U.S. patent number 3,788,479 [Application Number 05/243,729] was granted by the patent office on 1974-01-29 for disc conveyor flame ionization detectors.
This patent grant is currently assigned to Shell Oil Company. Invention is credited to Julius J. Szakasits.
United States Patent |
3,788,479 |
Szakasits |
January 29, 1974 |
DISC CONVEYOR FLAME IONIZATION DETECTORS
Abstract
Effluent to be tested is deposited on a porous alumina disc, the
disc being rotated into a heater where the eluent is vaporized
leaving a residue (the sample) whereupon the sample is then
transported by the conveyor into a dual jet flame ionization
detector (FID). After passing through the FID the disc then passes
through an oxidizer where any remaining residue from the disc are
removed by oxidation whereupon the disc then passes through a
cooler, cooling the disc prior to the disc returning to a point
where more effluent will be deposited for further analysis.
Inventors: |
Szakasits; Julius J. (Deer
Park, TX) |
Assignee: |
Shell Oil Company (Houston,
TX)
|
Family
ID: |
22919891 |
Appl.
No.: |
05/243,729 |
Filed: |
April 13, 1972 |
Current U.S.
Class: |
210/198.2;
73/23.25; 422/78; 210/179 |
Current CPC
Class: |
G01N
30/68 (20130101); G01N 2030/8417 (20130101) |
Current International
Class: |
G01N
30/00 (20060101); G01N 30/68 (20060101); G01N
30/84 (20060101); B01d 015/08 () |
Field of
Search: |
;55/67,197,386,389,76
;210/31C,198C,179 ;73/23.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Adee; John
Attorney, Agent or Firm: Theodore E. Bieber et al.
Claims
I claim:
1. A chromatographic device comprising:
a circular disc conveyor mounted for rotation about a central
axis;
means for rotating said conveyor at substantially constant speed
about said central axis;
an applicator, said applicator being positioned adjacent the path
of said disc to deposit eluents from a liquid chromatographic
column near the outer edge of said conveyor;
a heater, said heater being disposed adjacent the path of the outer
edge of said conveyor, spaced from said applicator in the direction
of rotation of said conveyor and adapted to flash evaporate eluent
carried by said conveyor;
a flame ionization detector, said detector being disposed adjacent
the path of the outer edge of said conveyor to direct its flame
onto said conveyor;
an oxidizer, said oxidizer being disposed adjacent the path of the
outer edge of said conveyor and adapted to burn impurities carried
by said conveyor after said conveyor passes through said flame
ionization detector; and
a cooler, said cooler being disposed adjacent the path of the outer
edge of said conveyor adapted to cool said conveyor subsequent to
said conveyor passing through said oxidizer.
2. The apparatus of claim 1 wherein said circular disc conveyor is
of alumina.
3. The apparatus of claim 1 wherein said applicator is a Teflon
covered stainless steel syringe needle.
4. The apparatus of claim 1 further including an enclosure
substantially enclosing said flame ionization detector and
oxidizer, said enclosure being continuously purged with
nitrogen.
5. The apparatus of claim 1 further including an exhaust and cooler
blower for exhausting from said heater and said cooler, said
blowers being in fluid communication with said heater and said
cooler.
6. A chromatographic device comprising:
a circular disc, said disc being rotatably mounted on its central
axis;
a drive means coupled to said disc for rotating said disc at a
substantially constant speed;
an applicator, said applicator being mounted to deposit the eluents
from a liquid chromatographic column on the flat surface of the
disc adjacent the outer periphery thereof;
a heater, said heater having a passageway with a U-shaped
cross-section and mounted with the legs of said passageway
extending along the surfaces of said disc adjacent the periphery
thereof;
a flame ionization detector, said flame ionization detector having
a passageway with a U-shaped cross-section and mounted with the
legs extending along the surfaces of said disc adjacent the outer
periphery thereof;
an oxidizer, said oxidizer having passageway with a U-shaped
cross-section and mounted with the legs extending along the
surfaces of the disc adjacent the periphery thereof; and
a cooler, said cooler being disposed to cool both sides of said
disc adjacent the outer periphery thereof.
7. The chromatographic device of claim 6 wherein the passageway in
said heater has sufficient length to cover substantially
twenty-five percent of the periphery of said disc.
8. The chromatographic device of claim 6 wherein said flame
ionization detector utilizes a pair of nozzles to direct a flame
onto both sides of said disc.
Description
BACKGROUND OF THE INVENTION
The present invention relates to chromatographic devices and more
particularly to a chromatographic device using an alumina disc as a
sample carrier. The flame ionization detector has been combined
with a porous disc conveyor, on which a wide range of molecular
weight samples eluted from a liquid chromatographic column or other
source can be deposited and detected. This porous conveyor
eliminates the spiking noise usually associated with metal
conveyors (wire, belt or chain) produced as a result of sample back
diffusion along the metal conveyor.
DESCRIPTION OF THE PRIOR ART
By and large with commercially designed detectors either the total
effluent or a portion of it is deposited on a conveyor of some
type. The eluent is then flash evaporated in a heater leaving a
sample material on the conveyor. One method of detection involves
burning the sample material directly in the flame as the conveyor
passes through the detector. An alternate and most frequently used
concept removes the sample material by pyrolysis in a purged
enclosure from which the pyrolysis products are swept into a FID.
This technique is widely used in commercial detectors because it is
easier to achieve a better signal to noise ratio than is possible
with the direct burning technique. Nevertheless sample diffusion on
hot metal conveyors which manifest itself in the form of signal
spikes is still present with many of the pyrolysis designs. The
noise problem is more evident with all designs when broad peaks are
observed, as frequently encountered in gradient elution
fractionation and gel permeation chromatography. A U.S. Pat. No.
3,316,674 issued to Owens et al. illustrates using a perforate
metal support such as a platinum screen for a conveyor. When using
a metallic or glass surface, the sample deposited by the applicator
creeps as the conveyor enters the flame ionization detector which
results in back-mixing and noisy peaks in the readout. Another
disadvantage in using a metallic strip as a conveyor is that it
distorts due to the heat added during detection of the sample
causing the sample to creep even further than when deposited by the
applicator on the metal conveyor.
It has been the practice in the past for the applicator to be made
from a metal or glass tube preventing a uniform deposit of all of
the effluents on the conveyor without back diffusion or wetting
along the external surface of the applicator tubing (capillary
action). This behavior causes both loss and back-mixing. Sample
loss occurs when the carrier solvent vaporizes to deposit the
sample material in the form of rings 3 to 5mm above the tip. The
extent of this wetting will vary at constant flow rate and is
manifested by a slow pulsation along the applicator tube. As a
result, a portion or all of the sample material deposited by one
pulse can be diluted subsequently by a more extensive pulse which
dissolves and carries it down to the applicator tip, while placing
a new sample ring at a higher position. After analysis, a ring at
maximum wetting level is observed on glass and stainless steel
applicators. Therefore, the use of such applicators as shown by the
prior art devices causes a substantial variation in the analysis
results.
Prior art devices also do not reveal how to ensure against residue
build-up on the conveyor as a result of the vaporization process
leaving a residue on the conveyor resulting in eventual plugging of
the pores of whatever conveyor type is used. This is not a problem
with normal samples, however, when samples like pitch are analyzed,
a non-detectable carbonaceous residue is left on the conveyor which
can result in eventual plugging of the pores causing sample creep,
back-mixing and noisy peaks in the readout equipment.
An even further problem with the prior art devices is that cooling
of the conveyor is not accomplished other than by normal room air
currents. If the disc conveyor is not adequately cooled this
results in loss of sensitivity for lower boiling eluents such as
pentane, and increased base line instability or noise.
Prior art devices also corporate a single nozzle for the flame
ionization detector whereas if dual nozzles are used, uniform
coverage is accomplished eliminating sample blowout which is caused
when only one flame is used causing further loss of instrument
sensitivity and meaningful analysis results.
SUMMARY OF THE INVENTION
The present invention solves the above problems by incorporating a
disc conveyor preferably formed of alumina and having a high
apparent porosity approximating 40 percent which provides an
excellent conveyor for the sample as it is eluted from the
applicator. An even further advantage of the alumina disc conveyor
is its dimensional stability under the application of the heat in
the heater, FID and oxidizer assemblies.
A second significant advantage of the present invention is through
the use of an applicator in which a metal tip having a
polytetrafluoroethylene (trademark for Teflon) covered outer
surface. By so doing, the present invention has eliminated both
sample loss and back-mixing problems as described hereinabove.
A third advantage of the present invention is in the use of a dual
nozzle flame ionization detector resulting in uniform heating of
the disc conveyor yielding higher response and eliminating sample
blowout.
A further advantage of the present invention is through the
incorporation of an oxidizer downstream of the flame ionization
detector. By use of an oxidizer, the conveyor is burned clean of
any residues left after passing through the detection device
preventing residue build-up.
An even further advantage of the present invention is incorporation
of a cooler which surrounds the edge of the disc conveyor. Use of
the cooler extends the range of the detector to lower boiling point
eluents such as pentane greatly increasing sensitivity and base
line stability.
DESCRIPTION OF THE DRAWINGS
The present invention will be more easily understood from the
following detailed description of a preferred embodiment when taken
in conjunction with the attached drawings in which:
FIG. 1 is a pictorial view of the apparatus constructed according
to this invention;
FIG. 2 is an exploded view illustrating the flame ionization
detector and oxidizer according to the present invention;
FIG. 3 is a cross-sectional view of the disc conveyor; and
FIG. 4 illustrates the stable base line and descriptive peaks
obtained when using the apparatus of the present invention.
DESCRIPTION OF A PREFERRED EMBODIMENT
Referring to FIG. 1, there is shown the apparatus constructed
according to the invention and particularly adopted for
quantitative measurements of eluents from a liquid chromatograph.
More particularly, there is shown a control panel 30 in which a
preferred embodiment of the present invention is mounted comprising
essentially the disc conveyor 29, the applicator 27, the eluent
heater and exhaust assembly 25, the flame ionization detector and
oxidizer assembly 50, and the disc cooler assembly 31.
An ideal applicator uniformly deposits all of the effluent on the
conveyor 29 without back diffusion or wetting along the external
surface of the applicator wall. Stainless steel and glass tubing
have a high level of external wetting causing sample loss and
back-mixing. To eliminate sample loss and back-mixing the
applicator 27 is made from a teflon covered stainless steel syringe
needle resulting in excellent eluent deposition and width control
for deposition of the sample on the conveyor 29.
The disc conveyor 29 is preferably made of alumina because of its
excellent dimensional stability in the presence of heat as well as
its uniform porosity distribution. The use of an alumina disc as
the conveyor solves many of the problems inherent in prior art
devices using metallic as well as glass as conveyors, namely,
dimensional stability and sample containment after being deposited
on the conveyor. The general shape of the disc conveyor 29 is shown
in FIG. 3 and is shown as having a central bore 58 therethrough
with a flat lower surface. The outer flat surface 51 of the
conveyor 29 carries the eluted sample as deposited by the
applicator 27. Optional holes 52 may also be provided in the disc
conveyor 29 further lowering the thermal inertia of the conveyor
29. The disc conveyor is mounted on a shaft 48 and retained on the
shaft 48 by a keeper 49. The shaft 48 forms part of a variable
speed reversible D.C. motor 49 mounted on the back of control panel
30. The incorporation of a reversible variable speed motor allows a
stable base line to be established by reversing direction of
rotation of the conveyor 29 through the oxidizer burning any
residue left on conveyor 29. In operation, as the disc conveyor
rotates clockwise at constant speed an eluent from a
chromatographic column is deposited on the conveyor 29 by the
applicator 27. The position of the applicator 27 relative to the
conveyor 29 is controlled by two micrometer type adjustments 28 and
28a, one being adapted to position the applicator 27 over the
conveyor and the other serving to control the distance between the
applicator and the surface 51 of the conveyor 29.
Once the sample has been deposited on the conveyor 29 it next
passes into the eluent heater and exhaust assembly 25 where the
eluent is flash evaporated leaving the sample on the conveyor 29.
The heater and exhaust assembly covers approximately 25 percent of
the circumference of the disc conveyor 29 and is supported by an
exhaust duct 60 which is in turn connected to the heater exhaust
blower 10. The blower 10 pulls room air over the conveyor 29 and
through duct 60 giving a definite exhaust pattern eliminating
hydrocarbons from diffusing into the detector. The heating element
56 is a screw-plug type element with power regulation furnished by
a silicon-controlled rectifier (SCR) with the temperature being
controlled up to 250.degree. C.
Subsequent to being flash evaporated in the heater and exhaust
assembly 25 the sample to be analyzed next passes through the flame
ionization detector (FID) and oxidizer assembly 50. The assembly 50
as positioned relative to the disc conveyor 29 by a second set of
micrometer adjustments 13 and 14 providing both horizontal and
vertical adjustment capability.
The FID and oxidizer assembly 50 is made up of a housing 70 which
preferably has two chambers 42 and 43. The FID chamber 42 is
provided with bores 72 and 73 for receiving bushings 40 having an
eccentric bore 75 therethrough. Prior to installing bushings 40
into bores 72, 73 an FID nozzle 22 is inserted through bore 75 of
bushing 40 and locked in place with set screw 41. Subsequently, the
bushing 40 with nozzle 22 is installed in bores 72, 73 and
positioned approximately 2-10mm from the edge of the conveyor 29
prior to locking the bushing 40 in place by a second set screw 36
installed in housing 70.
A collector 37 is also positioned within the FID chamber 42. The
collector 37 consists of semi-circular rings approximately 1.8 cm
in diameter spaced 3mm apart and positioned approximately 2mm ahead
the FID nozzles 22. The collector 37 is positioned in the FID
chamber 42 using a bushing 38 through which an insulator 39 passes.
A set screw 37 installed in housing 70 contacting bushing 38 allows
the final adjustment of collector 37 relative to the FID nozzles 22
and conveyor 29. A view port 23 is provided in the housing 70 to
aid in positioning the detector relative to the conveyor 29.
As hereinbefore described the FID nozzles 22 are grounded to the
housing 70. The collector 37 is insulated from the housing 70 by
insulator 39. The collector lead wire 85 is connected in series
with a 300 volt battery (not shown) which in turn is connected in
series with an electrometer thus maintaining a positive collector
with respect to the FID nozzles 22. Both the collector 37 and FID
nozzles 22 are fabricated from platinum resulting in very low
thermonic noise emission (approximately 10.sup.-.sup.16
amp/cm.sup.2 at 1,200.degree. C).
The oxidizer chamber 43 is immediately above the FID chamber 42 and
separated from it by a partitioning element 90. Two oxidizer
nozzles 24 are inserted through perforations 91 in the housing 70
and each is locked in place by a set screw 36 installed in housing
70. The oxidizer chamber 43 is provided with two vent holes 92
allowing venting of excess heat from the chamber 43. By providing
an oxidizer chamber a "clean" conveyor is assured by the burning of
any residues left on the conveyor after passing through an FID
chamber making the apparatus more versatile and reliable.
An end plate 71 (FIG. 2) encloses the housing 70 opposite the
conveyor 29. The end plate 71 is provided with an upper cavity 102
with a shoulder 104 against which a sintered stainless steel disc
106 abuts. A lower cavity 103 with a shoulder 105 and sintered
stainless steel disc 107 are disposed in the lower portion of end
plate 71. A plurality of screws 111 mate end plate 71 with the
housing 70. Air is supplied to the upper cavity 102 by an air inlet
fitting 33 threadably inserted in a tapped hole 100. Likewise, air
is supplied to the lower cavity 103 through an air inlet fitting 21
threaded in a tapped hole 101. By supplying pressurized air to
cavities 102 and 103 covered with sintered stainless steel disc,
air is supplied at a low velocity such that laminar flow exists
insuring a steady flame in both the FID and oxidizer chamber. By
providing this laminar flow the present invention overcomes a
further disadvantage of prior art apparatus (point source type air
inlet).
Referring again to FIG. 1, a plurality of splitter valves having
one inlet and two outlets are shown. These valves are utilized to
facilitate detector (FID) and oxidizer split ratio for hydrogen and
air. Teflon tubes interconnect the various fittings for the supply
of air and hydrogen in appropriate volumes. Tube 115 connects
fitting 17 to fitting 33 thereby supplying air to the oxidizer
chamber. Tube 116 connects 18 to 21 supplying air to the FID
chamber. Tube 117 likewise interconnects fitting 20 to one of the
two FID nozzles 22 to supply hydrogen to the FID chamber.
Similarly, tube 118 interconnects 20a to the second nozzle 22.
Finally, tubes 119 and 120 interconnect fittings 19, 19a with
oxidizer nozzles 24 supplying hydrogen to the oxidizer chamber
43.
An enclosure 16 having a hingably mounted cover completely encloses
the FID and oxidizer assembly and the fittings hereinbefore
described. The enclosure is continuously purged with nitrogen
supplied through fitting 15 mounted in the control panel 30. By
enclosing the FID and oxidizer, background noise produced from room
air currents is eliminated further increasing instrument
sensitivity and reliability.
A further advantage of the present invention is through the
incorporation of a disc cooler assembly 31 which greatly extends
the range of the instrument to lower boiling point eluents such as
pentane. The assembly 31 is mounted on the control panel 30 having
an opening 124 in communication with a duct 125. A cooler exhaust
blower 34 draws large volumes of room air over the conveyor 29
exhausting room air is indicated by the arrows 35. Alternately, if
the room air temperature is higher than desired a fitting 130 is
provided in the disc cooler assembly 31 whereby nitrogen can be
supplied aiding in cooling of the conveyor 29. The disc cooler
eliminates residual heat in the conveyor and prevents vaporizing of
the eluent upon contact when deposited by the applicator 27 on
conveyor 29. Premature vaporizing will partially or completely
carry the sample material away with the vaporized eluent destroying
any meaningful results of the analysis. The use of a cooler further
increases sensitivity and base line stability of the
instrument.
* * * * *