JP2024012104A - Harmful oxide remover and harmful oxide removing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To discover a natural component that can easily and efficiently remove harmful oxides, such as NOx and SOx, and provide a harmful oxide remover by utilizing the discovered component.

SOLUTION: A harmful oxide remover contains Rutaceae plant extract as an active ingredient. A method for removing harmful oxides in the air includes bringing the harmful oxide remover into contact with the air containing harmful oxides.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a harmful oxide remover, and more particularly to a harmful oxide remover that can purify nitrogen oxides (NOx) and sulfur oxides (SOx) contained in various types of exhaust smoke and exhaust gas. This invention relates to a removing agent and a method for removing harmful oxides using the same.

BACKGROUND OF THE INVENTION With the operation of power plants, factory boilers, or garbage incinerators, exhaust gas containing various chemical substances including nitrogen oxides (NOx) and sulfur oxides (SOx) is emitted. Furthermore, it is known that automobile exhaust gas also contains various chemical substances harmful to the human body, such as NOx and SOx.

These NOx and SOx are not only harmful to the human body, but also cause acid rain. Furthermore, in the presence of NOx and non-methane hydrocarbons, photochemical smog is generated when photochemical reactions caused by sunlight are added. Photochemical smog is said to be a phenomenon in which hydrocarbons and NOx in the atmosphere absorb ultraviolet rays and cause a photochemical reaction, producing photochemical oxidants, which are harmful substances. However, countermeasures against NOx, especially NOx originating from mobile sources such as automobiles, have been delayed and have become a serious problem.

Currently, known NOx removal methods include treating NOx by passing it through an absorbing liquid such as a carboxylic acid or alkaline solution, or by passing it through a special machine. However, all of these methods have the problem of being laborious and expensive.

On the other hand, Patent Document 1 discloses essential oils obtained by steam distilling plants of the cypress family, camellia family, ginkgo family, grass family, and mint family, and a water-soluble fraction obtained during the steam distillation. , has disclosed a harmful chemical substance remover whose active ingredient is an aqueous solution containing a plant essential oil consisting of water. In addition, Patent Document 2 discloses that NOx in the air is incorporated into the terpene compound by making a terpene compound having a conjugated double bond such as α-terpinene, myrcene, alloocimene into a gaseous state and dispersing it in the air. A NOx removal method for removing NOx is described.

However, although it is stated that the method of Patent Document 1 is effective against NOx and SOx, actual tests were conducted only with carbon dioxide (CO ₂ ), and it is actually effective against NOx, etc. It is unclear whether In addition, the NOx and SOx removal effect of the compound described in Patent Document 2 is not sufficient, and it has been awaited to find a highly safe compound with higher removal ability and to provide a removal agent using this. .

The present inventors have also found compounds containing as active ingredients one or two compounds selected from the group consisting of β-phellandrene and ocimene (Patent Document 3), terpinen-4-ol, citronellal, and bornyl. The active ingredient is one or more compounds selected from the group consisting of acetate, cadinene, sabinene, α-terpineol, δ-3-carene, terpinolene, γ-terpinene, 1,4-cineole, and 1,8-cineole. (Patent Document 4), one type of tree selected from the group consisting of the genus Cypress of the family Cupressaceae, the genus Sugi of the family Cupressaceae, the genus Fir of the family Pinaceae, the genus Eucalyptus of the family Myrtaceae, the genus Kouyamaki of the family Araceae, and the genus Asunaro of the family Cupressaceae. Alternatively, a product containing essential oils of two or more types of wood and/or leaves as active ingredients has been proposed (Patent Document 5).

Japanese Patent Application Publication No. 2000-210526 Japanese Patent Application Publication No. 6-327934 Japanese Patent Application Publication No. 2012-121004 Re-published patent WO2010/098438 Re-published patent WO2010/098439

Therefore, an object of the present invention is to find a natural ingredient that can easily and efficiently remove harmful oxides such as NOx and SOx, and to provide a harmful oxide remover that utilizes this.

The present inventors were investigating the effect of plant extracts on removing harmful oxides, and found that essential oils obtained from plants of the Rutaceae family can be used as removal agents by removing harmful oxides very efficiently. This discovery led to the present invention.

That is, the present invention provides a harmful oxide remover containing an essential oil of a Rutaceae plant as an active ingredient.

The present invention also provides a method for removing harmful oxides, which comprises bringing the harmful oxide remover into contact with the atmosphere.

According to the present invention, various oxides harmful to the human body, such as NOx and SOx, can be efficiently removed.

The essential oil of a Rutaceae plant used as an active ingredient in the present invention is made from a Rutaceae plant. Examples of plants belonging to the Rutaceae family include plants of the genus Lamanta, genus Citrus, genus Citrus, and genus Kumquat.

Examples of plants in the Rutaceae family, Z. piperitum (L.) DC forma inerme (Makino), Z. piperitum (L. )DC forma brevispinosum Makino), Ryujin zansho (Ryujin sansho, Z. piperitum (L.)DC forma ovalifoliolatum (Nakai) Makino), Budo zansho (Budo sansho, no scientific name), Takahara sansho (Highland sansho), Crow Z. ailanthoides, Z. amamiense, Z. armatum, Z. armatum var. subtrifoliatum, Z. beecheyanum, Australia Satinwood in Australia (Z. brachyacanthum), Z. bungeanum, Z. dimorphophyllum, Z. fauriei, West Indian satinwood (Z. West Indian satinwood (Z. flavum) (synonym: Fagara flava), olon-vogo (Z. heitzii) (synonym: Fagara heitzii), Z. integrifoliolum, chenkring (Malaya: Z. myriacanthum), Z. nitidum (Roxb.) DC. , Z. piperitum (L.) DC., Malaya: hantar duri (Z. rhetsa), Z. scandens, Z. schinifolium (Synonyms: Z. schinifolium) Z. pteropodum), Z. simulans, and Z. yakumontanum. Among these plants belonging to the family Rutaceae and the genus Zanthrum, grape zanthium or Asakura zangsheng is preferred.

Examples of plants of the genus Citrus of the family Rutaceae include Citrus aurantium, Citrus unshiu x reticulata 'Siranui', Citrus junos, Citrus unshiu, and the like. Among these plants belonging to the Rutaceae family, Rutaceae genus, Daidai or Dekopon is preferred, and Daidai is more preferred.

Examples of plants belonging to the Rutaceae family, Citrus trifoliata, include Citrus trifoliata.

Examples of plants belonging to the genus Kumquat of the family Rutaceae include Fortunella japonica, Fortunella margarita, Fortunella obovata, and the like.

Preferred examples of these plants include plants of the genus Rutaceae or Rutaceae; among these, plants of the genus Citrus, or plants of the genus Citrus or Dekopon are preferred; More preferable are Sho, Asakura zansho of the genus Trifolium, or Daidai of the genus Citrus, particularly preferable are Grape zansho or Asakura zansho of the genus Citrus, and most preferable are Asakura zansho of the genus Trifolium.

Examples of plant parts from which essential oil can be obtained include branches, leaves, flowers, fruits, seeds, pericarp, and stems (fruit removed from clusters with fruits). A plurality of these plant parts may be used in combination. Among these plant parts, the pericarp, seeds, and stems are preferable, and the stems are more preferable. By using the shaft part that would normally be discarded, unused resources can be used effectively, helping to improve resource circulation and being environmentally advantageous. In addition, the parts of these plants may be fresh or dried to obtain essential oils.

Methods for obtaining essential oils from the above plants are not particularly limited, but examples include conventionally known essential oil collection methods such as atmospheric distillation, vacuum distillation, steam distillation, direct distillation, vacuum steam distillation, and solvent extraction. It will be done. Among these essential oil collection methods, direct distillation and steam distillation are preferred.

The essential oil of the Rutaceae plant described above may be further purified by filtration, column chromatography, etc.

In the present invention, preferred essential oils include, for example, essential oil obtained from the stems or pericarp and seeds of Grape Zancho or Asakura Zancho, essential oil obtained from the branches and leaves of Rutaceae, Rutaceae, Rutaceae, Rutaceae, Rutaceae, Rutaceae, Rutaceae, Rutaceae Preferred are the essential oils obtained from the pericarp of grape cherries, the essential oils obtained from the stems or pericarp and seeds of grape cherries, and the essential oils obtained from the branches and leaves of Rutaceae, genus Rutaceae; Essential oils obtained from the stems or pericarp and seeds are more preferred, essential oils obtained from the stems of grape daisies or Asakura daisies are particularly preferred, and essential oils obtained from the stems of Asakura daisies are most preferred.

In the present invention, the most preferred essential oil is one obtained by direct distillation from the stem of Asakura Zancho. This essential oil can be obtained, for example, by placing 80 kg of Asakura zansho stems in a container, adding 1 to 5 times the amount of water to the container, boiling it at 90 to 100 degrees Celsius, and collecting the essential oil with an essential oil sampling tube. .

The essential oil of this Asakura Zancho stem generally has a specific gravity of 0.8 to 0.95 (at 25° C.) and a refractive index of 1.4 to 1.5. Note that the specific gravity and refractive index can be measured by conventionally known measuring methods and measuring instruments. Incidentally, the essential oil of the grape vine stem, which is a preferred essential oil in the present invention, can also be obtained in the same manner as the above-mentioned essential oil of the grape vine stem, and the specific gravity and refractive index of the essential oil are also the same.

As the essential oils of these Rutaceae plants, commercially available products can also be used in addition to those obtained as described above.

The essential oil of the Rutaceae plant thus obtained (hereinafter also simply referred to as "essential oil") has the ability to remove harmful oxides such as nitrogen oxides and sulfur oxides, so using this as an active ingredient can eliminate harmful substances. It can be used as an oxide remover. Among harmful oxides, nitrogen oxides include nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), nitrous oxide (N ₂ O), and dinitrogen trioxide (N ₂ O ₃ ), dinitrogen tetroxide (N ₂ O ₄ ), dinitrogen pentoxide (N ₂ O ₅ ), and the like. Examples of sulfur oxides include sulfur monoxide (SO), sulfur dioxide (SO ₂ ), and sulfur trioxide (SO ₃ ).

Methods for measuring the removal activity of harmful oxides in essential oils are not particularly limited, but examples include a method in which harmful oxides are passed through the essential oil in a liquid state, a method in which the essential oil is converted into a gas state, and then the harmful oxides are directly reacted with it. Examples include measurement methods that allow

As a measurement method in which harmful oxides are passed through essential oil in a liquid state, for example, a filter paper uniformly impregnated with a certain amount of essential oil, along with a fan or the like to stir the gas if necessary, is used to pass the harmful oxides through the filter paper. In this method, a glass tube with an inner diameter of 5 mm is filled with a paper rag uniformly impregnated with a certain amount of essential oil, and one end of the tube is used to detect harmful oxides. For example, one method is to connect the gas to a Tedlar bag containing one gas, and connect the other end to a detection tube for these gases.

As a measurement method in which harmful oxides are directly reacted with the essential oil after converting it into a gaseous state, for example, by heating a Tedlar bag in which the essential oil has been sealed in advance, the essential oil is vaporized to prepare a saturated essential oil gas. Examples include a method in which the toxic oxide gas is introduced into a Tedlar bag containing toxic oxide gas, and after mixing, the concentration of the toxic oxide gas is detected and measured at fixed time intervals using a detection tube or an air pollutant measuring device.

The harmful oxide remover of the present invention can be prepared from the essential oil obtained as described above, or by combining it with a suitable carrier. Moreover, essential oils may be combined as necessary.

Suitable carriers for combination with essential oils include, for example, water, alcoholic solvents such as ethanol, isopropyl alcohol, propyl alcohol, glycol solvents such as propylene glycol and ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and propylene alcohol monomethyl ether. Examples include solvents such as glycol ether solvents such as ethyl ether and 3-methoxy-3-methyl-1-butanol. The harmful oxide remover of the present invention can be prepared by dissolving essential oil as an active ingredient in this solvent at a concentration of about 0.001 to 99% by mass.

Furthermore, optional components such as fragrances and surfactants can be added to the harmful oxide remover of the present invention within a range that does not impede the effects of the present invention. Examples of fragrances include d-limonene, linalool, l-menthol, anethole, citronellal, eugenol, ethyl vanillin, ethyl maltol, hinokitiol, γ-nonalactone, γ-undecalactone, acetate ester, butyrate ester, propionate ester, etc. can be mentioned. Further, examples of the surfactant include polyoxyethylene alkyl ether, fatty acid sorbitan ester, alkyl polyglycoside, fatty acid diethanolamide, alkyl monoglyceryl ether, and the like.

The toxic oxide remover of the present invention prepared as described above can be prepared in the same way as the method used for conventional toxic oxide removers, for example, by exposing the toxic oxide remover to the atmosphere containing harmful oxides. It can be used by contacting it.

Examples of the method of bringing the harmful oxide remover of the present invention into contact with the atmosphere containing harmful oxides include a method in which the harmful oxide remover is vaporized into the atmosphere containing harmful oxides. It will be done. Examples of the volatilization method include a method of volatilizing the harmful oxide remover of the present invention as it is or using an appropriate volatilization device, a pump spray, an aerosol, an ultrasonic vibrator, a pressurized liquid atomization spray, and a pressurized air atomization method. Examples include a method of atomizing and volatilizing using an atomizing device such as an atomizing device. Among these methods, a method in which the harmful oxide remover of the present invention is volatilized using a volatilization device is preferred.

Another method of bringing the harmful oxide remover of the present invention into contact with the atmosphere containing harmful oxides is, for example, to bring the harmful oxide remover of the present invention into contact with paper (pulp), nonwoven fabric, resin sheet, wood sheet, etc. A method of impregnating a filter composed of wood flour, resin beads, etc., and allowing air containing harmful oxides to pass through the filter, and bubbling the air containing harmful oxides in the harmful oxide remover of the present invention. Examples include a method of bringing the active ingredient into contact with the active ingredient. Among these methods, a method in which the atmosphere containing harmful oxides is passed through a filter impregnated with a harmful oxide removing agent is preferred.

As yet another method of bringing the harmful oxide remover of the present invention into contact with the atmosphere containing harmful oxides, for example, a gel containing the harmful oxide remover of the present invention is prepared, and this gel is mixed with harmful oxides. Examples include a method of bringing the atmosphere containing objects into contact with each other. The gel used for this is not particularly limited as long as it can maintain its gel even when containing the harmful oxide remover of the present invention, but a gel using metal soap is preferred.

Since the active ingredient of the harmful oxide remover of the present invention is a natural product obtained from plants, it poses no danger to the human body. Therefore, even if it comes into contact with or is sprayed into the atmosphere of a living space, it will not cause discomfort or adverse effects on humans or other animals and plants.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Implementation example 1
Production of grape zansho essential oil:
Approximately 80 kg of raw grape stalks (from Wakayama Prefecture) belonging to the Rutaceae family, the genus Chimney (produced in Wakayama Prefecture) (fruit removed from clusters with fruit) were placed in a stainless steel tank, and 2.5 times the amount of water was added. Thereafter, the tank was heated to 90 to 100°C and brought to a boil. The essential oil collection tube was filled with water up to the reference line before heating. Boiling was continued for 1 to 2 hours and the essential oil was distilled to obtain 200 mL of grape radish essential oil (Product 1 of the present invention). This essential oil had a specific gravity of 0.861 (at 25°C) and a refractive index of 1.47.

Implementation example 2
Production of Dekopon essential oil:
20 kg of the peel of Dekopon, a member of the Rutaceae family, Citrus genus, was crushed and placed in a vacuum steam distiller (16 kPa vacuum condition, steam temperature 60° C.) to obtain 100 mL of Dekopon essential oil by vacuum steam distillation (Product 4 of the present invention).

Implementation example 3
Nitrogen dioxide removal effect:
A pleated filter paper (radius 55 mm) was impregnated with 36 mg of grape radish essential oil (product 1 of the present invention) obtained in Example 1 and placed in a 10 L Tedlar bag with a fan about 30 seconds after impregnation. About 10 minutes after the impregnation, nitrogen dioxide gas with a concentration of about 70 ppm was injected, and the concentration of the remaining nitrogen dioxide gas was measured over time using a detection tube. As product 2 of the present invention, a commercially available grape sansho essential oil (trade name: FRAGRANT KISHU-WAKA sansho, extraction parts: peel, seeds, steam distillation method: manufactured by Nakano BC Co., Ltd.) was used. As product 3 of the present invention, essential oil of Morocco (product name: Petitgrain oil morocco, extracted parts: branches, leaves, steam distillation method: manufactured by Yamamoto Kogyo Co., Ltd.) of the genus Rutaceae was used. As the product of the present invention 4, the essential oil of Dekopon obtained in Example 2 was used. Tests similar to those for Inventive Product 1 were conducted using these. The results are shown in Table 1.

From the above results, it was found that all the essential oils of Rutaceae plants of the present invention remove nitrogen dioxide gas. Among these, it has a high removal effect on the essential oil of Grape Zanthium, which belongs to the genus Rutaceae, and the essential oil of Lamium spp. It was found that the removal effect of essential oil was significantly high.

Implementation example 4
Production of Asakura Sansho essential oil:
Approximately 5 kg of raw stalks of Asakura zansho (produced in Hyogo prefecture) belonging to the genus Rutaceae (Rutaceae) (fruits taken from clusters with fruits) were placed in a distillation kiln containing 6L of water, and the distillation kiln was heated at 90 to It was heated to 100°C and brought to a boil. The essential oil collection tube was filled with water up to the reference line before heating. Boiling was continued for 1 to 2 hours and the essential oil was distilled to obtain 15.8 mL of Asakura zansho essential oil (Product 5 of the present invention). The specific gravity of this essential oil was 0.844 (25°C) and the refractive index was 1.47.

Implementation example 5
Nitrogen dioxide removal effect:
A pleated filter paper (radius 55 mm) was impregnated with 36 mg of the grape radish essential oil obtained in Example 1 (invention product 1) and the Asakura zanshu essential oil obtained in Example 4 (invention product 5). Approximately 30 seconds after impregnation, it was placed in a 10L Tedlar bag with a fan. About 10 minutes after the impregnation, nitrogen dioxide gas with a concentration of about 80 ppm was injected, and the concentration of the remaining nitrogen dioxide gas was measured over time using a detection tube. The results are shown in Table 2.

From the above results, it was found that both the essential oils of plants belonging to the family Rutaceae and the genus Salmonella of the present invention product 1 and the present invention product 5 remove nitrogen dioxide gas. Among members of the genus Rutaceae, it was found that essential oil from the stems of Asakura chinensis has a significantly high nitrogen dioxide gas removal effect.

Implementation example 6
Hazardous oxide removers and their uses:
When 7 mL of the essential oil of Invention Product 1 was placed in a container containing a toxic oxide remover for car air conditioner louvers (Clear Forest manufactured by ST Co., Ltd., for car air conditioner louvers) and installed in the car air conditioner louver, nitrogen Removed harmful oxides such as oxides and sulfur oxides.

Implementation example 7
Hazardous oxide removers and their uses:
3-Methoxy-3-methyl-1-butanol and the essential oil of Invention Product 1 were blended in an amount of 50% by mass to produce a harmful oxide remover for space spraying. This harmful oxide remover was sprayed into the space using a heating evaporation device (deodorizing plug manufactured by ST Co., Ltd.) to remove harmful oxides such as nitrogen oxides and sulfur oxides.

Implementation example 8
Hazardous oxide remover:
A nitrogen dioxide removal filter was prepared by spraying 1 g of the essential oil of Invention Product 1 onto an air-permeable cellulose nonwoven fabric (fabric weight: 100 g/m3, manufactured by Futamura Chemical Co., Ltd.). After cutting this into 20 cm x 30 cm, 10 sheets were stacked to produce a filter for an automobile outdoor air intake.

Implementation example 9
Hazardous oxide removers and their uses:
A harmful oxide remover composition was prepared by mixing 1 g of essential oil of Invention Product 5, 1 g of perfume, 5 g of surfactant, and 393 g of water. When this harmful oxide remover composition was placed in a volatilization device (manufactured by ST Co., Ltd. for deodorizing entrances and living rooms) and installed indoors, it removed nitrogen oxides, sulfur oxides, etc. indoors for about 2 months. Removed harmful oxides.

Implementation example 10
Toxic oxide remover and its use A mixture of 0.5 g of the essential oil of the invention product 5 dissolved in 5 g of ethanol and a propellant (liquefied petroleum gas) is charged into a metered-dose aerosol, and a spray device ( When sprayed indoors at approximately 15-minute intervals using a deodorizing power automatic sprayer manufactured by ST Co., Ltd., harmful oxides such as nitrogen oxides and sulfur oxides were removed indoors for approximately 15 days. did.

The harmful oxide remover of the present invention can not only detoxify harmful oxides such as nitrogen dioxide and sulfur dioxide by efficiently contacting with the atmosphere, but also remove air pollutants that cause photochemical smock and household diseases such as sick house syndrome. It can also detoxify pollutants inside cars and harmful oxides in medical facilities such as hospitals.

Claims (8)

A harmful oxide remover whose active ingredient is essential oil from plants in the Rutaceae family. The harmful oxide remover according to claim 1, wherein the plant of the family Rutaceae is a plant of the genus Rutaceae or the genus Rutaceae. 3. The harmful oxide remover according to claim 2, wherein the plant belonging to the family Rutaceae, the genus Lamium spp. 4. The harmful oxide remover according to claim 3, which is essential oil of the stems of Grape trumpet or Asakura trumpet. A method for removing harmful oxides in the atmosphere, which comprises bringing the harmful oxide remover according to any one of claims 1 to 4 into contact with the atmosphere containing harmful oxides. The method according to claim 5, wherein the contact between the harmful oxide remover and the atmosphere containing the harmful oxide is carried out by volatilizing the harmful oxide remover into the atmosphere containing the harmful oxide. How to remove harmful oxides. 6. The contact between the harmful oxide remover and the atmosphere containing the harmful oxide is carried out by passing the atmosphere containing the harmful oxide through a filter impregnated with the harmful oxide remover. A method for removing harmful oxides from the atmosphere. 6. The method according to claim 5, wherein the contact between the harmful oxide remover and the atmosphere containing the harmful oxide is carried out by bringing the gel containing the harmful oxide remover into contact with the atmosphere containing the harmful oxide. How to remove harmful oxides from the atmosphere.