CATALYST FOR HYDROGEN-AMINE D

EXCHANGE

Content:
Abstract
Sources of Deuterium
Processes
Selection of catalyst.
purposed improvement
Observation and conclusion

Abstract
A process for deuterium isotopic enrichment by aminehydrogen exchange in which the exchange catalyst
comprises a mixture of alkyl amides of two metals
selected from the group consisting of the alkali metals.

Sources of Deuterium:
Water:the water is being converted to steam and the steam being
contacted with a stream of hydrogen at elevated temperatures to
transfer deuterium thereto.

Ammonia synthesis gas (For smaller plants) :The hydrogen

stream from the chosen source may then be contacted with an
organic
amine phase by an exchange process to ultimately yield a
stream of hydrogen or amine which is enriched in deuterium.

Process Types:
monothermal
bithermal.
In a bithermal process the hydrogen stream may be
contacted in two stages and at two different.
temperatures within the range from the melting point of
the amine up to about, 100 C. Where the hydrogen
stream is synthesis gas it may for example, be
contacted with the liquid amine in a cold stripping
tower, and then fed through hot and cold exchange
towers .

Catalyst slection:
Decreased hydride formation

Catalyst

alkali amides of
potassium(Prefered)

merits

demerits
On next slide.

Decreased thermal
decomposition of alkylamide.
Increased catalyst solubility
in the amine phase
Increased exchange
efficiency

Lithium methylamide in
methylamine

lithium or cesium
methylamide in
methylamine do not react
significantly with hydrogen

An exchange rate 100

times slower than
potassium methylamide.

sodium methylamide in
methylamine

Can be used

Half the exchange rate of

potassium methyl amide.

cesium methylamide

exchangerate comparable.
solubility limit for cesium
To potassium methylamide in
methylamide is only 15%
methylamine at the same
of that of potassium
catalyst concentration
methylamide.
Expensive

Demerits:
For
most economical operation the process should operate at elevated pressure

of about 3500Psi (1000-3500).

Under this condition potassium methyl amide catalyst reacts with the hydrogen
to form potassium hydride which is essentially insoluble in methylamine. The
reaction is:

Cont..
Potassium hydride is precipitated from the solution the
equilibrium is shifted to the right reducing the concentration of
potassium methyl amide catalyst in solution
This concentration has such a strong effect on the exchange
rate, lowers the exchange rate achievable without the
continuous addition of fresh potassium methyl amide catalyst.
The precipitation of the potassium hydride causes a disposal
problem because hydride can foul the surfaces of the equipment
and pumps and would have to be separated from the solution.

Cont..
Hydride precipitation also occurs with sodium methyl amide in methylamine, and in the
potassium

dimethyl amide, dimethyl amine system.

The potassium methyl amide methylamine system is that potassium methyl amide
decomposes thermally at temperatures above 25 C.

The ammonia formed reacts with the potassium methyl amide to form potassium amide:
potassium amide has a low solubility in methylamine and precipitation occurs as
decomposition proceeds. Thus thermal instability reduces exchange efficiency of the
potassium methyl amide-methylamine system by reduction of the catalyst concentration.'

Improvements
Use of different alkali metals amides with addition to the
potassium amide preferably equimolar solution.
Following advantages are obtained.
Reduced KH precipitation
Thermal stability
Reduced reaction of potassium methyl amide with H2

Purposed combination
Particular combinations which showed reduced or
negligible hydride formation under hydrogen pressure
are: Li alkylamide and K alkylamide; Li + Na; and
Na+Cs
Some of these combinations also showed a
synergistic increase in exchange rate K+ Cs methyl
amide mixture showed an increased exchange rate
but with some hydride precipitation

Other Exhange Amines

dimethylamine,
aminoethane,
2-aminopropane,
,2-diaminoethane
1,2-diaminopropane.

Observations
Case 1:
A solution containing 0.5 millimoles of potassium
methylamide per gram of methylamine solution when
contacted at room temperature with hydrogen at 1000
psi precipitated potassium hydride so that the
maximum potassium methylamide concentration in
solution became 0.067 millimoles/g
An decrease of 2 times in exhange rate

 Case 2.
A second solution containing 0.49 millimoles potassium
methylamide per 50gram of solution plus 0.52 millimole
lithium methylamide per gram of solution when
contacted similarly with hydrogen at 1000 psi did not
precipitate potassium hydride.
No prompt decomposition of catalysts happened
Exchange rate of Deuterium increased by a factor of 2.3

Contd
For case 1,thermal decomposition at 70C was 0.8 days
For case 2, thermal decomposition at 70C was 5 days.
For case 1,soluabilty at 25C was 0.57mmoles/grams
For case 2,soluabilty at 25C was incresed.it was found
to be 2.5 mmoles per gram