JP2017145169A - Production method and device of mercury sulfide - Google Patents

Abstract

[Problem] To provide a method for stabilizing mercury recovered as waste by converting it into mercury sulfide, and a manufacturing apparatus for the same. [Solution] A method for producing mercury sulfide by reacting mercury and sulfur in a grinding process, in which cooling is performed during the reaction process. The mercury sulfide manufacturing apparatus includes a grinding pot 1 having multiple metal balls for grinding inside, and a vibrator 5 for vibrating the grinding pot 1, and the grinding pot 1 is equipped with cooling mechanisms 6 and 7 for cooling using a refrigerant. [Selected Figure] Figure 5

Description

  The present invention relates to a method and apparatus for producing mercury sulfide for reacting mercury and sulfur to produce stable mercury sulfide.

  The method and apparatus for producing mercury sulfide according to the present invention was born from a request for stabilization of mercury recovered as waste. In recent years, the amount of recovered products in Japan has greatly exceeded the amount of mercury demand. In addition, the global import and export of mercury tends to be restricted, and a huge amount of surplus may occur in the future. Therefore, it has been required to establish a mercury stabilization method for stably storing surplus mercury for a long period of time.

  One method of stabilizing mercury (Hg) is to produce mercury sulfide (HgS) by reacting liquid mercury with powdered sulfur (S) (mechanochemical reaction) in the pulverization step, There is a method of solidifying by mixing with cement.

  For example, according to Patent Document 1, mercury and sulfur are produced by a ball milling process to produce mercury sulfide, and then gravel, sand, calcium carbonate, sulfur and sulfur polymers are further mixed and reacted at a high temperature. Stabilization is achieved by solidifying as polymer cement.

  However, this method is aimed at stabilization in the state of cement finally solidified, and no consideration has been given to the stability of mercury sulfide produced in the process.

  In the method disclosed in the cited document 1, mercury sulfide is produced using a planetary mill, but the apparatus can handle only a relatively small amount (about 100 g) of mercury. Moreover, since the structure of the device is complicated, it is difficult to increase the size. Therefore, in order to efficiently stabilize about 100 tons of mercury per year, an inexpensive and simple apparatus capable of reacting a large amount of mercury such as several kilos to several tons at a time is required.

Special table 2013-503729 gazette

  In view of the circumstances as described above, an object of the present invention is to provide a method and apparatus for producing mercury sulfide that allows mercury and sulfur to react in a pulverization step to produce stable mercury sulfide. is there.

  In order to achieve the above object, a method for producing mercury sulfide according to the present invention is a method for producing mercury sulfide by reacting mercury and sulfur in a pulverization step, wherein cooling is performed during the reaction step. To do.

  The pulverization step may be performed by a pulverizer that incorporates a ball for pulverization.

  In addition, the cooling can be at least a degree of cooling that reduces a temperature increase due to collision and friction of the balls for grinding in the grinding step.

  The cooling step may cool the outer wall of the pulverizer with a refrigerant. In addition, a refrigerant | coolant here means the liquid or gas for taking heat away from the outer wall of the grinder which is object.

  Further, the present invention is a manufacturing apparatus for manufacturing mercury sulfide according to another aspect, and the apparatus vibrates the grinding pot having a plurality of metal balls for grinding inside, and the grinding pot. And the pulverizing pot includes a cooling mechanism for cooling by water cooling.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method and apparatus of mercury sulfide which can react mercury and sulfur by a grinding | pulverization process and can manufacture the stable mercury sulfide are provided.

It is a perspective view which shows the grinding | pulverization apparatus used for 1st Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is a front view which shows the grinding | pulverization apparatus used for 1st Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is a side view which shows the grinding | pulverization apparatus used for 1st Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is the front view and side view which show the pot for grinding | pulverization used for 1st Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is a schematic side view which shows the air-cooling type cooling device used for 1st Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is a schematic side view which shows the water-cooling type cooling device used for 1st Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is a figure which shows the container sectional drawing and lid | cover of the pot for a grinding | pulverization used for 2nd Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is a figure which shows the container sectional drawing and lid | cover of what installed the water cooling mechanism in the pot for grinding | pulverization used for 2nd Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is a front view which shows the grinding | pulverization apparatus used for 3rd Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is a side view which shows the grinding | pulverization apparatus used for 3rd Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is a schematic diagram which shows operation | movement of the grinding | pulverization apparatus used for 3rd Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention. It is a graph showing the relationship between the manufacturing temperature and evaluation (elution value) of the mercury sulfide manufactured by 1st Embodiment of the manufacturing method of the mercury sulfide which concerns on this invention.

  First, the stability evaluation method and evaluation criteria for mercury sulfide produced by the method for producing mercury sulfide according to the present invention will be described.

  First, the method for producing mercury sulfide according to the present invention is a method for producing mercury sulfide that satisfies a predetermined stability level. As a method of evaluating the resulting mercury sulfide, it is assumed that the mercury sulfide will be finally landfilled with the ratification of the Minamata Convention on Mercury signed in Geneva in 2013. The evaluation based on the inspection method of industrial waste for landfill disposal announced by the Ministry of the Environment (Environment Agency Notification No. 13) is generally adopted.

  This Environmental Agency Notification No. 13 stipulates a method for testing the stability of mercury sulfide and the like. According to this notice, 50 g of mercury sulfide powder (particle size: 0.5 mm to 5 mm) to be tested is put into 500 ml of pure water (A3 or A4 water shown by JIS K 0557) as a solvent. , Shake horizontally for 6 hours at a cycle of 200 times / minute. Thereafter, centrifugation is performed for 20 minutes under the condition of a centrifugal acceleration of 3000 G, and the eluate is collected. Then, the eluate is filtered using a membrane filter having a pore size of 1 μm, the components of the test solution after filtration are analyzed, and the elution value of mercury is measured. In the case where stable mercury sulfide cannot be produced, unreacted mercury is eluted in this test more than the standard value, which is not preferable. In addition, based on the test by Environment Agency Notification No. 13, the present inventors evaluated mercury sulfide on the basis that the concentration of mercury eluted in the liquid is 0.005 mg / L or less. , Have earnestly studied.

A head space test is also used as one of the methods for evaluating the stability of mercury sulfide. The Environmental Agency Notification No. 13 test is a method for evaluating the elution of mercury into water, while the headspace test is a method for evaluating the degree of diffusion of mercury into the atmosphere. As a specific method of this head space test, first, mercury sulfide (10 g) is introduced so as to be uniformly distributed on the bottom of a 120 ml wide-mouthed stopper bottle. Then, the bottle is covered with a rubber stopper having two pipes for gas inflow and outflow. Thereafter, gas is passed through one pipe at a flow rate of 1 l / min, and the mercury concentration in the gas discharged from the other pipe is measured. This measurement is performed at a humidity of 60% and under various temperature conditions such as 10 ° C., 25 ° C., 30 ° C., 40 ° C., and 70 ° C. When implemented at 70 ° C., the test is performed in a nitrogen gas atmosphere assuming environmental conditions at the time of disposal of mercury sulfide. In addition, the present inventors have accumulated earnestly examination by evaluating mercury sulfide on the basis that the concentration of mercury measured in gas is 0.001 mg / m ³ or less.

  Hereinafter, embodiments of a method and apparatus for producing mercury sulfide according to the present invention will be described in detail with reference to the accompanying drawings.

[First Embodiment]
First, the manufacturing method and manufacturing apparatus of mercury sulfide according to the first embodiment will be described with reference to FIGS.

  1 to 3 show a pulverizer 10 for producing mercury sulfide by reacting mercury and sulfur with impact, friction, shear, and compression energy. The pulverizer 10 constitutes an embodiment of a mercury sulfide production apparatus according to the present invention. The pulverizer 10 includes a vibrator 5 for vibration at the center. The vibrator 5 has a motor inside, and is supplied with electric power from the outside via the earthquake-resistant cable 12. Further, inside the shaft end 51 of the vibrator 5, a weight is provided at the shaft end of the motor so as to be unbalanced with respect to the shaft center. Thereby, it has a structure which generates a vibration by rotation of a motor.

  FIG. 4 shows the pulverization pot 1 mounted on the pulverizer 10 removed from the apparatus. As shown in FIG. 4, a lid 16 and a container 15 are provided. Further, the lid 16 of the crushing pot 1 is fixed to the container 15 by screwing the lid 16 with a fixture 17. Inside is a plurality of metal balls. When the pulverizing apparatus 10 is used, liquid mercury and powdery sulfur are further sealed in the pulverizing pot.

  The vibrator 5 is fixed to a vibration stage 13, and the vibration stage 13 is fixed to a base 8 fixed to a ground surface via a spring 9. Further, the crushing pots 1 and 1 are fixed on the vibration stage 13 at equal positions with the vibrator 5 interposed therebetween. The crushing pot 1 is arranged uniformly on both sides of the vibrator 5, so that it can be expected to balance the vibration and stabilize the vibration operation and the vibration width. The crushing pot is firmly fixed to the vibration stage 13 by the fastener 4.

  The pulverizing apparatus 10 has a structure in which the entire apparatus can be covered with an openable / closable cover 11 having a predetermined sound insulation performance because a relatively large operating noise is generated during operation. The cover 11 is configured to open and close in the left-right direction in FIG.

  As shown in FIG. 5, an air-cooling type cooling device 6 for cooling the outer wall surface of the grinding pot 1 can be installed in the grinding device 10. In the cooling device 6, the air is sent by a fan 61 provided outside the cover 11, and the air sent to the outer wall of the crushing pot 1 is applied through the duct 62 to cool the crushing pot 1. ing. Further, the temperature of the outer wall of the crushing pot 1 is measured by a non-contact sensor 63 provided in the cover 11. Further, the measured temperature data is sent to a PLC (programmable logic controller) 64 provided outside the cover 11, and a control signal from the PLC is sent to the fan 61 via the inverter 65 to control the operation of the fan 61. doing. The operation of the fan 61 starts when the value of the sensor 63 exceeds a predetermined threshold value. It is also possible to set the threshold stepwise and set the operation speed of the fan 61 stepwise according to the temperature. The temperature of the outer wall of the crushing pot 1 is displayed on a display 66 provided outside the cover 11 so that the operator can check it.

  As shown in FIG. 6, the pulverizing apparatus 10 can be provided with a water-cooling type cooling apparatus 7 for cooling the outer wall surface of the pulverizing pot 1. In the cooling device 7, a cooling water is pumped by a pump 71 provided outside the cover 11, and the cooling water pumped up through the duct 72 is applied to the outer wall of the grinding pot 1 to cool the grinding pot 1. It has become. Further, the temperature of the outer wall of the crushing pot 1 is measured by a non-contact sensor 73 provided in the cover 11. Further, the measured temperature data is sent to a PLC (programmable logic controller) 74 provided outside the cover 11, and a control signal from the PLC is sent to the pump 71 via the inverter 75 to control the operation of the pump 71. doing. The operation of the pump 71 is started when the value of the sensor 73 exceeds a predetermined threshold value. It is also possible to set the threshold stepwise and set the operation speed of the pump 71 stepwise according to the temperature. The temperature of the outer wall of the crushing pot 1 is displayed on a display 76 provided outside the cover 11 so that the operator can check it. Further, the cooling water applied to the outer wall of the crushing pot 1 is collected in the collection container 78 by the discharge duct 77. Then, the cooling water recovered in the recovery container 78 is cooled again by the cooler 79 and supplied to the cooling water container 80. In this way, the cooling water that has been used once is recovered and can be reused. A cooler similar to the cooler 79 can be further provided in the pump duct 71. By providing the cooler at a plurality of locations, the cooling performance of the cooling water can be enhanced.

  An embodiment of the method for producing mercury sulfide according to the present invention will be described by explaining the operation of the pulverizing apparatus 10 having the above configuration. First, it vibrates by a motor built in the vibrator 5 that has obtained electric power via the earthquake-resistant cable 12. Since the vibration stage 13 that has received the vibration energy by the vibrator 5 is fixed to the base 8 via the spring 9, the vibration stage 13 vibrates independently of the base 8 and integrally with the vibrator 5. Further, the crushing pot 1 fixed to the vibration stage 13 also vibrates integrally with the vibration stage 13.

  When the crushing pot 1 vibrates, the metal ball enclosed inside moves in various directions and crushes the enclosed mercury and sulfur while stirring. Mercury and sulfur react with each other by impact, friction, shear, and compression energy generated by the pulverization, and mercury sulfide is produced. The pulverizing apparatus 10 according to the present embodiment can efficiently apply larger energy to the object to be pulverized as compared with the pulverizing apparatus having a rotating structure. Therefore, a relatively large amount of mercury can be handled at a time.

  Here, in the pulverization step described above, the metal balls are mixed with other balls, the inner wall surface of the pulverization pot, mercury and sulfur before reaction, and mercury sulfide after reaction inside the pulverization pot 1. There is severe collision and friction between them. Thereby, the inside of the pot 1 for grinding becomes very high temperature (for example, 100 ° C. or more). When mercury sulfide is produced in such a very high temperature state, the present inventors have found a tendency that the stability of mercury sulfide is reduced in the evaluation by the test method described above.

  Such a temperature rise phenomenon has not been a problem in the conventional method. In the conventional method, the amount of mercury to be handled is about several hundred grams, and the high energy pulverization method as described in the present embodiment has not been required. This is because a method of rotating in the horizontal direction has been taken. In this case, it is considered that the energy of collision of the balls for pulverization was relatively small, and the amount of temperature increase was relatively small. On the other hand, in the manufacturing method according to the present embodiment, the amount of mercury handled is as large as several kilos to several tons, and in order to efficiently process this large amount of mercury, the pulverization step with higher energy As a result, the amount of heat generated is enormous.

  Therefore, in the present embodiment, in the pulverization step, the outer wall surface of the pulverization pot 1 is cooled by the water injection device described above. As a result, the outer wall of the grinding pot 1 whose temperature rises during the grinding process is cooled, and the inside of the grinding pot 1 is indirectly cooled.

  By performing such cooling during the pulverization process, the manufactured mercury sulfide is evaluated by the environmental agency notification No. 13 and the stability evaluation by the head space test.

  As a method for measuring the temperature of the crushing pot 1 in the present embodiment, the temperature of the container bottom or the like on the outer wall of the pot is measured with a non-contact type thermometer (for example, radiation for measuring using infrared rays or visible light). Thermometer) or a contact-type thermometer (for example, a thermocouple). Thus, as a method of measuring the temperature inside the pot during the pulverization step, a method of estimating from the surface temperature of the outer wall (for example, the bottom surface on the side opposite to the opening surface) can be employed. For example, it is possible to more easily manage the temperature inside the pot by checking in advance the relationship between the temperature rise inside the crushing pot 1 and the temperature rise at a specific location on the outer wall surface of the pot, and grasping the correlation between them. Can do.

[Second Embodiment]
A method and apparatus for producing mercury sulfide according to the second embodiment will be described with reference to FIGS. Since the second embodiment is a modification of the first embodiment (FIGS. 1 to 6), the same or similar parts will not be described repeatedly, and the differences will be described in detail. Explained.

  In the second embodiment, instead of cooling the pulverizing pot by applying the coolant to the pulverizing pot as shown in the first embodiment, a cooling mechanism is provided so that the pulverizing pot can be cooled more efficiently. I have to.

  First, FIG. 7 is a sectional view of a container 25 of a crushing pot according to the second embodiment and a view of a lid. As shown in FIG. 7, the lid 26 and the container are detachable.

  On the other hand, FIG. 8 shows an example in which a cooling mechanism is added inside the container 25 of the crushing pot shown in FIG. Specifically, the inner wall 22 is provided inside the outer wall 21 of the body portion of the container 25. Thereby, a gap is formed between the outer wall 21 and the inner wall 22, and a space for injecting the refrigerant is secured. Furthermore, in this space, pipes 24 for injection and discharge are provided. The pipe 24 is passed through a hole 23 provided in the lid 16 when the lid 16 is fixed to the container 25.

  Thus, by providing the cooling mechanism, the refrigerant is supplied over the entire body portion of the container 25, and the inside of the container where heat is generated by the pulverization process can be effectively cooled. Further, the refrigerant injected from one pipe 24 can be recovered from the other pipe 24. Furthermore, in the pulverization step, the wall surface of the container 25 has a double structure, and a space is also present inside, so that an effect of blocking noise generated inside can be expected. Moreover, since the refrigerant | coolant collect | recovered becomes high temperature, it can also collect | recover thermal energy and can utilize for another purpose.

  In the second embodiment as well, the internal temperature can be estimated by measuring the temperature of the outer wall of the grinding pot. Here, according to the second embodiment, since the cooling mechanism is provided in the body portion of the container 25, the temperature of the outer wall of the body portion may not have a corresponding relationship with the temperature inside the container, It is not preferable. However, since the cooling mechanism is not provided at the bottom of the container, the temperature inside the container can be estimated by measuring the temperature of the bottom of the container.

  In the second embodiment, the refrigerant used for cooling can be recovered via the pipe 24. Therefore, by observing the temperature and flow rate of the recovered refrigerant, the amount of heat taken by the cooling water from the pulverizer can be estimated.

  The temperature and heat quantity data thus obtained is transmitted to the controller that controls the cooling mechanism, so that the controller can control the effective cooling operation of the pulverizer.

[Third Embodiment]
A method and apparatus for producing mercury sulfide according to the third embodiment will be described with reference to FIGS. Since the third embodiment is a modification of the first embodiment and the second embodiment, the same or similar portions will not be described repeatedly, and the details of the differences will be described. Explained.

  FIG. 9 shows a pulverizing apparatus 30 which is an embodiment of a manufacturing apparatus used in the method for manufacturing mercury sulfide according to the present invention. As shown in FIG. 9, the crushing device 30 according to the third embodiment includes a vibrator 35 at the center and one crushing pot 31 above and below the vibrator 35. The vibrator 35 and the crushing pot 31 are integrally fixed by a support 33. The support 33 is supported by the upper ends of the side springs 34 on the lower sides of the left and right ends in FIG. The side springs 34 are respectively fixed at the lower ends to the upper ends of the columns 36. Further, the lower end of the column 36 is fixed to the base 40.

  A charging port 38 is provided in the upper part of the crushing pot 31 provided above the vibrator 35, and it is possible to input crushing mercury and sulfur from the upper part. Further, the crushing pot 31 provided below the vibrator 35 is provided with a discharge port 39 in the lower part thereof. Further, the upper and lower crushing pots are connected by a duct 37 so that mercury, sulfur, mercury sulfide and the like can flow from the upper crushing pot to the lower crushing pot.

  Moreover, as shown in FIG. 10, the support 33 is provided in two places of the axial direction of a vibrator. Furthermore, the support 33 is provided with two side springs 34 respectively. Therefore, in the present embodiment, a total of four side springs 34 are installed. On the other hand, the insertion port 38 and the discharge port 39 are respectively provided in the axial direction of the vibrator 35 toward the rear in the drawing in FIG. Further, the duct 37 is provided in the axial direction of the vibrator 35 toward the front in FIG.

  As shown in FIG. 9, the crushing device 30 operates as follows with the above configuration. First, the vibrator 35 vibrates, so that the support fixed integrally, the upper and lower grinding pots, and the duct 37 connected thereto vibrate integrally. As a result, the grinding balls provided inside the upper and lower grinding pots move vigorously. At this time, by adding mercury and sulfur from the charging port, they are stirred and pulverized in the upper pulverization pot. Further, mercury, sulfur, and some manufactured mercury sulfide move through the duct 37 to the lower crushing pot, thereby further promoting stirring and crushing. The upper and lower grinding pots are provided with a threshold 32 so that the grinding balls 50 do not come out of the grinding pot. Further, the threshold 32 is provided with a hole through which powder and liquid can pass, so that mercury, sulfur, and mercury sulfide can pass therethrough.

  Through these steps, mercury and sulfur continuously input to the input port 38 are produced into mercury sulfide inside the apparatus and are continuously discharged from the discharge port 39. Thereby, the trouble of putting in and collecting mercury and sulfur by opening and closing each crushing pot can be saved, and mercury sulfide can be produced efficiently.

  Here, also in the third embodiment, a cooling mechanism can be provided. For example, the crushing pot can be cooled by providing the cooling device 6 or the cooling device 7 as shown in the first embodiment and applying a coolant to the outer wall of each crushing pot. Further, as shown in the second embodiment, the wall surface of the body portion of each crushing pot can have a double structure, and a cooling space can be provided. The inside of the crushing pot can be cooled by injecting the refrigerant into the space from the refrigerant supply device provided outside and then discharging the refrigerant.

  The pulverizer 30 in the third embodiment is different from the pulverizers in the first and second embodiments described above in that the operation for continuously producing mercury sulfide is possible. Therefore, the opportunity to stop the operation is reduced and the time during which the device is naturally cooled by the outside air is shortened. Thereby, the pot 31 for grinding | pulverization and the temperature of the inside may become higher temperature. However, efficient cooling can be aimed at by providing the above cooling mechanisms. Thereby, stable mercury sulfide can be continuously produced.

[Other aspects]
The description of the embodiment described above is an example for explaining the method and apparatus for producing mercury sulfide according to the present invention, and does not limit the invention described in the claims. Moreover, each part structure of this invention is not restricted to embodiment mentioned above, A various deformation | transformation is possible within the technical scope as described in a claim.

  For example, although the metal balls are made of chrome steel in this description, balls or rods (rods) made of iron, stainless steel, ceramic, etc. can be used. In addition, although the description has been made using stainless steel as the material for the pulverizing pot, the material can be appropriately changed such as using iron or titanium in consideration of cooling efficiency and strength against impact. Furthermore, the outer diameter, axial length, ball outer diameter, and pulverization time of the pulverizing pot can be appropriately changed according to the amount of mercury sulfide to be produced. In addition to air and water, for example, liquid nitrogen having a high cooling efficiency can be used as the refrigerant used for cooling. In addition, by using an antifreeze liquid mainly composed of ethylene glycol or glycerin, the cooling liquid can be prevented from freezing even in a cold region.

  Here, the example which implemented the manufacturing method and apparatus of the mercury sulfide which concerns on 1st Embodiment, and examined cooling temperature is shown below.

  FIG. 12 shows the mercury sulfide produced by controlling the temperature of the pulverizing pot in the pulverization step in the range of about 140 ° C. to about 55 ° C. in the first embodiment, according to the test of Environmental Agency Notification No. 13. The result of evaluating the mercury elution value is shown. According to this result, it can be seen that the elution value tends to decrease by cooling during the pulverization step. More preferably, when the temperature of the grinding pot is 60 ° C. or lower, the stability of the produced mercury sulfide is further increased and tends to be 0.005 mg / L or less, which is a reference value. In this test, 170 chrome grinding balls having an outer diameter of 25 mm were used and 1.5 kg of mercury was crushed for 45 minutes. Note that a water-cooled cooling device 7 is used for cooling in the first embodiment.

In the first embodiment, powdery sulfur (s) having a bulk specific gravity of 0.6 was mixed with 1000 g of liquid mercury (Hg) having a purity of 99.9% and a density of 13.57 kg / m ³ , and pulverized. The pot 1 was filled to produce mercury sulfide. At this time, the molar ratio of mercury: sulfur is 1.0: 1.05.

  The crushing pot 1 mounted on the crushing apparatus 10 is a stainless steel container having an outer diameter of 165 mm, an inner diameter of 135 mm, a depth of 180 mm, and a thickness of 6.4 mm. The amount was 3000 ml. Moreover, the motor for vibrating this pot 1 for grinding used output 0.85kw, power supply voltage 200V, and power supply frequency 50Hz. Further, the water injection device installed inside the cover 11 is designed to supply about 0 ° C. water to the outer wall of each crushing pot 1 at a rate of 250 ml per minute.

  Next, the results of studying the outer diameter and grinding time of a chromium steel grinding ball using the method and apparatus for producing mercury sulfide according to the second embodiment are shown below.

  Here, the supply amount of the cooling water in Example 2 was 4 liters per minute, and the water temperature of the cooling water was about 0 ° C. The capacity of the gap for cooling water inside the container 25 was 0.7 l, and the capacity of the crushing space located inside the container 25 was 2 l. In addition, the same stainless steel as the outer wall 21 was used for the material of the inner wall 22. The pipe 24 was an iron pipe having an inner diameter of about 3 mm and an outer diameter of about 5 mm.

  110 metal balls (7.2 kg) made of chromium steel having an outer diameter of about 25 mm were used as the metal balls for grinding put into the container 25.

  According to the second example, optimum parameters for obtaining stable mercury sulfide existed in the outer diameter of the ball for grinding and the grinding time. For example, in Table 1 shown below, the appearance evaluation results, the head space test results, and the evaluation results of the Environmental Agency Notification No. 13 test when mercury sulfide is produced by changing the outer diameter of the ball for grinding and the grinding time are shown. Show. Appearance evaluation as used herein refers to visual evaluation of whether or not the reaction product is in a preferred powder state. When the powder is not in the form of powder, a lump or silver-white paste-like substance is mixed as a reaction intermediate of liquid mercury and powder sulfur. According to the results of this appearance evaluation, the ball outer diameter was good at φ25, and the grinding time was good at about 45 minutes to 60 minutes.

DESCRIPTION OF SYMBOLS 1 Crushing pot 4 Fastener 5 Vibrator 6 Cooling device 7 Cooling device 8 Base 9 Spring 10 Crushing device 11 Cover 12 Seismic cable 13 Vibration stage 15 Container 16 Lid 17 Fixing tool 21 Outer wall 22 Inner wall 23 Hole 24 Pipe 25 Container 26 Lid 30 Crushing device 31 Crushing pot 32 Threshold 33 Support 34 Side spring 35 Vibrator 36 Strut 37 Duct 38 Input port 39 Discharge port 40 Base 50 Crushing ball 51 Shaft end 61 Fan 62 Duct 63 Sensor 64 PLC
65 Inverter 66 Display 71 Pump 72 Duct 73 Sensor 74 PLC
75 Inverter 76 Display 77 Discharge duct 78 Recovery container 79 Cooler 80 Cooling water container

Claims (5)

  A method for producing mercury sulfide by reacting mercury and sulfur in a pulverization step, wherein cooling is performed during the reaction step.   The method for producing mercury sulfide according to claim 1, wherein the pulverizing step is performed by a pulverizer including a ball for pulverization.   3. The method for producing mercury sulfide according to claim 2, wherein the cooling is at least a degree of relaxation of a temperature rise caused by collision and friction of the balls for grinding in the grinding step.   The said cooling process is a manufacturing method of the mercury sulfide of any one of Claim 1 thru | or 3 which cools the outer wall of the said grinder with a refrigerant | coolant. A crushing pot having a plurality of metal balls for crushing therein;
A vibrator that vibrates the grinding pot;
The pulverization pot is an apparatus for producing mercury sulfide provided with a cooling mechanism for cooling with a refrigerant.

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