March 22, 1960

D. R. STERN
PREPARATION oF LITHIUM PERcHLoRATE

Filed June 28, 1957

2,929,680

United States Patent O

2,929,680

CC

Patented Mar. 22, 1960

2
lithium perchlorate drops on hot crushing rolls 8 main
tained at a temperature in excess of 180 C. The per
chlorate is then reduced in size in a pug mill 9. The
ground product is sized on screen 10, oversize being re
turned to the crusher, the undersize to the reactor and

2,929,680
PREPARATION 0F LITHIUM PERCHLORATE
David R. Stern, Fullerton, Calif., assigner- to American

the product being recovered as desired.

The exhaust gas is passed through a lithium hydroxide
scrubber i1, which selectively removes carbon dioxide
as lithium carbonate, which is removed through line 12

Potash 8: Chemical Corporation, a corporation of Del

aware

Application .lune 28, 1957, Serial No. 668,769

5 Claims. (Cl. 23---85)

10 to a centrifuge 14.

Wet solids from the centrifuge are

dried in flash drier 16 and returned as make-up lithium
carbonate. The liquid stream from the centrifuge con~
rains a small amount of carbonate and this stream is
sent to the lithium hydroxide dissolver 17 or a portion
can be removed to prevent impurities from accumulating.
The lithium hydroxide stream is fed by pump 1S to the

This invention relates to a process _for the preparation

of anhydrous lithium perchlorate.

Lithium perchlorate is in increasing demand as a solid

/lme.m

filter 19 and thence to the absorber 11.

oxidizer in rocket propellants. lt has a high available

Typical examples illustrating the practice of this inven
oxygen content, is relatively stable, meltingat 25.0 C.,
tion are as follows:
has a high density, and yields a rather high specic impulse 20
since its iiame temperature is high and the average molec
ular weight of its combustion products are low.

Batch
I

Exftmnlp

Mellor cites three methods of preparing lithium per

chlorate. They may be represented chemically as follows:

348

348

NH4CIO4 (lbs.) ..... __

1105

1105

2.0

2.0

Reaction Time (min.) ........... __

__

90

58

Reactor Temperature ( C.) ......... __

._

22o-240

20u-230

1006

Product (lbs.) ______________ __

NH3

expensive and diicult to handle perchloric acid. More 30

Continuous
g

LizC O; (lbs.) ....... __

Mol Ratio (N HlCIOlLirC OJ) _ _

These methods have the disadvantage that they require

Recovered

(lbs.)- _ _ _ _ _ _ _ _

_ _ . _ _ _ _ _ . _ _.

132

Rate of Conversion (percent/

1.00

1. 725

Product Purity (percent) ____ __

Yield (percent) ______________________ ._

99. 7
96. 0

99. 4
100. 0

over, since they are carried out in the presence of water,

the stable trihydrate of lithium perchlorate is formed.

The hydrated water must be removed by dilricult drying
techniques since the trihydrate is so soluble that it will
melt in its own water of crystallization before dehydrating.
i propose to prepare lithium perchlorate in a molten

Chemical analyses of the products from the above are

given below:

Product, Example l:
Compound-_

Wt. Percent

state by the following reaction:

LiClO4t __________________________ __ 99.68

NH._ClO4 ________________________ __ 0.14
Li2CO3 ________________________ __
Nil

if one compares this system with those of Equations 40

l, 2 and 3, it will be seen that one theoretically could
evaporate per mole of lithium perchlorate six, ive and

Cl

four times as much water. lf Reactions 1, 2 or 3 are

carried out in an aqueous medium, the quantity of water
may be ten to fifteen times as much, while the present 45

process is carried on under anhydrous conditions. The

process of Equation 4 has several advantages over earlier
methods as follows:

_____ __

0.12

99.94

roduct, Example li:

LiClO., ___________________________ __ 99.4

NH4C1O4 _________________________ __ 0.42
Li2CO3 __________________________ __ Nil
Cl

__ 0.14

(l) Uses readily available chemical raw materials in

99.96
their industrial available form, i.e., LiOH-HZO and 59 Although l have illustrated the process with the perchlo~
rate, it will be obvious to those skilled in the art that am
(2) Considerable less water evaporation required since

NH4CIO.,.

reaction takes place in a completely anhydrous medium

and lithium carbonate is practically insoluble.

monium nitrate can be substituted for ammonium per

chlorate and the same process equipment employed. A

typical example illustrating this process with the nitrate

(3) No vacuum or extreme drying times are required. 55 is
presented below:
(4) Process readily conducted on a continuous basis.

(5) Any closed plant cycle requires an impurity blow

Example III

Batch
down stream. The chemical efhciency of this process
I_i2C03 (lbs.) _____________________________ __ 536
will be high since the blow down takes place with a stream
_ 1161
which contains very little lithium. Any plant using an 00 NH4NO3 (lbs.)

aqueous stream cycle containing LiClO4 loses considerable

lithium since lithium perchlorate is extremely soluble.
(6) rEechnical LiOH and Li2CO3 and NH4C104 con

Reaction
iii/101 ratio time (min.) _______________________
________________ __
_..

90

Reactor temperature ( C.) _________________ __

237

Product (lbs.) _
1000
tains organics which can give an oti color product. React
ing these materials at elevated temperatures oxidizes the 05 NH3 recovered (lbs.) ______________________ __ Rate of conversion (percent/min.) ___________ __
1.0
organics to carbon dioxide giving a white product.

A ow sheet and material balance for the process are

given in Figure 1.

Product purity (percent) ___________________ __ 99.9

Yield (percent) ___________________________ __

98.0

Solid NH4CIO4 and Li2CO3 are mixed in a screw feeder.

I claim:
This mixture drops into a heel of molten LiClOrJ main
l. A process for the preparation of lithium perchlorate
70
tained at 250-275 C. in a reactor 7. Reaction takes
comprising: heating lithium perchlorate sutiiciently to

place liberating NH3, CO2 and water vapor. The molten

'

render it molten; passing ammonium perchlorate and

2,929,880
lithium carbonate into said molten lithium perchlorate and
allowing said materials to react whereby to produce ad

ditional lithium perchlorate.

2; A process for the preparation of lithium perchlorate
comprising: heating lithium perchlorate to a temperature
of at least about 250 C. whereby to render it molten;
passing ammonium perchlorate and lithium carbonate ,

into said molten lithium perchlorate and allowing said

materials to react whereby to produce additional lithium

perchlorate.

comprising: heating lithium perchlorate to between about

' 250 and 275 C. wherebylto render it molten; passing

ammonium perchlorate and lithium carbonate into said

molten lithium perchlorate; allowing said materials to
react whereby to form additional lithium perchlorate; and
maintaining said lithium perchlorate at an elevated tem
perature for a time suicient to drive oi substantially all
ammonia gas, carbon dioxide and water vapor produced
by said reaction.

References Cited inthe Vtile of this patent

3. A process for the preparation of lithium perchlorate

comprising: heating lithium perchlorate to a temperature
between about> 250 and 275 C. whereby to render
it molten; passing ammonium perchlorate and lithium c_ar
bonate into said molten lithium perchlorate; and allowing 15
said materials to reactwhereby to produce additional

1,276,499

Dantsizen ____________ __ Aug. 20, 1918

1,738,930

Smith ..-____i__________ __ Dec. 10, 1929

1,824,101

Smith _______________ __ Sept. 22, 1931

lithium perchlorate.

2,413,644

Nicholson' ____________ __ Dec. 31, 1946

2,489,574Y

-Hampel ...._'__..'_ ______ __ Nov. 12, 1949

- '4. The process of claim 3-wherein the carbon dioxide ' Y

UNITED YSTATES PATENTS

also produced is recovered and thereafter reacted with

OTHER REFERENCES
lithium hydroxide whereby to form additional lithium 20
Ind.
and
Eng.
Chem. (Anal. Ed.), vol. 17, No. 8, page
carbonate which in turn is recycled in said process.
474 (August 1945).
S. A process for the preparation of lithium perchlorate

It.