JPH0726950B2 - Carbon content measuring device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a TOC meter (TOTAL ORGANIC CARBON analyzer), and particularly to a carbon content measuring device capable of measuring both organic carbon content and inorganic carbon content. It is about.

“Prior art and its problems” In general, when conducting a water quality test, it is necessary to measure both the amount of inorganic carbon and the amount of organic carbon. As a device for measuring such carbon amount, an inorganic carbon amount measuring device is used. And an organic carbon content measuring device have been conventionally used. The inorganic carbon measuring device is for measuring the amount of carbon dioxide which is inorganic carbon, and the organic carbon measuring device is for measuring the amount of organic carbon in the sample liquid after degassing carbon dioxide. It is a thing.

Further, in these measuring devices, one measuring line for measuring the sample is provided for each of the inorganic carbon measuring device and the organic carbon measuring device, whereby the measurement of the inorganic carbon amount or the organic carbon measuring device is performed. When measuring the amount of carbon, it is necessary to prepare a dedicated analyzer for each, which increases the equipment cost, and the dedicated analyzer requires a large installation area for the device.

This invention has been made in view of the above circumstances, by sharing a part of the measurement line, it is possible to measure both the amount of organic carbon and inorganic carbon,
An object of the present invention is to obtain a carbon content measuring device which can reduce the installation area for arranging the device.

"Means for Solving Problems" The present invention relates to a sample supply means for supplying a sample containing a carbon compound, a reaction solution supply means for supplying a reaction solution to the sample, and an organic carbon in the sample. A reactor that reacts with the reaction liquid to generate carbon dioxide, and a measuring means that extracts carbon dioxide from the reaction completion liquid that has passed through this reactor and measures the amount of carbon contained in the sample. Is provided
In addition, the sample supply means, a first pipe line in which a deaerator for degassing carbon dioxide contained in the sample is arranged between the sample supply means and the reactor, and the degasser. A two-system pipeline consisting of a second pipeline bypassing the aerator is provided, and further, the reaction solution supply means is provided with a reaction solution control means for stopping the supply of the reaction solution, and the first flow path is provided. A flow path selecting means for switching between the first and second flow paths is provided in a branch path between the first flow path and the second flow path.

[Operation] According to the present invention, the sample supplied from the sample supply unit is degassed by the flow path selection unit selecting the first flow path and the reaction liquid control unit supplying the reaction liquid. Via the channel, the degassing of the carbon dioxide contained in the sample takes place. Then, the sample that has passed through the deaerator reacts with the reaction liquid in the reactor to generate carbon dioxide from the organic carbon contained in the sample. Further, the amount of organic carbon contained in the sample can be measured by quantifying the produced carbon dioxide in the reaction completed liquid that has passed through the reactor by the measuring means.

On the other hand, the flow path selecting means selects the second flow path, and
When the reaction solution control means stops the supply of the reaction solution, the sample supplied from the sample supply means bypasses the deaerator, whereby the carbon dioxide contained in the sample is quantified by the measuring means. The carbon dioxide contained in the sample, that is, the amount of inorganic carbon can be measured.

[Embodiment] An embodiment of the present invention will be described below with reference to FIGS. 1 and 2.

In FIG. 1, reference numeral 1 is a supply pump (sample supply means).
A supply line connected to the first sample supply line 2 to which the sample is directly supplied and the second sample supply line 3 to which the sampled sample is supplied to the suction side 1a of the supply pump 1. 4 are provided. A three-way solenoid valve 5 is provided at the confluence of the sample supply line 2 and the sample supply line 3, and by switching the three-way solenoid valve 5, an in-line (not shown) of the first sample supply line 2 is provided. The supplied sample and the sampled sample are selectively sent to the supply line 4.

A pipe 6 is provided on the discharge side 1b of the supply pump 1, and a means for supplying a reaction liquid (reaction) that reacts with the carbon compound in the sample sent from the supply pump 1 is provided in the middle of the pipe 6. A liquid supply means) 7 is provided.

The reaction liquid supply means 7 will be described below.
The reference numeral 10 is the first reaction liquid supply line used when measuring the amount of organic carbon contained in the sample supplied from the supply line 4, and the reference numeral 11 is the sample 2 is a second reaction liquid supply line used when measuring the amount of inorganic carbon contained in.

The reaction liquid supplied from the first reaction liquid supply line 10 is a solution composed of an aqueous solution of sulfuric acid which is an acidic solution and a solution of potassium persulfate which is an aqueous solution of persulfate (hereinafter referred to as reaction liquid A). Suitable and second reaction liquid supply line
As the reaction liquid supplied from 11, an aqueous solution of sulfuric acid which is an acidic solution (this solution is hereinafter referred to as reaction liquid B) is suitable.

The first reaction solution supply line 10 and the second reaction solution supply line 11 are connected to the suction side 13 of the supply pump 13 via the supply line 12.
The discharge side 13b of the supply pump 13 is connected to
It is connected to the pipe 6 through a pipe 14. A three-way solenoid valve (reaction liquid control means) 15 is provided at the confluence of the supply lines 10 and 11, and by switching the three-way solenoid valve 15, the supply line 10 and the supply line 11 are connected. The two types of reaction solutions supplied from the above are selected (the three-way solenoid valve 15 stops the supply of the reaction solution potassium persulfate aqueous solution).

On the other hand, a three-way solenoid valve 20 is disposed downstream of the pipe 6, and by switching the three-way solenoid valve 20, the pipe 6 becomes the pipe 21 (first flow path) or the pipe 6 Are respectively connected to the pipes 22 (second flow paths). That is, the pipe 6 is divided by the three-way solenoid valve 20 into two lines of the pipe 21 and the pipe 22.

A deaerator 23 for extracting carbon dioxide in the sample supplied by the supply pump 1 is provided in the middle of the pipe 21. The degasser 23 degasses the carbon dioxide from the sample sent into the degasser 23 by making an inert gas such as helium into a bubble and blowing it into the mixed liquid of the reactor and the sample liquid. It has become.

A three-way solenoid valve 24 is provided at the downstream merging portion of the pipe 21 and the pipe 22, and by switching the three-way solenoid valve 24, the pipe 21 becomes the pipe 25 or the pipe 22 becomes the pipe 25. It is designed to be connected to. That is, the three-way solenoid valve
Piping 21 and piping divided into two lines by 20
The three-way solenoid valve 24 integrates 22 into the pipe 25 of one system (the three-way solenoid valves 20 and 24 form a flow path selecting means).

Also, the three-way solenoid valves 15, 20, 24 are select switches.
The switching is made by 26.
That is, when the amount of organic carbon contained in the sample supplied from the supply line 4 is measured, the organic carbon measurement signal O is sent from the select switch 26 to the three-way solenoid valves 15, 20, 24.
Is output, and the supply line 10 and the line 12 are connected, and the pipe 6 and the pipe 25 are connected by the pipe 21. When measuring the amount of inorganic carbon contained in the sample supplied from the supply line 4, the select switch 26 outputs an inorganic carbon measurement signal I to the three-way solenoid valves 15, 20, 24 to supply the inorganic carbon. The line 11 and the pipe 14 are connected, and the pipe 6 and the pipe 25 are connected by the pipe 22.

On the other hand, the downstream side of the pipe 25 is the suction side 30 of the pressurizing pump 30.
It is attached to a and also the discharge side 30b of this pressurizing pump 30.
A pipe 32 in which a reactor 31 is provided is attached in the middle of the pipe.

The reactor 31 will be described with reference to FIG. 2. The middle portion of the pipe 32 is arranged along a groove 33a formed in a spiral shape around the drum heater 33. The pipe wall of the pipe 32 by the heat supplied from
The temperature of 32a is raised to cause a reaction between the reaction liquid flowing through the pipe 32 and the sample. A thermocouple 34 is attached to the pipe wall 32a of the pipe 32, and based on the temperature of the power distribution 32 detected by the thermocouple 34,
The control unit indicated by the reference numeral 35 in FIG. 1 adjusts the temperature of the drum heater 33 so as to be constant, and when the temperature inside the pipe 32 suddenly decreases, the pressurizing pump is operated. 3
0, the driving of the supply pumps 1 and 13 is stopped, and the drum heater 3
The power supply to 3 is stopped.

On the other hand, the downstream side of the pipe 32 is an extractor via a pressure reducing valve 40.
Connected to 41. This extractor 41 removes carbon dioxide contained in the sample as an inorganic carbon, and carbon dioxide generated from organic carbon in the sample by adding the reaction solution B (a reaction process will be described later in terms of action). ,
It is extracted from the reaction completion liquid supplied from the reactor 31. Then, the carbon dioxide extracted by the extractor 41 is sent to the infrared spectroscopic analyzer 43 by the pipe 42 provided at the upper part of the extractor 41 to be quantified, and after the carbon dioxide is extracted. The waste liquid is sent to a waste liquid storage section (not shown) by a pipe 44 provided in the lower part of the extractor 41.

The extractor 44 and the infrared spectroscopic analyzer 43 constitute a measuring means 45.

Next, the operation of the carbon content measuring device configured as described above will be described in the order of steps.

First, the process of measuring the amount of organic carbon contained in the sample will be described.

(1) A sample is supplied from the first sample supply rank 2 or the second sample supply line 3.

(2) The organic carbon measurement signal O output from the select switch 26 connects the first reaction solution supply line 10 and the supply line 12, and also connects the pipe 6 and the pipe 21. As a result, both the sample and the reaction solution A are sent to the deaerator 23.

(3) In the deaerator 23, carbon dioxide, which is an inorganic carbon material contained in the sample, is degassed by the sulfuric acid of the reaction solution A.

(4) The select switch 26 connects the pipe 21 and the pipe 25.

(5) The sample after deaeration of carbon dioxide in the deaerator 23 is sent to the reactor 31 via the pressure pump 30.

(6) In the reactor 31, the organic carbon contained in the sample reacts with potassium persulfate, whereby carbon dioxide is produced from the organic carbon.

(7) In the extractor 41, the carbon dioxide produced in the previous step is extracted from the reaction completed liquid that has passed through the reactor 31.

(8) The carbon dioxide extracted by the extractor 41 is connected to the pipe 42.
Is sent to the infrared spectroscopic analyzer 43 via the, and its quantification is performed. At this time, the infrared spectroscopic analyzer 43
In some cases, an inert gas such as helium supplied in the deaerator 23 may be mixed in, but it does not affect the analysis of carbon dioxide.

Next, the process of measuring the amount of inorganic carbon contained in the sample will be described.

(1) A sample is supplied from the first sample supply line 2 or the second sample supply line 3.

(2) By the inorganic carbon measurement signal I output from the select switch 26, the second reaction solution supply line 11 and the supply line 12 are connected, the pipe 6 and the pipe 22 are connected, and the pipe 22 is further connected. And the pipe 25 are connected. As a result, the sample and the reaction solution B bypass the deaerator 23, and the reactor 31
Sent to.

(3) In the reactor 31, carbon dioxide, which is an inorganic carbon material contained in the sample, is separated from the sample solution by the sulfuric acid of the reaction solution B.

(4) The carbon dioxide separated from the sample is extracted by the extractor 41.

(5) The carbon dioxide extracted by the extractor 41 is sent to the infrared spectroscopic analyzer 43 via the pipe 44, and its quantitative determination is performed.

In the above carbon content measuring device, the three-way solenoid valves 15, 20,
By switching 24, it is possible to select two systems, that is, the flow path C passing through the deaerator 23 and the flow path D bypassing the deaerator 23, whereby the dioxide contained in the sample is contained. carbon,
That is, when measuring the amount of inorganic carbon, it is possible to select the channel D, extract the carbon dioxide in the sample as it is, and further quantify the extracted carbon dioxide in the infrared spectroscopic analyzer 43. it can.

Further, when measuring the amount of organic carbon contained in the sample, first, by selecting the flow path C, first, the inorganic carbon material (that is, carbon dioxide) contained in the sample
It is possible to degas and further generate carbon dioxide from the organic carbon in the sample in the reactor 31, then extract this and quantify it with the infrared spectroscopic analyzer 43.

Therefore, in the above carbon content measuring device, the three-way solenoid valve
By switching between 15, 20, and 24, both the amount of inorganic carbon and the amount of organic carbon can be measured.Compared with the conventional measuring device that measured the amount of inorganic carbon and the amount of organic carbon respectively with a dedicated machine. In addition, both the equipment cost and the installation area can be reduced.

Further, since switching to these solenoid valves 15, 20, 24 is performed by the select switch 24, automatic measurement is possible and the operation can be easily performed.

On the other hand, the pipes 32 and the like in the reactor 31 are damaged, or the pipes 32 are corroded by the reaction liquids A and B, and the reaction liquids A and B and the sample water leak, which causes
When it is detected that the temperature of the pipe 32 has dropped sharply, the control unit 35 stops driving the pressurizing pump 30, the supply pumps 1 and 13, and stops supplying power to the drum heater 33. Therefore, the operation in an abnormal state such as leakage of the reaction liquids A and B and the sample water is prevented, and the amount of carbon contained in the sample can always be measured accurately.

Although potassium persulfate, which is an aqueous solution of persulfate, was used as a reagent for oxidizing organic carbon, it is not necessarily limited thereto. Permanganate such as potassium permanganate, chromate such as potassium chromate, etc. Etc. may be used.

Further, the reaction liquid supplied from the reaction liquid supply means 7 is only a potassium persulfate aqueous solution which is an aqueous persulfate solution, and in addition to the reaction liquid supply means 7, a sulfuric acid aqueous solution which is an acidic solution is exclusively supplied. May be provided.

"Effects of the Invention" As described in detail above, according to the present invention, sample supply means for supplying a sample containing a carbon compound, reaction solution supply means for supplying a reaction solution to the sample, and the sample By reacting the organic carbon in the reaction liquid with the reaction liquid to generate carbon dioxide, and extracting carbon dioxide from the reaction completion liquid that has passed through this reactor, the amount of carbon contained in the sample can be determined. A measuring means for measuring is provided, and a deaerator for deaerating carbon dioxide contained in the sample is arranged midway between the sample supply means, the reaction solution supply means and the reactor. Two channels, one channel and a second channel bypassing the deaerator, are provided, and further, the reaction solution supply means is provided with a reaction solution control means for stopping the supply of the reaction solution. At the same time, in the branch path between the first flow path and the second flow path,
Since the flow path selecting means for switching the first and second flow paths is provided, the flow path selecting means selects the first flow path, and
When the reaction solution control means supplies the reaction solution, the sample supplied from the sample supply means passes through the deaerator, and in the deaerator, degassing of carbon dioxide contained in the sample is performed. Then, carbon dioxide is produced from the organic carbon contained in the sample in the reactor. Then, in the measuring means, the amount of organic carbon contained in the sample is measured by quantifying the carbon dioxide produced from the organic carbon.

On the other hand, the flow path selecting means selects the second flow path, and
When the reaction liquid control means stops the supply of the reaction liquid, the sample supplied from the sample supply means bypasses the deaerator, whereby the carbon dioxide contained in the sample is quantified by the measuring means. Then, the carbon dioxide contained in the sample, that is, the amount of inorganic carbon is measured.

Therefore, in the present invention, both the amount of inorganic carbon and the amount of organic carbon can be measured by stopping the supply of the reaction liquid by the reaction liquid control means and switching the first and second flow paths by the flow path selection means. Therefore, it is possible to reduce both the equipment cost and the installation area of the conventional measuring device, which measures the inorganic carbon amount and the organic carbon amount by a dedicated machine.

[Brief description of drawings]

1 and 2 are views showing an embodiment of the present invention. FIG. 1 is a system diagram showing the overall schematic configuration, and FIG. 2 is a front sectional view showing a part of a reactor. 1 ... Supply pump (sample supply means) 7 ... reaction solution supply means 15 ... three-way solenoid valve (reaction solution control means) 20, 24 ... three-way solenoid valve (flow path selection means) 21 ... piping (first) 22 …… Pipe (second flow path) 23 …… Deaerator 31 …… Reactor 45 …… Measuring means

Claims (3)

[Claims] 1. A sample supply means for supplying a sample containing a carbon compound, a reaction solution supply means for supplying a reaction solution to the sample, and an organic carbon in the sample and the reaction solution are reacted to each other, It comprises a reactor for producing carbon, and a measuring means for extracting carbon dioxide from the reaction completion liquid passing through this reactor to detect the amount of carbon contained in the sample, the sample supplying means, the reaction liquid Between the supply means and the reactor, there is provided a first flow path in which a deaerator for deaerating carbon dioxide contained in the sample is arranged, and a second flow path bypassing the deaerator. Two lines of a flow path and a flow path are provided in parallel, and the reaction solution supply means is provided with a reaction solution control means for stopping the supply of the reaction solution. Two
A carbon content measuring device, characterized in that a flow path selecting means for switching between the first and second flow paths is provided in a branch path from the flow path. 2. The carbon content measuring device according to claim 1, wherein the reaction solution is composed of a persulfate aqueous solution. 3. The reaction liquid supplied from the reaction liquid supply means comprises a first reaction liquid composed of an acidic solution and a second reaction liquid composed of an acidic solution and a persulfate aqueous solution. Further, the reaction liquid control means includes the first,
The carbon content measuring device according to claim 1, wherein the second reaction liquid is selectively supplied.