JP6438721B2 - Ozone hydrate transport container - Google Patents

Description

  The present invention relates to an ozone hydrate transport container for generating ozone using a high-concentration ozone hydrate that can be stored stably at a low temperature for a long period of time, and performing treatment such as sterilization with the ozone.

  Conventionally, it has been proposed to produce ozone hydrate in order to obtain high-concentration ozone (Patent Document 1). The ozone hydrate is produced under high pressure of 13 MPa or more and low temperature of −25 ° C. or less. Since it is necessary to make ozone and water contact with each other, it is difficult to produce ozone hydrate in large quantities.

The present applicant mixes low-temperature water and ozone (O ₃ ) with carbon dioxide (CO ₂ ) as an auxiliary guest agent, so that the hydrate is 2 to 3 MPa and the temperature is about 0 according to the mixing ratio of ozone and carbon dioxide. The manufacturing method of the ozone hydrate produced | generated at degreeC was proposed (patent document 2, 3).

  In this proposal, when ozone hydrate is generated, the ozone hydrate generation pressure can be lowered by using a mixed gas in which about 70 mass% of carbon dioxide is included in ozone. The ozone concentration can be dramatically increased to 20000 ppm or more, and the hydrate can be generated at a relatively low pressure (2 to 3 MPa) by cooling the heat of ozone hydrate generation with low-temperature water at about 0 ° C. There is.

  This ozone hydrate can be stored for a long time without being decomposed by storing it in a supercooled state of about −20 ° C. or less even under atmospheric pressure, and when it is −5 ° C. under atmospheric pressure, Since the ozone hydrate is decomposed into ozone, it can be mixed with water to obtain sterilizing ozone or ozone water.

JP 2007-210881 A JP 2011-168413 A JP 2012-240901 A

  However, ozone hydrate is at a low temperature of −25 ° C., and its half-life is shortened and decomposes and disappears as the temperature rises. To transport it to the ozone sterilization site, the ozone hydrate must be kept cold. However, when it is carried to the site, ozone hydrate must be ready for use immediately.

  Then, the objective of this invention is providing the ozone hydrate transport container which can solve the said subject, can carry ozone hydrate, and can use ozone hydrate immediately in the sterilization field.

  In order to achieve the above object, the present invention is an ozone hydrate transport container characterized in that a discharge tube for dispensing ozone hydrate is provided in an ozone hydrate container having heat insulation properties for accommodating ozone hydrate. .

  The outer periphery of the ozone hydrate container is preferably covered with a cold insulating material.

  It is preferable that the ozone hydrate container is formed of a double shell tank, and the inside and outside shells are filled with a cooling agent and evacuated.

  It is preferable to connect a screw-type dispensing pump to the dispensing cylinder.

  According to the present invention, the ozone hydrate transport container is provided with heat insulation to prevent decomposition of the ozone hydrate due to temperature rise, and by providing a discharge tube, the discharge pump is provided after transport to the site where ozone sterilization is performed. The ozone hydrate can be dispensed by connecting the, and can be used immediately.

It is a figure which shows one embodiment of this invention. It is a figure which shows other embodiment of this invention. It is a figure which shows the ozone generator which generates ozone using the ozone hydrate transport container of this invention. It is a figure which shows the sewage process with the ozone generator shown in FIG. It is a figure which shows the ozone water generator which generates ozone water using the ozone hydrate transport container of this invention. It is a figure which shows the sewage treatment in the ozone water generator shown in FIG.

  A preferred embodiment of the present invention will be described below in detail with reference to the accompanying drawings.

  First, the high-concentration ozone hydrate used in the present invention will be described.

  As proposed in Patent Documents 2 and 3 described above, high-concentration ozone hydrate is produced by using xenon or carbon dioxide as an auxiliary gas, ozone as a guest gas, and contact with water at 2 to 3 MPa at about 0 ° C. Can be manufactured.

  This high-concentration ozone hydrate is in the form of a powder that does not contain a liquid component, thereby making it possible to generate ozone using the high-concentration ozone hydrate.

  FIG. 1 shows an ozone hydrate transport container 10.

  The ozone hydrate transport container 10 covers the outer periphery of an ozone hydrate container 11 for storing ozone hydrate with a cold insulating material 12 such as urethane, and a discharge cylinder 13 for discharging hydrate to the ozone hydrate container 11. It is provided.

  The ozone hydrate container 11 is provided with a manhole 14 for filling ozone hydrate.

  The dispensing cylinder 13 is provided with a flange 15. When dispensing, the cover 15 c of the flange 15 is removed, and the tip of the screw 17 of the screw-type dispensing pump 16 is inserted into the dispensing cylinder 13. By connecting the flange 18 to the flange 15, ozone hydrate can be paid out.

  Since this ozone hydrate transport container 10 has heat insulation properties, it can be stored for a long period of time below the decomposition temperature of the stored ozone hydrate. When using the stored ozone hydrate, a discharge screw is attached to the discharge cylinder 13. By inserting and connecting, the ozone hydrate in the ozone hydrate transport container 10 can be immediately paid out.

  FIG. 2 shows another embodiment of the present invention, wherein the ozone hydrate transport container 10 is constituted by a double shell tank of an inner shell 20 and an outer shell 21 for containing ozone hydrate, and between the inner and outer shells. In addition, pearlite grains are filled as a cooling agent, and a vacuum or multilayer heat insulating film is provided to form a vacuum multilayer heat insulating (vacuum MLI heat insulating) structure.

  The ozone hydrate transport container 10 of FIG. 2 is suitable for a small-sized ozone hydrate transport container 10 because the cost is higher than that of the ozone hydrate transport container 10 of FIG.

  FIG. 3 shows an ozone generator 30 that generates ozone from ozone hydrate using the ozone hydrate transport container 10 shown in FIGS. 1 and 2.

  A discharge pump 16 is connected to the ozone hydrate transport container 10 (FIG. 1), and a nozzle 31N at the lower end of the discharge pipe 31 connected to the discharge pump 16 is surrounded by an air nozzle 32 to which dry compressed air is supplied. A hydrate nozzle 33 is used as a double structure. This hydrate nozzle 33 is connected to a vertical ozone air mixer 34V.

  Compressed air is supplied from the compressor 35 to the ozone air mixer 34V, and ozone hydrate is shielded and sprayed from the hydrate nozzle 33 by dry air from the air nozzle 32 from the nozzle 31N. As a result, the ozone hydrate is decomposed by the heat of the compressed air in the ozone air mixer 34V to become ozone and mixed with the compressed air, and supplied as ozone gas from the ozone supply line 36 to the customer.

  FIG. 4 shows an example in which the ozone generator 30 shown in FIG. 3 sterilizes the treated water in the sewage treatment tank 38 as a demand destination.

  The sewage treatment tank 38 is provided with an ozone ejection pipe 40 that ejects ozone from the ozone generator 30 described in FIG. 3 through the ozone supply line 36, and ozone is ejected from the ozone ejection pipe 40. . Although the nozzle 31N may be frozen due to an erroneous operation or the like, the freeze can be released by stopping the ejection of the hydrate nozzle 33 for a short time and flowing the dry air from the air nozzle 32.

  In FIG. 4, the horizontal ozone air mixer 34 </ b> H is shown, but a vertical ozone air mixer 34 </ b> V may be used as shown in FIG. 3.

  The treated water 41 flows into the sewage treatment tank 38, and the treated water 41 is subjected to ozone sterilization treatment with ozone jetted from the ozone ejection pipe 40. After the ozone treatment, the treated water 41 is discharged from the sewage treatment tank 38 as purified water 42. Further, the ozone-containing air floating on the treated water is exhausted after the ozone is decomposed by the deozonizer 43.

  FIG. 5 shows an ozone generator 50 that generates ozone water from ozone hydrate using the ozone hydrate transport container 10 shown in FIGS. 1 and 2.

  A discharge pump 16 is connected to the ozone hydrate transport container 10 (FIG. 1), and a nozzle 31N at the lower end of the discharge pipe 31 connected to the discharge pump 16 is surrounded by an air nozzle 32 to which dry compressed air is supplied. A hydrate nozzle 33 is used as a double structure. This hydrate nozzle 33 is connected to a vertical ozone water mixer 54V.

  Dissolved water is supplied to the ozone water mixer 54V from the water pump 55, and ozone hydrate is shielded and sprayed from the hydrate nozzle 33 by dry air from the air nozzle 32 from the nozzle 31N. Thereby, the ozone hydrate is decomposed by the heat of the dissolved water in the ozone water mixer 54V to become ozone and is mixed with the dissolved water, and is supplied as ozone water from the ozone water supply line 56 to the customer.

  FIG. 6 shows an example in which the ozone generator 50 shown in FIG. 5 sterilizes the treated water in the sewage treatment tank 38 as a demand destination.

  The sewage treatment tank 38 is provided with an ozone water ejection pipe 60 that ejects ozone water from the ozone generator 50 described in FIG. 5 through the ozone water supply line 56, and ozone water is ejected from the ozone water ejection pipe 60. To be done.

  In FIG. 6, the horizontal ozone water mixer 54H is shown, but a vertical ozone water mixer 54V may be used as shown in FIG.

  The treated water 41 flows into the sewage treatment tank 38, and the treated water 41 is subjected to ozone sterilization treatment with ozone water injected from the ozone water ejection pipe 60. After the ozone treatment, the treated water 41 is discharged as purified water 42 from the sewage treatment tank 38. To do. Further, the ozone-containing air floating on the treated water is exhausted after the ozone is decomposed by the deozonizer 43.

  A part of the purified water 42 is returned to the suction port of a water pump 55 for supplying water to the ozone water mixer 54H through a circulation line 67 and circulated for use as ozone-dissolved water.

  As described above, the ozone hydrate transport container 10 of the present invention is transported to the site where ozone sterilization is performed, and the ozone generators 30 and 50 are simply assembled at the site, and the ozone hydrate in the ozone hydrate transport container 10 is removed. It becomes possible to generate ozone by using it.

  Next, the specific example about the heat insulation of the ozone hydrate transport container 10 and the storage time until decomposition | disassembly of ozone hydrate is demonstrated.

(1) Ozone hydrate transport container (volume 10m ³ )
Container type Cylindrical capacity Evaporation volume (m ³ ) 10
Dimensions Diameter (m) 1.6
Body length (m) 5
Ozone hydrate properties O ₃ content (mass%) 2.23
O ₃ hydrate density (kg / m ³ ) 1130
Hydrate free water rate (mass%) 30
Free water + hydrate density (kg / m ³ ) 1091
O ₃ content (kg) 75
Apparent filling rate (%) 50
Loading volume ratio (%) 95
(a) Ozone hydrate container covered with cold insulation material
Insulation thickness (m) 0.15
Cold insulating material Urethane Cold insulating material surface area (m ² ) 34
Container surface area (m ² ) 27
Heat input (kcal / h) 329
Outside temperature (℃) 35
Internal temperature (℃) -25
Cooling effective time (h) 10.1
(It is assumed that the hydrate that is 5cm on average from the inner wall of the container rises in temperature)
Hydrate amount (m ³ ) 9.0
Same (kg) 8837
Free water + hydrate density (kg / m ³ ) 1091
Hydrate temperature rise (kcal / m ³ ) 1.25
Average allowable temperature rise (℃) 2.5
Maximum temperature (° C) -20
Temperature rise hydrate amount (kg) 2652
From the above, a 10 m ³ hydrate transport container insulated with urethane can be stored for about 10 hours without decomposing ozone hydrate.
(b) Ozone hydrate container with double shell structure Inner shell dimensions:
Diameter (m) 1.6
Body length (m) 5
Outer shell volume (m ³ ) 15
Volume difference between inner and outer shells (m ³ ) 5.0
Inner / outer shell spacing (m) 0.15
Cold insulation thickness Perlite-filled vacuum insulation (m) 0.15
Thermal conductivity (degree of vacuum 4 × 10 ⁻⁴ Torr) (W / mK) 0.001
Same (kcal / mh ° C) 0.0009
Inner shell surface area (m ² ) 27
Surface area of outer shell (m ² ) 34
Heat input (kcal / h) 14.2
Outside temperature (℃) 35
Internal temperature (℃) -25
Examination of effective time when hydrate temperature rise is observed Hydrate amount (m ³ ) 9.0
Same (kg) 5085
Apparent filling rate (%) 50
Hydrate density (kg / m ³ ) 1130
Thermal diffusion distance from inner shell;
Approximate expression x = (12 * κ * t) ^1/2 (m) 0.8
κ = λ / (ρ * Cp) 0.003
ρ (kg / m ³ ) 565
Cp (J / kgK) 0.58
Elapsed time t (s) 14
t (h) 0.004
t (min) 0.24
After about 0.3 minutes (14 seconds) from the above, the temperature starts to rise at the center of the ozone hydrate container.
(c) Examination of heat transfer to hydrate phase and temperature rise
In the examination of the item (b), since the heat diffusion time is short, the heat input reaches the center of the hydrate relatively quickly, so that the entire hydrate absorbs heat.
Average heat transfer area of hydrate phase (m ² ) 18.1
Average heat transfer distance (m) 0.53
Heat input from vacuum heat insulating layer to hydrate phase Average temperature rise of hydrate phase (° C / h) 0.033
Heat input (kcal / h) 85.0
Heat input of container heat insulation layer (kcal / h) 14.2
Heat insulation layer average area (m ² ) 30.44
Heat input from manholes (kcal / h) 70.8
Magnification of heat insulation heat input 5
Allowable time (h) 149 when allowable temperature rise is 3 ° C.
(D) 6.2
Average allowable temperature rise (℃) 5
Allowable center temperature (° C) -20.05
Shell inner wall allowable center temperature (℃) -20
From the above, a 10 m ³ hydrate transport container filled with pearlite with a double shell and vacuum-insulated can be stored for about 149 hours without decomposing ozone hydrate.

  In addition, when the ozone hydrate transport container is configured by vacuum multilayer insulation (vacuum MLI insulation) using a radiation reflecting film in addition to pearlite-filled vacuum insulation, the details of the calculation are omitted, but the entry into the hydrate phase is omitted. The amount of heat was 71.4 kcal / h, and the allowable time when the allowable temperature increase was 3 ° C. on average was 177 hours.

(2) Examination of small ozone hydrate transport container Container type Cylinder (Double shell vacuum MLI insulation structure)
Capacity Vaporization volume (m ³ ) 0.1
Dimensions Diameter (m) 0.4
Body length (m) 0.8
Ozone hydrate properties O ₃ content (mass%) 2.23
O ₃ hydrate density (kg / m ³ ) 1130
Hydrate free water rate (mass%) 30
Free water + hydrate density (kg / m ³ ) 1091
O ₃ content (kg) 0.75
Apparent filling rate (%) 50
Loading volume ratio (%) 95
Estimate the allowable days from the volume (V / Vo) ratio with the large container in (1) (calculated assuming proportional to the square root of the volume ratio)
(V / Vo) ^1/2 0.100
Heat input (kcal / h) 7.1
Hydrate average temperature rise (° C / h) 0.276
Allowable time (h) when allowable temperature rise is 3 ° C on average 17
(D) 0.7
Average allowable temperature rise (° C) 4.8
Approximate temperature difference between hydrate inner wall and center (° C) 0.413
Initial temperature (° C) -25
Allowable center temperature (° C) -20.41
Shell inner wall allowable temperature (℃) -20
In a small ozone hydrate transport container (0.1 m ³ ), ozone hydrate can be stored for about 17 hours without being decomposed.

DESCRIPTION OF SYMBOLS 10 Ozone hydrate transport container 11 Ozone hydrate container 12 Cold insulating material 13 Discharge cylinder 20 Inner shell 21 Outer shell

Claims (3)

An ozone hydrate container having heat insulation for accommodating ozone hydrate ;
A dispenser provided in the ozone hydrate container, for dispensing the ozone hydrate ;
A screw-type dispensing pump connected to the dispensing cylinder,
The ozone hydrate transport container , wherein the discharge pump has a screw inserted into the discharge cylinder and inserted into the ozone hydrate container. The ozone hydrate transport container according to claim 1 , wherein a valve is provided on a discharge side of the discharge pump . The ozone hydrate transport container according to claim 1 or 2 , wherein the discharge pump and the discharge tube are flange-connected to each other .

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