5341 5345.output

* GB785749 (A)
Description: GB785749 (A) ? 1957-11-06
Electric time-piece actuated by a battery
Description of GB785749 (A)
PATENT SPEUCIFICATION
785,749 Date of Application and filing Complete Specification March
27, 1956.
lv ki By No 9464156.
Application made in Switzerland on April 2, 1955.
Complete Specification Published Nov 6,1957.
Index at acceptance: -Classes 37, K( 1 CX: 2); 40 ( 6), T; and 139, A
5 X.
International Classification: G 04 c H 011 H 03 f.
COMPLETE SPECIFICATION
Electric Time-piece Actuated by a Battery We, OMEGA Lou Is BRANDT & F
Rit RE S A, a Swiss Company, of 96 Staempflistrasse, Bienne
Switzerland, do hereby declare the invention, for which we pray that
patent may be granted to us, and the method by which it is to be
performed, to be particularly described in and by the following
statement: -
This invention relates to an electric timepiece actuated by a battery
The time-piece may be used in any time indicating device such as
clocks or watches.
Electric time-pieces actuated by a direct current source have already
been proposed in which the spring of usual time-pieces is replaced by
an electric battery and the wheels and escapement of a usual
time-piece is replaced by an electrically driven mechanical
oscillator, for instance, a balance wheel, a pendulum or the like
Therefore the time governor of the time-piece was always constituted
by a mechanical oscillator, for instance, a balance wheel with a
spiral, a pendulum, a tuning fork of a tuning fork oscillator, a
crystal, for instance a quartz or the like.
Such mechanical oscillatory systems have many disadvantages when
driven by an electrical source The power required for sustaining the

oscillation of such oscillators is rather high and unsufficient
lubrication and different positions of the time-piece may often cause
appreciable deviations of the oscillating frequency and therefore of
the time indicated from the accurate value and other external
influences, particularly a voltage drop of the electric source may
effect the accuracy of the time-piece.
For watches and where the disposable energy is rather limited such as
when the timepiece is actuated by a battery, control of the time-piece
by the oscillation of a mechanical oscillator such as a quartz is not
feasible because of lack of space and because a multistage frequency
divider is to be provided for reducing the very high frequency of the
quartz controlled oscillator to a frequency which may be used for
driving a synchronous motor or the like for actuating the clock hands,
lPrice 3 S 6 d 1 It is an object of this invention to provide an
electronic governor for time-pieces whfch practically does not depend
on voltage changes 50 of the battery and at the same time may be of a
size to be housed in a watch The timepiece according to this invention
is broadly characterized in that the governor of the timepiece is
constituted by a delay circuit for 55 delayed transmission of
electro-magnetic waves, electronic amplifying means being associated
with the said delay circuit for generating a self-sustained
oscillation of periodic electric pulses and ithe time-piece being 60
advanced by such electric pulses By means of this arrangement
relatively low pulse frequencies may be obtained which may be used for
driving a synchronous motor, a pulse motor or the like without
preliminary frequency divi 65 sion as was usual with quartz clocks and
the like.
For further details of the invention reference may be had to the
drawings in which three embodiments of the time-piece accord 70 ing to
this invention are illustrated by wav of example in Fig 1 to 3 whereas
Fig 4 to 7 are examples of delay circuits which may be used in the
time-piece according to this invention.
In the embodiments shown an amplifying 75 element 1 constituted by a
transistor is fed from a battery 2 as follows: The collector of the
transistor 1 is connected to the input of a suitable delay circuit 3
(later described in detail) of which the output is suitably coupled 80
with the base electrode of the transistor 1 If a voltage pulse is
applied to the base of the transistor 1 this causes a pulse-like
current variation in the collector circuit of the transistor and the
pulse which is amplified in this 85 way is applied to the input of the
delay circuit 3 This delay circuit 3 may be constituted by a cable
having a very high delay coefficient or by a delay line built up by
inductors and capacitors or the like or the delay circuit may 90
preferably include a material having suitable delav properties such as

germanium, silicon or another suitable semi-conductor The transit time
of the pulse passing through the delay 785,749 network 3 only depends
on the properties of the circuit elements used in this network and is
particularly independent of variations in the pulse amplitude, which
may occur due to variations of the other circuit elements of the
time-piece by external influences such as temperature and pressure
variations and the like or due to aging of the amplifying elements or
due to a voltage drop on the battery 2 This is one of the most
important advantages of the time-piece according to this invention
over all the above mentioned known time-pieces having mechanical
oscillators such as quartz crystals or the like, of which the
oscillating frequency does not only depend on the temperature of the
quartz or the like but also on the amplitude of the oscillation set up
in the mechanical oscillating system The amplitude of the oscillation
of such known systems greatly depends on the voltage of the electric
source, for instance an electric battery and also on the properties of
the active circuit elements such as tubes, transistors or the like
Therefore the electric time-piece according to this invention is
particularly suited for being fed by a battery, because the pulse
oscillator including the delay system always operates at constant
frequency for widely varying battery voltages and therefore the
accuracy of the timepiece is not affected by the gradual voltage drop
of the battery which cannot be avoided.
In tne time-piece schematically illustrated in Fig 1 the pulses
leaving the delay network 3 with a given delay are fed over condenser
5 back to the base of transistor 1 and are again amplified in the
transistor, whereby the amplifying factor of the transistor and the
feed-back ratio are so designed that the circuit will remain in
oscillating state.
The collector circuit of the transistor also comprises a resistor 6
and a synchronous motor or pulse motor 4 The resistor 6 avoids undue
coupling between the circuit of the motor 4 and the base circuit of
the transistor amplifier Mechanical or electric transmision means, for
instance a reduction gear or stepping gear, are controlled or driven
by the motor 4 for advancing the hands of a clock or watch.
Fig 2 illustrates another embodiment of the time-piece wherein the
transistor 1, the battery 2 and the delay circuit 3 are interconnected
substantially as shown in Fig 1 The motor 4 has a secondary winding by
which the collector circuit of the transistor is inductively coupied
to the base of the transistor, the feedback pulse being produced in
the secondary winding of the motor 4.
In the circuits shown in Fig 1 and 2 the self-sustained oscillations
do not start automatically and therefore an external starting pulse
has to be applied for starting up the feedback oscillation.

Fig 3 shows a circuit which starts to oscillate automatically when the
battery is connected thereto, but still the oscillating frequency of
the circuit is only determined by the delay circuit 3 The transistor 1
and the transformer 4 are connected and designed to constitute a
feed-back oscillator, preferably a blocking osillator fed by the
battery 2 The natural frequency of this oscillator is determined
substantially by the time constant of the condenser 7 and the resistor
8 This frequency shall be somewhat below the frequency that would be
determined by the delay time of the delay network 3 In this way a
synchronisation of the blocking oscillator 1, 4 is obtained at the
frequency determined by the delay network in the following manner:
When the battery 2 is connected to the circuit the blocking oscillator
starts to oscillate whereby a first pulse is applied to the delay
network 3.
This pulse leaving the delay network 3 after a given delay time is fed
back over the secondary winding of the transformer 4 and the condenser
7 to the base of the transistor 1 and starts another oscillation of
the blocking oscillator In this way the blocking oscillator is
synchronized by the delay network 3 The transformer 4 may be a
synchronous motor or a pulse motor, or such a motor is coupled with
the transformer 4, and the clock or watch hands are driven by this
motor.
More than one amplifying stage might be provided and other amplifying
elements such as vacuum tubes or magnetic amplifiers might be used.
Fig 4 schematically illustrates a delay network which may be used in
the time-piece according to this invention in the form of a lumped
constant line having inductors L and L/2 respectively and capacitors C
Calculation of such lumped constant lines is very simple.
The delay time of such a delay line is:=rk/LC seconds fi w)Y 2 wherein
n =number of sections of the line, =.cut-off frequency, X =working
frequency and wherein u O In order to obtain good stability O shall be
high as compared with lo.
For obtaining an oscillating frequency of 800 cycles lhich may be used
for directly driv 115 ing a synchronous motor or the like the
following elements may be used in a delay line as shown in Fig 4:L= 0
15 Hy C= 0 02 1 AF 120 In this case a delay of 55 lts is obtained per
section of the delay line and therefore 23 sections are required for
producing the desired 785,749 frequency of 800 cycles The values of
such a line are:line impedance Z O = 2500 ohms %O = 36 300 cycles
w,/c= 73 If circuit elements having suitable temperature coefficients
are used for the delay line very high stability of the line properties
and therefore of the generated oscillation may be obtained, this
stability being higher than the corresponding stability of quartz
controlled oscillators under the same temperature variations.

Instead of a lumped constant delay line as shown in Fig 4 a suitable
distributed constant line, for instance a cable or the like might be
used in the delay network 3 Existing cables have delay coefficients of
up to 5,us per meter of cable length and it should be possible to
obtain much higher delay coefficients by suitable cable construction
Such cables having very small size might be wound to coils for being
used in the delay network 3 of the timepiece according to this
invention.
In Figures 5 to 7 delay circuits are illustrated comprising delay
elements made of semi-conductors Experiments made with an arrangement
substantially as illustrated in Figure 5 have shown that appreciable
delay occurs in the transmission of an electric pulse through a
semi-conductor Figure 5 shows a body 10 of a semi-conductor for
instance germanium, silicon or the like, this element 10 being
connected with one face to the conductor interconnecting the terminals
11 and 12 and two points 15 and 16 being applied at a distance of 1 mm
against the opposite face of the element 10, the points 10 being
interconnected with terminals 13 and 14 respectively An electric pulse
applied to the terminals 11 and 13 appears at the terminals 12 and 14
after a delay time of 5 to 10 pus: Experiments have shown that this
delay time is very constant and practically independent of the pulse
amplitude.
In order to increase the delay time of 5 to us, which is insufficient
for the purpose of this invention, the arrangement illustrated in
Figure 6 may be adopted in which the distance between points 15 and 16
is much greater than in the experimental arrangement of Figure 5.
By this means the delay time may appreciably be increased Another
increase in delay time may additionally be obtained by the use of
special semi-conductor materials having particularly good delay
properties The distance between points 15 and 16 of the delay element
shown in Figure 6 may be of any desired value, whereby the body 10 of
the semi-conductor material may be given the form of a thread and may
be wound to a coil, the points and 16 being applied near the coil
ends.
Of course the delay time may also be increased by series connection of
a number of semi-conductor delay elements as shown in Figure 5 or 6
Such a series connection is shown in Figure 7, wherein the points 15
and 16 are replaced by surface contacts 17 and 18 respectively of the
type used in junction transistors Such a series connection of semi 70
conductor elements may produce an appreciable delay in the
transmission of an electric pulse from the terminals 11 and 13 to the
terminals 12 and 14 The delay elements of the delay network may be
very small particularly 75 when semi-conductor elements are used as
shown in Figure 5 to 7 so that the time-piece including such a delay

network may be very small and may be accommodated in a watch if
desired 80
* Sitemap
* Accessibility
* Legal notice
* Terms of use
* Last updated: 08.04.2015
* Worldwide Database
* 5.8.23.4; 93p
* GB785750 (A)
Description: GB785750 (A) ? 1957-11-06
Improvements in or relating to brushes
PATENT SPECIFICATION
Inventor: CHARLES MANBERG 7 &, , % Date of Application and filing
Complete Specification: May 18, 1956.
No 15653156.
Complete Specification Published: Nov 6, 1957.
Index at acceptance:-Class 19, A( 1 BI: 3 E), H.
International Classification:-A 46 b, d.
COMPLETE 8 SPECIFIGATION Improvements in or relating to Brushes We,
AKTIEBOLAGET l HUSQVARNA BORSTFABRIR, a Swedish Body Corporate, of
'Huskvama, Sweden, do hereby declare the invention for which we pray
that a patent may be granted to us, and the method iby which it is to
be performed, to be particularly described in and by the following
statement: -
The invention relates to brushes formed of brush strips and the
manufacture thereof For cleaning and polishing metal surfaces;
cylindrical brushes are used which are formed 'by winding a brush
strip comprising a U-shaped bristle holder into helical form The
bristles are folded around a metal wire and pressed together by the
holder.
As the respective turns of the brush strip are not rigidly connected,

with each other, the handling of such cylindrical brushes is
difficult, and the brush may easily be deformed.
In use the turns of the brush must be pressed together by press
plates, and as the metal Ushaped holder requires a certain axial space
the brushes cannot be made sufficiently thick.
The bristles bear against the sharp edge of the metal holder and in
consequence become worn.
When the brush strip is wound around a cylin, drical core the holder
is liable to open, and' the brushes must, consequently, be made with
an often unnecessary great diameter.
According to the invention the brush strip has the bristles folded
around a wire and the folded portions of the bristles sewn together,
and the adjacent base portions of the brush strip are glued together
to form a solid body with a substantially cylindrical inner surface.
As no metal holder is used the turns of the strip lie close to one
another, and thus the brush is thick and even The inner diameter of
the strip may be reduced, and, as no holder is used the bristles are
not subjected to undue wear The brush forms a rigid body, which
maintains its form and, requires no special plates for pressing the
turns together.
The bristles may consist for example of horsehair or fibres such as
agave fibres or synthetic fibres, and as binding agent glue,
artificial resin 'or vulcanized rubber for example lPrice 3 s 6 d l
85,750 may be used, As all bristles are united by the binding agent
individual fibres cannot loosen, and the ends of the 'brush strip
cannot be 50 thrown outwards by the centrifugal force owing to
insufficient axial pressure.
Specific embodiments of the invention will now be described by way of
example, reference being made to the accompanying draw 55 ing, in
which:Figure 1, is a side elevation of a brush strip machine; Figure 2
is a corresponding plan, view; Figure 3 ' is a partial horizontal
section of a 60 detail on an enlarged scale, and Figure 4 is a partial
section through a finished brush Referring to Figure 1 the bristles 2
are delivered from a hopper 1 of known construc 65 tion on to two
endless V-belts 3 in such, a manner as to lie transversely to the feed
direction.
The belts 3, pass over two pairs of guide wheels 4 and 5, of which the
pair 5 is driven Between the guide wheels 4 two press discs 6 and 7,
are 70 provided, of which the disc 16 is secured, by means of a flange
9 (Figure 3) to a driving shaft 8 rotating in a bearing 10 The end 11
(Figure 3) of the shaft '8 carries a ball 'bearing 17 with a spherical
outer bearing ring, and the 75 axis 12 of the outer ring forms a
variable angle to the axis 13 of the inner ring and the shaft 8 The
disc 7 is secured to the outer ring and has a turned annular cavity 14

into which a complementary portion 15 of the disc 6 is 80 partly
introduced when the axes 12 and 13 are as shown in Figure 3 The disc 7
has a tubular stem 16 with, an attached disc 18, the peripheral
portion of which forms a frustoconical surface which bears against a
friction 85 roller 119 The roller 19 is attached to a shaft 21, which
is pivotably mounted on a shaft (Figure 2) and by means of a spring 22
the roller 19 is pressed against the disc 18.
A wheel 24 (Figure 1) freely rotatable on a 90 shaft 23 serves as a
guide wheel for a metal wire 25 ', which is brought in contact with
the bristles 2 between the belts 3 The middle portion on the bristles
is thereafter pressed into a space or groove formed between the discs
6, 7 having their axes directed, as shown in Figure 3 so that the
width of the groove decreases in the direction of feeding The portions
of the bristles on each side of the wire are successively raised by
the edges of the discs, and at the point opposite to the friction
roller 19, as seen in Figure 1, where the width of the groove is at a
minimumr the folded portions of the bristles are substantially
parallel When the brush strip passes said point the needle 27 of a.
sewing machine 26, joins together both portions of the bristles by
means of a seam 28, preferably a chain seam, close to the wire which
is thereby connected with the bristles to form a brush strip The
sewing machine is driven by means of a bevel gear 29, a shaft 31 and a
belt 30 and a wheel on the shaft 8, so that the sewing machine
operates with a speed which is proportional to the feed of the wire
The brush strip can then be wound up on a suitable drum or directly on
to a cylinder for producing a finished brush.
When makling a bruslian end of the wire is fastened in a suitable
manner to the cylinder which is thereafter rotated The brush strip
passes over a glueing device and is wound tightly on to the cylinder
After each turn of the cylinder a glued pasteboard ring 32, (Figure 4)
or other suitable material, which is cut through at one point, is
applied on the brush strip at a short distance from the wire.
When the desired width of the brush is obtained, the brush strip is
cut off, Thereafter the brush is pressed between two press plates,
which are thereafter connected with each other by means of claws The
brush is finally removed from the cylinder and left to dry.
When the binding agent has set the base portions of the bristles
together with the wire form a solid body with a regular and even inner
cylindrical surface, which has a diameter corresponding to that of the
cylindrical holder in a cleaning or polishing machine.
* Sitemap
* Accessibility
* Legal notice

* Terms of use
* 5.8.23.4; 93p
* GB785751 (A)
Description: GB785751 (A) ? 1957-11-06
Improvements in and relating to the purification of germanium
Translate this text into Tooltip
[75][(1)__Select language]
Translate this text into
The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
Inventor: FREDERICK MURRAY REYNOLDS Date of filing Complete
Specification Nov 16, 1953.
Application Date Aug 15, 1952.
Complete Specification Published Nov 6, 1957.
Index at acceptance: -Class 1 ( 3), AID 10, A 1 G( 54: 541 D 10), A 1
N 54.
International Classification: -CO 1 g.
Improvemnerlts in and relating to the Purification of Germanium We,
NATIONAL RESEARCHDEVELOPMENT CORPORATION, a Britishi Corporation, of
1, Tilney Street, London, W 1, do hereby declare the invention, for
which we pray that a patent may be granted to us, and the method by
which it is to be performed, to be particularly described in and by
the following statement: This invention relates to the freeing of
germanium from arsenic contamination.
Germanium always occurs associated with arsenic and as the two
elements have closely similar properties, the removal of arsenic has

presented difficulties This is particularly the case when the
germanium is required for instance for certain electrical uses, for
which removal of arsenic down to very low limits is necessary.
The usual method for freeing germanium from such contamination is by
the distillation of germanium tetrachloride which boils at 84 C,
whereas arsenic trichloride boils at C It has been customary to distil
in the presence of some excess of chlorine to maintain the arsenic as
far as possible in the nonvolatile pentavalent state Varying results
have been reported on the completeness of the separation attainable,
the variations apparently depending on variations in the experimental
conditions Thus in " Chemical Engineering ", April, 1952, page 160,
distillation of germanium tetrachloride from strong hydrochloric acid
is disclosed, chlorine being bubbled through the solution, but it is
stated that even so, a back reaction occurs, with formation of arsenic
trichloride and chlorine.
Dennis & Papish, J A C S, 1921, 43, 2137, state that the separation so
far as chemical determination shows is complete provided that a high
concentration of chlorine is maintained.
On the other hand, Muller, J A C S, 1921, 43, 2549, reported that with
this method the distillate always contains small quantities of arsenic
Dennis & Johnson, J A C S, 1923, 45, 1380/1391, using the same method
in conlPricn junction with an 80 cm fractionating column reported less
than one part of arsenic in 200,000 in germanium dioxide prepared from
the distillate, determined by a spectroscopic method of which the
limiting sensitivity was 50 about 1 in 200,000 None ot these
references discloses, however, all the conditions which are essential
to ensure vanishingly low arsenic contents and which are discussed
below.
In practice, the arsenic content of ger 55 manium chloride prepared by
distillation from hydrochloric acid in the presence of chlorine has
been found to be not low enough for some purposes and the only
satisfactory method hitherto known to reduce the arsenic content 60
further is to reflux the germanium chloride through a column packed
with copper turnings The arsenic trichloride reacts slowly with the
copper, forming copper arsenide It has been stated that by reiluxing
for 12 to 15 65 hours it is possible by this means to reduce the
arsenic content to better than 0 1 part per million and the best
commercial germanium, which has hitherto been purified in this way,
has an arsenic content of about 0 05 part per 70 million.
It has been discovered by the present inventor that if the
distillation is carried out under certain conditions, easily complied
with, a reduction of arsenical contamination to a dis 75 appearingly
small value, namely no more than 0.005 part per million of the
tetrachloride, equivalent to no more than 0 01 part per million in the

dioxide prepared from the dis.
tilled tetrachloride which is equivalent to 80 0.013 part per million
in the germanium metal itself recovered from the dioxide, can be
simply and rapidly attained in a single stage of distillation with
very low loss of germanium en route, and the invention is based upon
this 85 discovery According to the invention, germanium tetrachloride
is distilled in the presence of a sufficient excess of chlorine to
saturate the system and in the presence of such an amount of aqueous
hydrochloric acid as to 90 785751 No 20601152.
785,751 form a second liquid phase, the initial acid concentration
being from 5 5 to 6 N Practical tests show that the acid concentration
must be about 6 N to avoid hydrolysis of the germanium tetrachloride,
while if substantially higher it tends to favour reduction of the
arsenic to the trichloride Furthermore acid of approximately this
concentration is a solution having a constant boiling point at
atmospheric pressure and accordingly substantial changes in the
concentration of the acid during distillation are avoided It is
believed, but the invention is not limited to this theory, that the
chlorine in the presence of aqueous hydrochloric acid, oxidises the
arsenic to pentavalent arsenic, probably as ortho-arsenic acid (H, As
04) whereas arsenic pentachloride is not a stable compound and
chlorine alone is therefore not able to prevent distillation of 2 C
some arsenic trichloride.
When arsenic is distilled in hydrochloric acid an equilibrium is set
up represented by: H As 04 + 5 H 1 l C 'As Cl, +C 12 + 4 H 1,0 A high
concentration of hydrochloric acid favours the reduction to arsenic
trichloride, while a high concentration of chlorine favours the
oxidation In considering the above equilibrium it will be seen that
working with 6 N, i e the approximate composition of the constant
boiling solution, for a given quantity of arsenic, the greater the
volume of acid used the greater is the concentration of the acid
relative to the concentration of arsenic, so that the equilibrium will
tend to shift towards the right With smaller volumes of acid the
equilibrium will tend to move to the left.
When distillation of germanium tetrachloride containing arsenic is
carried out it is essential to have sufficient hydrochloric acid
present to prevent hydrolysis of the germanium tetrachloride, and at
the same time to avoid having the acid present in quantities which
will tend to cause formation of appreciable quantities of volatile
arsenic trichloride Germanium tetrachloride is not very soluble in
dilute aqueous hydrochloric acid and solution is not achieved with
concentrations of acid much below 6 N.
The minimum amount of acid necessary for these two purposes is
achieved by the use of a 2 phase liquid system in which the

concentration of the acid is approximately 6 N Since in distillations
of aqueous hydrochloric acid the constant boiling solution is always
reached whether the initial concentration of the acid is higher or
lower than that of the constant boiling mixture, it might be possible
to start with acid of lower concentration than 6 N and distill off the
excess water, and provided with a two phase system was achieved before
distillation of the germanium tetrachloride, obtain an arsenic free
distillate In practice, however, this would be difficult to carry out
and it is simpler and more economic to start with acid of
approximately 6 N concentration If initial concentrations appreciably
higher than 6 N are used, even with a two phase system, the higher
concentration of acid will shift the above equilibrium to the right
and the distillate of germanium tetrachloride 70 will be contaminated
with arsenic.
The chlorine can be produced by the addition of an oxidising agent to
the aqueous hydrochloric acid, but it is preferred to use a separate
supply of chlorine introduced as such 75 as the results in the former
case are not quite so good.
The method according to the invention is applicable to germanium
tetrachioride containing a substantial proportion of arsenic, at least
So up to several per cent.
In detail, on a small scale, the method can be carried out as
follows:The apparatus may consist essentially of a ml flask with a
side-arm carrying a 25 cm & 5 high Vigreux column At the top of the
column a lead-off tube passes to a water condenser 60 gm arsenical
germanium tetrachloride, together with 2/3 its volume of 6 N
hydrochloric acid is transferred to the flask, 90 the mixture forming
two layers with the germanium chloride at the bottom A rapid stream of
chlorine is passed in through a tube extending into the lower layer,
the germanium chloride rapidly absorbing the gas and becom 95 ing a
greenish-yellow colour The chlorine may be supplied from a potassium
permanganate-hydrochloric acid generator, a bubbler of sulphuric acid
serving to dry the gas When the system is saturated with chlorine the
flask 100 is gently heated so that the germanium chloride refluxes in
the lower part of the column After refluxing for 5 minutes the heat is
increased and the germanium chloride distilled, the rate being such
that some 2-3 105 drops per second issue from the lead-off tube.
At this stage the rate of passage of gas is reduced to about 2-3
bubbles per second, this rate being maintained from now on The
operation is continued until, with the same 110 application of heat,
no more germanium chloride distills over; under these conditions all
but some 4-5 ml appear in the distillate.
By this method using a sample which contained 100 microgm of arsenic
in 60 gm of 115 germanium tetrachloride, the factor of reduction was

greater than 10 ' as determined by using radioactive arsenic as a
tractor and the germanium dioxide to which the purified tetrachloride
was converted in the well-known 120 manner by hydrolysis with
distilled water, showed an arsenic content of but O 005 parts per
million Using a similar procedure but providing the chlorine by adding
potassium dichromate or chlorate to the aqueous hydro 125 chloric
acid, the reduction factor was 103 or a little better.
The figures quoted above were obtained with silica apparatus However,
even with glass (Pyrex-Registered Trade Mark) appar 130 785,751 atus
which itself contains a small proportion of arsenic, the dioxide
contained but 0 01 part per million of arsenic It is probable that the
limiting factor was the purity of the distilled water, the arsenic
content of which was found to be oi the order of 0 001 part per
million.
* Sitemap
* Accessibility
* Legal notice
* Terms of use
* 5.8.23.4; 93p
* GB785752 (A)
Description: GB785752 (A) ? 1957-11-06
Reaction apparatus for carrying out exothermic gas reactions
Reaction apparatus for carrying out Exothermic Gas Reactions Ani e,
RHEINPRF.USSEN AKTIENGESEF,L- SCELFT FUER BERGBAU UND CHEMISE, a
German Company, of Homburg, Niederrhein, Germany, do hereby declare
the invention, for which we pray that a patent may be granted to us,
and the method by which it is to be performed, to be particularly
described in and by the following statement
The invention relates to apparatus for carrying out exothermic

catalytic gas reactions in the presence of catalysts dissolved or
suspended in a non-cirenlating liquid medium, in which an internally
cooled reaction chamber, being relativelv tall as compared with the
diameter, is divided into vertical shafts which are open at both ends
with the lower ends of the shafts terminating above the base of the
reaction chamber within the liquid medium and with the upper ends of
the shafts extending above the liquid medium into the gas space, and
which are formed by heat-conducting plates connected to coolin tubes
or pipes through which the coolant flows upwardly in the same
direction as the flow of gas through the reaction chamber.
In catalytic gas reactions, particularly in the hydrogenation of
carbon monoxide in accordance with the Fischer-Tropsch process when it
is desired to obtain a substantially complete conversion of the
synthesis gas in one step and with a single pass of the gas, it has
been found to be advantageous to allow the reaction temperature to
increase in the direction of flow of the gas and in proportion to the
impoverishment of the gas in initial reaction constituents, such as CO
and 112. By adjusting the reaction temperature to the partial pressure
of the reactants, not only is higher gas conversion obtained, but
undesirable side-reactions such as the formation of methane or the
separation of carbon, are suppressed, whilst the quality of the
synthesis products is at the same time improved.
A number of proposals have been made to obtain the rise of
temperature, that is, a positive temperature gradient, in reaetion
chambers provided with internal cooling means. Thus, according to one
proposal, a number of cooling elements are provided one above the
other through each of which flows a separate stream of coolant and to
each of which a separate vapour collector or drum is connected if a
vaporizing coolant, such as water, is used.
According to another proposal, a nonvaporizing coolant is passed at a
controlled rate through tubes extending over the total height of the
reaction chamber in such manner that the coolant is heated to the
desired degree and the reaction heat is transferred to water in an
external heat exchanger, thereby generating steam. Both proposals
necessitate additional devices which complicate the cooling operation.
It is also possible to obtain a rise of temperature or a positive
temperature gradient by reducing the number or the cross-sections of
the cooling tubes, so that the area of the cooling surfaces decreases
in the direction of flow of the gas, and the distance between the
cooling areas is increased.
However, when the coolant used is water, and in view of the fact that
the temperature of the water is uniform throughout, there will occur
within the reaction chamber horizontal differences in temperature
which increase in the direction of flow of the gas stream and which

result in disadvantageous effects on the reaction.
It is an objeet of the invention to provide a reactor in which such
disadvantages are avoided or mitigated.
According to the invention, a reactor for carrying out exothermie gas
reactions in the presence of a catalyst dissolved or suspended in a
liquid medium comprises a reaction chamber provided at its lower end
witll means whereby the gaseous reactants may be passed upwardly
through the liquid medium in the reaction chamber, one or more bundles
of cooling tubes through which a liquid heat transfer medium may be
passed, the bundle or bundles of cooling tubes being disposed in the
main reaction zone in the lower two thirds of the reaction chamber,
and a series of heat-conducting plates connected to the cooling tubes
and forming a series of openended vertical shafts which extend
substantially over the whole cross-section of the reaction chamber,
each vertical shaft being of relatively small crosssectional area, the
lower ends of the heatconducting plates being disposed above the
bottom of the reaction clamber and within the liquid medium, and the
upper ends of the heat-conducting plates extending above the upper
level of the cooling tubes to a position adjacent to the top of the
reaction chamber to form extensions of the vertical shafts above the
surface of the liquid medium. The length of the main reaction zone is
generally from about onethird to at most two-thirds of the height of
the reaction chamber, the actual length of the main reaction zone
depending on the specific reaction and on the conditions nnder which
the reaction is carried out.
In one construction the bundle or bundles of cooling tubes may be
disposed wholly within the lower third of the total height of the
reaction chamber. In another eonstruetion, the cooling tubes may be so
provided that they are reduced in number in the upward direction from
approsimately a mid-position of the main reaction zone.
The vertical shafts may be circular in cross-section, and of a
diameter in the range 5-30 centimetres depending on the length of the
vertical shafts and the diameter or cross-sectional area of the
reactor.
In the hydrogenation of carbon monoxide in a liquid medium, it
appeared that approximately 70% of the conversion occurred relatively
rapidly in the lower third or at most within the lower half of the
layer required for a complete conversion. From this zone, there is
obtained a larger proportion of the total reaction heat utilizable for
the generation of steam or vapour than corresponds to the respective
proportion of converted gas, because it has been found that a large
portion of the free reaction heat is nsed in the upper zone for the
required increase of temperature. The weak fliermal flus to the
cooling tube zone, which moreover decreases decreases in the upward

direction within the heat-conducting plates which forms the walls of
the vertical shafts, permits a second wave of reaction to occur in
synthesis gas in the upper zone which is free from cooling tubes in
spite of the fact that tile concentration of the reactive components
in the synthesis gas is much lower in this zone ciue to the initial
reaction in the main reaction zone. A substantial rise of temperature
thns occurs in the upper part of the reactor with the result that the
CO 112 in the gas can be converted almost completely and almost
without any disturbing side-reactions.
It has also been found that the reactor is particularly suitable tor
the produetion, from CO and H,, of low-boiling synthesis products
which are rich in olefines and substantially enriched in
iso-hydrocarbons.
Due to the high temperature in the upper reaction zone, these products
are obviously discharged more rapidly and more completely from the
reactor. The temperature of the end gas escaping at the top of the
reactor which is up to 500 C., or more higher than the mean
temperature of the main reaction zone, renders it possible to preheat
the synthesis pays, lvhiell is fed illto the bottom of the reactor, in
heat exchangers almost to the initial synthesis temperature. Any
excess reaction heat of the seeond or upper reaction zone which cannot
he dissipated through the heatconducting plates to the cooling tubes,
is, therefore, also utilized in the form of vapour for the preheating
of the synthesis gas.
The invention is illustrated by way of example in the accompanying
drawings, in which
Fig. 1 is a perspective view of the upper part of one construction of
a set or bundle of shafts at the level of the collecting pipes through
which the cooling medium passes out of the reaction chamber:
Fig. 1A is a transverse section on the line A-A of Fig. 1;
Fig. 2 is a perspective view of part of a further construction of a
set or bundle of shafts;
Fig. 2A is a transverse section oI, the line B-B of Fig. 2; and
Fig. ', is a perspective view, at the lower ends of the shafts. of
some of the feed tubes for tbe eooling medium.
As illustrated in Figs. 1 and 2. a series of heat-conducting plates 11
are connected together in such manner as to form a series of
liqllid-tinht, leD:nonal, vertical shafts 10. The vertical shafts 10
are open Xlt their upper and lower ends, the lower ends of the shafts
terminating at a position above the lease or as l'strihirn4in lplatrX
of the reactor. whereby the liquid medium.
when the reactor is in use, may circulate l)elow the lower ends of the
vertical shafts.
Cooling tubes 12 are provided to run vertically at the angles of the

shafts 10, the heat-conducting plates 11 being joined to the tubes 12
in a manner which ensures that the joints are both liquid-tight and
efficient conductors of heat. The tubes 12 extend from the lower ends
of the shafts 10 to a position short of the upper ends of the shafts,
such position being approsimately at the upper end of the main
reaction zone; above such position the reaction space is free from
cooling tubes and the p]ates 11 are directly joined to one another to
form the liquid-tight shafts 10.
The tubes 12 are connected at their upper ends to horizontal,
collecting pipes or tubes 13, the pipes 13 being alternately
staggeared in the construction illustrated in
Fig. 1 and being all at the same level in the construction illustrated
in Fig. 2. It will
be understood that the collecting pipes 13
may be provided at a slight angle to the
,'iorizonta] in order to avoid vapour or steam pockets.
When the reactor is in operation, the
cooling medium flows upwardly through
the tubes 12 and passes into the collecting
tubes 13 through which it is led out of the
reactor. The collecting pipes 13 may, for
example, lead into a main colleci'ing pipe
or header which is formed to a circular
arc and bears on the inner wall of the
reaction chamber and, to provide a
resilient equilization of differences in
thermal expansion of the cooling tube
system and the wall of the reactor, the
pipe connecting the main collecting pipe
to the vapour or steam drum is preferably of adequate length and leads
from the
reaction chamber to the outside only at the end of a sufficiently long
pipe connection which is mounted on the outer wall.
Instead of providing only a single arcuate main collecting pipe, it is
also possible to use two or more arcuate main collecting pipes which
are provided opposite and/or above one another. The pipes leading to
the vapour or steam collector or drum may also extend upwardly at
right angles from the main collecting pipe or pipes to pass,
advantageously through glands or stuffing boxes, through the head or
top of the reaction chamber to the outside.
The cooling medium is passed into the cooling tubes 12 through feed
pipes 14 which are provided below the lower ends of the vertical
shafts 10, (Fig. 3).
The formation of the feed pipes 14 is similar to that of the

collecting pipes 13 which are provided at the upper ends of the tubes
12. It will be appreciated that the feed pipes 14, which extend
horizontally across the lower part of the reaction chamber, do not in
any way impede or interfere with the distribution of the synthesis gas
in the liquid medium in which the synthesis is effected. The gas
distributing jets or nozzles may be provided uniformly over the
whole of the base of the reaction chamber, without any regard to the
position of the transverse feed pipes 14. The feed pipes 14 may
themselves also rest directly on the gas distributing plate at the
base of the reaction chamber, in which case the gas distributing
nozzles may advantageously be provided adjacent to the feed pipes 14
and/or the cooling tubes 12.
The lower ends of the vertical shafts 10 are spaced from the base of
the reaction chamber, so providing a path at the base of the reaction
chamber along which the liquid medium, in which the synthesis or
reaction is carried out, may circulate.
The diameter of the cooling tubes 12 is small relatively to the
diameter or width of the shafts 10, being less than 1:2.
In reactors, the reaction chambers or spaces of which have a total or
overall height of from about 5 metres to about 12 metres, one cooling
unit or bundle of cooling tubes is sufficient to dissipate all
of the excess reaction heat, since in this
case the process is only carried out with
cross-sectional loads of up to approximately 40 working litres of
synthesis gas per square centimetre of eross-section of the reaction
spaee per hour. The term
working litre" denotes a litre of the gas under the temperature and
pressure eonditions of the reaction.
However, when reactors are used in which the total or overall height
of the reaction chamber or space exceeds 12 metres, and which may, for
example, be up to 25 metres, it has been found to be advantageous to
divide the cooling tube system, which in accordance with the invention
is provided in the main reaction zone, into two or more sets or
bundles of cooling tubes disposed one above the other, each of which
is advantageously connected to its own vapour or steam collector or
drum, and each of which is preferably provided with its own
temperature regulating means, so that even within the main reaction
zone the synthesis temperature may be increased in stages in the
upward direction.
In order to obtain a substantially constant space-time yield of
reaction products, it is necessary for the cross-sectional load of the
synthesis gas to be increased in accordance with the extent to which
the height of the reaction chamber is increased. For example, for the
same spacetime yield, and with otherwise constant conditions of

pressure and temperature,] the cross-sectional load of synthesis gas
required in a reaction chamber hazing a heist of 25 metres, is five
times as treat as that required in a reaction chamber haring a height
of 5 metres. With tall reaction chambers, the cross-sectional load may
lie increased to 100 working litres per sq. em., and the length of the
main reaction zone cooled by a cooling medium is correspondingly
extended in view of the high vdocity of ascent of the gas bubbles.
In view of this, the percentage gas conversion per unit of length in
the main reaction zone is correspondingly less than ii low reactors so
that on this account and also in view of the more vigorous turbulenee
of the liquid medium, the reaction temperature can only rise bv
accumulation of heat to a correspondingly slight degree ahol-e the
temperature of the cooling medium.
Therefore, with increasing height, the rise in the reaction
temperaftire within the region of the main reaction zone necessary to
maintain an adequate conversion of gas, is advantageously ensured by
providing several cooling tube units as proposed according to the
invention in the manner hereinbefore described. In this reactor, a
subsequent or second wave of reaction also occurs in the manner
hereinbefore described in the zone in which the vertical shafts are
free from the cooling tubes.
What we claim is
1. A reactor for carrying out exofliermic gaseous reactions in the
presence of a catalyst dissolved or suspended in a liquid medium,
comprising a reaction chamber provided at its lower end with means
whereby the gaseous reactants may be passed upwardly through the
liquid medium in the reaction chamber, one or more bundles of cooling
tubes through v;hieh a liquid heat transfer medium mav be passed, the
bundle or bundles of cooling tubes being disposed in the main reaction
zone in the lower two-thirds of the reaction chamber, and a series of
heat-conducting plate sconneeted to the cooling tubes and forming a
series of open-ended vertical shafts which extend substantially over
the whole cross-section of the reaction chamber, cach vertical shait
being of relatively small cross-sectional area, the lower ends of the
heat-conductin' plates being disposed above the bottom of the reaction
chamber and within the liquid medium. and the upper ends of the
heatconductii~ plates eNtendin} above the upper level of the eooliI
tubes to a pfiSi- tion adjacent to the top of the reaction chamber to
form extensions of the vertical shafts above the surface of the liquid
medium.
2. A reactor according to Claim 1, in wllich the bundle or bundles of
cooling tubes are disposed wholly within the lower third of the total
height of the reaction chamber.
3. A reactor according to C'laim 1. in which the cooling tubes are

reduced in number in the upward direction from approximately a
mid-position of the main reaction zone.
4. A reactor according to any one ot the preceding claims. in which
the collecting pipes through which the cooliiio medium flows out from
the cooling tubes, extend horizontally, or upwardly at a slight angle
to the horizontal, through the system of shafts.
5. A reactor according to any one of the preceding claims, in which
with verv tall reaction chambers and/or when the reaction requires a
sharper rise in temperature in the direction of florr of the gas
stream, two or more sets of cooling tubes are provided one above the
other in the main reaction zone, each of which sets is provided with
its own temperature regulating means.
6. A reactor for carrying out esothermic reactions with gaseous
reactants, substantiallv as hereinbefore described with reference to
Figs. 1 and 3 or to Fig. 2.
7. A process for the synthesis of hydrocarbons from carbon monoxide
and hydrogen by the Fisclier-Tropsch process.
in which the synthesis is carried out in the presence of a catalyst in
a liquid medium in the reactor claimed in any one of the preceding
claims.
* GB785753 (A)
Description: GB785753 (A) ? 1957-11-06
Improvements in or relating to expansible capsule devices
Date of Application and filing Complete Specification: April 14, 1954.
785,753 No 11004/54.
i 1 Application made in United States of America on April 17, 1953.
Complete Specification Published: Nov 6, 1957.
Index at acceptance:-Classes 38 ( 5), B 1 S( 2 C 2:12); 64 ( 2), T( 3
C 4:13); and 106 ( 2), H 3 82 w International Classification:-G 01 k,
I, HO 2 c.

Improvements in or relating to Expansible Capsule Devices We, IGRANIC
ELECTRIC COMPANY LIMITED, a British Company of Elstow Road, Bedford,
Bedfordshire, do hereby declare the invention, for which we pray that
a patent may be granted to us, and the method by which it is to be
performed, to be particularly described in and by the following
statement:-
This invention relates to expansible capsule devices comprising a
capsule having opposite faces or diaphragms which are both
simultaneously movable towards and away from each other under the
influence of pressure changes within said capsule.
Devices of this kind, in which the capsule contains a thermometric
filling are frequently employed in the temperature control of
refrigerators and the like.
One object of the present invention is to provide a device of the
above nature which will be inexpensive to manufacture and mount and
which will be of a robust character.
The present invention consists broadly of a structure comprising a
capsule having opposite faces or diaphragms which are both
simultaneously movable towards and away from each other according to
the pressure in said capsule, and an arm extending from said capsule
laterally relatively to the movement of said faces or diaphragms, said
arm having a longitudinal passage therein, in communication with the
interior of said capsule and being adapted to support said capsule in
the manner of a cantilever.
The foregoing and other features of the invention will be more clearly
understood from the following description of preferred examples of the
invention now to be described with the aid of the accompanying
drawings.
In the drawings Fig 1 is a plan view of a power element device
embodying the invention; Fig 2 is a partly schematic and partly
crosssectional illustration of a switch actuating system employing the
power element device lPrice 3/6 l shown in Fig 1; Fig 3 is a plan view
of an alternative form of a power element device embodying the
invention; and Fig 4 is a partly schematic and partly cross 50
sectional illustration of a switch actuating system employing the
power element device shown in Fig 3.
Referring to Figs 1 and 2 of the drawings, the numeral 10 generally
designates a power 55 element device comprising a pair of like
combined diaphragm and stem members 12, 12 assembled in back-to-back
relationship and joined together along an endless seam 16 as by
welding Members 12, 12 each have a 60 diaphragm disc portion 18 and a
stem portion 22 Each diaphragm disc portion 18 has a central boss 24
and each stem portion 22 is formed to provide therein a longitudinal
groove 26; the grooves 26, 26 jointly com 65 municating with the

respective diaphragm disc portions 18, 18.
When the members 12, 12 are assembled as illustrated in Fig 2,
diaphragm disc portions 18, 18 jointly provide a capsule 28, and the
70 stems 22, 22 form a cantilever arm 30 having a channel 32 therein
closed at one end and communicating at its other end with the interior
34 of the diaphragm 28 According as the pressure within the capsule
varies, said 75 capsule contracts or expands by the diaphragm disc
portions both simultaneously moving towards or away from each other,
and it will be seen that the cantilever arm extends laterally relative
to the movement of 80 said diaphragm disc portions.
The stems 22, 22 and thus also the assembled cantilever arm 30, are
provided, as shown, with ears 36 formed integrally therewith at some
preselected distance from the 85 capsule 28 These ears have alined
openings 38 therein respectively which are adapted to accommodate any
suitable fastening means, such as screws or bolts 39.
The embodiment illustrated in Figs 3 and 4 9 o 785,753 employs a power
element device like that shown in Figs 1 and 2 except that the stem
portions forming the cantilever arms 40 terminate at some suitable or
desired length S beyond the ears 42 A tube 44 having one end closed or
sealed in any well known manner and one end open has its open end
inserted in the channel or passage at the outer end of the cantilever
arm 40 and may be considered part thereof The opposite end portion of
the tube may be coiled as shown at 46 to provide, in effect, a bulb.
The power element devices illustrated are each provided with a
thermometric fill 48 such as a saturated vapor and its liquid The
capsule expands and contracts in accordance with the temperature of
the liquid or the pressure exerted by the vapor.
Capsule 28 is shown in a relatively unexpanded state in Fig 2 The boss
24 of the lower disc 18 engages surface or stop 50 which is fixed
relatively to the mounting surface 51 for ears 36 and to a switch
device represented by contacts 52 and bridging contact 54 Means 56
connecting the boss 24 or face of the upper diaphragm disc 18 with the
bridging contact 54 are provided to transmit the expansive motion of
capsule 28 for actuation of the switch, in a manner like that
illustrated in Fig 4.
Capsule 58 (see Fig 4) is shown in expanded condition The cantilever
arm 40 cantilevers about its fixed point 62 through an arc determined
by the expansion of lower disc 64 The capsule 58 tends to act as part
of the cantilever system, thus reducing the strain at the junction of
the capsule 58 and the cantilever arm 40 While not essential, it is
considered preferable that the stem portions be formed integrally with
their respective diaphragm discs.
The diaphragm discs 18 and 64 may be corrugated according to the
force-displacement characteristic required A central boss may be

provided as in the diaphragm discs illustrated to insure uniform
transmission of the expansive motion of the capsule.
While the power element devices illustrated are provided with mounting
ears, it will be apparent that such ears may be omitted and other
means provided for mounting the devices Such means might be a part or
parts of the power element device or might comprise separate devices.
The fill may be introduced into the power element device by completing
the same except for sealing the cantilever arm 30 or the tube 44 and
then placing the power element device, or at least its unsealed
portion, in an atmosi 60 phere of thermometric fill wherein the
unsealed portion is sealed in any well known manner Some of the fill
will be sealed withinthe element A predetermined amount of fill may be
so introduced by-maintaining the fill atmosphere at some preselected
pressure and temperature The manner of selecting such pressure and
temperature is well known in the art.
The power element device illustrated in Figs 3 and 4 may be made by
completing the 70 same except for attaching the tube 44 to cantilever
arm 40 and then placing at least the open end of tube 44 and
cantilever arm 40 in an atmosphere of thermometric fill The open end
of the tube 44 is then inserted within 75 the outer, open end of the
cantilever arm 40 and the end of the cantilever arm is crimped over
the end of the tube Finally the tube and cantilever are bonded
together as by soldering or welding Or, as will be apparent 80 to
those skilled in the art the power element device may be completed
except for sealing the outer end of the tube 44 Then such outer end is
placed in an atmosphere of fill where it is sealed 83
* Sitemap
* Accessibility
* Legal notice
* Terms of use
* 5.8.23.4; 93p

5341 5345.output

Recommended

Recommended

More Related Content

What's hot

What's hot (20)

Viewers also liked

Viewers also liked (17)

Similar to 5341 5345.output

Similar to 5341 5345.output (20)

More from Иван Иванов

More from Иван Иванов (20)

5341 5345.output