JP2016209850A - Organic material decomposition apparatus and organic material decomposition method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic material decomposition apparatus and an organic material decomposition method capable of effectively deodorizing a production facility of a liquid product.SOLUTION: There is provided an organic material decomposition apparatus 1 which comprises a supply pipe 120 for supplying a cleaning liquid to a facility to be cleaned F, a recovery pipe 110, ozone gas supply means 10, pressure supply means 20 for pressure-supplying ozone gas and a cleaning liquid after mixing, a reaction part 130 and a deaeration part 50, wherein an organic material is decomposed and a deaerated cleaning liquid is re-supplied to the facility to be cleaned F. There is provided an organic material decomposition method which comprises: a step of supplying a cleaning liquid to a facility to be cleaned F to carry out cleaning and returning the cleaning liquid which cleaned the facility to be cleaned F, a step of supplying ozone gas to the recovered cleaning liquid to dissolve the ozone gas in the cleaning liquid under a pressurized state and decompose an organic material contained in the cleaning liquid; a step of performing gas-liquid separation of the cleaning liquid in which an organic material is decomposed; and a step of re-supplying the deaerated cleaning liquid in which an organic material is decomposed and deaerated to the facility to be cleaned F.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an organic matter decomposing apparatus and an organic matter decomposing method used for stationary cleaning of a liquid product manufacturing facility.

  Manufacturing equipment for liquid products including beverages includes equipment such as pipes, tanks, and pumps. Such a cleaning method for manufacturing equipment is roughly classified into disassembly cleaning (Cleaning Out Place; COP) and stationary cleaning (Cleaning In Place; CIP). In the disassembly cleaning, the manufacturing equipment is disassembled, and cleaning is performed mainly on hand washing for each part. On the other hand, in the stationary cleaning, the cleaning is performed by automatically passing the cleaning liquid through the manufacturing line without disassembling the manufacturing equipment.

  In-place cleaning is a cleaning method that does not involve disassembly of manufacturing equipment, so it is suitable for ensuring the reliability and safety of cleaning operations compared to disassembly cleaning, and it can also shorten the cleaning time. Yes. Therefore, as a cleaning method for manufacturing equipment for liquid products, stationary cleaning that contributes to improving the operating efficiency of the manufacturing equipment is the mainstream. In-place cleaning is generally performed by circulating and supplying a cleaning liquid to a production line by a stationary cleaning apparatus provided in a manufacturing facility.

  In stationary cleaning of liquid product manufacturing facilities, alkaline cleaning liquids for decomposing organic substances such as proteins and carbohydrates, acidic cleaning liquids for removing inorganic substances such as inorganic salts, surfactants and disinfectants are used. It is often done. Also, fresh water is often used for pre-cleaning and rinsing purposes. These cleaning liquids are heated to a hot water region or higher and then passed through a production line to improve cleaning efficiency and sterilization. Since the circulating supply of the cleaning liquid is performed for a long time, the total amount of the cleaning liquid and the amount of heat consumed for the heating have reached a level that cannot be neglected.

  Usually, seal members such as gaskets and packings are interposed in pipes, tanks, and connecting parts of equipment such as pumps provided in a liquid product manufacturing facility. When fragrance | flavor etc. are used in manufacture of a liquid product, it is known that the fragrance | flavor component contained in a fragrance | flavor will adhere to the surface of a sealing member, or osmose | permeate to the deep part of a sealing member. The flavoring of the aromatic component thus generated is remarkable in a seal member made of ethylene / propylene / diene rubber (EPDM), nitrile rubber (NBR), silicon rubber or the like.

  It is difficult to remove the fragrance component scented on the seal member in a short time even by alkali cleaning or acid cleaning. If a fragrance component remains in the seal member or the like, it continues to elute even after the product is switched on the production line, and shifts to another product to cause a problem of scent transfer. Conventionally, deodorization cleaning for the purpose of deodorizing a production line has been performed as a countermeasure for such a problem. Deodorizing cleaning is performed in conjunction with alkali cleaning and acid cleaning, and a large amount of hot water is consumed by performing deodorizing cleaning, and the time required for stationary cleaning is prolonged.

  Conventionally, a technique using ozone water for deodorizing and cleaning has been studied. For example, Patent Document 1 discloses a cleaning apparatus that cleans an object to be cleaned in a food manufacturing facility, an ozone generator that generates ozone for cleaning the object to be cleaned in the food manufacturing facility, and an ozone that is dissolved. A heating device for heating water, a mixer for preparing heated ozone mixed water by mixing ozone generated by the ozone generator and water heated by the heating device, and heating ozone mixing prepared by the mixer A cleaning apparatus including a pipe for supplying water to an object to be cleaned of the food production facility is disclosed (see claims 1 and 2). Examples of the object to be cleaned include food manufacturing equipment, a food manufacturing tank, or connection piping provided with a silicon rubber sealing material. Also, a cleaning method for cleaning an object to be cleaned in a food manufacturing facility, generating ozone for cleaning the object to be cleaned in the food manufacturing facility, heating water for dissolving ozone, and the generated ozone Prepare ozone-mixed water by mixing with heated water, and prepare food to be cleaned consisting of food manufacturing equipment, food manufacturing tank, or connecting pipe with silicon rubber sealant for the food manufacturing equipment A cleaning method is disclosed in which the aromatic component adhering to the sealing material is removed by cleaning with the ozone mixed water (see claim 6).

Japanese Patent No. 4919388

  In the technology disclosed in Patent Document 1, ozone mixed water is supplied to an object to be cleaned of a food manufacturing facility, and by cleaning a food manufacturing device, a food manufacturing tank, and a connecting pipe having a silicon rubber sealing material, The aromatic component adhering to the sealing material is removed. At this time, when heated ozone mixed water heated by a heating device is used, the aroma component adsorbed on the sealing material can be efficiently removed.

  However, in the method of supplying ozone mixed water to the equipment to be cleaned that is to be fixedly cleaned, ozone cannot sufficiently contribute to the decomposition of the aroma components. This is because the ozone supplied to the equipment to be cleaned is decomposed at an early stage in the presence of moisture and organic matter, and it is difficult to reach the terminal side of the equipment to be cleaned. In general, from the viewpoint of increasing the decomposition rate of aromatic components by ozone, it is desirable that the temperature of the ozone solution is high. However, when the liquid temperature is high, ozone decomposes before reaching the presence of the fragrance component, and therefore hardly contributes to the decomposition of the fragrance component. Further, it is known that the solubility of ozone decreases as the liquid temperature increases. Therefore, even if an attempt is made to deodorize the entire equipment to be cleaned including the terminal side, it is difficult to decompose the aroma component with ozone in a state where both an appropriate decomposition rate and an appropriate dissolved concentration are achieved.

  Further, in the method of supplying the ozone-mixed water to the equipment to be cleaned, the ozone supplied into the equipment to be cleaned is decomposed into molecular oxygen having a low solubility, and bubbles are generated inside the pipe or the like. If a large amount of such bubbles accumulates, an air pocket is formed inside the piping or the like, and there is a possibility that a location where the cleaning liquid is difficult to reach locally occurs. That is, due to such a situation, the aroma component removability of the equipment to be cleaned is deteriorated.

  Further, in the method of supplying the ozone mixed water to the equipment to be cleaned, the supplied ozone and the aromatic component eluted from the seal member react exclusively in the equipment to be cleaned. In a to-be-cleaned facility in which the reaction atmosphere is not managed, the reaction efficiency between ozone and fragrance components is poor, and the efficiency of the chain reaction that starts when ozone self-decomposes becomes low. In particular, the hydroxyl radical generated by this chain reaction is not effectively used for the decomposition of the aromatic component.

  As described above, in the method of supplying the ozone-mixed water to the equipment to be cleaned, the deodorization efficiency by ozone hardly reaches the required level even though power is consumed for generating ozone. Therefore, it becomes necessary to continue the circulation supply of ozone mixed water for a long time until the fragrance component in the equipment to be cleaned is sufficiently decomposed. As a result, the time required for stationary cleaning becomes longer, and the amount of heat required for heating the ozone mixed water also increases. Moreover, since the fragrance component which was not decomposed | disassembled appropriately by ozone can be circulated and supplied to the to-be-cleaned equipment and re-scented, the motive power required for the production | generation of ozone will be wasted and it is not efficient.

  Then, an object of this invention is to provide the organic substance decomposition | disassembly apparatus and organic substance decomposition | disassembly method which can deodorize efficiently the manufacturing equipment of a liquid product.

  In order to solve the above problems, an organic matter decomposing apparatus according to the present invention includes a supply pipe for supplying a cleaning liquid to a facility to be cleaned, a recovery pipe for recovering the cleaning liquid for cleaning the cleaning equipment, and ozone gas in the recovered cleaning liquid. The ozone gas supply means for supplying the pressure, the pressure feeding means for gas-liquid mixing and feeding the supplied ozone gas and the cleaning liquid, the pressurized ozone gas and the cleaning liquid are maintained in a pressurized state, and the ozone gas causes the A reaction section for decomposing organic substances contained in the cleaning liquid; and a degassing section for performing gas-liquid separation of the cleaning liquid from which the organic substances have been decomposed. It is characterized by being re-supplied to the equipment.

  In addition, the organic matter decomposition method according to the present invention includes a step of supplying a cleaning liquid to a facility to be cleaned for cleaning, a step of recovering the cleaning liquid for cleaning the target facility, and supplying ozone gas to the recovered cleaning liquid, A step of dissolving the ozone gas in the cleaning liquid under pressure and decomposing the organic matter contained in the cleaning liquid, performing a gas-liquid separation of the cleaning liquid in which the organic matter has been decomposed, and decomposing the organic matter And a step of re-supplying the degassed cleaning liquid to the equipment to be cleaned.

  ADVANTAGE OF THE INVENTION According to this invention, the organic substance decomposition | disassembly apparatus and organic substance decomposition | disassembly method which can deodorize efficiently the manufacturing equipment of a liquid product can be provided.

It is a figure which shows schematic structure of the organic substance decomposition | disassembly apparatus which concerns on 1st Embodiment of this invention. It is a figure which shows an example of the relationship between the deodorizing time of an aromatic component, and the residual amount of an aromatic component. (A) is a figure which shows the relationship about a linalool oxide, (b) is a figure which shows the relationship about ethyl isobutyrate. It is a figure which shows the half time in the clear water of ozone. It is a figure which shows the dissolution rate with respect to the clear water of ozone. It is a figure which shows the pressure required for making ozone fully melt | dissolve with respect to fresh water.

  Hereinafter, an organic matter decomposition apparatus and an organic matter decomposition method according to an embodiment of the present invention will be described.

FIG. 1 is a diagram showing a schematic configuration of an organic matter decomposing apparatus according to an embodiment of the present invention.
As shown in FIG. 1, an organic matter decomposition apparatus 1 according to this embodiment includes a recovery pipe 110, a supply pipe 120, an ozone gas supply means 10, a gas-liquid mixing pump (pressure feeding means) 20, a reaction tube (reaction section). ) 130 and a deaeration device (a deaeration part) 50. The organic matter decomposing apparatus 1 is an apparatus that performs stationary cleaning of a manufacturing facility for liquid products such as beverages, and decomposes organic matter contained in a cleaning liquid collected from the manufacturing facility using ozone.

  As shown in FIG. 1, the organic matter decomposing apparatus 1 is attached to a liquid product manufacturing facility (cleaned facility F) to be subjected to stationary cleaning. Liquid products include non-food liquid products such as cosmetics, pharmaceuticals, quasi-drugs, and hygiene products, as well as beverages, liquid foods, fluid semi-solid foods, and the like. The equipment F to be cleaned includes, for example, pipes through which liquid materials such as liquid products, semi-finished products, and raw materials flow, tanks in which liquid materials are stored, and the like. And in the to-be-cleaned equipment F, the flow path (liquid to be cleaned p) of the liquid substance used as a manufacturing line is formed by connecting piping, a tank, etc.

  In the liquid material flow path (cleaned flow path p), all or part of various processes such as raw material preparation, extraction, heating, cooling, degassing, gas injection, sterilization, and filling are performed in the manufacture of liquid products. Implemented inline. For this reason, the flow path (cleaned flow path p) is provided with devices such as a pump, a valve, a heat exchanger, a measuring instrument, and a filter so as to be in contact with the liquid material to be handled. In the stationary cleaning, the cleaning object is cleaned by passing the cleaning liquid through the cleaning channel p of the cleaning facility F.

  As shown in FIG. 1, the switching valve V1 is connected to the inlet of the to-be-cleaned flow path p which the to-be-cleaned equipment F has via the pipe line. A circulation pump 70 and a heating device 80 are installed in this pipe line. One end of the liquid supply pipe 101 is connected to the switching valve V1. Moreover, the switching valve V2 is connected to the exit of the to-be-cleaned flow path p via the pipe line. One end of the drainage pipe 102 is connected to the switching valve V2. The circulation pump 70, the heating device 80, the liquid supply pipe 101, the drainage pipe 102, the switching valve V1 and the switching valve V2 may be independently provided integrally with the organic matter decomposition apparatus 1, or the organic matter decomposition apparatus. 1 may be provided separately from the cleaning equipment F or other stationary cleaning apparatus (unit). Moreover, the heating apparatus 80 may serve as the function of the heat sterilizer in a manufacturing process.

  The liquid supply pipe 101 forms a flow path for supplying a cleaning liquid to the equipment F to be cleaned. The other end of the liquid supply pipe 101 whose one end is connected to the switching valve V1 is normally branched into a plurality of pipes (not shown) and connected to a plurality of cleaning liquid supply sources. The supply of the cleaning liquid from each of the cleaning liquid supply sources is controlled to be switched at predetermined time intervals according to the fixed cleaning plan, and the fixed cleaning is performed. As a result, various cleaning liquids are sequentially supplied to the cleaning flow path p of the cleaning target facility F through the switching valve V1.

  For example, an alkaline cleaning liquid containing sodium hydroxide, sodium hypochlorite, a surfactant and the like is supplied to the equipment F to be cleaned, and an acidic cleaning liquid containing nitric acid, a surfactant and the like is supplied for the acid cleaning. Supplied. In addition, for sterilization, a cleaning liquid for sterilization such as sodium hypochlorite is supplied, and before rinsing performed before alkali cleaning or acid cleaning, or during rinsing between and after these cleanings, Supply of fresh water substantially free of salt and metals is performed.

  The circulation pump 70 pumps the supplied cleaning liquid and supplies the cleaning liquid to the equipment F to be cleaned. The heating device 80 heats the cleaning liquid supplied to the equipment F to be cleaned. The cleaning liquid pumped by the circulation pump 70 is heated to the hot water area or the hot water area by the heating device 80, and the generated high temperature cleaning liquid is passed through the equipment F to be cleaned. The cleaning liquid flows through the channel to be cleaned p of the facility to be cleaned F to clean the object to be cleaned, and is then discharged from the outlet of the channel to be cleaned p.

  The drainage pipe 102 forms a flow path for discharging the cleaning liquid that has cleaned the object to be cleaned. The other end of the drainage pipe 102 whose one end is connected to the switching valve V2 is connected to a cleaning liquid supply source (not shown). The cleaning liquid flowing through the cleaning flow path p is transferred to the cleaning liquid supply source through the drain pipe 102 and then circulated and supplied to the cleaning equipment F through the liquid supply pipe 101 again. The cleaning liquid that has been repeatedly supplied to the cleaning equipment F over a predetermined time to clean the object to be cleaned is discharged out of the system from the downstream of the drainage pipe 102 or the intermediate part of the channel p to be cleaned, and cooled as necessary. After being treated, it is drained.

  In a liquid product manufacturing facility (cleaned facility F), a fragrance may be used in manufacturing a liquid product. The fragrance contains various organic substances such as hydrocarbons, esters, ketones, aromatics, fatty acids, aldehydes, alcohols and ethers as fragrance components. As the aromatic component, compounds of various elemental compositions such as sulfur-containing compounds and nitrogen-containing compounds can be used in addition to hydrocarbon compounds such as terpene compounds. In addition, the types of interatomic bonds, the degree of volatility, and the like are diverse.

  On the other hand, sealing members such as gaskets and packings are usually interposed in connecting portions of equipment such as piping, tanks, and pumps provided in the manufacturing facility (cleaned facility F). Such a sealing member is generally made of ethylene / propylene / diene rubber (EPDM), nitrile rubber (NBR), silicon rubber or the like. The sealing member of such a material has the property that the fragrance component (organic substance) contained in the fragrance is easily scented.

  Therefore, when a liquid product or semi-finished product to which a fragrance is added is handled in the liquid flow path (cleaned flow path p) of the manufacturing equipment (cleaned equipment F), various aroma components are sealed. It adheres firmly to the surface of the member or penetrates to the deep part of the seal member. In this way, the aromatic component scented on the sealing member often remains in the deep part of the sealing member even after the alkaline cleaning liquid or acidic cleaning liquid is circulated and supplied to the equipment F to be cleaned.

  Therefore, deodorizing and cleaning for the purpose of deodorizing the fragrance component is performed on such a liquid product manufacturing facility (cleaned facility F). Specifically, the cleaning liquid is circulated between the organic matter decomposing apparatus 1 and the equipment to be cleaned F, so that the aromatic components perfume on the seal member in the channel to be cleaned p are eluted into the cleaning liquid. And the to-be-cleaned equipment F is deodorized by returning the washing | cleaning liquid which the fragrance component eluted to the organic substance decomposition | disassembly apparatus 1. FIG. Specifically, the deodorizing cleaning is performed by switching the switching valves V1 and V2 to close the liquid supply pipe 101 and the drain pipe 102, and operating the circulation pump 70 to remove the cleaning liquid from the organic matter decomposing apparatus 1 and the equipment F to be cleaned. By circulating at a constant flow rate between.

  The cleaning solution preferably used in the deodorizing cleaning is a cleaning solution in a warm water region of 50 ° C. or more and less than 60 ° C., or a cleaning solution in a hot water region of 60 ° C. or more. The liquid temperature of the cleaning liquid may be 80 ° C. or higher, or 90 ° C. or higher. The cleaning liquid is preferably fresh water substantially free of salt or metals, but may be tap water or the like. By passing a high-temperature cleaning liquid through the equipment F to be cleaned, the solubility of the fragrance component is increased and the diffusion rate of the fragrance component penetrating into the deep portion is improved, and the time for diffusing in the seal member is shortened. Therefore, the fragrance component permeating the seal member is easily eluted into the cleaning liquid, and efficient deodorization cleaning is performed without increasing the required time. Moreover, if it is high temperature fresh water or tap water, there will be little damage to a sealing member.

  The recovery pipe 110 forms a flow path for recovering (returning) the cleaning liquid from the equipment F to be cleaned. One end of the recovery pipe 110 is connected to the switching valve V2. Since the switching valve V2 is connected to the outlet of the cleaning flow path p of the cleaning target facility F via a pipe line, the cleaning target facility F is cleaned by the switching of the switching valve V2, and the fragrance is cleaned from the cleaning target facility F. The cleaning liquid from which the components (organic substances) are eluted is collected in the organic substance decomposition apparatus 1. At this time, the flow path on the drain pipe 102 side of the switching valve V2 is closed. On the other hand, the other end of the recovery pipe 110 is connected to the gas-liquid mixing pump 20, and a flow path from the gas-liquid mixing pump 20 to the supply pipe 120 through the reaction pipe 130 and the degassing device 50 is connected.

  The supply pipe 120 forms a flow path for supplying the cleaning liquid to the equipment F to be cleaned. One end of the supply pipe 120 is connected to the deaeration device 50. On the other hand, the other end of the supply pipe 120 is connected to the switching valve V1. Since the switching valve V1 is connected to the inlet of the cleaning flow path p of the cleaning equipment F via a pipe line, the cleaning liquid is supplied from the organic substance decomposition apparatus 1 to the cleaning equipment F by switching the switching valve V1. Will be. At this time, the flow path on the liquid supply pipe 101 side of the switching valve V1 is closed. The cleaning liquid that has cleaned the equipment to be cleaned F is recovered through the recovery pipe 110 and then re-supplied to the equipment to be cleaned F through the supply pipe 120 and circulates.

  The concentration of the aroma component in the cleaning liquid gradually increases as the cleaning liquid is repeatedly supplied to the equipment F to be cleaned. As a result, the eluted fragrance component reattaches to the seal member, and the efficiency of deodorization of the fragrance component decreases. For this reason, in general, it is necessary to frequently replace the cleaning liquid being circulated. However, since the deodorizing cleaning must be stopped when the cleaning liquid is replaced, the time required for the stationary cleaning is increased. Moreover, the amount of water used is required for the replacement of the cleaning liquid, and reheating of the newly replaced cleaning liquid requires a large heating cost.

  Therefore, in the organic matter decomposing apparatus 1, an organic matter decomposing process is performed for decomposing the aroma component (organic matter) contained in the cleaning liquid recovered from the equipment F to be cleaned using ozone. The organic matter decomposing method according to the present embodiment includes a step of supplying a cleaning liquid to the equipment to be cleaned F for cleaning, cleaning the equipment to be cleaned F, and returning the cleaning liquid from which the organic matter has eluted from the equipment to be cleaned. Mixing ozone gas into the cleaning liquid, dissolving ozone gas in the cleaning liquid under pressure and decomposing the organic matter contained in the cleaning liquid, degassing the cleaning liquid in which the organic matter has been decomposed, And a step of resupplying the cleaning liquid degassed and degassed to the equipment F to be cleaned.

  In this organic matter decomposition method, in particular, the cleaning liquid recovered from the equipment F to be cleaned and the diffused ozone gas are gas-liquid mixed, and the ozone contained in the ozone gas is substantially completely contained in the cleaning liquid under pressure. Dissolve to break down fragrance components eluted in the circulating cleaning liquid. Then, after deodorizing the cleaning liquid in which the fragrance component is decomposed, the deodorizing cleaning is continuously performed by supplying the cleaning liquid again to the equipment F to be cleaned.

  As shown in FIG. 1, the ozone gas generation means 10 includes a compressor 11, an oxygen concentrator 12, an ozone generator 13, and a concentration meter 14. The ozone gas generating means 10 is a device that generates ozone gas containing ozone and supplies the ozone gas to the cleaning liquid recovered from the equipment F to be cleaned. Air is supplied to the compressor 11 included in the ozone gas generation means 10.

  The compressor 11 generates compressed air by compressing air. Then, the generated compressed air is introduced into the oxygen concentrator 12. The oxygen concentrator 12 is, for example, a PSA (pressure swing adsorption) method, and includes an adsorption tower filled with an adsorbent such as zeolite. The adsorbent has adsorbability with respect to nitrogen, moisture, etc., and removes nitrogen, moisture, etc. contained in compressed air pressurized to a predetermined pressure or higher.

  The oxygen concentrator 12 removes nitrogen, moisture, and the like from the compressed air introduced into the adsorption tower, and generates an oxygen enriched gas with an increased oxygen concentration. On the other hand, the adsorbent of the oxygen concentrator 12 desorbs adsorbed nitrogen, moisture and the like for air having a pressure lower than a predetermined pressure. Therefore, in the oxygen concentrator 12, the generation of the oxygen-enriched gas and the regeneration of the adsorption capacity of the adsorbent are repeated by repeating the pressurization and depressurization.

  The ozone generator 13 generates ozone by generating ozone in the oxygen-enriched gas. The ozone generation method in the ozone generator 13 can be an appropriate form such as a discharge type, an electrolysis type, or an ultraviolet type. However, a preferable form is a discharge type suitable for mass production of ozone. The discharge type ozone generator 13 includes, for example, an electrode pair covered with a dielectric. Oxygen-concentrated gas is introduced between the electrodes and an alternating voltage is applied, so that ozone gas is generated as silent discharge occurs.

Ozone gas is a hybrid gas containing ozone at a concentration of 230 g / m ³ or less, with the balance being mainly composed of oxygen. The ozone gas generated in the ozone generator 13 is supplied to the cleaning liquid collected from the equipment F to be cleaned. At this time, the concentration of the supplied ozone gas is measured by the densitometer 14. The organic matter decomposing apparatus 1 is operated so that, for example, the concentration of supplied ozone is kept constant with respect to the flow rate of the cleaning liquid. The ozone concentration of the ozone gas is preferably 50 g / m ³ or more and 210 g / m ³ or less and around 200 g / m ³ .

  The gas-liquid mixing pump 20 gas-liquid mixes the cleaning liquid collected from the equipment to be cleaned F and the ozone gas generated by the ozone gas generation means 10 and pumps them. The gas-liquid mixing pump 20 is a pump that pumps liquid and gas and pressurizes the gas-liquid two-phase flow. As this type of gas-liquid mixing pump 20, a vortex pump in which an impeller is housed in a cylindrical casing, a self-absorbing diaphragm pump, a vortex pump, or the like can be used. The ozone gas and the cleaning liquid are pressurized while being gas-liquid mixed by the gas-liquid mixing pump 20 and are pumped to the reaction tube 130.

  The reaction tube 130 is a tubular reactor that holds the pressurized ozone gas and the cleaning liquid in a pressurized state. One end of the reaction tube 130 is connected to the gas-liquid mixing pump 20. On the other hand, the other end of the reaction tube 130 is connected to a flow rate control means (throttle valve) 40. The flow rate control means 40 functions to restrict the flow rate of the cleaning liquid flowing through the reaction tube 130 and maintain the internal pressure in the reaction tube 130. In FIG. 1, a throttle valve is provided as the flow control means 40, but the throttle valve may be variable in opening or invariable. In place of the throttle valve, an orifice, a perforated plate, or the like may be provided.

  In the reaction tube 130, the cleaning liquid recovered from the equipment to be cleaned F and the ozone gas generated by the ozone gas generation means 10 are gas-liquid mixed under a pressurized atmosphere, whereby the solubility of ozone gas in the cleaning liquid is increased. Then, the ozone gas efficiently dissolved in the cleaning liquid decomposes the aromatic components (organic substances) eluted from the object to be cleaned into the cleaning liquid. Specifically, most of the ozone contained in the ozone gas dissolves in the cleaning liquid and decomposes aroma components directly in the liquid phase by oxidation, or self-decomposes by reacting with hydroxide ions in the presence of moisture. Or Moreover, the remainder of ozone decomposes the aromatic component volatilized in the gas phase by direct oxidation, or self-decomposes in the gas phase to generate oxygen radicals together with molecular oxygen. Furthermore, triggered by the self-decomposition of ozone in the liquid phase and gas phase, various radical species and active oxygen species are generated, and these active species also contribute to the decomposition of the aromatic component. The residence time of the cleaning liquid in the reaction tube 130 is maintained at a specified time required for the decomposition of the aroma component, depending on the return amount of the cleaning liquid, the opening degree of the flow rate control means 40, and the like.

  The rate of decomposition of the aroma component is affected by the oxidizing power of ozone and other active species. The oxidation-reduction potential of ozone is about 2.07V. Therefore, carbon-hydrogen (C—H) bonds, double bonds, aromatic rings, ether bonds, etc., which have relatively low binding energy, are cleaved by direct oxidation with ozone, and the aroma components are rapidly decomposed. become. On the other hand, the decomposition of an ester bond or the like having a relatively large binding energy is difficult to proceed by direct oxidation with ozone.

On the other hand, in the chain reaction initiated by the self-decomposition of ozone, radical species having stronger oxidizing power can be generated. For example, oxygen radicals (O) may be generated due to decomposition of ozone in the gas phase. The redox potential of the oxygen radical is about 2.42V. In addition, ozone self-decomposes in the presence of moisture, and hydroxyl radicals (OH) can be generated through the generation of hydrotrioxyl radicals (HO ₃ ). The oxidation-reduction potential of the hydroxyl radical is particularly high at about 2.81V. According to these radical species, it is possible to cleave a bond having a relatively large bond energy such as an ester bond.

FIG. 2 is a diagram illustrating an example of the relationship between the deodorization time of the fragrance component and the residual amount of the fragrance component. (A) is a figure which shows the relationship about a linalool oxide, (b) is a figure which shows the relationship about ethyl isobutyrate.
2 (a) and 2 (b), the horizontal axis indicates the time (minutes) required for deodorizing the aqueous solution in which each aromatic component is dissolved, and the vertical axis indicates the concentration (residual amount) of each aromatic component in the aqueous solution (ppb). Is shown. Moreover, the broken line has shown the minimum density | concentration used as the detection limit of an aroma component. Plots are results when ozone gas is gas-liquid mixed with an aqueous solution in which each fragrance component is dissolved, and plots with ● are results when pure oxygen gas is gas-liquid mixed with an aqueous solution in which each fragrance component is dissolved.

  As shown in FIG. 2 (a), with respect to linalool oxide, which is an oxide of a terpene compound, the residual amount of the fragrance component is rapidly reduced below the detection limit by gas-liquid mixing ozone gas. In addition to the C—C bond, linalool oxide is formed by bonds with low bond energy such as C═C bond, C—H bond, C—O bond, and O—H bond. It can be confirmed that it is decomposed. On the other hand, since there is no reduction in the residual amount due to gas-liquid mixing of pure oxygen gas, the decomposition by various active species contributes to deodorization of this type of aroma component, not volatilization in the gas phase. I understand that

  On the other hand, as shown in FIG. 2B, for ethyl isobutyrate classified as esters, the residual amount of the fragrance component is reduced by gas-liquid mixing of ozone gas, but linalool oxide and In comparison, it takes time to deodorize. In addition to the C—C bond, ethyl isobutyrate is formed by a C—H bond or a C—O bond and an ester C═O bond having a large bond energy, so that it can be decomposed in a short time depending on ozone. It can be confirmed that it is difficult. On the other hand, it is recognized that the residual amount is also reduced by mixing pure oxygen gas with gas and liquid, and deodorization due to volatilization can be effectively achieved.

  The pressure condition in the reaction tube 130 is maintained at a pressure condition suitable for generating hydroxyl radicals with strong oxidizing power from the viewpoint of promptly decomposing the hardly decomposable aromatic component that is difficult to decompose only by ozone. That is, in the reaction tube 130, ozone gas and the cleaning liquid are gas-liquid mixed under a pressure at which the supplied ozone is almost completely dissolved in the cleaning liquid, so that substantially the entire amount of the generated ozone is brought into the presence of moisture. Self-decomposes to generate hydroxyl radicals efficiently and in large quantities. Then, various kinds of active species containing a large amount of hydroxyl radicals realize rapid and reliable decomposition of aroma components.

FIG. 3 is a diagram showing the half-life of ozone in fresh water. Moreover, FIG. 4 is a figure which shows the dissolution rate with respect to the clear water of ozone. Moreover, FIG. 5 is a figure which shows the pressure required for making ozone fully melt | dissolve with respect to fresh water.
The vertical axis in FIG. 3 indicates the half time (seconds) required for the concentration of ozone dissolved in fresh water under normal pressure and in the dark to be halved. FIG. 3 shows the result of measuring the half-life of ozone with an initial concentration of 10 ppm by gas-liquid mixing ozone with a supply rate of 4 g / min into fresh water with a flow rate of 400 L / min. Moreover, the vertical axis | shaft in FIG. 4 has shown the dissolved amount of ozone which can melt | dissolve with respect to fresh water under a normal pressure as a relative value (ozone dissolution rate) of the dissolved amount in the water temperature of 0 degreeC. Moreover, the vertical axis | shaft in FIG. 5 has shown the minimum pressure (atm) required in order to melt | dissolve the ozone contained in ozone gas completely with respect to fresh water. FIG. 5 shows the pressure when the ozone concentration reaches 10 ppm due to the total dissolution of ozone at a supply rate of 4 g / min by pressurizing and dissolving ozone gas at a supply rate of 20 L / min in fresh water at a flow rate of 400 L / min. It is the result.

  As shown in FIG. 3, ozone self-decomposes into molecular oxygen even in fresh water that does not contain salt or metals. The decrease in ozone concentration becomes more prominent as the water temperature is higher because self-decomposition is accelerated by heat. For example, at a water temperature of 80 ° C., half of ozone is decomposed in about 10 seconds. Therefore, from the viewpoint of efficiently generating hydroxyl radicals by initiating a chain reaction initiated by ozone self-decomposition, the temperature of the cleaning liquid is preferably in a warm water region or a hot water region, and more preferably in a hot water region. It can be determined that it is preferable. Further, FIG. 3 means that ozone disappears quickly in the high temperature cleaning liquid, so it is understood that the ozone mixed with the high temperature cleaning liquid needs to be immediately present in the presence of the aroma component. The

  On the other hand, as shown in FIG. 4, the dissolution rate of ozone that can be dissolved in fresh water tends to decrease as the water temperature becomes high, and it is recognized that the water temperature is less than 10% around 50 ° C. Therefore, when the temperature of the cleaning liquid is in a hot water area or a hot water area of 50 ° C. or higher, it is difficult to sufficiently dissolve ozone in the cleaning liquid at normal pressure. If the dissolution rate of ozone is low, most of the ozone is likely to disappear without generating hydroxyl radicals, and the power required to generate ozone is wasted.

  On the other hand, as shown in FIG. 5, it is recognized that when ozone gas is pressurized, it is possible to completely dissolve ozone. Although the pressure required to completely dissolve ozone gradually increases as the water temperature increases, the pressure is 1.4 atm (141.9 kPa) at a water temperature of 5 ° C., and 1.8 atm (182.4 kPa) at a water temperature of 20 ° C. Total dissolution is achieved at 2.5 atm (253.3 kPa) at a water temperature of 50 ° C. and 3.0 (304.0 kPa) at a water temperature of 90 ° C. Therefore, in the organic matter decomposition apparatus 1, from the viewpoint of efficiently dissolving the ozone in the hot or hot water cleaning liquid recovered from the equipment F to be cleaned and generating hydroxyl radicals efficiently, the cleaning liquid is supplied to the reaction tube 130 at a predetermined pressure. The pressure is maintained as described above to allow flow.

  In a preferred embodiment, the pressure in the reaction tube 130 is maintained at an absolute pressure of 2.5 atm or higher in relation to the temperature of the cleaning liquid. If the absolute pressure is maintained at least at 253.3 kPa (2.5 atm) or higher, ozone can be completely dissolved in a cleaning solution at 50 ° C. or higher that can efficiently generate hydroxyl radicals. The utilization efficiency can be improved. The pressure in the reaction tube 130 is more preferably 304.0 kPa (3.0 atm) or more. If kept at such a high pressure, it is possible to completely dissolve ozone in a cleaning solution in a hot water region of 80 ° C. or higher. The upper limit of the pressure in the reaction tube 130 is not particularly limited, but is preferably 608.0 kPa (6.0 atm) or less. Within such a pressure range, even if the ozone gas supply means 10 does not have a high partial pressure ozone supply capability, it is possible to completely dissolve ozone.

  The end of the reaction tube 130 is connected to the flow rate control means 40 as shown in FIG. For this reason, the cleaning liquid that has been mixed with ozone gas and decomposed into aromatic components is reduced in pressure by passing through the flow rate control means 40 and transferred to the deaerator 50.

  The deaerator 50 performs gas-liquid separation of the cleaning liquid in which the organic matter is decomposed. The deaeration device 50 is configured by, for example, a vacuum deaeration device including a gas-liquid separation membrane of an appropriate form such as a membrane type or a hollow fiber type. One end of a supply pipe 120 is connected to the primary side of the gas-liquid separation membrane, and the exhaust treatment device 60 is connected to the secondary side via a pipe line. A suction pump 62 is provided on the exhaust side of the exhaust treatment device 60.

  The cleaning liquid is passed through the primary side of the gas-liquid separation membrane provided in the deaeration device 50 by the circulation pump 70. On the other hand, the suction side of the gas-liquid separation membrane is evacuated by the suction pump 62. Therefore, the circulating cleaning liquid is gas-liquid separated by cross-flow filtration, and unreacted ozone, oxygen generated by self-decomposition of ozone, undecomposed aroma components, various gas components generated by decomposition of aroma components Etc. are efficiently degassed. Then, the degassed cleaning liquid is supplied again to the equipment to be cleaned F through the supply pipe 120. On the other hand, the gas separated from the cleaning liquid is sent to the exhaust treatment device 60.

  The exhaust treatment device 60 performs detoxification treatment of ozone that can be contained in the gas that has been gas-liquid separated from the cleaning liquid. The exhaust treatment device 60 is configured by, for example, a cooler, an ozonolysis device, and the like arranged in series. The cooler removes moisture contained in the exhausted gas and returns it to the deaeration device 50, etc., and the ozone decomposer decomposes ozone contained in the exhausted gas into oxygen molecules by an ozone decomposition catalyst. Prevent unintentional release to. Thereafter, the gas rendered harmless in the exhaust treatment device 60 is exhausted out of the system through the suction pump 62.

  In addition, in the said organic substance decomposition | disassembly apparatus 1, although the reaction tube 130 is provided as a reactor (reaction part), it may replace with the reaction tube 130 and may be provided with the reaction tank. The pressure conditions in the reaction tank are the same as those in the reaction tube 130 described above. Further, the degassing device 50 is replaced with a heating degassing device that performs gas-liquid separation by boiling, a centrifugal degassing device that performs gas-liquid separation on the principle of centrifugal separation, or an ultrasonic wave by transmitting ultrasonic waves, instead of a vacuum degassing device. You may comprise by the degassing apparatus, the gas-liquid separation apparatus using a tank, etc. The deaeration device 50 may be a device in which these gas-liquid separation principles are combined.

  According to the organic substance decomposing apparatus 1 described above, a cleaning solution in a hot water area or a hot water area suitable for elution of an aroma component is circulated to the equipment to be cleaned F, whereby the aroma component adhering to or permeating the object to be cleaned is efficiently removed. Can be eluted. At this time, a cleaning liquid that does not substantially contain ozone is supplied to the equipment F to be cleaned. Normally, ozone mixed in the cleaning liquid rapidly self-decomposes, so the decomposition of the aromatic components by ozone ends in a short time immediately after the cleaning liquid and ozone gas are mixed, and the cleaning liquid flows through the equipment to be cleaned. It is hard to last until it is finished. Therefore, even if ozone is introduced into the equipment F to be cleaned, the residual amount of undecomposed aroma components is large, and re-fragrance is likely to occur due to the circulation supply of the cleaning liquid.

  On the other hand, according to the organic matter decomposing apparatus 1, the aroma component efficiently eluted in the warm water or hot water cleaning liquid can be decomposed by ozone outside the equipment F to be cleaned. In the reactor (reaction part) outside the equipment F to be cleaned, it is possible to more appropriately manage the reaction conditions such as pressure. In addition, by supplying ozone, which is easily decomposed at an early stage in a high temperature range, by the gas-liquid mixing pump 20, it is possible to immediately put it in the presence of an aroma component. Therefore, according to the organic substance decomposition | disassembly apparatus 1, most of the produced | generated ozone and the various active species produced by the self-decomposition of ozone can be made to react with an aroma component rapidly. Specifically, most of ozone is dissolved in the cleaning liquid and self-decomposes in the liquid phase to efficiently generate hydroxyl radicals. As a result, the utilization factor of ozone is increased, the aroma components are reliably decomposed, and the power required for generating ozone is not wasted. Specifically, it is possible to deodorize the extremely low concentration organic substance to be decomposed contained in the cleaning liquid at a concentration of 300 ppb or less, and the concentration of the organic substance to be decomposed can be reduced to about 0.1 ppb or less. . Further, since the cleaning liquid containing the fragrance component is not re-supplied to the equipment F to be cleaned, re-scenting to the seal member or the like is prevented. The time required for deodorizing and cleaning is shortened by efficiently decomposing aromatic components and preventing re-scenting, and the frequency of cleaning liquid replacement and the amount of heat required for heating the cleaning liquid are also reduced.

  Further, according to the organic matter decomposition apparatus 1, the cleaning liquid degassed by the gas-liquid separation is supplied again to the equipment F to be cleaned. For this reason, the ozone gas supplied into the equipment to be cleaned hardly generates bubbles, and it is difficult to form an air pocket in the equipment to be cleaned. Therefore, it is possible to reliably deodorize and clean the entire area of the flow path to be cleaned without causing a portion where the cleaning liquid does not easily reach due to the presence of the air pool. Also, since ozone is less likely to stay in the equipment to be cleaned, deterioration of the object to be cleaned by ozone can be prevented, and ozone detoxification can be simplified when discharging the cleaning liquid out of the system. It has become. Therefore, according to the organic substance decomposing apparatus and the organic substance decomposing method according to the present embodiment, it is possible to efficiently deodorize the production equipment for liquid products by reliably decomposing aromatic components by ozone and gas-liquid separation of the cleaning liquid.

  In addition, in the organic matter decomposing apparatus 1, since a part of the undecomposed aroma component is actively volatilized and degassed by gas-liquid separation, the deodorizing cleaning is performed as compared with the case of deodorizing only by decomposing with ozone. Efficiency is even higher. Further, in the organic matter decomposing apparatus 1, since the cleaning liquid in the hot water area or the hot water area that substantially does not contain ozone is circulated and supplied to the equipment to be cleaned F, the heating apparatus 80 does not need to deal with ozone dissipation. It is advantageous in that an appropriate heating principle can be adopted such as a heat exchanger, an electric heating device, a direct heating device that performs steam heating with gas-liquid contact, and the like.

DESCRIPTION OF SYMBOLS 1 Organic substance decomposition | disassembly apparatus 10 Ozone gas supply means 11 Compressor 12 Oxygen concentrator 13 Ozone generator 14 Concentration meter 20 Gas-liquid mixing pump (pressure feeding means)
40 Flow rate control means 40
50 Deaerator (Deaerator)
60 Exhaust treatment device 62 Suction pump 70 Circulation pump 80 Heating device 101 Supply pipe 102 Drain pipe 110 Supply pipe 120 Recovery pipe 130 Reaction pipe (reaction section)
F Equipment to be cleaned p Channel to be cleaned

Claims (9)

A supply pipe for supplying cleaning liquid to the equipment to be cleaned;
A recovery tube for recovering the cleaning liquid for cleaning the equipment to be cleaned;
Ozone gas supply means for supplying ozone gas to the recovered cleaning liquid;
A pressure feeding means for gas-liquid mixing and feeding the ozone gas and the cleaning liquid supplied;
A reaction section that holds the pressurized ozone gas and the cleaning liquid in a pressurized state and decomposes organic substances contained in the cleaning liquid with the ozone gas;
A degassing part for performing gas-liquid separation of the cleaning liquid in which the organic matter is decomposed,
An organic matter decomposing apparatus, wherein an organic matter is decomposed and degassed cleaning liquid is supplied again to the equipment to be cleaned. The facility to be cleaned is a liquid product manufacturing facility,
The organic matter decomposing apparatus according to claim 1, wherein the organic matter is an aroma component used for manufacturing the liquid product.   The organic matter decomposing apparatus according to claim 1 or 2, wherein the temperature of the cleaning liquid supplied to the equipment to be cleaned is 50 ° C or higher.   The pressure in the said reaction part is hold | maintained to 253.3 kPa or more, The organic substance decomposition | disassembly apparatus as described in any one of Claims 1-3 characterized by the above-mentioned. Supplying the cleaning liquid to the equipment to be cleaned for cleaning, and collecting the cleaning liquid for cleaning the equipment to be cleaned;
Supplying ozone gas to the recovered cleaning liquid, dissolving the ozone gas in the cleaning liquid under pressure, and decomposing organic substances contained in the cleaning liquid;
Performing a gas-liquid separation of the cleaning liquid in which the organic matter has been decomposed;
An organic matter decomposing method, and a step of re-supplying the degassed cleaning liquid to the equipment to be cleaned. The facility to be cleaned is a liquid product manufacturing facility,
The organic matter decomposition method according to claim 5, wherein the organic matter is an aroma component used for manufacturing the liquid product.   The organic matter decomposition method according to claim 5 or 6, wherein the ozone gas dissolved in the cleaning liquid is held at 253.3 kPa or more.   The organic matter decomposition method according to any one of claims 5 to 7, wherein the temperature of the cleaning liquid supplied to the equipment to be cleaned is 50 ° C or higher.   The organic matter decomposition method according to any one of claims 5 to 8, wherein the concentration of the organic substance to be decomposed contained in the cleaning liquid recovered from the equipment to be cleaned is 300 ppb or less.

Images