JP4288094B2 - Photochemical reaction method, liquid processing method and liquid processing apparatus - Google Patents

Description

【００７２】
実施例１、実施例２、実施例３及び実施例４より、光照射を行い、かつ、触媒を存在させることにより、分解反応が進行していることが判る。
比較例１、比較例２、比較例５及び比較例８より、触媒が存在しても光照射を行わない場合には、反応が進行していないことが判る。
比較例３、比較例６及び比較例９より、光照射を行っても触媒が存在しない場合には、反応が進行していないことが判る。
比較例４、比較例７及び比較例１０より、触媒が存在せず、かつ、光照射も行わない場合には、反応が進行していないことが判る。
【００７３】
以上の結果から、触媒に吸着させた反応分子に、この吸着反応分子を励起させるエネルギーを有する光を照射して反応性を高めると同時に触媒を作用させることによって反応を高効率で進行させることができることが判った。すなわち、反応分子を直接光分解する程のエネルギーを有する光を用いずとも、反応分子の吸収波長領域程度の比較的低いエネルギーを有する光を照射することで反応を進行させることができる。また、光触媒のように触媒を光励起させなくとも触媒に吸着した反応分子の励起により反応を進行させることができる。従って、低コストで高効率な化学反応が実現可能である。
【００７４】
【発明の効果】
以上説明したように本発明によれば、反応分子を触媒に吸着させるとともに、吸着反応分子に光を照射して励起させることにより反応分子の反応性を高めると同時に触媒作用により反応の活性化障壁を下げることで、光化学反応による化合物の合成・分解反応を進行させることができる。よって、低エネルギー、高効率で反応を進行させることが可能であり、例えば、ダイオキシン類などの有害物質を含む排水を低コスト、かつ効率的に処理することができる。
【図面の簡単な説明】
【図１】 光化学反応装置の説明に供する概略構成図。
【図２】 光化学反応の説明に供する図面。
【符号の説明】
１０ 水処理装置
１１ 有害物質吸着装置
１２ 触媒供給装置
１３ 反応容器
１４ 光源[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photochemical reaction using a catalyst. More specifically, the present invention relates to a reaction of an organic compound using a photochemical reaction, and further relates to a liquid processing method and a processing apparatus for processing harmful substances such as dioxins contained in industrial wastewater or groundwater using a photochemical reaction method.
[0002]
[Prior art]
Until now, many literatures are disclosed about the chemical reaction process using light energy. In particular, for example, the following has been reported as a document relating to the treatment of harmful substances, and each has the following problems.
[0003]
(1) In Japanese Unexamined Patent Publication No. 2000-5562 (Patent Document 1), an organic chlorine compound contained in soil or water (for example, A method for decomposing trichloroethylene, tetrachloroethylene, etc.) is disclosed.
[0004]
In the treatment method according to Patent Document 1, an organic chlorine compound is decomposed by an oxidizing agent and / or a catalyst, and further treated by irradiation with ultraviolet rays. As described above, the organic chlorine compound is processed by the individual effects of the oxidizing agent, the catalyst, or the ultraviolet rays, and no technical idea about the correlation between the oxidizing agent, the catalyst, and the ultraviolet rays is described. Further, paying attention to the effect of ultraviolet rays, it is directly used for photodecomposition (ultraviolet oxidative decomposition) of an organic chlorine compound, so that high energy and large energy ultraviolet rays are required, and energy loss is large.
[0005]
(2) Japanese Patent Laid-Open No. 2002-18240 (Patent Document 2) discloses a photolysis reaction step of decomposing harmful organic substances by irradiating exhaust gas with ultraviolet rays including a vacuum ultraviolet region, and photocatalyst with ultraviolet rays not including a vacuum ultraviolet region. A treatment method for detoxifying harmful organic compounds (for example, trichloroethane) contained in exhaust gas by performing a photocatalytic reaction step in which the exhaust gas that has been subjected to the previous step by contacting the photocatalyst with a photocatalyst is decomposed It is disclosed.
[0006]
According to this Patent Document 2, in the photolysis reaction step, since vacuum ultraviolet light having low luminous efficiency and extremely low transmittance in air is used, it is not used for decomposing harmful organic substances among the input energy. The rate of consumption as thermal energy is high and the efficiency is poor, and sufficient decomposition efficiency cannot be obtained with only one processing step. In the photocatalytic reaction step, decomposition treatment is performed by contact reaction of harmful organic substances on the surface of the catalyst photoexcited with the photocatalyst, but only examples using titanium dioxide are specifically described as the photocatalyst. In addition, the reaction is limited to those in which the characteristics of titanium dioxide can be used, and cannot be applied to various types of harmful substances.
[0007]
(3) In Japanese Patent Laid-Open No. 11-335204 (Patent Document 3), a transparent rod-shaped body is placed on the soil, and light rays are collected from the exposed portion and guided into the soil along the rod-shaped body. A soil purification method is disclosed in which a photocatalyst carried on the surface of the rod-shaped body is irradiated to sterilize and sterilize nearby soil by a photocatalytic reaction.
[0008]
According to Patent Document 3, since sunlight can be used as a light source, the cost is low. However, it is difficult to secure sunlight depending on the change in weather conditions, and the reliability is low. In addition, titanium oxide as a photocatalyst is excited. Since the arrival of light (ultraviolet rays) having sufficient energy to the ground surface is limited, the reaction efficiency is low. Another problem is that only the vicinity of the rod-shaped body carrying the photocatalyst can be sterilized.
[0009]
As described above, many documents have been disclosed regarding the decomposition process of harmful substances using light energy as it is or the decomposition process of harmful substances using photoexcitation of a catalyst such as titanium dioxide.
[0010]
[Patent Document 1]
JP 2000-5562 A
[Patent Document 2]
JP 2002-18240 A
[Patent Document 3]
JP 11-335204 A
[0011]
[Problems to be solved by the invention]
In other words, practical techniques for chemical reactions using light energy can be broadly classified into the following two types, and each has the following problems.
[0012]
(1) A method of directly photolyzing reactive molecules with light energy. In this method, light energy is used to break chemical bonds in the molecule (that is, electrons existing in binding orbitals are excited to antibonding orbitals), so it is necessary to use high-energy light such as vacuum ultraviolet light. There is. In other words, when considering bond breaking only by light energy, in general, a plurality of bonds that are bonded at a larger energy (deep energy level) than electrons that are bonded at a smaller energy (shallow energy level). Since it is effective to excite electrons into antibonding orbitals, it is necessary to irradiate light with high energy and large energy that frees multiple electrons bound to the deep energy level. As a result, energy consumption is large and economically inferior.
[0013]
(2) A method of reacting reactive molecules using a photocatalyst. In this method, since light energy is used for excitation of the photocatalyst, light having a constant energy enough to excite the photocatalyst is always necessary regardless of chemical reaction, and energy efficiency is low. In this case, the excited photocatalyst is often a multistage reaction in which the reaction proceeds through a hydroxyl radical generated by reacting with water or the like, a superoxide ion, and the energy required for photoexcitation of the catalyst is It is greater than the energy required for the reaction and is less energy efficient.
[0014]
Moreover, the reaction which can be utilized will be limited. In other words, at present, photocatalysts that can be used with practical efficiency are almost limited to those mainly composed of titanium dioxide, and irradiation with light (ultraviolet rays) corresponding to the energy gap of titanium dioxide is indispensable. Since the use of is generally difficult, the efficiency is low. In addition, since it is practically limited to those utilizing the characteristics of titanium dioxide, it cannot be used for reactions that require an energy equivalent to or greater than the energy gap of titanium dioxide, and the reaction proceeds with less energy. The difference is wasted.
[0015]
Therefore, a chemical reaction that can be used for various chemical reactions and that is low in cost and highly efficient is desired, and it is an object of the present invention to provide a reaction method thereof.
[0016]
[Means for Solving the Problems]
In order to solve the above-mentioned problem, the invention of the photochemical reaction method according to the first aspect of the present invention is a photochemical reaction method in which a reaction molecule is caused to undergo a photochemical reaction and the reaction molecule is changed into a desired product molecule, Energy that enhances the reactivity of the reactive molecule after adsorbing the reactive molecule to the catalyst without causing the reaction to change the reactive molecule to the product molecule The energy of the catalyst is within a range not allowing the reaction to proceed with the catalyst alone. The adsorbed reaction molecule in the state adsorbed on the catalyst is photoexcited by irradiating with light having a photocatalytic property, and the photoexcited reaction molecule has an electron state in the excited state between the reaction molecule and the desired product molecule. It is characterized in that a reaction for obtaining the product molecule is caused by the action of a catalyst for reducing the activation barrier.
[0017]
According to this feature, the reaction activation barrier can be lowered by adsorbing the reaction molecules to the catalyst, and the reactivity can be increased by photoexcitation of the adsorbed reaction molecules, thereby improving the reaction rate. The reaction can proceed smoothly.
[0018]
The invention of the photochemical reaction method according to the second aspect of the present invention is characterized in that, in the first aspect, the reaction molecule is an organic halogen compound.
[0019]
Further, the invention of the photochemical reaction method according to the third aspect of the present invention is characterized in that, in the first aspect or the second aspect, the reactive molecule is present in a liquid phase.
[0020]
According to this feature, for example, when the reactive molecule is a harmful substance such as an organic halogen compound contained in the wastewater or the like, the harmful substance can be removed from the wastewater by being adsorbed by the catalyst. The hazardous substance can be reliably treated by reacting while obtaining the effect in the embodiment.
[0021]
The invention of the photochemical reaction method according to the fourth aspect of the present invention is characterized in that in any one of the first aspect to the third aspect, the catalyst is a metal oxide. .
[0022]
The invention of the liquid processing method according to the fifth aspect of the present invention is to treat a liquid using the photochemical reaction method according to any one of the first to fourth aspects. It is characterized by.
[0023]
Further, the invention of the liquid processing apparatus according to the sixth aspect of the present invention is a liquid processing apparatus that causes a reaction molecule that is a harmful substance present in a liquid to undergo a photochemical reaction and converts the reaction molecule into a desired product molecule. A reaction having a harmful substance adsorbing means for adsorbing the reaction molecule, which is a harmful substance existing in a liquid, to the catalyst, and a light source for irradiating light to the adsorption reaction molecule, which is a harmful substance adsorbed to the catalyst, and photoexciting. An energy for enhancing the reactivity of the reactive molecule within a range in which the reaction for converting the reactive molecule into the generated molecule does not proceed. The energy of the catalyst is within a range not allowing the reaction to proceed with the catalyst alone. And the catalyst reacts with the photo-excited adsorption reaction molecule to act on the electronic state of the adsorption reaction molecule in the excited state and the desired generated molecule. It is comprised by what raise | generates the reaction which obtains the said production | generation molecule | numerator by reducing the activation barrier between these.
[0024]
According to this feature, the harmful substance present in the liquid can be surely removed by the harmful substance adsorbing means, and the harmful substance adsorbed on the catalyst is irradiated with light, so that the harmful substance adsorbed by the catalytic action can be reliably ensured. Can be processed.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
The photochemical reaction method of the present invention is a method in which a reactive molecule is photochemically reacted. After the reactive molecule is adsorbed on a catalyst, light having an energy for exciting the reactive molecule is irradiated to photoexcite the adsorbed reactive molecule to excite it. This is carried out by reacting the reacted molecules by catalysis.
[0026]
In the present invention, light energy is used to excite reactive molecules.
By irradiating the reaction molecule with light having sufficient energy to excite the reaction molecule, the reaction molecule becomes free of some electrons from the ground state in which the binding orbitals are filled with electrons and a strong bond is formed. The excited state is excited in the antibonding orbital. That is, some of the electrons in the binding orbital gain energy and move to a more reactive antibonding orbital. Since this excitation is generally one-electron excitation, the reaction can proceed with less energy than the energy for photolyzing the reaction molecules. In addition, since the irradiation light only needs to have sufficient energy necessary for excitation of the individual reaction molecules, it is possible to reduce energy consumed in vain in principle compared to the case of the photocatalyst.
[0027]
The reaction molecule in the excited state is generally more reactive than the reaction molecule in the ground state, so that the reaction can proceed with less energy than the molecule in the ground state. In addition, since the reactive molecules are adsorbed on an appropriate catalyst, the activation barrier of the reaction can be lowered by the catalytic action, and the reaction can be advanced more smoothly.
[0028]
In other words, by increasing the reactivity by irradiating light to the reaction molecules adsorbed on the catalyst, and at the same time lowering the activation barrier of the reaction by catalysis, the reaction can proceed smoothly and low-cost and highly efficient chemical reaction Can be realized.
[0029]
Note that the photochemical reaction in the present invention has a different reaction mechanism (for example, electrons move from an excited reaction molecule to a catalyst) different from a normal catalytic reaction in which a reaction molecule in a ground state is reacted via a catalyst. Therefore, the desired reaction can be realized by appropriately selecting the reaction conditions such as the light source, catalyst, reaction temperature, pressure, and coexisting substances. That is, the photochemical reaction in the present invention can be applied to reactions such as bond cleavage, isomerization (rearrangement), cycloaddition, ring closure, ring opening, addition, substitution, oxidation, reduction, synthesis, and decomposition. It is effective for dehalogenation reaction, oxidation reaction, and decomposition reaction when the reaction molecule is an aromatic organic halogen compound. This is because, in the ground state, electrons in bonding orbitals are excited to antibonding orbitals by light energy, so that the bonding force of carbon-chlorine bonds and specific carbon-carbon bonds in the aromatic ring is weakened, causing a decomposition reaction. This is thought to be due to a significant improvement in performance.
[0030]
The photochemical reaction according to the present invention can be used for the treatment of harmful substances such as dioxins present in a liquid phase, particularly in an aqueous phase. That is, it can be effectively used as a liquid treatment method for detoxifying treated water such as industrial wastewater, domestic wastewater, groundwater, rivers, and lake water containing harmful substances by using a photochemical reaction.
[0031]
It can also be used to treat harmful substances contained in soil and incinerated ash. That is, harmful substances contained in soil and incinerated ash can be taken into the liquid phase by extraction treatment, and the liquid phase in which these harmful substances are taken in can be treated. It is also possible to take in harmful substances once into the gas phase by extraction processing, and then bring the gas phases into contact with the liquid phase to take in harmful substances into the liquid phase and make this liquid phase the object of treatment.
[0032]
The reactive molecule is not particularly limited as long as it is a substance that is excited by irradiated light. For example, organic compounds, aromatic ring organic compounds, halogen-containing compounds contained in industrial wastewater, groundwater, rivers, lake water, etc. And harmful substances such as Here, as the organic compound, for example, carbonyl compound, alkane, alkene, aromatic hydrocarbon, conjugated unsaturated carbonyl compound, carboxylic acid, halogen compound, carbonitrile, alcohol, ether, nitrogen-containing organic substance, sulfur-containing organic substance, phosphorus-containing Examples thereof include organic substances, silicon-containing organic substances, heteroaromatic compounds, and organometallic complexes.
[0033]
Furthermore, organic coloring substances such as Blue Pigment No. 1, aromatic ring organic compounds such as anthracene, organochlorine compounds such as dioxins, dioxin precursors such as benzenes or phenols, endocrine disrupting chemicals (so-called environmental hormones) And monocyclic or polycyclic aromatic halogen compounds represented by In particular, an aromatic ring organic compound is often excited by visible light by a functional group and can be excited relatively easily.
[0034]
Moreover, these reactive molecules may be contained in industrial wastewater or groundwater. That is, the photochemical reaction method of the present invention can be used as a liquid processing method for detoxifying harmful substances such as dioxins contained in an aqueous phase such as industrial wastewater or groundwater by decomposing them.
[0035]
Any catalyst can be used without particular limitation as long as it is capable of adsorbing reactive molecules and has an effect of reducing the activation barrier between the excited reaction molecule's electronic state and the desired product molecule. . Note that the catalyst need not be a photocatalyst.
[0036]
Specific examples of preferable catalysts include, for example, Mg, Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Ru, Rh, Pd, Ag, Ta, W, Re , Os, Ir, Pt, Au, or a metal oxide thereof or a composite metal oxide thereof can be used. Here, as the metal oxide, for example, magnesium oxide, aluminum oxide, silicon oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, zirconia oxide, Niobium oxide, silver oxide, thallium oxide, tungsten oxide, etc., and examples of composite metal oxides include titanium, silicon, aluminum, platinum, ruthenium, niobium, tantalum, strontium, barium, sodium, potassium, tungsten, bismuth. , Cerium, antimony, iridium, yttrium, gallium, and other multicomponent composite systems.
[0037]
Since these catalysts usually have an adsorption function per se, the reaction molecules can be adsorbed on the catalyst by increasing the chance of contact with the reaction molecules.
[0038]
The catalyst is preferably in the form of a powder, particles or the like having a large surface area and easily adsorbing reactive molecules. Moreover, what improved adsorption ability by surface-treating a catalyst can also be used. Moreover, what has a strong adsorption function, such as a zeolite, a silica gel, activated alumina, can also be used. Moreover, what carried | supported the catalyst on substrates, such as a zeolite, a silica gel, an alumina, activated carbon (what is called a supported catalyst) can also be used. In this case, the adsorptive capacity is improved, so that the reactive molecules can be adsorbed reliably, and zeolite, silica gel, alumina and the like function as a catalyst as they are.
[0039]
Further, the catalyst is added so as to have a predetermined addition amount with respect to a target such as water to be treated so that the reaction molecules can be reliably adsorbed. The addition amount can be appropriately set according to reaction conditions such as reaction molecules, reaction temperature, and reaction time.
[0040]
Moreover, what contains metal oxides or composite metal oxides, such as soil and incineration ash, can be used as a catalyst. That is, a metal oxide or a composite metal oxide contained in soil or incinerated ash can be used as it is as a catalyst. Here, examples of the metal oxide or composite metal oxide contained in the soil include magnesia, silica, alumina, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, and copper oxide. And zinc oxide. In order to promote the reaction, the above metal, metal oxide or composite metal oxide can be further added to the soil or the like.
[0041]
The light with which the reaction molecules are irradiated needs to have at least sufficient energy to excite the reaction molecules, and can be appropriately set according to the reaction molecules. Note that it is preferable to use light having energy that excites the reactive molecules but does not excite the catalyst.
[0042]
Although it does not specifically limit as a light source, Natural light or a desired artificial light source can be utilized. Natural light can be used when long-time exposure processing is possible or when processing is performed at low cost without using an artificial light source.
[0043]
Artificial light sources can be used when efficient processing in a relatively short period of time is required, such as incoherent light sources (eg xenon lamps, halogen lamps, mercury lamps, deuterium lamps, metal halide lamps) and wavelength selection A highly coherent light source (for example, an excimer laser, an argon ion laser, a ruby laser, a semiconductor laser, or the like) can be appropriately used depending on the reactive molecule. When a light source with high wavelength selectivity is used, the reactive molecule can be selectively excited to selectively react with the reactive molecule.
[0044]
For example, when the reactive molecule is a dioxin, since the dioxin has an absorption band in the ultraviolet region (that is, a wavelength region that is photoexcited), an ultraviolet light source such as a mercury lamp can be selected. Conditions such as light irradiation time and luminous intensity can be appropriately set according to reaction conditions such as reaction molecules, reaction time, and reaction temperature.
[0045]
The energy (wavelength) capable of photoexciting the reactive molecule is specific to the state of the reactive molecule. For example, when the reactive molecule is dioxin without chlorine, 350 nm, when the reactive molecule is a 4-chlorine dioxin, 300 nm, 8 chlorine value 400 nm for dioxins, 170 nm for chloroform / carbon tetrachloride, 180 nm for lower alcohols, around 300 nm for aldehydes, a condensed polycyclic aromatic of naphthalene / pyrene / phenanthrene. 300 to 400 nm in some cases, 620 nm in the case of indigo, 520 nm in the case of eosin, 480 nm in the case of β-carotene, 660 nm in the case of chlorophyll α, 7 in the case of zinc phthalocyanine / copper phthalocyanine / phthalocyanine. 00 nm, 620 nm for malachite green, 660 nm for methylene blue, 630 nm for blue dye No. 1, 400 nm for anthracene, 350 nm for 2,4,5-trichlorophenol , Etc.
[0046]
Next, the liquid processing apparatus of the present invention will be described with reference to the drawings.
Here, FIG. 1 is a drawing showing a schematic configuration of a water treatment apparatus 10 according to an embodiment of the liquid treatment apparatus of the present invention. This water treatment device 10 includes a harmful substance adsorption device 11 as a harmful substance adsorption means for adsorbing a harmful substance contained in water to be treated to a catalyst, a catalyst supply device 12 for supplying a catalyst to the harmful substance adsorption device 11, and a catalyst. The light source 14 emits light for irradiating the harmful substances adsorbed on the reaction vessel 13, and includes a reaction vessel 13 for reacting the harmful substances, and a not-shown treated water inlet and outlet. In the present embodiment, the harmful substance adsorbing device 11 and the reaction vessel 13 are provided separately, but they can be configured integrally.
[0047]
The harmful substance contained in the water to be treated introduced into the harmful substance adsorption device 11 is adsorbed by the catalyst present in the harmful substance adsorption device 11. In order to efficiently adsorb harmful substances to the catalyst, it is preferable to increase the contact frequency between the water to be treated and the catalyst. Specifically, for example, maintaining a sufficient amount of catalyst, ensuring sufficient residence time of the water to be treated, sufficiently stirring the water to be treated, circulating the water to be treated multiple times to the catalyst. It is preferable to make it contact and to make it a suction device long in the longitudinal direction. Further, by concentrating or drying the water to be treated, harmful substances can be reliably adsorbed on the catalyst. In this case, it is preferable to provide means for assisting evaporation, concentration, and drying of the water to be treated, such as a heating means, a water vapor discharge means, and a negative pressure means, in the harmful substance adsorption device 11.
[0048]
The harmful substance adsorbed on the catalyst is transferred to the reaction vessel 13 and excited by the light from the light source 14. In this case, not only the harmful substance is photoexcited, but also a complex of the harmful substance and the catalyst constituted by adsorption of the harmful substance to the catalyst may be photoexcited. Then, the excited harmful substance is oxidized and decomposed by a catalytic action to be processed.
[0049]
It is also possible to collect and reuse the catalyst from which harmful substances have been removed. In this case, it is preferable to increase the activity of the recovered catalyst by heat treatment or the like.
[0050]
The reaction vessel 13 can be provided with a heating means. Thereby, excitation of harmful substances can be promoted to allow the reaction to proceed more smoothly, and the activity of the catalyst can be enhanced to further reduce the reaction activation barrier. The heating temperature can be appropriately set according to reaction conditions such as a catalyst, a harmful substance, and a reaction time.
[0051]
Further, the reaction vessel 13 can be provided with oxygen introducing means. By introducing oxygen, the oxidation reaction of harmful substances in the reaction system can be promoted, and the oxidation reaction and decomposition reaction of harmful substances such as dioxins can be rapidly performed. The oxygen concentration in the reaction system can be appropriately set according to reaction conditions such as harmful substances, reaction temperature, reaction time, and catalyst.
[0052]
The reaction vessel 13 can also be provided with a stirring means. By stirring the inside of the container, the harmful substance can be sufficiently irradiated with light, the harmful substance can be reliably excited, and the reaction of the harmful substance can be promoted.
[0053]
[Action]
Here, the mechanism considered as a reaction mechanism of this invention is demonstrated along FIG.
In a normal chemical reaction (indicated by a dotted line in FIG. 2), the activation energy of E1 is required for the reactive molecule to cross the barrier and become a generated molecule. That is, since the reaction does not proceed unless energy corresponding to E1 is supplied, the reaction rate is slow and high energy is required to promote the reaction.
[0054]
On the other hand, in the photochemical reaction in the present invention (shown by a solid line in FIG. 2), the adsorbed reaction molecule is brought into an excited state by irradiating light having energy sufficient to photoexcite the reaction molecule adsorbed on the catalyst. The internal energy of itself can be increased to increase the reactivity, and at the same time, the activation barrier of the reaction can be lowered by catalysis. That is, a new reaction path having an activation energy of E2 smaller than E1 can be formed. Thus, since it becomes an activation barrier smaller than a normal chemical reaction, it is easy to advance the reaction, the efficiency of the reaction is high, and energy is saved.
[0055]
【Example】
EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited at all by these.
[0056]
Blue dye No. 1 (produced by Tokyo Chemical Industry Co., Ltd .; model number F-0147) excited by light having a wavelength of around 630 nm as a reactive molecule, Anthracene (produced by Wako Pure Chemical Industries, Ltd .; model number) excited by light having a wavelength of around 400 nm 011-009855), 2,4,5-trichlorophenol (manufactured by Wako Pure Chemical Industries, Ltd .; model number 500-34441) excited by light having a wavelength of around 350 nm, and excited by light having a wavelength of about 200 nm or less as a catalyst. Silicon oxide (Fuji Silysia Chemical Co., Ltd .; model CARiACT-Q30), zirconium oxide excited by light with a wavelength of about 250 nm or less (Daiichi Rare Element Chemical Co., Ltd .; model RC100) is used, and the light source emits light. Black light with a wavelength of 300 to 400 nm and an output of 15 W (manufactured by Nippon Electric Co., Ltd .; model number FL15BLB) It was used. The light from the black light used as the light source has sufficient energy to excite the reactive molecules, but has insufficient energy to excite the catalyst.
[0057]
Example 1
A blue dye aqueous solution was prepared by dissolving 0.5 g of Blue Dye No. 1 in 1000 ml of distilled water. A predetermined amount of this blue dye aqueous solution is dropped onto 10 g of silicon oxide using a whole pipette, and after sufficient stirring, it is dried to prepare a sample in which blue dye No. 1 is adsorbed to the catalyst, and this sample is prepared in a dark room The sample was left at 1 cm directly under the black light so that light was sufficiently irradiated. And after irradiating light for 24 hours in a humid environment, the decomposition rate of blue pigment No. 1 was evaluated by quantitative analysis using GC-MS. The results are shown in Table 1.
[0058]
Comparative Example 1
It carried out like Example 1 except not having implemented light irradiation.
[0059]
Example 2
The same procedure as in Example 1 was performed except that zirconium oxide was used in place of silicon oxide as a catalyst.
[0060]
Comparative Example 2
It carried out similarly to Example 2 except not having implemented light irradiation.
[0061]
Comparative Example 3
The same procedure as in Example 1 was performed except that silicon oxide was not used.
[0062]
Comparative Example 4
The same procedure as in Example 1 was performed except that light irradiation was not performed and silicon oxide was not used.
[0063]
Example 3
Anthracene / acetone water mixed solution was prepared by dissolving anthracene in the acetone water mixed solution to a concentration of 100 ppm. A predetermined amount of this mixed anthracene / acetone solution was dropped onto 10 g of zirconium oxide using a whole pipette and stirred sufficiently, and then dried to prepare a sample in which anthracene was adsorbed on a catalyst, and this sample was prepared in a dark room. The sample was left at 1 cm directly under the black light so that light was sufficiently irradiated. And after irradiating light for 24 hours in a humid environment, the decomposition rate of anthracene was evaluated by quantitative analysis using GC-MS. The results are shown in Table 1.
[0064]
Comparative Example 5
It carried out like Example 3 except not having implemented light irradiation.
[0065]
Comparative Example 6
The same operation as in Example 3 was performed except that zirconium oxide was not used.
[0066]
Comparative Example 7
The same procedure as in Example 3 was performed except that light irradiation was not performed and zirconium oxide was not used.
[0067]
Example 4
2,4,5-Trichlorophenol was dissolved in the acetone water mixed solution to a concentration of 100 ppm to prepare a 2,4,5-trichlorophenol / acetone water mixed solution. A fixed amount of this 2,4,5-trichlorophenol / acetone water mixed solution was dropped into 10 g of zirconium oxide using a whole pipette and stirred well, and then dried to adsorb 2,4,5-trichlorophenol to the catalyst. The prepared sample was prepared, and this sample was allowed to stand so that light was sufficiently irradiated to 1 cm directly under the black light prepared in the dark room. And after irradiating light for 24 hours in a humid environment, the decomposition rate of 2,4,5-trichlorophenol was evaluated by quantitative analysis using GC-MS. The results are shown in Table 1.
[0068]
Comparative Example 8
It carried out like Example 4 except not having implemented light irradiation.
[0069]
Comparative Example 9
The same operation as in Example 4 was performed except that zirconium oxide was not used.
[0070]
Comparative Example 10
It carried out like Example 4 except not having implemented light irradiation and not using a zirconium oxide.
[0071]
[Table 1]

[0072]
From Example 1, Example 2, Example 3 and Example 4, it can be seen that the decomposition reaction proceeds by light irradiation and the presence of a catalyst.
From Comparative Example 1, Comparative Example 2, Comparative Example 5, and Comparative Example 8, it can be seen that the reaction does not proceed when light irradiation is not performed even if a catalyst is present.
From Comparative Example 3, Comparative Example 6 and Comparative Example 9, it can be seen that the reaction is not progressing if no catalyst is present even after light irradiation.
From Comparative Example 4, Comparative Example 7 and Comparative Example 10, it can be seen that the reaction does not proceed when no catalyst is present and no light irradiation is performed.
[0073]
From the above results, it is possible to increase the reactivity by irradiating the reaction molecule adsorbed on the catalyst with light having energy for exciting the adsorption reaction molecule, and at the same time, the reaction can proceed with high efficiency. I found that I can do it. That is, the reaction can proceed by irradiating light having a relatively low energy in the absorption wavelength region of the reactive molecule without using light having an energy sufficient to directly photolyze the reactive molecule. In addition, the reaction can proceed by exciting reaction molecules adsorbed on the catalyst without photoexciting the catalyst as in the case of a photocatalyst. Therefore, a highly efficient chemical reaction can be realized at a low cost.
[0074]
【The invention's effect】
As described above, according to the present invention, the reactive molecules are adsorbed on the catalyst, and the reactivity of the reactive molecules is enhanced by irradiating the adsorbed reactive molecules with light to excite them. The compound synthesis / decomposition reaction by the photochemical reaction can be advanced by lowering. Therefore, it is possible to advance the reaction with low energy and high efficiency, and for example, wastewater containing harmful substances such as dioxins can be efficiently processed at low cost.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram for explaining a photochemical reaction device.
FIG. 2 is a drawing for explaining a photochemical reaction.
[Explanation of symbols]
10 Water treatment equipment
11 Toxic substance adsorption device
12 Catalyst supply device
13 reaction vessel
14 Light source

Claims (6)

A photochemical reaction method in which a reactive molecule is caused to undergo a photochemical reaction to convert the reactive molecule into a desired generated molecule,
After the adsorption of the reactant molecules into the catalyst, an energy to enhance the reactivity of the reactant molecules in a range not to proceed the reaction for changing the reactant molecules to the product molecule, the only the catalyst for the catalytic Irradiating light having energy in a range that does not allow the reaction to proceed , photoexcited the adsorbed reaction molecules adsorbed on the catalyst,
A reaction for obtaining the product molecule by causing a catalyst that reduces an activation barrier between an electronic state in the excited state of the reaction molecule and the desired product molecule is caused to act on the photoexcited reaction molecule. And photochemical reaction method.   2. The photochemical reaction method according to claim 1, wherein the reactive molecule is an organic halogen compound.   3. The photochemical reaction method according to claim 1, wherein the reactive molecule exists in a liquid phase.   The photochemical reaction method according to any one of claims 1 to 3, wherein the catalyst is a metal oxide.   The liquid processing method characterized by processing a liquid using the photochemical reaction method as described in any one of Claims 1-4. A liquid processing apparatus for causing a photochemical reaction to a reactive molecule that is a harmful substance present in a liquid to convert the reactive molecule into a desired generated molecule,
A harmful substance adsorbing means for adsorbing the reaction molecule, which is a harmful substance present in the liquid, to the catalyst;
A reaction vessel having a light source that irradiates light to the adsorption reaction molecules, which are harmful substances adsorbed on the catalyst, and is photoexcited;
The light source is energy that enhances the reactivity of the reactive molecule within a range in which the reaction for changing the reactive molecule to the product molecule does not proceed, and energy in a range that does not allow the catalyst to proceed with the catalyst alone. It is configured to irradiate light having a photoexcitation of the adsorption reaction molecule,
The catalyst acts on the photo-excited adsorption reaction molecule to reduce the activation barrier between the electronic state of the adsorption reaction molecule in the excited state and the desired product molecule, thereby causing the reaction to obtain the product molecule. A liquid processing apparatus, characterized in that the liquid processing apparatus is configured to be awakened.

Images