JP4220429B2 - Sulfuric acid equipment - Google Patents

Description

  The present invention relates to a sulfuric acid apparatus that further ensures safety and suitably treats generated harmful gas.

  Conventionally, a number of inventions have been disclosed in this type of technology, and their contents are diverse.

  For example, as seen in JP-A-2002-60208, when purifying and recovering sulfuric acid, the boiling liquid level of sulfuric acid is detected from the outside through the body of the distillation column with a light-controlled liquid level sensor, Sulfuric acid is provided with a sleeve smaller in diameter than the inner diameter of the column of the distillation column, and the lifetime of the distillation column is increased by further reducing the degree of impurity adhesion and precipitation (degree of devitrification) on the cylinder wall. There is a purification device.

Also, for example, in Japanese Patent Laid-Open No. 6-80407, a filler made of a forging material or a casting material in contact with hot concentrated sulfuric acid or fuming sulfuric acid up to 10% by weight is Ni 15.5 to 17.5% by weight, Cr 10-12. % By weight, 5.7-6.5% by weight silicon, 0.06% by weight carbon, 1.5% by weight Mn, 0.03% by weight phosphorus, 0.03% by weight sulfur, 0.03% by weight titanium. 15 Sulfuric acid treatment equipment made of austenitic alloy consisting of 15 wt%, zirconium up to 0.8 wt%, nitrogen up to 0.2 wt%, molybdenum up to 0.3 wt% and the balance iron to suppress corrosion based on sulfuric acid Or a manufacturing method is disclosed.
Japanese Patent Laid-Open No. 2002-60208 JP-A-6-80407

  The above Japanese Patent Laid-Open No. 2002-60208 is a technique for suppressing the devitrification phenomenon accompanying precipitation of sulfuric acid impurities generated during the purification of sulfuric acid, and the above Japanese Patent Laid-Open No. 6-80407 is a hot concentrated sulfuric acid. Or, it is a technology to improve the corrosion resistance of welding fillers that come into contact with fuming sulfuric acid, both of which are intended to maintain the life of the component equipment longer, but it is possible to further ensure safety associated with impurities of sulfuric acid produced No mention of suitable treatment.

  In general, this type of technology is strongly required to have safety measures and treatment of generated impurities from the viewpoint of health and environmental pollution of the harmful gas generated during the purification of sulfuric acid to field workers.

  The present invention has been made based on such a situation, and during the purification of sulfuric acid, the generated harmful gas is monitored and controlled to ensure further safety and appropriate processing. An object is to provide a sulfuric acid apparatus.

In order to achieve the above-mentioned object, a sulfuric acid apparatus according to the present invention contains a heater for heating a sulfuric acid solution to be filled in the container and is provided with a heat retaining device outside the container. A main body, a cooling system connected to the container main body for cooling the gas generated during operation, an exhaust gas treatment system connected to the cooling system for purifying the cooled gas, and a sulfuric acid solution in the container main body A sulfuric acid supply system for supplying gas, and a state quantity of a gas and a sulfuric acid solution generated during operation of the container body, and a calculation signal calculated based on the detected state quantity is sent to the sulfuric acid supply system and the container body A control device for supplying the heater, and the heater concentrically surrounds the outside of the heating wire and has a sulfuric acid detection sensor attached thereto, and an outer layer pipe that concentrically surrounds the outside of the inner layer pipe. in in what you have configured That.

  In order to achieve the above-mentioned object, the sulfuric acid apparatus according to the present invention includes a temperature sensor for detecting each of the temperature of the sulfuric acid solution and the temperature of the sulfuric acid solution to be filled, and the pressure in the vessel. A pressure sensor for detecting toxic gas, a toxic gas detection sensor and a hydrogen gas detection sensor for detecting toxic gas and hydrogen gas generated during operation, a sulfuric acid liquid level detection sensor for detecting the level of sulfuric acid to be filled, A gas supply pipe having a safety valve for releasing the gas when the gas pressure in the vessel exceeds a predetermined gas pressure, a pressure adjusting valve for guiding the gas generated during operation to the cooling system, And a sulfuric acid supply pipe for supplying a sulfuric acid solution to each other.

Further, the sulfate apparatus according to the present invention, in order to achieve the above object, as described in claim 3, sulfuric acid supply system, a sulfuric acid storage tank for storing the sulfuric acid solution, the operation signal from the control device And a pump that controls the sulfuric acid solution from the sulfuric acid storage tank and supplies it to the sulfuric acid supply pipe of the container body.

Further, the sulfate apparatus according to the present invention, in order to achieve the above object, as described in claim 4, the cooling system is generated in the container main body, the gas supplied via the sulfuric acid supply pipe An air-cooled cooler that cools and a cooler that cools the gas that has left the air-cooled cooler again are provided.

Moreover, in order to achieve the above-mentioned object, the sulfuric acid device according to the present invention includes a cooling medium supply device as described in claim 5 .

In order to achieve the above object, the sulfuric acid apparatus according to the present invention is characterized in that, as described in claim 6 , the exhaust gas treatment system includes a recovery tank for recovering the gas supplied from the cooling system, and the recovery tank. And a cleaning device for purifying the exhaust gas supplied from.

Further, sulfuric apparatus according to the present invention, in order to achieve the above object, as described in claim 7, the temperature sensor may surround the outer thermocouple wire concentrically, it is deposited sulfate detection sensor The inner layer pipe and the outer layer pipe concentrically surrounding the outer side of the inner layer pipe are configured.

Moreover, in order to achieve the above-mentioned object, the sulfuric acid apparatus according to the present invention has a container main body provided with a harmful gas detection sensor and a hydrogen gas detection sensor on the outside as described in claim 8 .

In order to achieve the above-mentioned object, the sulfuric acid apparatus according to the present invention includes a harmful gas detection sensor and a hydrogen gas detection sensor as described in claim 9 .

Further, the sulfate apparatus according to the present invention, in order to achieve the above object, as described in claim 10, the inner pipe and outer pipe heaters, which is characterized in that both quartz or ceramic material It is.

Further, sulfuric apparatus according to the present invention, in order to achieve the above object, as described in claim 11, the inner pipe and outer pipe temperature sensor is characterized in that it is both quartz or ceramic material Is.

In order to achieve the above-mentioned object, the sulfuric acid apparatus according to the present invention is characterized in that, as described in claim 12 , the temperature sensor includes at least the sulfuric acid solution in the container body, the sulfuric acid solution free surface, and the container body. Are provided at respective positions in the space.

  The sulfuric acid apparatus according to the present invention monitors and controls the means for efficiently treating the gas generated during operation of the container body filled with the sulfuric acid solution, and the temperature, pressure, and state quantity of the sulfuric acid solution liquid level in the container body. Therefore, further safety can be ensured.

  Embodiments of a sulfuric acid apparatus according to the present invention will be described below with reference to the drawings and the reference numerals attached to the drawings.

  FIG. 1 is a conceptual diagram showing a first embodiment of a sulfuric acid apparatus according to the present invention.

  The sulfuric acid device generally indicated by reference numeral 1 includes a heat retaining device 3 that surrounds a container body 2 that boils sulfuric acid having a concentration of 1 ppm to 99.9% to a temperature of 300 ° C. to 450 ° C., and pipes 6 and 6 in the container body 2. A cooling system 7 and an exhaust gas treatment system 8 that are sequentially connected to each other and a sulfuric acid supply system 4 that supplies a sulfuric acid solution to the container body 2 via a sulfuric acid solution supply pipe 5 are provided.

  Further, the sulfuric acid device 1 detects state quantities such as temperature and pressure in the container body 2, calculates based on the detection signal, and gives this calculation signal to the sulfuric acid supply system 4 and the like via the cable wires 11 and 12. A control device 10 is provided.

Among these components, as shown in FIG. 2, the container body 2 has a connection end for connecting the cable wire 22 of the heater 21 for heating the sulfuric acid to be filled to the cable wire 11 of the control device 10 shown in FIG. 23. A temperature sensor mounting end 25 for detecting the temperature in the container 2 and the temperature of sulfuric acid and mounting temperature sensors 24 arranged at a plurality of predetermined water level positions, and a pressure sensor 26 for detecting the pressure in the vessel are mounted. A pressure sensor mounting end 27, for example, a noxious gas detection sensor mounting end 29 for mounting a noxious gas detection sensor 28 for detecting noxious gases such as SO ₂ gas, and a hydrogen gas detection sensor for mounting a hydrogen gas detection sensor 30 for detecting hydrogen gas. A mounting end 31 is provided.

  In addition, the container body 2 releases a sulfuric acid level detection sensor mounting end 33 for mounting a sulfuric acid level detection sensor 32 for detecting the sulfuric acid level when the gas inside the container exceeds a predetermined pressure. A gas supply pipe which includes a safety valve 34 and a pressure adjustment valve 36 and guides gas such as sulfuric acid gas, hydrogen gas and water vapor vaporized in the vessel to the cooling system 7 shown in FIG. 35. A sulfuric acid supply pipe 37 for supplying a sulfuric acid solution into the vessel is provided.

  The container body 2 is made of a noble metal such as quartz or a ceramic material, gold, platinum or the like and an alloy containing a noble metal, which is resistant to a pressure of 100 atm and excellent in concentrated sulfuric acid resistance.

  On the other hand, the heater 21 accommodated in the container body 2 is a type that directly heats the sulfuric acid solution. As shown in FIG. 3, the heating wire 40 is concentrically surrounded, and the sulfuric acid detection sensor 43 is attached to the outer surface. For example, the inner layer pipe 41 made of quartz or a ceramic material, the inner layer pipe 41 concentrically surrounding each other, the outer layer pipe 42 made of, for example, quartz or a ceramic material, the sulfuric acid detection sensor 43, and the heating wire 40 are respectively connected. Lead wires 44 and 45 connected to the cable wire 22 shown in FIG. 2 are provided.

  In the heater 21 having such a configuration, when the sulfuric acid detection sensor 43 detects that the outer layer pipe 42 has been damaged and sulfuric acid has entered, the cable wire 22 and the lead are in accordance with a command from the control device 10 shown in FIG. The current flowing through the heating wire 40 via the wire 44 is interrupted.

  Further, as shown in FIG. 4, the sulfuric acid supply system 4 includes a pump 51 connected to the sulfuric acid storage tank 50 via a pipe 52, and a valve 53 connecting the pump 51 to the sulfuric acid supply pipe 37 shown in FIG. The pump 51 is provided with a cable line 12 for giving an ON / OFF command from the control device 10 shown in FIG.

  In addition, as shown in FIG. 5, the cooling system 7 is connected to the pipe 6, and an air-cooled cooler 60 and a water-cooled or oil-cooled cooler 61 are arranged in series from the container main body side. A refrigerant supply device 62 to be connected is provided, and the smoke gas or vaporized sulfuric acid gas is cooled by the air-cooled cooler 60 and further cooled by the refrigerant supplied from the cooling supply device 62 to the cooler 61 and recovered. . Note that the components that come into contact with fuming or vaporized sulfuric acid gas are made of, for example, quartz or a ceramic material excellent in sulfuric acid resistance, or an alloy such as gold or platinum or a noble metal.

Further, as shown in FIG. 6, the exhaust gas treatment system 8 is disposed on the downstream side of the recovery tank 70 for recovering liquid sulfuric acid supplied from the cooling system 7 via the pipe 6, and is connected to the pipe 72. For example, a cleaning device 71 for cleaning exhaust gas such as SO ₂ supplied from the recovery tank 70 and an exhaust gas outlet pipe 9 for discharging the exhaust gas purified by the cleaning device 71 to the outside. Note that water or an alkaline solution is used as the cleaning liquid for purifying the exhaust gas.

  On the other hand, as shown in FIG. 7, the temperature sensor 24 for detecting the temperature of the sulfuric acid filled in the container body 2 concentrically surrounds the thermocouple wire 80 and is made of, for example, quartz or a ceramic material excellent in concentrated sulfuric acid resistance. An inner layer pipe 81 that is manufactured and has a sulfuric acid detection sensor 83 attached to the outer surface, an outer layer pipe 82 concentrically surrounding the inner layer pipe 81 and made of, for example, quartz or a ceramic material, a sulfuric acid detection sensor 83 and Lead wires 84 and 85 for connecting the thermocouple wires 80 to the cable wires 22 shown in FIG. 2 are provided.

  When the outer layer pipe 82 is damaged and the sulfuric acid detection sensor 83 detects that the sulfuric acid has entered the temperature sensor 24 having such a configuration, the cable wire 22 according to the command from the control device 10 shown in FIG. The current flowing through the thermocouple wire 80 via the lead wire 84 is interrupted.

  The temperature sensor 24 can detect at least three or more locations in the container body 2, for example, the temperature of the sulfuric acid solution, the liquid surface temperature of the sulfuric acid solution, and the temperature at a position 1 mm to 10 cm away from the liquid surface.

  As described above, in the present embodiment, the heat retaining device 3 is provided outside the container main body 50 that houses the heater for heating the sulfuric acid solution to be filled, and the sulfuric acid supply system 4, the cooling system 7, and the exhaust gas are provided on the head side of the container main body 2. While each of the processing systems 8 is provided, state quantities such as temperature, pressure, sulfuric acid solution temperature, harmful gas, hydrogen gas, etc. in the vessel are detected and calculated based on the detected state quantity signals. 21 and the sulfuric acid supply system 4 are provided with the control device 10 to control, so that further safety can be ensured under appropriate management of impurities generated in the vessel, and appropriate treatment of impurities Can be performed.

  FIG. 8 is a conceptual diagram showing a second embodiment of the sulfuric acid apparatus according to the present invention.

  In the present embodiment, a harmful gas detection sensor 28 and a hydrogen gas detection sensor 30 are provided on the outside of the container body 2 and the outside of the exhaust gas treatment system 8 in the sulfuric acid apparatus 1.

  As described above, this embodiment includes various sensors provided in the vessel, and the harmful gas detection sensor 28 and the hydrogen gas detection sensor 30 provided on the outside of the container body 2 and the outside of the exhaust gas treatment system 8, respectively. Since the gas generated during the operation of the container main body 2 is monitored, further safety of the container main body 2 and the exhaust gas treatment system 8 can be ensured.

  FIG. 9 is a conceptual diagram showing a third embodiment of the sulfuric acid apparatus according to the present invention.

  In the present embodiment, a material applied to, for example, a semiconductor, a superconductor, a generator, and a heat-resistant coating component is immersed in a sulfuric acid solution as a test piece 90 in the sulfuric acid solution of the container body 2 in the sulfuric acid apparatus 1.

  As described above, in the present embodiment, the test piece 90 as a material to be applied to a semiconductor is immersed in the sulfuric acid solution of the container body 2, for example, and data collection of the test piece 90 is coupled with the purification of sulfuric acid. It is effective for.

The conceptual diagram which shows 1st Embodiment of the sulfuric acid apparatus which concerns on this invention. The conceptual diagram which shows the container main body applied to the sulfuric acid apparatus which concerns on this invention. The conceptual diagram which shows the heater applied to the sulfuric acid apparatus which concerns on this invention. The conceptual diagram which shows the sulfuric acid supply system applied to the sulfuric acid apparatus which concerns on this invention. The conceptual diagram which shows the cooling system applied to the sulfuric acid apparatus which concerns on this invention. The conceptual diagram which shows the waste gas processing system applied to the sulfuric acid apparatus which concerns on this invention. The conceptual diagram which shows the temperature sensor applied to the sulfuric acid apparatus which concerns on this invention. The conceptual diagram which shows 2nd Embodiment of the sulfuric acid apparatus which concerns on this invention. The conceptual diagram which shows 3rd Embodiment of the sulfuric acid apparatus which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sulfuric acid apparatus 2 Container body 3 Thermal insulation apparatus 4 Sulfuric acid supply system 5 Sulfuric acid solution supply piping 6 Piping 7 Cooling system 8 Exhaust gas treatment system 9 Exhaust gas outlet pipe 10 Controller 11,12 Cable line 21 Heater 22 Cable line 23 Connection end 24 Temperature sensor 25 Temperature sensor mounting end 26 Pressure sensor 27 Pressure sensor mounting end 28 Toxic gas detection sensor 29 Toxic gas detection sensor mounting end 30 Hydrogen gas detection sensor 31 Hydrogen gas detection sensor mounting end 32 Sulfuric acid level detection sensor 33 Sulfuric acid level detection sensor mounting End 34 Safety valve 35 Gas supply pipe 36 Pressure adjustment valve 37 Sulfuric acid supply pipe 40 Heating wire 41 Inner layer pipe 42 Outer layer pipe 43 Sulfuric acid detection sensors 44 and 45 Lead wire 50 Sulfuric acid storage tank 51 Pump 52 Pipe 53 Valve 60 Air-cooled cooler 61 Cooling 62 Refrigerant supply device 70 Recovery tank 71 Cleaning device 72 Pipe 80 Thermocouple wire 81 Inner layer pipe 82 Outer layer pipe 83 Sulfuric acid detection sensor 84, 85 Lead wire 90 Test piece

Claims (12)

A container body that contains a heater that heats the sulfuric acid solution to be filled in the vessel and has a heat retaining device outside the vessel, a cooling system that is connected to the vessel body and cools the gas generated during operation, and this cooling An exhaust gas treatment system connected to the system for purifying the cooled gas, a sulfuric acid supply system for supplying a sulfuric acid solution to the container body, and a state quantity of the gas and sulfuric acid solution generated during operation of the container body. And a control device for supplying a calculation signal calculated based on the detected state quantity to the sulfuric acid supply system and a heater provided in the container body , the heater concentrically enclosing the outside of the heating wire, A sulfuric acid apparatus comprising: an inner layer pipe to which a detection sensor is attached; and an outer layer pipe concentrically surrounding the outer layer pipe . The container body detects the temperature in the vessel and the temperature of the sulfuric acid solution to be filled, the pressure sensor that detects the pressure in the vessel, and the harmful gas and hydrogen gas generated during operation. Harmful gas detection sensor and hydrogen gas detection sensor, sulfuric acid liquid level detection sensor for detecting the level of sulfuric acid to be filled, and safety valve for releasing the gas when the gas pressure inside the container exceeds a predetermined gas pressure And a gas supply pipe provided with a pressure regulating valve for guiding the gas generated during operation to the cooling system, and a sulfuric acid supply pipe for supplying a sulfuric acid solution into the vessel. 1. The sulfuric acid device according to 1. The sulfuric acid supply system comprises a sulfuric acid storage tank for storing a sulfuric acid solution, and a pump that is controlled by a calculation signal from the control device and supplies the sulfuric acid solution from the sulfuric acid storage tank to a sulfuric acid supply pipe of the container body. The sulfuric acid apparatus according to claim 1, wherein The cooling system includes an air-cooled cooler that cools the gas generated in the container body and supplied through the sulfuric acid supply pipe, and a cooler that cools the gas that has left the air-cooled cooler again. The sulfuric acid device according to claim 1. 5. The sulfuric acid device according to claim 4 , wherein the cooler includes a cooling medium supply device. 2. The sulfuric acid apparatus according to claim 1, wherein the exhaust gas treatment system includes a recovery tank that recovers the gas supplied from the cooling system, and a cleaning device that purifies the exhaust gas supplied from the recovery tank. The temperature sensor is constituted by an inner layer pipe concentrically surrounding the thermocouple wire and having a sulfuric acid detection sensor attached thereto, and an outer layer pipe concentrically surrounding the outer side of the inner layer pipe. 2. The sulfuric acid device according to 2. 2. The sulfuric acid apparatus according to claim 1, wherein the container body includes a harmful gas detection sensor and a hydrogen gas detection sensor on the outside. The sulfuric acid apparatus according to claim 1, wherein the exhaust gas treatment system includes a harmful gas detection sensor and a hydrogen gas detection sensor. Inner pipe and outer pipe of the heater are both sulfuric apparatus according to claim 1, characterized in that the quartz or ceramic material. 8. The sulfuric acid apparatus according to claim 7 , wherein both the inner layer pipe and the outer layer pipe of the temperature sensor are made of quartz or a ceramic material. 3. The sulfuric acid apparatus according to claim 2, wherein the temperature sensor is provided in each position of at least the sulfuric acid solution, the free surface of the sulfuric acid solution, and the space in the container main body in the container main body.

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