JPS61270660A - Method and device for discriminating specific component fromfluid sample - 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 The present invention relates to a method and apparatus for detecting the presence of chemicals in a fluid, such as a stream of air or other gas. The present invention is suitable for 1) identifying unknown components of fluid samples such as toxic, hazardous or other chemicals.

There are many platforms where the chemical composition of a fluid 1J-umble must be quickly identified. For example, in chemical processing it is often necessary to monitor the produced gases or vapors or effluents from Plan 1, and in medical diagnostics it is often necessary to quickly measure the presence of gases in samples of blood or exhaust gas. Analytical laboratories often need to measure the concentration of one gaseous chemical and the presence of another; Is it necessary to measure it according to JR?
, there are many other cases that one would like to measure.

If you use some expensive and troublesome equipment,
It is currently possible to selectively divide 1 into 4 Jr. , for this it is usually necessary to collect the gaseous rimples (,j2) and send them to the sect for a remote location (Jr3, which costs J, and l+,' It takes 6d.

Even more powerful 1.1 laboratory equipment semi-11 belt type or near 1.
It seems that f market l is taken (this happened. However, such a hI device (sometimes the same limit is 1:i). −
It cannot operate in mode. The red Tato ray analyzer is based on its volume, Φ speed and enemy
It requires a delicate optical system with 11M passage 4. Furthermore, if such a hI device (J1 communication (A) is operated, its analysis results (3J), if it is pre-arranged by a skilled expert, it will not be possible.

Many existing sensitizers are characterized by a virtually non-reactive component.
If the temperature is low, it is impossible to detect chemical components at low temperatures. 1! l 84 i'l-March 2 "1 out 1
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1 + iS > (13 (3J1, easily sensed chemical activity l'1.8g '!' A catalytically catalytic reaction force has been disclosed. The apparatus of the present invention, and most of the portable type (1a, 1a, 1a, 'M plate bent (31) , H1 has been set up exclusively for the detection of specific chemical components, and has not yet been established.
J: Sea urchin 13", which detects and identifies one component, is not set.

Detectors 1.11. has been developed using an array of electrochemical sensors, each operated in one or more predetermined modes or modes, and assembled to identify one of a number of gas classes. The correct response will be 1)). Such detector 1j, U.S. Patent Application No. 58.1, filed March 21-1, 198.1. '+, No. 6!39 (corresponding to "Ippon" 1. "I Kaimei 60-205351j)".

However, such devices can still identify relatively few components without using a large number of sensors, each with J, -
), the equipment becomes more complex as it becomes more complex. It utilizes a sensor that produces a steady-state output signal that changes as the environment changes. ``The goal is to create a device that can easily monitor and measure the single parameter or chemical in question, eliminating the risk of electric shock, but actually accomplishing this goal.'' For example, a power transducer can be used to measure methane and methane.
[? April 1, 2015, there is a tendency to respond to most of the hydrogen υi hydrides.

In order to minimize this tolerance sensitization, expensive 41-stage gears are used extensively, and if R 4-J is used, it will be better.

Typical Chemical 1Zn January 311, Focus 1-6171 Output characteristics when exposed to certain chemicals (e.g. electric current.

It is defined as a device in which the electric current (F, absorption, resistance, fluorescence, size, etc.) changes. Changes in response are usually investigated at equilibrium or steady state, and the magnitude of the response is related to concentration.The apparatus is set up so that a response occurs only when the specific chemical of interest is present. A lot of effort is put into making sure that this steady-state method uses only one sensor.

It does not provide enough data to analyze the hundreds of thousands of chemicals that may be in the limple using an IF instrument, or a sensor array.

U.S. Pat. No. 4,399,68.1 discloses a gas measurement method in which a metal oxide gas sensor is sequentially heated and cooled during exposure to the gas in the sample. This recovery reveals that during such thermal cycling, a continuous, concentration-dependent, unique signature is created for the stomach gas.

This distinguishing characteristic includes the ratio of the two 1 non-pulls of Sen 1) Deno J Shingetsu taken at a given time during a thermal cycle.

Is this characteristic a marker of known temperature? (Comparison with the natural discrimination property yields sufficient information to identify the gas concentration.However, since the created discrimination characteristic has a hot stone dependence fat'7, each of them can identify the unknown component of the lean pull with the discrimination layer - This i'i iT i,i,, the disclosed method or the unidentified 9.11 gas may not be used to imply scales or such identification. Please give an explanation of why it is right-handed.

The generality of the present invention [-1 (ma, i;
An improved detection device which avoids the disadvantages of the method and provides greater accuracy than the IM i detector and the operator.
'+r and hθ(.

An objective of the present invention is to provide a method particularly suitable for field use for identifying unknown components in a fluid sample.

10) of the present invention! In connection with the objective of 1, another objective is to develop a method for measuring the temperature of the identified chemicals (;
? Another object of the present invention is to provide a method of the above type j((j? be.

In connection with the above-mentioned objects of the present invention, another object is to
It is an object of the present invention to provide a method of the above type that utilizes a sensor in dynamic mode for measuring dynamic or chemical reaction related parameters.

Another object of the invention is to provide a detection device for implementing the above-mentioned method.

Another object of the present invention (41) is to provide such a sensing device which operates by energy modulation of the sensing device.

Another object of the present invention is to provide a sensing device of the above type which has a simple and economical construction and which is also small and compact;

Another object of the present invention 1; J: Identification of chemical components;
It is an object of the present invention to provide a detection method and apparatus of the above type for rapidly and selectively determining b and concentration.

Another object of the invention is to provide a detection method and device of the above type that is capable of detecting chemical components at very low concentrations.

The method of identifying a specific component from a fluid sample according to the present invention involves first detecting this fluid ripple using a sensing unit that receives an energy input and interacts with the specific component to generate a response.
The process of exposure to ~! ! -Li.

This phase n action has parameters that change depending on the component acting on 4[]T7. This digital input is then modulated to generate a response that is proportionally adjusted to the aforementioned parameters, and from the modulation of this response characteristic parameters for identifying specific components are measured. , exchange
When the chemicals are introduced, they are reacted, the degree of this reaction is modulated in a cyclical or regular pattern, and the progress of this reaction is sensed and tracked with all four heads. The information generated during this modulated recording is sufficient to enable the sensing device to identify and measure the chemicals involved.
(“There is.

On the other hand, according to the present invention, a sensing device which generates a response by applying a phase n action with a specific component in a fluid sample with a parameter that changes depending on the energy input and which changes depending on the component. Sensing the fluid sample - ] Ni 1
an apparatus for modulating said energy horn to generate a modulated response proportional to said parameter; and an apparatus for processing said response to identify and/or determine said particular component. It is necessary to have a device for measuring parameters.

The present invention will be further explained below with reference to Examples.

In its broadest aspect, the present invention is a technique for modulating sensor signals to generate unique information or data about a sample medium using a single sensor.

In general, the present invention (1) relates to the energy modulation of the phase N action between the detected component and the modulated output beam produced from the detector. This modulation information is then used to derive a parameter (related to the kinetic or thermal properties of a chemical substance or chemical reaction) that can be used to identify the specific component of interest and to determine the degree of opening. It can be used. Using a number of different types of sensors and modulation purchasing,
Although it is possible to accurately determine the gastric parameters specific to the chemical being used, the above-mentioned conditions may differ from Example G,
I1, electrochemical 1! Utilizing the thermal modulation of the heat sink, it is detected and identified by the heat exchanger system (modulator and heat exchanger),
Chemicals that are determined? ′Iσ) Chemical reaction with air [−
1) Kinetic parameters (kin
etic parameterer ) is determined.

FIG. 1 A3 and FIG. 2 show the ! l? T'J81 in the whole doji that embodies 1 mold
The detector represented by 0 is shown.

The detector 10 is a gas condenser 11, an air inlet 1] 12, etc.
-'U air person [113 or another person 1 connected to either Linsol gas population 14] through the appropriate I T valve
-1. With this arrangement, the ambient air containing the detected chemical components is transferred to the gas mixer 11!
1 is inserted, and +J1. Identification and restoration of the Rimple for Senryoku ("☆ Desired in x'f prior to analysis by preparation/senkiri)
It is mixed with air in the gas mixer 11 up to the fetal range.

Gas mixer 111. -1. Optionally, the desired platform, ambient air, or other source of ripple to be detected can be directly connected to the remainder of the detector 10.

The output 115 of the gas mixer 11 is coupled to the sensing-I unit 20.
′! Electrooxidation of incoming chemicals (J,
The electrochemical ['! Including Green 21. The sensing unit 20 also includes a heating filament 23 that heats the gas rift before it is introduced into the electrochemical sensor 1y21. 23 to the filament 1 is preferably used as a heater (not l, but also as a catalytic reactor).
~23 is determined by the appropriate +A
stones, such as [t, Pd, I-<h, ALJ, I r.

Like the immortal catalyst, it is very likely that it is a QC:1 metal. In the experimental model of the present invention (for F3, filamen 1 to
A metal catalyst made of a platinum metal such as 23 ia R11 or a metal catalyst such as 1;1 molybdenum can be used. Additionally, any [-microcatalytic] reactor capable of repeating lJ and producing rapid modulation (e.g., faster than the response of the sensor) can be used.

Filamen 1 to 23 are powered by power source 3], function generator 3243
and a current amplifier 33. More specifically, the power supply 331 is connected to the function generator 32
and current amplifier 33. The function generator 32 is connected to the filament 2301 via the current amplifier 33.
The terminals of the filaments 1 to 23 are connected to the power source 31 via a current 134 to create an output signal with a predetermined waveform, such as a sawtooth waveform applied to two terminals.

An electric FH 135 may be connected to both ends of the Noiramen l-23. The current through filament 23, and therefore its hot stone, is modulated by the output signal from function generator 32, as explained in more detail below.

The sample gas exits the electrochemical 1=n')-21 and passes through a meter 36 and a pump 37 to a suitable ventilation node (not shown). This allows chemicals that may be toxic or dangerous.
C' can also be safely discharged.

Electrochemical sensor 21 produces an electrical output signal produced by potentiostats 1-22 and read by electronic processor 40. The electronic processor 1) can also include a microprocessor. processor 40
The sensor 1 receives the output signals from the sensors 1 to 20, and also has a suitable storage device 42, such as a semiconductor memory device.
Preferably, a comparator 41 is also coupled to the comparator 41.

Standard response parameters for a plurality of different chemicals are stored in storage device 42 . Modulation of filament 23 causes a corresponding modulation of the output signal from electrochemical sensor 21, producing a characteristic output response parameter. This response parameter is stored in the storage device 42 in the comparator 41.
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If a match is detected, the identification of the chemical component detected and an appropriate indication of the temperature will be displayed on the display/13. You can use the following. For example, the display board/'13 can provide readout to a digital display only device, such as a CRI-and other types of display devices.

Now, referring also to Fig. 3a and Fig. 3[), the detector '1
Taking as an example the detection of 41 non to create 0 and convert 1 to cyclo, ηβ(
Because of this [-1, electrochemical Renri 2
141. As C○ Senri, Noiramen 1-233 are [
<1) Fillamen 1~. 20Orpm Schiff [1
The air contaminated with 11 phosphorus flows through 23 to 10 liters and is passed to 1 Yin 21. The modulator 30 adjusts the temperature lα of the filaments 1 to 23 to about 1500'C with the ambient temperature stone.
The actual range of change will be determined by the output No. 15 from the function generator 32.

Finomen 1 to 23 uses the reaction in Schiff's notebook to cause the thermal decomposition reaction of 15 = Schiff [1 = 4-phosphorus air (20% oxygen) = C0-
1 - Product low temperature polishing, e.g. below about 200'C, little or no thermal decomposition of Schiff[]hex1J occurs (i.e. reaction), the powder is low at this temperature, and once The electrochemical sensor 21 reading is zero. However, as the stone is exposed, this reaction begins to become noticeable and responds to an increase in flash intensity.

CO', 1 - Growth rate 1 True speed 1 meal The normal kinetic equation (1) is as follows: d(Co)/d-1 -1゛[Schiff]-1 to Kirin] (Air) (C) However, C) is a catalyst hot stone that is usually taken up to 1 east, and r
is the rate constant. Air or Schiff [1 hex 1 J-n warm stone (J) can be taken up to any power.The rate constant is expressed as follows: , = A o-F/kt where A' is the pre-exponential coefficient. , 1- is the absolute warm stone, k is the small Ruthmann constant, and ``is this reaction 16 prima facie activity 1] 1 cation-1-nel''.

In this case, the function generator 32 generates a sawtooth-shaped output waveform, the result of which is the filament 1 according to the waveform 50 in Figure 38.
~) The sawtooth-shaped modulation of a hemp is a cow, and a warm stone goes through one complete cycle in about 40 seconds. The temperature is about 600°0 i1 (
It circulates between a low point 51 and a high point 52 of about 1000°Q. This modulation of ficimen 1~temperature continually changes the Co production rate and produces a modulated output signal from sensor 21, as shown by waveform 60 in Figure 3b.

Line 61 of FIG. 3b represents the output produced by Renly 21 in response to a background or baseline level, ie, pure air, while the actual pure air response signal is shown by portion 62 of the waveform. As more gas is introduced into the sensor 21, the response strengthens and approaches the steady state level shown by the right portion of waveform 60. As you can see from the graph, this response (j
, a modulated signal 63 varying between an upper peak 6/1 and a lower peak 65. The peak-to-peak amplitude of the signal 63 is a-b, where a is the distance between the upper peak 64 of the baseline 61 and b is the distance between the lower peak 65 of the baseline 61.

CO production [As seen from the above kinetic equation for body, the rate of Co production, and hence the sensor output signal, is proportional to the temperature of cyclohexane if the air and catalyst temperatures are kept constant. Particularly good. Also, parameters unrelated to concentration are Schiff [1 hexane? FaW
Co production rate divided by d(CO)/(cyclobequinone)dl=r(air)
[C], which is constant at a given concentration and temperature.

Thus, as can be seen from the above equation, which closes to the rate constant r, a change in the temperature of the filament 1 results in a varying CO concentration, which is determined by the pre-exponential index A and the activation energy. .This reaction rate constant r+J is very specific for chemical reactions.Thus, between the thermally modulated COi [σ(511, heated 1 pe [1 Neuramen 1~ Activity 1 for producing CO from 11J to syn l-1 of F
(1 conversion) ■ Proportional to the net energy.Since the Co concentration of υ1 in the cyclohekirin hot stone is unrelated to the ``1 hegirin hema,'' this information is It can be used to identify as

This information is represented by the normalized parameter h/'a. Here h=a-b, that is, waveform 6
It is expressed by dividing the peak-to-peak amplitude of 0 by the height of the L portion peak 64. Upper peak 6/1
It is known that the height of is proportional to cyclohe4phosphorus 1α.

Furthermore, as shown in Figure 4, the parameter h/a is a pseudo-value for many of the investigated chemical components such as ammonia, acrylonitrile, cyclohenylA-phosphorus, methane, acrylonitrile, and benzine. Live 1 No 1 King Nergi (
It has also been found that it is proportional to (kcal/mol). It has also been found that the peak-to-peak amplitude [ ] of the signal response waveform 60 and the height I a of the upper peak 64 are proportional to I1 and to the intensity Iσ of the chemical component to be detected.

Thus, f rl-t putri/1.01J, (Morichi I
Actuates based on the output waveforms from 1 to 20 (〕-(
While determining M h and J-1 and parameter h/a,
Comparing this parameter with 6Ki 1 Cargo Ff / 12 (Ko Furuichi n) Zasawai (! Parameter (Lee-41 Wara pseudo-activation 1) 1 ka dried flannel-V), Shin [1 Identify the 41 contaminant 7J1, such as 4-phosphorus, and record its concentration.

10) In a preferred practical example, the catalytic surface of the filament 23 is separated from the electrochemical liquid 21. However, the principles of the present invention can be modified to simulate a warm contact reaction on a semiconductor substrate, and then this same surface is used as a gas detector.
This suitable real M!!
Although the example describes thermal modulation of an electrochemical CO sensor for hydrocarbon detection, the present invention is immediately applicable to other types of modulation of other types of sensors and other types of interaction. b is applied to Thus, for example, in order to modulate the photon input to the ionization detector for measuring the ionization energy of the phase n effect,
The infrared input to the remopile detector is modulated to detect the chemical compound 'd, which is a strong infrared absorber of methane. Infrared training 11■ It is possible to measure the coefficient -C. Similarly, the ionization potential can be measured by thermoelectrically modulating the thermal Nerugi input to the ionization detector.Another alternative is to
For example, modulating a chemiluminescent detector, such as an A-sin, to determine the rate order. Such a method is
For example, detection of nitric oxide could be used. Another method is to use a microwave detector and Jj (
This method uses magnetic modulation, and this method has the following disadvantages:
Used to detect odd molecules that have electrons. in general,
What is needed for the present invention is a means (e.g., energy input) for chemically modulating the phase effects of the chemical to be detected in the sample, and other methods (e.g., energy input). means for detecting the detected signal. This allows one to determine the kinetic or thermodynamic parameters of Provide selected information.

One Middle Eastern aspect of the invention is that the minimum number of parts can be
It is possible to selectively identify a large number of chemical components using a single detector, resulting in a widely available detector that is conveniently miniaturized for portable and field use. . Furthermore, the detector 1 of the present invention. -J, H1 can be configured to produce an output display that is easy to understand and can be used by inexperienced editors.

Although the above explanation has explained the operation of the gas 1 non-polymer, it should be understood that the principle of the present invention can also be applied to the analysis of chemical substances in a liquid medium.

-22= 1, li”Hi in the drawing 1111. Light Figure 1 (9
1. The number of detections in this defense is 11" 1° fl-1 ivy diagram, 2nd
The figures are clearly used in this explanation.
;Jbi☆chokiσ) Ten 111! For example, i1Y thin (, 7 shows 1J
Figure 11'1, Figure '3ε] is a heat generator) 114 Old style of Grano, Figure 3B is a barrel model or 20flrl
The modulated output from the Schiff[1-) phosphorus-containing air 4) when sensing -1-tsu1~ of +... is expressed by n;', the same as in Figure 3[). Grano, OJ, Ge Figure 4 1
;i, Rh Meiramen 1~upper (kodenki 11'', scientific (
J-Katsu・1] Pseudo-Katsu 1-1 for making 71 compounds from 1 compound
Express the relationship between the chemical T channel 1' and the bassimeter l'l/21. k:, f parable 1) 1
-1 channel 71゛ is made smaller.

1(-)...detection);;(,20...]X&ri,1
11 nits, 21...71X Ki 41', Gakurenri,
22...Bonshi E] Stats 1~. 23...Nietsu-Noiramen 1~. 330...modulator, 40...f
I"'l lryo・sori.

Claims (1)

Claims: 1. exposing a fluid sample containing a particular component to a sensing unit that has an energy input and interacts with the particular component with parameters that vary with the component to generate a response; modulating an energy input to generate a modulated response proportional to the parameter; and measuring the parameter to identify and/or quantify the specific component from the modulation of the response. A method for identifying specific components from a fluid sample. 2. a sensing unit having an energy input and interacting with a particular component in a fluid sample to produce a response with parameters varying depending on the component; and a device for directing the fluid sample to the sensing unit; an apparatus for modulating an energy input to generate a modulated response proportional to the parameter; and processing the response to identify the particular component and/or
or a device for measuring the parameter for quantitative determination.