JP2004081932A - Hydrothermal reactor and hydrothermal reaction treatment method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrothermal reactor capable of performing appropriate neutralization when an acid group-containing organic compound which forms an acid is subjected to supercritical hydroxylation decomposition. <P>SOLUTION: The hydrothermal reactor is characterized by being provided with a pH measuring means 38 to measure the pH of a reaction product in a discharge pipe 25 connecting a hydrothermal reaction vessel 13 with a cooler 23, a neutralizer injecting means to inject a neutralizer into the discharge pipe 25, and a neutralizer concentration and/or injection amount controlling means to control the injection rate of the neutralizer injected by the neutralizer injecting means according to the pH measurement measured by the pH measuring means 38. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a hydrothermal reaction device and a hydrothermal treatment method. In particular, the present invention relates to a hydrothermal reaction apparatus and a hydrothermal reaction treatment method capable of performing appropriate neutralization when performing supercritical hydroxylation decomposition of an organic compound containing an acid group that generates an acid.
[0002]
[Prior art]
In recent years, as one form of application of hydrothermal reaction, a method of treating waste by oxidizing or hydrolyzing organic substances and the like in the waste has attracted attention. In this method, the waste containing organic matter is reacted with the oxidizing agent (or water) in a supercritical or subcritical state of water, and the organic matter in the waste can be almost completely decomposed in a short time.
[0003]
The supercritical state of water is a state in which the temperature is 374 ° C. or higher and the pressure is 22 MPa or higher. The subcritical state is, for example, at a temperature of 374 ° C. or more and a pressure of 2.5 MPa or more and less than 22 MPa, or at a temperature of 374 ° C. or less and a pressure of 22 MPa or more, or at a temperature of 374 ° C. or less, The pressure is less than 22 MPa, which is a high-temperature and high-pressure state close to the critical point (see JP-A-2002-1088).
[0004]
When oxidatively decomposing organic substances in waste by a hydrothermal oxidation reaction, waste, an oxidizing agent, and water are supplied into a hydrothermal reaction vessel and reacted. Then, the organic matter is oxidatively decomposed (or hydrolyzed), and mainly water and carbon dioxide are generated. The generated reaction product is separated into gas and liquid after energy recovery or cooling and decompression.
[0005]
In such a hydrothermal oxidation reaction, when the reactant is an organic compound containing an acid group such as a halogen atom, a sulfur atom, and a phosphorus atom, when oxidative decomposition is performed in supercritical water, halogen ions such as chlorine As a result, acidic ions such as sulfate ions and phosphate ions are generated, and the pH of the processing fluid in the hydrothermal reaction vessel decreases. As described above, when the pH of the processing fluid in the hydrothermal reaction vessel decreases, the heat exchanger for cooling the hydrothermal reaction vessel, the fluid to be treated, and the like are corroded. Since the hydrothermal reactor used for the hydrothermal oxidation reaction is exposed to high temperature and high pressure, it is necessary to replace the corroded heat exchanger in consideration of safety, but the higher the frequency of replacement, the higher the running cost There is a problem.
[0006]
In order to solve such a problem, a method has been proposed in which an organic compound containing an acid group such as a halogen atom, a sulfur atom, and a phosphorus atom is treated with hot water under pressure, neutralized, and then subjected to hydrothermal oxidation. I have. According to this method, the neutralized reactant can be introduced into the hydrothermal reaction vessel. However, even if the reactant is neutral, acid groups such as a halogen atom, a sulfur atom, and a phosphorus atom are removed. In the case of containing, there is a problem that acid ions are generated after being oxidatively decomposed, and the acid ions corrode the heat exchanger and the like.
[0007]
In order to solve the above problem, the pH of a waste liquid which is oxidized and decomposed and separated into gas and liquid in a hydrothermal reaction vessel is measured, and water capable of adding a pH adjuster to the hydrothermal reaction vessel according to the measured pH value. Thermal reactors have been proposed. Usually, in a hydrothermal reactor, the pH of the liquid is problematic from the viewpoint of corrosion in a high-temperature and high-pressure part, but since the pH of the high-temperature and high-pressure fluid cannot be measured, the liquid is cooled and then cooled. The pH of the waste liquid separated is measured.
[0008]
This hydrothermal reactor will be described with reference to the drawings. FIG. 7 is a schematic configuration diagram showing a configuration of a conventional hydrothermal reactor.
A hydrothermal reactor 70 shown in FIG. 7 includes a hydrothermal reactor 73, a supply system 74 for supplying an oxidizing agent such as an object to be processed, a reaction aid, water, and air to the hydrothermal reactor 73, It mainly comprises a cooling gas-liquid separation system 75 for cooling the reaction product coming out of the reaction vessel 73 and gas-liquid separation.
[0009]
A supply pipe 77 for a waste liquid (waste) to be treated, a reaction aid, water, air, and the like is connected to an inlet of the hydrothermal reaction vessel 73. The waste liquid is pressurized by the high-pressure pump 79a and supplied to the hydrothermal reaction vessel 73 through the waste liquid supply pipe 77a and the supply pipe 77. The reaction aid is pressurized by a high-pressure pump 79b and supplied to the hydrothermal reaction vessel 73 through the reaction aid supply pipe 77b and the supply pipe 77. The water is pressurized by the high-pressure pump 79c and supplied to the hydrothermal reaction vessel 73 through the water supply pipe 77c and the supply pipe 77. The high-pressure pumps 79a, 79b, 79c are high-pressure boostable and capacity-controllable pumps such as reciprocating pumps, and can adjust the supply amounts of waste liquid, reaction aid, and water to the hydrothermal reaction vessel 73. It has become.
An air supply pipe 77d including an air compressor 81 is connected to the supply pipe 77. The air as the oxidant is taken into the air compressor 81 and compressed, and is supplied from the air supply pipe 77d to the hydrothermal reaction vessel 73 through the supply pipe 77.
[0010]
An outlet pipe 85 provided with a cooler 83 is connected to the outlet of the hydrothermal reaction vessel 73. The end of the discharge pipe 85 is connected to a gas-liquid separator 87. The reaction products and the like discharged from the outlet of the hydrothermal reaction vessel 73 pass through the discharge pipe 85, are cooled to almost normal temperature by the cooler 83, and then exhausted by the gas-liquid separator 87 (N₂, CO₂Etc.) and drainage.
[0011]
An exhaust gas pipe 93 having a pressure reducing valve 95 is connected to the upper end of the gas-liquid separator 87, and the exhaust gas supplied from the gas-liquid separator 87 is reduced to a pressure close to the atmospheric pressure by the pressure reducing valve 95. Exhausted. A drain pipe 89 provided with a pressure reducing valve 91 is connected to the bottom of the gas-liquid separator 87. The waste liquid from which gas-liquid separation has been performed is reduced to a pressure close to the atmospheric pressure by a pressure reducing valve 91 and sent to a processing liquid tank (not shown).
[0012]
The pH of the discharged liquid discharged from the pressure reducing valve 91 is measured by a pH meter 94, and the result is sent to a chemical injection pump control device (not shown).
On the other hand, a neutralizing agent supply pipe 97 is connected to the discharge pipe 85. The neutralizing agent is pressurized by the high-pressure pump 98 b and supplied to the discharge pipe 85 through the neutralizing agent supply pipe 97. The chemical pump control device operates according to the pH value measured by the pH meter 94, and the chemical pump control device operates the chemical pump 98a when the pH deviates from near neutral. Then, the neutralizer stock solution is sent to the neutralizer mixing tank 92, and the neutralizer adjusted to an appropriate concentration by water supplied through the water supply pipe 99 is supplied to the discharge pipe 85 via the high-pressure pump 98 b. This prevents the cooler from becoming acidic.
[0013]
According to the hydrothermal reactor shown in FIG. 7, when an acid is generated by treating an organic compound containing an acid group such as a halogen atom, a sulfur atom, and a phosphorus atom, the reaction product contained in the discharge pipe 85 is removed. By neutralizing, the corrosion of the cooler 83 can be prevented to some extent. However, it takes time for the reaction product discharged from the hydrothermal reaction vessel 73 to be gas-liquid separated through the gas-liquid separator 87 and to reach the pH meter 94 through the pressure reducing valve 91, and the actual cooling takes place. There may be a difference between the pH in the vessel 83 and the value measured by the pH meter 94. When the acid groups in the object to be treated are non-uniform, or when the acid generated by the hydrothermal reaction becomes a salt, deposits in the hydrothermal reaction vessel 73, and the salt peels off discontinuously, The pH of the reaction product will change at one time.
[0014]
As a result, the timing of adding the neutralizing agent is delayed, the neutralization is not properly performed, and the decomposed liquid having a low pH flows into the cooler 83, and the temperature of the cooler 83 becomes lower than the critical temperature of the corrosive environment. In some cases, the damage was serious.
To cope with such a problem, there has been proposed a method in which an acid group is previously converted to an acid under normal pressure conditions and neutralization is completed before supplying the acid group to a high-pressure container. However, it could not be applied to a waste liquid which was difficult to neutralize in advance. In addition, this results in the addition of extra inorganic salt to the hydrothermal reactor, which promotes corrosion of equipment materials and blockage due to salt precipitation inside the hydrothermal reactor under supercritical conditions of water where salt easily precipitates. There was a problem.
[0015]
[Problems to be solved by the invention]
The present invention has been made in view of the above problems, and when performing supercritical hydroxylation decomposition of an organic compound containing an acid group that generates an acid, a hydrothermal reaction capable of appropriately performing neutralization. It is an object to provide an apparatus and a hydrothermal reaction treatment method.
[0016]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, a hydrothermal reactor of the present invention is connected to a hydrothermal reactor and a cooling pipe that is connected to the hydrothermal reactor by a discharge pipe and cools a reaction product discharged from the hydrothermal reactor. , A pH measuring means for measuring the pH of a reaction product in a discharge pipe connecting the hydrothermal reaction vessel and the cooler, and a neutralizing means in a discharge pipe connecting the hydrothermal reaction vessel and the cooler. A neutralizing agent injecting means for injecting the agent, and a neutralizing agent concentration for controlling the concentration and / or the amount of the neutralizing agent injected by the neutralizing agent injecting means by the pH measurement value measured by the pH measuring means. And / or injection amount control means.
[0017]
According to the above-described hydrothermal reactor, before the reaction product discharged from the hydrothermal reaction vessel is cooled in the cooler, its pH is measured, and the pH is measured and the reaction product is injected into the reaction product according to the measured value. The sump concentration and / or injection volume is controlled. Therefore, the pH can be measured closer to the neutralizing agent injection point than in the conventional hydrothermal reactor, and the time delay from the pH measurement to the neutralizing agent injection is reduced, and effective neutralization is performed. Is possible. Examples of the neutralizing agent include sodium hydroxide and the like, but are not limited thereto. The pH measuring means is provided downstream of the neutralizing agent injection point where the neutralizing agent is injected. By doing so, the reaction product and the neutralizing agent are sufficiently mixed, so that the effect of the injection of the neutralizing agent can be measured.
[0018]
In the hydrothermal reactor of the present invention, the cooler includes a first cooler and a second cooler connected in series, and the first cooler, the second cooler, And at least one second pH measuring means for measuring the pH of the reaction product in the discharge pipe connecting the first cooler and the neutralizer is injected into the discharge pipe connecting the first cooler and the second cooler. At least one second neutralizing agent injecting means, and measuring the concentration and / or the amount of the neutralizing agent injected by the second neutralizing agent injecting means with the pH measured by the second pH measuring means. At least one second neutralizing agent concentration and / or injection volume control means controlled by the measured value.
The second pH measuring means is provided downstream of the second neutralizing agent injecting means. By doing so, the reaction product and the neutralizing agent are sufficiently mixed, so that the effect of the injection of the neutralizing agent can be measured.
[0019]
With the above configuration, the pH of the reaction product passing between the first cooler and the second cooler is measured, and the measured value controls the neutralizing agent concentration and / or the injection amount. . Therefore, finer pH control can be performed.
[0020]
In the hydrothermal reactor of the present invention, the temperature of the reaction product in the discharge pipe connecting the hydrothermal reactor and the cooler is preferably 200 to 650 ° C. By setting the temperature of the reaction product in the discharge pipe connecting the hydrothermal reaction vessel and the cooler within the above range, the corrosion of the cooler in a subcritical region where corrosion is severe can be effectively suppressed. .
[0021]
The hydrothermal reaction treatment method of the present invention is a hydrothermal reaction treatment method in which an organic substance is oxidatively decomposed in a hydrothermal reaction vessel, and a generated reaction product is cooled and discharged in a cooler. Before cooling the product in the cooler, the pH of the reaction product is measured, and the pH of the reaction product is measured to neutralize the reaction product while controlling the neutralizing agent concentration and / or the injection amount. It is characterized by injecting an agent.
[0022]
The hydrothermal reaction method of the present invention measures the pH of the reaction product before gas-liquid separation of the reaction product cooled in the cooler by a gas-liquid separator, and measures the pH of the reaction product. The neutralizing agent may be injected into the reaction product while controlling the neutralizing agent concentration and / or the injection amount according to the measured pH value.
[0023]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the hydrothermal reactor of the present invention will be described with reference to the drawings.
FIG. 1 is a diagram illustrating a configuration of a hydrothermal reactor 10 according to a first embodiment of the present invention.
A hydrothermal reactor 10 shown in FIG. 1 includes a hydrothermal reactor 13, a supply system 14 for supplying an oxidizing agent such as an object to be processed, a reaction aid, water, and air to the hydrothermal reactor 13, It mainly comprises a cooling gas-liquid separation system 15 that cools the reaction product coming out of the reaction vessel 13 and separates it into gas and liquid.
[0024]
A supply pipe 17 for a waste liquid (waste), a reaction aid, water, air, and the like, which is an object to be treated, is connected to an entrance of the hydrothermal reaction vessel 13. The waste liquid is pressurized by the high-pressure pump 19a and supplied to the hydrothermal reaction vessel 13 through the waste liquid supply pipe 17a and the supply pipe 17. The reaction aid is pressurized by a high-pressure pump 19b and supplied to the hydrothermal reaction vessel 13 through the reaction aid supply pipe 17b and the supply pipe 17. The water is pressurized by the high-pressure pump 19c and supplied to the hydrothermal reaction vessel 13 through the water supply pipe 17c and the supply pipe 17. The high-pressure pumps 19a, 19b, and 19c are high-pressure boostable and capacity-controllable pumps such as reciprocating pumps, and can adjust the supply amounts of waste liquid, reaction aid, and water to the hydrothermal reaction vessel 13. It has become.
[0025]
An air supply pipe 17d including an air compressor 21 is connected to the supply pipe 17. The air as the oxidant is taken into the air compressor 21 and compressed, and is supplied from the air supply pipe 17d to the hydrothermal reaction vessel 13 through the supply pipe 17.
[0026]
An outlet pipe 25 having a cooler 23 is connected to the outlet of the hydrothermal reaction vessel 13. The end of the discharge pipe 25 is connected to a gas-liquid separator 27. The reaction products and the like discharged from the outlet of the hydrothermal reaction vessel 13 pass through the discharge pipe 25, are cooled to almost normal temperature by the cooler 23, and then are exhausted (N) by the gas-liquid separator 27.₂, CO₂Etc.) and drainage.
[0027]
An exhaust gas pipe 33 provided with a pressure reducing valve 35 is connected to the upper end of the gas-liquid separator 27. The exhaust gas supplied from the gas-liquid separator 27 is reduced to a pressure close to the atmospheric pressure by the pressure reducing valve 35. Exhausted. A drain pipe 29 having a pressure reducing valve 31 is connected to the bottom of the gas-liquid separator 27. The waste liquid from which gas-liquid separation has been performed is reduced in pressure to a pressure close to the atmospheric pressure by a pressure reducing valve 31 and sent to a processing liquid tank (not shown).
[0028]
A discharge pipe 25 connecting the hydrothermal reaction vessel 13 and the cooler 23 branches off immediately after the hydrothermal reaction vessel 13 and is connected to a pH measurement sample discharge pipe 34 having a pH meter 38. The reaction product that has passed through the pH measurement sample discharge pipe 34 is cooled by the cooler 36, depressurized to near atmospheric pressure by the pressure reducing valve 37, and the pH is measured by the pH meter 38. The pH value measured by the pH meter 38 is sent to a drug injection pump control device (not shown).
[0029]
The sample discharge pipe 34 for pH measurement has a smaller cross-sectional area than the discharge pipe 25. Therefore, the amount of the reaction product sent from the discharge pipe 25 to the pH measurement sample discharge pipe 34 is extremely small, and therefore the pH measurement sample (reaction product) cooled by the cooler 35 is very small, and the time required for cooling is small. Is shorter than the time for cooling by the cooler 23. Further, unlike the hydrothermal reactor shown in FIG. 7, in the apparatus shown in FIG. 1, since the sample does not pass through the cooler 23, the gas-liquid separator 27, etc. until the sample is sent to the pH meter 38, the apparatus shown in FIG. The distance becomes shorter. Therefore, the time required for the pH measurement sample to reach the pH meter 38 is shortened.
[0030]
The reaction product whose pH has been measured by the pH meter 38 passes through the discharge pipe 39 and joins the drain pipe 29, and is sent to a processing liquid tank (not shown). The reaction product whose pH was measured by the pH meter 38 was not separated into gas and liquid. As described above, since the amount of the sample is very small, it is not particularly necessary to install the gas-liquid separator, but it may be installed depending on the situation.
[0031]
On the other hand, a neutralizing agent supply pipe 40 is connected to the discharge pipe 25. The neutralizing agent is pressurized by the high-pressure pump 41b and supplied to the discharge pipe 25 through the neutralizing agent supply pipe 40. The chemical pump control device operates according to the pH value measured by the pH meter 38, and the chemical pump control device activates the chemical pump 41a when the pH deviates from near neutral. Then, the neutralizer stock solution is sent to the neutralizer mixing tank 42, and the neutralizer adjusted to an appropriate concentration by water supplied through the water supply pipe 49 is supplied to the discharge pipe 85 via the high-pressure pump 41 b. Is done. The appropriate concentration can be controlled by the pH value measured by the pH meter 38. That is, the concentration of the neutralizing agent can be increased when the fluctuation of the pH is severe, and the concentration of the neutralizing agent can be lowered when the fluctuation of the pH is gentle. The injection point of the neutralizing agent is provided upstream of the pH measurement sample discharge pipe 34 by a pipe distance that allows the neutralizing agent and the reaction product to be sufficiently mixed.
[0032]
In the hydrothermal reactor 10 shown in FIG. 1, the pH is measured before the reaction product discharged from the hydrothermal reaction vessel 13 is cooled by the cooler 23, and the neutralized agent is contained in the reaction product based on the measured value. Is injected. Therefore, the pH can be measured closer to the neutralizing agent injection point than in a conventional hydrothermal reactor. Further, since the amount of the sample sent to the pH meter 33 is very small and does not require a long time for cooling, the time delay from the pH measurement to the injection of the neutralizing agent is reduced, and effective neutralization is possible.
In the hydrothermal reactor 10 shown in FIG. 1, the concentration and the injection amount of the neutralizing agent can be controlled. In the hydrothermal reactor of the present invention, only the concentration of the neutralizing agent or only the injection amount is used. It may be controlled.
[0033]
Next, a hydrothermal reactor according to a second embodiment of the present invention will be described with reference to the drawings. FIG. 4 is a diagram showing a configuration of the hydrothermal reactor 20 according to the second embodiment of the present invention. The basic configuration of the hydrothermal reactor shown in FIG. 4 is substantially the same as that of the hydrothermal reactor shown in FIG. 4, components that are the same as those in FIG. 1 are given the same reference numerals, and descriptions thereof will be omitted.
[0034]
In the hydrothermal reactor shown in FIG. 4, a cooler 45 is provided between the cooler 23 and the gas-liquid separator 27. The reaction product cooled to almost normal temperature by the cooler 23 passes through the cooler 45, is cooled again, and is separated into the exhaust gas and the waste liquid by the gas-liquid separator 27. The discharge pipe 25 branches off upstream of the cooler 45 and is connected to a pH measurement sample discharge pipe 44 provided with a pH meter 43. The reaction product that has passed through the pH measurement sample discharge pipe 44 is cooled by a cooler 48, depressurized to a pressure near atmospheric pressure by a pressure reducing valve 46, and the pH is measured by a pH meter 43. The pH value measured by the pH meter 43 is sent to a chemical pump control device (not shown).
[0035]
The sample discharge pipe 44 for pH measurement has a small cross-sectional area like the sample discharge pipe 34 for pH measurement, and therefore, a small amount of reaction product is sent from the discharge pipe 25 to the sample discharge pipe 44 for pH measurement.
The reaction product whose pH has been measured by the pH meter 43 merges with the drain pipe 29 through the drain pipe 47 and is sent to a processing liquid tank (not shown). The reaction product whose pH has been measured by the pH meter 43 is not subjected to gas-liquid separation, for the same reason as described above.
[0036]
In addition, a neutralizing agent supply pipe 50 is connected to the discharge pipe 25 between the cooler 23 and the cooler 45. The injection point of the neutralizing agent is provided upstream of the pH measurement sample discharge pipe 44 by a pipe distance that allows the neutralizing agent and the reaction product to be sufficiently mixed. The neutralizing agent is pressurized by the high-pressure pump 51 b and supplied to the discharge pipe 25 through the neutralizing agent supply pipe 50. The chemical pump control device operates according to the pH value measured by the pH meter 43, and the chemical pump control device activates the chemical pump 51a when the pH deviates from near neutral. Then, the neutralizer stock solution is sent to the neutralizer mixing tank 52, and the neutralizer adjusted to an appropriate concentration by water supplied through the water supply pipe 59 is supplied to the discharge pipe 85 via the high-pressure pump 51b. Is done.
[0037]
In the hydrothermal reactor 20 shown in FIG. 4, the pH is measured before the reaction product discharged from the hydrothermal reactor 13 is cooled by the cooler 23, similarly to the hydrothermal reactor shown in FIG. The neutralizing agent is injected into the reaction product according to the measured value, and the pH of the reaction product during cooling is measured again, and the injection of the neutralizing agent is controlled according to the measured pH value. By doing so, finer pH control in the hydrothermal reactor can be performed.
[0038]
For example, by using a low-concentration neutralizing agent injected from the neutralizing agent supply pipe 40, it is possible to prevent the neutralizing agent from being rapidly injected even when the pH of the reaction product suddenly changes. For example, in the case where the pH temporarily becomes strongly acidic and then immediately returns to almost neutral, if a high concentration neutralizing agent (alkaline) is injected, the cooler will be exposed to strong alkali, The cooler will be corroded. This can be prevented by using a low-concentration neutralizing agent. On the other hand, if a high-concentration neutralizing agent is injected from the neutralizing agent supply pipe 50, the neutralizing agent is neutralized only when the neutralizing agent cannot be neutralized by injecting the neutralizing agent from the neutralizing agent supply pipe 40. Since the agent is injected from the neutralizing agent supply pipe 50, the pH in the hydrothermal reactor can be finely controlled.
[0039]
Hereinafter, the present invention will be described in more detail with reference to Examples. It goes without saying that the scope of the present invention is not limited to such examples.
Example 1
Using the hydrothermal reactor shown in FIG. 1, the pH of the waste is changed over time and supplied into the hydrothermal reactor 13 to perform the hydrothermal oxidation reaction. , And the pH of the treatment liquid (the effluent after gas-liquid separation). When the pH of the waste is slowly changed (when the pH of the reaction product immediately after the reaction vessel changes to about 4) or when the pH is greatly changed (when the pH of the reaction product immediately after the reaction vessel changes to about 2) Measurement). Note that a sodium hydroxide solution was used as a neutralizing agent.
[0040]
The results are shown in FIGS. FIG. 2 shows the results of using the hydrothermal reactor of the present invention shown in FIG. 1 to slowly change the pH of waste and supply the waste to the hydrothermal reactor 13 to perform the hydrothermal oxidation reaction. It is a graph which shows the result of having measured pH of the reaction product in a part.
2 and 3, the horizontal axis represents time, and the vertical axis represents pH (the same applies to FIGS. 5, 6, 8 and 9 below). As shown in FIG. 2, the pH immediately after the hydrothermal reaction vessel 13 (indicated by (1) in FIG. 2) rises to about 4, but the pH inside the cooler 23 (indicated by (2) in FIG. 2). The change in pH was slight, and the change in pH of the treatment solution (indicated by (3) in FIG. 2) was slight.
[0041]
FIG. 3 is a graph showing the results of using the hydrothermal reactor of the present invention shown in FIG. It is a graph which shows the result of having measured pH of the reaction product in a part. As shown in FIG. 3, the pH immediately after the hydrothermal reaction vessel 13 rises to about 2, but the fluctuation in the pH of the inside of the cooler 23 and the pH of the processing solution is up to about 6, and the pH of the waste material changes drastically. Even in this case, the changes in the pH of the cooler 23 and the processing liquid were slight.
[0042]
Example 2
The test was performed in the same manner as in Example 1 except that the hydrothermal reactor shown in FIG. 4 was used. In the present embodiment, the pH in the first half and the second half of the pH inside the cooler 23 was measured. The results are shown in FIGS. FIG. 5 is a diagram showing a case where the pH of waste is gradually changed and supplied into the hydrothermal reactor 13 to perform the hydrothermal oxidation reaction using the hydrothermal reactor of the present invention shown in FIG. It is a graph which shows the result of having measured pH of the reaction product in a part.
As shown in FIG. 5, the pH immediately after the hydrothermal reaction vessel 13 (indicated by (1) in FIG. 5) rises to about 4, but the first half inside the cooler 23 (in (2) in FIG. 5). ), The pH in the latter half of the cooler 23 (indicated by (2) 'in FIG. 5) is small, and the pH of the processing solution (indicated by (3) in FIG. 5) is small. there were.
[0043]
FIG. 6 is a graph showing the results obtained by using the hydrothermal reactor of the present invention shown in FIG. 5 to drastically change the pH of waste and supplying the waste to the hydrothermal reactor 13 to perform the hydrothermal oxidation reaction. It is the result of measuring the pH of the reaction product at the site. As shown in FIG. 6, the pH immediately after the hydrothermal reaction vessel 13 rises to about 2, but the fluctuation in the pH of the inside of the cooler 23 and the processing liquid is up to about 6, and the pH of the waste material changes drastically. Even in this case, the changes in the pH of the cooler 23 and the processing liquid were slight.
[0044]
Comparative Example 1
The test was performed in the same manner as in Example 1 except that the hydrothermal reactor shown in FIG. 7 was used. The results are shown in FIGS. FIG. 8 is a graph showing the results of using the hydrothermal reactor of the present invention shown in FIG. 7 to gradually change the pH of waste and supplying the waste to the hydrothermal reactor 13 to perform the hydrothermal oxidation reaction. It is a graph which shows the result of having measured pH of the reaction product in a part.
As shown in FIG. 8, the pH immediately after the hydrothermal reaction vessel 13 (indicated by (1) in FIG. 7) rises to about 4, and the inside of the cooler 23 (indicated by (2) in FIG. 7) The pH of the liquid (indicated by (3) in FIG. 7) also changed in the same manner as immediately after the hydrothermal reaction vessel 13. Further, when the acidity immediately after the hydrothermal reaction vessel 13 became strongly acidic, a large amount of the neutralizing agent was injected, and the pH of the inside of the cooler 23 and the pH of the processing solution became strongly alkaline thereafter.
[0045]
Further, FIG. 9 shows the results of using the hydrothermal reactor of the present invention shown in FIG. 7 and changing the pH of the waste intensely and supplying the waste into the hydrothermal reactor 13 to perform the hydrothermal oxidation reaction. It is a graph which shows the result of having measured pH of the reaction product in a part. As shown in FIG. 9, the pH immediately after the hydrothermal reaction vessel 13 rises to about 2, and the inside of the cooler 23 (indicated by (2) in FIG. 9) and the processing liquid (indicated by (3) in FIG. 9). ) Also changed in the same manner as immediately after the hydrothermal reaction vessel 13. Further, when the acidity immediately after the hydrothermal reaction vessel 13 became strongly acidic, a large amount of the neutralizing agent was injected, and the pH of the inside of the cooler 23 and the pH of the processing solution became strongly alkaline thereafter.
[0046]
As is clear from the above results, in the conventional hydrothermal reactor (FIG. 7), the pH of the treatment liquid (effluent) was measured, and the neutralizing agent was injected based on the measured value. Although the timing of adding the agent is delayed and appropriate neutralization is not performed, in the hydrothermal reactor (FIGS. 1 and 4) of the present invention, the pH is measured before the reaction product is cooled, and the pH is measured. Since the neutralizing agent is injected based on the measured value, effective neutralization can be performed.
[0047]
【The invention's effect】
As is clear from the above description, according to the hydrothermal reactor of the present invention, when the organic compound containing an acid group that generates an acid is subjected to supercritical hydroxylation and decomposition, the reaction product discharged from the hydrothermal reactor is The pH of the product can be measured before it is cooled, a neutralizing agent can be injected based on the measured value, and effective neutralization can be performed.
According to the hydrothermal reaction treatment method of the present invention, when supercritical hydrothermal oxidative decomposition of an organic compound containing an acid group that generates an acid is performed, the pH of the reaction product discharged from the hydrothermal reaction vessel is cooled. The neutralizing agent can be injected based on the measured value, and effective neutralization can be performed.
[Brief description of the drawings]
FIG. 1 is a diagram showing a configuration of a hydrothermal reactor of the present invention.
FIG. 2 shows a reaction product at each site when a hydrothermal reaction apparatus of the present invention is used to gradually change the pH of waste and supply the waste to a hydrothermal reaction vessel to perform a hydrothermal oxidation reaction. 5 is a graph showing the results of measuring the pH of the sample.
FIG. 3 is a diagram illustrating a reaction product in each site when a wastewater is subjected to a hydrothermal oxidation reaction by drastically changing the pH of waste and supplying the waste to a hydrothermal reaction container using the hydrothermal reaction device of the present invention. It is a graph which shows the result of having measured pH.
FIG. 4 is a diagram showing a configuration of a hydrothermal reactor of the present invention.
FIG. 5 is a diagram showing a reaction product at each site when a wastewater is gently changed in pH and supplied into a hydrothermal reaction vessel to perform a hydrothermal oxidation reaction using the hydrothermal reactor of the present invention. 5 is a graph showing the results of measuring the pH of the sample.
FIG. 6 is a diagram illustrating a reaction product of each site when a hydrothermal oxidation reaction is performed by using the hydrothermal reactor of the present invention to drastically change the pH of waste and supplying the waste to a hydrothermal reactor. It is a graph which shows the result of having measured pH.
FIG. 7 is a schematic configuration diagram showing a configuration of a conventional hydrothermal reactor.
FIG. 8 shows that the pH of the waste is gradually changed using a conventional hydrothermal reactor, and the waste is supplied into a hydrothermal reactor to perform a hydrothermal oxidation reaction. It is a graph which shows the result of having measured pH.
FIG. 9 shows the pH of the reaction product at each site when the wastewater pH was drastically changed and supplied into a hydrothermal reaction vessel to perform a hydrothermal oxidation reaction using a conventional hydrothermal reactor. 5 is a graph showing the results of measuring the.
[Explanation of symbols]
10 hydrothermal reactor 13 hydrothermal reactor
14 supply system 15 gas-liquid separation system
17 supply pipe 17a waste liquid supply pipe
17b {reaction auxiliary agent supply pipe} 19c} high pressure pump
17c water supply pipe 17d air supply pipe
19a high pressure pump 19b high pressure pump
20 Hydrothermal reactor 21 Air compressor
23 cooler 25 discharge pipe
27 gas-liquid separator 35-pressure reducing valve
29 drainage pipe 31 pressure reducing valve
33 exhaust gas pipe 38 pH meter
34 Sample discharge pipe for pH measurement 36 Cooler
37 pressure reducing valve 39 discharge pipe
39 Neutralizer supply pipe 41a Pump
41b {High pressure pump} 42} Neutralizer mixing tank
43 pH meter 44 Sample discharge tube for pH measurement
45 cooler 46 pressure reducing valve
49 water supply pipe 50 neutralizer supply pipe
51a Drug injection pump 51b High pressure pump
52 Neutralizer mixing tank 59 Water supply pipe
70 Hydrothermal reactor 73 Hydrothermal reactor
74 supply system 75 gas-liquid separation system
77 supply pipe {77a} waste liquid supply pipe
77b {reaction aid supply pipe} 77c} water supply pipe
79a high pressure pump 79b high pressure pump
79c high pressure pump 77d air supply pipe
81 air compressor 83 cooler
85 discharge pipe 87 gas-liquid separator
89 drain pipe 91 pressure reducing valve
92 Neutralizer mixing tank 93 Exhaust gas pipe
94 pH meter 95 drain pipe
95 Reducing valve 97 Neutralizer supply pipe
98a Pumping pump 98b High pressure pump
99 water supply pipe

Claims (6)

A hydrothermal reactor,
A cooler connected to the hydrothermal reaction vessel by a discharge pipe and cooling a reaction product discharged from the hydrothermal reaction vessel;
PH measuring means for measuring the pH of the reaction product in the discharge pipe connecting the hydrothermal reaction vessel and the cooler,
Neutralizing agent injecting means for injecting a neutralizing agent into a discharge pipe connecting the hydrothermal reaction vessel and the cooler,
A neutralizing agent concentration and / or injection amount controlling means for controlling the neutralizing agent concentration and / or the amount injected by the neutralizing agent injecting means by a pH measurement value measured by the pH measuring means;
A hydrothermal reactor comprising: The above-mentioned cooler is composed of a first cooler and a second cooler connected in series,
At least one second pH measuring means for measuring the pH of a reaction product in an exhaust pipe connecting the first cooler and the second cooler;
At least one second neutralizing agent injecting means for injecting a neutralizing agent into a discharge pipe connecting the first cooler and the second cooler;
At least one second neutralizing agent for controlling the concentration and / or amount of the neutralizing agent injected by the second neutralizing agent injection means by the pH measurement value measured by the second pH measuring means; Concentration and / or injection volume control means;
The hydrothermal reactor according to claim 1, comprising: 3. The hydrothermal reactor according to claim 1, wherein a temperature of a reaction product in an exhaust pipe connecting the hydrothermal reactor and the cooler is 200 to 650 ° C. 4. A hydrothermal reaction method in which an organic substance is oxidatively decomposed in a hydrothermal reaction vessel, and a generated reaction product is cooled in a cooler and discharged.
Measuring the pH of the reaction product before cooling the reaction product in a cooler,
A hydrothermal treatment method comprising injecting a neutralizing agent into the reaction product while controlling a neutralizing agent concentration and / or an injection amount based on a measured pH value of the reaction product. Measuring the pH of the reaction product during cooling in the cooler,
5. The hydrothermal treatment method according to claim 4, wherein the neutralizing agent is injected into the reaction product while controlling the neutralizing agent concentration and / or the injection amount based on the measured pH value of the reaction product. The hydrothermal treatment method according to claim 4 or 5, wherein the temperature of the reaction product into which the neutralizing agent is injected is 200 to 650 ° C.

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