U.S. patent number 3,578,757 [Application Number 04/744,517] was granted by the patent office on 1971-05-18 for chromatograph for determination of admixtures in gases.
Invention is credited to Jury Markovich Genkin, Viktor Ivanovich Samuilov, Maria Dmitrievna Suvorova.
United States Patent |
3,578,757 |
Samuilov , et al. |
May 18, 1971 |
CHROMATOGRAPH FOR DETERMINATION OF ADMIXTURES IN GASES
Abstract
A chromatograph for the determination of admixtures in gases,
comprises a chromatographic column bent in the form of at least a
single helix coil or an arc of circle and which is rigidly secured
on the shaft of a drive device in a plane perpendicular to the axis
of the shaft. The shaft is mounted in stationary supports so that
at the same time one portion of the chromatographic column is
immersed in a refrigerant bath and the other portion of the column
is in a heater, and during the rotation of the shaft said portions
of the column subsequently pass through the cooling and heating
zones.
Inventors: |
Samuilov; Viktor Ivanovich
(Moskovskaya Oblsst, SU), Genkin; Jury Markovich
(Moscow, SU), Suvorova; Maria Dmitrievna (Moscow,
SU) |
Family
ID: |
24992995 |
Appl.
No.: |
04/744,517 |
Filed: |
July 12, 1968 |
Current U.S.
Class: |
73/23.25; 422/89;
95/87; 96/101; 73/23.39 |
Current CPC
Class: |
G01N
30/30 (20130101); G01N 30/6052 (20130101); G01N
30/6047 (20130101); G01N 2030/3076 (20130101); G01N
2030/3015 (20130101) |
Current International
Class: |
G01N
30/60 (20060101); G01N 30/30 (20060101); G01N
30/00 (20060101); G01n 031/08 (); B01d
015/08 () |
Field of
Search: |
;73/23,23.1,53 (C)/
;55/53,67,78,80,197,386,390 ;23/232 (C)/ ;23/254 (C)/
;23/(Inquired) |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Queisser; Richard C.
Assistant Examiner: Snee, III; C. E.
Claims
We claim:
1. A chromatograph for the determination of admixtures in gases,
said chromatograph comprising a chromatographic column for
receiving a gas to be analyzed, refrigerant means and heater means
spaced proximate one another for constituting cooling and heating
zones respectively, said chromatographic column being rotatably
supported and interposed between said cooling and heating zones
such that one portion of said chromatographic column is within said
cooling zone and a further portion thereof is within said heating
zone, drive means connected to said chromatographic column for
imparting rotation thereto to thereby pass successive portions of
said chromatographic column between said zones, said
chromatographic column including at least a single coil having an
inlet for receiving said gas to be analyzed and an outlet for
discharging said gas, support means for rotatably supporting said
coil, said support means being provided with an inlet channel and
an outlet channel communicating with said inlet and outlet of said
coil respectively, detector means connected to said outlet of said
support means, and recorder means connected to said detector means
for receiving signals therefrom, said signals indicating the amount
of admixtures in said gas being analyzed.
2. A chromatograph as claimed in claim 1, wherein said coil is
substantially circular.
3. A chromatograph as claimed in claim 1, wherein said coil is
helical.
4. A chromatograph as claimed in claim 1, wherein said support
means includes a shaft to which said chromatographic column is
fixedly connected, and stationary end supports, said shaft
including opposite end portions rotatably supported one in one of
each of said end supports, said inlet and outlet channels of said
support means extending respectively from a respective one of said
end supports to said shaft.
5. A chromatograph as claimed in claim 1, wherein said heater means
includes a substantially U-shaped member embracing said coil.
6. A chromatograph as claimed in claim 1, wherein said refrigerant
means includes a liquid refrigerant bath wherein said coil is
immersed.
Description
This invention relates to chromatographs for determination of gas
admixtures, and can particularly be used to advantage for
determination of admixtures in gases, boiling at low temperatures,
such as helium and neon.
Known in the art are chromatographs for determination of gas
admixtures, comprising a bath filled with a refrigerant, a heater,
a chromatographic column in the form of a coil, and a drive unit
which moves the chromatographic column in the cooling and the
heating zones. In chromatographs of this type the entire
chromatographic column is first placed into the refrigerant bath
and then into the heater.
Disadvantages of the prior art chromatographs consist in their
complicated construction and in the requirement for a preliminary
cooling of the entire chromatographic column which considerably
prolongs analytic procedure.
An object of this invention is to provide a chromatograph capable
of operating in the continuous process stream without changing over
gas streams or electrical circuits while in operation. Another
object of the invention is to provide a chromatograph for
determination of admixtures in gases which would be convenient in
use and simple in construction.
With these and other objects in view, the chromatograph for
determination of admixtures in gases comprises, according to the
present invention, a chromatographic column which is a helical tube
of at least one coil fixedly attached to a shaft of a drive unit,
said shaft being borne in stationary supports so that one part of
the column is immersed in the refrigerant in the cold bath, while
the other part of the column is in the heater zone, and during
rotation of the shaft the column passes in turn to and from the
cold and the heater zones, the shaft and stationary supports being
provided with interconnected communicating channels for gas
delivery into and discharge from the chromatographic column.
The shorter time of the analysis with the present chromatograph has
been achieved due to the use of a temperature field which shifts
along the sorbent bed without preliminary cooling of the entire
sorbent bed.
These and other objects and advantages of the invention will be
better understood from the description of specific embodiments
thereof and the appended drawings, in which:
FIG. 1 is a general view of the chromatograph provided by the
invention, with partial cutaway;
FIG. 2 is a schematic axonometric view of the chromatograph
according to the invention;
FIG. 3 is a schematic axonometric view of an alternative
modification of the chromatograph;
FIG. 4 is a section taken along the axis of the shaft of the drive
unit of the chromatograph according to the invention;
FIG. 5 illustrates a diagram of gas flow in the chromatograph shown
in FIG. 2;
FIG. 6 illustrates a gas flow diagram for the chromatograph shown
in FIG. 3; and
FIG. 7 is an electrical circuit diagram of the chromatograph
according to the invention;
FIG. 8 is a typical detector trace according to the invention.
The chromatograph according to the invention comprises a
refrigerant bath 1 (FIGS. 1--3) and a heater 2, which ensure
refrigeration and heating of the chromatographic column
respectively, and a chromatographic column 3, manufactured from
stainless steel.
In one embodiment of the invention the chromatographic column 3 is
an open coil and is a helical tube in the other embodiment of the
chromatograph as shown in FIGS. 2 and 3, respectively.
The column 3 is filled with a suitable sorbent and is intended to
concentrate and separate gas admixtures. The said column 3 is
rotatably supported due to a drive unit 4 comprising a shaft 5
borne in stationary supports 6 and 7 (FIG. 4) packed with special
bushes 8 and 9, and operatively associated with an electric motor
10 (FIGS. 2 and 3).
The chromatographic column 3 is fixedly attached to the shaft 5
with the aid of pins 11 and 12 perpendicularly to the shaft 5, so
that one part of the chromatographic column is immersed into the
refrigerant bath 1, while its other part is in the heater 2. As the
shaft 5 rotates the column parts pass in turn through the cold and
warm zones. Channels 13 and 14 in the shaft 5 (FIG. 4), intended to
pass the analyzed gas, are connected with the chromatographic
column inlet and outlet openings by means of metal capillary tubes
15 and 16 (FIGS. 5, 6).
The stationary supports 6 and 7 also have channels 17 and 18 (FIG.
4) which communicate with channels 13 and 14, respectively.
The packing bushes 8 and 9 manufactured of flaro-plast (fluorinated
plastic material) perform the functions of both packing glands and
bearings. The packing bushes 8 and 9 are made in the form of
cylinders with conical bases.
The shaft 5 and stationary supports 6 and 7 also have cones which
accept the cones of the bushes 8 and 9. The surfaces of the cones
of the packing bushes and their matching surfaces of the shaft 5
and of the stationary supports 6 and 7 are polished.
In order to prevent gas leakage, one stationary support 7 can be
shifted in the direction of the shaft 5 by manipulating an
adjusting screw 19 and a spring 20. The low coefficient of friction
between metal and flaro-plast ensures rather free rotation of the
shaft 5 mounting in the chromatographic column 3.
The heater 2 is a U-shaped rectangular ceramic housing. The inner
surface of the housing has grooves 21 (FIGS. 2, 3) parallel to the
housing axis into which a heating element (not seen in the drawing)
is placed. An autotransformer 22 (FIG. 7) serves to control the
operation of the heater.
An electric fan 23 cools a portion of the chromatographic column 3
(FIG. 2) or several portions of the chromatographic column (FIG. 3)
prior to their being immersed into the refrigerant bath 1.
The chromatograph has a special inlet device 25 for connection to
the cylinder 24 (FIGS. 5 and 6) containing the analyzed gas, which
allows a quick flush required during the change of cylinders. The
inlet device 25 is connected with the chromatographic column
through a flexible metal capillary tube 26 and comprises a housing
27 with a coupling nut 28, a control valve 29, a valve 30 and a
pressure gauge 31. The control valve 29 maintains the preset flow
rate of the gas to be analyzed, the valve 30 serves for flushing
the system, and the pressure gauge 31 measures the pressure within
the gas cylinder 24.
All connections in the chromatograph are made with metal capillary
tubes.
During the period between analyses, the control valves 29 and an
outlet valve 32 are closed, while the system confined therebetween
remains under the pressure of the analyzed gas. The residual
pressure is controlled by the pressure gauge 33.
For the detection of admixtures separated from the chromatographic
column use is made of a detector 34 (for example, a katharometer)
adapted to deliver signals of certain value (depending upon the
amount of each component of the admixtures) to a recorder 35
serving to record said signals on plotting paper.
The inlet unit 25 is connected by the coupling nut 28 to the
cylinder 24 containing helium to be analyzed and a valve 36 (FIGS.
5, 6) of the cylinder 24 and the valve 30 are opened. After the
system has been given the required flush, the valve 30 is closed
and the control valve 29 and the outlet valve 32 are opened one
after another.
From the cylinder 24, through the control valve 29 and a flexible
metal tube 26, the gas is continually delivered into the comparator
chamber of the detector 34. Further, the gas passes through the
channel 17, packing bush 8, channel 13 and metal capillary tube 15,
and finally enters the chromatographic column 3. From the
chromatographic column 3 the gas passes through the metal capillary
tube 16, channel 14, packing bush 9 and channel 18, and finally
enters the working chamber of the detector 34. Through the outlet
valve 32 the gas is discharged from the detector 34 to atmosphere.
Now the following electrical connections are made: a tumbler switch
37 (FIG. 7) cuts in the mains voltage, a tumbler switch 38 makes
the circuit of the bridge, a tumbler switch 39 starts the electric
motor 10, a tumbler switch 40 cuts in the fan 23 and a tumbler
switch 41 makes the circuit of the heater 2. The rotary motion of
the electric motor 10 is transmitted through a reducing gear 42
(FIGS. 2, 3) to a driven gear 43 fixed on the shaft 5. By selecting
a proper gear in the reducer 42, the required speed of rotation of
the chromatographic column 3 is obtained. The sense of rotation is
opposite to the direction of the gas flow through the
chromatographic column 3. Further, the bath 1 is primed with the
refrigerant-- liquid nitrogen--and the flow rate of the analyzed
gas is adjusted with the aid of the control valve 29 and a soap
film flowmeter (not shown in the drawing) which is installed at the
chromatograph outlet.
As the chromatographic column 3 rotates (FIGS. 2 and 5) the
temperature field, having the gradient with an interval of from the
temperature of the refrigerant to the sorbent regeneration
temperature, moves in the direction of the gas flow. The
temperature field helps to separate and concentrate the admixtures
which separately pass to the working chamber of the detector 34, as
the chromatographic column 3 outlet enters the heater 2 zone.
As the chromatographic column 3 (FIGS. 3 and 6), made in the form
of a helical tube rotates, a number of temperature fields, each
having the temperature gradient with an interval of temperatures
from that of the refrigerant to the sorbent regeneration
temperature, move along the sorbent bed in the direction of the gas
flow. These temperature fields follow one after another, their
number being equal to the number of the helix coils.
In accordance with the number of the temperature fields, the same
number of zones move along the chromatographic column 3 in which
the admixtures are separated and concentrated. The amount of
admixtures accumulated in each zone, corresponds to the number of
admixtures contained in that part of the gas which enters the
chromatographic column 3 during one complete revolution.
Considering a specific case of analysis, let a gas, for example,
helium containing microadmixture of neon, oxygen, nitrogen and
methane be continuously passed through the chromatographic column 3
in a direction opposite to that of the column rotation.
The chromatographic column 3 rotates continuously within the
cooling and heating zones. At the same time, along the bed of
sorbent, there is moved a temperature field with a temperature
gradient ranging from minus 196.degree. C. to 350.degree. C. (when
using liquid nitrogen as refrigerant).
The direction of motion of the temperature field and the decrease
of temperature inside the latter (from plus 350.degree. to minus
196.degree. C.) coincides with the direction of flow of gas under
analysis, however, the rate of the gas flow is in all cases higher
than that of the temperature field displacement and depends upon
the desired sensitivity of the instrument.
With an appropriate type of sorbent, rate of gas flow and rate of
the column rotation, the bulk of the gas being analyzed, in this
particular case, helium, will freely pass through the bed of
sorbent in the temperature field, while admixtures will be
entrapped by the sorbent at their characteristic temperatures and
will concentrate in certain zones corresponding to various
components of the admixture.
Those zones occupy certain portions of the temperature field
(depending upon the admixture properties), are immovable with
respect to the refrigerant bath 1 and the heater 2 and move on the
bed of sorbent during rotation of the column 3.
Thus, during the whole period of one complete revolution of the
column 3, there will be taking place the concentration of the
admixture components in said zones and, at the moment the outlet of
the column 3 passes through said zones, all the components will
separately pass to the recording instrument 34, that is, the full
cycle of analyzing all the admixtures takes place during one
revolution of the column 3. The chromatogram of an analysis of
admixtures in helium is merely an example presented for clarifying
the mode of the chromatograph operation.
The above is equally true both for chromatographs with a column in
the form of an arc of a circle or a single helix coil, and for
chromatographs with a column made as several helix coils.
The coils following the first one serve to make up for a possible
passage of admixture components through the bed of sorbent in the
temperature field, for when a component passes through the bed of
sorbent in the first temperature field, it get to the bed of
sorbent in the second temperature field.
The first results of the analysis may be read from the instrument
after the chromatographic column 3 completes the number of
revolutions equal to that of the helix coils. Then the readings can
be obtained after each revolution, as the chromatographic column 3
outlet enters the heater 2 zone.
Before the chromatograph is taken out of operation, the refrigerant
is discharged from the bath 1, then the outlet valve 32, control
valve 29, and valve 36 of the cylinder 24 are closed one after
another. Finally, tumbler switches 37, 38, 39, 40 and 41 are turned
off.
The present chromatograph automatically determines admixtures in
low-boiling gases, for example in helium. No pure carrier gas is
required for the analysis. The chromatograph is free from
disadvantages inherent in the prior art instruments of the same
kind, in which gas sampling is employed. The chromatograph may
operate in the continuous process stream without changing over gas
streams or electrical circuits. Results of the analyses are
recorded on a paper chart at 6 minute intervals.
While a specific embodiment of the chromatograph has been disclosed
in the description, it will be understood that various
modifications and changes within the spirit of the invention may
occur to those skilled in the art. Those modifications and changes
are considered to be falling within the scope of the invention as
set forth in the appended claims.
* * * * *