U.S. patent number 3,897,213 [Application Number 05/386,259] was granted by the patent office on 1975-07-29 for automated quantitative analysis of ionic species.
This patent grant is currently assigned to The Dow Chemical Company. Invention is credited to William H. Parth, Timothy S. Stevens.
United States Patent |
3,897,213 |
Stevens , et al. |
July 29, 1975 |
Automated quantitative analysis of ionic species
Abstract
Integrated system for quantitative analysis, using ion exchange
resins, of ionic species, typically at a remote location, includes
an eluant water reservoir, a sample injection valve, a pump
delivering water to the sample injection valve, ion exchange resin
means for ion separation with or without treatment for interfering
ions or for total conversion of all ions by ion exchange to a
single preselected ion pair, a conductivity cell with associated
readout means, and clean-up resin bed means, all connected in
series and in a closed loop, the clean-up resin bed means
delivering deionized water to the water reservoir, means for
delivering sample solution and standard solution, at mutually
exclusive times, to the sample injection valve, and a
computer-controller coordinating sample delivery and readout.
Preferably means is provided for occasionally flushing the sample
solution delivery system with a bactericide. The readout means may
include a teletype or other means for transmitting the analysis
results to a remote location.
Inventors: |
Stevens; Timothy S. (Midland,
MI), Parth; William H. (Saginaw, MI) |
Assignee: |
The Dow Chemical Company
(Midland, MI)
|
Family
ID: |
23524844 |
Appl.
No.: |
05/386,259 |
Filed: |
August 6, 1973 |
Current U.S.
Class: |
422/81; 73/61.55;
210/284; 210/656; 210/662; 436/129 |
Current CPC
Class: |
G01N
30/88 (20130101); G01N 30/96 (20130101); G01N
2030/625 (20130101); G01N 33/18 (20130101); G01N
2030/645 (20130101); Y10T 436/201666 (20150115) |
Current International
Class: |
G01N
30/96 (20060101); G01N 30/00 (20060101); G01N
30/88 (20060101); G01N 30/62 (20060101); G01N
33/18 (20060101); G01N 30/64 (20060101); B01d
015/08 (); G01n 027/00 () |
Field of
Search: |
;23/23R,253R,253A
;210/24,25,31C,37,38,284,294 ;127/9,46A ;73/61.1C |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Wolk; Morris O.
Assistant Examiner: Marantz; Sidney
Attorney, Agent or Firm: Schilling; Edward E.
Claims
We claim:
1. Integrated system utilizing ion exchange resin means in
automated analysis of a sample solution containing at least one
ionic species to be quantitatively determined, which comprises:
a reservoir for eluant water;
valve means for selecting a predetermined-sized quantity of sample
solution;
hydraulic pressure means for delivery of the eluant water to the
said valve means;
ion exchange resin bed means receiving eluant water and selected
sample solution from the valve means;
a conductivity cell receiving the effluent from the ion exchange
resin bed means;
clean up resin bed means receiving the effluent from the
conductivity cell;
liquid conduit means connecting in series in a closed loop in the
following sequence: the reservoir, the hydraulic pressure means,
the valve means, the ion exchange resin bed means, the conductivity
cell, and the clean up resin bed means;
readout means associated with the conductivity cell;
means for delivering to the said valve means, at mutually exclusive
times, sample solution, and standard solution;
and a computer-controller coordinating the introductions of sample
solution and of standard solution with the readout means.
2. The system as in claim 1 wherein each resin bed means is a
single tubular column.
3. The system as in claim 1 wherein the ion exchange resin bed
means consists of a first and a second ion exchange resin bed means
connected in series.
4. The system as in claim 3 wherein the first and second ion
exchange resin bed means are each a single tubular column.
5. The system as in claim 4 wherein the first column is charged
with a cation exchange resin in easily elutable cation form and the
second column is charged with an anion exchange resin in easily
elutable anion form.
6. The system as in claim 5 wherein the easily elutable cation form
is selected from lithium and sodium ion forms and the easily
elutable anion form is selected from acetate and hydroxide ion
forms.
7. The system as in claim 4 wherein the first column is charged
with a cation exchange resin in the silver ion form and the second
column is charged with a cation exchange resin in the hydrogen ion
form.
8. The system as in claim 7 wherein the cation exchange resin in
the second column is a homogeneously sulfonated copolymer of
styrene and divinylbenzene.
9. The system as in claim 8 wherein the cation exchange resin is a
low exchange capacity resin.
10. The system as in claim 1 wherein the ion exchange resin bed
means is a single tubular column.
11. The system as in claim 10 wherein the column is charged with a
cation exchange resin in easily elutable cation form.
12. The system as in claim 10 wherein the column is charged with an
anion exchange resin in easily elutable anion form.
13. The system as in claim 1 wherein the readout means associated
with the conductivity cell includes means for transmitting the
readout to a remote location.
14. The system as in claim 1 wherein the means for delivering
sample solution to the valve means includes means for selecting the
sample solution from natural waters or a manufacturing plant
effluent aqueous waste discharge.
15. The system as in claim 1 wherein the means for delivering
sample solution and standard solution to the valve means also
includes means for passing bactericidal solution through such
delivery means at times mutually exclusive to the delivery of the
sample solution and of the standard solution.
16. The system as in claim 1 wherein the hydraulic pressure means
is a pump.
17. The system as in claim 1 wherein the clean up resin bed means
is a single tubular column.
18. The system as in claim 17 wherein the single tubular column is
charged with an ion exchange resin selected from the group
consisting of: cation exchange resin in the hydrogen ion form,
anion exchange resin in the hydroxide ion forms, and, a combination
of cation exchange resin in the hydrogen ion form and anion
exchange resin in the hydroxide form.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
In a copending application of Hamish Small and Timothy S. Stevens,
Ser. No. 386,263, filed even date herewith, is described a method
and apparatus for determining the total ionic content of an aqueous
sample solution in which all the ionic species present are
converted by ion exchange to a single preselected ion pair and the
concentration thereof determined utilizing a conductivity cell.
In another copending application of Hamish Small and Timothy S.
Stevens, Ser. No. 386,264, filed even date herewith, there is
described a method and apparatus for separating and determining
organic carboxylic acids or the carboxylate salts thereof, with or
without prior removal of interfering halides. Acid separation and
halide removal are accomplished with the use of ion exchange
resins.
In a further copending application of Hamish Small and Timothy S.
Stevens, Ser. No. 386,265 filed even date herewith, there is
described a method and apparatus for determining the content, in a
sample solution, of a single ion species wherein the single ion
occurs in the presence of a plurality of countervalent ions. The
countervalent ions are exchanged, by ion exchange, for a single
easily elutable species and the resulting single ion pair
determined using a conductivity cell.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to an integrated system for the automated
quantitative analysis of one or more ionic species utilizing one or
more ion exchange resin beds for separations or exchanges, with or
without removal of interfering ions, and detecting eluted ion
species with conductivity cell. The invention more particularly
relates to an integrated system for quantitative analysis of one or
more ionic species using water for elution of the sample from an
ion exchange bed and recycling the water, after purification, for
re-use.
2. Description of the Prior Art
There is a constant and ever increasing demand for a rapid,
inexpensive method of analysis of large numbers of samples of, for
example, surface waters, i.e., natural waters, boiler blow-down,
and manufacturing plant effluents for total dissolved solids or a
measure thereof. There is also a great need for simple automatable
apparatus for carrying out such analysis as well as for analysis of
process streams for a specified single ion occurring along except
for a plurality of countervalent ions, or, for analysis of a
mixture of organic carboxylic acids or the carboxylate salts
whether or not in admixture with soluble metal halides.
The determinations in each such case have generally been carried
out using old classical, slow, and relatively costly, methods. Even
where ion exchange separations, chromatographically or by exchange,
have been utilized, the fractions obtained have generally been
analyzed by classical methods or by methods which usually require a
different test and/or a different instrument for each species to be
determined. Therefore, a new approach with new apparatus appears to
be needed.
SUMMARY OF THE INVENTION
Automated quantitative analysis of one or more ionic species in
sample solution utilizing ion exchange resin means is readily
carried out using a system which includes: a reservoir for eluant
water; valve means for selecting a predetermined-sized quantity of
sample solution; a pump for delivery of the eluant water to the
valve means; ion exchange resin bed means receiving eluant water
and selected sample solution from the valve means; a conductivity
cell receiving the effluent from the ion exchange resin bed means;
a clean-up resin bed means receiving effluent from the conductivity
cell and liquid conduit means interconnecting the parts in series
and closing the loop with a connection between the clean-up resin
bed means and the reservoir for eluant water. In addition, the
system includes means for selecting sample solution and conveying,
at mutually exclusive times, sample solution and standard solution
to the sample injection valve and a computer-controller
coordinating injection of sample and standard solutions with
readout. The system, when used for some specific analyses, utilizes
ion exchange resin bed means consisting of one column charged with
resin, and in other cases two such columns connected in series.
Preferably the system includes means to occasionally flush the
sample conveying line with a bactericide at times mutually
exclusive to the conveyance of sample and standard solutions.
BRIEF DESCRIPTION OF THE DRAWING
The single FIGURE of the drawing is a schematic representation of
an integrated system for selecting and quantitatively analyzing a
solution of one or more ionic species according to the
invention.
FURTHER DESCRIPTION OF THE INVENTION
The present integrated system for automated analysis as shown in
the drawing includes an eluant reservoir 10, normally containing a
substantial quantity of water 11, a sample injection valve 12, a
pump 13 for conveying eluant water 11 to the sample injection valve
12, a first tubular column 14, which is charged with a pre-selected
ion exchange resin when ready for use, a second tubular column 15,
which likewise is charged with a pre-selected ion exchange resin
when ready for use, a conductivity cell 16 receiving the effluent
from the second column 15, a clean-up resin bed column 17 which,
when ready for use, is charged with an appropriate ion exchange
resin for cleaning up, i.e., deionizing, the used eluant water,
liquid conduit means connecting such parts in the sequence
indicated by the above recital, as well as connecting the clean-up
resin bed column 17 to the eluant reservoir 10.
In addition, the system includes apparatus for selecting and
conveying sample solution to the sample injection valve 12. Such
apparatus includes means for withdrawing sample solution from
natural waters, such as surface waters in the form of a lake, pond
or river, or the equivalent of such apparatus adapted to withdraw
sample, for example, from a boiler blow-down line or a chemical
process stream or a manufacturing plant effluent line or discharge
ditch. In the apparatus shown, the means for withdrawing sample
solution includes a liquid conduit means extending into a body of
surface water 23 to be sampled and leading to a pump 18 which
elevates the sample to a constant level sample solution reservoir
19 from which liquid conduit means leads to a filter 20, which may
be omitted if the sample is adequately settled or otherwise free of
suspended solids, and thence to a three-port valve 21. The
three-port valve, when appropriately set, discharges sample
solution to a pump 22 which supplies the sample solution to the
sample injection valve 12.
The readout means associated with the conductivity cell 16 consists
of a conductivity meter 24, which includes means for impressing a
voltage, generally an alternating current voltage, across the
electrodes of the cell and measuring resulting current flow, and a
computer-controller 25 which translates the meter readings into ion
concentrations in the sample solution. In the event the present
system is remotely located, it will be found convenient and
generally desirable to transmit the computer results as by
teletypewriter 26 to a central location remote from the system.
To assure accurate results by making corrections from time to time
for such changes as instrument component drift, it is highly
desirable and usually considered essential to supply a known or
standard solution to the analyzer section on an intermittent basis
and mutually exclusively to the supplying of sample solution.
Accordingly, standard solution stored in a reservoir 27 is supplied
as by gravity through a three-port selector valve 28 to the
three-port valve 21, which, when appropriately set, delivers
standard solution to the pump 22 and the sample injection valve 12,
which stopping the flow of sample solution for the duration of the
running of the standard solution to the sample injection valve.
To prevent the growth of bacteria, algae or anerobic organisms in
the system, it is found desirable, especially in the sampling and
analysis of natural waters, to provide means for periodically
flushing the three-port valve 21, the pump 22 and parts of the
sample injection valve 12 and the liquid conduit means
interconnecting the same with a bactericide solution such as either
of aqueous sulfuric acid, or inhibited hydrochloric acid, having a
concentration of, e.g., 4 normal, or an aqueous solution of most
any of the organic chemical bactericidal, algicidal or slimicidal
compounds used in keeping cooling towers, sampling lines, and the
like free from organisms, may be used. Such bactericide solution is
stored in a container 29 which serves as a reservoir and, on
appropriately setting the selector valve 28, the bactericide
solution flows to the three-port valve 21 and into the sample
supply system, at times when sample and also standard solutions are
mutually exclusively shut off, relative to the bactericide
solution.
The sample injection valve 12 is of the general type commonly used
for chromatographic analysis and typically is provided with a
measuring bore in the valve plug of known volume or a pair of ports
to the valve body are connected by a tubing loop of known volume,
and the valve is provided with bypass means for continuously
directing eluant water through the valve to the first ion exchange
column and through the system while sample solution, or standard
solution as the case may be, flows continuously through the
measuring bore or the tubing loop and discharges continuously to a
waste
At a time directed by the computer-controller 25, the valve is
manipulated to bring the sample-filled volume into series with the
stream of eluant water constantly passing through some portion of
the valve, and the selected sample or standard portion is thereby
swept on into the system.
The computer-controller 25 is shown for the sake of simplicity of
illustration to be electrically connected to the sample injection
valve 12 which is to be understood to be provided with electrical
actuating means. More generally, the valve 12 will be pneumatically
actuated under the control of the computer-controller as well
understood in the art of valve actuation in industrial
processes.
The computer-controller 25 is also programmed to coordinately
actuate the three-port valve 21 and the selector valve 28 at
appropriate times to bring sample solution or standard solution or
bactericide solution into the sample supply line and to coordinate
the readout of the computer with the type of solution passing
through the analyzer section. The three-port valve 21 and the
selector valve 28 are to be understood to each be provided with
electrical actuators, but as in the case of the sample selection
valve 12, will be more generally pneumatically actuated under the
control of the computer-controller 25.
In the event the analysis being carried out requires the use of
only one column containing ion exchange resin, the effluent from
the first column 14 may, by appropriate setting of three-way valves
30 and 31, be bypassed around the second column 15.
The use of pumps 13, 18 and 22 is not critically necessary. A
sufficiently elevated reservoir or pressurized source of eluant
water 11 may be used without employing pump 13, providing it is not
necessary to recycle the eluant water through a clean up resin bed
and back to the reservoir in order to have a water supply. As a
practical matter, however, pump 13 will most generally be used as
providing more certain, reliable, reproducible results.
The pump 18 is unnecessary if the surface water sample is
sufficiently confined and pressurized, or, is elevated by other
means to provide suitable gravity flow, or, if the sample is drawn
from a pressurized source such as a pressurized process stream. The
pump 22 is also unnecessary if the sample reservoir, bactericide
reservoir, if used, and the standard solution reservoir are each
sufficiently elevated to provide a reasonable gravity flow. As used
herein, and in the claims, the term "hydraulic pressure means" is
meant to encompass the use of a pump as well as the use of an
operable gravity head or pressurized source capable of pushing the
requisite liquid flow through the applicable portion of the
system.
The pumps 13 and 22 or equivalent hydraulic pressure means should
provide a flow of about 100 to 500 milliliters/hour for most
analyses while the pump 18 or equivalent should provide enough flow
against gravity, e.g., to keep a 0.5 to 4 liter capacity reservoir
filled and overflowing. The sample injection valve 12 is preferably
either a rotary valve such as the Model R 6031 SVA-K valve supplied
by Chromatronix Inc., or a slide valve such as the Model CSVA-K
valve from the same supplier or the equivalent of either. When
using remotely actuated valves, as here, the valves must each be
provided with actuators therefor and the valve employed must be
adapted to be operated by the kind of actuator used whether
electrically or pneumatically operated.
The sample injection valve should provide for measuring and
injecting a predetermined sample size in the range of about 2 to
1,000 microliters. Typically chosen sample sizes adequate for
detecting most ionic materials and small enough to avoid
unnecessary exhaustion of the ion exchange resin used are in the
range of about 5 to 50 microliters.
The computer-controller may be most any digital computer adapted to
the function as well understood in the art. An analog computer is
also usable, is less simple to adapt but is quite satisfactory in
use. The term computer-controller is intended to also extend to the
combination of a motor driven multi-cam actuated multi-position
switch used in conjunction with a recorder, preferably an
integrator-recorder, and coordinated in order to discriminate
between standard and sample readings.
The columns used to house the ion exchange resins, such as columns
14 and 15, are best selected from glass or metal columns now
readily available commercially and having the proper fittings to be
easily connected into the system. While larger columns may be used,
if desired, such as those having 25 to 50 mm. inside diameter (ID),
the smaller columns utilizing smaller resin beds better serve the
purposes of obtaining rapid, sharp analytical separations and the
preferred column sizes are in the range of about 1 to 10 mm. ID and
from about 5 to 1,000 cm. length, but more generally selected sizes
are 2.8 mm or 9 mm ID and a length of about 25 cm.
The columns when charged with ion exchange resin contain about 20
to 25 grams of resin per 25 cm. length of 9 mm. ID column and about
one-tenth that much resin per 25 cm length of 2.8 mm ID column.
The resin charged to the columns 14 and 15, respectively, when
carrying out total ionic content analyses should be preferably,
high exchange capacity ion exchange resins. The column 14 should be
charged with a cation exchange resin in an easily elutable cation
form such as sodium ion or lithium ion form. The column 15 should
be charged with an anion exchange resin in easily elutable anion
form such as hydroxide ion or acetate ion form.
When using the present system for the separation and determination
of carboxylic acids or carboxylate salts in the presence of soluble
metal halides, the column 14 is charged with a cation exchange
resin in the silver ion form while the column 15 is charged with a
cation exchange resin in the hydrogen ion form. Preferably, the
resin in this latter case is a low exchange capacity homogeneously
sulfonated copolymer of styrene and divinylbenzene.
In the event the system is used for the analysis of a mixture of
carboxylic acids or of carboxylate salts substantially free of
interference by halide salts or other ionic material that is not
readily separated in the present system from the carboxylic acids
or their salts, the column 14 is charged with the described cation
exchange resin in the hydrogen ion form and the column 15 is simply
by-passed upon appropriately regulating the valves 30 and 31.
In carrying out analysis of solutions containing substantially only
a single cation species paired with a plurality of anion species,
the column 14 is charged with an anion exchange resin in easily
elutable anion form such as hydroxide ion or acetate ion and column
15 is not needed and is by-passed, or the column is omitted from
the system.
In carrying out analysis of solutions containing substantially only
a single anion species paired with a plurality of cation species,
the column 14 is charged with a cation exchange resin in easily
elutable cation form such as sodium ion or lithium ion form.
The ion exchange resins used for chromatograhic separations herein
exhaust quite slowly, while those which are used for exchange of
ion species gradually become exhausted according to their specific
exchange capacities, amounts of resin used, and number of
equivalents of ion species in the samples exchanging with the ions
at the active sites of the resins. Preferably, for the sake of
economy of operator attention the number of equivalents in selected
sizes of samples and the total exchange capacity of the ion
exchange resins used permit the analysis of about 1,000 to 10,000
or more samples before the charge of resin in a given column
becomes exhausted.
As the ion exchange resins approach exhaustion, and generally, at a
time determined by experience, the columns are simply removed and
replaced by columns charged with resin in the appropriate form.
The ion exchange resins usable in the present method and apparatus
are typically polystyrene or modified polystyrene copolymers
cross-linked, e.g., with divinylbenzene, and carrying nuclear
groups, the latter providing active exchange sites. The cation
exchange resins carry nuclear sulfonic acid or sulfonate groups
along the polymer chain. The strong base anion exchange resins
carry nuclear chloromethyl groups which have been quaternized.
For further information on ion exchange theory, processes and
resins synthesis reference is made to the monograph "Dowex: Ion
Exchange" 3rd Ed. 1964, published by The Dow Chemical Company,
Midland,Mi., and the two volume work "Ion Exchange" Ed. by Jacob A.
Marinski and published by Marcel Dekker Inc., New York, 1966.
Chapter 6, Vol. 2, of "Ion Exchange" is devoted to a description of
synthesis of ion exchange resins of various types usable
herein.
The dimensions of the column 17 used to house the clean up resin
bed are not critical as analytical separations are not carried out
therein. Most any geometry suffices so long as the ion exchange
resin placed therein has a total exchange capacity sufficient to
deionize the eluant water effluent from the conductivity cell for a
very large number of samples, preferably handling at least as many
samples as the ion exchange resins in columns 14 and 15. Usually a
column with the same bed volume as that of columns 14 or 15
suffices.
In general, the column 17 will be charged with either a two layer
bed or a mixed bed resin for deionization of the eluant water. In
carrying out total ionic content analyses, both anions and cations
in the effluent from the conductivity cell will need to be
exchanged for hydroxide ions and hydrogen ions respectively in the
clean up bed resin. In other analyses where the effluent is only
acidic or basic in character, it may be adequate to utilize, in the
clean up resin bed column, a single ion exchange resin in the
hydroxide ion, or hydrogen ion form, as required, to neutralize the
effluent and effectively transform it into substantially deionized
water. The quality of the deionized water should be such as to give
a very low base line reading, e.g., about 2 micromho/cm, when
passed through the conductivity cell.
The conductivity cell employed is most any of the conventional
commercially available models regularly used in conductimetric
detection chromatography.
An example of a suitable conductivity cell is Model MCC 75
available from Chromatromix, Inc. A suitable conductivity meter for
use therewith is Model CM 1A from the same supplier. Most any meter
selected is preferably modified, for the present purposes, to
reduce zero suppression.
The standard solution used for all but total ionic content
analysis, is a simple aqueous solution containing, for any given
analysis, a mixture of each of the ion species to be determined, in
known concentration, and substantially free of ion species which
will interfere with analysis by the present method using the
present apparatus. The standard used for total ionic content
determination may be the preselected ion pair issuing from column
13 but also may be any soluble salt solution of known total ionic
content.
The teletypewriter 26 may be any of the commerically available
models with a capability of receiving a signal from the
computer-controller 25 and producing a print-out or other readout
thereof at a remote location.
* * * * *