Patented Jan. 3, 1933
1,893,331
‘UNITED STATES PATENT oFFIc'E'
WALTHER KANGRO AND AGNES LINDNEIR, OF BRUNSWICK, GERMANY
PROCESS OF SEPARATING BERYLLIUM COMPOUNDS FROM BEIRYLLIUM CONTAINING
>
MINERALSOR OTHER SUBSTANCES
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No Drawing. Application ?led July 23, 1930, Serial No. 470,224, and in. Germany July 30, 1929,
The invention relates to a process of sepa compounds, particularly the oxides, silicates,
rating beryllium compounds from beryllium aluminates;alumino-silicates and other com
containing minerals or other substances by pounds of beryllium, that volatile beryllium
chlorine compounds are formed, mainly chlo~
The object of our invention is to simplify rides, perhaps also oxychlorides, and free
means of chlorination.
5
the process and to carry it through in such a
manner that the material of the furnace is
not endangered and so that the process may
be carried through under ?xed or constant
lO
55
oxygen. Chemically balanced conditions are
set up which at lower temperatures are such
that in the balanced mixture there exist main
ly beryllium oxide and chlorine besides very
conditions and in continuous operation.
minu’:e quantities of beryllium chloride and
According to our invention the chlorina oxygen. With rising temperature the ratio
60
ticularly in a current or stream of these chlo quantities of beryllium chloride, oxygen and
rine-like gases, the temperature and the pres chlorine above solid beryllium oxide are sta
sure of these gases being so adjusted that the ble side by side in the balanced mixture.
65
tion is carried through by means of chlorine of the substances in relation to one ‘another
or gases containing chlorine, and more par alters in such a way that steadily increasing
substances present in the reaction ‘chamber
If two constituents of this mixture, viz.
have the tendency to form a mixture in a state beryllium chloride and oxygen are continu
of chemical equilibrium or balance in which ously removed from this balanced mixture the
‘besides chlorine there exist mainly volatile
beryllium-chlorine compounds and oxygen or
oxygen containing gases and the substance
containin solid beryllium.
According to a preferred embodiment of
entire solid oxide of beryllium, even if com- _70
bined with aluminium oxlde, s1l1con dioxide -
our invention the‘bery'llium chlorine com
pounds and the oxygen or the oxygen-con
may be accelerated either by working at a 75
from the reaction chamber as soon as a state
oxygen to the balanced mixture brings about
or other compounds, is gradually converted
into volatile chlorine compounds. The .con
version into beryllium-chlorine compounds
reduced total pressure, or with an overpres
taining gases are continuously discharged sure of chlorine. Conversely, an addition of
‘tending towards a balanced mixture has be
a displacement in so far as beryllium oxide
3 come stationary or constant or substantially and free chlorine is again formed from the 80
stationary or constant.
beryllium chloride.
‘
_
>
According to another preferred embodi
ment of our invention the chlorine-like gases
are passed by a pressure gradient through
the process.
We wish it to be understood that wher
ever in this speci?cation and the claims the
term chlorine-like gases is used this term'is
50
Our improved process is carried out in the
following manner:
‘
Beryllium mineral or the-substances con
tain ing beryllium such as Waste from previous
?nishing or manufacturing processes, or
beryllium alloys are, preferably in the ‘dry
state, heated to comparatively high tempera
intended to cover chlorine or gases which con
tures. preferably more than 1000° in a shaft
tain chlorine in -mechanical mixture or in
furnace constructed of clay, alumina, quartz
90
chemical combination, and likewise that the sand or any other. ceramic material which is '
term oxygen-like gases is intended to cover refractory‘ and indifferent to chlorine gas,
oxygen or gases which contain oxygen 1n mix andtlien exposed to the action of a' stream of
, ture or in combination.
chlorine gas or gases containing chlorine. 95'
The chemical principles underlying our im-_ The then developed volatile beryllium com
proved process will be understood from the pounds. mainly chloride or also oxychlorides following novel chemical conversions :‘
of beryllium are discharged from the furnace
It has been ascertained that pure chlorine by the stream of chlorineJor chlorine contain;
gas‘ at high temperatures. preferably above ing gas, and pass into a suitably cooled cham
10009 0., acts'in such a manner on beryllium ber in which they, deposit ‘in solid form and 10::
2
1,898,831 '
in a substantially pure state; The chlorine is. set free during the conversion into beryl
or the‘chlorine containing gases are prefer lium oxide. The quantity of oxygen sup
ably used in excess over the beryllium chloride plied must beso proportioned that it at least
forming. The gases may also be employed neutralize the ‘action of the chlorine which
under increased pressure. The aggregate is present in excess at the beginning. Pref 70.
pressure of all the gases existing in the re erably the process is carried out with an ex
action~chamber amounting in the substan cess of oxygen, more particularly vwith oxy
tially stationary, or equilibriunrstate, for gen of increased pressure.‘ It is, further
more, advantageous to give the stream of
instance, to less than one atmosphere.
10
The velocity of ?ow ‘of the chlorine or oxygen a direction opposite to the stream 75
chlorine containing gas'may vary Within wide ‘ of the chlorine gas so that the volume of gas
limits. Preferably it is not kept too low since escaping from‘ the furnace at a relatively
a higher speed permits of a reduction of the high velocity are subjected to a braking ac
working temperature and the working time.
15
tion. ' In‘ this way the gases are caused to re
The same result is attained if the material - main a little longer. in a chamber of medium
80
to be roasted in ‘the furnace, is reduced in temperature while, on the other hand, the
size or disinegrated prior to subjecting it vto beryllium oxide precipitated in a very ?ne
the roasting process. The beryllium-chlo granular state is not carried along too far
_
rine compounds so produced, as far as they and atomized.
Instead of oxygen, air or any other gas
are notused as such, are dissolved in water.
A very considerable amount of heat is de mixture containing oxygen may be employed
veloped therewith which may be utilized for in this modi?cation of our process.
85
drying the minerals or the compounds pro-’ The heating of the reaction material may
duced or for other heating'purposes. The be effected in any suitable manner, for in- '
aqueous solution of beryllium chloride may stance by means of a heating chamber ap 90
on the one hand be worked with sodium propriately ?tted in the reaction chamber
chloride into beryllium sodium chloride, suit but closed towards it in a gas tight manner, or
able as fused electrolytes or electrolysis in the in customary manner from‘ outside. Another
fused state. On the other hand beryllium manner of heating consists in app-lying the
hydroxide and beryllium oxide respectively ' heat to the reaction material by means of
may be obtained from the solution by pre
hot gases which sweep over the material.
cipitation with lye. The chloride produced Gases may then be used which are inert or
in this way-is preferably regenerated electro neutral to the reaction product, or the reac
lytically into lye and free chlorine which are‘ tion gas. the chlorine, itself. The heating of
the chlorine gas or of the heating-gas neces
both again introduced into the process.
100
Another embodiment of our invention sary for this purpose, may take place in va
leads directly to the pure beryllium oxide rious ways, either by means of a flame. the
by a dry process. This process consists in chlorine gas then ?owing through external
blowing oxygen into the hot- gases'escaping ly heated tubes of clay or a refractorv ma
from the roasting furnace which consists es
terial, or by electrical means, in which case
105
i
sentially of chlorine, beryllium-chlorine the chlorine gas is subjected to preheating in
£5
compounds and some oxygen or oxygen con resistance bodies of carbon. such as carbon
taining gases, through a nozzle of ceramic tubes, carbon grids, carbon granules and so
~
material located, conveniently in the gas on or in the electric arc ?ame.
The beryllium compounds obtained by the
stream. The solid beryllium oxide then sepa
rates from the equilibrium mixture in the chlorinating roasting are directly obtained
purest state, the quantity of' chlorine which in a perfectly pure state, provided that in
110
had been combinedwith the beryllium being the raw materials there are contained no
set freeagain. From the remaining mixture substances which enter into volatile combi
of chlorine and oxygen or oxygen-like gases nations with the chlorine at the temperatures 115
the chlorine is recovered by known methods employed. If, on the other hand such foreign
and again applied to the roasting process.
substances are contained in the raw mate
In order to obtain as complete a conver rials, it is necessary to isolate them from the
sion as possible into beryllium oxide the oxy beryllium if their presence is‘ undesirable
gen or' oxygen-like gases are preferably for the further use of the beryllium com 120
raised. to such a temperature that the entire pounds. Iron'ox'ide vis the most frequently
' gas mlxture is not cooled down too suddenly occurring contamination of this kind in the
but remains for some time at temperatures mineral, less frequently magnesium oxide.
near the boiling point of beryllium chloride, ‘The iron may easily be separated from'the 125
for instance at 400 to 800°; i. e. at such tem_ beryllium by reason of the fact that iron
peratures at which, as already pointed out, oxide is quantitatively converted by chlorine
reconversion of the beryllium chlorine com
65
into the volatile iron chloride at far lower
pounds into beryllium oxide takes place. A temperatures, say 800 to 900°, and carried
slowing down of the cooling is also effected off. It is therefore advisable to supjec't be
by the considerable quantity of heat which ryllium minerals or substances, which contain
.
130
H
3
1,898,881
iron, at low temperatures, for instance 800° ployed with advantage upon such raw mate
to 1000°, to a chlorinating preroastingpproc rials containjng beryllium which would re
ess and to collect the chloride of iron formed quire such a relatively high'temperature for‘
thereby separately. Beryllium does not pass treatment as to produce decomposition of the
70
over as yet. Only after all the iron has been raw materials.
removed from the raw material the tempera
All minerals or substances containing
ture is raised up to the point necessary for the beryllium are suitable as raw materials for
formation of chloride of beryllium. An our improved process. If beryllium alloys
analogous separation or isolation by frac are to be employed in the process it may be
v10 tional volatilization may be carried through advisable to convert the metals of these al 75
with all those admixtures ofztlie raw or ini loys ?rst into oxides and then to separate the
tial material which combine with chlorine mixture of the oxides according to our im~
to chlorine compounds at other temperatures proved process.
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than the beryllium.. For this purpose we
The process is also suitable for the sepa 80
1.5
next pass in the reaction chamber containing . ration or isolation of the beryllium from such
the raw material a chlorine-like. stream of substances in which the presence of beryllium
gas‘over the material containing the beryl
20
lium and for the purpose of removing foreign
metal constituents first adjustthe tempera
is undesirable.
'
‘What is claimed is:
1. The process of separating beryllium
ture and the pressure in the reaction chamber compounds from ores, minerals or substances
in such a mannerthat the substances con which contain beryllium, which consists in
tained in the reaction chamber tend towards passing
a chlorine-like stream of gas over the
a mixture in chemical equilibrium in which
material
containing the beryllium in a reac-'
besides the chlorine there exists mainly chlo
chamber, and adjusting the temperature
rine compounds of’ those- metals, then dis tion the
pressure in the reaction chamber in
‘charge those compounds and then adjust and
such a manner that the substances ‘contained
90
the temperature and the pressure in the re
act-ion chamber in such a maniier that the therein tend to attain a mixture in chemical
30
35
40
substances'contained in the reaction chamber equilibrium, in which besides chlorine there
tend towards a fresh ‘mixture in chemical exist mainly volatile beryllium-chlorine com
equilibrium in which besides chlorine there pounds, oxygenating gases and the material.
2. The process of separating beryllium
exist mainly volatile beryllium-chlorine com
pounds, oxygen-like gases and, the material. compounds from ores, minerals or substances
In this way the admixtures may on their which contain beryllium, which consists in
part be recovered‘ in the pure state. The passing a chlorine-‘like stream of gas over the
beryllium may also be separated from mag material containing the beryllium in a reac
- I
in water and remains quantitatively behind in tend to attain a mixture in chemical equi
within the solution when the beryllium hy librium, in’ which besides chlorine there exist
105.
nesium since the magnesium chloride, which tion chamber, adjusting the temperature and
is volatilized together with the beryllium the pressure in the reaction chamber in'such
chloride, goes into solution’ when dissolved a manner that thesubstances contained there
mainly vol’atil'e beryllium-chlorine com
pounds, oxygenating gases and the material,
ess need not be perfectly dry. It has been and continuously discharging the beryllium
‘ droxide is precipitated.
95
100
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The chlorine gas employed in our proc
45
50
ascertained that minute quantities. of mois
ture do not retard the conversion into beryl
lium chlorides.‘ Excessive quantities of wa
compounds and the oxygenating gases as soon
in equilibrium has become substantially sta
ter, such as occur inmoist minerals. on the tionary in the reaction chamber.
3. The process of separating beryllium
other hand, retard the conversion or reac
compounds from ores, minerals or substances
Under some conditions hydrogen chloride which contain beryllium, which consists in
gas may be admixed with the chlorine. The passing a chlorine-like stream of asunder
tion.
‘
-
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.
110
as the state tending to bring about a mixture
115
'
action on“the beryllium compounds then takes a pressure drop or gradient over th material
place in a manner quite analogous to that containing beryllium in a reaction chamber.)
of the free chlorine with the difference only adjusting the temperature and the pressure
120
that some aqueous vapour is formed instead’ in said chamber in such a manner that the sub
of the free oxygen. Thesegases will there stances contained therein tend to attain a
fore preferably be used in cases where moist mixture in chemical equilibrium, wherein beminerals are to-be dealt with or such-which sides chlorinev there exists mainly ‘volatile
contain chemically combined water; Gases beryllium-chlorine compounds, oxygenating
which contain combined chlorine, such as hy gases and the material, and continuously dis
drogen or sulphur monochloride or carbon charging the beryllium compounds and the
' tetrachloride and others or mixtures of these oxyge'nating gases as soon as the state tending
' or anygof them with chlorine may be em-v . to bring about a mixture in equilibrium has
125
130
4
1,893,331
become substantially determined in said which contain beryllium, which consists in
chamber.
-
’~’
~passing a chlorine-like stream of gas under
-
4. The process of separating beryllium a pressure drop or gradientover the mate
compounds from ores, minerals or substances rial containing the beryllium in a reaction
which contain beryllium, which consists in chamber, adjusting the temperature and the
passing achlorine-like stream of gas at in
pressure in said chamber inv such a manner
70
creased pressure under a pressure drop or that the substance contained in the reaction
gradient over the material containing the chamber tends to attain a mixture in chemi
beryllium in a reaction chamber, adjusting cal equilibrium, in which besides chlorine
10
the temperature and the pressure in the re
action chamber in such a manner that ‘the
‘there exists mainlycvolatile beryllium-chlo
rine compounds, oxygenating gases and the
75
substances contained in the reaction chamber material, and continuously discharging the
tend to attain a nnxture 1n chemical equili beryllium compounds, the oxygenating gases
‘. brium, in which besides'chlorine there exist and the excess of chlorine as soon as the state
mainly volatile beryllium-chlorine
15
com-' tending to bring about a mixture in equilib
80
, pounds, oxygenating gases and the material, rium has become substantially stationary in
and continuously‘ discharging the beryllium the reaction chamber, whereupon additional
compounds and the oxygenating gases as soon oxygenating gases are admixed with the con
as the state tending to bring about a mixture stituents discharged from the process, viz.
in equilibrium has become substantially de
20
termined in the reaction chamber.
chlorine, beryllium-chlorine compounds and
85
the oxygenating gases containing some oxy
5. The process of separating beryllium gen, in such a manner that beryllium-oxygen
. compounds from ores, minerals or substances compounds separate therefrom.
25
30
35
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-
8. The process of separating beryllium
which contain beryllium, which consists in
passing a chlorine-like stream of gas over compounds from ores, minerals or substances
the material containing the beryllium in a re which contain beryllium, which consists in
action chamber, adjusting the temperature passing a chlorine-like stream of gas under
and the pressure in said chamber in such a a pressure drop or gradient over the material
manner that the substances contained in the containing the beryllium in a reaction cham
reactionchamber tend to attain a mixture in ber, adjusting the, temperature and the pres
chemical equilibrium, in. which besides chlo sure in the reaction chamber in such a man'-v
rine there exist mainly volatile beryllium ner that the substances contained therein
chlorine compounds, oxygenating gases and tend to attain a mixture in chemical equilib
the material, and continuously discharging
the beryllium compounds and the oxygenat
-
A
j
-
'
.
.
rium, 111 which besides chlorine there exists
mainly volatile beryllium-chlorine‘ com
100
ing gases as soon as the state tending to bring pounds, oxygenating gases and the material,
about a mixture in equilibrium has become and continuously discharging the beryllium -
40
45
substantially determined in the reaction’ compounds, and the oxygenating gases as
chamber, the aggregate pressure of all the soon as the state tending to bring about a
gases existing in the reaction chamber mixture in’ equilibrium in the reaction cham
amounting in this substantially stationary ber has become substantially stationary,
whereupon additional oxygenating gases at
state to less than one atmosphere. '
'
6. The process of separating beryllium increased pressure are admixed with the con
compounds from ores, minerals or substances stituents discharged from the process, viz. 110
which contain beryllium, which consists in chlorine, beryllium-chlorine compounds and
passing a chlorine-like stream of gas over the oxygenating gases containing some oxy
the material containing the beryllium in a gen, in such a manner that the beryllium-‘
. reaction chamber, adjusting the temperature oxygen compounds separate therefrom.
9. The process of ‘separating beryllium
and the: pressure in said chamber in such a
50 manner that the substances contained there? compounds from ores, minerals, or substances
115
in tendto attain aimixture in chemical equi which contain beryllium, which consists in
librium, in which besides chlorine there exists passing a chlorine-like stream of gas under
mainly volatile beryllium-chlorine. com a pressure drop or gradient over 'the material
pounds, oxygenating gases and the material, ‘containing the beryllium in a reaction cham- ' 120
and continuously discharging the beryllium ber, adjusting the temperature and the pres
‘compounds and the oxygenating gases as soon sure in the reaction'chamber 1n such' a'-man~
as the state tending to bring about a mixture ner‘ that the substances contained -therein _
in equilibrium'has become substantially de- ' tend to attain a mixture in chemical equilib
60
termined in the reaction chamber, whereupon rium, in which‘besides chlorine there'exists
the beryllium compounds discharged from mainly volatile beryllium-chlorine com»
theprocess are dissolved in water. and_the. pounds, oxygenating gases and‘the material,
heat of solution is usefully employed in the and continuously discharging-the beryllium
compounds, the oxygenating gases and the
process‘.
,
v
i "7‘. The‘- process of separating beryllium_
excess of chlorine as soon as the state tend-_
compounds from oresyminerals or substances ing to bring about a mixture of equilibrium
12.7
1,893,331
5
in the reaction chamber has become substan_ chamber tend towards a mixture in'chemical
tially stationary, whereupon additional oxy equilibrium
in which besides the chlorine
genating gases at increased pressure are ad there exist mainly chlorine compounds of
mixed in counter-?ow with the constituents said foreign metals, discharging said com
discharged upon the process, viz. chlorine,
and then adjusting the temperature 70
beryllium-chlorine compounds and the oxy pounds
and the pressure in the reaction chamber in
genating. gases containing some oxygen, in such a manner that the substances contained
such a manner that the beryllium-oxygen therein tend towards a fresh mixture in
compounds separate therefrom.
10
20
25
'
chemical equilibrium in which besides chlo
v10. The process of separating beryllium rine there exists mainlyvolatile beryllium
compounds from ores, minerals or substances chlorine compounds, oxygenating gases and
which contain beryllium, which consists in the material.
passing a chlorine-like stream of gas under a
13. The process of separating beryllium
pressure drop or gradient over the material compounds from ores, minerals or substances
containing the beryllium in a reaction chamj which contain beryllium, which consiststin
ber, adjusting the temperature and the pres passing a chlorine-like stream of gas over
sure in the reaction chamber in such a man the material containing the beryllium in a
ner that the substances contained therein
tend to attain a mixture in chemical equi~
librium, in which besides chlorine there ex
ists mainly volatile beryllium-chlorine com
75
80
reaction chamber and for the purpose of re
moving foreign metal constituents ?rst at a
temperature in the vicinity of or between
85
800-1000° C. adjusting the ‘pressure in the
pounds, oxygenating gases and the material, reaction chamber in such a manner that the
continuously discharging the beryllium com— substances contained therein tend towards a
pounds, the oxygenating‘ gases and the ex mixture in chemical equilibrium inwhichbe
cess of chlorine as soon as the state tending sides the chlorine there exist mainly chlo
to bring about a mixture ‘in equilibrium in rine compounds of said foreign metals, dis 90
the reaction chamber has become substan charging said compounds, and then adjust
tially stationary, whereupon additional ing the temperature and the pressure in the
o'xygenating gases at a temperature in the reaction__chamber in such a manner that the
vicinity or between 400—800° C. are admixed substances contained in the reaction chamber
with the constituents‘ discharged from the tend towards afresh mixture in chemical
process, ‘viz. chlorine, beryllium-chlorine‘ equilibrium in which besides chlorine there
compounds and the oxygenating gases con exists mainly volatile beryllium-chlorine
taining some oxygen.
compound/s“, oxygenating gases and the ma_
11. The process of separating beryllium terial.
100
-
compounds from ores, minerals or substances
‘In testimony whereof we a?ix our signa- '
which contain beryllium, which consists in tures.
passing a chlorine-like stream of gas under '
a pressure drop or gradient over the mate
40
rial- containing the beryllium in a reaction
WALTI-IER KANGRO.
AGNES‘ LINDNERJ
105
chamber, adjusting the temperature and the
45
pressure‘ in the reaction chamber in such a
manner that the substances contained therein
tend to attain a mixture in chemical equi
librium, in which besides chlorine there ex
110'
ists mainly volatile beryllium-chlorine com
pounds, oxygenating gases and the material,
continuously discharging the beryllium com
50
pounds, the oxygenating gases and'the excess
.of chldrine as soon as the state tending to
115
bring about a mixture in chemical equilib
rium in the reaction chamber has become
substantially
stationary, the. discharged ’
_
chlorine
being
again introduced into the
55
working cycle of the process.
,
'12. The process of separating beryllium
I
120
compounds from ores, minerals or substances
60
which contain beryllium, which consists in
passing a chlorine-like stream of gas over'
the material containing the beryllium in a
reaction chamber, and‘for the purpose of re
125,
moving foreign metal constituents ?rst ad~
justing the temperature and the pressure in '
65
the reaction chamber in such armanner that
the substances contained in the reaction
130
CERTIFIGATE OF CORRECT/ION;
‘ _ "January ‘3, ‘I933.
'Patent'No. 1,893,331.‘
WALTHER KANGRO, 'ET AL.
It is hereby certified that error appears in the printed specification of the
above numbered ‘patent requiring correction as follows:v Page 2, line 69, for
"neutralize"'read "neutralizes", and line 76', for "volume" read, "volumes";
page '3, line 63, after the syllable "drogen" insert the word "chloride"; and
that thesaid Letters Patent should be read with these corrections therein that
I
the same-maynconform to the record of'the case in the Patent Office.
Signed and ‘sealed this 21st day of February, A. 0/1933.‘ ‘
'
- M. J. Moore.
,(Sell)
Acting Commissioner of Patents;