U.S. patent number 3,675,466 [Application Number 05/065,215] was granted by the patent office on 1972-07-11 for sampling valve and system for the detection of predetermined compounds in air.
This patent grant is currently assigned to Hydronautics-Israel, Ltd.. Invention is credited to Amos Linenberg.
United States Patent |
3,675,466 |
Linenberg |
July 11, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
SAMPLING VALVE AND SYSTEM FOR THE DETECTION OF PREDETERMINED
COMPOUNDS IN AIR
Abstract
A sampling valve for use with a chromatographic column or any
other appropriate detection device for enabling the detection of
predetermined compounds in an ambient medium, such as air. The
valve includes a housing member having a plurality of apertures
therein for enabling respective communication with at least a
carrier medium, the ambient medium and the chromatographic column.
A movable valve body member is mounted within the housing and is
provided with a plurality of apertures for selective communication
with predetermined ones of the housing member apertures. A platinum
gauze member is retained within a predetermined one of the valve
body member apertures and is selectively exposed to the ambient
medium. The valve body member is then moved and the platinum gauze
member is heated to desorb the predetermined compound in the
presence of the carrier medium, such as helium, and the carrier
medium together with the predetermined compound are passed through
the chromatographic column to enable detection of the presence of
the predetermined compound.
Inventors: |
Linenberg; Amos (Rehovot,
IL) |
Assignee: |
Hydronautics-Israel, Ltd.
(Rehovot, IL)
|
Family
ID: |
22061116 |
Appl.
No.: |
05/065,215 |
Filed: |
August 19, 1970 |
Current U.S.
Class: |
73/864.82;
422/89; 73/23.42 |
Current CPC
Class: |
G01N
30/20 (20130101); G01N 2030/128 (20130101) |
Current International
Class: |
G01N
30/00 (20060101); G01N 1/00 (20060101); G01N
30/20 (20060101); G01N 30/12 (20060101); G01n
001/22 (); G01n 031/08 () |
Field of
Search: |
;73/23,23.1,421.5R,421.5A,422R,422GC,422TC ;23/232 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Queisser; Richard C.
Assistant Examiner: Snee, III; C. E.
Claims
What is claimed is:
1. In a detection device, a sampling valve for concentrating at
least one predetermined compound in an ambient medium
comprising:
a housing having a first aperture having an inlet and outlet end,
both communicating with the ambient medium and a second aperture
communicating with the detection device;
a valve body movably mounted within the housing and having a
V-shaped aperture therein for selective communication with the
housing apertures;
means for adsorbing said predetermined compound locatable in the
valve body aperture;
means for sequentially moving the valve body between a first
position where the valve body aperture communicates with the first
housing aperture to expose the adsorbing means located in the valve
body aperture to the ambient medium and to a second position where
the valve body aperture communicates with the second housing
aperture;
a tubular member in communicating relationship between the second
housing aperture and the detection device; said adsorbing means
passing into the tubular member when the valve body aperture is
moved to the second position from the first position;
means for selectively heating the adsorber means in the tubular
member to desorb the predetermined compound from the adsorber
means;
means for passing a carrier medium over the heated adsorber means
to pick up the desorbed compound and transmit it to the detection
device; and
means for returning the adsorbing means back to the valve body
aperture.
2. The device of claim 1, wherein the valve body aperture is sealed
to the ambient medium when in the second position.
3. The device of claim 1, in which the means for returning the
adsorbing means comprises:
a holder located within the tubular member for holding the
adsorbing means; and
means for selectively moving the holder within the tubular member
to impell the adsorbing means back into the valve body
aperture.
4. The device of claim 3, wherein the tubular member is inclined to
the vertical.
5. The device of claim 3, wherein the adsorbing means include a
substantially spherical mass of adsorptive material.
6. The device of claim 3, wherein the heating means includes an
oven surrounding the tubular member for selectively heating the
adsorbing means in its holder.
7. The device of claim 3, wherein the holder is of magnetizable
material and the moving means includes an electromagnet surrounding
the tubular member.
8. The device of claim 3, wherein the carrier medium is supplied to
the tubular member between the valve body and the holder.
9. The device of claim 8, including means for purging the valve
body aperture with the carrier medium as the valve body aperture
moves between said first and second positions.
10. The device of claim 9, where the purging means includes a purge
aperture in the housing that communicates with the valve body
aperture and permits the carrier medium to pass through the valve
body aperture.
11. A device for the detection of a predetermined compound in air
comprising:
a. a gas chromatographic column for separating compounds in a gas
stream;
b. detection means downstream from said column for indicating the
presence of said predetermined compound in the gas stream;
c. a sampling valve for concentrating the compound from the air and
transferring the compound from the air in an air-free atmosphere to
the gas column, said sampling valve comprising:
i. a valve housing having an air inlet and outlet, and a discharge
outlet communicating with the gas chromatographic column,
ii. a valve body movably mounted within the valve housing and
having an aperture therein for selective communication with the
housing's air inlet and outlet when the valve body is in a first
position and with the discharge outlet when the valve body is in a
second position,
iii. means for moving said valve between said first and second
positions, and
iv. adsorber means located within the valve body aperture for
adsorbing and concentrating the compound from air;
d. means for passing air through the valve housing and the valve
body aperture in said first position to expose the adsorber means
to the air;
e. purge means communicating the valve body aperture with a supply
of air-free carrier gas as the valve body passes through a position
intermediate said first and second positions to purge the valve
body aperture and the adsorber means of residual air;
f. heater means for selectively heating the adsorber means after it
has adsorbed the compound and been purged of residual air to desorb
the compound from the adsorber means; and
g. means for passing air-free carrier gas over the heated adsorber
means when the valve body aperture is in said second position to
pick up the desorbed compound and transmit it to the gas
column.
12. The device of claim 11 wherein said heating means include:
a storage capacitor;
leads in circuit with said adsorbing means and said capacitor;
and
a switch in circuit with said leads and said capacitor for enabling
the selective discharge of said capacitor through said adsorber
means.
13. The device of claim 11 wherein said adsorbing means include a
piece of platinum gauze or any other adsorptive material of any
metal or chemical fixidly mounted within the valve body
aperture.
14. The device of claim 11, wherein the purge means comprises a
carrier gas inlet and an outlet for the carrier gas in the valve
housing, said inlet and outlet communicating with the valve body
aperture as it passes through said intermediate position.
15. The device of claim 14, including a passage in the valve body
communicating with the carrier gas inlet and the discharge outlet
when the valve body is in said first position, said carrier gas
inlet also communicating with the valve body aperture when the
valve body is in said second position to transmit the desorbed
compound to the gas column, thereby maintaining a substantially
constant flow of carrier gas to the column.
16. The device of claim 15, wherein the carrier gas inlet comprises
a first aperture in the housing communicating with the valve body
aperture when said valve body is at said intermediate position and
a second aperture in the housing communicating with the valve body
aperture when the valve body is at said second position and with
the valve body passage when the valve body is at said first
position; said first and second apertures communicating with a
common supply of carrier gas.
17. The device of claim 11, wherein the adsorber means is retained
within the valve body aperture during exposure and heating.
18. A device for the detection of a predetermined compound in air
comprising:
a. a gas chromatographic column for separating compounds in a gas
stream;
b. detection means downstream from said column for indicating the
presence of said predetermined compound in the gas stream;
c. a sampling valve for concentrating the predetermined compound
from the air comprising a valve housing having an air inlet and
outlet and a discharge outlet communicating with the gas
chromatographic column;
d. a valve body movably mounted within the valve housing and having
a V-shaped aperture therein for selective communication with the
housing's air inlet and outlet when the valve body is in a first
position and with the discharge outlet when the valve body is in a
second position;
e. means for moving the valve body between said first and second
positions;
f. adsorber means located in the V-shaped aperture when the valve
body is in the first position for adsorbing and concentrating said
predetermined compound from the air;
g. a tubular member in communicating relationship between the
discharge outlet and the column, said adsorber means falling out of
the valve body aperture and into the tubular member when the valve
body is in the second position;
h. means for selectively heating the adsorber means to desorb the
compound from the adsorber means when the adsorber means is located
in the tubular member;
i. means for passing carrier gas over the heated adsorber means to
pick up the desorbed compound and transmit it to the detection
means; and
j. means for returning the adsorber means back into the valve body
aperture.
19. The device of claim 18 including means for purging the valve
body aperture of ambient medium as it moves between said first and
second positions.
20. The device of claim 19, wherein the carrier medium is supplied
to the tubular member and the purging means includes a purge outlet
in the valve housing, said valve body aperture communicating with
the purge outlet and the discharge outlet of the valve housing as
the valve body moves between said first and second positions to
flush the aperture and adsorber means of residual air.
Description
The present invention relates to a sampling valve and detector
system and more particularly to a sampling valve for use with a
chromatographic column or any other appropriate detection device
for enabling the detection of at least one predetermined compound
in an ambient medium, such as air.
Detection of specific organic or other compounds in air is required
for various scientific applications. With the recent increased
interest in the problems of pollution of the atmosphere, the
requirement for a suitable gas detection device has become
extremely important. The need for a highly sensitive, continuously
operating, portable, automatic, highly selective and versatile
compound detector is not only present in the field of pollutant
detection but is also a need which has existed for considerable
time in other areas, such as mine safety, where the detection of
explosive gases in the air is highly important for the safety of
lives and property.
Numerous attempts have been made to develop a suitable detection
device to detect specific compounds in air. Plasma chromatographic
detectors, mass spectrometers, U. V. and I. R. spectrophotometers,
fuel cells, gas chromatographs and various ionization detectors are
among the instruments that have been developed in attempting to
provide a highly sensitive, continuously operating, portable,
automatic, highly selective, and versatile detection device.
Although most of these instruments are used successfully in
particular fields, none of them satisfies all of the aforementioned
requirements which should be present in an instrument adapted to
accurately and conveniently detect specific compounds in air. Gas
chromatography seems to be the method with the widest range of
applications; however, two major problems are encountered when the
gas chromatograph is adapted to selective and sensitive detection
of organic compounds in air. These problems are sampling and
selectivity. High selectivity may be obtained by choosing a
suitable column and a selective detector, but sampling still
remains a problem.
Injection of air samples into a gas chromatographic column or any
other appropriate detection device is usually made with a syringe
or by use of a gas sampling valve. Although these methods and the
particular valves heretofore used have been found to be useful,
they have several important disadvantages. For example, air may
interfere when injected with the organic vapors to be analyzed, and
this interference is due to the high concentrations of nitrogen and
oxygen in air as compared to the low concentrations of organic
vapors that may be present.
A sudden injection of 5 or 10 cc of air may cause serious
interference in the flow rate of the carrier gas through the
chromatographic column, the stability of which is very important.
Furthermore, the maximum amount of 10 cc of air that may be
injected into the gas chromatograph is insufficient for sensitive
determinations of the presence of organic compounds. Air samples of
sizes of several liters must be injected to allow the detection of
quantities of one ppb and below.
It is, therefore, an object of the present invention to provide a
unique sampling valve for use with a chromatographic column or any
other appropriate detection device for enabling the detection of at
least one predetermined compound in an ambient medium, such as
air.
Another object is to provide a simply constructed, sturdy and
inexpensive sampling valve for use with a chromatographic column
system for enabling the detection of organic compounds in air.
A further object of the invention is to provide a highly sensitive,
selective and versatile apparatus for detecting the presence of
organic compounds in a large sample of air.
Additional objects and advantages of the invention will be set
forth in part in the description which follows, and in part will be
obvious from the description, or may be learned by practice of the
invention. The objects and advantages are realized and obtained by
means of the instrumentalities and combinations particularly
pointed out in the appended claims.
To achieve these objects, this invention provides apparatus that
embraces all the advantages of similarly employed detection devices
and possesses none of the aforedescribed disadvantages. As embodied
and broadly described the invention utilizes a single, unique
sampling valve, that together with a chromatographic system,
provides a highly sensitive detection system which has a minimal
response time and which is highly selective and versatile so that
it can be readily used for the detection of a number of compounds.
The device of this invention is also compact and portable and may
be operated automatically.
The sampling valve includes a housing member having a plurality of
apertures therein for enabling respective communication with at
least a carrier medium, an ambient medium, and a chromatographic
column. A valve body member is movably mounted within the housing
member and has a plurality of apertures therein for selective
movement into communication with predetermined ones of the housing
member apertures. In addition, the valve comprises means for
adsorbing a predetermined compound from the ambient medium, and
this adsorbing means, preferably platinum gauze, is in operative
relationship with the valve body member for being retained within a
predetermined one of the valve body member apertures at least
during selective exposure to the ambient medium. Means are also
provided in operative relationship for selectively heating the
adsorber means to desorb any compounds previously adsorbed by the
platinum gauze and the desorbed compounds are carried into the
through the chromatographic column by a carrier gas, such as
helium.
It should be understood that both the foregoing description and the
following detailed description are exemplary and explanatory and
are not restrictive of the invention.
The accompanying drawings illustrate examples of preferred
embodiments of the invention and together with the description
serve to explain the principles of the invention.
FIG. 1 is a sectional view of one embodiment of the sampling valve
of this invention in a first position which respect to a
chromatographic column;
FIG. 2 is a sectional view of the embodiment illustrated in FIG. 1
showing movement of an adsorber ball into the sampling valve;
FIG. 3 is a sectional view of the arrangement illustrated in FIG. 1
wherein the sampling valve is in a second position;
FIG. 4 is a sectional view of the embodiment shown in FIG. 1
representing return of the adsorber ball to a position adjacent the
chromatographic column;
FIG. 5 is a detailed view, partly in section, of another embodiment
of the sampling valve of this invention in a first position;
FIG. 6 is a view, partly in section, of the valve illustrated in
FIG. 5 in a second position;
FIG. 7 is a view, partly in section, of the sampling valve
embodiment shown in FIG. 5 and wherein the valve is in a third
position;
FIG. 8 is a section of the sampling valve taken on the line 8--8 of
FIG. 7 looking in the direction of the arrows;
FIG. 9 is a view, partly in section, of still another embodiment of
the sampling valve of this invention wherein the valve is in a
first position;
FIG. 10 is a view, partly in section, of the valve shown in FIG. 9
and wherein the valve is in a second position;
FIG. 11 is a view, partly in section, of the valve shown in FIG. 9
and wherein the valve is in a third position;
FIG. 12 is a partial section of the sampling valve taken on the
line 12--12 of FIG. 9 looking in the direction of the arrows;
FIG. 13 is a diagrammatic view of one embodiment of a detector
system of this invention; and
FIG. 14 is a diagrammatic view of another embodiment of a detector
system in accordance with this invention.
Basically, the detector system of this invention utilizes a valve
body member which is preferably made of polytetrafluoroethylene and
which is free to rotate in a housing member preferably made of
stainless steel. Other suitable materials can be used for the valve
body member and for the housing member. The housing member is
connected to a gas chromatographic column and is designed in such a
way that at one position ambient atmospheric air flows through the
valve while at a second position the valve is open to the
chromatographic column and closed to the ambient air.
A small ball of platinum gauze which may be coated with the
appropriate liquid phase is used for the adsorption of the
compounds to be detected. When air is forced through the valve and
through the porous ball, organic compounds, for example, will be
adsorbed by the ball while other gases will pass through the ball
without being adsorbed thereby. Selective adsorption is achieved
through the use of the proper phase as is well known in the art.
After adsorption is complete, the platinum ball is heated and all
the compounds previously adsorbed on the ball are immediately
desorbed and are carried into the chromatographic column by an
inert carrier gas, such as helium, for analysis and for indication
of the presence or absence of the compounds.
With specific reference now to the drawings, wherein like reference
characters designate like or corresponding parts throughout the
several views, there is shown in FIGS. 1-4 one embodiment of the
sampling valve of this invention in various positions of
operation.
A housing member 20 having a plurality of apertures 22, 24, 26, and
28 therein is mounted with aperture 26 in communicating
relationship with a chromatographic column 30 via a tubular member
32. Apertures 22 and 24 are in communicating relationship with an
ambient medium, such as the atmosphere, while aperture 28 is in
communicating relationship with a supply of carrier gas, such as
helium.
A valve body member 34 is movably mounted within housing member 20
to be rotated about a centrally located axis. Valve body member 34
has a plurality of apertures 36 and 38 therein which are in
communication with each other in a substantially V-shaped
configuration.
In accordance with the invention, means for adsorbing a
predetermined compound are provided in operative relationship with
valve body member 34 for being retained within a predetermined one
of the valve body member apertures at least during selective
exposure to the ambient medium or atmosphere. As here embodied, the
adsorbing means is a platinum gauze ball 40 which is normally held
within a magnetizable iron holder 42 located within tubular member
32. In accordance with this embodiment of the invention,
electromagnetic means are provided in operative relationship for
selectively moving holder 42 within tubular member 32 to cause the
adsorbing ball 40 to be impelled into a first one 38 of the valve
body member apertures. As here embodied, the electromagnetic means
is an electromagnet 44 which surrounds tubular member 32. The
invention also provides means in operative relationship for
selectively heating the adsorber means 40. As here embodied, the
heating means is an oven 46, a portion of which is illustrated in
FIGS. 1-4 and which is shown in its entirety in FIGS. 13 and 14.
The oven 46 encloses electromagnet 44 and at least a portion of
tubular member 32.
In operation of the sampling valve embodiment illustrated in FIGS.
1-4, the small platinum gauze ball 40 is initially situated in the
magnetizable (iron) gauze holder 42. The holder is at the lower end
of tubular member 32 and is surrounded by electromagnet 44. As
previously stated, the electromagnet and tube 32 are situated
within oven 46 so that the temperature of chromatographic column 30
and of the column inlet is controlled. The valve body member 34 is
rotated to a first position (the sampling position) whereby a first
one of the valve body member apertures 36 is sealed at one end by
housing member 20 while a second one of the valve body member
apertures 38 is in communication with chromatographic column 30 and
with tubular member 32. This position is illustrated in FIG. 1.
A plurality of voltage pulses are then applied to electromagnet 44
via two connections 50 and 51 so that iron gauze holder 42 together
with platinum gauze sphere 40 are caused to jump upwardly. As a
result, the ball 40 is thrown into valve body member 34 and into
the aperture 36 where it remains. Tubular member 32 and the entire
assembly illustrated in FIGS. 1-4, are preferably located at a
relatively slight angle with respect to the vertical so that
platinum gauze ball 40 is readily retained within aperture 36 (FIG.
2).
Valve body member 34 is then rotated clockwise until apertures 36
and 38 are in communication with apertures 24 and 22, respectively.
See FIG. 3. If air is then passed through the apertures and over
the platinum gauze ball, certain compounds, if present in the
atmosphere, will be adsorbed by the ball. Thus, air is
conventionally passed through the apertures by means of a pump 124
(FIGS. 13 and 14) which forces air through apertures 22, 38, 36,
and 24 so that platinum gauze ball 40 adsorbs the compound or
compounds which may be in the atmosphere and the detection of which
is desired.
After the atmosphere has been passed over platinum gauze ball 40
with valve body member 34 in the second position (FIG. 3) for the
desired length of time, valve body member 34 is rotated back to its
first or sampling position (FIG. 4) where the apertures 36 and 38
as well as ball 40 are sealed from the atmosphere and so that ball
40 will drop down to its original position within gauze holder 42.
Because the platinum gauze ball 40 is now located within the oven
46, any compounds which may have been adsorbed by the gauze ball
are immediately desorbed and are carried into chromatographic
column 30 by a carrier gas, such as helium entering through
aperture 28.
The presence of predetermined compounds in the atmosphere is then
determined by means of chromatographic column 30 together with
additional detection and indicating elements, which will be
described later with respect to FIGS. 13 and 14.
FIGS. 5-8 illustrate another embodiment of the sampling valve of
this invention. A housing member 20' is provided with a plurality
of apertures therein for enabling respective communication with at
least a carrier medium, an ambient medium, such as the atmosphere,
and a chromatographic column. As here embodied, housing member 20'
includes apertures 52 and 54, which are in communication with a
carrier gas, such as helium. Additional apertures 56 and 58 are
provided in communication with the ambient medium, such as air. A
purge aperture 60 is also provided in communication with the
ambient medium and an aperture 62 is provided in communication with
chromatographic column 30.
Valve body member 34' is movably mounted within housing member 20'
and includes a plurality of apertures therein for selective
movement into communication with predetermined ones of the housing
member apertures. As here embodied, valve body member 34' includes
apertures 64 and 66 which are in different planes with respect to
one another and which may be perpendicular with respect to one
another. Although apertures 64 and 66 are shown and described as
being perpendicular with respect to one another, it should be
understood that they need not be perpendicular and that they can be
oriented at any number of angles with respect to one another as
long as the apertures in the housing member 20' are appropriately
located.
As illustrated in FIG. 8, housing member 20' includes two keyways
70 and 72 in communication with apertures 54 and 62 for enabling
selective communication of each of the valve body member apertures
64 and 66 with housing member apertures 54 and 62 whereby flow of
the carrier medium through the chromatographic column is maintained
substantially constant during operation of the valve. This feature
will be explained in more detail infra where the operation of this
valve embodiment is set forth.
In this embodiment, platinum gauze ball 40' is captured within
valve body member aperture 64. A storage capacitor 74, for example,
or any other suitable electrical energy storage means, is
electrically coupled to platinum gauze 40' via leads 76 and 78, and
a switch 80 is located in circuit with capacitor 74 together with
an electrical source 82 whereby capacitor 74 is selectively charged
by energy source 82 and discharged by closing of the switch 80.
Capacitor 74 through leads 76 and 78 is utilized to heat the gauze
since the gauze is not dropped into the oven, as was the case with
the embodiment illustrated in FIGS. 1-4. In addition, gauze 40'
need not be spherical in shape but may be of a flat configuration,
for example.
In operation of the sampling valve embodiment shown in FIGS. 5-8,
valve body member 34' is rotated to a first position as shown in
FIG. 5, valve body member aperture 64 is in communication with
housing apertures 56 and 58 and with the atmosphere or ambient
medium. At the same time second valve body member aperture 66 is in
communication with keyways 70 and 72 and with housing apertures 54
and 62. In this first position the carrier gas, such as helium,
passes through tube 90, aperture 54, aperture 66 and aperture 62 so
as to pass into and through chromatographic column 30.
Simultaneously, air from the ambient medium is drawn through
apertures 56, 64, and 58 by means of a pump (124 in FIGS. 13 and
14) so that air passes through platinum gauze 40' whereby certain
compounds that are present in the atmosphere are adsorbed by the
gauze.
Accurate temperature control and a steady carrier gas flow rate
through chromatographic column 30 are required to obtain accurate
and reproducable results in the detection of predetermined
compounds. Accordingly, an important feature of this embodiment of
the sampling valve is that it provides a substantially continuous
and steady carrier gas flow rate through the chromatographic column
via aperture 66 even when the platinum gauze 40' is being subjected
to the atmosphere.
After gauze 40' has been exposed to the air for the desired length
of time valve body member 34' is rotated clockwise to the position
shown in FIG. 7. Before reaching that position, however, valve body
member 34' passes through a second position (FIG. 6) whereby first
valve body aperture 64 containing the gauze ball 40' is placed in
communication with the carrier medium via apertures 52 and 60
whereby first aperture 64 is flushed of any residual air from the
atmosphere by means of the carrier gas. At this position second
aperture 66 is sealed by housing member 20'. By flushing the
apertures the accuracy of the results is markedly enhanced since
all air is expelled from the system prior to the desorbing step. In
this way, extraneous readings are avoided and only the presence of
the predetermined compound as it is absorbed from the platinum
gauze 40' is detected as it passes through the chromatographic
column 30. The ball 40' is not heated at this time so the carrier
gas does not flush out any of the compounds adsorbed by the
ball.
Valve body member 34' is then rotated to the third position (FIG.
7) and first aperture 64 is placed in communicating relationship
with the carrier medium via aperture 54 and with the
chromatographic column via aperture 62. The second valve body
member aperture 66 is offset and is not in communication with
housing apertures 56 and 58 and is therefore sealed by housing
member 20' when the valve body member is in the third position.
The flow of carrier gas from tube 90 into column 30 is interrupted
only for the very short time that it takes for valve body member
34' to rotate approximately 90.degree. from its first position
(FIG. 5) to its third position (FIG. 7). Thus, substantially
constant gas flow through the chromatographic column 30 is
maintained.
In the third position (FIG. 7) carrier gas flow through aperture
54, aperture 64, platinum gauze 40', aperture 62 and into and
through chromatographic column 30. As soon as valve body member 34'
reaches the third position, switch 80 (FIG. 8) is closed so that
capacitor 74 is discharged and the current passing through platinum
gauze 40' heats it so as to desorb any compounds which had
previously been adsorbed thereby. The carrier gas together with the
desorbed compounds then pass through the chromatographic column 30
and the presence of the compounds is determined by the determining
and indicating means shown and described in more detail with
respect to FIGS. 13 and 14.
In accordance with a third embodiment of the invention, as
illustrated in FIGS. 9-12, a housing member 20" is provided which
has a plurality of apertures therein for enabling respective
communication with at least a carrier medium, an ambient medium
such as air, and a chromatographic column. As here embodied, the
housing member 20" includes apertures 92 and 94, which are in
communicating relationship with the ambient medium or atmosphere.
In addition, housing member 20" includes a purge outlet or aperture
96 which is also in communicating relationship with the atmosphere.
An aperture 26' is in communicating relationship with
chromatographic column 30, and aperture 28' is provided in
communicating relationship with the carrier medium or gas, such as
helium.
Valve body member 34" of this embodiment has first and second
apertures 102 and 104, respectively, which are in a substantially
V-shaped configuration with one another. The second aperture 104 is
closed at one end 106 thereof, and a purge aperture 108 is provided
in communicating relationship with the V-shaped configuration. In
addition, a support member 110 is located across purging aperture
108 and adjacent to apertures 102 and 104 for holding the platinum
gauze ball when valve body member 34" is in a third position (FIG.
11).
As illustrated in FIG. 12, valve body member 34" of the embodiment
illustrated in FIGS. 9-12, has a tapered cross section for enabling
a better sealing fit within housing member 20". This configuration
also represents a preferred arrangement for the previously
described embodiments. Body member 34" is provided with an
extension 112 which has a member 114 fitted thereover and a knob
116 attached thereto for enabling manual rotation of valve body
member 34" about the axis 118.
In operation of the embodiment illustrated in FIGS. 9-12, the small
ball of platinum gauze is initially located in the cylindrical iron
holder 42. As in the embodiment of FIGS. 1-4, the holder is located
at the lower end of tubular member 32 which is surrounded by
electromagnet 44. The electromagnet and the tubular member are both
located in an oven 46 in which the temperature is controlled by a
temperature controller 121 (FIGS. 13 and 14). The valve is first
positioned as illustrated in FIG. 9. In the first position the
first one of the apertures 102 is in communication with tubular
member 32 and with chromatographic column 30 while purge aperture
108 is sealed at one end by housing member 20".
A plurality of voltage pulses are applied to electromagnet 44 via
leads 50 and 51, and iron gauze holder 42 is caused to jump
upwardly so as to throw the platinum gauze ball 40 into the valve
body member 34" and into closed aperture 104 where it remains. If
desired, the entire assembly, as illustrated in FIGS. 9-12, may be
located at an angle with respect to the vertical so that the gauze
ball is readily retained within the closed aperture 104.
Valve body member 34" is then rotated clockwise to a second
position, as illustrated in FIG. 10, to enable purge aperture 108
to be in communication with purge outlet 96. At the same time,
first aperture 102 in the V-shaped configuration is still in
partial communication with the carrier medium and aperture 28' so
that the carrier gas passes through aperture 102 and through purge
aperture 108 to purge the valve body member of any residual gases
prior to sampling which might remain therein. Valve body member 34"
is then rotated to a third position (FIG. 11) so that the first
aperture 102 is in communication with the atmosphere and with
housing aperture 92 and so that purge aperture 108 is in
communication with the atmosphere and with housing aperture 94. The
platinum gauze ball 40 falls onto and is supported by support
member 110.
With valve body member 34" in the third position (FIG. 11) the
ambient medium, such as air, is caused by means of a pump 124
(FIGS. 13 and 14) to pass through apertures 92, 102, 108, and 94.
If certain compounds are present in the atmosphere it will be
adsorbed on the gauze ball 40.
The valve body member 34" is then rotated in a counter-clockwise
direction from its position as illustrated in FIG. 11, and as
member 34" passes through the second position (FIG. 10) the carrier
gas again purges apertures 102, 104, and 108 of air to avoid
contamination of chromatographic column 30. Member 34" continues to
rotate in the counterclockwise direction until the first position
(FIG. 9) is reached. The platinum gauze ball then drops from its
position on support member 110 down and through tubular member 32
until it comes to rest within gauze holder 42. Any compounds which
may have been adsorbed by the platinum ball are desorbed
immediately within the heated environment of oven 46 and are
carried into chromatographic column 30 by the carrier gas which
passes into tubular member 32 via aperture 28.
In each of the three embodiments heretofore described organic
compounds that may have been adsorbed by the platinum gauze are
desorbed immediately when subjected to a preselected heat, and the
valve body member rotates back to the sampling position to again
expose the platinum gauze to the atmosphere and to accept another
sample. By the time the compounds reach the detector 138 (FIG. 14)
associated with the chromatographic column, a new sample will be
ready for injection. Thus, the entire cycle (retention time) will
last only as long as it takes for the compounds to reach the
detector 138 from the time of injection into the column.
The sampling apparatus of this invention and the sampling valve can
be operated completely automatically by means of systems as
illustrated in FIGS. 13 and 14.
The embodiment of FIG. 13 includes an automatic control circuit
120, which may be a conventional timing circuit and which acts as
the master control for operation of the entire system. In
operation, a motor 122 is activated to rotate the sampling valve of
this invention to the sampling position. Depending upon whether the
valve is of the embodiment illustrated in FIGS. 1-4, FIGS. 5-8, or
FIGS. 9-12, the platinum gauze is already located within the valve
or a series of voltage pulses applied to the electromagnet 44 cause
the iron gauze holder to jump upwardly so that the ball is thrown
into the valve body member where it is trapped. Motor 122 is again
activated by automatic control circuitry 120 and rotates until
stopped by a controlling microswitch (not shown) so that the
platinum ball is exposed to the atmosphere and air is passed
through the ball by means of fan 124.
After adsorption is complete, the valve rotates backwardly until it
is stopped by another controlling microswitch (not shown) at such
an angle that the ball drops down to its initial position, or in
the case of the embodiment of FIGS. 5-8, the ball is placed in
communication with the carrier gas and with the chromatographic
column. The ball is then heated so that any compounds which may
have been adsorbed by the platinum gauze are now desorbed
immediately and carried into the chromatographic column by the
carrier gas, which enters from aperture 28 and which is supplied by
carrier gas supply 124. Simultaneously, recorder 126 is activated
by automatic control circuitry 120 for a specified time, e.g. 1-3
minutes.
The compounds and carrier gas advance along the separation column
and the flow rate of the carrier gas through the column remains
constant. Both temperature and flow rate are chosen in each case in
accordance with the characteristics of the specific compound to be
detected. Any compound will reach the end of the chromatographic
column at a particular fixed time, depending upon the temperature
and flow rate and on the column packing, and this time is specific
to each compound.
Downstream of the column the compound reaches a conventional
ionization detector (not shown). This detector responds to organic
compounds by generating a current which is displayed on recorder
126 after being amplified by an electrometer amplifier 140.
Another arrangement for detecting the presence of compounds in air
is shown in FIG. 14. This particular apparatus is illustrated in
combination with the sampling valve of FIGS. 1-4 or of FIGS. 9-12;
however, the sampling valve embodiment illustrated in FIGS. 5-8
could be readily utilized with this system.
In operation of the system shown in FIG. 14, the ball of platinum
gauze 40 is thrown upwardly into the valve and is trapped there as
previously explained. Movement of the ball is observed by a
photoelectric cell 130, which is located under the valve. The
tubular member 32 in this embodiment has two windows 132 which
allow a beam of light from a small bulb 134 to reach the
photoelectric cell 130. A signal is generated each time the ball,
moving upwardly, intercepts the beam, and a different signal
results when the ball moves downwardly.
After the ball is received by the valve, motor 122 is activated to
rotate the valve until it is stopped by a controlling microswitch
(not shown). The platinum ball is then exposed to the atmosphere
and air containing the sample is passed through the ball by means
of the pump 124. During this operation the carrier gas (helium)
enters column 30 through the aperture 28 at the lower end of the
valve so that the flow of carrier gas through the column is not
affected by rotation of the valve. This is true for the valve
embodiments of FIGS. 1-4 and of FIGS. 9-12 while the helium flow is
only slightly interrupted as the valve body member of the
embodiment shown in FIGS. 5-8 rotates 90.degree..
After the air is passed over the ball and the compounds have been
adsorbed thereby, the motor is activated so that the valve rotates
in a backward direction until the system is stopped by another
controlling microswitch (not shown) so that the ball drops down
into its initial position within the gauze holder 42. The ball
movement is again observed by the photoelectric cell 130. Any
compounds which may have been adsorbed by the platinum ball are
desorbed immediately as a result of the heat applied by the oven 46
and are carried into the column 30 by the carrier gas originating
from the source 124.
The gases from the platinum advance along the column, which is kept
at a constant temperature. As one example, the column may be made
of polytetrafluoroethylene tubing 30 cm long and 1 1/2 mm I. D. and
is packed with 15 percent D.E.G.S. on 60-80 chromosorb W.A.W. The
flow rate of the carrier gas through the column 30 is constant and
both the temperature and flow rate are chosen in each case to
identify the specific compound sought to be detected. Any compound
will reach the end of the column 30 at a particular fixed time,
depending upon the temperature and flow rate and in other cases the
column packing. This time is characteristic for each compound.
At the end of the column the compound reaches a conventional
ionization detector 138. This detector responds to organic
compounds by generating a current which is displayed on recorder
126 after being amplified by electrometer 140'. Thus, if a compound
is present the recorder will indicate its presence to the
operator.
Because the time required for each compound to reach the end of the
column 30 is specific and depends on the temperature and gas flow
conditions, this time may be used for identification. An alarm
system is connected in parallel to the recorder and is activated
when a peak signal arrives in order to indicate when a specific
compound is present in the atmosphere.
The present invention, thus, provides for a unique sampling valve
and for unique apparatus for detecting the presence of compounds in
the atmosphere wherein the device is highly sensitive, has a short
time response, is portable, automatic, highly selective, and
versatile and wherein a gas chromatograph or any other suitable
detection device is utilized to enable the detection of extremely
low concentrations of organic vapors in the atmosphere.
The invention in its broader aspects is not limited to the specific
details shown and described and departures may be made from such
details without departing from the principles of the invention and
without sacrificing its chief advantages.
* * * * *