JPS60108732A - Method of continuously measuring concentration of various trace element in liquid stream containing whole highly dissolved solid matter - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Water hardness has historically been determined by measuring the concentration of calcium and magnesium, which is expressed as the concentration of calcium carbonate. Appropriate methods for measuring calcium and magnesium amounts are titration with EDTA and electrochemical methods with ion ratio electrodes. These methods are suitable for water with a relatively low dissolved solid content and a concentration exceeding 1.Oppm. When the total dissolved solids (TDS) concentration approaches 1% or exceeds 1 ton, the method described above has a large shift in the case of ion-specific electrodes, and the ED
In the case of TA titration, it is not suitable because of poor accuracy.

Softening of water with high TDS content is carried out using ion exchange resin methods. A characteristic feature of many of the resins utilized is the determination of the operational or dynamic exchange capacity of the resin for calcium and magnesium and the function of the resin during or after its regeneration. These studies are commonly performed by filling a column with resin and passing solutions of various compositions through the column. The column products are then collected and analyzed. Traditional analytical methods use a fraction collector to collect the effluent separation and then subject the sample to an inductively coupled plasma optical emission spectrometer (IC).
P-OES).

Hardness is the amount of calcium and magnesium dissolved in a given amount of solution.

Trace water hardness is defined as 1 ppm in a given amount of aqueous solution.
It means the ion concentration of calcium and magnesium below m.

A slurry consists of fine particles dispersed in a liquid medium that suspends the particles in a colloidal state.

High TDS means an amount of solids present in solution consisting of 0.5% W/v up to saturation concentration.

Simultaneous basis is characterized by simultaneous sampling and analysis of the sampled stream with continuous sampling from the stream to the aerosol generator, uninterrupted by manual manipulation and transfer of preparative samples. It is meant and thereby that the sample streams are sampled and analyzed substantially simultaneously.

Electrical plasma discharge refers to a series of physical forms of ionized gas created by a continuous or oscillating flow of electric current and voltage through a physical conductor such as a coil or electrode. This term is especially used for inductively coupled plasma (
ICp) and direct current plasma (DCP) generators.

The unique wavelength is due to the emission wavelength characteristics of calcium and magnesium or other trace elements that have sufficient Canet intensity and no spectral interference to detect trace elements.

By stream is meant any liquid that is transported and produced into an aerosol suitable for spectrophotometric analysis of trace elements to be detected using an electric plasma discharge. The term broadly includes slurry liquids and true solutions.

The trace element concentration is 1, except in the case of i amount of water hardness.
It means a concentration of 0.00 ppm or less. According to the present invention, high T
Elements that are easy to detect in trace amounts in DS streams include, but are not limited to, sodium, silicon,
These are copper, iron, molybdenum, potassium, strontium, boron and barium.

The total exchange power is the ion concentration that can create a complex with the ion converting material for a given volume of material. This amount is related to the specificity of the individual substances for the individual ions and is determined experimentally under static or equilibrium conditions.

Dynamic total exchange capacity has the same meaning as total exchange capacity, except that the measurements are made under flowing stream conditions and are potentially influenced by dynamic effects.

Depletion refers to the point at which the ion exchange material or bed no longer has the ability to remove individual ions or ion concentrations from the flowing stream such that the effluent exiting the bed is maintained within acceptable limits. It is.

Regeneration is a physical process in which the ion exchange material or bed is converted to an ionic form suitable for complexing or removing ions from a flowing stream, usually performed before depletion or when the ion exchange bed is It is carried out when there is a conversion from one ionic form to another.

The invention comprises: (a) changing the flow of a part of the stream to be measured and at the same time physically converting the diverted stream part into an aerosol; (C) detecting the emission of the plasma discharge at a wavelength characteristic of the trace element of interest; determining and reporting on a concurrent basis as a function of;
The present invention describes a method for detecting the concentrations of various trace elements in an IJ system on a real-time basis.

The present invention is more particularly a method for the continuous detection of ion exchange influents and effluents: its application as an improved water hardness monitor for high TDS streams.

Further objects, features, and advantages of the present invention will be partially pointed out, and may be learned to a certain extent, from the following detailed description of the invention, taken in conjunction with the accompanying drawings.

FIG. 1 is a three-dimensional diagram illustrating an embodiment and arrangement for implementing a method for detecting trace elements in a high TDS stream according to the principles of the present invention.

FIG. 2 illustrates a computer program advantageously used to program the computer of the apparatus of FIG. 1 to calculate and report dynamic total exchange capacity cheater, depletion data and stream softening data on a simultaneous basis. It is a flowchart.

FIG. 3 is a graph showing the test results of a representative ion exchange layer for xylem formation using it continuously until it is exhausted.
This graph shows the concentration of calcium and magnesium in the formation effluent as measured by the directly connected CP of FIG. 1 and ascertained using the fraction collector shown in FIG.

FIG. 4 is a graph showing dynamic resin regeneration data performed using the method of the present invention, in which regenerant is continuously fed to the depleted ion exchange bed and the bed effluent is detected. , which continuously detects the conversion of the layer to the regenerated ionic form.

An embodiment of an apparatus for carrying out the invention is shown in FIG. A reservoir (1) of high TDS solution is placed above the filter column (2) consisting of an ion exchange layer for gravity feeding of the column effluent. Two pumps (3), +4) are placed at the exit of the column to pump the solution out of the column at the aforementioned rate. pump(
4) For example G11son Minipuls 2 is a couple torch (6) that directs a small amount of solution from the main stream.
nebulizer (5) and another pump (3), for example Masterflex MDI 7014, delivers the solution at a rate equal to the difference between the small pump (4) and the total desired flow rate. The bath liquid from the Maeterflex is sent to the fraction collector (7) for subsequent analysis.

The torch (6) is a commercially available inductively coupled plasma (IOP).
equipment, such as P1a8ma Therm, Inc, M
DI, HF'L1500.27.12MH2,1,5
00Watts, which includes an RF generator and a matching circuit (8).

The electric plasma discharge (9) is generated by a fairly high excitation pressure source (maintained, for example, by argon gas or molecular gas).
75,000K). The column effluent was collected using an air sprayer (
5) The generated aerosol after being atomized in the plasma emitter (9) is fed into the center of the high plasma emitter (9).

The plasma desolvates, deoxidizes, μah, and energizes the calcium and magnesium or other trace elements of interest in the high T I)S stream, resulting in emission of wavelengths characteristic of these elements. This luminescence is detected by a detector as a function of time. Each detector is, for example, a 1Ocrnf1 monochromator-no+ (suitable one is Kratos Mdl GM-100), which is tuned to the desired wavelength (GalT is 393.3nm, M
g1f is set at 279.5 nm) and connected to an optical focusing optics (11) and a photomultiplier tube (12).The bandwidth of these commercially available valley monochromators is 0. .85nm and Q
, lnm. Table 1 shows the specifications of the monochromator pond. The slit height is limited to 1.5 nm, for example, by covering the slit.

Table 1 Small grating monochromator specifications Optical distance I# = 90 degrees aperture ratio f/4.7 Focal length: 100 Stray light 18 X 10
'Slit: 0.1 path generation 0.85 nm Bandwidth thickness: 6" x 2.5' x 1.5' Weight 1
lb each photomultiplier tube (12 is a two-channel high voltage power supply" f5 (Power Designs Inc.
, supplied at -800vd,c from 20) to Md1.27). The lbs from the photomultiplier tube are sent to a typical single end voltage converter which is made as a direct current to a voltage transformer with a variable range selector (not shown). The output pressure is controlled by a computer (13) such as DigitalE.
Equipment Corp., MTNC. For each of the two detections, a z-X metamorphosis stage, e.g. Ea
l, :ingCorp, Mal, 22-4899 installed on the side of the plasma box.
It rides on a triangular light rail. This distribution: Ka:
provides flexibility for determining and selecting the optimum visual distribution in the plasma discharge (9).

High solids sprayers such as GMK sprayers, Labtest.

Inc. is preferably used for high TDS#fff aspiration. A gas saturator is installed to moisten the aerosol gas to prevent salt formation at the tip of the sprayer and to aid in the delivery of sample to the CP torch (6). .

Valves and sample transfer lines are conventional. These are the T
- connector (14); The other T-connector branch line delivers a portion of the effluent stream to the manual selector pulp (10). standard solutions (necessary for calibration) to be sent to the nebulizer (5). Additionally, an optional reservoir (not shown) containing a blank solution can be provided in the form of reservoir (17) to continuously feed the nebulizer with samples, blanks and fixed blanks (i.e. standards) for line calibration purposes. can.

It may also be desirable to add a separate reservoir (not shown) to the apparatus containing a diluent for mixing with the high TDS stream. The diluent and high TDS streams could be pumped separately in a conventional manner.

For example, mixing is performed using a pump (4) through a connecting pipe provided outside the pump (4). This item prevents the components of the torch (6) from generating salt when suctioning high TDS liquid.
This is something that is usually installed effectively. In general, this is a conventional device that is advantageous for use with very high salt content, which is known to reduce the ashes of industrial CP torches.

The general operation of the device described above will be clear from the previous discussion of the device. The high TDS stream is in the column (2
). The hardness of the processing stream is
A portion of the column (2) effluent is transferred to the selector valve (16).
be detected on a concurrent basis by sending them to Either a fixed standard or a blank is selected depending on the pulp, and this is fed to the atomizer (5) by the pump (4). The nebulizer converts either the high TDS vapor or standard or blank into aerosol form and injects it into the electric concentric plasma (9).

After the characteristic wavelength of the target element is detected by a monochromator (10), the detected light intensity is converted into an electrical signal by a photomultiplier tube (02). These signals are processed by a computer (13
+, where the concentration of the target element is continuously recorded. Any samples collected in the fraction collector (7) are used to confirm the recorded density data determined by the computer (131).

First, when starting, pumps (3) and (4) are turned on at a predetermined speed, and then a high TD is applied to the pipes and lines of the equipment.
S) Let the IJ-me solution flow for several minutes. Next, start the CP torch (6) and raise the temperature according to the instructions in the equipment manual. After raising the temperature, start operating the computer program. A flowchart of the appropriate program is shown in FIG. The optical matching device (11) and the plasma discharge (9) are sufficiently adjusted to keep the plasma output amount, gas flow rate, and observation height constant and optimum.

While the operator instructs to aspirate the blank solution (see Figure 2), the computer (13) begins measuring the background intensity of the plasma after questioning several variables related to the properties of the solution. . Background values are determined for calcium and magnesium or other elements of interest by staggering the emission of each wavelength for, for example, 20 seconds. The operator then aspirates and interrogates standard solutions of calcium and magnesium of interest or pond elements of known concentration from the reservoir (1η).

The emission intensities generated from these solutions can be calculated using a computer (
+31 and a calibration factor established for each element of interest. Multiply this factor by the integrated raw turbulence intensity to directly calculate the ppm concentration of calcium and magnesium or other elements of interest. Once the instrument has been calibrated, the experiment continues and the computer (13) continuously monitors the progress of the experiment, prompting the operator to switch from aspiration of the blank solution to pumping from the column (2).
Start detecting 1Fp, effluent capacity, concentration of calcium and magnesium or other elements and ion exchange capacity. When these data are uploaded to the printer for hard copy, they are stored in filI# on a floppy disk for later recall. the computer graphically displays the concentration of calcium and magnesium or other detected elements as a function of time;
The information will be updated whenever new data points are received. For example, a preset “Breakthrough” for calcium
h) If the concentration is reached, the computer ends the continuous detection of the luminescence signal and continues calculating the ion exchange capacity at the predetermined concentration of calcium and magnesium or other elements.

Figure 3 shows that online data is stored on a computer (+3
1 shows the experimental and actual passage curves of a typical ion exchange layer recorded in 1. This chart shows raw data processed by computer and data from independent analysis using a fraction collector (7).

In the chart data of FIG. 3, the initial presence of calcium and magnesium is due to displacement of these ions from the bottom of column (2). The ion exchange layer regenerated with caustic soda usually retains small amounts of calcium and magnesium, which seep out of the column at the beginning of the test. Ryoryoku thione reaches its lowest concentration in calcium, which is usually found in large amounts.

As the ion-exchange layer begins to become saturated, the magnesium concentration begins to break through after the final calcium breakthrough. I was told that I could no longer do it,
Need to play.

Continuous detection of calcium and magnesium limits in the column (2) effluent can also be carried out during column regeneration. This determines when the material capacity of the ion exchange layer is fully regenerated. A typical regeneration curve for a depleted ion exchange layer is shown in FIG. The eluate of the regeneration solution drives out the calcium and magnesium, while the appropriate ionic form converts the layer to the sodium form.

This is indicated by the sharp increase in calcium and magnesium concentrations at the beginning of treatment. Regeneration ends when the concentration of calcium and magnesium reaches a predetermined amount. Simultaneous based detection of these two elements offers significant cost savings due to less regenerant and less time.

[Brief explanation of the drawing]

FIG. 1 is a three-dimensional diagram illustrating an embodiment and arrangement for implementing a method for detecting trace elements in a high TDS stream according to the principles of the present invention. FIG. 2 shows a computer program advantageously used to program the computer of the apparatus of FIG. 1 to calculate and report dynamic total exchange data, depletion data and stream softening data on a same-single basis. It is a flow chart explaining. FIG. 3 is a graph showing the test results of a typical ion exchange layer for water softening in continuous use until it is exhausted. FIG. 4 is a graph showing dynamic resin regeneration data performed using the method of the present invention. FIG.1

Claims (1)

[Claims] 1(a) Changing the flow of a portion of the stream to be measured and at the same time physically converting the diverted stream portion into an aerosol; (1-) l Aerosol (C) Detecting the emission of the plasma discharge at a wavelength with the target microbodies [%; and fd,) high Tl.
) determining and reporting on a real-time basis the symbolic mass elemental basis in the S stream as a function of the intensity of the detected characteristic wavelength below the tct;
A method for detecting the concentration of divine imitation elements in high TDS streams on a simultaneous basis. 2 The method reduces the amount of target trace elements in the effluent to about 1 ppp.
2. The method of claim 1, wherein the range of requirements for i<1 is determined by detecting the ion exchange layer stream 111 to determine and report a concentration of less than or equal to m. 3. The method determines and reports the water hardness in high TDS streams;
Calcium and Magne7 each! 4. The method according to claim 1, which comprises detecting the emission of plasma discharge at a certain wavelength. In order to determine the total exchange capacity data, θt should be calculated once a month.
Claim Iη2 or the method according to claim 3. 5. The method of claim 2 or i'R:3, wherein the method is used to determine ion exchange layer depletion data on a real-time basis. 6. The stream is fed to the ion exchange layer for raw purposes, and the method according to claim 4 of the present patent claim is carried out to remove the cal/lam and magnesium of the ion exchange layer once. The method according to Paragraph 1 of Patent Claim 11, which is used for producing Toya. 7. The process stream consists essentially of high TDS water to be 1-ζ-ized by feeding the water through an ion exchange bed, and the method of claim 1 continuously increases the hardness of the process water. 2. A method according to claim 1, which is used to detect the effluent of an ion exchange layer on a real-time basis for detection. 8. The method of claim 1, wherein the sample stream comprises the influent to the ion exchange layer.