Alkyl Amines

Alkyl amines limited is a worldwide supplier of amines and derivaties of amine to the
pharmaceuticals, agrochemical, rubber chemical & water treatment industries. It was
established as a public listed company in 1979. The manufacturing units consists of 9
production plants and related utilities at Patalganga and Kurukumbh in Maharashtra. The
inhouse technologies being developed by the R&D have been progressively helping in the
addition of new product processes. The company has been striving to provide to provide better
facilities of manufacture and a wide range of speciality chemicals in the last decade. This has
resulted in the company being occupying a dominant force in the domestic as well as the
international market. It boasts for over 100 products mostly produced by inhouse technologies
while being global leaders in Alkyl Amines. It has registered an annual sales of Rupees 400
crores thanks to the reliable service and quality products provided by the company.

Figure 1 Products and Market end uses

Figure 2 Gross revenue (Rs in crores)

 Figure 3: Product Circle of Alkyl amines

Alkyl amines has expertise over the chemical reactions and unit operations to get it’s diverse
products at high quality. The reaction which are the strengths of Alkyl amines and unit
operations are given below.
Reactions :
1.Reductive Amination
2.Hydrogenation
3.Cyanoethylation
4.Oxidation
5.Amidation

Distillations
1 Pressure / Atmospheric / Vacuum
2 Fractional / Azeotropic
3 Continuous /Batch.

Powder making facilities

 Dimethylamine.
Properties:
Colorless liquid or gas with strong ammoniacal odor; supplied commercially as an aqueous solution of
25% dimethylamine; also available in HCl form
Boiling point: 7.4°C
Vapor pressure: 1277 mmHg at 20°C
Vapor density (air = 1): 1.6
Specific gravity (liquid density): 0.65 at 20°C
Reaction: Amination
MeOH +NH3  MMA +H2O
MMA + MeOH  DMA +H2O
DMA + MeOH  TMA +H2O
Disproportion
2MMA DMA+ NH3
MMA +DMA  TMA +NH3
2DMA  TMA + MMA

Commercial process.
Most methylamines processes currently use amorphous silica-alumina catalysts for the exothermic
reaction, which takes place at approx. 390-430°C and approx. 20 atm. Adiabatic fixed bed plug flow
reactors are reported for this purpose . The product distribution obtained approaches equilibrium; DMA
production is enhanced by recycling TMA which can be costly. A simplified process diagram is given
in Fi 2. A new process has been reported by Nitto process that makes use of a modified mordenite
zeolite catalyst which minimizes TMA formation through product shape selectivity. The pore size of
the microporous mordenite catalyst is modified to an effective size smaller than TMA such that only
DMA and MMA can escape the catalyst.
This process has been commercialized in Japan with capacity estimated at about 100 MM lb/year. Two
kinds of modified mordenites have been described, an acid- and steam-treated one and a SiC14-
modified one The former reduces TMA production to about 17 mol% (at N/C=1.9, 320°C, 18 atm),
while the latter can reduce TMA to 1% (at N/C=1, 380°C, 1 atm).

Application
Dimethylamine is used as an accelerator in vulcanizing rubber, as an antiknock agent for fuels, in
photography, as a plasticizer, ion exchange agent, as an acid gas absorbent, a flotation agent, a dehairing
agent in the tanning of leather and in electroplating . Dimethylamine also serves as the base for a large
number of commercial products including detergent soaps, dyes, pharmaceuticals, textile chemicals,
surfactants and in the manufacture of unsymmetrical dimethylhydrazine (used in missile fuels), the
solvent dimethyl acetanilide and in the synthesis of dimethylformamide, one of the most commonly
used organic solvents.
 Figure 4: Process flow diagram for production of Dimethylamine

Cyclohexamine

Properties
Colourless to yellow liquid with a strong fishy, amine odur; flammable
Boiling point: 134.5°C at 760 mmHg
Melting point: -17.7°C
Flash point: 32.2°C (open cup)
Vapor density (air =1): 3.42
Specific gravity (liquid density): 0.8647 at 25°C
Reaction :
Aniline + H2 (Pt Catalyst)  Cycloheximide

Industrial production
Cyclohexylamine is produced by the reaction of ammonia and cyclohexanol at elevated temperature
and pressure in the presence of a silica-alumina catalyst . It is also prepared by a similar process of
catalytic hydrogenation of aniline at elevated temperature and pressure. Fractionation of the product of
this reaction yields Cycloheximide, aniline, and a high-boiling residue containing n-phenyl
cyclohexylamine and cyclohexylamine
 Figure5:Catalytic hydrogenation of aniline process to produce cyclohexylamine

Applications
The primary use of cyclohexylamine is as a corrosion inhibitor in boiler water treatment and in oil field
applications. It is also a chemical intermediate for rubber processing chemicals, dyes (acid blue 62,
former use), cyclamate artificial sweeteners and herbicides and a processing agent for nylon fiber
production . Windholz et al (1983) reports its use in the manufacture of insecticides, plasticizers,
emulsifying agents, dry-cleaning soaps, and acid gas absorbents.

Monoethylamine

Properties:
Colorless liquid or gas with a strong ammonia-like odor; exists as a gas at normal temperature and
pressure; also available in HCl form; supplied commercially as a 70% aqueous solution.
Boiling point: 16.6°C
Melting point: -81.0°C
Vapor pressure: 873 mmHg at 20°C
Vapor density (air = 1): 1.55
Specific gravity: (liquid density): 0.6828 at 15°C

Reaction

1) Reductive amination of alcohol with ammonia

 CH3CH2OH + NH3 +( Metal catalyst)→ CH3CH2NH2 + H2O , (Most common route)

2) Reductive amination of acetaldehyde with ammonia

CH3CHO + NH3 + H2 → CH3CH2NH2 + H2O

Industrial production

The methods employed to produce ethylamine are like those used for the methylamines. Differences
involve the alcohol used and its ratio to other reactants. The most common method involves
continuously passing ammonia and ethanol over a catalyst in a gas-solid heterogenous reaction. The
temperature is maintained at 300-500°C at 790-3550 kPa and the catalyst can be alumina, silica, Titania,
or tungstic oxides. As this procedure produces a mixture of water, alcohol, ammonia, and various
amines, the amines of interest are continuously separated by distillations and extractions. The amine
can be produced from ethyl chloride and alcoholic ammonia under heat and pressure or by
hydrogenation of nitroethane (HSDB 1989). Alternatively, ammonia, ethanol and hydrogen over a
dehydrogenation catalyst are passed continuously over a catalyst (supported metallic silver, nickel, or
copper) in a gas-solid heterogenous reaction. The reaction is run at 130-250°C at 790-3550 kPa and
also produces a mixture of amines. Ethylamine can also be produced using a similar procedure which
employs ammonia and an aldehyde or ketone and hydrogen over a hydrogenation catalyst under the
same conditions. However, this method is more expensive and is therefore not commonly used, except
in special cases (Schweizer et al 1978).

Figure6: Reductive amination of alcohol with ammonia process to produce monoethylamine

Application

Ethylamine has achieved widespread use as an intermediate in the manufacture of a variety of products.
It is used as a solvent for dyes, resins, and oils and as a vulcanization accelerator for sulfur-cured rubbers
as well as a stabilizer for rubber latex (NIOSH 1981; HSDB 1989). The amine is used in the production
of alkyl isocyanates for intermediates in the manufacture of products such as pharmaceuticals and
resins. It also serves as an intermediate in the manufacture of triazine herbicides, a corrosion inhibitor
(1,3-diethyl thiourea), and an agent used in wash and wear fabrics (dimethylolethyltriazone). Copious
salts of ethylamine can also be used in the refining of petroleum and vegetable oil (Sittig 1981). The
amine also has uses as an industrial solvent and as a chemical initiator in the preparation of various
solvents (HSDB 1989).

Monoisopropanolamine

Properties:
Molecular Weight: 75.13 (NTP, 1992)
Boiling Point: 313 to 316 ° F at 758 mm Hg (NTP, 1992)
Melting Point: 34.5 ° F (NTP, 1992)
Vapor Pressure: 2.59 mm Hg (USCG, 1999)
Vapor Density (Relative to Air): 2.6 (NTP, 1992)
Specific Gravity: 0.961 at 68 ° F (USCG, 1999)
Flash Point: 171 ° F (NTP, 1992)
Water Solubility: greater than or equal to 100 mg/mL at 67.6° F (NTP, 1992)

Reaction:
1) Isopropyl alcohol reacting with ammonia
IPA + NH3  MIPA + H2O
2) There is also a sequential reaction of MIPA and IPA to form di-isopropylamine (DIPA)
IPA + MIPA  DIPA + H2O
3) Reversible reaction
DIPA + NH3  2MIPA

Figure7: Process to produce MIPA from IPA and Ammonia.

Industrial Process
The commercial process takes IPA and ammonia as the feed and MIPA is obtained as product along
with DIPA as the byproduct. The IPA and Ammonia reacts in reactor maintained at pressure around 24
bar and temperature at 180C. The reaction is mildly exothermic in nature . The product stream has
MIPA, DIPA,IPA and water. The heat of product streams extracted through the series of heat
exchangers ,then sent to the train of distillation column to separate the products. In first distillation
column ammonia is separated from heavy fraction of MIPA,DIPA ,IPA and water. In second distillation
column the MIPA is separated out from the top and at bottom we get DIPA(mostly), IPA and water. In
last distillation column water is separated from DIPA which is recycled back to the reactor as shown in
figure 7
Application
Isopropylamine is a building block for the preparation of many herbicides and pesticides
including atrazine, bentazon, glyphosate, imazapyr, ametryne, desmetryn, prometryn, pramitol, dipropetryn
propazine, fenamiphos, and iprodione. It is a regulating agent for plastics, intermediate in organic synthesis
of coating materials, plastics, pesticides, rubber chemicals, pharmaceuticals and others, and as an additive
in the petroleum industry.

References
1. http://alkylamines.com/corporate/index.htm
2. http://www.alkylamines.com/corporate/ALKYL%20AMINES%20PRESENTATION.
pdf
3. https://ac.els-cdn.com/S0926860X01008134/1-s2.0-S0926860X01008134-
main.pdf?_tid=d630a867-371c-4f72-b412
4. https://pubs.acs.org/doi/pdf/10.1021/ie900965s
5. https://www.dow.com/amines/apps/index.htm