KR101528126B1 - Device for measuring TOC and TN based on non-catalytic heat-combution oxidization method - Google Patents

Abstract

Disclosed is an apparatus for measuring total organic carbon and total nitrogen in real time based on non-catalytic heat combustion oxidization method, which comprises a carrier gas pump (100); a pump terminal (11) having a first pump (102) for sucking a sample solution in order to supply the same to the next terminal, having a second pump (106) for sucking hydrochloric acid from a hydrochloric acid tank (104) in order to supply the same to the next terminal, and having a third pump (110) for sucking the sample solution acid-air bubbling-treated by a preprocess sample storing port (14) in order to supply the same to the next terminal; a three-way mixing connector (12) for mixing the sample supplied by the first pump (102) with the hydrochloric acid supplied by the second pump (106) in real time, in order to supply a sample solution mixed with the hydrochloric acid to the next terminal; a preprocess port (13) having an outlet (136) for supplying a homogeneous sample solution prepared by applying air-bubbles into the sample solution mixed with the hydrochloric acid to the next terminal; and a preprocess sample storing port (14) having a second sample solution inlet (140) supplied with the sample solution through the outlet (136) of the preprocess port (13), having a second outlet (142) for discharging a residual sample solution, and having a sample suction straw (144) installed therein for sucking the sample solution acid-air bubbling-treated which is supplied by the third pump (110) in order to supply the same to a non-catalytic heat combustion oxidization reactor (15) for measuring the same in the next terminal.

Description

TECHNICAL FIELD [0001] The present invention relates to a device for measuring total organic carbon and total nitrogen based on a non-catalytic hot-

The present invention relates to an apparatus for measuring total organic carbon and total nitrogen, and particularly relates to an apparatus for measuring total organic carbon and total nitrogen in real time based on a no-catalyst hot-smelting method and purifying air without using high purity nitrogen as a carrier gas So that the unit cost of the measurement is also low. The present invention relates to a total organic carbon and total nitrogen measuring device.

Conventional Total Organic Carbon Continuous Automatic Measuring Apparatus is a system for measuring the total organic carbon continuously measured by various steps including injection of reagent from a storage device, injection of reagent, pretreatment of sample, transfer of pretreatment sample to oxidizer, measurement after oxidation and washing Is completed. Therefore, since the measurement is performed at an interval of a predetermined time interval, for example, 10 minutes to 60 minutes, there is a limit in that a measured value can not be obtained within 2 minutes, which can be regarded as substantially continuous real time continuous automatic measurement.

SUMMARY OF THE INVENTION The present invention has been developed in order to solve the problems described above, and it is an object of the present invention to provide a method and apparatus for controlling the amount of hydrochloric acid and a sample water supplied from a hydrochloric acid storage tank, Port, and when hydrochloric acid is pretreated by air bubbling, it is transferred to a separate storage port and measured. Thus, it is possible to perform continuous pre-treatment in the pre-treatment port, Carbon and total nitrogen.

According to an aspect of the present invention, there is provided an apparatus for measuring total carbon, total organic carbon, total inorganic carbon,

A carrier gas pump 100 for supplying carrier gas and air of constant pressure for air bubbling treatment at the downstream end;

A second pump 106 for sucking hydrochloric acid from the hydrochloric acid tank 104 to provide the next stage and a second pump 106 for supplying acid and / or hydrocarbons from the pretreatment sample storage port 14, A pump stage (11) including a third pump (110) for sucking the air bubbled sample water and supplying it to the next stage;

A three-way mixing connector 12 for mixing the sample provided by the first pump 102 and the hydrochloric acid provided by the second pump 106 in real time to provide a sample solution containing hydrochloric acid as a next step;

A first sample water inlet 130 for receiving the sample water supplied from the three-way mixing connector 12, an air supply port 132 for receiving air supplied from the carrier gas pump 100, An air bubble forming unit 134 for discharging air bubbles to the inside by the positive pressure of the air received from the air supply port 132, and a homogenous sample water prepared by adding air bubbles to the sample water mixed with hydrochloric acid, A pretreatment port 13 comprising an outlet 136 for feeding into the stage;

A second sample water inlet 140 for receiving the sample water through the outlet 136 of the pretreatment port 13 and a second outlet 142 for discharging the remaining sample water, A sample aspiration straw 144 sucking the acid and air treated sample water provided by the non-catalytic hot-oxidation reactor 15 for the measurement at the next stage is connected to a pretreatment sample storage port (14);

A non-catalytic thermal oxidizer 15 for oxidizing the sample supplied through the sample suction straw 144 of the pretreatment sample storage port 14 by thermal combustion; And

And a measuring unit 504 for measuring the total organic carbon component or the total nitrogen component by receiving the oxidized gas.

Also, it is preferable that the pre-treatment sample storage port 14 is formed such that the bottom surface 146 is obliquely directed toward the lower side of the second outlet 142 so as to reduce the influence of the number of samples of the previous measurement on the number of samples of the next measurement Do.

Further, it is preferable that a plurality of air supply pipes 150, which are spaced apart from each other by substantially the same angle as each other, are installed on the upper part of the catalytic thermal oxidation / oxidation reactor 15 to receive the carrier gas.

The apparatus for measuring total time of total organic carbon and total nitrogen according to the present invention can measure the amount of TOC or TN discharged according to the steps of each step in the reaction production process without time lag, The TOC amount of the wastewater discharged after completion of the reaction can be measured in real time, so that the wastewater treatment time can be greatly shortened and the wastewater treatment efficiency can be drastically improved. In addition, since the total organic carbon can be continuously measured without any delay in the flow of the river and the river, the contamination state of the river and the river can be measured in real time.

FIG. 1 is a block diagram showing the structure of a real-time total organic carbon and total nitrogen measuring device based on the non-catalytic hot-rolled oxide method according to an embodiment of the present invention.
FIG. 2 is a view showing the structure of the pretreatment port provided in the real-time total organic carbon and total nitrogen measuring apparatus of FIG. 1,
FIG. 3 is a view showing a structure of a pretreatment sample storage port provided in the real-time total organic carbon and total nitrogen measuring apparatus of FIG. 1,
FIG. 4 is a perspective view showing a structure in which a plurality of air supply pipes are disposed on an upper portion of a non-catalytic hot-flame oxidation reactor provided in the real-time total organic carbon and total nitrogen measuring device of FIG.
5 is a view for explaining the flow of carrier gas in a real-time total organic carbon and total nitrogen measuring apparatus based on the non-catalytic hot-rolled oxide method according to the present invention,
6 is a view for explaining a state in which a sample, an acid solution, and a carrier gas are simultaneously injected for pretreatment of a measurement sample in a real-time total organic carbon and total nitrogen measurement apparatus based on the non- drawing,
FIG. 7 is a view for explaining a state in which a pretreated sample and carrier gas are injected simultaneously into a non-catalytic hot-oxidation reactor in a real-time total organic carbon and total nitrogen measuring device based on the non-catalytic hot- ,
FIG. 8 is a view for explaining a state of measuring TOC or TN in a real-time total organic carbon and total nitrogen measuring apparatus based on the non-catalytic hot-oxidizing method according to the present invention, and FIG.
9 is a view for explaining a state of discharging TIC, overflow or post-measurement treated samples and condensed water in a real-time total organic carbon and total nitrogen measuring device based on the non-catalytic thermal oxidation method according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.

FIG. 1 is a block diagram showing the structure of a real-time total organic carbon and total nitrogen measuring apparatus based on the non-catalytic hot-oxidation method according to an embodiment of the present invention. 1, a real-time total organic carbon and total nitrogen measuring apparatus according to the present invention comprises:

A carrier gas pump 100 for supplying carrier gas and air of constant pressure for air bubbling treatment at the downstream end,

A second pump 106 for sucking hydrochloric acid from the hydrochloric acid tank 104 to provide the next stage and a second pump 106 for supplying acid and / or hydrocarbons from the pretreatment sample storage port 14, A pump stage (11) including a third pump (110) for sucking the air bubbled sample water and supplying it to the next stage,

And a three-way mixing connector 12 for mixing the sample provided by the first pump 102 and the hydrochloric acid provided by the second pump 106 in real time, do.

Also, as shown in FIGS. 2 and 3, the real-time total organic carbon and total nitrogen measuring apparatus includes:

The three-way mixing connector 12 is of the open type that does not include any valves. Therefore, in the three-way mixing connector 12, the sample provided by the first pump and the hydrochloric acid provided by the second pump are mixed in real time without a time delay, and the sample water mixed with hydrochloric acid is supplied to the next stage preprocessing port 13 to provide. A first sample water inlet 130 for receiving the sample water supplied from the three-way mixing connector 12, an air supply port 132 for receiving air supplied from the carrier gas pump 100, An air bubble forming unit 134 for discharging air bubbles to the inside by the positive pressure of the air received from the air supply port 132, and a homogenous sample water prepared by adding air bubbles to the sample water mixed with hydrochloric acid, And a pre-treatment port 13 including an outlet 136 for supplying the pre-

The air bubble forming unit 134 includes an air injection tube inserted into the body through the outside of the side surface of the body as disclosed in Korean Patent Application No. 10-2014-0105706 filed by the present inventor, An air tank which is spaced apart from the inner wall of the body and is hollow and has an air tank for storing and buffering the supplied air and a glass filter portion formed at a lower end portion including the bottom of the air tank, Is most preferable.

In addition, the real-time total organic carbon and total nitrogen measuring device may further include:

A second sample water inlet 140 for receiving the sample water through the outlet 136 of the pretreatment port 13 and a second outlet 142 for discharging the remaining sample water, A sample aspiration straw 144 sucking the acid and air treated sample water provided by the non-catalytic hot-oxidation reactor 15 for the measurement at the next stage is connected to a pretreatment sample storage port (14).

If the sample is completely exhausted from the pretreatment sample storage port 14, air is sucked into the sample and not only a predetermined amount of sample is supplied, but also the measured value may fluctuate abruptly. Therefore, according to the present invention, the sample aspirating straw 144 for always supplying the sample to the rear stage catalystless thermal oxidizer 15 is always installed in the sample water reservoir. The pre- As shown in the drawing, the bottom surface 146 is formed obliquely toward the lower side of the second outlet 142. Therefore, the number of samples that become floated on the bottom side, that is, the number of samples of the previous measurement, is less influenced by the number of samples of the next measurement.

Also, since the bottom surface 146 of the pretreatment sample storage port 14 is formed obliquely toward the lower side of the second outlet 142, the number of samples of the previous measurement is prevented from affecting the number of samples of the next measurement, It should be noted that the amount of the sample of the measurement is reduced compared to the case where the bottom is flat, minimizing the influence of the previous sample which must be generated in real-time continuous measurement.

In addition, the real-time total organic carbon and total nitrogen measuring device may further include:

A non-catalytic thermal oxidizing reactor 15 for oxidizing the sample supplied through the sample suction straw 144 of the pretreatment sample storage port 14 by thermal combustion, and

And a measurement unit 504 for measuring the total organic carbon component or the total nitrogen component by receiving the oxidized gas.

FIG. 4 is a perspective view showing a structure in which a plurality of air supply pipes are disposed on top of the non-catalytic hot-flame oxidation reactor provided in the real-time total organic carbon and total nitrogen measuring apparatus of FIG. Referring to FIG. 4, a plurality of air supply pipes 150 spaced apart from each other by substantially the same angle as each other are installed on the upper portion of the catalytic thermal oxidation / oxidation (NOx) reactor 15, It was confirmed that the deviation of the measured value due to the air flow fluctuation was reduced by about 20% as compared with the case of supplying the single flow tube.

FIG. 5 is a view for explaining the flow of carrier gas in a real-time total organic carbon and total nitrogen measuring apparatus based on the non-catalytic hot-oxidation method according to the present invention. 5, an air bubble is formed by the air injected into the air bubble forming part 134 of the pretreatment port 13 to bubble air of hydrochloric acid and the sample, and the air bubble is formed in the pretreatment sample storage port 14 And is drained to the wastewater tank 500. In addition, a flow of carrier gas is simultaneously carried out for injecting the sample into the non-catalytic hot-smelting oxidation reactor 15 to be hot-rolled, cooled by the cooler 502, and fed into the measuring unit 504.

FIG. 6 is a graph showing the state of simultaneously injecting a sample, an acid solution, and a carrier gas for pretreatment of a measurement sample in a real-time total organic carbon and total nitrogen measuring apparatus based on the non-catalytic hot- Fig. Referring to FIG. 6, the first pump 102 sucks the sample water from the sample water storage tank 600 while air bubbling is being performed by the carrier gas pump 100 as described in FIG. 5, The pump 106 sucks the hydrochloric acid from the hydrochloric acid tank 104 and the three-way mixing connector 12 mixes the sample provided by the first pump 102 and the hydrochloric acid provided by the second pump 106 in real time And the sample water mixed with hydrochloric acid is introduced into the first sample water inlet 130 provided at the lower end of the pretreatment port 13 to perform air bubbling treatment. It is a matter of course that the sample, the acid solution and the carrier gas are simultaneously injected for the pretreatment of the measurement sample.

7 is a view for explaining a state in which a pretreated sample and carrier gas are simultaneously injected into a non-catalytic hot-oxidation reactor in a real-time total organic carbon and total nitrogen measuring device based on the non-catalytic hot- Respectively. Referring to FIG. 7, the third pump 110 sucks the sample pretreated from the sample storage port 14 and injects the sample into the non-catalytic thermal oxidation reactor 15, wherein the carrier gas is also supplied to the catalytic hot- 15). That is, the pretreated sample and the carrier gas are simultaneously injected.

FIG. 8 is a view for explaining a state of measuring TOC or TN in a real-time total organic carbon and total nitrogen measuring device based on the non-catalytic hot-oxidation method according to the present invention. Referring to FIG. 8, The hot-rolled gas in the catalytic hot-flame-oxidizing reactor 15 is cooled through the cooler 502 and the total organic carbon or total nitrogen is measured in the measuring unit 504.

9 is a view for explaining a state of discharging TIC and overflow or post-measurement treated samples and condensed water in a real-time total organic carbon and total nitrogen measuring device based on the non-catalytic hot-oxidizing method according to the present invention . 9, the TIC gas and the overflow are made through the outlet provided at the uppermost portion of the pretreatment port 13, and the sample water, which has been measured in the pretreatment sample storage port 14, is discharged through the discharge port into the waste water tank 500, Respectively. Also, the condensed water generated during cooling in the cooler 502 is collected by the fourth pump 900 into the wastewater tank 500.

The oxidation reactor 100 includes a cylindrical protection tube inserted into the reactor and provided with a sheave at a lower end thereof, a ceramic ball filled in the cylindrical protection tube, and a carbon ball And a temperature controller for supplying a current to the heater.

In addition, the apparatus according to the present invention as described above employs a method of charging a ceramic ball without using a platinum catalyst and heating it by heating at a high temperature, so that air can be purified and supplied without using high purity nitrogen as a carrier gas It is advantageous in that the unit price for measurement is low.

As described above, since the apparatus for measuring total time of total organic carbon and total nitrogen according to the present invention can measure the amount of TOC or TN discharged according to each step in the reaction production process without time delay, And the TOC amount of the discharged wastewater after the completion of the reaction can be measured in real time, so that the wastewater treatment time can be greatly shortened and the wastewater treatment efficiency can be drastically improved. In addition, since the total organic carbon can be continuously measured without any delay in the flow of the river and the river, the contamination state of the river and the river can be measured in real time.

In addition, the real-time total organic carbon and total nitrogen measuring device based on the non-catalytic hot-oxidizing method according to the present invention as described above provides a continuous automatic measuring structure designed simply and conveniently, And it is possible to perform real time measurement in which the breakage does not occur according to the flow of the sample to be measured since the oxidation time of the sample to be measured and the pretreatment time are minimized and the complete oxidation is performed.

Not only can it be used to control or establish the reaction process, but also the TOC amount of the wastewater discharged after completion of the reaction can be measured in real time, so that the wastewater treatment time can be greatly shortened and the wastewater treatment efficiency can be drastically improved. In addition, since the total organic carbon can be continuously measured without any delay in the flow of the river and the river, the contamination state of the river and the river can be measured in real time.

The present invention provides an apparatus for measuring total carbon, total organic carbon, total inorganic carbon, total nitrogen and volatile organic compounds, which is low in unit cost even when air is refined and supplied without using high purity nitrogen as a carrier gas.

100: Carrier gas pump
11: Pump stage
102: first pump 106: second pump
110: Third pump
104: Hydrochloric acid tank
12: 3-Way Mixed Connector
13: Pretreatment port
130: First sample water inlet port 132: Air supply port
134: air bubble forming unit 136:
14: Pretreatment sample storage port
140: second sample water inlet 142: second outlet
144: sample suction straw 146: bottom surface
15: Non-catalytic thermal oxidation reactor
150: air supply pipe

Claims (3)

A carrier gas pump 100 for supplying carrier gas and air of constant pressure for air bubbling treatment at the downstream end;
A second pump 106 for sucking hydrochloric acid from the hydrochloric acid tank 104 to provide the next stage and a second pump 106 for supplying acid and / or hydrocarbons from the pretreatment sample storage port 14, A pump stage (11) including a third pump (110) for sucking the air bubbled sample water and supplying it to the next stage;
A three-way mixing connector 12 for mixing the sample provided by the first pump 102 and the hydrochloric acid provided by the second pump 106 in real time to provide a sample water mixture of hydrochloric acid to the next stage;
A first sample water inlet 130 for receiving the sample water supplied from the three-way mixing connector 12, an air supply port 132 for receiving air supplied from the carrier gas pump 100, An air bubble forming unit 134 for discharging air bubbles to the inside by the positive pressure of the air received from the air supply port 132, and a homogenous sample water prepared by adding air bubbles to the sample water mixed with hydrochloric acid, A pretreatment port 13 comprising an outlet 136 for feeding into the stage;
A second sample water inlet 140 for receiving the sample water through the outlet 136 of the pretreatment port 13 and a second outlet 142 for discharging the remaining sample water, A sample aspiration straw 144 sucking the acid and air treated sample water provided by the non-catalytic hot-oxidation reactor 15 for the measurement at the next stage is connected to a pretreatment sample storage port (14);
A non-catalytic thermal oxidizer 15 for oxidizing the sample supplied through the sample suction straw 144 of the pretreatment sample storage port 14 by thermal combustion; And
And a measuring unit (504) for measuring a total organic carbon component or a total nitrogen component by receiving the oxidized gas. 2. The apparatus according to claim 1, wherein the pretreatment sample storage port (14)
Wherein the bottom surface (146) is formed obliquely downwardly of the second outlet (142) so as to reduce the number of samples of the previous measurement from affecting the number of samples of the next measurement. Device. The method as claimed in claim 1, wherein the catalytic NO x reduction reactor (15)
Wherein a plurality of air supply pipes (150) spaced apart from each other by substantially the same angle are installed on the upper part to receive the carrier gas.

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