amine groups. Anhydrous PIP has a fairly high freezing
point of 110°C (230°F) and a boiling point of 146°C (295°F) at 760 mm Hg. Since this
narrow liquid range makes it difficult to handle, commercial piperazine is often sold in
aqueous solutions to facilitate handling and storage. In addition, an anhydrous
piperazine is available in flake form.
HN NH
Among the major applications for PIP are anthelmintics, pharmaceutical preparations,
polyamides, and as an intermediate for the production of triethylenediamine
polyurethane catalyst.
Major end-uses for AEP include the production of urethane catalysts, epoxy curing
agents, and asphalt additives.
H2NC2H4NHC2H4OH
Principal end-uses include surfactants, fabric softeners, fuel additives, chelates, and
coatings.
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Apparent
Specific Vapor
Molecular Gravity Freezing Pressure at
Ethyleneamine Weight at 20/20°C Point, ˚C 20°C, mm Hg
Ethylenediamine 60.10 0.898 11 10.40
Diethylenetriamine 103.17 0.952 - 39 0.08
Triethylenetetramine 146.24(1) 0.980 - 35 < 0.01
Tetraethylenepentamine UHP 189.30(1) 0.994 - 46(6) < 0.01
Heavy Polyamine X 275(2) 1.015 - 32(6) < 0.01
Piperazine, 68% 86.14(3) 1.005(4) 54 3.5
Piperazine, Anhydrous 86.14 0.877(5) 110 0.10(7)
Aminoethylpiperazine 129.21 0.986 - 17 < 0.01
Aminoethylethanolamine 104.15 1.030 - 45(6) < 0.01
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Δ Boiling
Point/Δp, Absolute
Boiling Point, °C 750-770 mm, Viscosity
760 mm Hg 50 mm Hg 10 mm Hg °C per mm Hg at 20°C, cP
117.0 47.8 19.4 0.043 1.80
206.9 123.3 88.9 0.052 7.16
277(8) 183 144 0.058 26.0
288(8) 215 184 0.045 83.1
— 279(8) 236 — 460.7
117.8 54(17) 27(17) 0.036(17) 22.5(10)
146.1 — (9) — (9) 0.037 0.73(11)
221.0 134.3 100.9 0.056 15.4
242.8 161.3 127.0 0.049 140.6
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Figure 1:
Ethyleneamines,
Vapor Pressure vs. Temperature
Temperature, ыF
300
PIP
200
100
80
Vapor Pressure, mm Hg
60
50
40
30
20
10
8
6
5
4
EDA DETA AEEA TEPA UHP
3
68% PIP (1)
AEP TETA HPA X
1
-20 0 20 40 80 120 160 240 320
Temperature, ыC
(1)
Data shown for Piperazine, 65%
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Figure 2:
Ethyleneamines,
Viscosity vs. Temperature
10000.0
HPA X
1000.0
AEEA
TEPA UHP
100.0
TETA
Viscosity, cP
AEP
DETA
10.0
EDA
PIP
0.1
-50 0 50 100 150 200 250
Temperature, ыC
(1)
Data shown for Piperazine, 65%
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Figure 3:
Ethyleneamines,
Specific Gravity vs. Temperature
1.10
1.05 AEEA
68% PIP (1)
HPA X
AEP
1.00 TETA
DETA
Specific Gravity, tыC/20ыC
0.95
EDA
0.90
TEPA UHP
PIP
0.85
0.80
0.75
-20 20 60 100 140 180 220 260
Temperature, ыC
(1)
Data shown for Piperazine, 65%
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Figure 4:
Ethylenediamine Aqueous Solutions,
Freezing Point vs. Composition
15
Eutectic
-0.8ыC
-5
Temperature, ыC
-15
Composition of Monohydrate
-25
Composition of Dihydrate
-35
-45
Eutectic -53.0ыC
-55
0 10 20 30 40 50 60 70 80 90 100
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Figure 5:
Ethylenediamine Aqueous Solutions,
Vapor-Liquid Equilibria at 760 mm Hg
120
Vapor Phase
116
Liquid Phase
112
Temperature, ыC
108
104
100
0 10 20 30 40 50 60 70 80 90 100
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Figure 6:
Ethylenediamine Aqueous Solutions,
Heat of Solution at 22˚C
50
45
40
35
-Δ Hm, cal/gm of Solution
30
25
20
15
10
0
0 10 20 30 40 50 60 70 80 90 100
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Figure 7:
Ethylenediamine Aqueous Solutions,
Specific Gravity vs. Temperature
1.00
0.98
0.96
Specific Gravity at 20/20ыC
0.94
0.92
0.90
0.88
0 10 20 30 40 50 60 70 80 90 100
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Figure 8:
Piperazine Aqueous Solutions,
Freezing Point vs. Composition
120
100
80
Temperature, ыC
60
40
Eutectic
Composition of Hexahydrate
33.2ыC
20
0
Eutectic
-1ыC
-20
0 10 20 30 40 50 60 70 80 90 100
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Figure 9:
Piperazine Aqueous Solutions,
Vapor-Liquid Equilibria at 760 mm Hg
150
145
140
135
Vapor Phase
130
Temperature, ыC
125
Liquid Phase
120
115
110
105
100
95
0 10 20 30 40 50 60 70 80 90 100
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Reactions of Ethyleneamines†
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Reaction Notes
RX 1. - Inorganic Acids
Ethyleneamines react vigorously with commonly available inorganic acids, forming
crystalline, water soluble salts. Ethylenedinitramine, an explosive compound, is made
by reacting one mole of EDA with two moles of nitric acid and splitting two moles of
water from the salt at elevated temperatures (1).
RX 2. - Organic Acids
Ethyleneamines react with acids, esters, acid anhydrides, or acyl halides to form
amidoamines and polyamides. Various diamides of EDA are prepared from the
appropriate methyl ester or acid at moderate temperatures (2,3). Monoamides can be
cyclized to form imidazolines. This can be done without isolating the monoamide (4-8).
RX 3. - Nitriles
Hydrogen cyanide (HCN) and aliphatic nitriles (RCN) can be used to form
imidazolines (9-10).
RX 4. - Ureas
Ethyleneamines react with urea to form substituted ureas and ammonia (11).
RX 5. - Epoxides
Ethyleneamines react readily with epoxides, to form mixtures of hydroxyalkyl
derivatives (12-14). Product distribution is controlled by the amine-to-epoxide mole
ratio.
RX 6. - Aziridines
Aziridines react with ethyleneamines in an analogous fashion to epoxides (15-16).
Product distribution is controlled by the ethyleneamine-to-aziridine mole ratio.
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RX 8. - Halides
Alkyl halides and aryl halides, activated by electron withdrawing groups, react
with ethyleneamines to form mono- or disubstituted derivatives. Product distribution is
controlled by reactant ratio, metal complexation or choice of solvent. Mixing methylene
chloride and EDA reportedly causes a runaway reaction (19). Aliphatic dihalides, such
as ethylene dichloride, react with ethyleneamines to form various polymeric,
crosslinked, water-soluble cationic products or higher ethyleneamine products,
depending on the reactant ratio (20).
RX 9. - Aldehydes
Ethyleneamines react exothermically with aliphatic aldehydes. The products
depend on stoichiometry, reaction conditions, and structure of the ethyleneamine.
Reactions of aldehydes with such ethyleneamines as EDA or DETA give mono- and
disubstituted imidazolidines via cyclization of the intermediate Schiff base (21).
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Ethyleneamines Applications
Ethyleneamines are utilized in a wide variety of applications because of their unique
combination of reactivity, basicity, and surface activity. They are predominantly used as
intermediates in the production of functional products. The following table lists the
major end-use applications for these versatile materials.
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sludge and varnish deposits within internal dispersant-varnish inhibitors for lubricating oils
combustion engines by inhibiting the aggregation for two-stroke engines (59).
of particles, by solubilizing oil-insoluble liquids, Besides the more common means of linking
and by neutralizing acidic species formed in the long-chain hydrophobic moieties to ethylene-
combustion process. The ethyleneamine derivatives amines via the succinimide linkage, a different
most commonly employed for these tasks are the linkage is employed in another important class of
mono- and bis-polyisobutenyl-succinimides, ashless dispersants – the Mannich bases (60-70).
normally prepared by the condensation reaction They are prepared on a commercial scale by
of polyisobutenyl-succinic anhydrides (PIBSAs) reaction of an alkylphenol with formaldehyde and
(1, 2) with ethyleneamines (3-44). an ethyleneamine (71-76). The alkyl and ethylene-
The higher molecular weight ethylene- amine moieties are similar to those used in the
amines are most popular for these derivatives; succinimide products.
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Polyamide Resins
The main polyamide resin type, in addition used to modify alkyd resins in certain thixotropic
to the liquid resins used as epoxy hardeners, is coating systems (5), to plasticize nitrocellulose
that prepared generally by the condensation lacquers (6), and as corrosion inhibitors in alkyd
reaction of diamines with di- and polybasic fatty paints (7).
acids. EDA is a principal amine reactant (1); Polyamide resins find wide use as binders
however, tri- and tetramines are sometimes used in printing inks for flexogravure application on
at low levels to achieve specific performance (2). certain paper, film, and foil webs (8). Being
PIP and certain PIP derivatives are used with soluble in alcohol-based solvents and exhibiting
EDA in certain cases (3, 4). outstanding adhesion to polyolefins, polyester,
These polyamides are used in hot-melt, cellophane, and paper, they are particularly suited
pressure-sensitive, and heat-seal adhesives for to these applications. Thermoplastic polyamides
leather, paper, plastic, and metal. They are also are similarly used in formulating glossy, abrasion-
resistant, overprint varnishes.
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packaging paper products, represent a major end Certain pigment retention and drainage
use for ethyleneamines. The cationic formaldehyde additives made with ethyleneamines include
resins, both urea- and melamine-formaldehyde various polyamides (10, 11) and polyamines (12).
types (1, 2), incorporate ethyleneamines such as Ethyleneamines are also used in the preparation
DETA, TETA, and/or TEPA in the resin backbone of certain flocculating agents (13), waterproofing
to provide substantivity to the cellulose fibers in and sizing compounds (14-16), antistatic agents
paper. Even though they tend to be less expensive, (17-20), and paper coatings (21). The bis-amide
these types of paper wet-strength resins have made by reacting EDA with stearic acid, ethyl-
been decreasing in popularity due to the adverse enebis (stearamide), is used as a defoamer in
health effects associated with formaldehyde. paper mill operations.
The most popular paper wet strength resins The sulfur-free delignification of wood chips
are the modified polyamides typically made with with EDA-soda liquors has received some interest
DETA, adipic acid in the past few years
and epichlorohy- (22-24). Improved
drin (3-7). These rates of EDA recov-
resins can be used ery (25) have also
under less corrosive been developed for
neutral or alkaline EDA-sulfide pulping
conditions, rather processes (26, 27).
than the acidic con-
ditions required by
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The presence of different polyamino functionalities compatibility with liquid epoxy resins (9-13).
in the higher ethyleneamines allows partial Other modifications of the ethyleneamines
reaction with various modifiers while retaining include partial reaction with epoxy resin to form a
sufficient primary and secondary amino function- prepolymer; cyanoethylation, usually by reaction
ality for reaction with the epoxy resin portion of with acrylonitrile, to give derivatives providing
the system, and tertiary amino functionality to longer pot life and better wetting of glass (14);
catalyze that reaction. For ketimines, made by the
example, a common modi- reaction of EDA with
fication is the addition of acetone; Mannich bases
an alkylene oxide, such as prepared from a phenol,
ethylene oxide, to DETA (2) formaldehyde, and a
as shown above. polyamine; and a variety
of other ethyleneamine
modifications (15-18).
Bleach Activators
Tetraacetylethylenediamine (TAED) has It is prepared by first reacting EDA with two moles
been widely adopted for use in home laundry of acetic acid to form the bis-amide, which is then
products as an activator for peroxygen bleaches. reacted with two moles of acetic anhydride to
form the tetra-amide.
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AEEA and DETA are also used to make This property makes the ethyleneamines
similar polyacetic acid or acetate products. These useful in specialized applications, such as
compounds are produced on an industrial scale electroplating and electroless metal coating with
primarily through the reaction of the ethylene- specific metals and many alloys, where their
amine, sodium or hydrogen cyanide, and metal complexing properties are required; and as
formaldehyde in the presence of sodium hydrox- ingredients in systems for etching and for stripping
ide (1, 2). The intermediate polynitrile may either nickel and nickel alloy coatings.
be hydrolyzed in situ (3), or separated and
hydrolyzed separately (4, 5).
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elevated temperature to remove two moles of TETA, or TEPA and fatty acids also function as
water are all used. A variety of 2-alkylimidazo- water-in-oil or oil-in-water emulsifiers (12).
lines and their salts pre- TEPA, ethoxylated with an
pared mainly from EDA or average of 17 moles of
AEEA are reported to have ethylene oxide, improves
good foaming properties the soil antiredeposition
(3-8). AEEA-based imida- and clay soil removal
zolines are also important properties of certain liquid
intermediates for surfac- laundry detergents (13).
tants used in shampoos by
Anthelmintics (Dewormers)
Piperazine is the active ingredient in certain swine. The PIP salts have long been the agents
veterinary anthelmintic preparations – primarily of choice for use against roundworms and
for combating intestinal worms in poultry and pinworms (1).
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Fabric Softeners
Softeners are commonly added to textile generally with dimethyl sulfate, to yield com-
materials to make them less harsh, “softer” or pounds that can be formulated into softener
more pleasing to the touch. Softeners also act as products for home laundry use (4-6).
antistatic and antisoiling agents, and impart Amino esters are made from acids and an
fluffiness. Softeners are added to the home wash- amino alcohol, such as AEEA. The amino esters,
ing machine during a rinse cycle or as part of a as well as their quaternized derivatives, are more
detergent/softener combination product, or to the subject to hydrolysis than the amidoamine and
clothes dryer. Softening agents based on DETA imidazoline compounds. As a result, they have
and TEPA are also used in industrial textile pro- gained some popularity where environmental
cessing operations (1, 2). biodegradation concerns outweigh their
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Fungicides
The ethylenebisdithiocarbamates (EBDCs) primary commercial products. Zineb and maneb
are a class of broad-spectrum, preventative, con- are normally formed by the addition of zinc
tact fungicides first used in the early 1940’s. They or manganese salts to nabam solutions. The
are used on many fruit, vegetable, potato, and ammonium (amobam) and mixed zinc and
grain crops for prevention of mildew, scab, rust, manganese (mancozeb) salts are also known.
and blight. The EBDCs are prepared by reacting Other materials based on EDA have also been
EDA with carbon disulfide in the presence of an suggested as fungicides. The most important of
aqueous base. the imidazoline type (8) is 2-heptadecyl-2-imid-
CH2–NH–C–S–Na
H2C–CH2–CH2–NH2 + CS2 + 2NaOH + 2 H2O
CH2–NH–C–S–Na
This sodium derivative, nabam, was found to azoline (9), prepared from EDA and stearic acid.
be unstable. However, it is stabilized by conver- It is used as the acetate salt for control of apple
sion to certain other divalent metal salts. The scab and cherry leaf spot. A 2:1 EDA-copper
zinc (zineb) and manganese salts (maneb) are sulfate complex has been suggested for control of
especially effective (1-7) and are today the aquatic fungi (10).
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Textiles
Ethyleneamines are used in the textile- wool (5), static prevention (6), and mothproofing
related industries for a variety of applications, (7). Dye assist compounds for synthetic fibers
including the treatment of a wide variety of natural have been derived from EDA, DETA, TETA, and
and synthetic fibers for modification of certain TEPA (8-10). DETA is a component of Nylon 6
properties (1, 2); as precursors for certain (11). The bis-amidoamine condensate made from
compounds providing durable press (3), light TETA or TEPA and stearic acid is used as a
stabilization of spandex fibers (4), shrinkproofing defoamer in certain textile treatment baths.
Other Applications
Ethyleneamines find application in numerous and concrete coatings, plaster systems, ceramics,
other specific industries. They include coal-oil explosives, fire retardants, functional fluids,
emulsification and coal extraction, industrial pharmaceuticals, gas and water treating, ion
corrosion inhibition, petroleum production, exchange resins, and membranes.
polymer concrete and concrete additives, stone
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Shipping Data
Since governmental regulations are subject to change, additional information on
shipping data, labeling and container requirements may be obtained by contacting
Dow at the numbers on the back of this booklet. We will provide a technical contact to
discuss specific questions you might have.
Metric Units
Average Weight per liter, kg
Ethyleneamine at 20°C at 15.56°C
Ethylenediamine 0.896 0.900
Diethylenetriamine 0.949 0.953
Triethylenetetramine 0.977 0.980
Tetraethylenepentamine UHP 0.991 0.995
Heavy Polyamine X 1.011 1.015
Piperazine, 68% 1.005 (1,7) — (2,7)
Piperazine, Anhydrous — (2) — (2)
Aminoethylpiperazine 0.984 0.987
Aminoethylethanolamine 1.027 1.031
(1) At 65°C (2) Solid at this condition (3) At 20°C to 30°C (4) At 45°C to 65°C (5) At 80 °C
(7) Data listed is for Piperazine, 65%
Product Specifications
Product specifications and methods are available upon request. Please contact
Dow at the numbers on the back of this booklet.
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Δlb/gal/Δt
10°C to 30°C, Coefficient of Expansion, per °C Flash Point (6), °F
per °C at 20°C at 55°C Closed Cup Open Cup
0.00794 0.00106 0.00110 110 T 103 TO
0.00703 0.00089 0.00092 208 P 225 C
0.00661 0.00081 0.00083 300 P 310 C
0.00642 (3) 0.00081 0.00080 340 P 360 C
0.00623 (3) 0.00076 0.00076 345 P 445 C
0.00787 (4,7) — (2,7) 0.00095 (5,7) None P 180 C
— (2) — (2) — (2) 130 P 215 C
0.00680 (3) 0.00086 0.00085 215 P 250 C
0.00640 (3) 0.00077 0.00077 260 P 310 C
(6) T = Tag Closed Cup, ASTM Method D 56 C = Cleveland Open Cup, ASTM Method D 92
P = Pensky-Martens Closed Cup, ASTM Method D 93 TO = Tag Open Cup, ASTM Method D 1310
Δkg/liter/Δt
10°C to 30°C, Coefficient of Expansion, per °C Flash Point (6), °C
per °C at 20°C at 55°C Closed Cup Open Cup
0.000951 0.00106 0.00110 43 T 39 TO
0.000842 0.00089 0.00092 98 P 107 C
0.000792 0.00081 0.00083 149 P 154 C
0.000769 (3) 0.00081 0.00080 171 P 182 C
0.000747 (3) 0.00076 0.00076 174 P 229 C
0.000943 (4,7) — (2,7) 0.00095 (5,7) None P 82 C
— (2) — (2) — (2) 54 P 102 C
0.000815 (3) 0.00086 0.00085 102 P 121 C
0.000767 (3) 0.00077 0.00077 127 P 154 C
(6) T = Tag Closed Cup, ASTM Method D 56 C = Cleveland Open Cup, ASTM Method D 92
P = Pensky-Martens Closed Cup, ASTM Method D 93 TO = Tag Open Cup, ASTM Method D 1310
Product Availability
Products are available in bulk ocean tanker, rail car, tank truck, and nominan
55-gallon drums.
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The amines do not present any unusual flammability problem at ordinary temper-
atures. EDA has the lowest flash point (Tag Closed Cup): 43°C (110°F). As commercially
pure materials, ethyleneamines exhibit good temperature stability. At elevated temper-
atures some product breakdown may be observed in the form of ammonia and the
formation of lower and higher molecular weight species. This degradation increases in
rate as the temperature and/or time increases. Additionally, contaminants can lower
the onset of rapid exothermic thermal decomposition (for example, mineral acids
contamination). Testing for thermal stability is suggested whenever ethyleneamines
are mixed with other materials.
Ethyleneamines are typically maintained above their freezing points which may
require storage above ambient temperatures (particularly EDA and PIP). In addition,
heavier ethyleneamines may be stored at elevated temperatures (40-60°C) to ease in-
plant handling by lowering the viscosity. Storage at elevated temperatures can cause
vapors “breathing” from the tank to contain significant concentrations of product. All
amine vents should be routed to a safe location and “smoking vents” routed to water
scrubbers to capture the vapors.
Tank vents and safety devices are also susceptible to fouling by solid amine
carbamates formed by the reaction of the amines with carbon dioxide. Vent fouling can
be reduced by using nitrogen blankets on storage tanks to exclude atmospheric CO2.
Also, vent units and relief devices may be steam-traced to maintain 160°C, which causes
the carbamates to decompose. Vent units require periodic inspection to verify that
fouling is not occurring and to ensure that seals are functioning properly to exclude
air from the tank.
Additionally, although the amines are water-soluble, in certain concentrations,
solid amine hydrates may form, which can be a nuisance in handling. Hydrates can
plug processing equipment, vent lines and safety devices. Hydrate problems are usually
avoided by insulating and heat tracing equipment to maintain a temperature of at least
50°C. Water cleanup of ethyleneamine equipment can result in hydrate problems, even
in areas where routine processing is nonaqueous. Warm water cleanup can reduce the
extent of the problem.
This information is of a general nature. For additional information, contact Dow at
the numbers on the back of this booklet and request our Ethyleneamines Storage and
Handling Brochure and/or a technical contact who will discuss specific questions
about acceptable materials of construction and storage practices.
Health Effects
Information on health effects and their management, as well as recommended
safety procedures, may be found in the Material Safety Data Sheets, which are updated
as new information becomes available. For the latest Material Safety Data Sheets on
ethyleneamines, contact Dow at the numbers on the back of this booklet.
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(1) Measured by Chemical Oxygen Demand (COD) procedure published in Standard Methods for the Examination of Water and Wastewater, 17th ed.,
Public Health Assoc. (1989). Calculated value based on oxygen required to oxidize the chemical to carbon dioxide and water, while the nitrogen con-
verts to and remains as ammonia. The nitrogenous oxygen demand is calculated based on nitrogen being oxidized to nitrate by nitrifying bacteria.
(2) Measured in dilution bottle biochemical oxygen demand test published in Standard Methods. The biooxidation values are calculated as percentage
ratio of BOD and ThOD (BOD/ThOD x 100). Nonacclimated domestic sewage microorganisms used as seed.
(3) The measured biooxidation as a percent of the total carbonaceous and nitrogenous oxygen demand (sum of calculated carbonaceous and nitroge-
nous ThOD values) is presented for Days 5, 10, and 20.
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Product Safety
When considering the use of any Dow products in a particular application, you
should review our latest Material Safety Data Sheets and ensure that the use you intend
can be accomplished safely. For Material Safety Data Sheets and other product safety
information, contact Dow at the numbers on the back of this booklet. Before handling
any other products mentioned in the text, you should obtain available product safety
information and take necessary steps to ensure safety of use.
No chemical should be used as or in a food, drug, medical device, or cosmetic,
or in a product or process in which it may contact a food, drug, medical device, or
cosmetic until the user has determined the suitability and legality of the use. Since
government regulations and use conditions are subject to change, it is the user’s
responsibility to determine that this information is appropriate and suitable under
current, applicable laws and regulations.
Dow requests that the customer read, understand, and comply with the information
contained in this publication and the current Material Safety Data Sheet(s). The
customer should furnish the information in these publications to its employees,
contractors, and customers, or any other users of the product(s), and request that
they do the same.
(4) Determined by turbidity/growth procedures where the median inhibition concentration (IC50) is measured after 16 hours of incubation
with sewage microorganisms.
(5) Fathead minnows and Daphnia magna bioassays were conducted using procedures published by EPA and ASTM.
The 95% confidence limits (95% CL) are shown in parentheses.
(6) Biooxidation values for EDA and DETA are taken from tests with acclimated microorganisms.
No nitrification was measured in the acclimated systems.
(7) Data listed is for Piperazine, 65%
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References
Chemical Reactions
1. U.S. Patent 4,539,430 (U.S. Dept. of Energy, 9/3/85).
2. Chernova, I. K.; et. al., Plast. Massy, 1989, (7), 88; CA 112:8741u.
3. German Offen. DE 2,941,023 (Hoechst AG, 4/23/81).
4. German Offen. DE 2,615,886 (BASF AG, 10/20/77).
5. Czech. Patent 184,110 (Vodak, Z.; et. al., 7/15/80).
6. Spanish Patent 540,640 (Pujada, J.P., 11/16/85).
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8. Japanese Patent 54/63077 (Nisshin Oil Mills, 5/21/79).
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10. German Offen. DE 2,512,513 (BASF AG, 10/7/76).
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13. Czech. Patent 222,448 (Capka, M.; et. al., 9/15/85).
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15. Deyrup, A. and Hassner, A., ed., Chemistry of Heterocyclic Compounds, Vol. 42,
Small Ring Heterocycles, Pt. 1; Aziridines, 1-214, John Wiley & Sons, New York, N.Y., 1983.
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17. Geiger, T.W. and Rase, H.F., Ind. Eng. Chem., Prod. Res. Dev., 1981, 20, 688.
18. U.S. Patent 4,983,735 (The Dow Chemical Co., 1/8/91).
19. Heskey, W. A., Chem. Eng. News, 1986, 64 (21), 2.
20. U.S. Patent 3,523,892 (Calgon, 8/11/70).
21. Hine, J. and Narducy, K. W., J. Amer. Chem. Soc., 1973, 95, 3362.
22. German Offen. DE 2,703,312 (Bayer AG, 8/3/78).
23. Gaines, G. L., J. Org. Chem., 1985, 50, 410.
24. Lanbert, J.B., et. al., J. Org. Chem., 1969, 34, 4147.
25. German Offen. DE 1,075,118 (Bayer AG, 2/11/60).
26. U.S. Patent 3,481,933 (Air Products and Chemicals, 12/2/69).
38
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39
DSA97164.qxd:EA-5621.qxd 10/26/09 2:19 PM Page 40
Polyamide Resins
1. U.S. Patent 3,595,816 (Emery Industries, Inc., 7/27/71).
2. U.S. Patent 3,462,284 (General Mills, 8/19/69).
3. German Patent 2,361,486 (Schering A.G., 6/12/75).
4. German Patent 2,148,264 (Schering A.G., 4/5/73).
5. German Patent 1,745,447 (Schering A.G., 2/12/76).
6. U.S. Patent 2,663,649 (T.F. Washburn Co., 12/22/53).
7. U.S. Patent 2,379,413 (American Cyanamid Co., 4/3/45).
8. Polish Patent 60,441 (8/5/70).
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41
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42
DSA97164.qxd:EA-5621.qxd 10/26/09 2:19 PM Page 43
Anthelmintics
1. Goodman, L.S. and Gilman, A, eds., The Pharmacological Basis of Therapeutics,
5th Edition, Macmillan Publishing Company, New York, 1975, pp 1027-1028.
Fabric Softeners
1. Japan 53,065,494 (Miyoshi Oil and Fat Co., Ltd., 6/10/78); CA89(22):181184u.
2. Japan 02,160,976 (Nikka Chemical Industry Co., Ltd., 6/20/90); CA113(20):174057r.
3. U.S. Patent 3,933,871 (Armstrong Chemical Company, 1/20/76).
4. Germany 2,165,947 (S.C. Johnson and Son, Inc., 7/20/72).
5. U.S. Patent 3,954,634 (S.C. Johnson and Son, Inc., 5/4/76).
6. Germany 2,520,150 (Azote et Produits Chimiques S.A., 1/2/76)
7. U.S. Patent 3,887,476 (Ashland Oil, Inc., 6/3/75).
8. U.S. Patent 3,855,235 (Ashland Oil, Inc., 12/17/74).
9. U.S. Patent 3,898,244 (Ashland Oil, Inc., 8/5/75).
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Fungicides
1. Vrabel, V.; Gergely, S.; Lokaj, J.; Kello, E.; Garaj, J., Proc. Conf. Coord. Chem.,
1987, 11th, 473-4; CA108(16):142127u.
2. U.S. Patent 2,504,404 (E.I. du Pont de Nemours & Co., 4/18/50).
3. U.S. Patent 2,844,623 (Roberts Chemicals, Inc., 7/22/68).
4. U.S. Patent 2,317,765 (Rohm & Haas Company, 4/10/43).
5. Belgian Patent 617,407 (Rohm & Haas Company, 11/9/62).
6. Belgian Patent 617,408 (Rohm & Haas Company, 11/9/62).
7. U.S. Patent 3,379,610 (Rohm & Haas Company, 4/23/68).
8. Wellman, R.H., and S.E.A. McCallan, Contrib. Boyce Thompson Inst., 1946, 14, 151.
9. Cunningham, H.S., and E.G. Sharvelle, Phytopathology, 1940, 30, 4.
10. Germany 2,506,431 (Sandoz G.m.b.H., 9/18/75).
Textiles
1. Kim, Chang Il; Kim, Jong Chi, Choson Minjujuui Inmin Konghwaguk
Kwahagwon Tongbo, 1977, 25, 249-52; CA88(24):171601t
2. Lei, X. P.; Lewis, D. M., J. Soc. Dyers Colour., 1990, 106, 352-6; CA115(2): 10704q.
3. Bertoniere, N.R.; Rowland, S.P., J. Appl. Polym. Sci., 1979, 23, 2567-77; CA91 (6):40801x.
4. Eur. Pat. Appl. 342,974 (E.I. du Pont de Nemours and Co., 11/23/89); CA112(20):181345r.
5. Guise, G.B.; Jones, F.W., Text. Res. J., 1978, 48, 705-9; CA90(14):105492y.
6. Germany 2,824,614 (Chemische Fabrik Stockhausen und Cie, 12/13/79); CA92(18):148424m.
7. Japan Patent 63,264,506 (Toray Industries, Inc., 11/1/88); CA110(22):194615n.
8. Japan 53,114,984 (Sakai Textile Mfg. Co., Ltd.; Toho Chemical Industry Co., Ltd.,
10/6/78); CA90(14):105527p.
9. Japan 74,42,864 (Unitika, Ltd., 11/18/74); CA82:172502e.
10. Germany 2,249,610 (Chemische Fabrik Pfersee, G.m.b.h., 4/24/74).
11. Japan 62,104,913 (Teijin Ltd., 5/15/87); CA107(18):156248a.
44
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Emergency Service
The Chemical Manufacturers Association (CHEMTREC), Transport Canada (CANUTEC), and the
Chemical Emergency Agency Service maintain around-the-clock emergency service for all chemical
products:
Europe, Middle East, Africa, Latin America, Phone CHEMTREC (United States):
Asia/Pacific, and any other location worldwide (202) 483-7616 (collect)
DO NOT WAIT. Phone if in doubt. You will be referred to a specialist for advice.
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NOTICE: No freedom from any patent owned by Seller or others is to be inferred. Because use conditions and applicable laws may differ from one location
to another and may change with time, Customer is responsible for determining whether products and the information in this document are appropriate for
Customer’s use and for ensuring that Customer’s workplace and disposal practices are in compliance with applicable laws and other governmental
enactment. Seller assumes no obligation or liability for the information in this document. NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF
MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED.
Printed in U.S.A. *Trademark of The Dow Chemical Company Form No. 108-01347-1009 AMS